EPA-600/2-74-003
March 1974
Environmental Protection Technology Series
The Development of Phosphate-Free
Heavy Duty Detergents
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Office of Research and Development
U.S. Environmental Protection Agency
Washington, D.C. 20460
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and
Monitoring, Environmental Protection Agency, have
been grouped into five series. These five broad
categories were established to facilitate further
development and application of environmental
technology. Elimination of traditional grouping
was consciously planned to foster technology
transfer and a maximum interface in related
fields. The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL
PROTECTION TECHNOLOGY series. This series
describes research performed to develop and
demonstrate instrumentation, equipment and
methodology to repair or prevent environmental
degradation from point and non-point sources of
pollution. This work provides the new or improved
technology required for the control and treatment
of pollution sources to meet environmental quality
standards.
EPA REVIEW NOTICE
This report has been reviewed by the Office of Research and
Development, EPA, and approved for publication. Approval does
not signify that the contents necessarily reflect the views
and policies of the Environmental Protection Agency, nor does
mention of trade names or commercial products constitute
endorsement or recommendation for use.
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EPA-600/2-74-003
March 1974
THE DEVELOPMENT OF PHOSPHATE-FREE HEAVY DUTY
DETERGENTS
By
Anthony M. Schwartz
A. Eleanor Davis
Project 16080 FWE
Program Element 1BB045
Project Officer
Dr. A. Forziati
Office of Program Management
U.S. Environmental Protection Agency
Washington, D.C. 20460
Prepared for
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
For sale by the Superintendent of Documents, U.S. Government Printing Office
Washington, D.0.80408 - Price I2.W
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ABSTRACT
The purpose of this project was to demonstrate state-of-the-art possi-
bilities for producing phosphate-free household laundry detergents of
satisfactory environmental and performance characteristics. The work
involved formulation of several hundred experimental detergent compo-
sitions using different surfactant-builder combinations. These were
tested for laundering performance, acceptability of physical form,
biodegradability, aquatic toxicity, potential hazard in use, and growth
stimulation of algae. Feasibility of economical production on an
industrial scale was also considered. Some partially satisfactory
formulations were arrived at, their shortcomings being with regard
to performance and/or economic feasibility, the two factors that must
in the immediate state-of-the-art be traded off. These formulations
coincide remarkably with the formulations developed independently
by the industry and offered in jurisdictions where phosphate-con-
taining detergents are banned. Some new builders and surfactant-
builder combinations showed considerable promise, but could not be
completely checked out with regard to all stipulated characteristics.
Further work with these novel materials is recommended, but only
along environmental and health-hazard lines.
This report was submitted in fulfillment of Project Number 16080 FWE
and Contract Number 14-12-875 by Gillette Research Institute under the
sponsorship of the Environmental Protection Agency. Work was com-
pleted as of November 30, 1973.
ii
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TABLE OF CONTENTS
Page
Abstract ii
List of Figures iv
List of Tables x
Acknowledgements xiii
Conclusions xiv
Recommendations xvii
Sections
Introduction 1
Program Design 4
Experimental 15
Results - 26
Discussion 45
Tables 1-13 53
Figures 1-36 89
Appendix A. Test Methods, Non- Launder ing 125
Appendix B. Laundering Test Methods Development 155
Tables BG1 - BG9 174
Figures 37 - 49 187
Appendix C. Code List of Materials 200
Appendix D. Selected Recent Patents Relating to Phosphate-Free 210
Household Laundering Detergents
Appendix E. Chronic Aquatic Toxicity Tests 223
iii
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LIST OF FIGURES
Figure No. Title Page
1. Detergency v. concentration. Item 20-147 89
High titer soap. Series ref. 210.
Empa soil. 200 ppm water.
2. Detergency v. concentration. Item 86-706. 90
Soap-lime soap disperser. Series ref. 210.
Empa soil. 200 ppm water.
3. Detergency v. concentration. Item 86-707. 91
Soap-lime soap disperser. Series ref. 210.
Empa soil. 200 ppm water.
4. Detergency v. concentration. Item 86-708. 92
Soap-lime soap disperser. Series ref. 210.
Empa soil. 200 ppm water.
5. Detergency v. concentration. Item 90-730 93
anionic sulfonate. Series ref. 243.
Colgate soil. Tap water. Blend fabric.
6. Detergency v. concentration. Item 90-730 94
anionic sulfonate. Series ref. 243.
Colgate soil. Tap water. Cotton.
7- Detergency v. concentration. IAS and Item 95
90-730 anionic sulfonate. Series ref. 239C.
Colgate soil. 200 ppm water. Blend fabric.
8. Detergency v. concentration. IAS and Item 96
90-730 anionic sulfonate. Series ref. 239C.
Colgate soil. 200 ppm water. Cotton.
9. Detergency v. concentration. IAS and Item 97
90-730 anionic sulfonate. Series ref. 239.
Spangler soil multicycle. 200 ppm water.
Blend fabric.
iv
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LIST OF FIGURES (Continued)
Figure No. Title Page
10. Detergency v. concentration. IAS and Item 98
90-730 anionic sulfonate. Series ref. 239.
Spangler soil multicycle. 200 ppm water.
Cotton.
11. Detergency v. concentration. IAS and IAS- 99
CMOS (item 80-647) and Item 90-730 anionic
sulfonate. Series ref. 243. Spangler soil
multicycle. Tap water. Blend fabric.
12. Detergency v. concentration. IAS and IAS- 100
CMOS (item 80-647) and Item 90-730 anionic
sulfonate. Series ref. 243. Spangler soil
multicycle. Tap water. Cotton.
13. Detergency v. concentration. Items 42-350 101
and 42-353 zwitterionic. Series ref. 247
and 252 (for AATCCWOB). Colgate soil.
200 ppm water. Blend fabric.
14. Detergency v. concentration. Items 42-350 102
and 42-353 zwitterionic. Series ref. 247
and 252 (for AATCCWOB). Colgate soil.
200 ppm water. Cotton.
15. Detergency v. concentration. Items 104-856 103
and 108-880 anionics. Series refs. 252
(AATCGWOB) 250 and 256. Colgate soil.
200 ppm water. Blend fabric.
16. Detergency v. concentration. Items 104-856 104
and 108-880 anionics. Series refs. 252
(AATCCWOB) 250 and 256. Colgate soil.
200 ppm water. Cotton.
17. Detergency v. concentration. Items 104-855 105
(detergent D) and 96-782 (detergent E).
Series refs. 252 (AATCCWOB) and 248.
Colgate soil. 200 ppm water. Blend fabric.
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LIST OF FIGURES (Continued)
Figure No. Title
18. Detergency v. concentration. Items 104-855 106
(detergent D) and 96-782 (detergent E).
Series refs. 252 (AATCCWOB) and 248.
Colgate soil. 200 ppm water. Cotton.
19. Detergency v. concentration. Items 104-855 107
(detergent D) and 96-782 (detergent E).
Series refs. 253 and 254. Spangler multi-
cycle. 200 ppm water. Blend fabric.
20. Detergency v. concentration. Items 104-855 108
(detergent D) and 96-782 (detergent E).
Series refs. 253 and 254. Spangler multi-
cycle. 200 ppm water. Cotton.
21. Detergency v. concentration. Items 96-783 109
(detergent C) and 96-784 (detergent T).
Series ref. 240. Colgate soil. 200 ppm
water. Blend fabric.
22. Detergency v. concentration. Items 96-783 110
(detergent C) and 96-784 (detergent T).
Series ref. 240. C9lgate soil. 200 ppm
water. Cotton.
23. Detergency v. concentration. Series ref. 259 111
(AATCCWOB) 268 (HEIDA). Colgate soil.
200 ppm water. Blend fabric.
24. Detergency v. concentration. Series ref. 259 112
(AATCCWOB) 268 (HEIDA). Colgate soil.
200 ppm water. Cotton.
25. Detergency v. concentration. Item 100-823. 113
Series ref. 252 (AATCCWOB) 255 (item 100-823).
Colgate soil. 200 ppm water. Blend fabric.
vi
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LIST OF FIGURES (Continued)
Figure No. Title Page
26. Detergency y. concentration. Item 100-823. 114
Series ref. 252 (AATCCWOB) 255 (item 100-823).
Colgate soil. 200 ppm water. Cotton.
27. Detergency v. concentration. Item 104-860. 115
Series ref. 259 (AATCCWOB) 257 (item 104-860).
Colgate soil. 200 ppm water. Blend fabric.
28. Detergency v. concentration. Item 104-860. 116
Series ref. 259 (AATCCWOB) 257 (item 104-860).
Colgate soil. 200 ppm water. Cotton.
29. Detergency v. concentration. Item 106-866. 117
Series ref. 258, 259, 260. Colgate soil.
200 ppm water. Blend fabric.
30. Detergency v. concentration. Item 106-866. 118
Refs. 258, 259, 260. Colgate soil. 200 ppm
water. Cotton.
31. Detergency v. concentration. Item 106-866. 119
Series ref. 267. Spangler multicycle.
200 ppm water. Blend fabric.
32. Detergency v. concentration. Item 106-866. 120
Series ref. 267- Spangler multicycle.
200 ppm water. Cotton.
• 33. Detergency v. concentration. Item 80-647. 121
Series ref. 243. Colgate soil. 200 ppm water.
Blend fabric.
34. Detergency v. concentration. Item 80-647. 122
Series ref. 243. Colgate soil. 200 ppm water.
Cotton.
35. Detergency v. concentration. Item 90-279. 123
Series ref. 240. Colgate soil. 200 ppm water.
Blend fabric.
vii
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LIST OF FIGURES (Continued)
Figure No. Title Page
36. Detergency v. concentration. Item 90-279. 124
Series ref. 240. Colgate soil. 200 ppm water.
Cotton.
37. Fabric finish study. Spangler multicycle. 187
200 ppm water. AATCCWOB 0.3%. Cotton.
38. Fabric finish study. Spangler multicycle. 188
AATCCWOB 0.3%. Dacron.
39. Fabric finish study. Spangler multicycle. 189
200 ppm water. AATCCWOB 0.3%. Blend fabric.
40. Fabric finish study. Colgate soil. 200 ppm 190
water. AATCCWOB. Cotton. Green reflectance
values.
41. Fabric finish study. Colgate soil. 200 ppm 191
water. AATCCWOB. Cotton. Whiteness values.
42. Fabric finish study. Colgate soil. 200 ppm 192
water. AATCCWOB. Dacron. Green reflectance
values.
43. Fabric finish study. Colgate soil. 200 ppm 193
water. AATCCWOB. Dacron. Whiteness values.
44. Fabric finish study. Colgate soil. 200 ppm 194
water. AATCCWOB. Blend fabric (commercial
permanent press finish). Green reflectance
values.
45. Fabric finish study. Colgate soil. 200 ppm 195
water. AATCCWOB. Blend fabric (commercial
permanent press finish). Whiteness values.
46. Chelation curves of typical strong, high 196
efficiency chelants, NTA and maleic acid
telomer.
viii
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LIST OF FIGURES (Continued)
Figure No. Title Page
47. Chelation curves of weak, moderate efficiency 197
chelants, Na citrate and CMOS.
48. , Low efficiency polymeric chelants. Akzo 294-10 198
moderately strong, POCNa moderately weak.
49. Effect of molecular weight on chelating behavior 199
in polyacrylic acids (Calnox). Akzo OS starch
typical of low efficiency moderate strength poly-
meric builders.
ix
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LIST OF TABLES
Table No. Title .r, ..Page
1 Detergency of Surfactants without Builder 53
la Detergency of Surfactants without Builder 57
2 Detergency of Surfactant - Carbonate For- 59
mulations
3 Detergency of Surfactant - NTA Formulations 60
3a Detergency of NTA - Alpha Olefin Sulfonate 61
Formulation at Varying Water Hardness and
Concentration
4 Detergency of Surfactant - SAND Formulations 62
5 Detergency of Surfactant - SHIM Formulations « 63
6 Detergency of Polymeric Builder - Surfactant 64
Formulations
6a Detergency of Polymeric Builder - Surfactant 66
Formulations
. ' \
7 Detergency of Monomeric Builder - Surfactant 70
Formulations
> •',
la Detergency of Monomeric Builder - Surfactant 74
Formulations
, _- ;•
7b Effect of Concentration on Whiteness of 75
Soiled Swatches
4
•• t
7c Effect of Water Hardness on Whiteness-of 76
Soiled Swatches
:->J
8 Representative Drum-Drier Formulations of 77
Satisfactory Character
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LIST OF TABLES (Continued)
Table No. Title Page
8a Representative Liquid Formulations of 78
Satisfactory Character
9 Stimulatory Effect on Growth of Algae 79
10 Acute Aquatic Toxicity of Detergents and 82
Their Ingredients
ll Estimation of Biodegradability of Materials 84
Used in Detergent Formulations "
12 Hazard Test Results. Detergent Formulations 86
12a Identification of Formulations in Table 12 87
13 Effect of Multiple Washings on Build Up of 88
Impurities in Fabric
BG1
BG2
k.
K
BG2A
BG3
BG3A
BG4
BG4A
Instrumental Reflectances of Laundered
Pillowcases After Six Cycles in Bundle Test
Tergotometer Soil Removal Values
Cotton, 0.2%, Tap Water
Tergotometer Redepositlon Values
Cotton, 0.2%, Tap Water
Tergotometer Soil Removal Values
Durapress, .2%, Tap Water
Tergotometer Redeposition Values
; Durapress, 0.2%, Tap Water
Tergotometer Soil Removal Values
Cotton, 0.3%, Tap Water
Tergotometer Redeposition Values
Cotton, 0.3%, Tap Water
174
175
176
177
178
179
180
xi
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LIST OF TABLES (Continued)
Table No. Title
BG5 Tergotometer Soil Removal Values 181
Durapress, 0.3%, Tap Water
BG5A Tergotometer Redeposition Values 182
Durapress, 0.3%, Tap Water
BG6 Rankings of Detergents in Different 183
Washing Procedures
BG7 Whiteness Rankings of Soiled Swatches 184
in Procedures 1 and 2
BG8 Whiteness Rankings of Soiled Swatches 185
in Procedures 3, 4 and 5
BG9 Whiteness Rankings of Soiled Swatches 186
Detergents M and D in Procedures 3,
4 and 5.
xii
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ACKNOWLEDGEMENTS
The writers wish to acknowledge the invaluable assistance of the
project's staff, especially those whose responsibility extended over
the entire period of its performance: Dr. Vera Usdin for biological
and biochemical aspects of the program; Mr. Julian Berch and
Mr. Abraham Fookson for chemical analysis and formulation;
Dr. Ruth Patrick and Dr. Arthur Scheier of the Academy of Natural
Sciences, Philadelphia, who supervised and conducted all the work on
aquatic toxicity. We extend special thanks to the EPA staff members
who advised on and monitored the work; and finally to the many com-
panies in the detergent and chemical industries that generously con-
tributed materials and information for use in the program.
.Xiii
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CONCLUSIONS
1. The problem was to provide a phosphate-free heavy duty household
laundering detergent having the stipulated environmental properties
and consumer-acceptable laundering performance. The most immediately
applicable technical solutions worked out in the course of this pro-
ject are as follows:
a. A detergent consisting essentially of a mixture of conven-
tional surfactants substantially unbuilt, the surfactant
content being in the range of 40% or higher, i.e., two or
more times the surfactant content of current conventional
phosphate-built detergents. This detergent would be
liquid in form.
b. A detergent consisting of about 25% conventional sur-
factant and 20-40% of silicate or mixed silicate-carbonate
as a builder. The carbonate content of this mixture
should not be higher than about 25%. This detergent
would be solid.
c. A detergent consisting of a mixture of conventional sur-
factants or special surfactants of high washing power
together with sodium citrate or citrate and silicate
as the builder. These detergents can be liquid or solid
depending on the surfactant.
xiv
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It is of interest that detergents in all three of these
classes have been developed by the industry and offered
in the marketplace in jurisdictions where phosphate-
built detergents are banned.
2. Soap and soap-lime soap disperser combinations are not considered
to offer performance of the type to which detergent users are ac-
customed. Even in moderately hard water a high concentration is
needed to provide good soil removal, and the build-up of residues
in the fabric can become objectionably high.
3. From the performance point of view NTA is a satisfactory sub-
stitute for phosphate. Its adoption in commercial product would ap-
pear to hinge on questions of possible hazard, outside the scope of
this project.
4. The product beta hydroxyethyl iminodiacetic acid (abbreviated
SHIM or HEIDA) appears to be a very promising potential substitute
for phosphate. It has high building power and passes the stipulated
tests for environmental acceptability. It appears close to the FDA
and CPSC borderlines with regard to toxicity, and requires further
testing on this point. It appears more suited to liquid than to
solid formulations.
5. The product carboxymethyloxysuccinic acid (abbreviated CMOS)
is a potential substitute for phosphate. In building power it is
somewhat stronger than citrate, particularly with the most widely
used surfactants, but not as strong as phosphate. Environmentally
it appears acceptable.
xv
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6. The polymeric product POCNa, produced and offered In Germany
as a substitute for phosphate builder, appears to have some potential
as a phosphate substitute. It is relatively weak in building power,
however, and possibly too slow in biodegradation.
7. Several other polymeric products appear to provide satisfactory
building action and be at least partially biodegradable. Whether or
not they are satisfactorily biodegradable has not yet been settled.
8. A large number of patents have recently issued and continue to
issue on phosphate-free detergents that purport to be environmentally
acceptable. Several of the patent examples have been partly investi-
gated, and some show promise.
9. The concept of laundering with low concentrations of unbuilt,
environmentally acceptable, non-hazardous surfactants, in water
softened by in-situ ion exchange resins, has been cursorily explored.
It is proposed as a concept worthy of further investigation.
10. The satisfactory replacement of current phosphate-built deter-
gents by environmentally acceptable non-hazardous phosphate-free
detergents of substantially equal performance is a very difficult
economic problem as well as a technical problem. Technical an-
swers appear to be near realization, although the complete establish-
ment of environmental acceptability and lack of hazard is a long and
difficult task (cf. NTA). The necessity for a trade-off between
cost and performance must be realized, since phosphate is a relatively
inexpensive commodity. Furthermore, the economic dislocations and
the time involved in effecting such a replacement would under the
best of circumstances be formidable.
xvi
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RECOMMENDATIONS
In view of the findings of this project, summarized in the DISCUSSION
and CONCLUSIONS sections of this report, it is recommended that:
1. Performance and/or sponsorship of experimental work directed
explicitly toward the formulation of phosphate-free detergents be
discontinued. This relates especially to the measurement and im-
provement of laundering performance.
2. The detergent industry and its suppliers be encouraged to
develop complete data on the environmental and hazard characteristics
of new non-phosphate detergent formulations and their essential
ingredients.
3. Full cooperation in this endeavor be offered with regard to
stipulating the various characteristics and establishing test pro-
tocols and standards of acceptability for them.
xvii
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INTRODUCTION
When this project was started in the summer of 1970 essentially all of
the heavy duty household laundering detergents marketed in the U.S.A.
contained as a necessary ingredient a substantial proportion of sodium
tripolyphosphate. The potential ecological hazards of this material
and other phosphorus compounds had been recognized, but no generally
acceptable phosphate-free laundering compositions had been developed
to the stage of commercial feasibility. The objective of the project
accordingly was to formulate a phosphate-free heavy duty household
laundering detergent which would be:
a. satisfactorily biodegradable.
b. non-stimulating to undesirable algae.
c. non-toxic to fish and representative lower organisms in fish food
chains.
d. safe to use and to have in the household.
e. satisfactory to the consumer in its performance.
f. economically feasible to produce and market on a scale comparable
with that of currently used phosphate-containing detergents;
i.e. industrially and commercially feasible.
This was intended essentially as a demonstration program. The aim was
to find out if such a product could be made using known materials and
existing technology. It was understood that there could be no compro-
mise with either the environment or product safety requirements
(items a-e). These could be clearly defined in terms of test protocols,
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and no inordinate difficulty was anticipated in reaching agreement on
such protocols. Industrial feasibility and satisfactory performance,
.\ «
however, are not so easily defined and agreed upon. With regard to
these items- the following stand was adopted.
• Industrial feasibility implies that raw materials are adequate and pro-
duction process.es sufficiently developed to allow reasonably early pro-
duction in the mi11ion-ton per year range. Judgment of industrial
'feasibility is based partly on our knowledge of the chemical industry
•and partly oji assurances of those offering the candidate materials.
Commercial feasibility is based on two factors, cost and performance.
Performance is in turn made up of a large number of sub-factors which
»
the household consumer considers in making her final judgment of ac-
ceptability. These include not only soil removing power (the factor
Usually weighted most heavily) but also convenience of physical form,
rapid solubility at laundering temperatures, no adverse effects on fab-
rics or washing machine, etc. It is in the cost and performance factors
where some flexibility is allowable (in fact, inevitable) and where
trade-offs can be made. Just as there are several different types of
commercially successful phosphate detergent, we visualized more than
ome type pf phosphate^-free detergent as being able to make a commercial
' ' .•'••''•
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keep fully abreast of announced developments and follow up on any that
appeared meritorious. We could thus be regarded not only as researchers
seeking to develop a new product but in a limited sense as surrogate
consumers assaying the suitability of products that might appear from
other sources.
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PROGRAM DESIGN
A. LIMITATIONS ON MATERIALS SELECTED
To be considered as candidate detergent ingredients (surfactant, builder
or auxiliary) the materials used in this program had to meet certain
economic and commercial requirements relating to cost and availability.
Furthermore, certain types of auxiliary ingredients have been excluded
from the study entirely. Among the more important items in this latter
category are enzymes, bleaches (both peroxygen and chlorine types),
brighteners, fabric softeners, emollients, anti-tarnish, anti-caking
and anti-dusting agents. The mission was to find a non-phosphate for-
mulation that performed like the phosphate-containing ones. Phosphate
contributes, along with the surfactant, to true physical removal of
soil; and therefore this was the key performance effect we studied.
Enzymes and bleaches remove soil by chemical rather than physical
action. Brighteners contribute only the appearance of soil removal.
The other ingredients are not only unrelated to soil removal but are
unaffected by the presence or absence of phosphate. Thus the ingre-
dients of interest in this study were surfactants, builders, anti-
redeposition agents, and any other materials (solvents, inorganic de-
tergents, etc.) that might contribute to physical soil removal.
The economic requirements were somewhat more difficult to pinpoint.
As mentioned above, it was not considered likely that a replacement
formulation could be found equal;in cost efficiency to the phosphate
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detergents. The objective was to minimize the sacrifice that would
have to be made in cost efficiency, and to satisfactorily balance the
cost factor against the performance factor. The performance can be,
and was, measured in the laboratory with some precision. Costs are
more difficult to estimate unless one is actually in commerce, ready
to negotiate firm purchase and sales contracts. They can be estimated
with reasonable closeness, however, if the process of manufacture is
known, by extrapolation from raw material costs, or from present prices
if the material is now being made on a limited scale. Almost as im-
portant as the cost is the potential availability of the candidate
material on a large scale. Detergent phosphate is used at a rate of
well over one million tons per year, and detergent compositions at a
rate of over three million tons per year. The only materials considered
seriously were those that seemed potentially available in the million
ton per year range at a cost not too far removed from present deter-
gent component costs.
Cost is of special importance when considering the builder alone rather
than the whole detergent formulation. Many surfactants (soap is pos-
sibly the best known example) can deliver good laundering performance
if used at sufficiently high concentration. In such cases, the builder
must be less costly than the surfactant for a builder*-surf act ant combina-
tion to make economic sense. >
No formal limitation was placed on the source of the experimental mate-
rials. Most of the surfactants were available as items of commerce,
although a few were submitted as development samples by established
surfactant manufacturers. Most of the builders were in the category
of development samples from established chemical manufacturers. A
very small proportion of the builders were synthesized in our labora-
tories, in most instances to establish guidelines on the relationship
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between chemical structure and detergent building effect. It was an
explicit policy to avoid or at least minimize the use of newly synthe-
sized compounds, because the complete proving of safety, performance
and feasibility would take too long a time. Primary attention was
given to materials about which such information was available.
B. LIMITATIONS ON CONSUMER ACCEPTABILITY
To gain customer acceptance a detergent product must meet certain re-
quirements with regard to physical form. Suspensions or emulsions that
tend to settle or break in the package are not considered acceptable.
Powdered or beaded products that sinter to a solid cake or deliquesce
are similarly unacceptable. The paste form, although acceptable for
industrial detergents, is not favored for household use. Acceptable
forms include the spray dried bead, dry blend coarse powder, tablet,
and liquid. We did not undertake to produce the formulations in their
final ready-to-package physical form. We did determine, by drum drying,
whether stable solid non-hygroscopic, non-caking forms could be pro-
duced. We also determined whether our formulations could be made into
stable liquids of adequately high concentrations. No attempts were
made to produce any of the formulations in tablet form,
An experimental liquid formulation was not considered satisfactory
unless it contained only one liquid phase and was sufficiently con-
centrated to match currently successful commercial liquids. Solid
formulations were considered satisfactory only if they were non-
caking, non-hygroscopic and free-flowing. Aside from these require-
ments relatively little emphasis was placed on the physical form of
our formulations. Preferences in physical form, appearance, fragrance,
etc. vary widely from one detergent manufacturer to another. They
are greatly influenced by considerations of large scale production
-------
and market Lag, and therefore we regarded the perfecting of physical
form as a secondary rather than a primary requirement of the project.
<
C. SCOPE OF THE TESTING PROGRAM
/
To be considered satisfactory the final formulations had to pass tests
in five different categories: 1) Algal stimulation; 2) Aquatic toxi-
city; 3) Biodegradability; 4) Hazard in use (human toxicity) and 5)
Laundering performance. It is evident that such tests might be extend-
ed ad infinitum, and that the set of test protocols must be adopted on
a more or less arbitrary basis. The tests specified in the contract
were judged at the time of their adoption to be optimum selection with-
in the budgetary and time limits of the project. During the course of
the project they have changed relatively little, although some new tests
have been added.
Basic protocols for the tests in all five categories are given in Appen-
dix I. The algal stimulation test procedures were adopted from the pro-
visional algal assay procedures ("PAAP") of the Pacific Northwest Water
Laboratory, EPA, and were periodically revised to keep in conformity
with PAAP revisions. The aquatic toxicity tests have remained unchanged
throughout the course of the program and require little comment. It
should be noted that although the results of the snail and fish tests
are reported to two or three significant figures their reproducibility
is sometimes no better than two or three fold. This is not uncommon
in bioassays where the number of specimens is limited. The reprodu-
cibility of the diatom growth inhibition test is considerably better,
but it merits no more than a second significant figure.
In a program of this character the testing of biodegradability pre-
sents a difficult problem. Even under the most favorable circumstances
it is difficult to determine the ease with which an organic compound
will be oxidatively consumed by microorganisms in a natural (stream)
-------
or artificial (sewage plant) environment. The usual procedure is to
follow the disappearance of the test material by direct chemical anal-
ysis. This requires an analytical method that is reliable in the parts
per million range. Such analytical methods were not available for the
great majority of surfactants and organic builders of interest in this
program nor was it feasible to develop them. Another difficulty in
testing for biodegradability is that the distribution of microorganism
species in the inoculum or "seed" that is used differs greatly from
source to source. A third major difficulty is that almost all seeds
must undergo a period of acclimation before they can attack an organic
material that is new to them, even if that material proves ultimately
to be biodegradable. Contrariwise, by careful acclimation microbes
can be nurtured and developed to oxidatively consume almost any organic
material, even some that are considered germicides. There is according-
ly much arbitrariness in specifying an acclimation procedure and a
source of microbes.
Except in those few cases where analytical methods were available we
used the biochemical oxygen demand (BOD) to indicate aerobic biodegrad-
ability, comparing it with the chemical oxygen demand (COD) and with
the BOD of standard compounds known to be readily biodegradable. A
variety of acclimation conditions and procedures were used when neces-
sary. Similarly, a variety of different sludge sources were tried in
cases where the first one tried (EPA experimental sewage disposal unit
in the District of Columbia) failed to initiate biodegradation.
The estimation of hazard in use is another area in which compromises
and arbitrary decisions must be made in setting the procedure. At the
start of the program five tests were specified and written into the
contract: acute oral toxicity on rats, acute dermal toxicity on rab-
bits, opthalmic irritation on rabbits, primary skin irritation on rab-
bits, and primary skin irritation and sensitization on humans.
8
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Food and Drug Administration protocols were used. Relatively early in
the course of the project controversy over the possible teratogenic and
carcinogenic effects of NTA received much public attention. At a some-
what later date similar' concern was expressed over possible esophageal
damage by excessively alkaline detergents. It was decided not to per-
form any tests of carcinogenesis or teratogenesis on candidate formula-
tions, but to include a test for esophageal damage. The test adopted
was a provisional test, utilizing rabbits as the test animal, provided
by the Bureau of Product Safety, FDA. Obviously, materials such as NTA,
i
that have been objected to for properties we do not assess, were exclu-
ded from the program.
Tests with regard to laundering performance can be extended almost in-
definitely and can be the subject of much argument. The test with which
we started and the rationale for adopting them were set forth in the
original proposal and incorporated into the contract. They are outlined
in Section I of Appendix B. The major points guiding their adoption
were: 1) that true soil removal and soil redeposition should be the
parameters of interest rather than optical effects due to brighteners;
2) that foaming was of minor importance, except insofar as a too per-
sistent foam might indicate poor rinsability; 3) that effects on the
fabric, including ash build-up and the build-up of organic residues,
were important parameters of performance. During the course of the
project a low level but continuing effort was devoted to checking,
extending and modifying the test methods with a view toward greater
accuracy (accuracy here means the extent to which the tests correspond
with results obtained in actual practice) and more general acceptabil-
ity. It should be. pointed out that there are at present no standard
laboratory tests for rating on an absolute basis the soil removing
power of laundry detergents. Each manufacturer of these products has
his own set of protocols, and the accuracy of any single simple test
-------
procedure is not easy to defend. Our methods development work and its
adoption in the overall program is presented in Appendix B.
D. PLANNED TECHNICAL APPROACHES
Keeping in mind the scope and the limitations outlined above it was
planned to divide the experimental work into three main areas. The
first and most important area would be the actual preparation and test-
ing of new detergent formulations. From the formulations would ulti-
mately come the new formulation we were seeking. The second area of
investigation would involve the chemical analysis and performance evalu-
ation of existing commercial detergents that appeared to be of interest.
A large number of new detergents appeared in the market during the
course of the project. A knowledge of their composition and their
laundering performance was obviously of utmost importance to the pro-
ject. The third area of experimental work was to be concerned with
methods development. As mentioned above there was perforce a consid-
erable degree of arbitrariness in the initial selection of test methods,
We realized from the beginning that the methods would probably require
modification as the experimental work proceeded and that the methods
most likely to require modification would be those relating to launder-
ing performance.
The examination of existing products and the development of more ef-
fective and realistic test methods required little advance planning.
The formulating and testing program however had to be carefully plan-
ned even though, as in all R and D work, these plans would have to be
continuously modified and reoriented on the basis of incoming results.
We can consider the plan in two separate parts, a formulations part
and a testing part.
10
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Detergent formulations can be grouped into three large classes. First,
those that are based on straight surfactant; second, those that are,'
based on surfactant plus a precipitating builder; and third, those
based on a surfactant plus a non-precipitating or chelating builder.
, I
This third class is represented by the conventional tripolyphosphate
built detergent. In all three of these classes, it is understood that
the formulation can and usually does contain a certain amount of sili-
cate as an anti-corrosive agent. This usually constitutes 5 to 10% of
the total mixture. It also contains in the range of .5 to 1.5% sodium
carboxymethyl cellulose as an anti-redeposition agent and 'may contain
similarly small amounts of other anti-redeposition agents that are sup-
posedly more effective on the non-cellulosic man-made fibers. The
formulation may also contain fillers and standardizing materials,
usually sodium sulfate, as well as minor amounts of brightener, perfume,
color and other adjuvants. We shall consider in this discussion only -
* '
the surfactant and the builder, assuming that the other ingredients will
be present as required in the final formulation.
It is generally recognized that straight synthetic surfactants, unlike
soap, are poor in cotton washing. Historically this is the reason.that
the market for synthetic surfactants remained quite limited until the
discovery of the specific building effect of the cbndensed phosphates.
It is also known, however, that this inferior cotton washing property
varies considerably from surfactant to surfactant. IAS, the most com-
monly used surfactant, is a mediocre cotton washer,. Soap is notably
good. We planned to explore systematically the cotton washing powers
of a range of surfactants, paying special attention to those claimed
to wash well in the absence of builders. We refer to th,ese for brevity
as "supersurfactants." Testing would be limited of course to suRetr .
* * ' "
surfactants that appeared economically feasible. It was also- planned" '
to test mixtures of soap with various lime soap dispersing surfactants.
11 -
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Such compositions have been widely mentioned from time to time as pos-
sible substitutes for phosphate formulations in heavy duty laundering,
and they have been used in bar toilet soaps for personal use.
The theory of detergent action teaches broadly that the cleaning or
deflocculating effect of the surfactant is opposed by the presence of
polyvalent metallic cations in the solution, calcium ion being the com-
monest and most important offender. Possibly the most important action
of a builder (although by no means its only action) is to remove cal-
cium ions from solution. One of the ways in which the builder may do
this is by precipitating the calcium as an insoluble compound. The
best known example of such an effect is the use of sodium carbonate as
a builder, the sodium carbonate precipitating out calcium ion and there-
by allowing the surfactant to do its work. Despite the first order
simplicity of this theory it is known that the building effect of sodium
carbonate varies greatly from one surfactant to another. Formulations
based essentially on a non-ionic surfactant plus a very high proportion
of sodium carbonate were introduced on a large scale not too long after
experimental work on the project started. Due to their high alkalinity
these materials appeared to have certain drawbacks with regard to
safety in use, and were therefore not considered ideal answers to the
problem of developing a phosphate free detergent. At a ^ater date
household detergents containing a lower proportion of carbonate, usu-
•ally with an equivalent amount of silicate, were introduced in the
market. At about the same time there appeared detergents containing
little or no carbonate, but a high proportion of. silicate, in the
range of 20-25% .of a high silica-to-soda ratio material. This mate-
rial has building properties although it is neither .strictly precipita-
ting or sequestering. The carbonate and silicate built materials
however, be grouped together for purposes of discussion.
12
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The non-precipitating or sequestering builders remove calcium ion
by chemical reaction without forming a precipitate. The prototype
of such builders is of course sodium tripolyphosphate. The main
thrust of the program involved finding and formulating new builders
of this type.
Relatively few non-precipitating builders had been extensively explored,
or if they had been the information was not publicly available. The
big exception was NTA which had not only been quite thoroughly'explored,
but had been used on a limited commercial basis and was generally con-
sidered to be the logical successor to the condensed phosphates. Be-
cause of certain limitations with regard to physical form and large
scale manufacture, however, it was stated at that time that NTA could
be used only as a partial replacement for phosphate rather than a com-
plete replacement. A considerable number of other possible candidates
were known but virtually nothing was known of their actual effect in
practical formulations. It was strongly suspected that the building
effect of these materials would vary depending upon the surfactant with
which they were combined, i.e., certain of these builders might be very
effective with some surfactants but ineffective with LAS (the commonest
and least expensive synthetic surfactant but one of the more difficult
to build). It was planned to solicit such materials from chemical
companies that were willing to supply them and to test them with a
variety of surfactants. It was also planned to synthesize builders of
this type which might appear to be particularly promising, provided
they could not be obtained from primary chemical manufacturers. It
was not envisioned, however, that such synthesis would constitute a
major proportion of the program. We did not consider that the in-
vention of new builders was our primary mission, and intended to re-
sort to it only when necessary.
13
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It was planned to make up the formulations for launderability testing
without actually putting them together, i.e., the ingredients in pro-
per proportions would be put into the wash liquor without pre-mixing.
A separate aspect of the program would be undertaken for those combina-
tions of ingredients that performed well. This would involve putting
together the ingredients into a final formulation which would have to
have the acceptable physical characteristics mentioned above.
It was realized that the testing program, involving five different types
of tests, could not be well planned in advance but would have to be or-
ganized on an ad hoc basis. The reason for this was the discrepancy in
the times required to carry out each test. A chronic aquatic toxicity
test, for example, may take as much as a year to complete whereas a
soil accumulation test takes only about three days. In general, the
laundering evaluations were conducted first. Biodegradation and algal
stimulation tests followed in that order. Materials that looked pro-
mising in these tests were then submitted for acute aquatic toxicity
tests. Product safety tests and chronic aquatic toxicity tests, as
well as bundle tests for laundering effectiveness were only conducted
on formulations which were entirely satisfactory from all other points
of view. These tests are by far the most time consuming and expensive.
It was planned in the testing program to make full use of all the in-
formation that could be obtained either in the open literature or from
the suppliers of the candidate materials. Checking the validity of
such previously available information is considerably less time con-
suming than developing it from scratch.
14
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EXPERIMENTAL
The basic soil removing formulations being sought were visualized as
consisting either of surfactant alone or of surfactant plus a non-
phosphate builder. The candidate materials entering the program
were accordingly either surfactants or builders. Depending on the in-
formation available, these materials might be tested first for biode-
gradability or aquatic toxicity or they might be made up into a formu-
lation and given the preliminary tests for laundering effectiveness.
Throughout the program most of the major areas of investigation were
being worked on simultaneously. Whenever a material or a formulation
failed definitely to meet any of the important requirements it was
dropped from further consideration. For efficiency in the program
the simpler tests were usually conducted first, and the more time
consuming tests later on the successful candidates.
A. FORMULATING AND WASH TESTING
A total of several hundred different formulations were made up and
wash tested during the course of the program. For purposes of discus-
sion they can be grouped into eight classes, based on the type of
builder used, as follows:
1. Unbuilt surfactants. It is well known that surfactants
differ from one another in their washing power. They also differ in
their response to any given builder. Candidate surfactants were
generally tested by themselves to see if they were unusually effective
15
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and might be made the basis of a completely unbuilt formulation. Soap
and mixtures of soap with lime soap dispersing agents (which are them-
selves surfactants) are included in the cateogry of unbuilt surfactant
formulations.
