EPA-600/R-98-043
April 1998
Low-VOC Coatings Using Reactive Diluents
Demonstration Project
By:
Gregory Roche
Ecotek
330 Main Street, Suite 201
Seal Beach, CA 90740
Subcontractors to:
South Coast Air Quality Management District
Ranji George, Project Manager
Technology Development Office
21865 E. Copley Drive
Diamond Bar, CA 91765
EPA Cooperative Agreement CX819072
EPA Project Officer:
Robert C. McCrillis
National Risk Management Research Laboratory
Air Pollution Prevention and Control Division
Research Triangle Park, NC 27711
Prepared for:
U.S. Environmental Protection Agency
Office of Research and Development
Washington, D.C. 20460
-------
TECHNICAL REPORT DATA ,, i|||i niii i ¦ i ¦ m
(Please read Instructions on the reverse before comp - III llll IIIIIII | III I 1 1 III
1. REPORT NO. 2.
EPA-600/R-98-043
PB98-137383
4. TITLE AND SUBTITLE
Low- VCC Coatings Using Reactive Diluents
Demonstration Project
5 report DATE
April 1998
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Gregory Roche
8. PERFORMING ORGANIZATION REPORT NO.
9, PERFORMING ORGANIZATION NAME ANO ADORESS
Ecotek
330 Main Street, Suite 201
Seal Beach, California 90740
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
CX819072 (South Coast Air
Quality Management Distr.)
12. SPONSORING AGENCY NAME ANO ADORESS
EPA, Office of Research and Development
Air Pollution Prevention and Control Division
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVEREO
Final; 2/94 - 12/96
14. SPONSORING AGENCY CODE
EPA/600/13
IS.SUPPLEMENTARYnotesAPPCD proJ.ect officer is Robert c. McCrillis, Mail Drop 61, 919/
541-2733.
is. abstract Tke report gives results of an investigation of the possibility of replacing
a fraction of conventional solvents with one-third, two-thirds, and fully epoxidized
vegetable oils. Applications investigated were: in an aerosol product, in a 55~gal.
drum refinishing operation, and in a dry film lubricant. For the aerosol, dry time
was too extended. The drum refinisher found that the reformulated coating did not
have sufficient corrosion resistance. The dry lubricant manufacturer could not get
acceptable chemical resistance with the new coating. There may be other, less de-
manding applications where the reformulated, lower volatile organic compound (VOC)
coating would be satisfactory. (NOTE; Reactive diluents are compounds that might be
used to replace organic solvents in conventional high-VOC coatings. Reactive diluents
function like solvents in adjusting coating viscosity for various applications. How-
ever, rather than evaporating like conventional solvents, reactive diluents participate
in a chemical reaction with the coating resin during the curing process, and become
incorporated into the cured coating. Earlier studies had indicated that a natural vege-
table oil derived from the vernonia plant could serve as a reactive diluent, but it is
not grown commercially. Further studies indicated that partially epoxidized soy and
linseed oils could serve as low-cost substitutes for vernonia oil.)
17. KEY WORDS ANO DOCUMENT ANALYSIS
a, descriptors
b. 1DENTIF1ERS/OPEN ENDED TERMS
c, cosati Field/Group
Pollution Coatings
Organic Compounds Aerosols
Volatility Finishing
Diluents Lubricants
Emission
Solvents
Pollution Prevention
Stationary Sources
Volatile Organic Com-
pounds (VOCs)
Dry Lubricants
13 B 11C
07C 07D
20 M 13 H
11G 11H
14G
11K
18. distribution statement
Release to Public
19. SECURITY CLASS (This Report/
Unclassified
21. NO. OF PAGES
166
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
-------
NOTICE
This document has been reviewed in accordance with
U.S. Environmental Protection Agency policy and
approved for publication. Mention of trade names
or commercial products does not constitute endorse-
ment or recommendation for use.
PROTECTED UNDER INTERNATIONAL COPYRIGHT
ALL RIGHTS RESERVED.
NATIONAL TECHNICAL INFORMATION SERVICE
U.S. DEPARTMENT OF COMMERCE
-------
FOREWORD
The U. S. Environmental Protection Agency is charged by Congress with pro-
tecting the Nation's land, air, and water resources. Under a mandate of national
environmental laws, the Agency strives to formulate and implement actions lead-
ing to a compatible balance between human activities and the ability of natural
systems to support and nurture life. To meet this mandate, EPA's research
program is providing data and technical support for solving environmental pro-
blems today and building a science knowledge base necessary to manage our eco-
logical resources wisely, understand how pollutants affect our health, and pre-
vent or reduce environmental risks in the future.
The National Risk Management Research Laboratory is the Agency's center for
investigation of technological and management approaches for reducing risks
from threats to human health and the environment. The focus of the Laboratory's
research program is on methods for the prevention and control of pollution to air,
land, water, and subsurface resources; protection of water quality in public water
systems; remediation of contaminated sites and groundwater; and prevention and
control of indoor air pollution. The goal of this research effort is to catalyze
development and implementation of innovative, cost-effective environmental
technologies; develop scientific and engineering information needed by EPA to
support regulatory and policy decisions; and provide technical support and infor-
mation transfer to ensure effective implementation of environmental regulations
and strategies.
This publication has been produced as part of the Laboratory's strategic long-
term research plan. It is published and made available by EPA's Office of Re-
search and Development to assist the user community and to link researchers
with their clients.
E. Timothy Oppelt, Director
National Risk Management Research Laboratory
EPA REVIEW NOTICE
This report has been peer and administratively reviewed by the U.S. Environmental
Protection Agency, and approved for publication. Mention of trade names or
commercial products does not constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Information
Service, Springfield, Virginia 22161.
-------
Abstract
Reactive diluents are a class of compounds that might be used to replace organic
solvents in conventional high-VOC (volatile organic compound) coatings. Reactive
diluents function like solvents in adjusting coating viscosity for various applications.