2. Carbonate and/or silicate-built formulations. Carbonate was
a standard builder for soaps and also for synthetic surfactants before
the advent of condensed phosphates. It is a precipitant for calcium
ion rather than a sequestrant. A relatively small proportion, usual-
ly 8%, of a high ratio silicate (2:1 to 3.22:1) was included in all
our formulations to serve as a corrosion inhibitor. This is common
practice in detergent formulation. Higher quantities (up to 40%) have
been recommended as builders and as adjuncts in combination with other
builders. We tried them in both ways. Silicates having an SiCL to
Na20 molar ratio less than 2:1 were not used because their high alkali-
nity was considered too great a hazard in use.
3. NTA. At the start of the project NTA was regarded as the can-
didate builder most likely to prove satisfactory and be adopted by the
industry. Its properties were therefore checked. No work with NTA
was done after the controversy developed over its possible hazards.
4. An analog of NTA was submitted as a candidate builder early
in the program. This compound, code named SAND, contains an acid amido
group (-CONH2) in place of one of the carboxyl groups of NTA. This
was tested to a limited extent, but later in the program was deempha-
sized in favor of another NTA analog described below.
5. The material code named SHIM or HEIDA is the di-sodium salt
of phydroxyethylimino-diacetic acid. This material was tested very
extensively. SHIM is the earlier code name. HEIDA is the more recent
name coined by the supplier. Both names are used in this discussion,
16
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i-j-
SHIM referring to earlier samples and HEIDA to more recent ones.
(«-
There appears to be no significant differences between them.
'• .3-
6. Formulations based on organic polymeric builders. It was
known at the start of the program that certain water-soluble polycar-
boxylated polymeric materials, of both natural and synthetic origin,
were builders of the sequestering type. A considerable number of these
were explored and several were later tested intensively. They included
only compounds containing no elements other than C, H and 0.
7. Formulations based on monomeric sequestering agents contain-
ing only C, H and 0. Citric acid (as sodium salt) and carboxymethyl
oxysuccinic acid (abbreviated CMOS) were the most extensively tested.
8. A system of washing with unbuilt surfactants including an ion
exchange resin in the bath'to sequester the hardness was explored in a
preliminary manner.
The initial procedure for estimating the laundering potential of a new
compound was as follows:
If the compound was a surfactant it was made up into a formulation
containing 12 - 25% active surfactant, 8% sodium silicate, 1% sodium
carboxymethylc-ellulose (NaCMC), 0'- 50% (sometimes more) builder, and
enough sodium siilfate to bring the total to 100%. The exact percent-
age 6f surfactant used depended on its chemical composition and on the
type of surfactant against which it was being compared. The magnitude
of the cleaning effect without builder1 was often a useful index of the
value of the surfactant in combinations. The selection of builder and
the percentage used varied, depending on the surfactant and the infor-
mation being sought. The two surfactants used most often as standards
of comparison were our standard IAS sample and a widely used fatty
17
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alcohol ethoxylate coded 68-127.* The IAS was usually used at the
20 to 25% level in its formulations and the 68-127 at 12%. New surfac-
tants being compared against them were used at corresponding levels.
If the compound of interest was a builder it was in most instances
tested with at least three surfactants, two of them being IAS and
68-127. The third and other surfactants would be those of specific in-
terest in connection with the builder being tested. The formulations
generally contained 12% of 68-127 or 25% IAS or an appropriate percen-
tage of whatever other surfactant was being used. In practically all
instances the formulations contained 8% silicate and 1% NaCMC. The
percentage of builder was most often 30%, but 20% or 50% was some-
times used. In the primary launderability tests 0.3% total formula-
tion was used in 200 ppm hard water. If the calcium sequestering
power of the builder was known a high enough percentage (20% or 30%)
was used to take care of the hardness. If the, calcium sequestering
power was unknown, and/or was suspected of being low, 50% was used.
In the later stages of the program experimental builders were rou-
tinely tested for calcium sequestering power. This was done by
titrating with a standard solution of calcium chloride, using an
Orion Research, Inc., Divalent Cation Electrode model 92-32 to mon-
itor the calcium ion concentration. The genera.1 procedure was to
*%
start with 100 ml of 2 x 10*" molar calcium chloride solution
(equivalent to 200 ppm hardness as CaCOo) and titrate into a 2%
solution of the sequestrant. Typical titration curves for strong v.
weak and high efficiency v. low efficiency sequestrants of interest
are shown in Figures 46-49.
(*See Appendix C for description of coded materials.)
18
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The primary launderability test used throughout most of the pro-
gram is described in Appendix B. Four cycles of soiling and washing
were usedj and four soil-fabric combinations: dry vacuum cleaner
soil and .sebum soil, on cotton and a 50:50 cotton polyester blend
finished for durapress. (permanent press).. Earlier straight polyester
(unfinished) was also used as a test fabric, and some 65 polyester:
35 cotton durapress finished fabric was also used. The launder-
ability behavior of these fabrics was sufficiently close to that of
the 50:50 blend to justify dropping them, and devoting the time saved
to examining more detergents. The AATCC #124 and AHAM detergents
were us-ed as standards, together with any other comparison deter-
gents that were considered appropriate to the specific test. The
reflectance readings were automatically transferred to punched tape
which was fed to a computer. The computer was programmed to print
out not only absolute reflectance readings but also the differences
in reflectance between the test detergent washed swatches and the
standard detergent washed swatches. These differences, or "delta
values", greatly facilitate comparison. Their significance can be
judged on the basis of their statistical confidence limits, also
printed out by the computer but not included in the tables of this
report. In most of the runs shown in the tables delta values less
than one unit do not indicate a difference that would be signifi-
cant in practice. Modifications of this primary multicycle test are
detailed in Appendix B. Table headings indicate which of the tests
was, used to obtain the data in the tables.
Aside from the primary multicycle tests three other tests for
launderability were used. These tests were applied mainly to the
more promising formulations. They were: single cycle detergency
v. concentration tests using purchased cotton soil cloth (Empa);
single cycle detergency v. concentration tests on cotton and blend
19
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soil cloths prepared in this laboratory ("Colgate" soil); and the
bundle test (ASTM D-2960-7IT). These are described in Appendix B.
Data from the single cycle tests are shown in the Figures as plots
of soil removal v. detergent concentration. Some of the multi-
cycle tests were extended to include a range of detergent concentra-
tions less than the 0.3% used in screening. Data from these tests
are also presented in graphic form. Data from the bundle tests are
included in the text of the sections headed RESULTS and DISCUSSION
respectively. In many instances launderability tests were performed
at water hardnesses other than 200 ppm. This is indicated in table
and graph headings and in the Text.
In all tests for launderability, including single cycle, multi-
cycle, and bundle tests (except where specifically noted), rede-
position swatches were included and measured. The data accumulated
on redeposition is therefore fully as voluminous as the data on
soil removal. It did not at any point, however, present any ano-
malies nor did it differ from what might have been expected on the
basis of the soil removal results. It is therefore omitted from this
report on the basis that any added significance it might contribute
would not justify the excessive space required.
B. PHYSICAL FORM
Experimental work directed toward producing formulations of commer-
cially acceptable physical form was necessarily limited. The abil-
ity to produce a beaded solid form of detergent on a large scale
cannot be guaranteed by laboratory scale experimentation. We had
available, however, a laboratory size drum drier (sometimes referred
to as a roller drier), and the behavior of materials in this equip-
ment can usually be extrapolated with confidence. In particular,
20
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drum drying on a laboratory scale can indicate very well whether the
formulation will be hygroscopic, or have a tendency to sinter or
become compacted, or have other unacceptable faults. Liquid formu-
lations that are satisfactory when made on a laboratory scale usually
present no difficulty in large scale operation.
The only formulations that we tried to put together in assembled
form (solid if possible; liquid if a satisfactory solid form could
not readily be made on the drum drier or by dry mixing) were those
that appeared most promising in the primary launderability tests and
had not been rejected in any of the other tests. These included
SAND and SHIM formulations, silicate-citrate formulations and NTA
formulations. The NTA formulations were developed during a period
when eventual NTA acceptance (frpm the hazard-in-use point of view)
was considered highly probable. In preparing the dry formulations
the ingredients were dissolved or slurried in a sufficient amount
of water to enable easy transfer to the hot drums, and were thor-
oughly mixed while transferring to assure homogeneity. No lengthy
hot crutching, common in large scale spray drying operations, was
used; and the possible effects of such treatment were not determined.
C. EFFECT ON FABRIC
Detergents that contained large proportions of soap and/or of car-
bonate, and that had proved promising in preliminary tests were
tested for effect on fabric as follows: Swatches of the fabric
were put through a series of 20 to 50 washing-drying cycles with no
intermediate soiling. They were then analyzed for ash content and
for alcohol extractable content in the usual manner.
21
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D. AQUATIC TOXICITY
Two types of aquatic toxicity test were included in the program:
an acute test and a chronic or long term test. Both are described
in Appendix A. All aquatic toxicity testing was done by the Depart-
ment of Limnology, Academy of Natural Sciences, Philadelphia. The
acute test was applied only to compositions that showed promise of
good performance. Together with biodegradability and algal stimu-
lation the acute aquatic toxicity test constituted the second level
of testing to which candidate compositions were submitted.
The chronic toxicity test consists of an extensive series performed
over a protracted period on a relatively large number of species.
Only two compositions over the whole duration of the program were
put through the chronic test protocols. These were the citrate-
silicate-ether carboxylate composition identified as 64-1, and the
control detergent AATCCWOB. It was considered necessary to test the
latter compound because no literature exists on the aquatic toxicity
of well identified, typical, phosphate-containing, heavy duty house-
hold laundering detergents. The AATCCWOB detergent qualifies on
all counts and can therefore provide a benchmark against which can-
didate formulations can reasonably be judged. Although the deter-
gent with brightener would have been more realistic the brightener-
free material was better suited as a standard of comparison for the
brightener-free candidate experimental detergents.
E. BIODEGRADABILITY AND ALGAL STIMULATION
Tests for biodegradability and stimulation of algal growth, like the
acute aquatic toxicity tests, were applied only to candidates that
showed promise of good laundering performance. The protocols for
these tests are described in Appendix A.
22
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F. HAZARD IN USE
Testing for hazard in use, as outlined in Appendix A, is lengthy and
extensive. Very few of the materials and compositions used in the
program were submitted to these procedures. Materials known to be
hazardous were excluded from the program. Suppliers were requested
to submit all data on hazard which they had, and, in the case of
materials which looked especially promising from other standpoints,
to develop as much valid acceptable data on hazard as was possible.
G. WASHING WITH ION EXCHANGE RESINS
The concept of using a suitable packet of cation exchange resin in the
washing machine, to serve as a substitute for the phosphate builder
component of the detergent, was first considered by the group working
on this project about April 1971. Experimental work to demonstrate
its feasibility was performed during the following two months and was
reported in Monthly Reports Nos. 12 and 13 of this series dated
June 10, 1971 and July 10, 1971 respectively. This work was not men-
tioned in the Interim Report dated January 7, 1972. It is included
herein for purposes of record, and to serve as a basis for future
work that might be undertaken along these lines.
It is well known that many surfactants, including some of the inex-
pensive ones commonly used in detergent compositions, give good wash-
ing performance at low concentrations in the absence of builder
I [
provided the concentration of Ca or other polyvalent metallic cations
in the system is very low. It would seem, on this basis, that an
efficient convenient water softener system would enable the house-
holder to do her laundry with surfactant alone. The catch in this
proposition is that the concentration of Ca-H- must be very low,
preferably less than 10" molar (0.1 ppm as CaCO-) for LAS, and
23
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not more than about 5 ppm for the more effective surfactants. The
amount of Ca++ introduced by the soiled fabric is often sufficient to
exceed this limit even after it has become completely diffused into
and diluted by the wash water. Until such time as it has become dif-
fused, the concentration at the fiber surface where detergent action
is occurring far exceeds this limit. We therefore must soften the
wash water in the machine as the washing is taking place. There are
at least two ways to do this. One would be to have an ion exchange
unit mounted on the washing machine together with a pump to circulate
the wash liquor through the unit. A simpler way, and one which could
be used with existing washing machines, would be to put a cloth bag
(or other sturdy porous container) of ion exchange resin beads into
the wash liquor with the laundry load. Calculations indicate that
the amount of resin necessary to soften the incoming water and take
care of calcium ion from the fabric load would not be excessive,
and the cannister or bag of resin should remain effective through
several launderings. When spent (or after a stipulated number of
uses) it could be regenerated with brine by the householder or turned
in for regeneration in exchange for a fresh bag. To explore the
feasibility of this idea EMPA cotton soil cloth, which behaves quali-
tatively (although not quantitatively) like cotton in soil accumu-
lation tests, was washed in 200 ppm hard water with an unbuilt IAS
formulation, with and without ion exchange resin present in the
wash bath. The resin beads were contained in a sturdy cotton bag,
which was stirred around in the wash liquor as part of the fabric
load. The load of resin in each bag was 5 grams, corresponding
to about 11 oz. in an ordinary 17 gallon washing machine. This is
theoretically adequate to soften several batches of 200 ppm wash
liquor before requiring regeneration. For purposes of comparison
similar washings were performed using the unbuilt formulations in
24
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distilled water and using phosphate-built formulations in hard water,
both in the absence of resin. The unbuilt formulations were also
used in hard water in the absence of resin, and gave the expected
poor soil removal. Two cation exchange resins were used, both in
the sodium form: Dowex 50 W-X8, a sulfonic acid type; and Amber-
lite IRC-50, a carboxylic type.
25
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RESULTS
The experimental data involve seven categories of properties: laun-
derability, physical form, effect on fabric, aquatic toxicity, biode-
gradability, algal stimulation and hazard in use. They also involve
eight different categories of compositions: unbuilt surfactants,
carbonate/silicate, NTA, SAND, SHIM-HEIDA, polymeric builders, mono-
neric builders and ion exchange resins. It is obvious that not all
compositions, nor even a representative of every category of composi-
tion, were examined with regard to all property categories. Some com-
positions were studied much more extensively than others and, due to
changing priorities during the course of the program, it was not always
the most promising compositions that received most attention. Among
the property categories launderability provided the most data. For
purposes of presentation the processed data are therefore organized
from two different standpoints. Data on all of the properties except
launderability (also referred to as washing power or soil removing
power) are presented in single tables which show the results for in-
dividual compositions of several different categories. In the laun-
derability category the data are partly tabulated, partly graphed
and partly (bundle test data) presented in the text. By no means all
of the formulations that were examined are reported in the tables.
Omitted are those which failed badly in one respect or another at an
early stage. Also omitted are those poorly characterized or otherwise
failing to meet the requirements discussed earlier in this report.
26
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Results of the screening program on launderability are presented in
Tables 1-7. These tables are the product of considerable processing,
abridgement and condensation of raw data obtained over a period of
three years. The changes in washing procedure details that occurred
during this period are explained fully in Appendix B, and each pro-
cedure is described. For convenience in following the presentation,
b
however, the following explicit notes on column headings in the tables
are given. Tables 1, 2, 3, 3a, 4, 5, 6, and 7 refer to the multi-
cycle or soil accumulation washing procedures outlined in Appendix B
as "procedures 4 and 5" or as the "dry soil" and "oily soil" procedures
In the column headings of these tables "vacuum soil" is synonymous
with "dry" or "procedure 4" soil. "Sebum soil" is synonymous with
"oily" or "procedure 5" soil. The "blend fabric" referred to is a
50:50 cotton-polyester sheeting finished for permanent press. It is
also referred to at places in this report as "durapress" fabric.
These tables show only the "delta 6" values against the AATCC standard
detergent after four cycles of soiling and washing. These values are
the difference in reflectance between the fabrics washed in standard
detergent and those washed in test detergent, as measured on the re-
flactometer with the green filter in place. As shown in Appendix B,
measurements were also made with the yellow and blue Bx filters and
confidence limits and whiteness values were computed. Redeposition
swatches were also included in the wash load. Their reflectances
were measured and the data processed in the same way. The redepos-
ition results have been omitted for the sake of brevity. There is
of course a much smaller range of reflectance and whiteness values
among the redeposition swatches than among the soiled swatches, and in
ranking the formulations for overall laundering performance soil re-
moval performance greatly outweighs redeposition performance. In
practically all instances the redeposition behavior paralleled the
27
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soil removal behavior closely enough to have negligible effect on the
ranking. Also omitted are delta 6 (and "delta BX") values against the
AHAM standard detergent which was used in almost all the important runs,
and against various commercial detergents (notably Tide XK and Sears
non-phosphate detergent) which were used in a considerable proportion
of the runs. In a large number of the earlier runs 100% polyester
swatches were included with cotton and/or blend fabric. These data
have also been omitted.
The delta G values in the tables represent the number of reflectance
units difference between the standard-washed swatches and the test-
washed swatches. A positive value means the standard-washed swatches
were brighter; a negative value means the test-washed swatches were
brighter. Values in different series are not directly comparable, be-
cause the intensity of soiling necessarily varies from series to series,
although with care it can be held reasonably constant. Strong soiling
generally leads to larger delta G values whether positive or negative.
The "Proportions" column gives the percentage composition of the for-
mulation. The first number in line represents percentage of surfac-
tant; the second number percentage of silicate. When no letters follow
the silicate number it means that silicate G (Philadelphia Quartz Co.)
was used. Letters indicate other types of silicate (all in this re-
port from this same supplier). The third number is NaCMC, in all but
a very few instances used at the one percent level. The fourth number
is percent builder; and the last number percent sodium sulfate unless
otherwise designated. If the surfactant is a mixture (as in items 16 -
18 in Table 2) the first two numbers give the percentage of each sur-
factant .
Tables la, 6a and 7a relate to "Spangler soil" ("procedure 3") three
cycle soil accumulation runs, and show the "delta W" (delta whiteness)
28
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values on blend and cotton fabrics. Tables 7b and 7c give whiteness
values and show results for all five washing procedures described in
Appendix B. The calculation of "whiteness" from the primary reflectance
readings is also shown in Appendix B.
Studies of washing power (launderability or soil removal) of the various
compositions tested as a function of detergent concentration are re-
ported in graphic form in figures 1-36. Most of these studies were
made with the Colgate soil, also referred to as "procedure 2" in Appen-
dix B. Some were made with Empa cotton ("procedure 1") and some by
the Spangler soil multicycle procedure ("procedure 3"). The procedure
in each case is shown in the legend.
Data on physical form are shown in Tables 8 and 8a. All of these were
developed during the first half of the program. As the program de-
veloped it was realized that commercially satisfactory forms might be
capable of development in large scale equipment by experienced manu-
facturing organizations, even though they could not be made in our
limited laboratory facilities. Emphasis was therefore placed on those
other properties of the formulation that could be more realistically
assessed.
Work performed with respect to effect of the formulations on the sub-
strate fabric was also limited and is summarized in Table 13.
Acute aquatic toxicity data are summarized in Table 10. The complete
reports on the two chronic aquatic toxicity tests that were performed,
one on Formulation 64-1, the other oil the control high-phosphate de-
tergent AATCCWOB, are presented separately as Appendix E.
Estimates of biodegradability are presented in Table 11. As explained
in Appendix A these estimates are based on BOD and COD tests and
therefore relate only to aerobic biodegradation. A definitive study
29
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of the biodegradability of any single compound is in itself an ex-
tensive project, and even a complete study of BOD (varying temperatures,
acclimation conditions, duration of test, etc.) is lengthy. The data
obtained in this program, although quantitative and extensive, are
considered too limited in scope to merit tabulation. The compounds
and formulations are therefore grouped into three classes: those
readily biodegraded in the test and therefore judged almost certain
to biodegrade satisfactorily in natural waters and in secondary sewage
treatment; those sufficiently resistant in the test to be judged un-
likely to biodegrade in a reasonable time under the above conditions;
those of intermediate resistance, on which extended studies should be
made before judging their acceptability.
Data on algal stimulation are summarized in Table 9.
Data on hazard in use are summarized in Table 12.
All of the above tables and diagrams will be referred to in the pre-
sentation of results immediately following. The presentation is
arranged according to composition categories.
A. UNBUILT SURFACTANTS
Referring to Table 1 it appears that relatively few straight surfac-
tants, or surfactants built only with silicate, have a chance of
washing satisfactorily at practical concentration levels.
The anionic sulfonates, particularly LAS, showed relatively little
washing power in the unbuilt state (Items 60 through 66) even when used
at the 25% level in the formulation. The same was true for the alpha
olefin sulfonates (Items 31 through 35) and the ether sulfates (Items
36 through 42) although these were not tested at a level higher than
20%. The fatty alcohol ethoxylates, the most extensively tested
30
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surfactants (Items 19 through 21), showed increasing effectiveness
on sebum soil with increasing concentration, but they still did not
appear effective enough for practical consideration. One of the
hydroxylated nonionics, Code 43-83, and the commercial detergent ex-
tract 32-237 did a creditable job at the 25% level particularly when
built with excess silicate (Items 26 and 58). Possibly the most power-
ful non-soap surfactants in the unbuilt state were the sulfo zwit-
terionic materials (Items 52 and 55). Even these did not appear strong
enough to be considered practical competitors for phosphate detergents.
The one material that appeared to wash as well as the reference phos-
phate-built detergent was soap. Item 69 indicates that a formulation
consisting essentially of 85% low titer soap and 15% of a high ratio
silicate washed about as well as the standard phosphate detergent.
It must be borne in mind, of course, that both formulations are being
tested at the same concentration, namely .3%, and that the standard
phosphate detergent contains only about 20% active surfactant whereas
this soap formulation contains 85% active surfactant. Item #70,
which contains in addition to soap a substantial proportion of a
lime-dispersing anionic surfactant, performed even better than the
straight soap.
Continuing in Table la, IAS (items 81-84) and fatty alcohol ethoxylate
(items 74-76) still appear significantly poorer than the control deter-
gent even at the relatively high concentration of 27%. The mixture
of fatty alcohol ethoxylate (FAEN) and fatty diethanolamide (items 79-
80) appears better than the FAEN alone, giving another indication that
mixtures of surfactants might be better than single species. The
first such indication was the performance of the commercial detergent
extract 32-237 (items 57-59 in Table 1). Surfactant 90-730 was stated
by the supplier to be intended for use without phosphate, but in
this test it proved distinctly inferior to the control detergent and
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about equal to unbuilt IAS. The soap-lime soap dispenser (LSD)combina-
tions (items 85-87) again showed superior launderability.
Detergency vs. concentration studies were performed on the more prom-
ising of these materials. Figures 1-4 show the results of tests on
soap and soap-LSD combinations on Empa cotton soil cloth. In the
200 ppm water of this test all the soap-based compositions (at approx-
imately 85% surfactant) were inferior to the control detergent (approx-
imately 20% surfactant) up to .2% concentration. Above .2% the soap
compositions performed better than the control detergent in this test.
The sulfonate zwitterionics1 behavior on Colgate soil is shown in
Figures 13-14. These materials performed remarkably well in a 30%
ative composition, being especially effective in the concentration
range under .15% and especially under .1%. These zwitterionics are
not identical to those of Table 1, but they behave in a similar manner.
The behavior of two lime soap dispersing agents (used in the soap LSD
compositions and purported to have good detersive properties when used
alone) is shown in Figures 15-16. They did not fulfill expectations.
Surfactant 90-730 was tested extensively, not only against the control
detergent AATCCWOB (Figures 5-6) but also against IAS in a comparable
formulation (Figures 7-10) and against one of the more promising
non-phosphate built compositions (Figures 11-12). On both Spangler
and Colgate soils it exhibits the same behavior. It is superior
to AATCCWOB at concentrations under .15% (in this 200 ppm water) bat
significantly less effective at higher concentrations. It is super-
ior to LAS at all concentrations under .3%. Like most other non-
phosphate compositions the 90-730 formulation looks comparatively
better on cotton than on blend fabric.
32
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Following up on the idea that mixtures of surfactants might be more
effective than the single components two commercial liquid non-
phosphate detergents consisting essentially of surfactants without
builder were tested. Results are shown in Figures 17-20. These pro-
ducts, both of which contain in the neighborhood of 40% surfactant
and include both anionic and nonionic surfactants, behaved remarkably
alike. In the low concentration ranges, below .1 to .15%, they are
superior to AATCCWOB. Above about .15% they are not quite equal to
AATCCWOB, although on cotton fabric they are almost equal.
The only unbuilt surfactant that was bundle tested was the 90-730
formulation containing 27% active surfactant. This was tested
against AATCCWOB at .15% in Rockville tap water. Both the panel
ratings and the reflectometer readings showed the AATCCWOB signifi-
cantly superior at the end of 6 cycles. At this low concentration,
however, even the AATCCWOB did not get the laundry satisfactorily
clean, and the test cannot therefore be considered satisfactory. No
further launderability work, however, was done with the 90-730 sur-
factant. The sample at hand had caused more yellowing than the control
in all the tests. Properties other than launderability are shown
in the appropriate tables.
The soap and soap-LSD formulations were examined for effect on the
fabric. Data in Table 13 show that the ash content increases con-
siderably more and the alcohol extractable content much more with
these detergents than with AATCCWOB. The LSD helps to keep the ash
content down to a reasonable level, but has less effect on the al-
cohol extractable content.
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B. FORMULATIONS BUILT WITH CARBONATE AND/OR SILICATE
Early in the course of the project interest in carbonate as a builder
was very high. This was largely a result of the introduction into
the retail market by Sears Roebuck of a detergent containing approxi-
mately 10% of a fatty alcohol ethoxylate surfactant and 65% sodium
carbonate. A relatively small number of high carbonate formulations
were accordingly prepared and examined for launderability with re-
sults shown in Table 6. These data indicate that certain nonionic
surfactants and some surfactant mixtures provide reasonably good
laundering performance in high carbonate formulations, provided a
sufficient percentage of surfactant is present. Later in the program
two commercial detergents, one containing about 20% carbonate and the
other free of carbonate but containing about 20% of silicate, were
tested using Colgate soil. The results are shown in Figures 21-22.
The fact that detergents of high carbonate content cause extensive
ash build-up in the substrate fabric is evidenced in Table 13.
Data in Tables 1, la, 7 and 7a show that a high silicate content
tends to improve launderability significantly, and the effect on the
fabric (Table 13) is not too objectionable.
High carbonate apparently has no unfavorable effect on algal growth
(item 8, Table 9), nor on acute aquatic toxicity (item 10, Table 10).
It may pose a possible hazard problem with regard to esophageal ir-
ritation (Table 12).
C. FORMULATIONS BUILT WITH NTA (nitrilotriacetic acid)
In the early stages of the program, and within the soap and deter-
gent industry even before regulatory action on phosphate was being
considered, NTA was regarded as the most promising phosphate
34
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replacement. Accordingly a modicum of launderability testing was
done to check the efficacy of this compound.
Table 3 shows that NTA is a powerful builder for all the classes of
surfactant which were tested. It is particularly effective with the
alpha olefin sulfonates (Items 3 and 7) giving negative delta G
values on all four fabric-soil combinations. One of the big ques-
tions with regard to NTA, aside from the question of its possible
hazard in use, was whether it could be made into a detergent of ac-
ceptable physical form. It was found, as shown in Table 8, that the
combination of NTA with alpha olefin sulfonate formed a dry powder
of good physical characteristics.
This formulation (Item 7 of Table 3) was examined for laundering per-
formance over a range of water hardnesses and at concentrations rang-
ing from .1 to .3%. The results are shown in Table 3-A. It is
evident that this formulation is a rasonably good match for the stan-
dard phosphate detergent over the whole range of use conditions.
It is significantly inferior only on sebum soiled blend fabric at
low concentrations in hard water. When enough detergent is used to
soften the water the performance again matches that of the phosphate
standard. In this connection it should be borne in mind that this
formulation contains 30% NTA as against 40% tripolyphosphate in
the standard detergent.
Acute aquatic toxicity tests on NTA showed it to have no adverse
effects on the test organisms even at 500 ppm (Table 10, item 23).
BOD tests (data not shown) indicated that NTA is not as rapidly
biodegraded as LAS or some of the other proposed phosphate replace-
ments such as citrate.
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D. SAND FORMUIATIONS
SAND is the abbreviation for the disodium salt of the monoamido
derivative of nitrilotriacetic acid. This material was offered for
testing relatively early in the program. The supplier, on the basis
of his own laboratory work was convinced that this material strongly
resisted hydrolysis and therefore could not be considered simply as
a reservoir or source for NTA. On this basis the compound was tested
for launderability and other properties. Launderability data on
the more important SAND formulations are shown in Table 4. SAND,
like NTA, is a good builder for all types of surfactants but appears
less effective on LAS and on the alkane sulfonate type of surfactant
than might be desired. It is exceptionally effective with some of
the ether carboxylate surfactants (Item 6) and also with the fatty
alcohol ethoxylates.
Table 8 shows that SAND is a very desirable constitutent of dry mixes,
being one of the very few materials that appears to form a satisfac-
tory dry mix with the fatty alcohol ethoxylates as well as with other
surfactants that are normally easier to dry.
As shown in Table 10, item 25, SAND has no significant effect on the
test organisms used in the aquatic toxicity tests. Biodegradability
tests (data not shown) indicated about the same degree of resis-
tance to aerobic biodegradation as shown by NTA.
E. SHIM (HEIDA) FORMUIATIONS
SHIM, later abbreviated HEIDA by the supplier, was submitted for study
early in the program. It is the disodium salt of beta hydroxyethyl
iminodiacetic acid.
36
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Referring to Table 5, SHIM, like SAND, is a good builder for all types
of surfactants although it is less effective on IAS than on the others.
Comparing Items 1 and 2 it appears that 30% SHIM in a formulation
is sufficient when the formulation is used at the .3% level in 200 ppm
water. In our essentially limited! work on physical forms we found
that SHIM compositions failed to give good drum dried products. It
did prove possible, however, as shown in Table 8-A, to make stable
liquid formulations containing SHIM as a builder. A hydrotrope was
necessary, sodium octenyl succinate being best for the nonionic,
and sodium xylene sulfonate being best for the anionics. The essen-
tial antiredeposition agent NaCMC would not dissolve in any of these
compositions, but it can presumably be suspended satisfactorily as
it is in present day commercial heavy duty liquids.
When used as a builder for LAS at the 30% level SHIM showed excellent
performance in the Colgate soil test (Figures 23-24). At a concen-
tration level of .2% or higher, where sufficient SHIM is present to
overcome all the water hardness, the absolute level of soil removal
is equal to that of the control high-phosphate detergent, even on
blend fabric.
Two different SHIM formulations were bundle tested. The first was a
20/8/1/30/41 formulation in which the surfactant was alpha olefin sul-
fonate code 22-155. This was tested at 0.2% concentration in Rockville
tap water against the AHAM detergent (cf. Appendix B) . At the end of
six cycles the panel rated AHAM superior by a score of 9.75 to 6.25.
This difference was later shown to be due to a larger residue of the
original mill-finish fluorescent whitening agent in the AHAM washed
fabrics, than in the SHIM washed fabrics. The former appeared slightly
whiter to the eye in daylight even though the soil content,was not
lower. Instrumental readings on the pillowslips of both blend and
cotton fabrics showed no significant difference between the test and
the control formulations. The second bundle test was performed on
37
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a 20/8/1/30/41 formulation in which the surfactant was IAS. This
was tested at 0.3% in tap water against AATCCWOB. In this test
the panel gave the SHIM formulation the non-significant numerical
edge 9.65 to 9.35. Instrumental measurements of reflectance were
made on all the laundered items (not only on the pillowslips). Sta-
tistical analysis as well as eyeball judgment of the data showed no
significant difference between the two detergents. At this ample con-
centration both bundles of laundry were satisfactorily clean from
the consumers' point of view.
SHIM proved to be fully satisfactory with regard to biodegradability
(Table 11) acute aquatic toxicity (Table 10) and algal stimulation
(Table 9). Hazard tests were run on a 25% aqueous solution of the
unformulated material (item 56-445 in Table 12) and on two finished
formulations 65-1 and 65-2 containing respectively 18% and 25% of
100% active SHIM. The results (Table 12) suggest that SHIM is close
to the borderline with regard to both oral and dermal toxicity, and
that the toxicity of a composition containing SHIM may depend to a
great extent on the character of the accompanying surfactant. It
should be noted that these data are quite limited, and that much more
extensive testing is needed before judging the degree of hazard which
SHIM presents.
F. FORMULATIONS BASED ON POLYMERIC BUILDERS
The launderability data in Table 6 which were developed early in the
program show that the polymeric builders vary quite widely in their
effect, and even those which are effective with one type of surfac-
tant may be quite unsatisfactory with another. Several of the
materials in this table, notably the builder coded 40-310, are de-
scribed in the patent literature as being quite effective. It is
unfortunately quite resistant to biodegradation under ordinary
38
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circumstances. None of the materials shown in this table has been
satisfactorily biodegradable. There are of course many polymers, such
as the proteins and some of the carbohydrates, that are readily bio-
degradable, and there is no reason why a combination that exhibits good
biodegradability together with good building power should not exist.
A continuing effort was made throughout the course of the project to
discover polymeric builders that were biodegradable. Preliminary
launderability tests (made prior to or simultaneously with biode-
gradability tests) are shown in Table 6a. The polyacrylic acid
builders were studied more extensively than any other class for the
following reasons: first, they had a more favorable economic picture
than most of the other materials; second, they were available in a
wide range of molecular weights; third, they were known to be toxi-
cologically harmless and non-stimulating to the growth of algae.
The philosophy was that monomeric acrylic acid is biodegradable but
not a builder; acrylic polymer of high molecular weight is a good
builder but is not biodegradable. Somewhere in between we must come
to a molecular weight range where the material has both biodegrad-
ability and building power or has neither. The series of acrylic
polymers 92-745, 100-823 and 100-824 graded in average molecular
weight from about 3000 to well under 1000 were studied on this basis.
The chelation curves in Figure 49 show that the lower molecular weight
material has considerably lowered sequestering power, but still
might have a satisfactory building effect. Figures 25 and 26 show
the detersive effect of Calnox 214 DN a polyacrylic acid with a
stated mean molecular weight of 750. It performed remarkably well
on cotton on this test, and even on blend fabric it was fully satis-
factory in the IAS formulation, at 0.3% concentration. This material
has low aquatic toxicity. It is at least partially biodegradable,
although the action is slow.
39
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A polymeric builder that has been extensively explored and reported
upon by the producer is the hydroxylated acrylic identified as
POCNa (code 104-860). The sequestration curve on this material
(Figure 48) indicates that a high proportion would have to be used
in a detergent formulation to produce a satisfactory building effect.
Figures 27-28 show that in an IAS formulation at 50% active content
it performed well in the concentration range about 0.2%, especially
on blend fabric. This material was made up with IAS to a 20/8/1/50/21
formulation, and was bundle tested against AATCCWOB at 0.3% in tap
water. After 6 cycles both bundles were satisfactorily clean. The
panel rated the control detergent 10.9 against 9.1 for the POCNa for-
mulation, an insignificant difference. Instrumental reflectance read-
ings were made on all laundered items. They showed no significant
difference between the two detergents. The biodegradation was faster
and more extensive than that of any other polymeric builder tested
(Table 11). The aquatic toxicity, like that of all other polymers
tested, was low.
Homopolymers and copolymers of maleic acid have long been known to
have remarkably good building powers, but to be quite resistant to
biodegradation. A recent patent application (Netherlands Applica-
tion 7205685 to Shell International Research) describes certain low
molecular weight telomers of maleic acid which are stated to be bio-
degradable. A telomer of this type was prepared, following the patent
example closely, using isopropyl acetate as the telogen. The product
was purifed thoroughly and characterized by the usual tests, and
given the code designation 106-866. The chelation curve (Figure 46)
showed it to be an exceptionally powerful and efficient sequestrant.
Detergency data are shown in Table 6a, items 37-40, and in Figures 29-
32. When used in equal quantities it appears fully equal to sodium
tripolyphbsphate as a builder for LAS in these testing regimens.
40
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Due to termination of the program this material was not bundle tested,
It performed well in the aquatic toxicity test. In the BOD test it
showed moderately extensive and rapid oxygen absorption, in contrast
to a maleic homopolymer which showed no oxygen absorption whatsoever.
However, the molecular weight is such that the isopropyl acetate
telogen moiety could have accounted for a large part of the oxygen
take-up. At this stage of the investigation therefore the biode-
gradability of this particular example of the products described in
Netherlands Application 7205685 must be regarded as questionable
(Table 11).
Two other polymeric materials gave indications of being at least
partly biodegradable. One of these, coded 102-834, is stated to be
a starch derivative. Its chelation curve is shown in Figure 48, and
its detergency performance in Table 6a, items 51 and 52. The other
material coded 100-821 was not identified by the supplier. The de-
tergency screening data (Table 6a, items 60-63) were not especially
promising.
G. FORMULATIONS BASED ON NON-NITROGENOUS MONOMERIC BUILDERS
Data on the more important monomeric builders tested in the earlier
stages of the program are shown in Table 7. Diglycollic acid
(coded 38-279) showed moderate promise as a detergency builder,
and was biodegradable (Table 11). The supplier, however, indicated
that it posed a toxicity problem so it was not studied further.
Item 13, mellitic acid (coded 74-606) is one of a group of similar
compounds described as builders in a series of recent patents.
Although promising, this compound was not studied further because
of poor availability. Item 15, the furan derivative coded 76-620,
had good building action but failed the biodegradability test
(Table 11).
41
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Of the other materials, citric acid was studied most extensively.