However, rather than evaporating like conventional solvents, reactive diluents
participate in a chemical reaction with the coating resin during the curing process, and
become incorporated into the cured coating. Earlier results had indicated that a natural
vegetable oil derived from the vernonia plant would serve as a reactive diluent but, it is
not a commercially grown crop. Further studies indicated that partially epoxidized soy
and linseed oil would serve as low cost substitutes for vemonia oil. This project
investigated the possibility of replacing a fraction of conventional solvents with one-
third, two-thirds, and fully epoxidized vegetable oils. Three applications were
investigated: in an aerosol product, a 55 gallon drum refinishing operation, and in a dry
film lubricant. In the case of the aerosol, dry time was too extended, while the drum
refinisher found that the reformulated coating did not have sufficient corrosion
resistance. The dry lubricant manufacturer could not get acceptable chemical
resistance with the new coating. Further development work would be needed to
achieve success in these applications. There may be other, less demanding
applications where the reformulated, lower VOC coating would be satisfactory.
Page ii
-------
Table of Contents
Page
Abstract ii
Figures iv
Tables iv
Executive Summary 1
Overview 1
Technology Description 1
Results 2
Conclusions 3
Introduction 4
Project Participants 4
Reports & Publications 6
Phase 3 Project Objectives 6
Phase 3 Project Scope 6
Task 1: Laboratory Applied Development 6
Task 2: Laboratory Demonstration Test 7
Task 3: Demonstration Seminar 7
Task 4: Field Test Program 7
Project Background 7
Phase 1 Research Program 10
Phase 2 Research Program 12
Phase 3 Discussion 13
Technical Advisory Committee 13
Commercial Products 13
Task 1: Laboratory Applied Development 15
Alkyd Coatings Study 15
Epoxy Coatings Study 16
Task 2: Laboratory Demonstration Program - Frazee Industries 16
Target Application 17
Coating Type 17
Test Results 17
Task 2: Laboratory Demonstration Program - Seymour of Sycamore 18
Target Application 18
Coating Type 18
Test Results 18
Page ill
-------
Task 2: Laboratory Demonstration Program - Drilube 19
Target Application 19
Coating Type 19
Test Results 19
Change of Direction 20
Glycidyl Ethers Study 20
Task 3: Demonstration Seminar 21
Task 4: Field Tests 21
Summary of Test Results 21
Conclusions 22
Acknowledgment of Support and Disclaimer 23
References 23
Appendix A. Technical Advisory Committee Members A-1
Appendix B. Papers Describing Commercially Available Reactive Diluents B-1
Appendix C. Drilube Company Test Report C-1
Appendix D. Low VOC Coatings Demonstration Project (Ecotek) - Alkyds . D-i
Appendix E. Low VOC Coatings Demonstration Project (Ecotek) - Epoxies E-i
Figures
Figure 1. Project Organization 4
Tables
Table 1. SCAQMD Rules for Coating Operations 8
Table 2. Sample VOC Limits in SCAQMD Rules for Metal Surfaces 9
Table 3. Organizations contacted for TAC Participation 14
Table 4. TAC Meeting Schedule 15
Page iv
-------
Executive Summary
Overview
Coatings and solvents are a significant source of stationary and area volatile organic
compound (VOC) emissions. Rules promulgated by South Coast Air Quality
Management District (SCAQMD) and other agencies have resulted in reduced VOC
content for many coatings. However, significant additional reductions are required to
meet future air quality goals.
In addition, the production phase-out of 1,1,1-trichloroethane due to ozone depletion
concerns has eliminated this chemical solvent as a low-VOC technology for coatings.
The Clean Air Act Amendments of 1990 have also created incentives to reduce the
Hazardous Air Pollutant (HAP) content of coatings and solvents. Many HAP
compounds are also VOC.
This project addressed VOC reductions in coatings for metal substrates. While many
metal coating applicators have converted to low-VOC technologies such as powder and
water-base, many others have not been able to make this conversion because of
performance requirements, technology conversion issues, and cost. A significant and
broad range of metal coating applicators are still in need of low-VOC alternatives.
SCAQMD, EPA, and other interests have sponsored a series of research projects that
investigated vegetable oil based reactive diluents as a means to reduce VOC content in
traditional solvent coatings. The general term "reactive diluents" refers to compounds
that undergo cross-linking type reactions as part of the coating curing process. In this
document, the term "reactive diluents" refers to vegetable oil based reactive diluents
unless otherwise specified. This project, sponsored by SCAQMD and EPA, was the
third and final phase of the research program. A Technical Advisory Committee (TAC)
with representation from coating companies, resin suppliers, applicators, and other
interested parties provided guidance to the project contractors.
Technology Description
Reactive diluents are a class of compounds that might be used to replace solvents in
conventional high-VOC coatings. Reactive diluents function like solvents in adjusting
coating viscosity for various applications. However, rather than evaporating like
conventional solvents, reactive diluents participate in a chemical reaction with the
coating during the curing process. Coatings are extended since the reactive diluent
becomes part of the coating rather than evaporating like solvents.
It appears that reactive diluent coatings could potentially be used by applicators without
major technology conversion issues. This is in contrast to other low-VOC technologies
that can require significant changes to production processes.
In Phase 1, work by the Eastern Michigan University (EMU) Coatings Research Institute
Page 1
-------
(CR1) found that reactive diluents formulated from vernonia oil offered VOC reductions
and some property improvements. Vernonia oil is obtained from a rare plant so that
commercial supplies are not currently available. Further work by CRI in the Phase 2
research program suggested that readily available soybean and linseed oils could be
partially epoxidized to imitate vernonia oil properties. In Phase 3, this project continued
the research and development of partially epoxidized soybean and linseed oils as
reactive diluents. This report focuses on Phase 3 work, but includes brief summaries of
the work completed under the prior two phases.
Results
In Phase 3, the project subcontractor PRA Laboratories performed applied laboratory
development studies {Task 1) to advance the basic academic research performed by
CRI. This work investigated partially epoxidized soybean and linseed oils to formulate
both alkyd and epoxy coatings. The purpose of this effort was to transfer the
technology from the academic research environment to the applied research arena.
Laboratory development and testing was performed on alkyd and epoxy systems.
Pigmented and clear coatings were tested. Testing involved substituting solvents in
standard coating systems. Test variables included the amount of solvent replaced,
types of reactive diluents used, pigment types, and performance additives. Solvent
substitutes were one-third, two-thirds, and fully epoxidized soy and linseed oils. Results
from PRA work indicated that it is feasible to use partially epoxidized vegetable oils as a
reactive diluent in alkyd and epoxy coatings.
Initially five companies, all TAC members, volunteered to participate in Task 2. All five
companies received samples of fully or partially epoxidized linseed or soybean oils. For
various business reasons only three companies actually reported working on the
samples obtained.
A diverse group of products were evaluated in Task 4. One company was very
interested in being able to lower the VOC of aerosol products. Another company was
interested in developing new business in the drum finishing market. The third company
was interested in dry film lubricants. These companies interests represented three
distinct product types. The aerosol product was a quick air dry product. The drum
coating was to be a black, forced air dry alkyd coating. The dry film lubricant was a
baked epoxy coating.
The aerosol manufacturer was unable to obtain an acceptable dry time of the applied
product. After numerous attempts using various drier combinations and seeking help
from drier suppliers, they were not able to obtain an acceptable product.
The company developing a drum enamel was initially encouraged that their work might
lead to a viable product with lower VOC. However, upon further testing it was found
that corrosion resistance was not acceptable and their work was discontinued.
Page 2
-------
The dry film lubricant manufacturer found that the inclusion of the epoxidized oil in
epoxy systems lowered the chemical resistance to an unacceptable level. It was
necessary for them to evaluate exempt solvents. They remain convinced that the basic
concept of a reactive diluent is viable. But, at least for their requirements, epoxidized
vegetable oils are not acceptable.
It appears that competing technologies, for example, exempt solvents, provide a
quicker/better solution at the present level of development. Even the commercially
available reactive diluents are not finding success in the market place.
For differing reasons none of the participating companies was able to develop a
commercially viable product using the epoxidized vegetable oils. While the basic
research and development efforts appear to indicate that this approach to formulating
lower VOC products has merit, in practical product development it has not proven to be
acceptable at this time.
Conclusions
Reactive diluents trade VOC reductions for property changes. In practical formulations,
reactive diluents exhibit increased dry times and reduced hardness. While the
significance of property-changes depends on the specific coating application, these
changes are generally undesirable. Because of these limitations, the commercial
coating companies that participated in this project determined that the technology is not
commercially viable at the present level of development.
Page 3
-------
Introduction
This report documents the work performed by the project contractors for the South
Coast Air Quality Management District (SCAQMD) under Contract S-C94149. Contract
S-C94149 was originally executed by SCAQMD on June 8, 1994, and modified May 31,
1996 (S-C941491), and August 1, 1996 (S-C941492).
The purpose of the project was to develop and demonstrate low-VOC coatings using
reactive diluent technology for metal substrate applications. The project was the final
phase of a three phase research program. Phases 1 and 2 were performed by other
contractors. The project was funded through SCAQMD by a VOC Pollution Prevention
Cooperative Agreement from the U.S. Environmental Protection Agency (EPA).
Project Participants
Project organization is shown in Figure 1.
Figure 1. Project Organization.
Page 4
-------
The project participants include:
U.S. Environmental Protection Agency
Contact: Robert C. McCrillis
Emissions Characterization and Control Branch
Air Pollution Prevention and Control Division
National Risk Management Research Laboratory
Research Triangle Park, NC 27711
919-541 -2733
South Coast Air Quality Management District
Contact: Ranji George, Program Supervisor
21865 East Copley Drive
Diamond Bar, CA 91765
909 - 396 - 3255
Ecotek
Contact: Greg Roche
330 Main Street, Suite 201
Seal Beach, CA 90740
310-626-8200
RAM Consulting
Contact: Bob McNeill
9918 Foster Road
Bellflower, CA 90706
310-866-3968
Pacific Technical Consultants
Contact: John Gordon
25836 Sunrise Way
Loma Linda, CA 92354
909-799-6414
PRA Laboratories, Inc.
Contact: John Massengill
430 West Forest
Ypsilanti, Ml 48197
313-483-3401
An ad hoc Technical Advisory Committee (TAC) was formed to help guide the project.
The TAC was composed of the Project Team and interested parties from coating
manufacturers, end-use applicators, academia, consultants, and other interested
parties. TAC membership varied throughout the project depending on individuals'
interests and availability. The final roster is shown in Appendix A. The TAC met
Page 5
-------
periodically to review the project, provide input, and review results. The TAG also
participated in telephone and mail surveys,
Reports & Publications
The following reports and publications were prepared as part of this Phase 3 project;
• Low VOC Coatings Demonstration Project, prepared by PRA
Laboratories, to report on work conducted under Task 1 for alkyd coatings
(see Appendix D).
• Low VOC Coatings Demonstration Project, prepared by PRA
Laboratories, to report on work conducted under Task 1 for epoxy
coatings (see Appendix E),
• Development and Field Demonstration of Low-VOC Coatings Using
Reactive Diluents, September 1,1995, prepared by Greg Roche of Ecotek
under Task 3 for the SCAQMD Technology Advancement's Contractors
Review Meeting (included in this report).
Phase 3 Project Objectives
This project had the following objectives:
1. Develop low-VOC coatings using reactive diluent technology for metal substrate
applications, building on research performed in Phases 1 and 2.
2. Demonstrate reactive diluent coatings in field application trials.
3. Determine the commercial feasibility of reactive diluent coatings.
4. Determine the regulatory compliance potential of reactive diluent coatings.
Phase 3 Project Scope
The project was designed to be performed in four sequential tasks. Successful
completion of a task would lead to performing the following task. Unsuccessful
completion of a task would require re-evaluation of the following task to make
necessary adjustments.
Task 1: Laboratory Applied Development
This task performed laboratory applied development to advance the basic coatings
research performed by EMU CRI in Phases 1 and 2. This task developed alkyd and
epoxy formulations suitable for transferring to the next project task. PRA Laboratories
performed this work effort at their facilities in Ypsilanti, Michigan. PRA took the work
performed in the CRI Phase 1 and 2 basic research programs, performed additional
Page 6
-------
testing, and refined formulations to produce alkyd and epoxy formulations with
favorable VOC, performance, and cost characteristics.
Task 2: Laboratory Demonstration Test
This task performed laboratory commercial development to advance the coatings
formulated in Task 1, This work was performed on a voluntary basis by commercial
coatings formulators in the TAC. Commercial formulators were requested to participate
so that reactive diluent coatings could be fine-tuned for specific end-user applications.
Task 3: Demonstration Seminar
This task was to conduct one or more technical seminars to secure the participation of
coating applicators in the Task 4 Field Test Program. Coatings produced by the
commercial laboratories in Task 2 were to be presented to facilities interested in
participating in the field testing.