As is evident from the data it has proved to be particularly effec-
tive when used with about 20% of a high ratio silicate. Under our
conditions of concentration and water hardness a minimum of about
30% citrate appears to be necessary to get maximum effect. This is
evidenced abundantly in the table. The silicate citrate combination
is most effective with the fatty alcohol ethoxylate nonionics
(Item 22), certain ether carboxylates (Item 31), and the sulfo zwit-
terionics (Items 35 and 36). The latter formulations dry very well
as shown in Table 8, and the nonionic formulation can be made into
a satisfactory liquid as shown in Table 8-A.
Later in the program the builder carboxymethyl oxysuccinate (CMOS
coded 96-789) was studied extensively. The screening data shown in
Table 7a indicate that it is a builder for both anionic and non-
ionic surfactant types. It also proved to be biodegradable, non-
toxic to aquatic organisms and without effect on algal growth.
Further data on CMOS built compositions are shown in Figures 11-12
and 33-34. When used at the 30% level with IAS, full effectiveness
of the detergent is reached at .3% concentration.
A 20/8/1/30/41 formulation of LAS and CMOS was bundle tested against
AATCCWOB at two different concentrations, .15% and .3%. At .15%
the panel preferred AATCCWOB by a margin of 14 to 5, a significant
difference supported by the reflectance readings. At .3% the
CMOS was preferred by a score of 10.65 to 7.35, a non-significant
difference also supported by the reflectance data.
Several citrate compositions were tested extensively, based on the
promising results of the screening tests shown in Table 7. These
were based on surfactants other than LAS. Three of these composi-
tions were solids, all containing 30% sodium citrate and 20% silicate
42
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and having the proportions 20/20/1/30/29. Formulation 64-1 used an
ether carboxylate surfactant coded 60-486. Formulation 64-2 used a
sulfozwitterionic surfactant coded 54-433, and Formulation 67-1
another sulfozwitterionic coded 42-348. A liquid composition,
listed as item #1 in Table 8a, was also prepared for further testing.
Formulations 64-1 and 64-2 were tested against the two control de-
tergents at various concentrations and water hardnesses. All five
test procedures (soils) as outlined in Appendix B were used. For
quick reference the procedures are: #1 Empa soil single cycle;
#2 Colgate soil single cycle; #3 Spangler soil multicycle; #4 Vacuum
cleaner dry soil multicycle; #5 Vacuum cleaner sebum or oily soil
multicycle. The results are shown in Tables 7b and 7c. These for-
mulations 64-1 and 64-2 were bundle tested against the AHAM deter-
gent at .2% concentration in Rockville tap water. The panels rated
64-1 equal to the control detergent, but 64-2 was rated inferior,
largely due to a slight yellowing effect. Details of these tests
are given in Appendix B.
Formulation 64-1 was chosen for one of the two chronic aquatic toxi-
city studies made during the course of the program. The other study
was made on the representative high-phosphate detergent AATCCWOB.
Both studies are reported together as Appendix E. The 64-1 formula-
tion appears to be no more harmful to aquatic life than the high-
phosphate material.
H. WASHING WITH ION EXCHANGE RESINS
Pata on the ion exchange resin washing experiments outlined in the
previous section of this report are presented qualitatively rather
than in tabular form.
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When given adequate time to soften the water the resins both performed
very well, enabling the unbuilt formulations to wash as well as in
distilled water and as well as the corresponding phosphate-built de-
tergents in hard water. The Dowex was quite slow, requiring almost
an hour to soften the water and effect the washing. The Amber lite
was more rapid in its action requiring only 30 minutes to produce
the full effect. Further tests using multicycle procedures on vacuum
cleaner soils gave essentially similar results. The ion exchange resin
facilitated soil removal but required considerable time to exert its
effect.
It is evident that a cation exchanger which worked more rapidly than
the two that were tried could probably provide a practical washing
system. Faster acting resins might be made by increasing the bead
porosity and decreasing its dimension, by making the resin in fib-
rous form, etc. The manner in which the resin is deployed in the
..., ij-t
bath could also be altered to increase the rate of Ca removal.
Circulation of the wash liquor through a bag of beads is obviously
not optimal.
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DISCUSSION
The various possibilities for developing satisfactory phosphate-
free detergent formulations are conveniently discussed according to
the classification scheme used in the previous section, i.e. eight
different composition categories and seven different categories of
performance or properties.
A. UNBUILT SURFACTANTS
The data indicate that synergy among two or more surfactants with re-
gard to soil removing power is a very real thing. A formulation con-
taining in the range of 40% total surfactant and no significant
quantity of builder appears able to perform reasonably well at
practical concentrations, provided the surfactant mixture is suitably
chosen. Possibly the best evidence of this is provided by the com-
mercial detergents D (Code 104-855) and E (code 96-782). Added evi-
dence is provided by the laboratory performance of the commercial
detergent extract coded 32-237.
Single surfactants such as LAS, FAEN or the experimental D-116
(code 90-730) appear less effective than the mixtures, although limit-
ed work with the sulfonated zwitterionics indicates that they might
prove sufficiently effective. They are at present costly, however,
and more a specialty than a bulk item.
45
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The soap-LSD combinations fall into a special category. To give
effective soil removal in hard water a high concentration is needed,
which makes the economics seem unattractive. Furthermore, as shown
in Table 13, although the LSD does lower the amount of undesirable
residue left on the fabric it does not lower it to the level expected
by consumers accustomed to phosphate containing detergents. It
should be noted that the soil removing power of these materials is
very high when used in sufficient concentration.
B. CARBONATE-SILICATE FORMULATIONS
A high carbonate content certainly increases the soil removal power
of certain surfactants and surfactant mixtures. It is objectionable,
however, in causing rapid build up of solid residues on the fabric
when used in hard water. A relatively low carbonate content, in the
range of 20%, is correspondingly less objectionable but may not con-
tribute enough extra washing power to be worthwhile (cf Figures 21
and 22).
The high ratio silicates appear to have some building power for cer-
tain surfactants but not for others. They also appear to be syner-
gistic with certain other builders, notably citrate as discussed
below. Silicates do not appear to have anywhere near the adverse
effects on fabric that carbonate has and are unobjectionable in
other respects as long as the ratio of silica to soda is in the
range of 2:1 or higher. Evidence of their effectiveness in appro-
priate formulations is provided by commercial detergent C (coded 96-
783) in which silicate appears to be the only builder present in
significant quantity.
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C. NTA FORMULATIONS
The present studies have confirmed the virtues of NTA, as evidenced
by all the data. It is an excellent builder for all surfactants
tested, including the large tonnage inexpensive surfactants now used
in phosphate formulations. Investigation of some possible disad-
vantages of NTA, reported in the technical literature and to a cer-
tain extent publicized, has not been within the scope of this pro-
gram.
D. SAND FORMUIATIONS
To the extent that it has been tested SAND is a good builder of de-
tergency, similar in this respect to NTA or phosphate.
The similarity in structure between SAND and NTA, and the fact that
SAND can in theory be converted to NTA by a simple hydrolysis reac-
tion, would make SAND subject to the objections that have been raised
against NTA. It would presumably be necessary to prove that these
objections were not valid in the case of SAND, a difficult and time-
consuming task outside the scope of this program.
E. SHIM (HEIDA) FORMUIATIONS
SHIM is an excellent builder for the detergency of all surfactants
tested, in the same class as phosphate and NTA. It is readily bio-
degradable and fully satisfactory with regard to biostimulation and
acute aquatic toxicity. SHIM is sufficiently different from NTA
in chemical composition so that the objections raised against NTA
could not legitimately be translated as applicable to SHIM. Its
toxicity is close to the limits recommended by FDA and Consumer
Products Safety Commission, and more extensive work would have to
47
-------
be done on SHIM formulations before they could be cleared in this
regard. SHIM may also be difficult to formulate into a satisfactorily
storable solid detergent although it can readily be formulated to
liquids.
l
F. FORMULATIONS BASED ON POLYMERIC BUILDERS
None of the polymeric builders tested provide the rapid biodegrad-
ability characteristic of the "soft" surfactants and some of the mono-
mer ic builders. Several, notably the acrylics and maleics, have
outstanding building action for the conventional tonnage surfactants.
It seems to be the general rule, however, that building effect must
be traded off against biodegradability. The best compromise in this
regard that we have seen so far is the POCNa hydroxylated acrylic
polymer (code 104-860). The formulation based on LAS surfactant
and containing 50% of this builder gave satisfactory laundering per-
formance at concentrations of 0.2% or higher. Two other polymeric
builders show promise of simultaneously meeting both the launder-
ability and biodegradability requirements. These are the very low
molecular weight acrylic (code 100-823) and the maleic telomer
(code 106-866). Considerably more work would be required on both
these products, however, before a final judgment on their overall
satisfaction could be rendered.
1 ",
Polymeric builders in general appear to be biologically inert: non-
toxic to aquatic life and non-stimulating to algal growth. This
characteristic extends to their lack of biodegradability.
48
-------
G. FORMULATIONS BASED ON NON-NITROGENOUS MONOMERIC BUILDERS
The two non-nitrogenous monomeric builders that appear as promising
replacements for phosphate are citric acid and CMOS, Of these
citric acid is by far the more thoroughly explored. The detergency
building action of citrate varies considerably from surfactant to
surfactant as might be expected of a relatively weak chelating agent
(cf. Figure 47). Formulation 64-1 shows that with a suitable sur-
factant citrate can provide reasonably satisfactory launderability.
It is highly probable that a synergistic mixture of surfactants could
also be satisfactorily built with citrate. The only citrate built
commercial- detergent tested (Detergent 0, coded 90-279, Figures 35-36)
was a European product designed for European washing conditions.
There is at least one widely used citrate built detergent in the
phosphate-free market in the U.S.A. Citrate has the great advantage
of being completely unobjectionable from the ecological and health
hazard standpoints.
CMOS appears to have the same advantages as citrate, and to be some-
what stronger with regard to both sequestration (cf. Figure 47) and
building action. It gives better results than citrate as a builder
for LAS. Time did not permit complete testing of CMOS with regard
to all the property categories, but on the basis of evidence at
hand it must be regarded as a serious contender in the phosphate-
substitute competition.
H. WASHING WITH ION EXCHANGE RESINS
From the environmental point of view a washing system based on ion
exchange resins is close to ideal. No soluble builder goes down
the drain. Since all acceptable builders are visualized as being
biodegradable, any combination of surfactant and sequestering
builder would increase the BOD load on the sewage disposal systems
49
-------
and/or the streams into which it flowed. In the ion exchange system
the surfactant would be the only source of significant BOD. The only
product which might seem to require special disposal is calcium chlo-
ride resulting from regeneration of the resin. However the calcium
is simply that which was removed from the laundry's water supply, and
the chloride is counterion to the sodium given up by the resin in the
softening step. The only net addition to the watercourse in this pro-
cess is the sodium chloride used in regenerating the resin.
Although we believe the ion-exchange resin system to be very promising
other priorities in the program precluded its further exploration.
Successful further development would most probably come from improve-
ments in the resin, and the form and manner in which it is used.
Such development would seem to be the province of researchers and
manufacturers of cation exchange resins. Detergent manufacturers
and formulators would also have to contribute, however, since com-
patibility with minor adjuvants of the formulation would have to be
worked out. Similarly, much new data would have to be elaborated on
the detersive power of various surfactants and surfactant mixtures
in softened water. Finally, the various difficulties that are in-
evitably involved when introducing a new process to the consumer
would have to be worked out. The projected ultimate advantages of
the process might nevertheless be worth any introductory difficulties.
In deciding which of the formulations developed in this program and
discussed above might be most promising it is of interest to see
what the soap and detergent industry has introduced into the phosphate-
free market since the start of the program. The first phosphate
substitute was NTA, no longer being used in the U.S.A. because the
hazard question has not (as of this writing) been definitely an-
swered. Some high carbonate (more than 45%) formulations have been,
and are still being marketed. A considerable number of low
50
-------
carbonate (20-25%) formulations are being marketed, some of which con-
tain about an equal amount of silicate. Some citrate formulations
have appeared, including some in which the citrate is augmented by
carbonate and/or silicate.
A final important group includes fonnuktions consisting essentially
of unbuilt surfactants or surfactants built only with silicate. To
the writers' knowledge no polymer-built formulations have been intro-
duced in significant quantity, nor have there appeared any formulations
built with nitrogenous or non-nitrogenous monomeric builders other
than citrate. There also seems to have been little increase in the
use of soap or soap-based compositions for heavy duty household
laundering in the phosphate-free jurisdictions. It is of little
profit to speculate on the reasons for this situation. There is no
doubt that costs play an important role. The leading surfactants
are themselves relatively inexpensive. If 50 parts of surfactant
alone will do as good a job as 20 parts surfactant plus 30 parts
builder, then the builder must be less costly than the surfactant
to justify its use. Provided that performance is adequate the choice
among formulations, whether they consist of surfactants alone or
surfactant-builder combinations, depends largely on overall cost ef-
ficiency. Other economic and technical factors, however, also enter
into consideration.
During the three year course of this program the rate at which patents
have been issued on phosphate-free detergent compositions has in-
creased greatly; and at the present writing it has not started to
diminish. Perusal of these patents, both U.S.A. and foreign, has
been of obvious value in conducting this program, and in some in-
stances (e.g. POCNa and the maleic telomer) has led to some very
promising formulations which might otherwise never have been made or
51
-------
tested. A selected list of recent patents, classified according to
the outline used in this report, is included as Appendix D. In
almost all citations the Chemical Abstracts (CA) reference as well
as the patent number is given to facilitate retrieval.
52
-------
Table 1. DETERGENCY OF SURFACTANTS WITHOUT BUILDER,
.3%, 4 washes, 200 ppm water
ui
Delta G Values
Item
No.
1
la
Ib
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Surfactant
Code No.
68-127
68-127
68-127
68-127
68-127
68-127
68-127
68-127
68-127
68-127
68-127
68-127
51-104
20-138
68-134
68-134
51-93
43-67
Surfactant Type Proportions
Fatty Alcohol Ethoxylate Nonionic 12/8/1/0/79
ii ti 11 ti ii
it ii ii ii it
" " " 12/8N/1/0/79
12/8D/1/0/79
" " " " 25/8/1/0/66
" " " 20/8/1/0/71
" " " " 20/8GD/1/0/71
11 " " 20/25/1/0/54
" " " 20/25GD/ 1/0/54
11 " " " 20/8D/1/0/71
" " " " 12/20GD/1/0/67
" " " " 25/8/1/0/66
25/8/1/0/66
" " " " 25/8/1/0/66
11 " " " 12/8/1/0/79
" " " " 25/8/1/0/66
" " " " 25/8/1/0/66
Series
Ref. No.
a
a
a
149-50
122,147
-b
c
92-3
92-3
92-3
122,147
102-3
14
-d
21-2
23-4
13
7
Vacuum
Blend
Fabric
4.5
2.1
6.2
5.3
7.2
3.8
5.0
6.7
4.7
7.4
7.2
10.1
4.1
6.0
4.5
7.4
3.5
Soil
Cotton
Fabric
2.5
1.1
4.3
2.1
4.5
1.7
2.2
2.8
1.6
3.1
4.7
8.9
-1.2
-.5
2.7
2.5
.1
1.4
Sebum
Blend
Fabric
4.2
2.4
5.4
5.4
6.3
1.9
2.6
5.1
3.5
3.6
3.4
6.9
-.5
3.1
Soil
Cotton
Fabric
2.0
1.6
3.2
2.3
4.5
-.2
1.1
1.6
-.2
.5
3.2
5.6
.7
1.2
(Continued)
-------
Delta G Values
Ul
Table
Item
No.
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
1 (Continued)
Surfactant
Code No. Surfactant Type
51-100 Fatty Alcohol Ethoxylate Nonionic
51-101 " " " "
51-105 " " " "
51-105 M " ™ "
51-105 " " " "
31-230 Hydroxylated Nonionic
26-191 " "
26-189 " "
43-83
43-83 " fl
20-144 " "
20-145 " "
48-374 Amine Oxide
51-91 Alkane Sulfonate Anionic
22-155 Alpha Olefin Sulfonate Anionic
22-155
74-604
"74-604
68-558
Proportions
25/8/1/0/66
25/8/1/0/66
15/8/1/0/76
25/8/1/0/66
40/8/1/0/66
25/8/1/0/66
25/8/1/0/66
25/8/1/0/66
25/8/1/0/66
25/50/1/0/24
25/8/1/0/66
25/3/1/0/6/5
25/8/1/0/66
25/8/1/0/66
20/8/1/0/71
20/20/1/0/59
20/8/1/0/71
20/20/1/0/59
20/8/1/0/71
Series
Ref. No.
.14
.14
132-3
132-3
132-3
87-8
23-4
23-4
23-4
23-4
11
5
84-5
10
— e
~f
145-6
145-6
124-5
Vacuum
Blend
Fabric
9.0
6.9
3.8
3.9
4.0
10.1
10.0
4,1
2.4
1.6
6.0
8.9
7.4
5.0
9.1
9.0
4.5
Soil
Cotton
Fabric
.3
-.5
1.2
.6
1.0
5.0
5.8
1.7
1.2
.7
2.0
4.2
5.1
3.5
4.7
3.2
4.*
5.0
4.3
Sebum
Blend
Fabric
7.4
4.3
2.7
9.6
5.6
6.1
1.2
2.5
9.9
7.5
5.8
8.3
6.7
3.5
Soil
Cotton
Fabric
5.9
3.9
2.2
3.1
2.7
3.3
.7
K3
3.8
2.8
2.4
4.2
3.1
-•2,1
(Continued)
-------
Delta G Values
in
Ui
Table
Item
Ko.
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
1 (.Continued)
Surfactant
Code No. Surfactant Type
58-471 Ether Sulfate Anionic
62-491
62-491
62-491
6Z-491
62-492
62-492
40-332 Ether Carboxylate Anionic
40-332.
60-486
60-486
60-486
60-486
68-109 Sulfonate Ampholytic
68-108
46-357 Carboay Betaine Zwitterionic
42-348 Sulfo Betaine Zwitterionic
42-348
54-431
Vacuum Soil
k
Proportions
12/8/1/0/79
12/8/1/0/79
20/8/1/0/71
12/20/1/0/67
12/20GD/1/0/67
12/8/1/0/79
20/8/1/0/71
12/8/1/0/79
25/8/1/0/66
12/8/1/0/79
12/20/1/0/79
.-;>* 12/20GD/ 1/0/79
20/20/1/0/59
25/8/1/0/66
25/8/1/0/66
25/8/1/0/66
25/8/1/0/66
20/20/1/0/59
25/8/170/66
Series
Ref. No.
106-7
104-5
104-5
102-3
102-3
104-5
104-5
62-3
62'3
106-7
102-3
102-3
128-9
15
87-8
84-5
84-5
—8
87-8
Blend
Fabric
4.8
3.9
4.1
6.4
9.2
4.0
3.9
6.7
4.6
2.8
7.8
7.0
1.5
4.1
5.5
3.3
1.4
3.2
4.5
Cotton
Fabric
3.6
1.9
2.2
5.2
4.2
1.6
1.8
1.9
2,1
1.2
6,2
5.5
.6
1.7
2.4
1.7
-.2
.8
2.1
Sebum
Blend
Fabric
2.7
3.5
4.0
7.8
9.0
4.8
4.3
8.1
3.7
6.4
10.0
8.0
2.8
12,3
3.9
4.4
3.5
5.3
Soil
Cotton
Fabric
.5
1.6
1.6
3.6
6.4
1.6
1.1
1.9
-.6
,5
4.9
3.9
-.1
3.5
.8
-.2
1.4
.6
(Continued)
-------
Delta G Values
Ui
Table ]
Item
No.
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
a * t
L (Continued)
Surfactant
Code No. Surfactant Type
54-433
54-433
32r-237
32-237
32-237
34-249
34-249
34-249
34-249
34-249
34-249
34-249
38-282
70-560
20-146
74-594
ive. of 14: 1
Sulf o Betaine Zwitterionic
11 «i H
Commercial Detergent Extract
ii ii M
II II H
Linear Alkylaryl Sulfonate (LAS)
„
ii ii ii ii
„
„
it ii it ii
„
Commercial Detergent, Approx.
70 nonionic, 20 amine soap
Commercial Detergent, Approx.
20 nonionic, 7 soap
Mixture 85 low titer soap,
15 silicate D
Mixture soap, lime-dispersing
anionic, silicate ER 544-15 1A
> « avg. of 4; c = avg. of 5; d = SM
Vacuum Soil
k
Proportions
25/8/1/0/66
20/20/1/0/59
25/8/1/0/66
25/50/1/0/24
25/8/3/0/64
25/8/1/0/66
20/8/1/0/71
20/8GD/1/0/71
20/25/1/0/54
20/25GD/1/0/54
20/20/1/0/59
20/20GD/ 1/0/59
as is
as is
as is
as is
'g. series 2, 4, 6,
Series
Ref. No.
87-8
130-1
28-9
28-9
28-9
--1
-J
92-3
92-3
92-3
94-5
94-5
62-3
126-7
142-3
142-3
11, 13, 14;
Blend
Fabric
.9
1.6
4.1
2.9
2.9
8.2
7.8
8.8
6.0
7.3
10.7
10.1
6.4
2.4
.1
-.2
e <• avg.
Cotton
Fabric
-.4
2.9
.9
-.1
.7
4.4
4.5
4.4
3.7
4.7
5.4
4,2
5.4
6.1
-.3
-1.3
of 7; f -
Sebum
Blend
Fabric
3.9
5.5
1.7
.9
1.3
7.0
6.8
7.3
4.9
6.2
7.0
6.3
6.8
2.2
0
-.6
avg. of 3;
Soil
Cotton
Fabric
-.3
2.1
-.6
-.4
-.1
4.7
4.7
3.8
2.9
3.2
5.1
5.0
5.2
4.5
.3
-1.6
g » avg. of 2; h «
k = % surfactant/
• alcohol extract of a leading commercial detergent; i » avg. of 9; J » avg. of 3.
% silicate/ % NaCMC/ % builder/ % sodium sulfate.
-------
TABLE 1A. DETERGENCY OF SURFACTANTS WITHOUT BUILDER
• 3X»SPANGLER SOIL*3 WASHES* 200 PPM WATER
DELTA W
ITEM
NO.
71
72
73
74
o, 75
-4
76
77
78
79
80
81
82
SURFACTANT
CODE NO. SURFACTANT TYPE
90-730
90-730
90-730
68-127
68-127
68-127
20-145
20-145
102-836
102-836
34-249
34-249
ANIONIC SULFONATE
ANIONIC SULFONATE
ANIONIC SULFONATE
FATTY ALCOHOL ETHOXYLATE
NONIONIC (FAEN)
FAEN
FAEN
HYDROXYLATED NONIONIC
HYDROXYLATED NONIONIC
FATTY ACID DIETHANOLAMINE
CON DEN SATE + FAEN
FATTY ACID DIETHANOLAMINE
CON DEN SATE + FAEN
LAS
LAS
PROPORTIONS
10/7/1/0/82
15/7/1/0/73
27/8/1/0/64
12/8/1/0/79
12/20/1/0/67
27/8/1/0/64
20/8/1/0/71
20/20/1/0/59
15+5/8/1/0/71
15+5/20/1/0/59
20/8/1/0/71
25/8/1/0/66
SERIES BLEND
REF.NO. FABRIC
213
213
231*234*239
215*233*235*238
244*245*249*251
238
234
211
211
246
246
236* 244* 245* 249
251
214*224*237
7.5
5*8
5.0
10*4
10*4
6.9
14.7
17.4
5.0
3*6
6.9
4.0
COTTON
FABRIC
3.4
1.3
1.6
7.7
5.0
3.4
8.5
6.4
0*3
-1.4
3.8
2.2
-------
TABLE 1A. (CONTINUED)
DELTA V
ITEM SURFACTANT
NO. CODE NO. SURFACTANT TYPE
83
84
85
86
u. 87
00
34-249
34-249
86-706
86-707
86-708
LAS
LAS
SOAP-LIME SOAP DI SPERSER
ER AF569- 144-1
SOAP-LIME SOAP DI SPERSER
ER AF569- 144-2
SOAP-LIME SOAP DI SPERSER
ER AF569-144-3
PROPORTIONS
25/20/1/0/54
27/8/1/0/64
AS IS
AS IS
AS IS
SERIES
REF..NO-
237
234* 239
216
216
216
BLEND COTTON
FABRIC FABRIC
3.6 0.6
4*9 2.2
-0.5 -0.1
-0.4 -2.2
-0.1 -1.7
-------
Table 2. DETERGENCY OF SURFACTANT - CARBONATE FORMULATIONS,
.37., 4 washes, 200 ppm water
Ui
vo
Delta G Values
Vacuum Soil
Item
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
a =
Surfactant
Code No.
68-134
68-134
51-93
51-101
51-105
68-127
68-127
26-191
26-189
43-83
32-237
34-249
34-249
51-105
51-105
36-278
36-277
36-276
avg. of 3; b =
Surfactant Type Proportions
Fatty Alcohol Ethoxylate Nonionic 25/8/1/66/0
12/8/1/66/13
" " " 25/8/1/66/0
25/8/1/66/0
" " " " 25/8/1/66/0
" " " " 25/8/1/66/0
" " " " 12/8/1/66/13
Hydroxylated Nonionic 25/8/1/66/0
" " 25/8/1/66/0
25/8/1/66/0
Commercial Detergent Extract 25/8/1/66/0
Linear Alkylaryl Sulfonate (LAS) 20/8/1/35/36
25/8/1/60/6
Fatty Alcohol Ethoxylate 12/8/2/66/12
" 12/20/2/66
Low Titer Soap, Nonionic Mixture 20/15/8/1/36/20
40/15/8/1/36/0
High " " " " 40/15/8/1/36/0
alcohol extract of a leading commercial detergent.
Series
Ref. No.
23-4
23-4
19-20
19-20
19-20
23-4
a
23-4
23-4
23-4
28-9
120-1
134
30-2
30-2
42-3
42-3
42-3
Blend
Fabric
8.3
5.2
.7
.3
1.6
1.7
3.5
3.6
-.7
2.6
1.2
4.5
4.3
.5
1.8
2.0
.1
Cotton
Fabric
1.7
.8
1.1
1.5
.9
-.8
.5
1.0
-.2
-.8
-.2
4.9
-.1
-2.3
1.1
.3
-.1
Sebum
Blend
Fabric
.9
1.6
1.3
.5
1.3
0
2.8
1.3
1.8
2.7
.4
4.3
3.5
5.3
4.7
4.8
3.8
.3
Soil
Cotton
Fabric
.1
.5
-.6
-.6
-.5
0
1.8
1.2
2.7
.7
-1.1
3.9
3.4
1.0
1.3
1.2
.4
.8
-------
Table J. UKILRGEMCY OF SUEFACTAKT - KTA POSMJIAT1O5S,
.31, 4 vashes, 200 ppa water
Item
Ko.
1
2
3
4
5
6
7
ov 8
o
9
Surfactant
Code Bo.
51-91
34-249
68-558
68-109
68-134
68-127
22-155
20-138
51-93
Surfactant Type Proportions
Allran* s%| frn% afp Anionic 20/8/1/30/41
Alkylaryl Snlfonate Anionic (IAS) 20/8/1/30/41
Alpha Olefin Sulfonate Anionic 20/8/1/30/41
Snlfntartt Aa^nlyfi r ?*>/fl/1/lQ/36
Fvt*7 Mrflitol Fthfwylflte Wtmionlr 25/8/1/10/^6
12/8/1/30/49
Alpha Olefin Sulfonate 2O/8/1/30/41
Fatty Alcohol F* *MP"y l^f** ^%?n1onic 25/8/1/30/36
25/8/1/30/36
Series
8ef. Ho.
100-1
a
124-5
21-2
21-2
72-3
a
a
a
Yacuua
Blend
Fabric
1.1
.7
-1.7
.2
2.0
-.3
-1.5
-2.5
-3.2
Delta G Values
i Soil
Cotton
Fabric
1.0
1.2
-.6
-.1
.1
.9
-.9
-4.0
-1.9
Sebua Soil
Blend
Fabric
.8
.7
-1.8
.2
-1.2
1.7
-.9
1.5
Gotten
Fabric
.6
.7
-1.2
1.1
.6
.1
-1.7
.6
a * avg. of 3.
-------
Water
ppn
50
50
50
50
125
125
125
125
200
200
200
200
330
300
300
300
Tab
Tut gill a ti on
CflHwmt r -at ion
percent
.10
.15
.20
.30
.10
.15
.20
.30
.10
.15
.20
.30
.10
.15
.20
.30
I ^ to v MKiuHrfv WJ Y OF
AT VAHVT1K
Soil - Vacant
f fivATlC ~ " ii^^^r
Delta G
-.5
-.5
-1.7
-1.6
.6
-.1
-.1
-.6
.4
-1.0
.6
-1.9
.8
.3
-3.3
-.2
HI& - AIPS&. 01EFIK SOLFCEA2E FCKJflJIATICK
Soil - Vacuoa
Fabric -.Cotton
Delta G
.1
-.2
-.8
-.3
.9
-.7
-1.0
-1.0
1.3
.7
.6
-.5
.5
.7
-3.4
-.2
Soil - Sebua
Fabric - Blend
Delta G
-.1
-.4
-.3
.2
3.0
.9
.3
-.6
7.0
3.6
.4
-.6
3.7
4.9
.9
-.8
Soil - Sebua
Fabric - Cotton
Delta G
.8
-1.2
-.8
-.2
1.8
-.2
-.4
-.6
4.0
1.4
-.4
-1.2
.8
1.1
.2
0
a * Alpha Olefin Solfonate Code 22-155, Formulation proportion 20/8/1/30/41
-------
N>
Table 4. DETERGENCY OF SURFACTANT - SAND FORMULATIONS,
.3%, 4 washes, 200 ppm water
Delta G Values
Vacuum Soil
Item
No.
1
2
3
4
5
6
7
8
Surfactant
Code No.
68-127
68-127
68-127
62-491
22-155
60-486
51-91
34-249
Surfactant Type
Fatty Alcohol Ethozylate Nonionic
ii ii ii ii
ii ii it ii
Ether Sulfate Anionic
Alpha Olefin Sulfonate Anionic
Ether Carboxylate Anionic
Alkane Sulfonate Anionic
LAS Anionic
Proportions
12/8/1/30/49
20/8/1/30/41
12/8/1/50/29
20/8/1/30/41
20/8/1/30/41
20/8/1/30/41
20/8/1/30/41
20/8/1/30/41
Series
Ref. No.
52-3
117-8
a
117-8
-b
117-8
117-8
c
Blend
Fabric
.2
-1.4
.5
-.3
_ o
-2.0
2.2
3.9
Cotton
Fabric
-.5
-1.2
*™ • J
-.2
-.5
-2.3
.8
2.2
Sebum Soil
Blend
Fabric
.9
-1.0
.5
-.7
.3
-2.4
1.4
3.0
Cotton
Fabric
.6
-4.1
.3
-3.9
-1.5
-5.1
-1.7
3.2
a «
avg. of 2; b = avg. of 3; c = avg. of 4.
-------
Ul
Table 5. DETERGENCY OF SURFACTANT - SHIM FORMULATIONS,
.3%, 4 washes, 200 ppm water
Delta G Values
Vacuum Soil
Item
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
Surfactant
Code No. Surfactant Type
68-127 Fatty Alcohol Ethoxylate Nonionic
68-127 " " " "
68-558 Alpha Olefin Sulfonate Anionic
22-155
74-604 " " " "
60-486 Ether Carboxylate Anionic
40-332
78-634 " " "
78-633 " " "
78-635 Fatty Alkyl Sulfate Anionic
58-471 Ether Sulfate Anionic
34-249 Alkylaryl Sulfonate Anionic (LAS)
34-249
Proportions
12/8/1/30/49
12/8/1/50/29
20/8/1/30/41
20/8/1/30/41
20/8/1/30/41
12/8/1/30/49
20/8/1/30/— b
20/8/l/30/—b
20/8/1/30/— b
20/8/1/30/— b
12/8/1/30/49
20/8/1/30/41
25/8/1/50/16
Series
Ref. No.
a
89-90
124-5
a
145-6
106-7
135-6
155-6
155-6
155-6
106-7
98-9
89-90
Blend
Fabric
.2
.4
.4
-.2
.7
-1.1
-.7
.fr
.4
-.3
1.3
1.6
1.2
Cotton
Fabric
-.3
-1.3
.3
.5
.6
-.7
-.9
.2
.1
0
1.5
2.4
1.4
Sebum Soil
Blend
Fabric
-1.4
-.7
-.6
-.1
1.2
-1.5
0
1.4
1.0
.6
1.3
1.6
.6
Cotton
Fabric
-1.5
.1
-.9
-.3
0
-2.6
-.9
.4
.6
.8
-.4
1.0
1.2
a * avg. of 3; b - liquid formulation: water plus 10% hydro trope.
-------
Table 6. DETERGENCY OF POLYMERIC BUILDER - SURFACTANT FORMULATIONS,
.37,, 4 washes, 200 ppm water
Delta G Values
Vacuum Soil
Item Builder Type
No. and Code
1 Acrylic 43-65
2
3 " 20-141
4 Maleic 40-310
C II II
6
-j H ti
8 "
g 11 it
10 Carbohydrate
Surfactant Type and Code
Sulfo Ampholytic 68-109
Fatty Alcohol Ethoxylate
Nonionic 68-134
Sulfo Ampholytic 68-109
Fatty Alcohol Ethoxylate
Nonionic 68-127
Fatty Alcohol Ethoxylate
Nonionic 68-127
Fatty Alcohol Ethoxylate
Nonionic 68-127
LAS 34-249
ti ii
ti ii
Proportions
25/8/1/30/36
25/8/1/30/36
25/8/1/30/36
12/8/1/30/49
12/8/1/3/76
12/8/1/0/79
25/8/1/30/36
25/8/1/3/63
25/8/1/0/66
Series
Ref. No.
21-2
21-2
21-2
52-3
77-8
77-8
52-3
77-8
77-8
Blend
Fabric
3.9
3.7
5.7
-2.7
1.4
2.4
-.4
3.9
5.7
Cotton
Fabric
3.4
2.3
4.5
-2.1
2.1
3.3
-.5
3.1
4.2
Sebum Soil
Blend
Fabric
3.9
-.4
7.2
-2.1
3.0
3.4
0
5.1
6.1
Cotton
Fabric
1.9
.7
1.9
-1.1
.3
1.1
.4
2.7
3.8
74-602
11 Carbohydrate
74-602
Fatty Alcohol Ethoxylate
Nonionic 68-127
25/8/1/50/16 147-8
12/8/1/30/49 147-8
3.9
4.1
2.5
2.6
2.1
3.6
2.3
1.9
12 Carbohydrate
66-530
Alpha Olefin Sulfonate
22-155
20/8/1/30/41 122-3
1.8
2.2
2.9
2.7
-------
Delta G Values
01
Table 6 (Continued)
Item Builder Type
No. and Code
13 Copolymer 66-532
14
15 " "
16 " 66-533
17
18
19 " 58-466
20 " 58-467
21
22
23
24
Surfactant Type and Code
Fatty Alcohol Ethoxylate
Nonionic 68-127
Alpha Olefin Sulfonate
22-155
LAS 34-249
Fatty Alcohol Ethoxylate
Nonionic 68-127
Alpha Olefin Sulfonate
22-155
LAS 34-249
ii ii
it ii
Fatty Alcohol Ethoxylate
Nonionic 68-127
Fatty Alcohol Ethoxylate
Nonionic 68-127
Alpha Olefin Sulfonate
22-155
Alpha Olefin Sulfonate
22-155
Proportions
20/8/1/30/41
20/8/1/30/41
20/8/1/30/41
20/8/1/30/41
20/8/1/30/41
20/8/1/30/41
20/8/1/30/41
20/8/1/30/41
12/8/1/30/49
12 /8N/ 1/30/49
20/8/1/30/41
20/8N/1/30/41
Series
Ref. No.
122-3
122-3
122-3
122-3
122-3
122-3
98-9
98-9
149-50
149-50
151-2
151-2
Vacuum
Blend
Fabric
2.2
4.5
5.7
-.2
1.0
1.6
2.0
2.5
.9
.7
.1
.3
Soil
Cotton
Fabric
1.6
4.6
4.1
-.4
.5
1.7
1.3
.7
-.6
-.2
.1
.8
Sebum
Blend
Fabric
2.7
3.7
5.3
-1.1
.8
2.0
2.2
1.6
1.6
-.2
.9
.4
Soil
Cotton
Fabric
1.9
3.1
5.0
.4
1.5
2.3
2.1
2.3
-.6
-.4
.1
.2
-------
TABLE 6A« DETERGEMCY OF POLYMERIC BUILDER-SURFACTANT FORMULATIONS
•3X*SPANGLER SOIL*3 WASHES*200PPM WATER
ITEM
NO. BUILDER TYPE AND COPE
SURFACTANT TYPE AND CODE
DELTA W
SERIES BLENDCOTTON
PROPORTIONS REF.NO. FABRIC FABRIC
ON
25
26
27
28
89
30
31
32
33
34
35
36
ACRYLIC
ACRYLIC
ACRYLIC
ACRYLIC
ACRYLI C
ACRYLIC
ACRYLIC
ACRYLIC
HYDROXYLATED
ACRYLIC
CO POLYMER
HYDROXYLATED
ACRYLIC
CO POLYMER
HYLi.OXYLATED
ACRYLIC
CO POLYMER
HYTROXYLATED
ACHYLIC
CO POLYMER
92-745
92-745
100-823
100-823
100-823
100-823
100-824
100-824
104-860
104-860
104-860
104-860
LAS
FAEN
LAS
LAS
FAEN
FAEN
LAS
FAEN
LAS
LAS
FAEN.