Task 4; Field Test Program
This task was to conduct field testing of coatings in actual manufacturing, industrial, and
commercial applications. The goal of the field demonstration testing was to evaluate
coatings based on realistic conditions experienced in a variety of application processes
and settings.
Project Background
The South Coast Air Basin (Basin) in Southern California is home to over 13 million
people. The Basin spans Orange County and the non-desert portions of Los Angeles,
Riverside, and San Bernardino Counties. Citizens and businesses in the Basin are
chronically exposed to serious air pollution levels of a variety of air contaminants.
Ozone is the most persistent air pollutant, exceeding state and federal health standards
by the widest margins of all criteria pollutants, and has shown the least decrease over
time with the implementation of many regulatory control measures. According to the
1994 Air Quality Management Plan (AQMP), the Basin:
• Has the worst ozone air quality in the nation';
• Is the only area designated by Federal Clean Air Act standards as Extreme
Nonattainment1;
• Exceeded the federal ozone health standard on 96 days in 19932;
• Exceeded the state ozone health standard on 160 days in 19932; and
• Experienced 19 days of Stage I Episodes in 19932.
Ozone is the result of complex chemical reactions that occur when certain compounds
Page 7
-------
are exposed to sunlight. These compounds are believed to be primarily reactive
hydrocarbons (commonly called Volatile Organic Compounds or VOC), and nitrogen
oxides (NOx), Regulatory policies to reduce ozone levels have focused on parallel
efforts to reduce both VOC and NOx. This non-selective strategy seeks to effectively
starve ozone production of both precursors.
SCAQMD implements air pollutant control strategies through rules that are either
general or source-specific. Source-specific rules have been the focus of most recent
efforts to control VOC and NOx. Source-specific rules are designed to achieve the
greatest possible level of control for a specific type of source. The source-specific
approach recognizes that there are significant differences in emission reduction
opportunities between sources. Sub-dividing the emission reduction problem allows for
the development of very specific solutions to the problem. A primary focus of source-
specific measures to control VOC emissions is to limit VOC content of coatings.
SCAQMD source-specific control measures that have been adopted are found in
Regulation XI rules3. The SCAQMD has source-specific rules that regulate virtually
every coating operation in the Basin. These coating rules are listed in Table 1.
Table 1. SCAQMD Rules For Coating Operations
Rule
Coatina Emissions Source
1104
Wood Flat Stock Coating Operations
1106
Marine Coating Operations
1106.1
Pleasure Craft Coating Operations
1107
Coating of Metal Parts and Products
1113
Architectural Coatings
1115
Motor Vehicle Assembly Line Coating Operations
1124
Aerospace Assembly and Component Manufacturing Operations
1125
Metal Container, Closure, and Coil Coating Operations
1126
Magnet Wire Coating Operations
1128
Paper, Fabric, and Film Coating Operations
1129
Aerosol Coatings
1130
Graphic Arts
1130.1
Screen Printing Operations
1136
Wood Products Coatings
1145
Plastic, Rubber, and Glass Coatings
1151
Motor Vehicle and Mobile Equipment Non-Assembly Line Coating Operations
1162
Polyester Resin Operations
1168
Control of VOC Emissions from Adhesive Application
Coating rules require the use of currently available emissions reduction technology,
practices, and procedures. The rules also provide phase-in schedules over varying
periods of time for reduced VOC contents in coatings. These future implementation
Page 8
-------
dates are called technology forcing requirements because the technology required to
achieve the reduction is not available at the time the rule is written. Representative
VOC limits for metal substrates contained in the rules are shown in Table 2.
Table 2. Sample VOC Limits In SCAQMD Rules For Metal Surfaces
Rule Application VOC Limit. Ib/qal
(VOC less water and exempt compounds)
1107 Metal Parts and Products General, Air Dried 2.8
General, Baked 2.3
Others, Air Dried 3.5
Others, Baked 2.3 to 3.5
1113 Architectural Primers, Sealers, Undercoats . . 2.9
Industrial Maintenance 2.8
1124 Aerospace Primer 2.9
Topcoat 3.5
Clear Topcoat 4.3
1125 Metal Container,
3-Piece Can Sheet Basecoat
. ... 1.9
Closure, and Coils
2-Piece Can Exterior Basecoat & Varnish ..
.... 2.1
2-Piece Can Interior Body Spray
.... 3.7
3-Piece Can Interior Body Spray
4.2
New Drum Exterior
. ... 2.8
New Drum Interior
. . . . 3.5
Reconditioned Drum Exterior
. ... 3.5
Reconditioned Drum Interior
. ... 4.2
Coil Coating
. ... 1.7
1126 Magnet Wire
Magnet Wire Coating
. . . 1.67
Studies have estimated that VOC and NOx emissions must be reduced by 80 to 90%
from current levels to meet the federal air quality standards4. Even deeper reductions
would be needed to meet state air quality standards. Easily implemented control
strategies have already been implemented as reflected by SCAQMD rules, but the
magnitude of the problem is still extreme. Clearly, the public policy strategy to achieve
ozone attainment through VOC reductions can only be successful with dramatic
technological improvements.
Success of the SCAQMD relies on the development of low-VOC coatings that have
acceptable cost and performance characteristics compared to current coatings and
coatings used in similar applications outside of the Basin. Coatings with favorable cost
and performance characteristics will be readily accepted by coating applicators, which
will accelerate attainment of SCAQMD goals. Concerns have been raised by industry
Page 9
-------
regarding whether new technology coatings will be available in the time-frame
established by the SCAQMD.
This project addressed VOC reductions for metal substrate coatings. While many metal
coating applicators have converted to low-VOC technologies such as powder and
water-base, many others have not been able to make this conversion because of
performance requirements and cost. A significant and broad range of metal coating
applicators are still in need of low-VOC alternatives.
The SCAQMD Technology Advancement Office (TAO) pursues development of
emissions reduction technologies through various initiatives. For example, TAO has
recently participated in projects ranging from alternate fuels, to electric vehicles, to
biofiltration5. TAO has also been involved with a long-term research program targeted
at reducing VOC content in coatings primarily for wood and metal substrates. The
research program discussed in this report was performed in three phases, of which this
report covers Phase 3. Phases 1 and 2 are summarized below for reference.
Phase 1 Research Program
In February 1989, the SCAQMD Governing Board authorized an agreement with
Eastern Michigan University, Coatings Research Institute (CRI). CRI was contracted to
develop and demonstrate low-VOC coating technologies using vernonia oil as a
substitute reactive diluent in alkyd and epoxy coatings. Phase 1 was funded by
SCAQMD and the Paint Research Association. The objective of the research was to
determine if vernonia oil could be substituted for standard solvents in alkyd and epoxy
coatings so that VOC would be lowered. This technology would create a new
formulation of low VOC. solvent-type coatings that could be easily used by industry with
very little retooling. Phase 1 work is summarized by the following6.
Vernonia oil is extracted from Vernonia Galamensis, which is a rare species of
ironweed grown in some regions of Africa and South America. Vernonia oil is a natural
epoxidized vegetable oil with no VOC and low viscosity. Vernonia oil has an
unsaturated carbon-carbon double bond and an epoxy ring. The oil is a transparent,
homogeneous liquid at room temperature and has excellent solubility in many organic
solvents, diluents, and paints. The viscosity is 300 centipoise (cP) at 50 F and 100 cP
at 85 F.
The unique structure of vernonia oil has suggested that it might be useful in paints and
coatings. Vernonia oil is a naturally occurring part of the seeds of Vernonia
Galamensis, a plant that grows as a weed in parts of Africa. Its unique feature is in the
chemical composition of its triglyceride oil. This interesting oil is a triglyceride of
vernolic acid. This fatty acid is the only one known at this time with a naturally occurring
epoxy group in the molecule. Its structure is the same as that of linoleic acid, but one of
the two double bonds has become an epoxy group. Like all vegetable oils, vernonia oil
is a tryglyceride of this unique acid.
Page 10
-------
Vernolic Acid7
CH3 (CH2)4 CH - CH CH2 CH = CH - (CH2)7COOH
\ /
O
Vernonia Oil:
3 Vernolic Acid + 1 Glycerol = Vernonia Oil + 3 HOH
So the structure of vernonia oil can be represented by:
O
CH3 (CH2)4 CH - CH CH2 CH = CH - (CH2)7 J C - 0 - CH2
\ /
0
o
CHg (CH2)4 CH - CH CH2 CH = CH - (CH2)7 - 0 - 0 - CH
\ /
o
o
CHg (CH2)4 CH - CH CH2 CH = CH - (CH2)7 - C - 0 - CH2
\ /
O
Another feature of vernonia oil is its low viscosity, 300 cP at 50 F, 210 cP at 68 F, and
100 cP at 85 F.
Of course, there are drawbacks:
1. The Vernonia Galamensis plant is very sensitive to climatic conditions. This limits
crop areas and therefore supplies are limited and cost is prohibitively high for
commercial coatings.
2. Only small quantities have been produced. Extraction, processing and refining
have not yet been studied.
Vernonia oil was substituted in clear alkyd coatings, long oil alkyd paint (pigmented
coating), medium oil alkyd paint, and epoxy coatings.
Clear coatings were evaluated by comparing a long oil alkyd to 100% vernonia oil and
the long oil alkyd with 20% vernonia oil. All three coatings were observed to have
Page 11
-------
similar properties so that the researchers concluded that vernonia oil does not
deteriorate the basic properties of the alkyd resin.
Long oil and medium oil alkyd paints had similar results. Using a special drier for the
vernonia oil system, faster dry times were obtained compared to the control. Can
stability was not changed by adding vernonia oil. Vernonia oil was found to improve the
gloss retention as measured by accelerated weathering tests in a QUV cabinet8. VOC
content was reduced due to the substitution of vernonia oil for the traditional VOC
solvent (mineral spirits).
Vernonia oil in epoxy coatings was found to improve fracture toughness and impact
resistance. Vernonia oil also reduced the water absorption.
The conclusion of Phase 1 research was that vernonia oil could be substituted in off-
the-shelf coatings to reduce VOC content without unacceptable changes in properties.
However, vernonia is a pre-commercial crop that was being investigated for a variety of
uses. Vernonia oil itself had little commercial viability at the time since it was only
available in limited research quantities.
Phase 2 Research Program
In August 1992, the SCAQMD Governing Board authorized an agreement for CRI to
develop low-cost vegetable oil substitutes to vernonia oil as reactive diluents. Phase 2
was funded by SCAQMD, Southern California Edison Company, State of Michigan
Research Excellence and Development Fund, and the U. S. Agency for International
Development. Due to the limited availability and high cost of vernonia oil, this project
was to evaluate whether partially epoxidized, commercially available vegetable oils
could be used in place of vernonia oil as reactive diluents. Phase 2 is summarized by
the following9,10,11.
Physical properties of vernonia oil were compared to soybean and linseed oils
subjected to varying degrees of epoxidation. Epoxidation levels were none, one-third,
two-thirds, and fully epoxidized. Testing included infrared spectra comparisons, gel
permeation chromatograms, and viscosity characteristics. Partially epoxidized linseed
and soy oils were found to be similar to vernonia oil.
Partially epoxidized soy and linseed oils were substituted in clear alkyd coatings,
pigmented alkyd coatings, and epoxy coatings.
In clear and pigmented alkyd coatings, the partially epoxidized vegetable oils reduced
VOC, drying time, and application viscosity. Coatings had excellent adhesion, flexibility,
impact resistance, and specular gloss. Can stability was found to be retained.
However, hardness was found to be lowered. The researchers recommended one-third
epoxidized oil as the best for alkyd coatings.
Page 12
-------
In epoxy coatings, the partially epoxidized vegetable oils were found to improve
flexibility, toughness, and impact resistance. Dry time was improved, but tack free time
increased. Force drying was found to cause yellowing. VOC reductions were found to
have no performance advantages over other commercially available reactive diluents.
However, the partially epoxidized vegetable oils cost significantly less than the
commercial diluents.
Phase 2 researchers concluded that the use of partially epoxidized vegetable oils as
reactive diluents in coatings had been shown to be feasible.
Phase 3 Discussion
Technical Advisory Committee
The Technical Advisory Committee (TAC) was formed to help guide the project. The
TAG was an ad hoc organization of individuals serving on a voluntary basis. The TAC
was composed of the Project Team and interested parties from coating manufacturers,
end-use applicators, academia, consultants, and other interested parties. The TAC
served a valuable role in the project through constructive review of project activities,
guidance on product commercial requirements, and as a forum for exchange of ideas.