FAEN
34-249
68-127
34-249
34-249
68-127
68-127
34-249
68-127
34-249
34-249
68-127
68-127
20/8/1/30/41
12/8/1/30/49
20/8/1/30/41
20/8/1/50/21
12/8/1/30/49
12/8/1/50/29
2O/8/1/30/41
12/8/1/30/49
20/8/1/30/49
20/8/1/50/29
12/8/1/30/49
12/8/1/50/29
236
215*235
244
245
244
245
244
244
251
251
251
251
1.4
1.8
3.3
1*6
7.7
2.5
2.9
3.6
2.9
2*7
7.5
4.8
1*0
-1.4
1*5
0.1
3*8
1.7
1.2
2.0
1.2
0.8
7.7
5.5
-------
TABLE 6A. (CONTINUED)
DELTA W
[TEM
NO.
37
38
39
40
4\
42
43
44
45
46
47
48
»*
BUILDER TYPE AND CODE
MALEIC TELOMER
MALEIC TELOMER
MALEIC TELOMER
MALEIC TELOMER
MALEIC HOMO- •
POLYMER
MALEIC HOMO- .
POLYMER
MALEIC
CO POLYMER
MALEIC
CO POLYMER
CARBOHYDRATE
CARBOHYDRATE
CARBOHYDRATE
CARBOHYDRATE
106-866
106-866
106-866
106-866
106-870
106-870
86-709
86-709
86-704
86-704
100-822
100-822
SURFACTANT
LAS
LAS
FAEN
FAEN
LAS
FAEN
LAS
FAEN
LAS
FAEN
LAS
LAS
SERIES BLEND
TYPE AND CODE PROPORTIONS REF.NO. FABRIC
34-249
34-249
68-127
68-127 '
34-249
68-127
34-249
68-127
34-249
68-127
34-249
34-249
20/8/1/30/41
20/8/1/50/21
12/8/1/30/49
12/8/1/50/29
20/8/1/30/41
12/8/1/30/49
25/8/1/30/36
12/8/1/30/49
25/8/1/30/36
12/8/1/30/49
20/8/1/30/41
20/8/1/50/21
251
251*
251
251
251
251
214
215
214*
215
244*
245*
•0.3
267-0.3
0.5
-0.5
0.3
0.4
1*3
3.9
224 4.7
9.8
249 4.2
249 1.6
COTTON
FAERIC
-0.2
-0.6
0.3
0-0
o.o
-0.6
-0.2
1.1
1.0
6.0
3. 1
-0. 1
-------
TABLE 6A. (CONTINUED)
DELTA V
00
ITEM
NO.
49
50
51
52
53
54
55
56
57
58
59
60
BUILDER TYPE AND CODE SURFACTANT
CARBOHYDRATE
CARBOHYDRATE
CARBOHYDRATE
CARBOHYDRATE
UNIDENTIFIED
CARBOXYLATED
K3LYMER
UN IDENTIFIED
CARPOXYLATED
POLYMER
UNIDENTIFIED
CARBOXYLATED
POLYMER
UNIDENTIFIED
POLYMER
UNIDENTIFIED
POLYMER
UNIDENTIFIED
POLYMER
UNIDENTIFIED
POLYMER
UNIDENTIFIED
100-822
100-622
102-834
102-834
86-705
86-705
86-705
98-806
98-806
98-807
98-807
100-821
FAEN
FAEN
LAS
FAEN
LAS
*
LAS
FAEN
LAS
FAEN
LAS
FAEN
LAS
TYPE AND CODE PROPORTIONS
68-127
68-127
34-249
68-127
34-249
34-249
68-127
34-249
68-127
34-249
68-127
34-249
12/8/
12/8/
20/8/
12/8/
"
25/8/
20/8/
12/8/
1/30/49
1/50/29
1/50/21
1/50/29
1/30/36
1/30/41
1/30/49
20/8/1/30/41
12/8/
20/8/
12/8/
20/8/
1/30/49
1/30/41
1/30/49
1/30/41.
SERIES BLEND
REF.NO. FAPRIC
244* 249
245* 249
245
245
214*224
236
215*235
236
235
236
235
244* 249
4*
3.
2*
3.
1.
5*
5.
1*
5*
1.
3.
3*
6
1
0
2
7
3
8
4
8
8
4
1
COTTON
FABRIC
3.9
3*5
0»0
1*6
0.5
1*1
1*6
1.4
1*2
1.4
-0.1
4. 1
FOLYMEh
-------
TABLE 6A. CCONTINUED)
ITEM
NO. BUILDER TYPE AND CODE
DELTA W
SERIES BLEND COTTOM
SURFACTANT TYPE AND CODE PROPORTIONS REF.NQ. FAPRIC FAPRIC
61 UNIDENTIFIED 100-821
POLYMER
62 UNIDENTIFIED 100-821
POLYMER
63 UNIDENTIFIED 100-821
POLYMER
LAS
FAEN
FAEN
34-249
68-127
68-127
20/8/1/50/21 249
5.3
12/8/1/30/49 244*249 4.3
12/8/1/50/29 249
3*8
3.0
3*4
0.5
-------
Table 7. DETERGENCY OF MONOMERIC BUILDER - SURFACTANT FORMULATIONS
.3%, 4 washes, 200 ppm water
Delta 6 Values
Vacuum Soil
Item
No.
1
2
3
4
5
6
7
8
9
10
11
Builder Type
and Code
Diglycollic Acid
38-279
Diglycollic Acid
38-279
Diglycollic Acid
38-279
Diglycollic Acid
38-279
Diglycollic Acid
40-309
Diglycollic Acid
40-309
Oxycarboxylic
Acid 66-541
Oxycarboxylic
Acid 66-541
Oxycarboxylic
AeLd-66-541
Oxycarbbxylic
Acid 74-596
Oxycarboxylic
Acid 74-596
Surfactant Type and Code
Fatty Alcohol Ethoxylate
Nonionic 68-127
Fatty Alcohol Ethoxylate
Nonionic 68-127
LAS 34-249
it it
Fatty Alcohol Ethoxylate
Nonionic 68-127
LAS 34-249
Fatty Alcohol Ethoxylate
Nonionic 68-127
Alpha Olefin Sulfonate
22-155 - -
LAS 34^249
Fatty Alcohol Ethoxylate
Nonionic 68-127
Fatty Alcohol Ethoxylate
Nonionic 68-127
Proportions
12/8/1/30/49
12/8/1/50/29
25/8/1/30/36
25/8/1/50/16
12/8/1/50/29
25/8/1/50/16 -
20/8D/1/30/41
20/8D/ 1/30/41
20/8D/ 1/30/41
12/8/1/60/19
low pH
12/8/1/60/19
high pH
Series
Ref. No.
45-6
52-3
45-S
52-3
' 52-3
a
122-3
122-3
122-3
137-8
149-50
Blend
Fabric
2.6
5.8
2.6
4.9
2.0
6.1
1.8
4.6
5.6
1.4
3.7
Cotton
Fabric
.2
4.6
2.2
1.8
~3
2*2
1.8
3.5
4.9
- .3
1.6
Sebum Soil
Blend
Fabric
4.2
2.4
6.4
3.8
2.0
5.1
U3
4.7
5.0
2.1
3.5
Cotton
Fabric
1.3
2.0
5.0
2.7
1.3
2.9
2.3
4U
5.7
.a
1.9
-------
Table 7 (Continued)
Delta G Values
Vacuum Soil
Item
No.
12
13
14
15
16 -•-
17
18
19
20
21
Builder Type
and Code
Monoe thanolamine
Carbonate 72-589
Mellitic Acid
74-606
Mellitic Acid
74-606
Tetrahydrofuran
Tetracarboxy
Acid 76-620
Tetrahydrofuran
Tetracarboxy
Acid 76-620
Clucohep tonic
Acid 20-151
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Surfactant Type and Code
Fatty Alcohol Ethoxylate
Nonionic 68-127
Fatty Alcohol Ethoxylate
Nonionic 68-127
LAS 34-249
Fatty Alcohol Ethoxylate
Nonionic 68-127
LAS 34-249
Fatty Alcohol Ethoxylate
Nonionic £8-127
Hydroxylated Nonionic
43-83
Fatty Alcohol Ethoxylate
Nonionic 68-127
Fatty Alcohol Ethoxylate
Nonionic 68-127
Fatty Alcohol Ethoxylate
Nonionic 68-127
Proportions
12/8/1/60/19
12/8D/1/30/49
25/8D/1/50/16
12/8/1/30/49
25/8/1/50/16
20/20/1/30/29
25/8/1/30/36
25/8/1/30/36
20/20G/1/20/39
20 /20GD/ 1/20/39
Series
Ref, No.
137-8
147-8
147-8
149-50
153-4
128-9
23-4
23-4
94-5
94-5
Blend
Fabric
3.6
4.8
2.7
1.9
1.7
3.6
.4
4.1
1.6
2.5
Cotton
Fabric
2.3
.6
2.2
.1
1.9
1.0
.2
.6
.8
.1
Sebum Soil
Blend
Fabric
1.7
1.7
1.8
1,4
U7
1.4
2.7
1.7
1.3
1.4
Cotton
Fabric
1.1
.9
2.1
.6
3.1
.9
.7
.8
.4
.5
-------
Delta G Values
to
Table
Item
No.
22
23
24
25
26
27
28
29
30
31
32
/ (.Continued)
Builder Type
and Code
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Vacuum Soil
Surfactant Type and Code
Fatty Alcohol Ethoxylate
Nonionic 68-127
Fatty Alcohol Ethoxylate
Nonionic 68-127
Ether Sulfate Anionic
62-491
Ether Sulfate Anionic
62-491
Alpha Olefin Sulfonate
Anionic 22-155
Alpha Olefin Sulfonate
Anionic 22-155
Alpha Olefin Sulfonate
Anionic 74-604
Ether Carboxylate Anionic
40-332
Ether Carboxylate Anionic
60-486
Ether Carboxylate Anionic
60-486
Ether Carboxylate Anionic
78-633
Proportions
12/20GD/1/20/47
20/20G/1/30/29
12/20G/1/20/47
12/20GD/1/20/47
20/20G/1/30/29
20/20D/1/30/29
20/20/1/30/29
20/20D/1/30/29
12/20/1/20/47
20/20/1/30/29
20 /20D/ 1/30/29
Series
Ref. No.
102-3
128-9
102-3
102-3
130-1
145-6
145-6
155-6
102-3
128-9
155-6
Blend
Fabric
3.0
-.1
4.0
5.0
.1
1.7
2.6
1.9
3.0
-.1
4.7
Cotton
Fabric
2.7
-.5
3.9
4.8
.7
.2
.1
-.1
3.1
.3
2.4
Sebum Soil
Blend
Fabric
2.2
-.1
6.8
7.5
.6
2.6
2.1
.7
6-1
-2.0
5.9
Cotton
Fabric
2.3
-.5
3.1
3.4
.3
0
0
-.5
3.1
-.6
2.8
-------
Delta G Values
u>
Table
Item
No.
33
34
35
36
7 (Continued)
Builder Type
and Code
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Citric Acid
20-152
Surfactant Type and Code Proportions
LAS 34-249 20/20G/1/20/39
" " 20/20GD/1/20/39
Sulfo Zwitterionic 42-348 20/20/1/30/29
11 " 54-433 20/20/1/30/29
Series
Ref. No.
94-5
94-5
a
130-1
Vacuum
Blend
Fabric
4.8
4.8
-.1
-.7
Soil
Cotton
Fabric
3.2
2.4
-1.8
-.1
Sebum
Blend
Fabric
3.6
2.0
.2
.7
Soil
Cotton
Fabric
3.5
2.7
-1.5
-.4
a = avg. of 2.
-------
TABLE 7A. DETERQENCY OF MONOMER!C BUILDER-SURFACTANT FORMULATIONS
*3X*SPANGLER SOIL*3 WASHES/SOOPPM WATER
DELTA W
ITEM
NO*
37
38
39
40
41
42
43
44
45
46
47
48
49
50
BUILDER TYPE AND CODE
CMOS
CMOS
CMOS
CMOS
CMOS
CITRIC ACID
CITRIC ACID
CITRIC ACID
CITRIC ACID
CITRIC ACID
CARBOXYETHYL
ACETONE
CARBOXYETHYL
ACETONE
CARBOXYETHYL
ACETONE
CARBOXYETHYL
96-789
96-789
96-789
96-789
96-789
20-1 58
80-158
80-152
20-152
20-152
102-833
102-833
102-833
102-833
SURFACTANT
LAS
LAS
LAS
FAEN
FAEN
LAS
LAS
LAS
FAEN
FAEN
LAS
LAS
FAEN
FAEN
TYPE AND CODE
34-249
34-249
34-249
68-127
68-127
34-249
92-752
34-249
68-187
68-127
34-249
34-249
68-127
68-127
SERIES
PROPORTIONS REF.NO.
20/8/1/30/41
25/8/1/30/36
25/8/1/50/16
12/8/1/30/49
12/8/1/50/29
25/8/1/30/36
25/8/1/30/36
25/20/1/30/24
12/8/1/3C/49
12/20/1/30/37
20/8/1/10/61
20/8/1/50/21
12/8/1/10/69
12/8/1/50/29
S36
837
237
235
238
214
224
237
215
238
245
245
245
245
BLEND
FABRIC
2.0
2.9
0.7
3. 1
2. 1
1.8
2*5
3.2
6*1
7.0
5.9
11.4
10.8
9*4
COTTON
FAEFU C_
0.7
-0.3
-0. 1
1.6
-0.8
1.2
0*1
0.8
3.5
4.4
-1.2
6.8
8.5
5.4
ACETONE
-------
Table 7B
-j
Ul
Detergent
EFFECT OF CONCENTRATION ON WHITENESS OF SOILED SWATCHES
Whiteness Units Lost as Concentration is Decreased (runs 173-196)
200 ppm Water
Purapress
Procedure 1
Concentration
.3% .2% .1%
Procedure 2
Concentration
.3% .2% .1%
Procedure 3
Concentration
.3% .2% .1%
Procedure 4
Concentration
• 3*o + £.b * -L/o
Procedure 5
Concentration
.3% .2% .1%
AATCC
ARAM
66-1 (D)
64-2(M)
0
0
0
0
-.6
.7
6.3
4.5
16.5
19.9
9.4
10.8
o i-o
0 -5
0 9.3
0 5.2
16.6
21.3
16.6
14.6
C
0
0
0
-1.9
.5
1.7
.6
2.1
7.3
4.1
2.5
0
0
0
0
.7
-.4
4.2
.7
5.9
7.2
14.1
6.1
Cotton
AATCC
AEAM
64-l(D)
64-2(M)
0 .4 2.8 0
0 .7 2.5 0
0 2.7 5.7 0
0 -.7 5.4 0
-.1
0
2.2
2.1
7.3
9.6
9.6
7.8
Tap
0 .7
0 .3
0 2.8
0 1.7
Water
10.7
12.6
8.4
7.1
C
0
0
0
.1
1.0
1.6
1.4
2.3
3.4
4.5
3.8
0
0
0
0
-.S
.5
1.4
.9
3.0
4.5
6.4
14.4
Durapress
AATCC
AHA!-!
64-l(D)
64-20-0
AATCC
AHA:-:
64-l'(D)
64-200
0
0
0
0
0 .5 1.2 0
0 -.1 -.3 0
0 .9 5.4 0
0 .4 4.5 0
-1.1
.6
4.9
3.5
-.4
.5
1.4
.4
6.3
8.6
12.1
13.6
C
4.5
5.7
4.S
3.5
0 -.8
0 -.1
0 6.8
0 4.1
otton
0 -.6
0 1.0
0 1.3
0 1.0
3.9
8.4
20.1
14.8
3.1
5.7
7.4
5.6
0
0
0
0
0
0
0
0
-.5
-.7
1.1
.5
-.1
.1
2.1
~ • _L
-.5
1.3
3.2
2.3
.6
.1
3,1
2.3
0
0
0
0
0
0
0
0
-.3
-1.3
1.8
-.2
-1.3
-.1
o
• /-
1.3
1.2
2.6
9.5
4.8
-1.8
.4
3.2
5.2
-------
Table 7C
EFFECT OF WATER HARDNESS ON WHITENESS OF SOILED SWATCHES
Whiteness Readings in Tap Water minus Whiteness Readings in Hard Water (200 ppm)
(Series 173-196)
Duraoress
Detergent
AATCC
AHAM
64-l(D)
64-2(M)
AATCC
AHAM
64-l(D)
64-2 (M)
Procedure 1 Procedure 2
Concentration Concentration
.3% .2% .1% .3% .2% .1%
.3
.4
4.8
1.5
.1 0 1.7 .4
1.1 1.9 3.9 .8
2.6 4.4 2.9 .6
1.3 1.4 2.2 -.7
.8
.5
6.2
2.5
.7
.3
1.4
1.0
10.5
11.7
2.1
-.3
3.3
4.7
5.4
2.6
Procedure 3
C or. cen t r a t i on
">.•/' 97 17
. ->A . f.n . JL/o
~. 7
.3
8.7
4.0
Cotton
1.2
1.5
5.2
4.4
1.1
.9
11.2
5.1
2.5
.8
6.7
5.1
13.0
13.2
5.2
4.6
8.8
8.4
6.2
5.9
Procedure 4
Concentration
. 3% . 2% . 1%
4.4
1.4
1.6
4.2
2.0
1.0
2.0
.8
2,8
2.6
2.2
4.3
1.0
-.1
1.5
2.1
7.0
7.4
2.5
4.4
3,7
4.3
3.4
l.S
Procedure 5
Concentration
« J/'o • *-/:• • J_.'n
1.9
1.0
-1.1
-1.2
1.8
1.7
.£
. 1.0
.5
1.9
1.3
-.3
2.3
1.3
1.6
.1
6.6
5.6
3.5
.1
6.6
5.8
3.6
o
• £-
-------
TABLE 8. REPRESENTATIVE DRUM-DRIER FORMULATIONS
OF SATISFACTORY CHARACTER8
1. 30 parts NTA; 20 parts alpha olefin sulfonate surfactant 22-155; I part
NaCMC; 8 parts silicate; D; 41 parts sodium sulfate (Formulation Ref. No.
64-511).
2. 30 parts SAND; 20 parts ether carboxylate surfactant 60-486; 1 part
NaCMC; 8 parts silicate D; 41 parts sodium sulfate (Formulation Ref.
No. 64-515).
3. 30 parts SAND; 20 parts ether sulfate surfactant 62-491; 1 part NaCMC;
8 parts silicate D; 41 parts sodium sulfate (Formulation Ref. No. 64-514).
4, 30 parts SAND; 15 parts fatty alcohol ethoxylate nonionic surfactant
68-127; 1 part NaCMC; 8 parts silicate D; 46 parts Na.SO, (Formulation
Ref. No. 64-516).
5. 30 parts sodium citrate; 20 parts silicate G; 20 parts sulfo zwitterionic
surfactant 54-433; 1 part NaCMC; 29 parts sodium sulfate (Formulation
Ref. No. 64-2).
6. 30 parts sodium citrate; 20 parts silicate G; 20 parts sulfo zwitterionic
surfactant 42-348; 1 part NaCMC; 29 parts sodium sulfate (Formulation Ref.
No. 67-1).
7. 30 parts sodium citrate; 20 parts silicate G; 20 parts ether carboxylate
anionic surfactant 60-486; 1 part NaCMC; 29 parts sodium sulfate (Formu-
lation Ref. No. 64T1). *
Fluorescent whitening agents and minor adjuvants can be added as desired
without essentially changing the physical character of the product.
Tendency to cake in storage, as a function of pressure and humidity,
not investigated.
77
-------
TABLE 8a. REPRESENTATIVE LIQUID FORMULATIONS
OF SATISFACTORY CHARACTER8
1. 10.6 parts fatty alcohol ethoxylate nonionic surfactant 68-127; 16 parts
sodium citrate; 11 parts silicate 0; 10 parts di-sodium octenyl succinate;
water q.s. 100 (Formulation Ref. No. 7?).
2. 14 parts ether carboxylate anionic surfactant 40-332; 5.7 parts silicate
D; 22 parts SHIM; 10 parts sodium xylene sulfonate (Formulation Ref. No.
71).
3* 10 parts fatty alcohol ethoxylate nonionic surfactant 68-127; 6.7 parts
silicate N; 25 parts SHIM; 4.5 parts di-sodium octenyl succinate; vatet
q.s. 100 (Formulation Ref. No. 59-1).
4. 12 parts alpha olefin sulfonate anionic surfactant 22-155; 4.8 parts
silicate D; 18 parts SHIM; 7.7 parts sodium xylene sulfonate; water
q.s. 100 (Formulation Ref. No. 65-1).
5. 12 parts alpha olefin sulfonate anionic surfactant 22-155; 4.8 parts
silicate D; 18 parts SHIM; 5.6 parts sodium xylene sulfonate; 8 parts
isopropanol; water q.s. 100 (Formulation Ref. No. 60-1).
a NaCMC does not dissolve readily in these formulations, but can be suspended
with or without other anti-redeposition agents and auxiliaries. About 1
part NaCMC per 15-20 parts surfactant is a suitable proportion.
78
-------
Table 9. STIMULATORY EFFECT ON GROWTH OF ALGAE
(Positive is stimulating - negative is inhibiting.)
SPECIES
Item #
1
2
3
4
5
6
Code //
20-146
22-155
43-83
68-127
68-134
Class of
Compound
Low titer
soap
Alpha
Olefin
Sulfonate
Sodium
tetasilicate
Hydroxylated
Nonionic
Fatty
Alcohol
Ethoxylate
Fatty
Alcohol
Ethoxylate
Anabaena
Slightly
positive at
10 ppm. No
effect at
0.1 and
1 ppm.
"
No effect
at 7 ppm.
Negative at
35 and
70 ppm.
No effect
at 5 ppm.
No effect
at 5 ppm.
Slightly
negative at
1 ppm.
Microcystis
No effect
at 1 and
10 ppm.
No effect
at 1 and
10 ppm.
No effect
at 50 ppm.
No effect
at 1 ppm.
Slightly
negative at
5 ppm.
—
Selenastrum
•
No effect
at 1 ppm
No effect
at 1 ppm.
No effect
at 1 ppm.
Navicula
No effect
at 0.1, 1,
and 10 ppm.
No effect
at 0.1 and
1 ppm.
Slightly
positive at
10 ppm.
Excess over
amount in
medium has
no effect.
No effect
at 1 ppm.
No effect
at 1 ppm.
79
-------
Table 9 (Continued)
SPECIES
Item #
7
8
9
10
11
12
13
Code 1
20-138
43-64
54-433
42-348
56-445
40-312
38-279
Class of
Compound
Fatty
Alcohol
Ethoxylate
Commercial
High
Carbonate
Detergent
Zwitter-
ionic
Sulfonate
Zwitter-
ionic
Sulfonate
SHIM
(HEIDA)
SAND
Diglycollic
Acid
Anabaena
No weight
effect,
but cells
altered
at 0.5
and 5 ppm.
No effect
at 5 ppm.
No effect
at 1 and
5 ppm.
Slightly
negative at
1 ppm. No
effect at
0 . 1 ppm.
No effect
at 1 and
5 ppm.
No effect
at 1 and
5 ppm.
-
No effect
at 1 and
5 ppm.
Micro cystis
No effect
at 0.5 and
5 ppm.
Negative
at 5 ppm.
No effect
at 1 and
5 ppm.
Slightly
negative at
1 ppm. No
effect at
0.1 ppm.
No effect
at 1 and
5 ppm.
No effect
at 5 ppm.
Slightly
negative at
1 ppm.
No effect
at 1 ppm.
Slightly
positive at
5 ppm.
Selenastrum
No effect
at 0.5 and
5 ppm.
Slightly
negative
at 5 ppm.
No effect
at 1 and
5 ppm.
Slightly
negative at
1 ppm. No
effect at
0.1 ppm.
No effect
at 1 and
5 ppm.
No effect
at 5 ppm.
Slightly
negative at
1 ppm.
No effect
at 1 and
5 ppm.
Navicula
No effect
at 5 ppm.
No. effect
at 1 and
5 ppm.
'
No effect
at; 0.1 and
1 ppm.
No effect
at 1 and
5 ppm.
i
No effect
at 1 and
5 ppm.
NO effect
at 1 and
5 ppm.
80
-------
Table 9 (Continued)
SPECIES
Item #
14
15
16
17
18
19
Code #
60-486
90-730
86-700
80-647
20-147
34-249
Class of
Compound
Ether car-
boxy late
anionic
s,ur fact ant
Anionic
sulfonate
surfactant
Standard
phosphate
built
detergent
Monomer ic
builder
CMOS
High titer
soap
IAS
anionic
surfactant
Anabaena
No effect
at 1.0 ppm.
Slightly
negative
at 0.1 ppm.
No effect
at 1.0
and 10.0
ppm.
No effect
at 10.0
and 20.0
ppm.
No effect
at 1.0
ppjn ,
Slightly
negative
at 10.0 .
ppm.
4
No effect
at 1.0 and
10.0 ppm.
Microcystis
No effect
at 1.0
and 5.0 ppm.
No effect
at 1.0 ppm.
Slightly
positive at
10.0 ppm.
Positive
<400%) at
10.0 ppm.
Positive
(2507.) at
20.0 ppm.
No effect
at 1.0 and
10.0 ppm.
No effect
at 1.0 and
10.0 ppm.
No effect
at 1.0 and
10.0 ppm.
Selenastrum
No effect
at 1.0
and 5.0 ppm.
NO effect
at 1.0
ppm.
Slightly
positive
at 10.0 ppm.
Positive
(200%) at
10.0 and
20.0 ppm.
No effect
at 1.0 and
10.0 ppm.
mw —
No effect
at 1.0 ppm.
Very slight-
ly negative
at 10.0 ppm.
Navicula
No effect at
1.0 and 10.0
ppm. Slightly
negative at
0.1 ppm.
No effect at
1.0 ppm.
Very slightly
negative at
10 ppm.
No effect at
10.0 ppm.
Very slightly
positive at
20.0 ppm.
No effect at
1.0 and 10.0
ppm.
'No effect at
1.0 ppm.
Slightly
negative at
10.0 ppm
No effect at
1.0 ppm.
Positive (163%)
at 10.0 ppm.
81
-------
Table 10
ACUTE AQUATIC TOXICITY OF DETERGENTS AND THEIR INGREDIENTS
oo
N>
Item
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
Code
20-151
20-152
20-138
43-67
68-127
51-101
51-100
68-134
51-93
43-64
26-189
26-191
43-83
38-279
20-141
42-353
54-433
Description
Glucoheptonic acid
Sodium citrate
Fatty alcohol ethoxylate nonionic surfactant
Fatty alcohol ethoxylate nonionic surfactant
Fatty alcohol ethoxylate nonionic surfactant
Fatty alcohol ethoxylate nonionic surfactant
Fatty alcohol ethoxylate nonionic surfactant
Fatty alcohol ethoxylate nonionic surfactant
Fatty alcohol ethoxylate nonionic surfactant
Commercial detergent-high carbonate type
Hydroxylated nonionic surfactant
Hydroxylated nonionic surfactant
Hydroxylated nonionic surfactant
Diglycollic acid builder
Polymeric builder
Sulfo zwitterionic surfactant
Sulfo zwitterionic surfactant
96 hr.
Tim
Fish
ppm.
>2000
1710
2.87
3.45
3.87
3.95
2.73
2.89
3.7
26.7
14.8
196
37
> 490
680
.76
7.7
96 hr.
TLm
Snail
ppm.
>2000
1415
23.1
6.01
6.1
4.03
4.3
3.33
9.5
25.8
>490
89.5
165
>490
420
1.0
6.6
ppm. to
cause
50% redn.
in growth,
7 days
Diatom
>1800
1200
4.5
185
313
900
270
625
123
155
890
125
100
750
62
3.8
35
-------
Table 10 (Continued)
GO
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
46^356
40-332
48-373
22-155
62-491
18-136
64-^511
40-312
56-445
64-1
64-2
67-1
80-647
90-730
104-860
10JO-823
106-866
Carboxy zwitter ionic surfactant
Ether Carboxy anionic surfactant
Amine oxide surfactant
Alpha olefin sulfonate anionic surfactant
Ether sulfonate anionic surfactant
NTA builder
Formulation of 22-155 and NTA
SAND builder
SHIM builder
Citrate formulation with 60-486 surfactant
Citrate formulation with 54-433 surfactant
Citrate formulation with 42-348 surfactant
CMOS monomer ic builder
D-116 anionic surfactant
FOCNa polymeric builder
Calnox 214 DN polyacrylic builder
Maleic telomer builder
t
10.5
3.15
3.7
4.25
.57
500
10.0
490
> 100
23.7
20.2
44.0
> 560
20.5
> 560
> 560
13.3
4.7
3.8
6.8
.84
500
15.6
490
> 100
24.0
98.1
56.0
> 560
32.3
> 560
> 560
16.4
64.5
6.0
24.2
25
500 •
54.9
870
> 100
> 100
21.6
22.1
229% growth
at 100 ppm
17.3
> 560
300% growth
> 560
> 560
(a)
at 100 ppm
890% growth
at 100 ppm
(a)
(a)
These figures indicate stimulation of growth.
-------
Table 11
ESTIMATION OF BIODEGRADABILITY OF
MATERIALS USED IN DETERGENT FORMULATIONS
I. Materials considered biodegradable
V.
Code No. Type
43-83 Hydroxylated nonionic surfactant
40-332 Ether carboxylate anionic surfactant
42-348 Sulfo zwitterionic surfactant
38-279 Diglycollic acid builder
66-541 Monomeric builder
74-606 Monomeric builder, Mellitic acid
56-445 SHIM builder
80-647 Monomeric builder, CMOS
60-486 Ether carboxylate surfactant
20-145 Sugar ester surfactant
90-730 Anionic sulfonate surfactant
104-860 Polymeric builder, hydroxylated acrylic
II. Materials considered non-biodegradable
Code No. Type
76-620 Monomeric builder
43-65 Polymeric builder
66-530 Polymeric carbohydrate type builder
74-602 Polymeric carbohydrate type builder
58-466 Polymeric builder
86-709 Polymeric builder, maleic copolymer
40-310 Polymeric builder, maleic copolymer
92-745 Polymeric builder, acrylic
43-74 Polymeric builder, acrylic
98-806 Polymeric builder
98-807 Polymeric builder
100-824 Polymeric builder, acrylic
100-822 Polymeric builder, carbohydrate
106-871 Polymeric builder, maleic
102-833 Monomeric builder
84
-------
Table 11 (Continued)
III. Materials of questionable (slow or incomplete) biodegradability
Code No. Type
100-821 Polymeric builder
100-823 Polymeric builder, acrylic
102-834 Polymeric builder, carbohydrate
106-866 Polymeric builder, maleic telomer
85
-------
Table 12
HAZARD TEST RESULTS. DETERGENT FORMULATIONS
oo
Ident. No.
64-2
65-1
65-2
64-1
67-1
56-445
43-64
LP-23
LP-24
LP-25
LD50 ORAL
mg/kg
> 5
< 5
> 10
> 10
4.13 (m)
3.55 (f)
2.61 (m)
3.83 (f)
> 5
> 5
> 5
LD50 DERMAL Rabbit skin Rabbit eye
rag/kg irrit .score irr it . W
^ n n (- » imt •
> *'** (39,25,21)
> 2 > 5.5 irrit.
(27,27,22)
0.99(a* 4.0 irrit.
(32,26,19)
> 2 2.9 irrit.
(35,27,22)
> 1, < 2(a) irrit.
(50,47,38)
o 91(a)
j.zi — -- -•••
> 2 0.38
> 2
> 2
Esophageal
irrit.
equal to
sucrose control
equal to
sucrose control
equal to
sucrose control
very slight
positive
(a) Wide variation; severe renal damage.
(b) Figures are eye scores at 24, 48 and 72 hours.
(c) Five week repeated insult patch test on 53 panelists,
Human patch test
negative
(c)
negative
negative
-------
Table 12a
IDENTIFICATION OF FORMUIATIONS IN Table 12
Ident No. Composition
64-2 20/20/1/30/29. Surfactant 54-433, Builder citrate, Solid.
65-1 12/4.8/0/18/7.7/qs H.O. Surfactant 22-155, Builder SHIM,
Hydrotrope Na xylene sulfonate, Liquid.
65-2 10/6,7/0/25/4.5/qs H20. Surfactant 68-127, Builder SHIM,
Hydrotrope Na octenyl succinate, Liquid.
64-1 20/20/1/30/29. Surfactant 60-486, Builder citrate, Solid.
67-1 20/20/1/30/29. Surfactant 42-348, Builder citrate, Solid.
56-445 SHIM (HEIDA) builder, 257. aqueous solution.
43-64 Commercial phosphate-free, high carbonate detergent.
LP-23 Sodium xylene sulfodate, 20% aqueous solution.
LP-24 Sodium octenyl succinate, 5% aqueous solution.
LP-25 Sodium nitrilotriacetate (NTA), 25% aqueous solution.
87
-------
Table 13
EFFECT OF MULTIPLE WASHINGS ON BUILD UP OF IMPURITIES IN FABRIC
00
00
Alcohol Extractable*
Content of Fabric, %
Ash Content*
of Fabric, %
Ident .
Number
86-700
88-722
88-726
86-706
86-707
86-708
20-147
••MM
Detergent
Type
AATCCWOB
'Commercial high carbonate
Commercial high silicate
Soap & lime soap disperser
Soap & lime soap disperser
Soap & lime soap disperser
Soap & silicate 85/15/0/0/0
None-Hard Water Alone
After
20 Washings
Blend
Fabric
.30
--
—
.74
1.43
1.14
2.09
.58
Cotton
.77
«• «•
—
1.49
2.41
1.47
3.31
.58
After
50 Washings
Blend
Fabric
.64
.54
.61
2.39
2.20
—
3.50
.78
Cotton
.36
.40
.50
2.33
2.12
—
5.71
.61
After
20 Washings
Blend
Fabric
.29
--
--
.37
.39
.39
.50
.28
Cotton
.09
—
—
.13
.24
.19
.60
.03
After
50 Washings
Blend
Fabric
.36
7.5
.80
.56
--
.54
.77
.31
Cotton
.08
10.6
.41
.39
--
—
1.19
.08
Original unwashed blend fabric averaged .81% alcohol extractable and .33% ash.
Original unwashed cotton fabric averaged .47% alcohol extractable and .05% ash.
-------
' I
AA' CCWOB
Sbaa-lsiliciktei
.1
.2
.3
.4
Detergent concentration in bath (%)
Figure 1. Detergency v. concentration. Item 20-147 high titer
soap. Series ref. 210. Empa soil. 200 ppm water.
89
-------
0)
c
0)
(V
O)
c
U
Detergent concentration in bath (%)
Figure 2. Detergency v. concentration. Item 86-706.
Soap-lime soap disperser. Series ref. 210,
Empa soil. 200 ppm water.
90
-------
Detergent concentration in bath (%)
Figure 3. Detergency v. concentration. Item 86-707.
Soap-lime soap disperser. Series ref. 210,
Empa soil. 200 ppm water.
91
-------
Detergent concentration In bath
Figure 4. Detargeney v. conctntratlon, Item 86-708.
Soap- lima soap dliparaer. Series raf. 210.
Empa loll. 200 ppm water.
92
-------
Detergent concentration in bath (%)
Figure 5, Detergancy v. concentration. Item 90-730 anlonlc
•ulfcmate. Serlea ref, 243. Colgate soil. Tup
water. Blend fabric.
93
-------
Detergent concentration in bath (%)
Figure 6. Detergency v. concentration. Item 90-730 anionic
sulfonate. Series ref. 243. Colgate soil. Tap
water. Cotton.
94
-------
.3
Detergent concentration in bath (%)
Figure 7- Detergency v. concentration. IAS and Item 90-730
anionic sulfonate. Series ref. 239C. Colgate soil.
200 ppm water. Blend fabric.
95
-------
V)
Cfl
0>
c
0>
0>
O)
c
CO
Detergent concentration in bath (%)
Figure 8. Detergency v. concentration. IAS and Item 90-730
anionic sulfonate. Series ref. 239C. Colgate soil.
200 ppm water. Cotton.
96
-------
Q>
I
•a
tn
(0
O
o>
Detergent concentration in bath (%)
Figure 9. Detergency v. concentration. IAS and Item 90-730
anionic sulfonate. Series ref. 239. Spangler soil
multicycle. 200 ppm water. Blend fabric.
97
-------
o
>>
u
•o
0)
in
o>
U4-J.Q JJA6
Figure 10.
Detergent concentration in bath (%)
Detergency v. concentration. IAS and Item 90-730
anionic sulfonate. Series ref. 239. Spangler soil
multicycle. 200 ppm water. Cotton.
98
-------
Figure 11.
Detergent concentration in bath (%)
Detergency v. concentration. IAS and LAS-CMOS (item 80-647)
and Item 90-730 anionic sulfonate. Series ref. 243.
Spangler soil multicycle. Tap water. Blend fabric.
99
-------
£
u
u
•o
o
•o
«
tf)
(20/8/1X30/41)
Detergent concentration in bath (%)
Figure 12. Detergency v. concentration. IAS and IAS-CMOS (item 80-647)
and Item 90-730 anionic sulfooate. Series ref. 243.
Spangler soil multicycle. Tap water. Cotton.
100
-------
10
(A
0
C
0
«
at
c
a
Figure 13.
Detergent concentration in bath (%)
Detergency v. concentration. Items 42-350 and 42-353
zwitterionic. Series ref. 247 and 252 (for AATCCWOB)
Colgate soil. 200 ppm water. Blend fabric.
101
-------
Figure 14.
Detergent concentration in bath (%)
Detergency v. concentration. Items 42-350 and 42-353
zwitterionic. Series ref. 247 and 252 (for AATCCWOB).
Colgate soil. 200 ppra water. Cotton.
102
-------
Detergent concentration in bath (%)
Figure 15. Detergency v. concentration. Items 104-856 and 108-880
anionics. Series refs. 252 (AATCCWOB) 250 and 256.
Colgate soil. 200 ppm water. Blend fabric.
103
-------
Crt
CO
0)
c
c
0)
.c
O
.3
Figure 16.
Detergent concentration in bath (%)
Detergency v. concentration. Items 104-856 and 108-880
anionics. Series refs. 252 (AATCCWOB) 250 and 256.
Colgate soil. 200 ppm water. Cotton.
104
-------
Detergent concentration in bath (%)
Figure 17. Detergency v. concentration. Items 104-855 (detergent D) and
96-782 (detergent E). Series refs. 252 (AATCCWOB) and 248.
Colgate soil. 200 ppm water. Blend fabric.
105
-------
c
a;
0)
a>
c
(J
AATdCWftE
i I
—I-
.1
.2
.3
Figure 18.
Detergent concentration in bath (%)
Detergency v. concentration. Items 104-855 (detergent D)
and 96-782 (detergent E). Series refs. 252 (AATCCWOB) and 248.
Colgate soil. 200 ppm water. Cotton.
106
-------
0)
73
1
IE
4)
(B
(0
(0
0)
Detergent concentration in bath (%)
Figure 19. Detergency v. concentration. Items 104-855 (detergent D)
and 96-782 (detergent E). Series refs. 253 and 254. Spangler
multicycle. 200 ppm water. Blend fabric.
107
-------
o
TO
•o
0)
0)
c
Figure 20.
Detergent concentration in bath (%)
Detergency v. concentration. Items 104-855 (detergent D)
and 96-782 (detergent E). Series refs. 253 and 254. Spangler
multicycle. 200 ppm water. Cotton.
108
-------
• AATCCWOB
* Detergent C
O Detergent T
.1 -2
Detergent concentration in bath (%)
.3
Figure 21.
Detergency v. concentration. Items 96-783 (detergent C) and
96-784 (detergent T). Series ref. 240. Colgate soil. 200 ppm
Blend fabric.
109
-------
30
Cotton
• AATCCWOB
* Detergent C
O Detergent T
.1 .2
Detergent concentration in bath (%)
Figure 22. Detergency v. concentration. Items 96-783 (detergent C) and
96-784 (detergent T). Series ref. 240. Colgate soil.
200 ppm water. Cotton.
110
.3
-------
Detergent concentration in bath (%)
Figure 23. Detergency v. concentration. Series ref. 259 (AATCCWOB)
268 (HEIDA). Colgate soil. 200 ppm water. Blend fabric.
Ill
-------
(A
C/>
Q>
c
c
U
Detergent concentration in bath (%)
Figure 24. Detergency v. concentration. Series ref. 259 (AATCCWOB)
268 (HEIDA). Colgate soil. 200 ppm water. Cotton.
112
-------
Detergent concentration in bath (%)
Figure 25. Detergency v. concentration. Item 100-823. Series ref. 252
(AATCCWOB) 255 (item 100-823). Colgate soil. 200 ppm water,
Blend fabric.
113
-------
0>
C
0)
O)
C
O
Figure 26.
Detergent concentration in bath (%)
Detergency v. concentration. Item 100-823. Series ref. 252
(AATCCWOB) 255 (item 100-823). Colgate soil. 200 ppm water,
Cotton.
114
-------
(A
tf)
0)
C
9
C
u
Detergent concentration in bath (%)
Figure 27. Detergency v. concentration. Item 104-860. Series ref. 259
.', - (AATCCWOB) 257 (item 104-860). Colgate soil. 200 ppm water.
Blend fabric.
115
-------
(A
to
Q>
'C
0)
0)
O)
C
Detergent concentration in bath (%)
Figure 28. Detergency v. concentration. Item 104-860. Series ref. 259
(AATCCWOB) 257 (item 104-860). Colgate soil. 200 ppm water.
Cotton.
116
-------
0>
c
JC
$
C
(0
Detergent concentration in bath (%)
Figure 29. Detergency v. concentration. Item 106-866. Series refs. 258,
259, 260. Colgate soil. 200 ppm water. Blend fabric.
117
-------
(A
0)
C
0>
0)
O)
Figure 30.
Detergent concentration in bath (%)
Detergency v. concentration. Item 106-866. Refs. 258, 259, 260,
Colgate soil. 200 ppm water. Cotton.
118
-------
0>
"o
•o
0)
8
-------
o
o
•o
0>
CO
(0
0>
0)
Figure 32.
Detergent concentration in bath (%)
Detergency v. concentration. Item 106-866. Series ref. 267
Spangler multicycle. 200 ppm water. Cotton.
120
-------
AATCCWOB
Detergent concentration in bath (%)
Figure 33. Detergency v. concentration. Item 80-647. Series ref. 243.
Colgate soil. 200 pptn water. Blend fabric.
121
-------
Detergent concentration in bath (%)
Figure 34. Detergency v. concentration. Item 80-647. Series ref. 243.
Colgate soil. 200 ppm water. Cotton.
122
-------
Figure 35.
Detergent concentration in bath (%)
Detergency v. concentration. Item 90-279. Series ref. 240.
Colgate soil. 200 ppm water. Blend fabric.
123
-------
.3
Figure 36.
Detergent concentration in bath (%)
Detergency v. concentration.' Item 90-279. Series ref. 240.
Colgate soil. 200 ppm. Cotton.
124
-------
APPENDIX A*
TEST METHODS, NON-LAUNDERING
I. BIODEGRADABILITY
A. Aerobic Biodegradability Tests
1. Affirm that the "active" organic surfactant is degraded aero-
bica*ily under conditions of the Bunch-Chambers test procedure
r
LR- L- Bunch and C. W. Chambers, J. Water Pollution Control
Fed., 39 (2), 181 (1967)].
2. Test whether the proposed builder candidate (if it is organic)
undergoes degradation in this static aerobic procedure.
a. If the builder is not degraded, re-test the organic
active in the presence of builder.
b. If the builder does undergo aerobic biodegradation,
re-determine the extent of degradation in the pre-
sence of the surfactant.
3. Test biodegradability of organic detergent formulation com-
ponents other than the active surfactant and builder.
a. Retest in presence of surfactant and builder to ascer-
tain that there is no interference in degradation of
any component. This is the test of the final formula-
tion.
B. Biostimulation by Biodegradation Products
Test whether algal growth is stimulated (or inhibited) by the degrada-
tion products from A.3.a., above.
C. Toxicity of Biodegradation Products
Test the toxicity of the biodegradation products from full detergent
formulations .(A. 3. a.).
For purposes of record the text of this appendix is reproduced
verbatim from material in the contract proposal and specifica-
tion. The protocols proposed and described herein are the ones
subsequently used in performing the contract.
125
-------
D. Anaerobic Biodegradability Tests
Test the complete detergent formulations as in A.3.a. except under
anaerobic atmosphere in the culture flasks.
In the biodegradability tests, A above, settled sewage (from the
Washington, D.C. area) or other inoculum specified by the Government
will be used to inoculate solutions of test materials in BOD water
containing yeast extract. The basal medium comprising BOD water (pre-
pared according to "Standard Methods for Examination of Water and Waste
Water", 12th ed. Amer. Pub. Health Assoc., New York, 1965) and yeast
extract will be prepared beforehand and sterilized at 121°C for 15 min-
utes in an autoclave. The concentration and yeast will be selected
consistent with the stimulation of microbial growth, but with minimal
oxygen depletion; for most tests, yeast concentrations of 20 mg/1 to
200 mg/1 are satisfactory. The concentration of test material will be
at least 20 mg/1 in screening tests. Our standard for biodegradation
of LAS type active will be dodecene-1 derived LAS and it must show
97.5% degradation (as determined by the methylene blue analytical
method) in order for us to consider the results valid. Surfactants
that are not methylene blue responsive will be analyzed by suitable
chemical procedures when such are available. Measurements of foaming
and/or surface tension will be used as auxiliary indications of sur-
factant content.
It is anticipated that analytical methods in the parts-per-million
and parts-per-billion range will be lacking for some components. In
•k
such cases the primary test for biodegradability will be a standard
BOD test. For this we use the method given in "Standard Methods for
the Examination of Water and Waste Water", American Public Health
Association, Inc. 12th ed. (1965) p. 415ff. This is modified to the
extent that the dissolved oxygen (DO) is measured by the method
126
-------
and kit equipment described in Catalog #10, second revised edition
of Hach Chemical Company, Ames, Iowa, p. 47ff. The BOD value, suitably
corrected, is an index of the biodegradability of the substrate.
II. ALGAL STIMULATION
The basic test for algal stimulation used in this program was the Pro-
visional Algal Assay Procedure ("PAAP test") issued by the Joint Indus-
try-Government Task Force on Eutrophication, February, 1969, and its
subsequently issued revisions. The test was made on four different
organisms. Details are as follows:
A. Organisms Used:
Selenastrum capricornutum (green)
Microcystis aeruginosa (blue green)
Anabaena flos-aquae (blue green)
Navicula seminulum (diatom)
B. Phyaica1 Arrangement s
Temperature - All algal work is carried out in a constant temperature
room maintained at 24°C ± 0.5°C. Ambient temperature is recorded con-
tinuously and 7-day chart records are kept.
Lighting and shaking rates - All cultures are illuminated with cool-
white fluorescent lamps. Light levels are checked weekly with a
Cossen Tri-Lux foot-candle meter. Navicula and Selenastrum are grown
on a laboratory-constructed shaker with a plexiglas platform, with
the lights placed underneath this platform i.e. with "bottom-illumina-
tion" at 200 foot candles. For Microcystis and Anabaena a commercial
(Eberbach Corporation) reciprocal shaker is used with overhead illumi-
nation at 150 foot candles. Both shakers are operated at 100 strokes/
minute with a 2 inch throw.
127
-------
C . Media for Carrying Stock Cultures
Three different stock culture media are used. All media are prepared
with glass-distilled water. Selenastrum capricornutum and Anabaena
f los -aquae are maintained on the medium of the published PAAP procedure,
Microcystis aeruginosa does not grow well in the PAAP medium, and
stock cultures are maintained in a solution described by Hughes, Gor-
ham and Zehnder*. The major nutrients can be prepared as individual
stock solutions, 1000X the final concentrations needed, so that 1.0 ml
of each is used for each liter of medium. The final concentrations of
major nutrients, in grams per liter of medium, are as follows: NaNO_,
0.496; I^HPO,, 0.039; MgS04=7H20, 0.075; CaCl^-Zfiy), 0.036; Na CO.,
0.020; Na SiCy9H20, 0.058; ferric citrate, 0.006; citric acid, 0.006;
EDTA, 0.001. The final medium also contains 0.10 ml/liter of a "micro-
nutrient" solution containing the following salt mixture (in grams/
liter): H3B03, 3.100; MnS04'4H20, 2.230; ZnSO^H^O, 0.287;
Mo7024-4H20, 0.088; CoCNO^-ei^O, 0.146; Na^O^E^O, 0.033; KBr,
0.119; KI, 0.083; Cd^O^^O, 0.154; NiSO^NH^SO^ei^O, 0.198;
VOS04-2H20, 0.020; and Al^SO^^SO^ 241^0, 0.474. Although, in
the original publication, autoclaving of this medium is recommended
it was found that a precipitate is formed when this medium is auto-
claved. The procedure has therefore been changed, and the medium is
filter- sterilized (0.45 micron millipore filter), leaving out the
ferric citrate and the "micronutrients" which are then added to. the
filtered medium. (Iron salts, and other heavy metal salts, tend to
precipitate out on Millipore filters). The final pH of this medium, is
9.5.
*E. 0. Hughes, P. R. Gorham, and A. Zehnder, "Toxicity of a Unialgal
Culture of Microcystis Aeruginosa" Can. J. Microbiol. 4, 225-236
(1958).
128
-------
Navlcula seminulum is maintained in the "soft water" medium described
in ASTM procedure D-2037-64T, "Evaluating Inhibitory Toxicity of In-
dustrial Waste Waters." The final medium contains the following salts
(in grams per liter): Ca(N03)2'4H20, 0.0761; K2HPO,, 0.0080;
0.0400; KC1, 0.0200; Na2Si03'9H20, 0.3540; CaCOg, 0.0100; and
0.0400. It also contains 4 ml/liter of soil extract (prepared by ex-
tracting 35g of "enriched garden soil" (commercial African Violet Soil)
with 350g of boiling water and filtering through ashless filter paper).
It also contains 1.0 ml/liter ferric citrate solution (1.820g ferric
citrate plus 1.30g citric acid per liter); and 1.0 ml/liter of micro-
metabolite solution (this contains the following salts, in mg/liter:
ZnS04, 20; MnS04, 14; AlCl^ei^O, 36; HgBO^ 20; LiCl, 10; and
CoCl2«6H20, 10). The major nutrients are prepared as concentrated
individual stock solutions. The micrometabolite solution is pre-mixed.
The pH of the medium, before sterilization, ranges from 9.8 to 10.5,
and is adjusted to pH 9.5 with HC1. The final solution is sterilized
by autoclaving at 20 psi for 20 minutes.
D. Experimental (Teat) Media
For Anabaena, test media and stock culture media are identical; for
Selenastrum the test media are half the concentration of the stock
media. In each case, after addition of the test material (but before
addition of culture inocula) the pH is readjusted to 7.5 by the addi-
tion of either IN NaOH or IN HC1 (usually, one or two drops per liter
of medium).
The test medium for Micorcystis is also the standard PAAP medium.
However, before use, Microcystis maintained in the "rich" stock
medium is subcultured twice, for 7 days each time, in the PAAF medium.
This is necessary to reduce the effects of nutrient carry-over.
129
-------
The ASTM medium used for Navicula stock cultures was designed for
toxicity testing rather than for evaluating biostimulatory potential
of materials, and is a "rich" medium. Therefore it must be diluted
if the addition of biostimulatory materials is to show any effect.
The test medium used at present contains one-fourth (1/4) the concen-
tration of all constitutents of the stock medium, except for sodium
metasilicate; the silicate concentration is kept at the original level.
The pH of this medium is adjusted to 9.5.
Before inoculation into test media, cells are centrifuged and washed,
essentially as described in the PAAP protocols, except that they are
washed with test medium rather than with distilled water. The volume
of inoculum (except for Anabaena) is adjusted so that, at the start
of the experiment, cell concentrations will be as follows: Selenastrum.
344
1 x 10 /ml; Microcystis, 5 x 10 /ml; and Navicula, 4 x 10 /ml.
Anabaena, a chain forming organism, is not counted. A uniform suspen-
sion is prepared (30 seconds in sterile Waring Blender) and aliquots
are dispensed into test flasks. A larger aliquot is filtered through
a 0.45n millipore filter and dried for determination of biomass.
(When 100 ml of 7-day stock culture are centrifuged, and the pellet
resuspended in 100 ml of medium, 50 ml of suspension yield approxi-
mately 5 mg of dried material.) Generally, 2.0 ml aliquots are used,
_3
leading to a "dry weight" level of 2 x 10 rag/ml.
For any of the organisms the concentration of test material added to
the test medium can vary widely, and the choice of a concentration
level should be guided by the expected action of the test material and
by its expected concentration in the field. It can advantageously
be set between .1 and 10.0 ppm (mg/liter) in most cases.
130
-------
E. Methods for Evaluating Growth
Three different methods for evaluating algal growth are used: (a)
direct cell count, (b) absorbance at 450 and 600 am; and (c) biomass
(dry weight).
The last method, gravimetric determination of dry weight, is used
only with Anabaena. Matched weight, 47 mm 0.45|i Millipore filters
ace used in a "double" assembly; that is, both filters of the matched
pair are placed in the filter holder, and the entire culture filtered.
Each filter is dried under identical conditions and weighed; the dif-
ference in weight between the two filters is taken as the dry weight
of Anabaena in the volume filtered. During this "screening" stage
7-day cultures of Anabaena are harvested and weighed, thus, this is a
single-point estimation of total growth, not an estimation of rate.
Navicula growth also is estimated by total growth during a fixed time
period (10 days or more) rather than by rate. Since Navicula tends
to stick to the walls of the flasks, and to form gelatinous masses,
all flasks are carefully scraped and the contents mixed rapidly in
a Waring Blender (as recommended in the ASTM procedure).
Growth of both Selenastrum and Microcystis is estimated both by total
growth, and by growth rate. Since these algae are unicellular and do
not tend to clump or adhere to vessel walls, small aliquots can be
removed periodically throughout the time of incubation, and increases
in cell numbers can be followed readily. These two organisms are
grown in 300 ml Nephelo flasks (Bellco Glass, Incorporated, Vineland,
New Jersey, Catalog No. 524) so that absorbance of the culture can
be measured with a B&L Spectronic 20 directly in the flask, without
removal of aliquots. For each experiment, 5 control flasks and 5
flasks supplemented with test compound are used.
131
-------
A Coulter Counter, Model Z I, equipped with a Mean Cell Volume/Hema-
a
tocrit attachment is used for cell counts and determination of mean
cell volumes. The same 70^ aperture can be used for each of the or-
ganisms counted. Isoton, a commercially available electrolyte solu-
tion, is used as the diluent.
;III. AQUATIC TOXICITY
Two types of test were used in the program, referred to for brevity
as the acute or screening test and chronic test. The chronic test re-
quiring a minimum of two months for fish and varying times for other
organisms, was ultimately used on only two formulations. The screen-
ing "-test involves a 96 hour exposure, and was used, as its name implies,
to screen out candidate materials that are definitely unsatisfactory
with regard to aquatic toxicity. Three test organisms are used in our
present screening procedure: a fish, a gilled snail, and a diatom.
In the chronic tests it is planned to use the following organisms:
1. Two diatoms (algae)--desirable food species, one typical
of lakes, the other typical of streams.
2. Insects—a genus and, if possible, a species typical of as
many types of streams as possible.
»
3. Two snails—a genus, and, if possible, species typical of
many types of lakes and streams as possible; a pulmonate
and a gill breather.
4. Crustacea—a genus and species typically found in lakes.
5. Fish--catfish or suckers, algae and detritus feeders.
6. Fish--sunfish species found in many types of lakes and
streams.
132
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A. Gene ra1 Acute Test ing Procedures
The following general considerations apply to acute testing procedures:
1. All acute bioassays will be conducted using continuous flow
rather than static techniques. The continuous flow method insures
that waste products of metabolism do not build up in the test container,
decrease the chances of test material adhering to the sides of the
container, allow minimum -nodification of the environment by the test
organism, eliminates the need for any aeration in the test chamber
since aerated dilution water is constantly flowing, and insures ac-
curate monitoring of test concentrations throughout the test period.
All these factors, if not controlled, result in inaccurate and un-
reliable test results.
2. All acute bioassay tests will be conducted over a 96-hour
test period with mortality readings taken every 24 hours. The 96-hour
exposure period is now the accepted acute exposure time by most au-
thorities . Shorter exposure times very often produce a distorted
picture because of possible lag of toxic effect.
3. A minimum of five concentrations plus control will be used
for each test material. The concentrations will be set up in a
logarithmic series as outlined in Standard Methods. This logarithmic
series has proved to be most efficient over the years in determining
critical toxic concentrations. Partial mortality of the test organ-
isms must be obtained at each of two concentrations, three if possible,
for each test period.
4. General observations concerning behavior will be made.
These include increase or lack of movement, erratic movement, loss of
equilibrium (partial or complete), and any uncommon reaction to the
test chemical.
133
-------
5. Simple graphic interpolations of dose effect will be made
in order to derive a 96-hour TLm (medium tolerance limit) and in
addition Lichfield and Wilcoxon's probit analysis method will be
employed to derive the LC, LC_0, and LC and their confidence
limits for each 24-hour test period.
6. All tests will be conducted in one dilution water, a soft
water and at one temperature.
This method gives the ED5Q, slope of the curve and their confi-
dence limits. It uses original data throughout and uses 0 and 100 per-
cent effects. The method recognizes heterogeneity when present and
gives corrected confidence limits in such cases and facilitates the
comparison of two curves for parallelism and computation of relative
potency with its confidence limits. The method is rapid and is used
without logarithms. Logarithmic-probability paper is used to plot
data in original units (i.e., percentages and arithmetic values)
equivalent to the use of logarithms and probits. Nomographs are used
to allow a simple arithmetic solution of a dose effect curve which is
equivalent to the solution by use of logarithms and probits. This
method is recommended by Pesticides Regulation Division Animal Biology
Section U.S.D.A. and we have found it to be very effective.
Specific Bioassay Test Techniques (fish and snail)
1. The fish bioassay experimental technique will consist of a
pump-fed system which meters calculated amounts of test sample and
aerated dilution water separately into a head jar where they are
mechanically mixed by magnetic stirrer. The mixed concentration of
sample in dilution water then flows a a fixed rate into the bottom
of a five-gallon wide mouth glass test container holding ten test
fish. The used mixture of test sample in dilution water overflows
the top of the test jar at the same rate that the new mixture enters
the bottom of the test jar. The rate of flow is one gallon per hour
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which past experience has shown is sufficient to maintain physio-
logical dissolved oxygens and C02 levels. Twenty fish are exposed to
each concentration in the test series, ten for each of two bioassay
test systems, 0.5 to 1.0 grams fish per liter of test water. Test
fish will be obtained from a hatchery, transported to the test site
in water comparable in temperature and quality to that used in the
hatchery and will be acclimated in the laboratory for at least two
weeks at the test temperature before use in the bioassay tests. Test
fish will receive no food for 36 hours prior to a test or during the
test period to mini-size waste production during the exposure period.
3. Snail bioassay experimental techniques will consist of the
same system as outlined above for the fish bioassay except that the
test containers will be 32 ounce glass jars with lids. Used test
water will overflow through a screened hole in the lid so that no
air space exists in the test jar which would allow the test snails
to remove themselves from the test solutions. Test snails will be
obtained from local waters. They will be acclimated in the labora-
tory in the same manner as the test fish.
Specific Bioassav Test Technique (Diatom)
The method used is ASTM D2037-64T "Tentative method of test for evalua-
ting inhibitory toxicity of industrial waste waters". This refers to
diatoms as part of the fish-food chain. Although it somewhat resembles
the FAAF test for biostimulation, both test programs are considered
necessary.
B. Detailed Acute Testing Procedures (account of an actual test)
1. Fish
The Test Organism - The bluegill sunfish, Lepomis macro-
chirus Raf., which has a wide distribution, was used for test purposes.
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The fish used in the tests were between 4 and 6 cin in length
measured from the anterior tip of the head to the end of the caudal
fin, or tail. In no individual test did the length of the largest
specimen exceed the length of the smallest by more than 50 percent.
The fish were acclimated in the laboratory for a period of two weeks
at the test temperature of 18°C. Test organisms received no food for
36 hours before a test or during the test period. Each fish was used
for only one test; only healthy fish were used. Stock cultures which
had more than 5 percent mortality during the period of acclimatiza-
tion were discarded.
Apparatus - The continuous flow experimental technique consisted
of a pump-fed system which metered calculated amounts of sample and
dilution water separately into a head jar where they were mixed.
The mixed concentration of sample in dilution water then flowed at
a fixed rate into the bottom of a 15 gallon glass stainless steel
framed aquarium in which were placed 20 test fish. The used dilution
water overflowed the top of the aquarium at about the same rate that
new dilution water entered the bottom of the aquarium. The rate of
flow was one gallon per hour. This was allowed to proceed for 96 hours
for each experimental concentration.
In all tests constant dilution waters were prepared from distilled
water and A.C.S. grade chemicals. Each chemical was pipetted sepa-
rately from a concentrated (200X) stock solution directly into dis-
tilled water in order to prevent the precipitation of chemicals.
Carbon dioxide was bubbled through the dilution water to get all the
chemicals into solution. The dilution water was then aerated until
the saturation point of oxygen was reached and the CO- brought to
the normal level. Dissolved oxygen was determined by the oxygen
136
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meter before the fish were introduced and every hour for six hours
thereafter. At least Eour D.O. readings were made during each
24-hour test period.
Conditions of the Tests
Constant Temperature:
Dissolved Oxygen:
Dilution Waters:
18°C
5 to 9 ppm
A prepared water similar in
chemical characteristics to a
soft water referred to as modi-
fied CHU 14.
KC1
NaHC03
MgS04 '
CaCO
Ferric nitrate
gms/liter
0.02
0.02
0.04
0.04
0.04
0.01
0.002
0.0018
The dilution water was made u? from distilled water to the quality
indicated above.
Addition of Test Organisms
Twenty fish, 4 to 6 cm long, were added to the mixed solution
after the dissolved oxygen had been raised to the required level.
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Control
A control tank was maintained with each experiment. In each con-
trol tank 100 percent survival was required.
Calculation of the Biologically Safe Concentration
Application factors for calculation of Biologically Safe Concentrations
are presently being discussed and several recommendations for these
factors are available. Perhaps one of the most recent and authorita-
tive recommendations coaies from the Report of the Committe on Water
Quality Criteria, FWPCA, U. S. Department of Interior, 1968. From
the section on "Water Criteria for Fish and Other Aquatic Life" the
proposal Is made that "Concentrations bf materials with non-cumulative
toxic effects should not exceed 1/10 of the 96-hour TLm value at any
time or place. The 24-hour average of the concentration should not
exceed 1/20 of the Tim value."
The above recommendation is probably the most widely accepted applica-
tion factor by state and federal agencies at this time.
2. Snail
The Test Organism - Amnicola limosa (Say.)> a gilled snail,
was chosen for test purposes. The snails used were adults averaging
3 mm in diameter. They were collected from the Brandywine Creek,
East Branch, outside of West Chester, Pennsylvania.
The snails were acclimated in the laboratory for a period
of four weeks to the dilution water. Test organisms received no food
for 36 hours before a test or during a test period. Each snail was
used for only one test and only healthy snails were used for test
purposes.
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Apparatus - Containers for snail tests were 1500 ml jars. Each
jar was fitted with a plastic lid and the lids were perforated to
allow for gas exchange. Calculated amounts of test samples and dilu-
tion water were pumped in two separate streams to a head jar where
they were mixed and the mixture then flowed into the bottom of the
test container at the rate of 100 mis. per hour. The used mixture
overflowed the top of the container at the same rate. The test period
was 96 hours. Dissolved oxygen was determined by the modified Winkler
method before the snails ware introduced. Two D.O. readings were made
during each 24-hour test period.
Conditions of the Tests
Same as Fish Tests.
Addition of Test Organisms
Twenty adult snails were added to this mixed solution as soon as
the dissolved oxygen had been raised to the required level.
Control
Same as with Fish.
Calculation of the Biologically Safe Concentration
Same as with Fish,
3. Diatom
The Test Organism - Navicula seminulup var. hustedii Patr.,
is a moderately sensitive fresh-water diatom common to many undis-
turbed streams.
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The diatoms were cultured for several months prior to the test
period in 500 ml Erlenmeyer flasks, containing soft water nutrient
solutions.
These stock cultures were maintained at 18°C ± 1°C. Light, an
important factor in the growth of diatoms, was provided by two 85 watt
daylight fluorescent lamps located .about six inches below a glass
shelf, furnishing an illumination of approximately 250-350 foot candles.
The cultures were placed on the shelf, and received 16 hours of this
illumination. Cultures were agitated constantly to insure even dis-
tribution of the diatoms throughout the flask.
Apparatus for Tests
The batch tests were conducted in sterile 125 ml Erlenmeyer
flasks. In each of the specific concentrations of sample in dilution
water there was a total of 50 mis of liquid. This provided a relat-
ively large surface-to-volume ratio, and thus allowed full exchange
of gases in the air.
Conditions of Tests
Temperature: 18°C + 1°C.
Light: 250-350 foot candles and as for stock cultures
above.
Dilution water: Same as Fish with the addition of soil extract
and micrometabolic solution.
Agitation
The batch tests were placed on a shaker during the 7-day test
period to insure an even distribution of the diatoms.
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Addition of the Test Organisms
The Inoculum was made uniform with the use of a Waring Blender.
One milliliter of the inoculum is pipetted into each test flask. After
seven days each fiask is scraped clean and the coiitents blended. Then
cell counts are made of diatoms. These counts are compared to the con-
trol to determine the reduction in growth.
Calculation of the Median Tolerance Limit
In calculating the effect of any sample, the concentration which pro-
duced a 50 percent reduction in growth is considered as significant for
diatoms.
In most cases no concentration in these tests produces exactly a 50
percent reduction in growth, and it is usually necessary to determine this
value by graphic interpolation of the test results. The 50 percent reduc-
tion in growth concentration corresponds approximately to the median toler-
ance limit (TLm) for fish.
IV. CHEMICAL, PHYSICAL AND TOXICOLOGICAL PROPERTIES
A. Chemical and Physical Propartleg
Characterization and standardization of detergent ingredients is par-
ticularly important because small differences in purity or composition
often make a big difference in performance. Chemical characteriza-
tion includes assurance and reproducibility of molecular structure,.
stability against hydrolytic or oxidative decomposition or other
types of chemical change under storage or use conditions, and quan-
titative knowledge of minor contaminants that may have a significant
effect on overall behavior. On this basis we propose to check the
various ingredients used in the detergent formulations in the follow-
ing manner. Manufacturers and suppliers' specifications with regard
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to chemical structure will be used except when they are inadequate
(incomplete) or where we have reason to suspect that they are inac-
curate. In such cases, using ASTM methods of test wherever available,
the following characterization tests will be applied: Builders will
be checked for sequestering power by the soap or oxalate titration
methods given for example in Chabarek and Kartell "Organic Sequestering
Agents," or by other appropriate methods. Surfactants will be checked
for active ingredient content and neutral oil (unsulfonated matter)
content. Polymeric materials will be checked by viscosity for average
molecular weight (paying attention to polyelectrolyte effects in the
measurements) and by chemical analysis for degree of substitution
(where indicated). If indicated, gel permeation chromatography will
also be used. All major ingredients will be checked for trace ele-
ments, using atomic absorption spectroscopy and/or emission spectral
analysis. This is considered important because trace elements can
have a significant effect on the biological effects of the product,
particularly the biostimulation. Final formulations will require
checking for stability, since many detergent ingredients tend to
suffer hydrolytic degradation during drying or other stages of pre-
paration. Tests for degree of degradation are routine but they vary
with the type of surfactant or builder involved.
Physical properties of importance include solubility and rate of
solution at various temperatures, bulk density, dustiness, and phy-
sical homogeneity. Physiological effects of the final formulations
are obviously of paramount importance. These include toxicity (by
ingestion as measured by LD-50 values on test aminals) skin irrita-
tion and sensitization and eye irritation. They will be determined
by methods outlined below.
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B. Toxlcological Properties
Background - A toxicity testing program to evaluate the safety of de-
tergents must be designed to include the intended use of the product.
Obviously, testing of a detergent composition intended for general use,
such as laundering and dishwashing, has to be more inclusive than of
one intended just for machine laundering. A general purpose household
detergent product can be evaluated by methods similar to those descri-
bed by Snyder et.al. (1964) and Opdyke et.al. (1964). These include:
acute oral toxicity and emetic dosing to evaluate accidental ingestion
hazards; chronic oral toxicity to evaluate ingestion from residues on
dishes and cooking utensils; subacute percutaneous toxicity to evaluate
continuous exposure to skin from residues on hands and clothing; human
patch test studies to evaluate the irritancy or sensitization poten-
tial of the detergent; opthalmic irritancy in rabbit eyes to determine
the hazard to eyes from accidental exposure; and tumorigenic activity
as measured by repeated topical and subcutaneous applications to mice.
Because we propose only preliminary testing, in preparation of a con-
sumer test, our proposal below is not so all inclusive.
Test Methods - The studies proposed here are sufficient to evaluate,
in a preliminary way, the medical safety of a heavy-duty household de-
tergent composition intended for machine laundering. The animal tests
listed below by themselves are intended to screen the medical suit-
ability of an ingredient for including in household product. The
combination of these animal tests and the human studies described
below are designed to evaluate the detergent to a degree sufficient
for a Consumer Test where human exposure is limited in numbers (say
up to 500 people) and in duration (say up to one month of normal use).
More complete testing would be necessary before the formulation should
be sold to larger numbers of people.
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Acute Oral Toxicity - Healthy, young albino rats ranging in body
weight from 125 to 200 grams will be used as test animals. All
animals will be kept under observation at least seven days prior to
experimental use, during which period they will be checked for gene-
ral physical health and suitability as test animals. The animals will
be housed in stock cages and permitted a standard laboratory rat diet
plus water ad libitum until 16 hours immediately prior to oral in-
tubation.
Initial screening will be conducted in order to determine the general
level of toxicity and then selected dose groups of four rats each
(two male and two female) will be intubated with previously calculated
doses of the test material. All doses will be administered directly
into the stomachs of the rats using a hypodermic syringe equipped with
a ball-pointed intubating needle.
Following oral administration of the test material, the rats will be
housed individually in observation cages (10" x 8" x 8") and observed
for the succeeding 14 days. Initial and final body weights as well
as all mortalities and/or reactions displayed will be recorded.
Arrangements will be made to autopsy any animal which might succomb
during the study as well as all surviving animals at the end of 14 days.
At the end of the observation period, all data will be collected and
arrangements will be made to calculate, if possible, the acute oral
median lethal dose (UDc0) of the test material using the techniques
of Weil (1952), Thompson (1947), and Thompson and Weil (1952).
Acute Dermal Toxicity - Young adult, New Zealand strain albino rab-
bits ranging in body weight from 2.3 to 3.0 kilograms will be em-
ployed as test animals. All rabbits will be kept under observation
in the laboratory for seven days prior to testing during which time
144
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the animals will be examined with respect to their general health
and suitability as test animals. The rabbits will b« housed indivi-
dually in hanging rabbit cages and maintained on a standard laboratory
rabbit ration. Food and water will be permitted ad libitum.
Twenty-four hours prior to the dermal applications, the backs of the
rabbits will be shaved free of hair with electric clippers. The
shaved area on each animal will constitute about ten percent of the
total body surface area. The animals will then be returned to their
cages to await testing on the following day. The 24-hour waiting
period will allow recovery of the stratum corneum from the disturbance
which accompanies the close-clipping procedure and also will permit
healing of any microscopic abrasions possibly produced during the pro-
cess.
/
On the testing day, the rabbits will receive skin applications of
the test material at several selected dose levels. Groups for each
dose level will consist of four rabbits (two male and two female).
After each application, the exposure site will be covered by wrapping
the trunk of the animal with an impervious plastic sheeting which
will be securely taped in place. This plastic wrap will insure in-
timate contact of epidermis and test material. To further prevent
oral ingestion of the test material, each animal will be fitted with
a lightweight flexible plastic collar which will be worn throughout
the observation period.
The test material will remain in contact with the skin for 24 hours.
Any reaction displayed by the animals will be observed and recorded,
during the contact period, after which the plastic sheeting will be
taken off each test rabbit and all residual test material removed.
The exposure sites will be examined for local skin reactions and the
animals returned to their cages. Observations for mortality, local
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skin reactions, and behavioral abnormalities will be continued for a
total of 14 days following the skin applications. Initial and final
body weights will also be recorded. Arrangements will be made to
autopsy any animals which might succumb during the study as well as,
all surviving animals at the end of the observation period.
At the end of the observation period, all data will be collected and
arrangements made to calculate, if possible, the acute dermal median
lethal dose (U5cQ) of the test material using the techniques of Weil
(1952), Thompson (1947), and Thompson and Weil (1952).
Opthalmic Irritation - Five young adult albino rabbits of the New Zeal-
and strain will be used to evaluate the eye irritating properties of
the test material.
The test method employed will be patterned after that of Oraize et al.
(1944). Exactly 0.1 ml or 0.1 g of a test material will be instilled
into the conjunctival sac of the right eye of each test rabbit. The
left eye of each animal will serve as a scoring control.
One, 24, 48, 72, 96 hours, and 7 days following the initial instil-
lations, the cornea, iris, and palpebral conjunctiva will be examined
individually and graded for irritation and injury according to a stan-
dard scoring system. The maximum possible score at any one examination
and scoring period is 110 points which indicates maximal irritation.,
and damage to all three ocular tissues. Zero score indicates no ir-
ritation whatever. The scoring system is presented in the following
Table.
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Eye Irritation Test - Albino Rabbits
Scale of Weighted Scores for Grading the Severity of Ocular Lesions
I. Cornea
A. Opacity - Degree of Density (area which is most dense
*( is taken for reading)
Jf Scattered or diffuse area - details of iris clearly
visible 1
Easily discernible translucent areas, details of
iris slightly obscured 2
Opalescent areas, no details of iris visible, size
of pupil barely discernible 3
Opaque, iris invisible 4
B. Area of Cornea Involved.
One quarter (or less) but not zero 1
Greater than one quarter but less than one-half 2
Greater than one-half but less than three quarters 3
Greater than three quarters, up to whole area 4
Score equals A x B x 5 Total maximum = 80
II. Iris
A. Values
Folds above normal, congestion, swelling, circum-
corneal injection (any or all of these or combina-
tion of any thereof), iris still reacting to light
(sluggish reaction is positive) 1
No reaction to light, hemorrhage, gross destruc-
tion (any or all of these) 2
Score equals A x 5 Total maximum = 10
III. Conjunctiva
A. Redness (refers to palpebral conjunctiva only)
Vessels definitely injected above normal 1
More diffuse, deeper crimson red, individual
vessels not easily discernible 2
Diffuse beefy red 3
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Eye Irritation Test - Albino Rabbits (Continued)
III. Conjunctiva
B. Chemosis
Any swelling above normal (includes nictitating
membrane) 1
Obvious swelling with partial eversion of the lids 2
Swelling with lids about half closed 3
Swelling with lids about half closed to completely
closed 4
C. Discharge
Any amount different from normal (does not include
small amount observed in inner canthus of normal
animals) 1
Discharge with moistening of the lids and hairs
just adjacent to the lids 2
Discharge with moistening of the lids and hairs
and considerable area around the eye 3
Score (A = B = C) x 2 Total maximum = 20
Note: The maximum total score is the sum of all scores obtained for
the cornea, iris and conjunctiva.