The TAC was chaired by Mr. David Roller, an active consultant-recruiter to the coatings
industry. Mr. Roller did a commendable job in coordinating TAC activities.
Intensive recruiting efforts were conducted to attract members to the TAC. Some of the
individuals and organizations contacted are shown in Table 3. Since the TAC was an
ad hoc organization of volunteers, TAC membership varied throughout the project
depending on individuals' interests and availability. The final roster is shown in
Appendix A.
Formal TAC meetings were conducted as shown in Table 4. The TAC also participated
in telephone and mail surveys. For example. TAC members were provided a survey so
that they could comment on the proposed work plan of one of the companies
performing coatings formulation work. This enabled the project to collect input from the
TAC without conducting a formal meeting.
A search on Internet found two articles on commercially available reactive diluents,
Dilulin and Tungsolve 2000. These are discussed in more detail later. No other
information was found regarding reactive diluents for coatings. In contrast, there were
thousands of hits for water-based coatings.
Commercial Products
There are currently two commercially available reactive diluents for coatings: Dilulin and
Tungsolve 2000. Copies of the articles regarding these two products are contained in
Appendix B.
Dilulin is manufactured by reacting linseed oil with cyclopentadiene. Tungsolve 2000 is
PclCfG 13
-------
manufactured by esterification of tung oil with methanol.
Table 3. Organizations Contacted For TAG Participation
1 -Day Faint
Ameritone Paint Corporation
Ameron Protective Coatings Division
Apex Drum Company
Billheimer Consulting
Cal-Trans
Cal-Western Paints
Cardinal Industrial Finishes
Coatings Resource Corporation
Consolidated Drum Reconditioning
David Roller, Alpha Consultants
Deft Coatings
DeVoe Coatings
Drilube Company
Dunn Edwards
Eastern Michigan Coatings Research
Institute
Frazee Industries
Kelly Moore Paint Company
MeWhorter Technologies
Metal Finishing Association of California
Rocketdyne
Sinclair Paint
Smiland Paint Company
Southern California Edison
Southern California Paint & Coatings
Assoc.
Surface Protection Industries, Inc.
Seymour of Sycamore
Technical Coatings Company
Trail Chemical Corporation
Varco BJ Drilling Systems
Vista Paint Corporation
MeWhorter Technologies, the manufacturer of Dilulin, has reported that neither of the
two commercial products has been an overwhelming success in the market place.
There is limited usage in specific areas but no industry wide acceptance. It is reported
that work is continuing to improve performance characteristics of dry time and
hardness.
Page 14
-------
Table 4. TAG Meeting Schedule
Date Location Attendees
8/16/94 SCAQMD, Diamond Bar 16
9/15/94 SCE CTACa, Irwindale 14
2/2/95 SCAQMD, Diamond Bar 20
9/7/95 SCAQMD, Diamond Bar 11
a. Southern California Edison, Customer Technology Application Center,
Task 1: Laboratory Applied Development
Note: Task 1 activities were documented in two reports produced by PRA, The reader
is referred to these reports (Appendices D and E) for details on the applied laboratory
development work. The following summarizes Phase 3, Task 1 work.
Both soybean and linseed oils are routinely made in large quantities, fully epoxidized for
commercial use. It was suggested that some quantities of partially epoxidized soybean
and linseed oils could be removed from the reactors for testing alongside the vernonia
oil studies. Soybean and linseed oils at one-third and two-thirds epoxidized were made
available. These were found to be roughly similar, chemically, to vernonia oil, taking
into account the several degrees of epoxidation and were included in the laboratory
evaluation. As a matter of fact, infrared spectra, gel permeation chromatograms,
viscosities, and equivalent epoxy values were nearly identical.
Alkyd Coatings Study
Practical studies of the use of vernonia oil, partially epoxidized linseed oil, and partially
epoxidized soybean oil did show some differences. Drying times were appreciably
increased as compared with vernonia oil, although they were all better than the alkyd
alone. Hardness of the dry films was less than the alkyd alone and about equal to the
vernonia oil blend. Dried films were softer with both of the alkyds in the test, Beckosol
10.060 and Aroplaz 6440 in clear coatings. These trends were noted in the white
pigmented paint. Data from the black pigmented paints are not believed to be reliable
because the black pigment was not dispersed properly.
In response to the question about the lack of driers in earlier reports, PRA in
cooperation with manufacturers of driers, investigated a number of different driers in
several combinations. The results did not indicate any particular best combination
except that aluminum seemed to show some improvements, but this was offset by a
tendency to viscosity problems in quantities over 0.1 % by weight of the binder under
test.
Increasing quantities of vernonia oil, or the one-third epoxidized soybean or linseed oils
gave a reduction in VOC and a speeding of drying in both clear and pigmented
coatings. These, however, cost a reduction in hardness. Both sward and pencil
hardness went down with the reduction of VOC. The gains were less than the cost in
Page 15
-------
decreased film properties would warrant.
Epoxy Coatings Study
Early work indicated that vernonia oil, epoxidized soybean and linseed oils, simply
added to an epoxy coating had the tendency to increase drying time to an undesirable
degree, so attempts were made to develop a procedure whereby this problem could be
overcome. Several "advanced" (i.e., pre-reacted) oils were prepared using selected
epoxy resins commercially available from Dow Chemical Co. and Shell Chemical Co.
Here, again, the modifying oils only lowered VOC when used in quantities so high that
drying speed was extended to an impractical degree. Advancement of the oil/resin
blend was only done with fully epoxidized linseed and vernonia oils. Even so, the
results were disappointing because an increase in VOC was observed in primers made
from them.
Test data were given to the TAC and several suggestions were offered;
1. No test data were presented for partially epoxidized soy and linseed oils in regard to
the preparation of pre-polymers.
2. No dry time studies were made.
3. Different solvents were used in the various samples.
4. No indication was provided on studying varying ratios of catalyst/resin.
5. The formula for the control formulation, EP-O, was not given.
Since there is no record of replies to these questions, it is unclear just what changes in
properties might have been observed. This is probably moot due to other data from
other studies.