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Rabbit Primary Skin Irritation - Four young adult albino rabbits of
the New Zealand strain will be used in the evaluation of primary skin
irritating properties of the test material. The test procedure em-
ployed will be modeled after that of Draize et.al. (1944).
Prior to the application of the test material, the hair will be clip-
ped from the backs and flanks of each rabbit. Two test sites located
at the midline of the back approximately ten centimeters apart will
then be selected. One of the two sites will be abraded by making
four epidermal incisions, two perpendicular to the other two, while
the other skin site will remain intact.
Exactly 0.5 ml or 0.5 g of the test material will be applied to the
prepared exposure sites on each rabbit and immediately occluded with
square gauze patches, two inches on a side. These will be affixed
directly over the skin test sites and secured in place with masking
tape. Following the patch applications, the entire trunk of each
test animal will then be wrapped in an impervious plastic sheeting.
This will help hold the patches in position and retard evaporation
during the 24-hour exposure period.
At the end of 24 hours, the plastic wrappings and patches will be
removed. The intact and abraded skin sites will then be individually
examined and scored separately for both erythema and edema on a
graded scale of 0 to 4. After 72 hours had elapsed, the sites will
be re-examined and rescored.
In evaluating the average irritation present, the mean scores for
erythema and edema of the intact skin sites at the 24- and 72-hour
reading intervals will be added. Similarly the mean scores for
erythema and edema of the abraded skin sites at the 24- and 72-hour
reading intervals will be added. These two values will then be
totaled and divided by four to obtain the mean primary irritation
149
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score. The scoring criteria for erythema and edema are shown in
the following Table.
Reaction
Erythema
Edema
Table
SCORING CRITERIA FOR SKIN REACTIONS
Description Score
Barely perceptible
(Edges of area not defined) 1
Pale red in color and area definable 2
Definite red in color and area well
defined 3
Beet or crimson red in color and/or 4
injury in depth (necrosis, escharosis)
Barely perceptible
(Edges of area not defined) 1
Area definable but not raised more 2
than 1 mm
Area well defined and raised 3
approximately 1 mm
Area raised more than 1 mm 4
Maximum Primary Irritation Score = 8
Human Primary Irritation and Sensitization - Semi-occlusive Patch Test
Procedure, 9-Day - 24 hours. (Eight repeated insults plus one chal-
lenge patch.)
This is a combined over-night primary irritancy and/or sensitization
test. Patches are applied Monday, Tuesday, Wednesday, and Thursday
to the same skin sites and allowed to remain on for 24 hours.
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Readings are made shortly after the patches are removed on Tuesday,
Wednesday, Thursday and Friday. Following two weeks of patching
and two rest weeks, a challenge patch is applied and readings taken
at 24, 48 and if necessary at 72 hours.
A panel of 50 subjects are employed on this test. Four materials
including controls can be run on this test. Two types of patches
are used on this test: 1) Closed elastopatch (Duke) 1-1/2" x 2"
with 3/4" x 1" special pad and 2) Semi-open elastoplast (Duke) pro-
tective covering for patch test 1" x 2" with 1" x 1" Webril (R) pad.
The material is applied to the patch which is then placed on the sur-
face of the upper arm. A marker (Gentian Violet) is used to indicate
the patch position on the arm. Readings are taken approximately 24
hours after each patch application. Following each reading, a new
patch is applied to the same unless the severity of the reaction pro-
hibits repatching. For the challenge application, patches are ap-
plied to adjacent sites on the arm. A second challenge is made if
there is a reaction to the first.
In most, if not all instances, the test product will be a solid mate-
rial. For the tests described above, it will be applied to the ani-
mal as a dilute, aqueous solution, approximately 5 percent wt/vol.
For human testing, the products will be tested as 1 percent wt/vol.
aqueous solution.
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References - Preliminary Mammalian Toxicity Testing
Draize, John H. , Woodard, Geoffrey, and Calvery, Herbert 0. (1944).
Methods for the study of irritation and toxicity of substances ap-
plied topically to the skin and raucous membranes. J. Pharm. and
Exp. Ther., 82, 377.
Opdyke, D. L. , Snyder, F. H. , and Ruberkoenig, H. L. (1964). Toxi-
cologic studies on household synthetic detergents. II. Effects on
the skin and eyes. Toxicol. Appl. Pharmacol., £, 141-146.
Snyder, F. H. , Opdyke, D. L. , Griffth, J. F., Ruberkoenig, H. L. ,
Tusing, T. W. , and Paynter, 0. E. (1964). Toxicologic studies on
household synthetic detergents. I. Systemic effects. Toxicol.
Appl. Pharmacol. j>, 133-140.
Thompson, W. R. (1947) . Use of moving averages and interpolation to
estimate median-effective dose. Bait. Rev. 11, 115-145.
Thompson, W. R. and Weil, C. S. (1952). On the construction of tables
for moving average interpolation. Biometrics, JJ, 51-54.
Weil, C. S. (1952). Tables for convenient calculations of median-
effective dose (H>rO
metrics, £, 249-263.
effective dose (H>rO or E1)c0) aiu* *-nstruct*-ons *-n their use. Bio-
152
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Provisional Test For Screening Potentially Corrosive Products
Method
Four healthy, adult, albino rabbits of either sex (weight range
2-3 kg.) will be used to test each material. The animals will be
fasted for 48 hours prior to testing with water available ad libitum.
'2
Each animal will be anesthetized with sodium pentobarbital, and the
oral cavity will be examined with the aid of a binocular loupe (mag-
nification 2-3X) and examining lamp. After recovery from anesthesia,
the animals will be placed in a restrainer, and the mouth forced open
with a plastic bit containing a 1/2" to 3/4" hole in the center. The
tongue will be drawn forward through the hole with a pair of long
forceps. A curved spatula or syringe will be used to administer the
dose (300-500 mg. of dry material, or 1 ml. of liquid) on the posterior
aspect of the tongue. The tongue will be released immediately allow-
ing the animal to complete the swallowing reflex. The animal will be
returned to its' cage with access to water, but no food. At 24 hours,
two of the test group will be sacrificed by overdose of anesthetic
(pentobarbital IV). The surviving animals will be given food, and
sacrificed at 96 hours. The tongue, adjacent pharyngeal structure,
esophagus., and stomach will be removed, examined grossly, and photo-
graphed (color). After thorough evaluation, these tissues will be
preserved in neutral buffered formalin for subsequent microscopic
evaluation as necessary.
Evaluation for corrosivity will be based on visible effects on
the oral cavity, pharyngeal structure, esophagus, and stomach. Each
test material will be arbitrarily classified as follows:
1. This is not an official test procedure.
2. If the animal's mouth can be examined easily without any discom-
for or anesthetic, the problems of anesthesia can be eliminated,
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a. Negative - No visible irritation or injury when examined at
24 or 96 hours. Histopathology may not be necessary as de-
termined by gross examination.
b. Irritant - Patchy areas of beefy redness with or without
edema present at 24 hours, but not at 96 hours. Histological
examination of tissue from the animals sacrificed at 96 hours
should be normal in appearance.
c. Corrosive - Necrotic lesions (i.e., esophageal perforation,
stricture, etc.) apparent at 24 or 96 hours will be con-
firmed by microscopic examination.
Since the test is primarily concerned with corrosive action, it
will be considered positive if any of the test animals at 24 or 96 hours
show signs of necrotic lesions in the mouth, pharynx, esophagus, or
stomach. The extent of injury will be confirmed by histological ex-
amination. Microscopic examination of tissue sections will not be
performed in the absence of visible irritation. Close-up photographs
will be considered as sufficient documentation. When gross lesions
are present or for borderline cases, histopatholgy will be performed
in addition to photographs. Color photography will be utilized as
often as warranted to provide a vivid documentation of gross effects.
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APPENDIX B
IAUNDERING TEST METHODS DEVELOPMENT
Detergent technologists and scientists have never been able to agree
upon any single simple laboratory test for measuring the soil removing
power (laundering effectiveness or washing power) of a detergent.
The basic experiment is simple and straightforward in concept. A
set of fabric swatches is soiled in some controlled manner to a uni-
form degree of dirtiness. Some of the swatches are then washed in
detergent A and others in detergent B, keeping the detergent concen-
trations, temperatures, and other parameters of detergency constant.
The washed swatches are then measured optically to determine which have
lost more soil. Disagreement arises over details of the test, es-
pecially over the type of soil that is used and the method by which it
is applied to the swatches. Each of the important laboratories of the
detergent industry has its own screening protocols and its own pro-
cedures for obtaining detergency data that they consider accurate
(i.e. representative of results that will be obtained in actual home
laundry practice). The details of these methods are not publicly
divulged. The one method for evaluating washing power that is agreed
upon is an actual miniature field trial under household conditions,
known as the bundle test. This test has been reasonably well stan-
dardized, at least in general format, and is described as ASTM Stan-
dard D2$60-71T. The bundle test, however, is far too lengthy and cum-
bersome to be used as a test method in research. It was therefore
necessary to adopt (or develop if necessary) a set of screening pro-
cedures that would at least be respected by all major segments of
the industry even though it might not coincide with their own favo-
rites. Throughout the program, therefore, special attention was paid
155
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to refinement and variation of the test methods even though this re-
quired a significant amount of laboratory work. The lengthier and
more extensive testing programs were reserved for the more promising
candidate detergents, but modifications of the simpler tests were
adopted as soon as they were proved to be valid and useful. The various
procedures, their modifications, and the experimental work connected
with their interpretation and validation are as follows:
A. The primary screening test for laundering effectiveness used in
this program was a soil accumulation test, following the general model
given in articles by Schwartz and Berch, Soap and Chemical Special-
ties, 39, 78, (May, 1963); Spangler, Cross and Schaafsma, J. Am. Oil
Chemists Soc. 42, 723 (1965); and Schwartz and Rader, J. Am. Oil
Chemists Soc. 42, 800 (1965). In this type of test one or more un-
known detergents are compared against a standard detergent under
identical conditions of soiling and washing. To illustrate the pro-
cedure for one unknown detergent: two identical sets of clean test
swatches are soiled simultaneously in a single large pool of soil.
The sets are then separated and washed separately, one set in the
standard detergent "S" and the other in the unknown detergent "X".
After washing and drying they are resoiled and again separated and
washed, each set going to its own detergent. After several cycles of
soiling and washing the sets are again measured for reflectance. Even
when two detergents are very close in cleaning power a significant dif-
ference in the set averages can usually be found after about 5 cycles.
Included with each set are some swatches that go through the washing
and drying steps but not through the soiling step. These swatches
accumulate soil by redeposition from the wash bath, and the decrease
in their reflectance is a measure of the antiredeposition effect of
the detergent. A wide variety of soils can be used, but some type of
"natural" soil is generally preferred.
156
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The Tergotometer was used as the washing device, run at either 100 or
125 cycles/minute. Three types of white fabric were used in the early
stages of the program: a permanent press 65 polyester-35 cotton blend;
a bleached but unfinished cotton print cloth; and an unfinished 100%
polyester. The three types of fabric were all washed simultaneously
in one bath, the load consisting of 3 soiled swatches and 2 redeposi-
tion swatches of each fabric, a total of 15 swatches in each one liter
bath. The swatches measured about 4.5 x 6 inches and averaged about
2 grams each in weight.
Both the water hardness and the temperature can be varied as desired,
but must be controlled and specified in the report. Our primary test
was made with 200 ppm water (4:1 Ca to Mg ratio) at 120 °F. The washing
time was 10 minutes. To ensure that the detergent was performing at
full effectiveness, i.e., that we were in the plateau region of the
soil removal v. concentration curve, the formulations were used at
0.3% concentration.
/
Two types of soil were used: a "dry" soil and an "oily" soil, both of
which were based on the dirt swept from rugs by vacuum cleaning. The
dirt was procured in large lots (20-50 pounds or more) from a commer-
cial rug cleaning establishment. It was processed by slurrying in
tap water and then filtering through cheesecloth and muslin to remove
lint and large particles. Quantity of water was adjusted so that the
final filtered slurry contained about 2% solids. The soil was also
checked to ensure that no soluble staining materials were present.
Batches of soil containing staining materials were rejected. The
2% solids slurry thus prepared constituted the "dry" soiling bath.
A small amount of preservative was added. The "oily" soil was pre-
pared by adding sufficient artificial sebum, (prepared according to
Spangler, Cross and Schaafsma, loc. cit.) to provide a sebum-to-so lid
157
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soil ratio of about 2 to 1. The water content was adjusted so that
the final slurry contained about 1.5% sebum-plus solid soil.
As standard detergents in these tests we used Formulation #124, fur-
nished by the American Association of Textile Chemists and Colorists.
This material is described as follows:
Standard AATCC Detergent
Lot 1-1 & Lot 2-1
Nominal Composition
Linear alkylate sulfonate - sodium salt (LAS)
Alcohol ethoxylate
Soap - high molecular weight
Sodium Tripolyphosphate
Sodium silicate (Si02/Na20 = 2.0)
Sodium sulfate
CMC
Moisture & Miscellaneous
100.00
In Standard Detergent with optical brightener (Lot 1-1 only) the mis-
cellaneous includes approximately .25% of a mixed brightener system
including balanced proportions of bis [triazinyl] stilbenedisulfonate,
and triazolystilbenesulfonate with a potential specialty brightener.
In the earlier phases of the program Lot 1-1 was used, and is refer-
red to in the text simply as AATCC or AATCC #124 detergent. At a
later stage Lot 2-1 was used. This is referred to as AATCCWOB.
Lot 1-1, which contains brightener, was the only standard reference
detergent available at the start of the program, and it was con-
sidered desirable to use in addition a reference detergent without
brightener. A supply of such a detergent was obtained from The Asso-
ciation of Home Appliance Manufacturers. This is referred to as the
158
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'a
fo
AHAM detergent, and has the following composition:
Tallow Soap 2%
Dodecylbenzene Sodium Sulfonate 14%
Nonionic Fluronic Type 2%
Sodium Tripolyphosphate 50%
Trisodium Silicate (2:1) 6%
NaCMC 0.5%
Sodium Sulfate 17%
Water 8.3%
Miscellaneous 0.2%
B. The above procedure, using "dry" and "oily" (or "sebum") vacuum
cleaner soil, was modified during the course of the program in two
respects, both of which simplified the testing and neither of which
changed the results to any significant extent. The first modification
consisted in using only three wash-soil cycles instead of four. At
the soil concentrations used it was found that three cycles were suf-
ficient. The second modification was a change in the method of pre-
paring oily soil swatches. Instead of combining the aqueous sebum
emulsion with the suspension of solid vacuum cleaner particulates and
soiling in a single step, a two step process was adopted. In this
process the first step was to prepare dry soiled swatches in the usual
manner. These were then wet to saturation with a perchloroethylene
solution of the artificial sebum ingredients, and were then air
dried. This process afforded much*better control and produced more
uniform and reproducible swatches than the one step procedure.
C. A third wash testing procedure adopted and used during the course
of the program was essentially that described by Spangler, Cross and
Schaafsma (J. Am. Oil Chemist's Soc., 42, 723 (1965). This is a
159
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multicycle soil-accumulation test of the same type as the tests de-
scribed in section A above. The soiling mixture is an aqueous emul-
sion containing the artificial sebum ingredients and particulate
solids obtained from air conditioner filters. To prepare the solids
portion of this mixture used air conditioner filters were washed with
isopropanol. This solvent stripped the filter fibers clean very rapid-
ly and easily. The washings were filtered on a Buchner funnel, and
the recovered solids were dried and ground. They were a very dark
gray in color, very finely divided (requiring little or no sieving
to remove lumps) and easily dispersed in the artificial sebum emul-
sion. This soil is referred to in the body of this report as
"Spangler soil" and was always used in the three cycle soil accumula-
tion procedure.
D. Primary screening test of washing power are usually made, as
outlined above, at a single detergent concentration. For a more
thorough evaluation it is necessary to measure the washing power at
a series of concentrations. This can be done using a multicycle test
procedure, as were some of the washing power evaluations in this pro-
gram, but it is inordinately time consuming. Single cycle tests are
usually considered adequate for detergency v. concentration studies.
Soil cloth suitable for single cycle testing can be purchased commer-
cially. In our experience, however, few if any of the man-made fiber
soil cloths or the permanent press finished soil cloths are suffic-
iently realistic or reliable. One commercial cotton soil cloth,
"Empa" from Test fabrics, Inc., New York, was used in some of the deter-
gency v. concentration studies. For most studies of this type on
cotton, and for all such studies on other fabrics, we prepared our
own soil cloth as follows:
160
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The soiling mixture was similar to the Spangler soil except that
the air conditioner dirt vas replaced by a mixture of particulates
consisting of 86% kaolin (Bandy Black #1 clay), 8% carbon (Germantown
Lampblack), 4% Mapico black iron oxide and 2% Mapico yellow iron oxide.
The aqueous soil suspension was applied by padding. By setting the
pad rolls at a pressure (about 50 psi) such that the wet pick-up was
about 100%, and by running the fabric through the pad forward and
reverse twice, large single pieces of fabric were soiled uniformly
and reproducibly. These could be cut into test-size swatches which
matched one another so closely in reflectance that they did not have
to be sorted nor read individually before use. This is referred to as
"Colgate soil.11
•
E. The instrument used for measuring reflectance was a Gardner XL-10
Color Difference Meter. The filters are such that it can read green
(G) amber (A) blue (B) and blue free of u.v. (Bx). The three readings
made routinely were G, A and Bx. The G reading by itself is generally
considered a good basis for comparing the appearance of cleanness
presented by a fabric swatch, and the delta G values were used for
comparisons in most of the earlier work. From the three primary re-
flectance readings, however, two additional reflectance parameters
can be calculated: "whiteness" (W) = 4Bx - 3G; and "yellowness"
= A-Bx • This was done routinely in the computer program. It was
G
found after bundle testing had been started, and visual judgments
were being compared with instrumental readings, that the W value was
usually a better index than the G value of the visual ratings. The
W value was therefore adopted as the main basis for comparison. The
Y value was important in cases where either the detergent or the fabric
finish changed the tint of the test swatches. Such cases are noted
in the text. Table headings in all cases indicate which reflectance
parameter is being considered.
161
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F. Bundle tests were made on seven formulations, the general pro-
cedure of ASTM, D2960-71T being followed in all cases. Rockville,
Maryland, tap water, averaging 110 ppm, was used. In the first three
tests the detergent formulation was used at 0.2% concentration and
instrumental readings were made only on pillowslips. The formula-
tions were as follows: (1) #64-1, also identified as "D", based on
citrate builder and ether carboxylate 60-486 surfactant. (2) #64-2,
also identified as "M", based on citrate builder and sulfozwitterionic
surfactant 54-431. (3) Composition B-S based on SHIM builder and
alpha olefin sulfonate surfactant 22-155. Two subsequent runs iden-
tified as 242 and 242a were made at 0.15% concentration, with pillow-
slips read instrument ally. At this low concentration even the con-
trol detergent AATCCWOB did not get the laundry satisfactorily clean.
The last three tests identified as 269, 270 and 271, were therefore
made at 0.3% concentration. In these latter tests all laundered
items were read instrument ally. The instrumental readings checked
the panel judgments without exception.
G. An essential part of the methods development program was to com-
pare the three multicycle and two single cycle wash tests outlined
above with one another and with the bundle test. This task was
carried out, and was written up and presented in the form of a paper
at the CID's International Congress on Surface Activity, Zurich,
September 1972. Title and authors are: "Soil Accumulation versus
Bundle Testing of Detergency," H. Alter, A. Eleanor Davis and
A. M. Schwartz. It is scheduled for publication in the Congress
Proceedings. The following is an abridgement of the paper.
EXPERIMENTAL
Five test procedures were used. Procedure #1 was single cycle
using Empa cotton. Procedure #2 was single cycle using Colgate soil.
162
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Procedure #3 was multicycle Spangler soil. Procedure #4 was multi-
cycle "dry" vacuum cleaner soil, and procedure #5 was multicycle
"sebum" vacuum cleaner soil, as described above. All except pro-
cedure #1 were carried out on both cotton and durapress (DP) 50 cotton:
50 polyester fabric. The prepared swatches were read on the re-
flectometer before and after washing. Alcohol extractable material
was determined on washed swatches and on representative swatches be-
fore washing.
The Tergotometer load consisted of 10 swatches, 6 soiled and
4 unsoiled (redeposition) swatches. In all but procedure 1 the load
was split evenly between cotton and durapress swatches. The volume
of detergent solution was 700 ml, and the pH of the detergent solu-
tion was checked before and after washing. Agitator speed was
125 cycles/min. Wash temperature was 120°F and wash time 10 minutes.
The swatches were given two one minute rinses at 105°F. After rinsing
the swatches were squeezed out, spread flat on cheesecloth and oven
dried at 120°F for 15-20 minutes.
Reflectance was measured at 4 areas (2 front and 2 back) on each
swatch. The swatches were layered and folded for measurement to pro-
vide 5 thicknesses of backing for soiled swatches and 3 thicknesses
for redeposition swatches. Readings were made with green, amber and
blue X filters. The data were automatically punched into computer
tape for processing.
Alcohol extractable matter was measured in the standard manner
via Soxhlet extraction with ethanol.
Three detergents were used in the bundle tests. The primary
standard-of-comparison detergent was the high phosphate formulation
furnished as a reference by the Association of Home Appliance Manu-
facturers (Identified as AHAM detergent). This material contained
163
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no fluorescent whitening agent. The other two detergents were ex-
perimental nonphosphate materials. Both contained 20 percent high
ratio silicate and 30 percent citrate as the builder. "Detergent D"
contained 20 percent fatty alkyl ether carboxylate as the surfactant.
"Detergent M" contained 20 percent of sulfo-zwitterionic surfactant.
Both detergents contained 1 percent sodium carboxymethylcellulose,
29 percent sodium sulfate, and no fluorescent whitening agent.
The above three detergents were also used in the Tergotometer
tests, together with another high phosphate type furnished by the
American Association of Textile Chemists and Colorists identified as
AATCC #124 and herein abbreviated "AATCC". Detergent AATCC contained
brightener (fluorescent whitening agent) and was therefore not used
in the bundle tests where the ratings are subjective. It was used in
all the other tests where the ratings were instrumental, and the ef-
fect of brightener could be eliminated by using the green and/or Bx
filter in the reflectometer.
The bundle tests were run at 0.2 percent detergent concentration
in tap water (approx. 110 ppm hardness) at 50°C. In all other re-
spects the conditions of ASTM D 2960-71T were followed. The Tergo-
tometer tests were run at 0.1 percent, 0.2 percent and 0.3 percent
concentration; in 200 ppm hard water (4 Ca to 1 Mg) as well as in
tap water. All tests were run at the same temperature, time of wash
cycle, and agitator speed.
RESULTS AND DISCUSSION
Bundle Tests
The bundle tests (0.2 percent concentration in tap water) were
carried out to six cycles. The panel rated detergent D substantially
equal to AHAM on both cotton and durapress items. It rated detergent
164
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M clearly inferior to AHAM on both fabrics. Analysis of the data for
detergent D with regard to fabric type showed that the panel chose
AHAM somewhat more frequently than D on cotton items, and vice versa
on durapress items.
Instrumental readings were made on pillowcases of both fabrics.
The data, as shown in Table BG1, supports the subjective evaluations.
D and AHAM are essentially equal in yellowness on both fabrics and
in whiteness on durapress. D is very slightly inferior to AHAM in
whiteness on cotton. M is significantly inferior to AHAM in white-
ness on both fabrics and slightly inferior in yellowness on cotton.
There are many ways in which the reflectance data might be com-
bined to give a single number purporting to correlate with the panel's
subjective rating. No such combination, however, would be entirely
free of arbitrary factors. It appears that graying was considerably
more important than yellowing in this bundle test, but is entirely
possible that with strongly yellow soils the yellowness rating would
become more important and could dominate in correlating with the
panel judgment.
It is noteworthy that the bundle test gives no indication of
the amount of invisible soil, solid or oily, remaining in the fabrics
after washing. The Tergotometer tests as performed in this study
provide a direct measure of oily soil removal, via alcohol extrac-
tion. No measurement was made of residual invisible, alcohol-insol-
uble soil.
Tergotometer Tests Relatable to Bundle Tests
Tests using procedures 1 and 2 were carried out on cotton and on
durapress at 0.2% concentration in tap water using the same three de-
tergents used in the bundle test. The results of these tests are
165
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therefore most directly comparable with the bundle test results.
Procedures 3, 4, and 5 were carried out on both fabrics with the same
three detergents at 0.3% concentration in tap water, and are there-
fore comparable except for the difference in concentration. This
difference can be considered minor since in tap water the detergency
plateau of these detergents appears to be reached at a concentration
less than 0.2%. Tergotometer tests at other concentrations and water
hardnesses can be related only indirectly to the bundle tests.
Table B62 presents the data for detergent D on cotton at 0.2%
in tap water obtained by procedures 1 and 2. Columns 2, 3, and 4
show the delta 6, delta whiteness and delta yellowness values (in
reflectance units) relative to AHAM detergent. These values are com-
puted as reflectance of AHAM washed sample minus reflectance of deter-
gent D washed sample. Thus, a positive value means that AHAM was
brighter, and a negative value that D was brighter. It is evident
that the differences in yellowness are negligible and that the dif-
ferences in delta 6 and delta whiteness parallel each other reason-
ably well. In view of the low yellowness values, ratings can safely
be based on the whiteness ratings. On this basis procedure 1 rates
AHAM best, followed in order by AATCC, M and D. The first three de-
tergents are quite close to one another and D would be considered
slightly but significantly poorer than AATCC or AHAM.
Columns 5 and 6 of Table B62 give the actual percentage of al-
cohol extractable material in the D washed swatches before the first
machine washing and after the last washing. Column 7 shows the com-
parison between AHAM washed samples and D washed samples. The num-
ber in column 7 is obtained by subtracting the column 6 value for
D from the Column 6 value for AHAM (not shown in the Table), i.e.
Column 7 = Column 6 AHAM - Column 6 D
166
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Thus, a negative value in column 7 indicates that the oily soil con-
tent of D washed material was higher than that of AHAM washed mate-
rial, i.e. AHAM was the more effective in removing oily soil. The
oily soil is a relatively low 1.19%, and none of the detergents was
outstandingly effective in removing it. Although the data indicate
AATCC most effective, followed in order by AHAM, D and M, the dif-
ferences are small.
Procedure 2 rates the detergents with regard to whiteness in the
order M best, D, AATCC and AHAM tied for poorest. With regard to
oily soil removal there is substantially no difference between any of
the four detergents. It is noteworthy that in procedure 2 the un-
washed swatches have a relatively high content of alcohol extract-
ables, a goodly portion of which remains after washing. Table B62A
gives the reflectance comparison of the redeposition swatches. It
is evident that the differences are small as compared with the dif-
ferences in reflectance of the soiled swatches.
Tables B63 and B63A give the numerical reflectance data for pro-
cedure 2 on durapress fabric. The differences are of the same order
as those obtained on cotton. Tables BG4 and BG4A give the data for
procedures 3, 4 and 5 on cotton at .3% in tap water; Tables B65 and
B65A give similar data on durapress fabric.
A comparison of bundle test results with results of testing by
the five different washing procedures leads to the following conclu-
sions: 1. The whiteness reading, rather than the yellowness or in-
dividual filtered readings, is the most realistic single basis for
relating to subjective judgment of appearance. 2. Soiled swatches
are better than redeposition swatches as a basis for Judgment. 3. Dif-
ferences in whiteness values less than about 1.5 are not significant
and do not correspond to a difference discernable by the panel judges.
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This finding is supported by our previous experience. 4. With re-
gard to alcohol extract able material, we have no basis* for setting
any numerical limit of significance on the delta values. We can rank
the detergents as to their effect in removing oily soil, but whether
or not these rankings have practical meaning is still an unanswered
question.
Table BG6 shows the ranking of the various detergents on the
basis of whiteness. The vertical bracket lines indicate a numerical
difference between the bracketed items of less than 1.5 whiteness
units. It is evident that procedures 1 and 2 are not sufficiently
discriminating; although both procedures, when they do discriminate,
do put AHAM ahead of M and D. In the one test where M and D are
significantly different however (procedure 2, 0.3%, DP) they rank in
opposite order to the bundle test. Procedures 4 and 5 definitely
favor the non-phosphate detergents over the phosphate, a result op-
posite to that of the bundle test. Procedure 3 appears to match the
bundle test results more closely than any of the other procedures.
This may indicate that the air conditioner soil of procedure 3 is a
better simulant than procedure 4-5 vacuum cleaner soil, at least for
the soil in these particular bundle tests.
Tergotometer Test not Directly Related to Bundle Tests
Table BG8 comparing procedures 3, 4 and 5 in hard water at 0.3%
detergent concentration, also indicates procedure 3 to be a better
match than 4 or 5 for these bundle tests, although the conditions are
not comparable. Table B68 indicates that results in hard water tend
to be much the same as in softer water, at least within the tested
range. This is borne out by Table B69 which shows the comparison of
detergents M and D at increasing concentrations in hard water. The
M and D ratings here can be compared with those of Table BG6.
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Since a single cycle procedure is less arduous than a multi-
cycle, and therefore would be desirable, an extended study of pro-
cedures 1 and 2 was made, with results shown in Table BG7. It is evi-
dent that procedure 1 is quite consistent, and sensitive neither to
concentration nor water hardness. In rating M above D, however, it
does not match the bundle test. This is probably due to the fact that
the carbon black soil of procedure 1 is not a good simulant for the
visible soil in the laundry bundles. Procedure 2 appears to be quite
sensitive to both concentration and water hardness. Procedures 1 and
4 use low-oil soils, and procedures 2, 3 and 5 use high-oil soils.
Tables BG2-BG5, together with extensive data on these systems not
herein presented, indicate that an unsatisfactory amount of oil re-
mains in the washed swatches when the high-oil soils are used, re-
gardless of what detergent is used. Furthermore, the presence of ex-
cessive oil in the soil does not appear to contribute to consistency
of results ( as regards variations in hardness and concentration) nor
to realism in matching the bundle test.
Redeposition data were obtained for all the tests tabulated. They
generally bear out the data of Tables BG2A-BG5A, indicating that a
high carboxymethylcellylose content improves the redeposition on cotton,
and that redeposition is a much less sensitive index of performance
than soil removal.
i
Conclusions
None of the procedures and soil mixtures used in this study has
fully simulated the bundle test, although procedure 3 using air con-
ditioner dirt as the colored soil ingredient is a reasonably good
simulant. There is an indication that a single cycle procedure could
be satisfactory if the right solid colored soil component were used.
169
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Neither carbon black nor the mixture of procedure 2 is completely
satisfactory. It is probable that a more detailed knowledge of the
colored solid components of the "natural" soil would be useful in
this regard. Of the two solid soils used in the multi-cycle procedures
air conditioner dirt appears to be a more realistic simulant than
vacuum cleaner dirt. This may, however, be true only for the type
of soil accumulated in these particular bundle tests. The ratio of
oily soil to solid soil in the mixture appears to be a factor of
relatively minor importance, as evidenced by the similarity of the
effects of procedures 4 and 5. A large proportion of the oily portion
of a high-oil soil remains in the fabric, even after most of the colored
soil components have been washed out. The excess oil may have an ad-
verse influence on the consistency of the test, particularly on its
sensitivity to variations in hardness and concentration, as evidenced
in Table BG7. Detergent concentration and water hardness have less
effect on detergent ranking than might be expected. The overlaps and
crossovers in ranking are not unexpected in the single cycle tests.
In the multi-cycle tests they indicate that more cycles are needed,
even after significant differences among the detergents begin to appear.
Since the bundle test is multi-cycle it is logical to expect
that a multi-cycle test would be the best simulant. The data support
this view, and in the present state of the testing art multi-cycle tests
appear more reliable than single-cycle. The most important factor
in simulation appears to be the colored components of the 'solids in
the soiling mixture. These should ideally be identical in chemical
composition and in particle size range to the colored components of
the natural soil deposited on laundry. There have been many excel-
lent studies on soil composition, but few reports we are aware of
on the nature of the soil that causes gradual graying of laundry on
repeated usage-washing cycles. More work in this field would ob-
viously be a valuable contribution. In the meanwhile the air
170
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conditioner soil of procedure 3 (rating AHAM over D and M) and the
vacuum cleaner soil of procedure 4 (rating D over M) appear to offer
the closest and most consistent simulation of £he bundle test.
H. One of the important questions in modern practical detergency is
the effect of permanent press treatment on the washability of cotton
and polyester fabrics, and on blends of these two fibers. Since
this laboratory is equipped to apply permanent press finishes under
controlled conditions, a study could be and was undertaken to de-
termine this effect. Five fabrics were used in the study: an un-
finished cotton (Testfabrics #400 M print cloth); an unfinished Dacron
batiste (Testfabrics #707); these same two fabrics with a permanent
press finish applied as described below, and purchased 50:50 cotton-
polyester Cannon sheets permanent press finish (the same "blend fabric"
used in most of the presently reported studies. The finish applied to
the cotton and Dacron was as follows:
Permafresh 114B 6% ow fabric
Velvamine 732 .33% ow fabric
Catalyst KR 25% ow resin
Triton X-100 2% ow bath
Water to 100%
This mixture was applied by padding to 70% wet pick up. The fabric
was dried at 150°F 5 to 10 minutes; pressed at 320°F, and cured at
340°F for 5 minutes. It is noteworthy that this treatment contains no
soil-release agent.
The soiling and laundering pf these fabrics was carried out by both
the Spangler multi-cycle and the Colgate single cycle procedures. The
detergent in all cases was AATCCWOB and the water was 200 ppm hardness,
4 Ca:lMg. In the Spangler tests the detergent concentration was 0.3%.
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The Colgate tests, as always, were run as detergency v. concentra-
tion series.
The results of the Spangler tests are shown in Figure 37-39.
The difference between the green reflectance values and the white-
ness indicates that the permanent press treatment tends to alter the
hue of the fabric slightly. This alteration is noticeable to the eye
on Dacron but not on cotton. The slope of the curves in Figures 38
and 39 indicate that the treatment makes the fabric less prone to
soil accumulation. The commercial blend fabric (Figure 39) loses
whiteness more rapidly than any of the other four fabrics.
The results of the Colgate tests are diagrammed in Figures 40-45.
They show the soil pick up during swatch preparation as well as the
washing behavior. The permanent press finish obviously makes cotton
much more prone to pick up soil than it is in the unfinished state.
It also raises the minimum effective concentration (MEG) of the de-
tergent, i.e. the concentration necessary to reach the detergency
plateau. Treatment has relatively little effect on the soil pick
up of the Dacron, but it does make the Dacron more difficult to
clean. The blend fabric (Figures 44 and 45) behaves as expected
like a mixture of treated Dacron and treated cotton. The fact that
the absolute reflectance level of the blend fabric is higher than that
of the laboratory treated fabrics is ascribed to a different finishing
treatment. It is probable that a soil release ingredient was in-
cluded in the treating formula used on the commercial fabric.
It is generally believed among textile chemists that the per-
manent press finish has little effect on the polyester component of
a blend fabric because the aminoplast prepolymer does not penetrate
to the fiber interior. The present study indicates that sufficient
final polymer remains adherent to the polyester's surface to change
its soiling and washing characteristics very markedly. The results
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indicate, in fact, that this typical permanent press finish affects
the polyester fully as much as the cotton with regard soilability
and launderability.
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Table BG1
INSTRUMENTAL REFLECTANCES OF IAUNDERED PILLOWCASES
AFTER SIX CYCLES IN BUNDLE TEST
AHAM durapress
D durapress
AHAM cotton
D cotton
AHAM durapress
M durapress
AHAM cotton
M cotton
G
83.8
84.0
90.1
90.4
83.3
83.0
88.9
87.6
Delta G
AHAM
0
-0.2
0
-0.3
0
0.3
0
1.3
Whiteness
76.2
76.0
76.5
75.2
71.3
67.8
66.1
59.6
Delta
Whiteness
AHAM
0
0,2
0
1.3
0
3.5
0
6.5
Yellowness
.01
.01
.03
.04>
.02
.03
.06
.08
Delta
Yellowness
AHAM
0
0
0
.01
0
.01
0
.02
174
-------
Table BG2
TERGOTOMETER SOIL REMOVAL VALUES
Cotton, 0.2%, Tap Water
Col. 1
Procedure
No..
1
2
1
2
1
2
2
3 | 4
Delta Values Reflectance
vs AHAM
G
3.10
-.20
l.AO
-1.60
.60
0
Whiteness
1.90
-.50
.60
-.80
.10
0
Yellowness
Detergent
D
.003
.002
Detergent
M
.003
-.002
Detergent
AATCC #124
.003
.004
5
.
'
Alcohol Extractable Material
% on soiled
swatches
1.19
7.76
1.19
7.76
1.19
7.76
% on washed
swatches
.75
2.61
1.01
2.68
.56
2. 64
Delta vs
AHAM
-.03
.03
-.29
-.04
.16
0
175
-------
Table BG2A
TERGOTOMETER REDEPOSITION VALUES
Cotton, 0.2%, Tap Water
Col. 1
Procedure
No.
1
2
1
2
1
2
2
3
4
Delta Values Reflectance
vs AHAM
G
-5.6
-0.6
-3.8
-0.3
-2.8
-0.7
Whiteness
-5.2
-1.3
-3.2
0.3
-1.5
0.1
Yellowness
Detergent
D
.004
.003
Detergent
M
.002
.Q01
Detergent
AATCC #124
.003
.002
5
, 1 ,
Alcohol Extractable Material '
% on soiled
swatches
% on washed
swatches
Delta vs
AHAM
176
-------
Table BG3
TERGOTOMETER SOIL REMOVAL VALUES
Durapress, .2%, Tap Water
Col. 1
Procedure
No.
2
2
2
2
3
4
Delta Values Reflectance
vs AHAM
G
11.6
7.80
-1.50
Whiteness
9.6
6.70
-1.30
Yellowness
Detergent
D
.001
Detergent
M
-.001
Detergent
AATCC #124
-.001
5
6
7
Alcohol Extractable Material
% on soiled
swatches
7.37
7.37
7.37
% on washed
swatches
2.35
2.58
1.82
Delta vs
AHAM
-.39
-.62
.14
177
-------
Table BG3A
TERGOTOMETER REDEPOSITION VALUES
Durapress, 0.2%, Tap Water
Col. 1
Procedure
No.
2
2
2
2
3
4
Delta Values Reflectance
vs AHAM
G
.3
-1.2
-0.3
Whiteness
.4
-0.8
-1.0
Yellowness
Detergent
D
.000
Detergent
M
.000
Detergent
AATCC #124
.004
5
6
7
Alcohol Extractable Material
% on soiled
swatches
% on washed
swatches
Delta vs
AHAM
178
-------
Table BG4
TERGOTOMETER SOIL REMOVAL VALUES
Cotton, 0.3%, Tap Water
Col. 1
Procedure
No.
3
4
5
3
4
5
3
4
5
2
3
4
Delta Values Reflectance
vs AHAM
G
-.80
-4.40
-4.80
-.90
-3.30
-4.40
-.50
-1.50
-1.70
Whiteness
1.20
-5.00
-4.70
1.90
-3.00
-4.10
1.00
.30
.30
Yellowness
Detergent
D
-.006
.011
.009
Detergent
M
-.010
.006
.007
Detergent
AATCC #124
0
.002
.001
5 | ,
7
Alcohol Extractable Material
% on soiled
swatches
Swatches
4.74
1.44
5.69
4.74
1.44
5.69
4.74
1.44
5.69
% on washed"
swatches
Swatches
3.29
.39
3.39
3.53
.45
3.37
3.07
.61
2.81
Delta vs
AHAM
.91
.18
-1.60
.67
.12
-1.58
-.87
-.04
-1.02
179
-------
Table BG4A
TERGOTOMETER REDEPOSITION VALUES
Cotton, 0.3%, Tap Water
Col. 1
Procedure
No.
3
4
5
3
4
5
3
4
5
2
3
4
Delta Values Reflectance
vs AHAM
G
-0.5
-1.4
-1.5
-0.4
-1.2
-1.2
-0.6
-1.5
-1.3
Whiteness
-0.3
-2.9
-3.0
-0.3
-2.2
-1.4
1.2
0.7
2.2
Yellovmess
Detergent
D
-.001
.007
.006
Detergent
M
-.001
.006
.001
Detergent
AATCC #124
.001
.002
-.004
5
6
7
Alcohol Extractable Material
% on soiled
swatches
% on cashed
swatches
'** "§
... |..
; I
!
Delta vs
AHAM
180
-------
Table BG5
TERGOTOMETER SOIL REMOVAL VALUES
Durapress, 0.3%, Tap Water
Col. 1
Procedure
No.
3
4
5
3
4
5
3
4
5
2
3
4
Delta Values Reflectance
vs AHAM
G
3.30
-2.50
-3.20
2.40
-2.80
-3.00
-.10
-.10
-.60.
Whiteness
4.60
-4.40
-4.00
4.30
-4.80
-3.00
-.80
-.50
-1.60
Yellowness
Detergent
D
-.010
.012
.010
Detergent
M
-.010
.013
.006
Detergent
AATCC #124
.002
.002
.006
5
6
7
Alcohol Ext rac table Material
% on soiled! % on washed
swatches 1
4.24
1.88
4.30
4.24
1.88
4.30
4.24
1.88
4.30
swatches
1.97
.65
1.99
1.60
.65
1.84
1.61
.72
1.72
Delta vs
AHAM
-.26
0
-.42
.11
0
-.27
.10
-.07
-.15
181
-------
Table BG5A
TERGOTOMETER REDEPOSITION VALUES
Durapress, 0.3%, Tap Water
Col. 1
Procedure
No.
3
4
5
3
4
5
3
4
5
2
3
4
Delta Values Reflectance
vs AHAM
G
-.1
.3
.4
0
.1
.2
0
-.1
0
Whiteness
1.0
-.8
-1.0
-.4
-.9
-.1
.2
-.5
-.9
Yellowness
Detergent
D
-.003
.004
.005
Detergent
M
.001
.003
.002
Detergent
AATCC #124
0
.001
.003
5
6
7
Alcohol Extractable Material
% on soiled
swatches
% on washed
swatches
Delta vs
AHAM
182
-------
Table BG6
RANKINGS OF DETERGENTS IN DIFFERENT WASHING PROCEDURES
Whiteness Ranking of Soiled Swatches
Procedure 0.2 % , Tap Water 0.3 %, Tap Water
Cotton DP Cotton
Bundle fAHAM fAHAM
|p |p
M M
i PAHAM
AATCC
X]
DJ
2 fM fAATCC
D LAHAM
AATCC M
.AHAM D
3
PD M
W D
"AHAM
M
AATCC
J>
"AHAM
D
AATCC
J«
"AHAM
AATCC"
J)
M
k D
fD fM M
1$ ID fAHAM
LAATCC
5 fD
D fM LM
M to AHAM]
AATCCJ
DP
"AATCC
AHAM
M
JD
fAATCC
LAHAM
Ml
Dj
B
AATCCl
AHAMJ
(3
LAATCC
AHAM
183
-------
Table BG7
WHITENESS RANKINGS OF SOILED SWATCHES IN PROCEDURES 1 and 2
Procedure
1
2
0.1 %,
Cotton
AHAM"]
AATCCJ
M
D
M
D
AATCCf]
AHAM J
Tap Water
DP
AATCC
AHAM
Ml
DJ
0.1 %,
Cotton
AATCC"!
AHAM J
M
D
M
AATCC]
D J
AHAM
Hard Water' 0.2 %
Hard Water'
DP , Cotton DP
i
M "|
AATCCj
AHA1VU
AATCC
AHAMl
M J
D
M
AHAM
AATCC
D
!
*
i
i
AATCC] 1
AHAM J !
M i
D i
0.3 %,
Cotton
AATCC "I
AHAM
M J
D
"AHAM
AATCC
M
P
Hard Water
DP
[AATCC
LAHAM
M
D
oo
•*>
-------
Table BG8
WHITENESS BANKINGS OF SOILED SWATCHES IN PROCEDURES 3, 4 and
0.3%; Hard Water
Procedure Cotton
3 AHAM]
"MTCQJ
M
i)
DP
AATCC]
AHAMJ
M
D
AHAM")
AATCCJ
AATCCl
AHAMJ
D
M
AATCC]
AHAMJ
fD
[M
AATCC]
AHAMJ
185
-------
Table BG9
WHITENESS RANKINGS OF SOILED SWATCHES
DETERGENTS M and D IN PROCEDURES 3, 4 and 5
of Ti^r-v T.T'-.-f-^v-. O T <~" T.Tr--w^-1 1,T^•(-/-.->-. C\ O ff
oo
Procedure
3
11
5
U.I 7o, •!'
Cotton
CJ
D
M
D
M
ap v.'a^er
DP
M
D
fM
LD
M
D
U.I /i, J:L£.
Cotton
fM
LD
P
LM
fM
LD
ra v/arer
DP
M
D
fD
M
D
U.el /o, He
Cotton
p.l
LD
P
LM
P
LM
ira vjare:
DP
M
D
K
M
D
r u.j "f,, tic
Cq>tton
fM
LD
P
LM
P
LM
ira v,!ater
DP
M
D
D
M
P
LM
-------
WHfTENLSS
ed_doi!ioii_
dotlon
OUntrea
4 Tr^ater
lEFltCTANCi
GREEN
Untrea
ed
Cotton
20
Figure 37-
1 2
Number of soil/wash cycles
Fabric finish study. Spangler multicycle. 200 ppm water,
AATCCWOB 0.3%. Cotton.
187
-------
Figure 38.
1 2
Number of soil/wash-cycles
Fabric finish study. Spangler multicycle.
200 ppm water. AATCCWOB 0.3%. Dacron.
188
-------
WHITENESS
.iL ' ..
I i i
1 2
Number of soil/wash cycles
Figure 39. Fabric finish study. Spangler multicycle.
200 ppm water. AATCCWOB 0.3%. Blend fabric,
189
-------
VO
o
Before
Soiling
Figture 40.
.1 .2
Detergent concentration in bath (%)
Fabric finish study. Colgate soil. 200 ppm water
AATCCWOB. Cotton. Green reflectance values.
.3
-------
100
vo
Before
Soiling
After
Soiling
Detergent concentration in bath (%)
Figure 41. Fabric finish study. Colgate soil. 200 ppm water.
AATCCWOB. Cotton. Whiteness values.
-------
(A
i
o
c —
0)
U
•C -:
Q>
Before
Soiling
After
Soiling
.1 .2
,.i- •<--— -^ -•
• Detergent concentration in bath (%)
Figure 42. Fabric finish study. Colgate soil. 200 ppm water.
AATCCWOB. Dacron. Green reflectance values.
-------
100
VO
(jO
Before
Soiling
After
Soiling
.1 .2
Detergent concentration in bath (%)
Figure 43. Fabric finish study. Colgate soil. 200 ppm water.
AATCCWOB. Dacron. Whiteness values.
-------
U
(A
i
i- U)
vo «*-
4>- '-
3
0»
U
c
(tf
+«
U
Before
Soiling
After
Soiling
.1 .2
Detergent concentration in bath (%)
Figure 44. Fabric finish study. Colgate soil. 200 ppm water.
AATCCWOB. Blend fabric (commercial permanent press finish).
Green reflectance values.
.a
-------
u
u
Cfl
10
0)
vo
Oi
tt)
U
c
10
<«•«
u
0)
or
Before
Soiling
After
Soiling
0 .1 .2
Detergent concentration in bath (%)
Figure 45. Fabric finish study. Colgate soil. 200 ppm water.
MTCCWOB. Blend fabric (commercial permanent press finish)
Whiteness values.
.3
-------
23456
ML 2% Mquestrant solution added
I.-. Jon curv«i of t/f/Jeal itrong, htgh efficiency
ch*Jant«, ,'i'cA
ttlomer,
-------
23456
ML 2% MquMtrant solution addtd
Figur* 47. ChfUtion curv«§ of w«ak, mod«rat« efficiency ch*Unt§,
Na cittaU and
197
-------
294-10 nSppm
2345
ML 2% sequestrant solution added
igure 48. Low efficiency polymeric chelants. Akzo 294-10 moderately
strong, POCNa moderately weak.
198
-------
TTMW 2SOO) IJLS
123456
ML 2% sequestrant solution added
Figure 49. Effect of molecular weight on chelating behavior in
polyacrylic acids (Calnox). Akzo OS starch typical of low
efficiency moderate strength polymeric builders.
199
-------
Code No.
APPENDIX C
CODE LIST OF MATERIALS
Type
Identity
20-138 Fatty alcohol ethoxylate surfactant
20-141 Polymeric builder
20-144 Hydroxylated nonionic surfactant
20-145 Hydroxylated nonionic surfactant
20-146 Low titer soap
20-147 High titer soap
20-151
Glucoheptonic acid builder
20-152 Citric acid (sodium salt) builder
22-155 Alpha olefin sulfonate surfactant
26-189 Hydroxylated nonionic surfactant
26-191 Hydroxylated nonionic surfactant
31-230 Sucrose Hexadecyl Ether
Plurafac A-38 (Wyan-
dotte Chem. Corp.
Experimental 18507-27
(Celanese Chem. Co.)
Ninol AA62 (Stepan
Chemical Co.)
Nittoester P-1570 (Dai
Nippon Sugar Mfg. Co.)
Seqlene S540 (Pfansti-
ehl Laboratories, Inc.)
Pfizer Chemicals Div.
Bioterge AS-35-CL
(Stepan Chem. Co.)
Experimental compound
IL728 (Atlas Chem.
Industries, Inc.)
Experimental compound
IL725 (Atlas Chem.
Industries, Inc.)
Experimental compound
1303-23, GRI
200
-------
Appendix C (Continued)
Code No.
Type
Identity
32-237 Commercial detergent extract
34-249 Alkyl aryl sulfonate (IAS)
36-276 Experimental formulation, GRI
36-277 Experimental formulation, GRI
36-278 Experimental formulation, GRI
38-279 Diglycollic acid (Na salt)
38-282
Commercial detergent
40-309 Diglycollic acid (Na salt)
40-310 Polymeric builder
40-312 SAND, Monoacidamide of nitrilo-
triacetic acid
40-332 Ether carboxylate anionic surfac-
tant
42-348 Sulfo zwitterionic surfactant
42-350 Sulfobetaine zwitterionic surfac-
tant
Alcohol soluble mate-
rial (surfactant) ex-
tracted from Tide XK
Ultrawet K Special
(Arco Chem. Co,)
*
40 Hi titer soap/15 Al-
fonic 1218-60/8G/1/36
40 Low titer soap/15
Alfonic 1218-60/8G/1/36
20 Low titer soap/15
Alfonic 1218-60/8G/1/
36/+20 H20
Biosoft SB-1
(Stepan Chem. Co.>
t
Concern (H.T.Develop-
ment , Inc.)
Purchased 1970
Experimental compound
SN1048 (Celanese
Chem. Co.)
Gantrex AN-119
(GAF Corp.)
(Bethlehem Steel Co.)
Experimental compound
1245 (Dow Chem. Co.)
Sulfobetaine DLM
(Textilana Corp.)
Sulfobetaine TA75
(Textilana Corp.')
201
-------
Appendix C (Continued)
Code No.
Type
' Identity
42-353
43-64
43-65
43-67
43-74
43-83
46-356
46-357
48-374
51-91
51-93
51-100
51-101
Sulfo zwitterionic surfactant
Commercial detergent, high carbon-
ate type.
Polymeric builder
Fatty alcohol ethoxylate surfac-
tant
Polymeric builder
Hydroxylated nonionic surfactant
Carboxy zwitterionic surfactant
Carboxy zwitterionic surfactant
Amine oxide surfactant
Alkane sulfonate anionic surfac-
tant
Fatty alcohol ethoxylate nonionic
surfactant
Fatty alcohol ethoxylate nonionic
surfactant
Fatty alcohol ethoxylate nonionic
surfactant
Sulfobetaine DP
(Textilana Corp.)
Sears Laundry Deter-
gent - Phosphate Free
Versicol E7 (Allied
Colloid Mfg. Co.)
Arosurf 63PE16 (Ash-
land Chemical Co.)
Experimental 18507-48
(Celanese Chem. Co.)
Experimental surfac-
tant 31-43 (Northern
Regional Laboratory
USDA)
Velvetex BC (Textilana
Corp.)
Tegobetaine C (Gold-
schmidt Chemical Div.)
Aromox C/12W (Armour
Industrial Chem. Co.)
Hostapur SAS-60
(American Hoechst Corp.)
Alfonic 1618-65
(Continental Oil Co.)
Arosurf 63-E15
(Ashland Chem. Co.)
Arosurf 42-E12
(Ashland Chem. Co.)
202
-------
Appendix C (Continued)
Code No.
Type
Identity
51-104 Fatty alcohol ethoxylate nonionic
surfactant
51-105 Fatty alcohol ethoxylate nonionic
surfactant
54-431 Sulfo zwitterionic surfactant
54-433 Sulfo zwitterionic surfactant
56-445 Hydroxyethylimino diacetic acid
58-466 Polymeric builder
58-467 Polymeric builder
58-471 Ether sulfate anionic surfactant
60-486 Ether carboxylate anionic surfac-
tant
62-491 Ether sulfate anionic surfactant
62-492 Ether sulfate anionic surfactant
66-530 Carbohydrate type polymeric builder
66-532 Polymeric builder
Plurafac B-26
(Wyandotte Chem. Co.)
Plurafac D-25
(Wvandotte Chem. Co.)
Miranol CS Cone.
(Miranol Chem. Co.)
Miranol DS
(Miranol Chem. Co.)
(Bethlehem Steel Co.)
Experimental Product
335 (Amicon Corp.)
Experimental Product
933 (Amicon Corp.)
Steol 4N (Stepan
Chem. Co.)
Experimental compound
7-26A (Dow Chem. Co.)
Alfonic 1412-5 (Con-
tinental Oil Co.)
Experimental compound
1218-EO-50-S (Con-
tinental Oil Co.)
Dicarboxyl starch
(fever Bros.)
Experimental deter-
gent builder S-10244-
137-1 (American Cya-
namid Co.)
203
-------
Appendix C (Continued)
Code No.
Type
Identity
66-533
66-541
68-108
68-109
68-127
68-134
68-558
70-560
72-589
74-594
Polymeric builder
Monomeric builder, carboxylic acid
type
Sulfo ampholytic surfactant
U.S. Patent 3,084,187
Sulfo ampholytic surfactant
U.S. Patent 3,084,187
Fatty alcohol ethoxylate nonionic
surfactant
Fatty alcohol ethoxylate nonionic
surfactant
Alpha olefin sulfonate anionic
surfactant
Commercial detergent
Monomeric builder
Soap type surfactant
74-596
Monomeric builder
Experimental detergent
builder S-10244-137-2
(American Cyanamid Co.)
Experimental compound
SN1152 (Celanese
Chemical Co.)
t
GRI experimental com-
pound #1303-6 (GRI)
GRI experimental com-
pound #1303-7 (GRI)
Alfonic 1218-60 (Con-
tinental Oil Co.)
Neodol 25-7 (Shell
Oil Co.)
Experimental compound
OLS07 (Gulf Research
and Dev. Co.)
Amway "L.O.C." Liquid
Organic Concentrate
•(Ataway Corp.)
Purchased 1971
Monoethanolamine
Carbonate (GRI)
#544-151A Soap/lime
soap dispersing agent/
builder (Eastern Uti-
lization Research &
Dev. Div. USDARS)
DL-tartaric acid
(Aldrich Chem. Co.)
204
-------
Appendix C (Continued)
Code No.
Type
Identity
74-602
74-604
74-606
76-620
,78-633
78-634
78-635
80-647
86-700
86-704
86-705
Carbohydrate type polymeric builder
Alpha olefin sulfonate anionic
surfactant
Monomeric builder
Monomeric builder
Ether carboxylate surfactant
Ether carboxylate surfactant
Fatty alkyl sulfate anionic surfac-
tant
Monomeric builder
Laundry Detergent
Carbohydrate builder
Unidentified carboxylated polymer
Carboxymethyl starch
(Northern Regioaal Re-
search Laboratories
USDA)
Bioterge AS40G (Stepan
Chemical Co.)
Mellitic acid (Chem.
Procurement Laboratories)
Tetrahydrofuran-2,3,4,
5-tetracarboxylic acid
(Aldrich Chemical Co.)
Sandopan DTC (Sandoz)
Sandopan DTC 100
(Sandoz)
Dupanol ME Dry
(Dupont Co.)
Carboxymethyl oxysuc-
cinic Acid
Standard Laundry De-
tergent AATCCWOB from
Am. Assoc. Textile
Chemists & Colorists
Methocel XDL 7823
(Dow Chemical Co.)
Polyelectrolyte
NX524 (Nalco Chem.Co.)
205
-------
Appendix C (Continued)
Code No.
Type
Identity
86-706
Soap type surfactant
86-707
88-723
88-726
Soap type surfactant
86-708 Soap type surfactant
86-709 Maleic copolymer builder
88-722 Laundry detergent
Laundry detergent
Laundry detergent
ER AF569-144-1 Soap/
lime soap dispersing
agent builder (Eastern
Utilization Research
and Dev. Div. USDARS)
ER AF569-144-2 Soap/
lime soap dispersing
agent builder (Eastern
Utilization Research
and Dev. Div. USDARS)
ER AF569-144-3 Soap/
lime soap dispersing
agent builder (Eastern
Utilization Research
and Dev. Div. USDARS)
Experimental compound
Maldene 270 (Borg-
Worner Co.)
Commercial laundry de-
tergent, purchased
Chicago, 111. 1972—
Breeze (Lever Bros.)
Commercial laundry de-
tergent, purchased
Chicago, 111. 1972—
Wisk (Lever Bros.)
Commercial laundry de-
tergent , purchased
Chicago, 111. 1972—
Ajax (Colgate-Palmol-
ive Co.)
206
-------
Appendix G (Continued)
Code No.
Type
Identity
90-727
Laundry detergent
90-729
94-760
96-782
96-783
96-784
98-806
Laundry detergent
90-730 Anionic sulfonate surfactant
92-745 Acrylic builder
92-752 Alkyl aryl sulfonate (LAS)
Laundry detergent
Laundry detergent
Laundry detergent
Unidentified Polymeric builder
Commercial laundry de-
tergent purchased
Chicago 1972 -- Cold
Power (Colgate-Palmol-
ive Co.)
Commercial laundry de-
tergent Opus (Fenom
Corp., Goteborg, Sweden)
Chevron D116 (Standard
Oil Co. of California)
Goodrite K732 (B.F.Good-
rich Chem. Co.)
Conoco C550 (Continen-
tal Oil Co.)
Bioterge TMS
(Stepan Chemical Co.)
Commercial laundry de-
tergent - purchased
1973 Era (Proctor &
Gamble Co.)
Commercial laundry de-
tergent purchased
Miami, Fla. 1973--
Cold Power (Colgate-
Palmolive Co.)
Commercial laundry de-
tergent purchased
Miami 1973—Tide
(Proctor & Gamble)
Experimental compound
IL 740 (Atlas Chem.
Indus tries, Inc.)
207
-------
Appendix C (Continued)
Code No.
Type
Identity
98-807
Unidentified polymeric builder
100-821 Unidentified polymeric builder
100-822 Carboxylated starch
100-823 Acrylic builder
100-824 Acrylic builder
102-833 Carboxyethyl Acetone
102-834 Carboxylated starch builder
102-836 Fatty acid diethanolamide
condensate surfactant
104-855 Laundry detergent
Experimental compound
IL741 (Atlas Chem'.
Industries, Inc.)
Experimental compound
XL,759 (Atlas-Chem.
Indus trie s, Inc.)
Experimental cpmppund
OS starch (Akzo Huishou-
delijke Produkten NV,
The Hague, Holland)
Experimental compound
CaInox 214DN (Aquanes s
Chem. Co.)
Experimental compound
Calnox 231 (Aquaness
Chem. Co.)
GRI experimental com-
pound prepared accord-
ing to U.S. Patent
3,716,487
Experimental compound
starch 294-10 (Akzo
Huishoudelijke Pro-
dukten NV, The Hague,
Holland)
Superamide L9A
Commercial laundry de-
tergent - purchased
Washington, D.C.-1973
Dynamo (Colgate-
Palmolive Co.)
208
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Appendix C (Continued)
Code No.
Type
Identity
104-856 Sodium dodecylbenzene
sulfonamodiethyl sulfate sur-
factant
104-.860 Hydroxylated acrylic
copolymer builder
106-866 Maleio telomer builder
106-871 Maleic homopolymer builder
108-880 Sulfopropionate surfactant
ER AF594-37 (Eastern
Utilization Research
& Dev. Div. USDARS)
Experimental compound
POCNA (DEGUSSA)
6RI experimental com-
pound
6RI experimental com-
pound
ER AFP610-007 (Eastern
Utilization Research &
Dev. Div. USDARS)
209
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APPENDIX D
Selected Recent Patents Relating to Phosphate-Free Household Laundering
Detergents '
A. Monomeric Builders
1. C.A., 22 (1972) 154319n N,N-Bis (phyroxyethyl) - substituted
amino acids as builders for detergents. Rempfer, Heinz;
Grossman, Heinrich (Chemische Werke Huels A.-G.) Ger. Offen.
2,103,725, 10 August 1972, 7 pp.
2. C.A., 7£ (1973) 60055s N-Substituted disodium aminodicarboxy-
lates as builders for detergents. Rempfer, Heinz (Chemische
Werke Huels A.-G.) Ger. Offen. 2,125,249, 30 November 1972,
11 pp.
N-substituted aspartates and iminodiacetates.
3. C.A., 77. (1972) 138233v Phosphate-free detergent composi-
tions. Kusashio, Koji; Ninagawa, Sadayoshi (Ajinomoto Co.,
Inc.) Japan Kokai 72 16,504, 2 September 1972, 5 pp.
Glutatnates and aspartates.
4. C.A., 7]_ (1972) 138238a Detergent formulations containing
nonphosphorus builders. Yang, Meiling T. (Ethyl Corp.)
U.S. 3,717,591, 20 February 1973, 6 pp.
Sulfoethylimino diacetic acid.
5. C.A., Ji (1972) 142706c Detergent formulations containing
water-soluble salts of N,N-bis(carboxymathyl)aspartic acid
as builders. Yang, Meiling T. (Ethyl Corp.) U.S.
3,637,511, 25 January 1972, 5 pp.
6. C.A., 26 (1972) 129230y Detergent formulations containing
nonphosphorus builders. Yang, Meiling T. (Ethyl Corp.)
U.S. 3,635,829, 18 January 1972, 5 pp.
Sulfopropylimino diacetic acid.
7. C.A., 78 (1973) 5729q Iminodisuccinic acid salts as deter-
gent builders. Tate, Bryce E.; Berg, Rudolph G. (Pfizer Inc.)
U.S. 3,697,453, 10 October 1972, 4 pp.
210
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8. C.A., 21 (1972) 154302b Detergent. Unilever N.V. Neth.
Appl. 72 00,084, 07 July 1972, 13 pp.
Pyridine dicarboxylic acid.
9. C.A., 7.7 (1972) 126134a Sulfonated alkanedicarboxylate
builders for detergents. Von Praun, Ferdinand; Amende,
Joachim (Chemische Werke Huels A.-G.) Ger. Offen. 2,143,010,
01 March 1973, 19 pp.
Sulfonated adipic acid and homologs.
10, C.A., J2 (1972) 138234w Sequestering agents and detergent
builders. Lannert, Kent Philip (Monsanto Co.) Ger.
Offen. 2,231,927, 18 January 1973, 21 pp.
2-oxa-l,3,3 butane tricarboxylic acid and analogs.
11. C.A,, 78 (1973) 99507r tf- Substituted-p -sulfosuccinic acids
as detergent builders. Lamberti, Vincent (Unilever N.V.)
Ger. Offen. 2,230,073, 28 December 1972, 37 pp.
ahydrbxy - B sulfosuccinic acid and analogs.
12. C.A., 2?_ (1973) 113083h Phosphate-free detergents.
Hentschel, Gerhard Oskar (Hentschel, Valter S.E.) Ger.
Offen. 2,228,252, 21 December 1972, 12 pp.
monopropyl ester of malic acid
13. C.A., 78. (1973) 45433v Detergent builders. Konort, Mark D.;
Lamberti, Vincent; Weil, Ira (Unilever N.V.) Ger. Offen.
2,220,295, 16 November 1972, 39 pp.
Carboxyalkyl substituted malic and aspartic acids.
14. U.S. Patent 3,692,685 Detergent cooipositions.
Vincent Lamberti, Mark D. Konort and Ira Weil to Lever
Brothers Company, September 18, 1972.
Carboxymethyloxysuccinic acid (CMOS).
15. C.A., 78, (1973) 45417t Detergent formulations.
Lannert, Kent P. (Monsanto Co.) U.S. 3,704,320, 28 November
1972, 2 pp.
2,4-dioxapentane-1,3,3,5-tetracarboxylic acid.
16. C.A., 77 (1972) 11639y Enzymic detergents containing ci-
trate builders. Mast, Roy Clark (Proctor and Gamble Co.)
Ger. Offen. 2,161,779, 29 Jun 1972, U.S. Appl. 98,114,
14 December 1970; 40 pp.
211
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17. C.A., 77 (1972) 166522m Built detergent formulations.
Harken, Russell D. (Monsanto Co.) U.S. 3,689,418,
05 September 1972, 2 pp.
Ethenetetracarboxylic acid.
18. Dutch Pat. Appl'n 70-17181, 24 November 1970,
D. S. Conner and J. E. Thompson to the Proctor and Gamble Co.
Built Detergent Composition. Corresponds to Belg. Pat.
759,283 and U.S. Serial No. 879,612.
Mellitic Acid.
19. C.A., 21 (1972) 116399£ Detergent builders.
Benjamin, Lawrence; Connor, Daniel Stedman (Proctor and
Gamble Co.) Ger. Offen. 2,161,768, 06 July 1972, 41 pp.
Mellitic acid used with carbonate and silicate.
20. U.S. Patent 3,661,787 Saturated Aliphatic Dicarboxylic Acid
Salts as Detergent Builders, George E. Brown, Jr. to the
Pollutrol Group, May 9, 1972.
Succinic and oxalic acids. Claims limited to potas-
sium palmitate as the surfactant.
21. C.A., 21 (1972) 50565y Detergent builders. Lamberti, Vincent
(Unilever N.V.) Ger. Offen. 2,150,544, 13 April 1972, 15 pp.
Oxydiacetic acid.
22. C.A., 21 (1971) 111128r Phosphate-free builders for deter-
gents. Konort, Mark D.; Lamberti, Vincent (Unilever N.V.)
Ger. Offen. 2,057,259, 09 June 1971, 17 pp.
Tetrahydrofuran tetracarboxylic acid.
23. C.A., 28 (1973) 5720e Tetrasodium tetrahydrofurantetra-
carboxylate builder for detergents. Jakobi, Guenter;
Perner, Johannes (Henkel und Cie. G.m.b.H) Ger. Offen.
2,113,730, 28 September 1972, 29 pp.
24. U.S. Patent 3,580,852 Detergent formulations containing
Tetrahydrofuran 2,3,4,5 - Tetracarboxylic Acid Salts as
Builders. Meiling T. Yang to Ethyl Corporation, May 25, 1971,
25. U. S. Patent 3,699,159 l,3,5-Trihydroxy-2,4,6-benzene tri-
carboxylic acid and water soluble salts thereof.
Daniel S. Conner and Harry Karl Krummel to the Proctor and
Gamble Company, October 17, 1972.
212
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26. C.A., 77 (1972) 128512a Phenolic calcium-complexing agents
for detergents. Conner, Daniel Steadman; Krummel, Harry Karl
(Procter and Gamble Co.) Ger. Offen. 2,164,872, 20 July 1972.
l,3,5-trisulfo-2,4,6-trihydroxy benzene and 1,3,5-tri-
carboxy-2,4,6-trihydroxy benzene.
27. C.A., 77 (1972) 128511z Tetracarboxylie acid detergents.
Cummins, Richard Williamson; Lancelot, Charles Julian
(FMC Corp.) Ger. Offen. 2,165,773 20 July 1972, 26 pp.
Ethane tetracarboxylic acid and butane-1,2,3,4-tetra-
carboxylic acid. Stated to be biodegradable.
28. U.S. Patent 3,635,830 Detergent compositions containing
oxydisuccinic acid salts as builders. Vincent Lamberti and
Mark D. Konort to Lever Brothers Company, January 18, 1972.
29. Ger. Offen. 1,926,422 M. D. Konort and V. Lamberti to Uni-
lever N.V., 4 December 1969, Detergent compositions. Corre-
sponds to Fr. Application 2,009,946.
Oxydisuccinic acid.
30. U. S. Patent 3,686,124 Carboxymethylated derivates of di- and
tri-saccharide compounds and detergent compositions contain-
ing them. Warren I. Lyness and James E. Thompson to the
Proctor and Gamble Co., August 22, 1972.
Carboxymethylated sucrose, lactose, and raffinose.
31. U.S. Patent 3,669,890 Builders for synthetic detergent com-
positions based on carboxyethyl derivatives of polyalcohols.
Martin M. Tessler and Morton W. Rutenberg to National Starch
and Chemical Corporation, June 13, 1972.
Carboxyethyl pentaeryfchritol.
32. U.S. Patent 3,725,290 Oxyacetic acid compounds as builders
for detergent compositions. Douglas Carlyle Nelson and
Edward Andrew Knaggs to Step an Chemical Company, April 3,
1973.
Carboxymethyl ethers of tri- and tetraglyeols,
pentaerythritol, etc.
33. C.A., 22. (1972) 77086e Builders for synthetic detergent com-
positions based on carboxyethyl derivatives of polyalcohols.
Tessler, Martin M.; Rutenberg, Morton W. (National Starch
and Chemical Corp.) U.S. 3,669,890, 13 June 1972, 5 pp.
Carboxyethyl ethers of pentaerythritol and gluconic acid.
213
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34. C.A., 76 (1973) 113105s Sulfosuccinate salt-containing der
tergents. Rempfer, Heinz; Schulze, Klaus (Chemische Werke
Huels A.-G.) Ger. Offen. 2,136,360, 01 February, 1973, 11 pp.
Sulfosuccinic esters of fatty alcohol ethoxylates
(surface active) used as builders for alkylbenzene
sulfonates.
35. U.S. Patent 3,725,286 Detergent compositions.
Robert Pettigrew to Lever Brothers Company, April 3, 1973.
Long chain succinic or malonic acids (surface active)
used as builders for alkylbenzene sulfonates.
36. C.A., _78 (1973) 73947J Laundry detergent. Unilever N.V.,
Fr. 2,107,437, 09 June 1972, 10 pp.
Alpha sulfonated fatty acids as builders.
37. C.A., 72 (1972) 22028g Solid and liquid detergent compo-
sitions. Davies, James Francis; Gauterin, Charles R.;
Ailbert, Philip A.; Griffiths, Storer C.C.; J*
Griffiths, David W. L. (Unilever N.V.) Ger. Offen. 2,144,592,
16 March 1972, 12 pp.
Alpha sulfonated fatty acids used as builders for
anionics or nonionics.
38. C.A., 2Z (1972) 116400z Textile detergents.
Davies, James Francis; Gauterin, Charles Rowland;
Griffiths, David W. L.; Storer, Christopher Charles (Unilever
N.V.) Ger. Offen. 2,161,726, 06 July 1972, 21 pp.
asulfonated fatty acids (surface active) used as
builders for alkylbenzene sulfonate.
39. C.A., 2§ (1973) 113088p Phosphate-free detergents.
Pettigrew, Robert; Tissington, Peter (Unilever N.V.)
Ger. Offen. 2,232,414, 25 January 1973, 11 pp.
Sodium 2-hydroxy-n-tetradecanoate used as builder
for alkylbenzene sulfonate.
40. C.A., 21 (1973) 31848x Laundry detergent.
Davies, James Francis; Gilbert, Philip Alan,
Thompson, Laurence (Unilever N.V.) Ger. Offen. 2,222,993,
16 November 1972, 23 pp. Corresponds to Belg. Patent
783,176.
Long chain alkane 1,2-disulfonates or 1,2-sulfonate-
sulfinate (surface active) used as builders for
alkylbenzene sulfonate.
214
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41. C.A., 72. (1970) 14116r Taurine derivatives for replacing
sodium tripolyphosphate in detergents. Lincoln, Robert M.;
Meyers, Joseph Andrew, III; Sauer, Richard W. (Atlantic
Richfield Co.) Fr. 1,556,816, 07 February 1969, 8 pp.
Corresponds to U.S. 3,579,457, May 18, 1971.
Long chain taurine derivatives (surface active) used
with carbonate as builders for alkylbenzene sulfonate.
B. Polymeric Builders
1. U.S. Patent 3,308,067. Detergent compositions.
Francis L. Diehl to Proctor and Gamble Co., March 7, 1967,
11 pp.
Describes a range of polymeric aliphatic carboxylic
acids. Homopolymers and copolymers of acrylic, maleic
and itaconic acids used as builders for sulfonated or
sulfated surfactants.
2. C.A., 21 (1972) 138227W (Alkyl)cyclopentene-maleic anhy-
dride copolymer salt builder for detergents. Tsukuni, Hajime;
Fujiki, Shun; Tsunoda, Teruo; Ooba, Yoichi (Hitachi Chemical
Co., Ltd.), Ger. Offen. 2,238,275, 15 February 1973, 19 pp.
3. C.A., 78 (1973) 86336j Biodegradable builders for deter-
gents. Kramer, J. K. (Shell Internationale Research
Maatschappij N. V.) Neth. Appl. 72 05,685, 31 October 1972,
26 pp.
Telomers of maleic acid. Methylisobutyl ketone and
other materials as telogens.
4. C.A., 72 (1972) 154318m Composite maleic anhydride-vinyl
methyl ether copolymer builders for detergents.
Grifo, Richard Anthony (GAF Corp.) Ger. Offen. 2,200,779,
20 July 1972, 21 pp.
5. C.A., 2§ (1973) 86308b New substitute for pplyphosphate in
detergents. Lauhus, Guenter P. (GAF G.m.b.H., Hamburg, Ger.).
Seifen, Oele, Fette, Wachse 1972, 98 (26), 869-75 (Ger.)
Copolymer maleic-methylvinyl ether.
6. C.A., 72 (1970) 33192d Textile detergent compositions.
Arthur, Ralph P.; Belden, M. Joanne (Borg-Warner Corp.)
Ger. Offen. 1,920,850, 20 November 1969, 14 pp.
Maleic-butadiene copolymer.
215
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7. C.A., 7_6 (1972) 74086y Polyelectroylte materials for use
in detergents. Lancelot, Charles J.; Mackellar, Donald G.
(FMC Corp.) Ger. Offen. 2,120,907, 11 November 1971, 26 pp.
Carbon monoxide-maleic copolymer.
8. C.A., 74 (1971) 77660a Poly (maleic acid) and salts for use
as detergent builders and surfactants. Bluraberg, John H.;
MacKellar, Donald G. (FMC Corp.) U.S. 3,557,065, 19 January
1971, 3 pp.
Light-colored sodium polymaleate.
9. C.A., 2§ (1972) 129218a Sodium polymaleate.
Blumberg, John H.; Finley, Joseph H.; Rizzo, John J. (FMC
Corp.) U.S. 3,637,609, 25 January 1972, 3 ?p.
Refers to a bleached white sodium polymaleate.
10. C.A., 77 (1972) 90407e Sulfonated copolymers as detergent
builders. Westernacher, Helmut; Schulze, Klaus (Chemische
Werke Huels A.-G.) Ger. Offen. 2,056,813 25 May 1972, 15 pp.