One area in which there was at least some success is the use of two-phase epoxy
thermosetting compositions. In these materials the modifying oil is first made into a
prepolymer by treating the oil with 4,4', Diaminodiphenyl Methane (DDM) to the point of
gellation. The pre-polymer is blended with epoxy resin, and the mixture is cured by
baking. At an epoxidized oil content of about 30% by weight, the oil in pre-polymer
form, causes a phase inversion with the gelled oil droplets, at 0.5 to 2.5pm, forming the
inner phase surrounded by cured epoxy resin. Two-thirds epoxidation seemed to be
the optimum starting point for the oil with regard to the improvement in physico-
mechanical properties of the cured coating. Curing, however, requires a fairly long
baking schedule, 4 hours at 75 C plus 2 hours at 150 C. This coupled with the extended
time to make the necessary pre-polymer at 120 C to 180 C for from 12 to 60 hours
would seem to limit this technology to highly specialized coating uses. None of this
work has any relation to either reactive diluents or air drying architectural or industrial
maintenance coatings. Nor does this lead to an actual reduction in VOC, except in the
special uses for which it might be used.
Task 2: Laboratory Demonstration Program - Frazee Industries
Page 16
-------
Target Application
Frazee Industries worked on developing a coating for the exterior of reconditioned
drums. The field test applicator was Apex Drum Company, one of the members of the
TAC. Coating requirements include 25 to 30 minute dry times, chemical and rust
resistance, acceptable gloss and hiding qualities, airless application, 6 mil wet film
thickness, and competitive cost. The coating is applied directly to the reconditioned
drum surface without a primer.
Coating Type
Frazee selected 30% epoxidized soybean oil as the reactive diluent for an alkyd resin
system. Coating color was black. The coating was formulated with 8% to 30% by
volume reactive diluent.
Test Results
The reactive diluent coating was compared against the standard solvent coating used
by Apex Drum as the control. Tests included:
• Corrosion resistance up to 200 hours in salt fog chamber
• Hardness
• Sagging
• Dry Time
Panels and preliminary results were presented at the September 7, 1995 TAC meeting.
Reactive diluent levels above 8% (9:1 dilution factor) had dry times longer than the
control (the current production coating). Formulation at 8% had equivalent dry times
and hardness to the control. The quality of the black coating was judged by the TAC to
be very good, in fact better than the control. Other types of testing such as corrosion
resistance had not yet been done. VOC levels of the diluent formulations compared to
the control and rule limit were:
VOC, g/l VOC, lb/gal
Rule 1125 Limit 420 3.50
Currently Used Coating 420 3.50
0% Diluent 341 2.84
8% Diluent Formulation 323 2.69
30% Diluent Formulation 308 2.57
Frazee decided to use a formulation with 7% reactive diluent for more rigorous testing.
They found that the reactive diluent product did not perform acceptably since corrosion
resistance was reduced. Frazee observed that at lower dilution rates, the properties
would be expected to improve, but the VOC would increase such that there would be
minimal benefits to using the reactive diluent. Frazee also noted that the resin system
selected for the reactive diluent coating was significantly more expensive than the resin
Page 17
-------
system in the current coating. Frazee concluded that the combination of slow dry time,
decreased corrosion resistance, and higher cost were prohibitive barriers to the use of
the partially epoxidized vegetable oils in their commercial products. Frazee did not
provide a formal write-up of their test program or test results.
Task 2; Laboratory Demonstration Program - Seymour of Sycamore
Target Application
Seymour of Sycamore is a manufacturer of aerosol paints, in which the paint at low
viscosity, under pressure, is sprayed onto a surface. This ordinarily requires a high
VOC content, so aerosol paint manufacturers are being pressed to lower VOC content.
Therefore, the possibility of lowering the VOC without changing the non-volatile of the
paint was of sufficient interest for them to devote laboratory time to the study of the use
of partially epoxidized vegetable oils. Seymour of Sycamore made arrangements with
City of Los Angeles maintenance personnel for field testing.
Coating Type
Resin replacement levels were set at 10%, 20%, and 30% by weight of the coating
resin. Two colors, white and black, were chosen because they are currently formulated
to meet VOC regulations in the San Francisco Bay Area and the January 1996
California State regulations. This test program was to determine if VOC levels could be
lowered even further.
Test Results
Properties that are important to Seymour of Sycamore are:
• Viscosity
• Dry Time
• Hardness
• Adhesion
• Impact Resistance (Direct and Reverse)
• Gloss
• Salt Fog Resistance
• Accelerated (QUV) Weathering
Additionally, the system must be compatible with the pressurizing system, a blend of
propane and isobutane. VOC levels are calculated from the formulas and by analysis
using Bay Area SCAQMD (BAAQMD) Method 35.
It was planned that successful formulas would be made up in small commercial batches
for field testing in both the Bay Area and South Coast Air Basin.
Early testing of laboratory produced paints indicated that:
Page 18
-------
1. Viscosities were not affected at any level of substitution,
2. Dry times at 20% and 30% were not acceptable. Dry times of the 10% substitution
samples were slow, but acceptable.
3. VOC was reduced as substitution was increased, but only the 10% sample could
be evaluated. In the 10% substitution sample, VOC was reduced from 63.59% to
60.59% by weight.
4. Gloss loss, after 144 hours of QUV, showed more loss with the 10% sample than with
the control.
5. An extensive study of drier combinations was made in cooperation with
manufactures of metallic driers, but it was not possible to improve the drying time to
a rate acceptable to Seymour's customers.
In spite of a real need to find a reactive, non-VOC diluent to use to reduce VOC in
spray paints, the extensive testing of a large number of formulations failed to produce
acceptable results. The main problem was an increase in drying time. Even an
extensive series of formulations, made in cooperation with manufacturers of paint
driers, failed to overcome this very important shortcoming. The results were most
disappointing, but our final conclusion is that the use of partially epoxidized soybean oil
is not practical in aerosol paints. Seymour of Sycamore has no further work planned in
this area.
Task 2: Laboratory Demonstration Program - Drifube
Target Application
Drilube Corporation formulates dry film lubricants for the aerospace industry. This and
other industries are being required to use products with lower VOC in all aspects of
their operations. The dry lubricants that this industry uses are manufactured to comply
with the requirements of Federal Military Specifications. These specifications will
shortly require a significant lowering of VOC. To meet this technology forcing
requirement, some companies are looking to water reducible products. Drilube believes
that the nature of the substrates used in the aerospace industry will not allow the use of
water due to immediate or delayed reaction weakening the substrate.
Coating Type
Initial efforts were aimed at modifying Molybdenum disulfide epoxy dry film lubricants.