Sulfonated ethylene-maleic copolymer.
11. C.A., J76 (1972) 74089b Sulfonated poly (maleic acid) deter-
gent builders. Blumberg, John H.; Rizzo, John J.;
MacKellar, Donald G. (FMC Corp.) U.S. 3,624,048 30 November
1971, 4 pp.
12. U.S. Patent 3,676,373 Detergent Compositions.
Stanley C. Paviak to Gulf Research & Development Company,
11 July 1972.
Styrene-maleic copolymer of mol. wt. at least 3000.
13. U.S. Patent 3,730,913 Synthetic detergent compositions.
Yoichi Oba, Chiharu Kato, Teruo Tsunoda, and Hajime Tsukuni,
assignors to Hitachi, Ltd., and Hitachi Chemical Company,
Ltd., May 1, 1973.
Copolymer of 3a,4,5,6,7,7a-hexahydro-4,7-methanoin-
dene and maleic anhydride.
14. C.A., 21 (1972) 138247c Detergent compositions containing
poly-electrolyte builders. Tokiwa, Fumikatsu; Imamura,
Tetsuya (Kao Soap Co., Ltd.) Japan, Kokai 73,12,807,
17 February 1973, 5 pp.
C_ .„ alkene-maleic copolymer. e.g. octene-maleic.
216
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15. C.A., 77 (1972) 141726t Cleaning and soil-preventive com-
positions. Schomburg, Noel L., (Monsanto Co.) U. S.
3,679,592, 25 July 1972, 2 pp.
Maleic-ethylene copolymer half butyl ester.
16. C.A., 7_6_ (1972) 115211f Detergent compositions.
Arthur, Ralph P.; Belden, M. Joanne (Borg-Warner Corp.)
Ger. Offen. 2,125,461, 02 December 1971, 22 pp.
Maleic-butadiene copolymer.
17. C.A., 2§ (1973) 60040h Detergent polyelectrolyte builders.
Martin, Preston Kuhn; Kelly, Richard Howard (Celanese Corp.)
U.S. 3,706,672, 19 December 1972, 6 pp.
Polyacrylic acid of controlled mol. wt.
18. C.A., 2§ (1973) 45424t Partial salts of polymerized ali-
phatic carboxylic acids, for use in detergents. Unilever N.V.
Fr. 2,075,287, 12 November 1971, 18 pp.
Polyacrylic acid.
19. U.S. Patent 3,692,704 Method of Laundering Fabrics.
James K. Stamm, Edwin R. Loder, Charles A. Brungs, and
Herman Kerst to Chemed Corporation, September 19, 1972.
Mixture of polyacrylic acid and poly
(N,N-dicarboxymethyl acrylamide).
20. C.A., 2§ (1973) 113104r Sodium poly (a - hydroxyacrylate)-
containing detergents. Wegemund, Bernd; Jakobi, Guenter
(Henkel und Cie. G.m.b.H.) Ger. Offen. 2,136,672,
01 February 1973, 34 pp.
21. C.A., 2§ (1973) 99517u Detergents and bleaches containing
dispersible complex-forming mixtures. Batka, Heimold;
Altenschoepfer, Theodor (Henkel und Cie. G.m.b.H.)
Ger. Offen. 2,134,695, 25 January 1973, 28 pp.
Aerolein-aerylie copolymer.
22. C.A., 2§ (1973) 99475d Poly (hydroxycarboxylates), a class
of multiply applicable complexing agents. Haschke, Heinz;
Morlock, Gerhard; Kuzel, Peter (Bereich Forsch. Chem.,
Degussa, Frankfurt/M., Ger.). Chem.-Ztg. 1972, 96(4),
199-207 (Ger).
The properties of the title compds., prepd. from salts
of aerolein-aerylie acid copolymer by the Cannizzaro,
reaction are described with respect to their application.
217
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23. French Patent 2,083,006. Product for washing. Degussa.
December 10, 1971.
Acrolein-acrylic acid copolymer converted by Cannizaro
reaction to allyl alcohol-acrylic copolymer.
24. U.S. Patent 3,629,121 Carboxylated starches as detergent
builders. Ibrahim A. Eldib, December 21, 1971.
25. C.A., _78 (1973) 5672r Dicarboxy group-containing starch
for detergents. Powers, Peter James; Reynolds, John Henry
(Unilever N. V.) Ger. Offen. 2,213,955, 28 September 1972,
19 pp.
Purified by treatment with sodium borohydride.
26. C.A., 75 (1971) 7765k Detergent composition. Unilever N.V.
Neth. Appl. 70 12,380, 23 February 1971, 41 pp.
Carboxylated starches and celluloses.
27. C.A., 72 (1972) 166520J Dicarboxymethyl starch detergent
compositions. Cornelissens, Emery G. P.; Ploumen, Jan J. H.
(Akzo G.m.b.H.) Ger. Offen. 2,207,917, 31 August 1972,
Neth. Appl. 71 02,556, 25 February 1971, 12 pp.
Dicarboxymethyl starch.
28. U.S. Patent 3,723,322 Detergent compositions containing
Carboxylated polysaccharide builders. Francis L. Diehl to
The Procter & Gamble Company, March 27, 1973.
Carboxylated alginic acid.
A
29. Starch-derived polyelectrolytes as builders in heavy duty
detergent formulations. C. A. Wilham, T. A. McGuire,
A. M. Mark and C. L. Mehltretter, J. Am. Oil Chemists Soc. 47.
No. 12,522 (1970).
C. Surfactants stated to perform well without builders:
1. U.S. Patent 3,714,076. R. G. Anderson to Chevron Research
Company, 30 January 1973.
Viscinal disulfates. ' '-
2. U.S. Patent 3,686,098 Novel detergent cdmpositioii; Ira Weil
to Lever Brothers Company, August 22, 1972.
Di-anionic sulfates and sulfonates.
218
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3. C.A., 7_6 (1972) 87551w Heavy-duty laundry detergents con-
taining polysulfonated alkyl phenols. Sharman, Samuel H.;
Danzik, Mitchell (Chevron Research Co.) Ger. Offen.
2,121,675, 25 November 1971, 27 pp.
4. C.A., 77 (1972) 77078d 2,2-Disulfonated dialkyl sulfoxides
and sulfones. Nooi, Jacobus Roelof (Lever Brothers Co.)
U.S. 3,666,796, 30 May 1972, 5 pp.
5. C.A., 77 (1972) 63801x Alkyl alkoxybenzene disulfonates.
Woo, Gar Lok (Chevron Research Co.) U.S. 3,663,609,
16 May 1972, 3 pp.
6. U.S. Patent 3,707,352 Linear Alkyl Hydrocarbyloxybenzene
disulfonates. Gar Lok Woo to Chevron Research Company,
December 26,1972.
7. U.S. Patent 3,697,573 Linear alkylphenol sulfate-sulfonate
phosphate-free detergent actives. Mitchell Danzik and
Ralph House to Chevron Research Company, October 10, 1972.
8. Belg. Appl'n 774,270. Detergent disulfates of 2-hydrocarbon
substituted butane diols. Anderson and Woo to Chevron Re-
search Company, 9 January 1970.
9. C.A., 7_8 (1973) 126125y l-(Sulfoalkyl)-4-undecylpyridinium
inner salts as active detergents. Roberts, David William
(Unilever N. V.) Ger. Offen. 2,238,371, 15 February 1973,
10 pp.
Zwitterionic sulfonate.
10. C.A., 7B. (1973) 60038p [(Alkylphenyl)dimethylammonio] pro-
panesulfonates. Crabtree, Peter William; Vipond, Peter
Wilfred (Unilever N. V.) Ger. Offen. 2,221,938, 23 November
1972, 12 pp.
Zwitterionic sulfonate.
11. C.A., 7_8 (1973) 73967r Phosphate-free detergents containing
glycol alkyl carboxymethyl ethers. Rempfer, Heinz;
Amende, Joachim; Stache, Helmut; Grossman, Heinrich
(Chemische Werke Huels A.-G.) Ger. Offen. 2,124,269,
30 November 1972, 15 pp.
Polyether carboxylate
219
-------
12. C.A., 2§ (1973) 45416s Heavy-duty household detergent com-
position. Shane, Hugh J. S. (Hart*Chemical Ltd.) Can.
912,395, 17 October 1972, 24 pp.
Polyether carboxylate
13. C.A., 77 (1972) 166529u Detergent composition. Arai,
Haruhiko; Minegishi, Yutaka; Takeuchi, Takeko (Kao Soap Co.,
Ltd.) Ger. Offen. 2,206,284, 31 August 1972, 17 pp. '
Polyether carboxylate
14. Can. Patent 873,295 Detergent Compositions. T. P. Matson
and J. E. Yates to Continental Oil Company, June 15, 1971.
Ether sulfonates
'.-
15. U.S. Patent 3,590,001 Phosphate free heavy duty detergent
formulations. Robert C. Taylor and Betty J. Wolsky to
Atlantic Richfield Company, June 29, 1971.
Taurine salts of alkylbenzene sulfonates.
16. U.S. Patent 3,084,187 Substituted aminoalkanesulfonic acids.
Van R. Gaertner to Monsanto Chemical Company, April 2, 19631
Amphoteric taurine derivatives.
D. Soap plus Lime-Soap dispersers:
i
1. C.A., 76 (1972) 129203s Soap-based detergent formulations.
I. Comparison of soap-line soap dispersing agent formula-
tions with phosphate-built detergents. Bistline, R. G., Jr.;
Noble, W. R.; Weil, J. K.; Linfield, W. M. (East Reg. Res.
Lab., Philadelphia, Pa.) J. Amer. Oil Chem. Soc. 1972, 49(1),
63-9.
2. C.A., 78 (1973) 31799g Soap-based detergent formulations.
IV. Synthesis and surface active properties of sulfopropyl
esters of N-substituted iminodiacetic acids. Micich, T. J.;
Sucharski, M. K.; Well, J. K.; Linfield, W. M. (East Reg.
Res. Lab., Agric. Res. Serv., Philadelphia, Pa.) J. Amer*
Oil Chem. Soc. 1972, 49(11), 652-5.
3. C.A., 78. (1973) 31798f Soap-based detergent formulations.
III. Surface activity of fatty derivatives of 3-hydroxy-
propane-sulfonic acid. Parris, N.; Weil, J. K.;
Linfield, W. M. (East Reg. Res. Lab., Agric. Res. Serv.,
Philadelphia, Pa.) J. Amer. Oil Chem. Soc. 1972, 49(11),
649-51.
220
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4. C.A., 22. (1972) 141710H Use of soap in modern detergent
formulations. Noble, W. R.; Bistline, R. G., J.;
' Linfield, W. M. (East Reg. Res. Lab., Agric. Res. Serv.,
Philadelphia, Pa.) Soap, Cosmet., Chem. Spec. 1972, 48(7),
38-42, 62.
5. U.S. Patent 3,660,470 Lime soap dispersants and compositions
containing them. David Graham Spencer Hirst to The Procter
and Gamble Company, May 2, 1972.
Alkylbenzyl di-lower alkylammonio alkane-1 sulfonates.
These are zwitterionic surfactants.
6. C.A., 7£ (1972) 115207J Soap compositions containing alkyl
amino diacetates as lime soap dispersants. Shen, Chung Yu
(Monsanto Co.) U.S. 3,630,927, 28 December 1971, 2 pp.
7. C.A., 2£ (1972) 15990r Soap compositions containing vicinal
hydroxyalkyl maleates. Kidwell, Roger L.; Payne, John H.
(Monsanto Co.) U.S. 3,607,762, 21 September 1971, 3 pp.
167. of the title compound (alkyl=Cig) plus 84% soap
used as lime resistant washing composition.
8. C.A., 77 (1972) 141718s Alkyl vic-hydroxyalkoxy ether
maleate compounds. Kidwell, Roger L. (Monsanto Co.)
U.S. 3,686,282, 22 August 1972, 3 pp.
16% of the title compound (alkyl=Cx6) plus 84% soap
used as lime resistant bar.
9. C.A., 22. (1972) 21998m Detergent compositions comprising
mixtures of surface-active compounds. Bakker, Pieter M.
' (Shell Internationale Research Maatschappij N.V.)
Brit. 1,269,919, 6 April 1972, 5 pp.
Sodium salts of Ci2-20 monocarboxylic acids made by
Reppe carbonylation of olefins. These have high
tolerance.
10. C.A., 72 (1972) 154320f Detergent compositions.
Davies, James Francis; Gauterin, Charles Rowland;
Gilbert, Phillip Alan (Unilever N. V.) Ger. Offen. 2,204,865,
17 August 1972, 25 pp.
20-60% sodium laurate plus 10-50% alkylbenzene sulfonate,
221
-------
E. Representative Carbonate-Silicate Formulations:
1. C.A., 21 (1972) 116391x Phosphate-free detergents.
Benjamin, Lawrence; Saylor, Jay Harold (Procter and Gamble
Company) Ger. Offen. 2,161,699, 29 June 1972, 33 pp.
Fatty alkyl sulfates, alkoxy-and acyloxy- alkane sul-
fonates used with 25% silicate and 25% carbonate.
2. U.S. Patent 3,708,428 Detergent compositions containing
silica colloids. Louis McDonald, January 2, 1973.
3. C.A., 2§ (1973) 45428x Phosphate-free detergent compositions.
Morton, Edgar J.; Donnan, Harold; Weisenfeld, Arnold (Witco
Chemical Corp.) Ger. Offen. 2,218,763, 16 November 1972,
16 pp.
Carbonate-silicate builder.
4. C.A., 2§. (1972) 129210s Phosphate-free detergents.
Cooper, Robert S.; Koschak, Joseph; Wood, Donald C.
(De Soto Inc.) Ger. Offen. 2,124,729, 20 January 1972, 19 pp.
High percentage carbonate-silicate builder.
F. Ion Exchange Resins as Builders:
1. C.A., 21 (1972) 77077c Divinylbenzene copolymer-containing
detergents. Frankenfeld, Klaus; Goetzmann, Karl;
Pietruck, Christel (Chemische Fabrik Budenheim Rudolph A.
Oetker K.-G.) Ger. Offen. 2,055,423, 18 May 1972, 10 pp.
Sulfonated styrene-divinylbenzene, and acrylic acid-
divinyIbenzene.
2. U.S. Patent 3,721,627 Builder for phosphate-free detergent
compositions. James William Adams, Henry Wilbert Hoftiezer
to American Can Company, March 20, 1973.
Insoluble cellulose-polyacrylic graft used in pulp
or powder form.
222
-------
APPENDIX E
CHRONIC AQUATIC TOXICITY TESTS
A Summary of Chronic Test Procedures
and Results for Test Sample 64-1
In order to establish a possible chronic toxicity profile for test
sample 64-1 a number of biological tests were performed. Test sample
64-1 was tested against nine aquatic organisms and in addition histological
studies of effects upon fish gill tissue and upon fish egg viability were
also performed. The test exposure periods varied because of differences
in the nature of the life cycle of the various test organisms. In addition,
although most of the test organisms were exposed to two temperatures and
three test dilution waters, not all the test organisms could be subjected
to the desired temperatures and waters.
Three test dilution waters, a soft, a hard, and a high alkaline
water,were synthesized using typical waters with these characteristics
found in the United States. Two temperatures,18°C and 30°C,were the
test temperatures.
Three test concentrations were incorporated, derived from the acute
tests of 64-1. These concentrations were, the highest concentration
allowing 1005? survival of the most sensitive organism over the 96-hour
test period, a theoretical biologically safe concentration calculated by
dividing the median tolerance concentration by one hundred, and a con-
centration mid-way between the two. The most sensitive test organism was
the blucgili sunfish and the highest concentration allowing complete
survival was 18 ppm. The other two test concentrations were 0.18 ppm
and 8.7 ppm.
In all tests continuous flow techniques were used and the methods
and procedures for the continuous flow procedures were the same as
described in the acute test reports. The crustacean and insect were
not tested acutely and these test procedures are described in this report.
The following chart lists the test organisms, length of exposure to
64-1, test dilution waters and test temperatures incorporated.
1,
Exposure
Test Organism Time
Bluegill sunfish 60 days
Lepomis macrochirus Raf.
Dilution
Water
soft
hard
alkaline
Temp.
18°C
30*C
2. Bullhead catfish 60 days soft 18°C
Amoiurus nobulosus hard 30*C
alkaline
223
-------
3.
4.
5.
6.
7.
8.
9.
Ter.t Organism
Brook trout
Salvclinus, fontinclis
Pond snail
Physa heterostropha Say
Gilled snail
Amnicola limosa Say
Diatom
Navicula seminulum var.
Diatom
Nitzschia pa lea
Crustacean
Daphnia pul sx
Insect mayfly
Isonychia bicolor
Exposure
Time
60 days
60 days
60 days
14 days
hustedtii
14 days
40 days
25 days
Live fish egg studies were performed on the
Dilution
Water
soft
hard
alkaline
soft
hard
alkaline
soft
hard
alkaline
soft
hard : . .
alkaline
soft
hard
alkaline
soft
hard
alkaline
soft
hard
alkaline
flagfish Jordanella
Temp.
18°C
18°C .
30*C
18°C
30°C
18°C
18'C
18°C
30°C
15°
floridae
and histological gill investigations were performed on the bluegill sunfish '
and catfish gills exposed for sixty days to the test material 64-1.
Results
I. Bluegill sunfish, Lepomis macrochirus Raf,.
A. No death at any test concentration over the sixty day test period.
B. No noticeable gross changes in feeding habits, general health or
general behavior during the sixty day test period.
II. Bullhead catfish, Ameiurus nebulosus
A. No death at any test concentration over the sixty day test period.
B. No noticeable gross changes in feeding habits, general health or
general behavior during the sixty day test period.
224
-------
II. Brook trout, Salvelinus font!nails
A. No death at any test concentration over the sixty day test period.
B. No noticeable gross changes in feeding habits, general health or
general behavior during the sixty day test period.
IV. Pond snail, Physa heterostropha Say
A. No death at any test concentration over the sixty day test period.
B. Reproduction proceeded normally and one generation was produced
during the sixty day test period.
V. Gilled snail, Amnicola limosa Say
A. No death at any test concentration over the sixty day test period.
B. No eggs were produced in test concentrations or controls during
the sixty day test period. At the same time eggs were produced
in the Amnicola culture tanks.
VI. The diatom Navicula seminulum var. hustedtii
Test
Concentration
0.18 ppm
,8.7 ppm
18.0 ppm
Control
Alkaline
Test Water
166?o growth
115% growth
120% growth
100J5 growth
Soft
tTest Water
108% growth
137J6 growth
715? growth
100% growth
Hard
Test Water
10455 growth
1325? growth
11695 growth
100J6 growth
VII, The diatom Nitzschia palea
0.18 ppm
8.7 ppm
18.0 ppm
Control
134J5 growth
106% growth
84% growth
10052 growth
144J6 growth
150JS growth
124% .growth
100% growth
168J6 growth
132% growth
165% growth
100$ growth
VIII. Crustacean Daphnla pulex
Ten pregnant females were placed in the continuous flow test chambers
containing the experimental dilutions and control. All tests were done in
duplicate. The number of eggs in each brood pouch were counted and those
not maturing were considered aborts. Young, born and living for 24 hours
were counted and all but ten were removed from the test chambers* these
ten were first generation test organisms. This process was repeated for
three generations over a forty day test period.
Test Cone. Alkaline Test Water
Control 100% survival of all
test organisms with no
aborts through three
generations. A total
of 228 eggs were
produced*
Soft Test Water Hard Test Water
10QSE survival of
all test organisms
with no aborts
through three
generations. A
total of 232 eggs
were produced.
100JS survival of all
test organisms with
no aborts through
three generations.
A total of 244 eggs
were produced.
225
-------
Test Cone.
Alkaline Tost Wnter
Soft Test Water
Hard Test Water
0.18 ppm Same as control.
A total of 243 eggs
were produced.
Same as control.
A total of 251 eggs
were produced.
Same as control.
A total of 229 eggs
were produced.
8.7 ppm 100?5 survival of
original 20 test
organisms, 84 eggs were
produced, 3/5 aborted
and 5% of the young
died. The 20 test
organisms in the first
generation produced 9
eggs and 100JS aborted.
100?o survival of
original 20 test
organisms, 74 eggs
v.-cre produced, 3$
aborted and 5/o of the
young died. The 20
test organisms in the
first generation pro-
duced 10 eggs, and
100J5 aborted.
100JS survival of
original 20 test
organisms, 87 eggs
were produced, 2/6
aborted and 49? of
young died. The 20
test organisms in
the first generation
produced no eggs.
18 ppm
0# survival of original
20 test organisms in
24 hours.
0# survival of
original 20 test
organisms in 4 days.
0% survival of
original 20 test
organisms in 5 days.
Control 100?5 survival of all
test organisms with no
aborts through three
generations. A total
of 243 eggs were pro-
duced.
30°C
100# survival of all
test organisms with no
aborts through three
generations. A total
of 241 eggs were pro-
duced.
10006 survival of all
test organisms with no
aborts through three
generations. A total
of 265 eggs were pro-
duced.
0.18 ppm Same as control. A
total of 267 eggs
were produced.
Same as control. A
total of 278 eggs were
produced.
Same as control. A
total of 249 eggs
were produced.
8.7 ppm 100% survival of
original 20 test
organisms. 96 eggs
were produced, 2#
aborted and 4.7J5 of
the young died. The
20 test organisms in
the first generation
produced 12 eggs and
aborted.
100JS survival of orig-
inal 20 test organisms.
86 eggs were produced
1% aborted and A% of
young died. The 20
test organisms in the
first generation pro-
duced 6 eggs, 100JS
aborted.
1005? survival of
original 20 test
organisms. 98 eggs
were produced, 1%
aborted and 5% of
young died. The 20
test organisms in the
first generation pro-
duced no eggs.
IGppm
05S survival of orig-
inal 20 test organisms
in 24 hours.
053 survival of orig-
inal 20 test organisms
in 5 days.
OJ6 survival of orig-
inal 20 test organisms
in 5 days.
226
-------
IX. Insect I^sonychia bicolor
Ten mature nymphs measuring about 1 to 1.5 cm in length not including
tail were placed in the continuous flow test chambers containing the experi-
mental dilutions and control. All tests wore done in duplicate. The tests
wore allowed to proceed until all nymphs reached the sub imago and adult
stage. Tests were conducted at 15°C. There were no deaths at any test con-
centration or control in any dilution water and all nymphs emerged successfully
after 25 days of exposure.
X. Gill histology,sunfish and catfish
Five fish were sacrificed from each concentration at each temperature in
each dilution water at the end of thirty days exposure and sixty days exposure.
Gill slides were prepared according to techniques as stated in Cairns and
Scheier, 1963. There were no apparent histological effects seen in either
sunfish or catfish gills at concentrations of 0.18 or 8.7 ppm. At 18 ppm
slight "clubbing" and adherence of gill lamellae were observed after 60 days
of exposure in both sunfish and catfish. This effect could also be seen in
the controls but its incidence appeared to be greater at 18 ppm. No epithelial
stripping or capillary rupture was observed.
XI. Survival of Jordanella embryos and fry
Twenty-five, twenty-four hour old Jordanella eggs were placed in test
chambers containing the test dilutions in soft, hard and alkaline water. Each
test was done in triplicate and the test temperature was 30°C. Hatching
occurred between the fourth and fifth day and the fry were observed for twelve
days. The following chart lists average % survival after seventeen days.
Test Water Control 0.18 ppm 8.7 ppm 18 ppm
soft 74.64J6 7256 7856 6256
hard 78.8456 925? 7656 92J6
alkaline 89.3256 -9256 9256 8456
It should be noted that this fish does not naturally occur in soft water,
Summary:
The only profound effects of the test material at the experimental con-
centrations appear to be its stimulatory effect upon diatom growth at all
concentrations and its extremely toxic effect upon Daphnia at the 8.7 ppm
and 18 ppm levels. We are proceeding with high temperature diatom tests
after having received two species of diatoms able to withstand the 30QC test
temperature.
Literature Cited
Cairns, Jr., J, , and Scheier, A. "The Acute and Chronic Effects of Standard
Sodium Alkyl Benzene Sulfonate Upon the Pumpkinseed Sunfish, Lepomis gibbosus
(Linn.) and the Blueglll Sunfish L. macrochirus Raf." Proc. 17th Industrial
Waste Conf. Eng. Ext. Ser. Series~No. 112 Purdue University, 1963.
227
-------
A Summary of Chronic Test Procedures and Results
for Test Sample 86-700 (AATCCWOB)
In order to establish a possible chronic toxicity profile for test
sample 86-700, a number of biological tests were performed. Test sample
86-700 was tested against nine aquatic organisms and in addition histo-
loglcal studies of effects upon fish gill tissue and upon fish egg via-
bility were also performed* The test exposure periods varied because of
differences in the nature of the life cycle of the various test organisms*
In addition, although most of the test organisms were exposed to two
temperatures and throe test dilution waters, not all the test organisms
could be subjected to the desired temperatures and waters.
Three test dilution waters—a soft, a hard, and a high alkaline
water—were synthesized using typical waters with these characteristics
found in the United States. Two temperatures—18°C and 30°C—were the
test temperatures, except for the insect tests which were done at 15°C.
Three test concentrations were incorporated, derived from the acute
tests of 86^-700. These concentrations were (1) the highest concentration
allowing 100K survival of the most sensitive organism over the 96-hour
test period, (2) a theoretical biologically safe concentration calculated
by dividing the median tolerance concentration by one hundred, and (3) a
concentration mid-way between the two. The most sensitive test organism
was the bluegill sunfish and the highest concentration allowing complete
survival was 13.5 ppm. The other two test concentrations were 6.5 ppm
and 0.153 ppm.
In all tests continuous flow techniques were used and the methods and
procedures for the continuous flow procedures were the same as described
in the acute test reports. The crustacean and insect were not tested
acutely, and these test procedures, are described in this report.
The following chart lists the test organisms, length of exposure to
86-700, test dilution waters, and test temperatures.
Test Organism
Exposure
Time
Dilution
Water
Temp,
1. Bluegill sunfish
Lepomis macrochirus Raf.
60 days
soft
hard
alkaline
18°c
30°C
228
-------
Test Organism
Exposure
.- Tiina
Dilution
Water
Temp.
2. Bullhead catfish
Ameiurus nebulosus
60 days
soft
hard
alkaline
180C
30°C
3. Brook trout
Salvelinus fontinelis Mitchell
60 days soft
hard
180C
4. Pond snail
Physa heterostropha Say
60 days soft 18°C
hard 30°C
alkaline •
5. Gilled snail
Amnicgla limosa Say
60 days soft 18°C
hard 30°C
alkaline
6. Diatom 14 days
Navicula seminulum var. hustedtii Patr.
soft
hard
alkaline
18°C
7. Diatom,
Gompho'nema parvulum
14 days
soft
hard
alkaline
18°C -
8. Crustacean
Daphnia pulex
40 days
soft 18°C
hard 30°C
alkaline
9» Insect (mayfly)
Isonychia bicolor
25 days
soft
hard
alkaline
15°C
Histological gill investigations were performed on the bluegill sun-
fish and catfish gills exposed for sixty days to the.test material 86-700.
229
-------
RESULTS
I. Bluegill sunfish, Leponds macrochirus Raf.
A. No death at any test concentration over the sixty-day test period.
B. No noticeable gross changes in feeding habits, general health, or
general behavior during the sixty-day test period.
II. Bullhead catfish, Ameiurus nebulosus
A. No death at any test concentration over the sixty-day test period*
B. No noticeable gross changes in feeding habits, general health, or
general behavior during the sixty-day test period.
III. Brook trout. Salvelinus fontinalis Mitchell
A. No death at any test concentration over the sixty-day test period*
B. No noticeable gross changes in feeding habits, general health, or
general behavior during the sixty-day test period.
IV. Pond snail, Physa heterostropha Say
A. No death at any test concentration over the sixty-day test period*
B. Reproduction proceeded normally, and one generation was produced
during the sixty-day test period.
V. Gilled snail, Amnicola limosa Say
A. No death at any test concentration over the sixty-day test period*
B. Eggs were produced in all test concentrations, but no hatching was
observed.
VI. The diatom Navicula seminulum var. hustedtii Patr.
Test Alkaline Soft Hard
Concentration Test Water Test Water Test Water
0.153 ppm 147.456 growth 105.656 growth 153.656 growth
6.5 ppra 333.356 growth 177.8^ growth 139.356 growth
13.5 ppm 284.456 growth 130.996 growth 139.356 growth
Control 10056 growth 10056 growth 10056 growth
VII. The diatom, Gomphonema parvulum
0.153 170.458 growth 58.556 growth 140.556 growth
6.5 ppm 199.156 growth 72.156 growth 154.556 growth
13.5 ppm 162.156 growth 115.356 growth 140.456 growth
Control 10056 growth 10056 growth 10056 growth
230
-------
VIII. Crustacean, Daphnia pulex
Ten pregnant females were placed in the continuous flow test chambers
containing the experimental dilutions and control. All tests were done in
duplicate* The number of eggs in each brood pouch'were counted and those
not maturing were considered aborts. Young, born and living for 24 hours,
were counted and all but ten were removed from the test chambers. These
ten were first generation test organisms. This process was repeated for
three generations over a forty-day test period.
Control
Alkaline Test Water
100% survival of all
test organisms with
no aborts through 3
generations. Total
of 241 eggs were
produced*
18°C
Soft Test Water
10056 survival of all
test organisms with
no aborts through 3
generations. Total
of 256 eggs were
produced.
Hard Test Water
10056 survival of all
test organisms with
no aborts through 3
generations. Tota1
of 233 eggs were
produced.
0*153 Same as control. A
ppm total of 236 eggs
were produced.
Same as control. A
total of 240 eggs
were produced.
Same as control. A
total of 247 eggs
were produced.
6*5 8056 survival, 1st
ppm generation test or-
ganisms) 94 eggs
produced, 9.556 abort-
ed, 14% young died.
6556 survival, 2nd
generation; 30 eggs
produced, 26.356
aborted, 31.556 young
died. 90% survival,
3rd generation; 27
eggs produced, 35.756
aborted, 50$ young
died.
9096 survival, 1st
generation test or-
ganisms} 86 eggs
produced, 756 abort-
ed, 2056 young died*
8056 survival, 2nd
generation; 29 eggs
produced, 31.256
aborted, 37.556 young
died. 8556 survival,
3rd generation; 22
eggs produced} 50$
aborted, 3056 young
died.
8556 survival, 1st
generation test or-
gan isms > 63 eggs
produced, 4*756 abort-
ed, 17$ young died*
9056 survival, 2nd
generation; 31 eggs
produced, 26.356
aborted, 33.356 young
died. 8555 survival,
3rd generation; 17
eggc produced; 30%
aborted, 5056 young
died.
13.5 OX survival, 1st
ppm generation test or-
ganisms in 10 days.
24 eggs produced,
956 aborted, no
young born.
0$ survival* 1st
generation test or-
ganisms in 6 days.
18 eggs produced,
6.356 aborted, no
young born.
Of survival, 1st
generation test or-
ganisms in 11 days.
23 eggs produced,
7.45? aborted, no
young born.
231
-------
30°C
Alkaline Test Water Soft Test Water
Hard Test Water
Control 1005? survival of all 10056 survival of all 10053 survival of all
test organisms with
no aborts through 3
generations. Total
of 231 eggs were
produced.
test organisms with
no aborts through 3
generations. Total
of 210 eggs were
produced*
test organisms with
no aborts through 3
generations. Total
of 254 eggs were
produced.
0.153 Same as control. A
ppm total of 225 eggs
were produced.
Same as control. A
total of 163 eggs
were produced.
Same as control. A
total of 239 eggs
were produced.
6.5 8556 survival, 1st
ppm generation test or-
ganisms ; 96 eggs
produced, 3.1% abort-
ed, 4.85? young died.
855? survival, 2nd
generation; 34 eggs
produced, Q% abort-
ed, 31.85? young died.
1005? survival, 3rd
generation; 10 eggs
produced, 20?? abort-
ed, 42.95? young died.
8055 survival, 1st
generation test or-
ganisms; 38 eggs
produced, 10.55? abort-
ed, 13.15? young died,
5056 survival, 2nd
generation. No eggs
produced in remain-
ing test organisms
of 2nd generation.
05% survival, 1st
generation test or-
ganisms; 101 eggs
produced, 3.95? abort-
ed, 11.356 young died.
855? survival, 2nd
generation; 21 eggs
produced, 0% abort-
ed, 42.156 young died.
9556 survival, 3rd
generation; 19 eggs
produced, 15.556 abort-
ed, 056 young died.
13.5 056 survival, 1st
ppm generation test or-
ganisms after 9 days,
42 eggs produced,
16.656 aborted, 10056
young died.
0% survival, 1st
generation test or-
ganisms after 7 days,
24 eggs produced,
25% aborted, no
young born.
05? survival, 1st
generation test or-
ganisms after 13 days,
35 eggs produced,
205? aborted, no
young born.
IX. Insect, Isonychia bicolor
Ten mature nymphs measuring about 1 to 1.5 cm in length, not including
tail, were placed in the continuous flow test chambers containing the experi-
mental dilutions and control. All tests were done in duplicate. The tests
were allowed to proceed until all nymphs reached the sub-imago and adult
stage. Tests were conducted at 15°C. There were no deaths at any test
concentration or control in any dilution water and all nymphs emerged
successfully after 25 days of exposure.
232
-------
X. Gill Histology—sunfi?h and catfish
Five fish were sacrificed from each concentration at each temperature
in each dilution water at the end of thirty days' exposure and sixty days'
exposure. Gill slides were prepared according to techniques outlined in
Cairns and Scheier (1963).
Histological effects were seen at all concentrations in all dilution
waters at the two test temperatures. At 30 days small amounts of epithalial
stripping could be detected in both bluegills and catfish in all dilution
waters and temperatures at all three concentrations. The intensity of the
stripping varied directly as the test concentration increased. At 0.153 ppm
approximately one-third of the examined gills showed some epithelial strip-*
ping, while 7558 of the 6*5 ppm gills showed effects* Almost all the 13*5 ppm
gills showed some epithelial stripping after 30 days' exposure. After 00
days1 exposure about 50JS of the 0.153 ppm gills showed effects in all dilu-
tion water and temperatures. Almost all 6.5 ppm and 13*5 ppm gills were
affected after 60 days' exposure.
XI. Survival of Jordanella embryos and fry
Twenty-five 24-hour old Jordanella eggs were placed in te,st chambers
containing the test dilutions in soft, hard, and alkaline water. Each test
was done in triplicate and the test temperature was 30°C. Hatching occurred
between the fourth and fifth day, and the fry were observed for twelve days*
The following chart lists average percent survival after seventeen days.
Test Water Control 0.153 ppm 6,5 ppm 13.5 ppm
Soft 94.558 96.055 80.0* 69.358
Hard 88.058 82.658 86.6? 78.658
Alkaline 92.0% 89.358 76.0$ 81.358
It should be noted that this fish does not naturally occur in soft
water.
233
-------
SUMMARY
The marked effects of this test material appeared to be its stimulatory
effect upon diatom growth at almost all concentrations, its toxic effect
upon Daphnia at the 6.5 ppra and 13.5 ppm level, and histological changes in
gill tissue at all concentrations. All effects were, for the most part,
independent of dilution water or temperature.
LITERATURE CITED
Cairns, J. Jr. and A. Scheier. 1963. The acute and chronic effects of
standard sodium alkyl benzene sulfonate upon the purapkinseed sunfish,
Lepomis gibbosus (Linn.) and the bluegill sunfish L. macrochirus Raf.
Proceedings 17th Industrial Waste Conf, Eng. Ext. Series No. 112,
Purdue University.
234 *US. GOVERNMENT PRINTING OFFICE: 1974 546-316/Z79 1-3
-------
SELECTED WATER
RESOURCES ABSTRACTS
INPUT TRANSACTION FORM EPA-600/2-
4. Title
Accession ffo.
7. .4 uthor(s)
The Development of Phosphate Free Heavy
Duty Detergents
Schwartz, A.M. and Davis, S.E.
9. Or_T,»m nation
Gillette Research Institute
1413 Research Boulevard
Rockville, Maryland 20350
in. Project No.
16080 FWF-
>. Contract/Grant fr;.
14-12-875
and
75. Supplementary Notes
Project Officer: Dr. A. Forziati, OR & D
U.S. EPA, Washington, D.C.
is. Abstract rpft& purpose of tliis project was to demonstrate state-of-the-art
possibilities for producing phosphate-free household laundry deter-
gents of satisfactory environmental and performance characteristics.
The work involved formulation of several hundred experimental deter-
gent compositions using different surfactant-builder combinations.
These were tested for laundering performance, acceptability of physi-
cal form, biodegradability, aquatic toxicity, potential hazard in use,
and growth stimulation of algae. Feasibility of economical production
on an. industrial scale was also considered. Some partially satisfac-
tory formulations were found, and their shortcomings assessed with
regard to performance and/or economic feasibility. These formulations
coincide remarkably with formulations developed independently by
industry. Further work with promising new builders and surfactant-
builder combinations is recommended, but only along environmental and
health hazard lines. This report was submitted in fulfillment of
Project No. 16080 FWE and Contract No. 14-12-875 by Gillette Research
Institute under the sponsorship of the Environmental Protection Agency
Work was completed as of November 30, 1973.
17a. Descriptors
17b. Identifiers
Economic Analysis
Detergents
Surfactants
Toxicity
Phosphate-Free
Water Quality
Soaps
Biodeterioration
Water Pollution
17c. COWRRField & Group 05C/05B
18. Availability
unlimited
Abstractor
Send To:
WATER RESOURCES SCIENTIFIC INFORMATION CENTER
U.S. DEPARTMENT OF THE INTERIOR
WASHINGTON. O. C. 2O24O
In&titutior.
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