These lubricants must withstand temperatures of 400 F and 24 hours immersion in
various solvents.
Test Results
Page 19
-------
initial efforts consisted of using one-third epoxidized and fully epoxidized linseed oil
produced films that cured when baked. Tests showed that the cured films did not
withstand the 24 hour immersion tests.
Change of Direction
In January 1996, after evaluating the epoxidized linseed oil, Drilube conducted an
extensive literature search to determine what has been done using reactive diluents in
epoxy coatings. Also studied were various other chemical reactions that might possibly
provide the type of reactions that would lead to viable films that could withstand the
tests required for dry film lubricants. This resulted in several laboratory attempts to
develop improved products. Some appeared to be interesting but none were
completely satisfactory. Exempt solvents were a possibility that had to be considered.
An evaluation of exempt solvents quickly appeared to be the best direction for
additional studies.
Glycidyl Ethers Study
Drilube performed basic principal studies and literature reviews to identify other types of
reactive diluent materials that may be useful in coatings they formulate. This research
identified glycidyl ethers of aliphatic or aromatic molecules as potentially viable
systems. Drilube's report of these formulation and test efforts is included in Appendix
C. This work is summarized below.
Butyl glycidyl ether was chosen to formulate in a black gloss coating using an epoxy
ester resin system. Exempt solvents including acetone, Oxysol 100
(parachlorobenzotrifluoride or PCBTF), and a methylated siloxane were used in the
formulation. A number of catalysts and cross-linkers were investigated and tested.
Coatings were sprayed on low carbon steel panels. Panels were allowed to air dry for
15 to 60 minutes. Two of the coatings reached a tack free state after the short air dry
time. Panels were then placed in an oven to force dry at 175 F to 180 F for one hour.
All coatings were tack free after the force dry, and a through cure was reached for the
same two coatings that were tack free after air dry. The third coating did not through
cure after the force dry. Additional curing at 300 F for 2 hours completely through cured
all of the coatings.
The two panels that were tack free after the air dry were coated with a formulation
utilizing 12-15% by weight reactive diluent, compounded with normal driers, and
sprayed on electrocleaned or lightly sandblasted panels. This resulted in a highly
glossy black coating, which passed the methyl ethyl ketone rub test, the 3M #250 tape
test, and the bend test (through 3/8" radius).
Drilube concluded that: "The preliminary success of this investigation provides full
indication that a stable, durable, and fairly well cured coating can be had from ordinary,
commercially available materials."
Page 20
-------
Task 3: Demonstration Seminar
This task was to conduct one or more technical seminars to secure the participation of
coating applicators in the Task 4 Field Test Program. Coatings produced by the
commercial laboratories in Task 2 were to be presented to facilities interested in
participating in the field testing.
Based on guidance provided by the TAG, the commercial coating companies that
worked on Task 2 actually selected field application sites prior to formulating coatings.
The TAC felt that early selection of applicators would improve the chances for success
since lab work would focus on a specific application, rather than more general research.
The TAC also felt that coating companies would be better positioned to locate field test
sites since these sites could be drawn from their customer base. TAC meetings then
essentially became the demonstration seminar.
Task 4: Field Tests
This task was to conduct field testing of coatings in actual manufacturing, industrial, and
commercial applications. The goal of the field demonstration testing was to evaluate
coatings based on realistic conditions experienced in a variety of application processes
and settings. Conducting Task 4 was contingent on successfully developing viable
coatings in Task 2, and locating test sites. While test sites could be located, it was the
opinion of the coating companies that coatings formulated in Task 2 were not viable for
field demonstration testing.
Summary of Test Results
Initially five companies, all TAC members, volunteered to participate in Task 2. All five
companies received samples of fully or partially epoxidized linseed or soybean oils. For
various business reasons only three companies actually reported working on the
samples obtained.
A diverse group of products were evaluated. One company was very interested in
being able to lower the VOC of aerosol products. One company was interested in
developing new business in the drum finishing market. The third company was
interested in dry film lubricants. These companies' interests represented three distinct
product types. The aerosol product was a quick air dry product. The drum coating was
to be a black forced air dry alkyd coating. The dry film lubricant was a baked epoxy
coating.
The aerosol manufacturer was unable to obtain an acceptable dry time of the applied
product. After numerous attempts using various drier combinations and seeking heip
from drier suppliers they were not able to obtain an acceptable product.
The company developing a drum enamel was initially encouraged that their work might
lead to a viable product with lower VOC. However, upon further testing it was found
Page 21
-------
that corrosion resistance was not acceptable and their work was discontinued.
The dry film lubricant manufacturer found that the inclusion of the epoxidized oil in
epoxy systems lowered the chemical resistance to an unacceptable level. It was
necessary for them to evaluate exempt solvents. They remain convinced that the basic
concept of a reactive diluent is viable. At least for their requirements, they concluded
that epoxidized vegetable oils are not acceptable.
It appears that competing technologies, for example, exempt solvents, provide a
quicker/better solution at the present level of development. Even the commercially
available reactive diluents are not finding success in the market place.
For differing reasons, none of the participating companies were able to develop a
commercially viable product using epoxidized vegetable oils. While the basic research
and development efforts appear to indicate that this approach to formulating lower VOC
products has merit, in practical product development it has not proven to be acceptable
at this time.
Conclusions
After a considerable amount of laboratory work by Coatings Research Institute (CRI),
Paint Research Associates (PRA), and volunteers from industry with several actual
plant trials, the following general conclusions have been reached:
1. Vernonia oil is interesting, but the probability of availability of commercial quantities
of the oil at an acceptable price is very remote at the present time.
2. The use of partially epoxidized, commercially available soybean and linseed oils
as reactive diluents in paints was studied as a substitute for vernonia oil in a
continuing search for ways to reduce VOC in coatings.
2.1. It appears that one-third and two-thirds epoxidized linseed and soybean
oils bracket the viscosity and epoxy content of vernonia oil, when these
were compared with vernonia oil in extensive tests. Comparison of the
viscosities and epoxide content of soybean and linseed oils at one-third,
two-thirds, and full epoxidation indicate that an optimum level of
epoxidation of one-half in either oil would most nearly duplicate vernonia
oil, but data from the use of the one-third and two-thirds epoxidation can
be used to evaluate the usefulness of these oils as replacements for
scarce, expensive vernonia oil.
2.2. Testing was done, first on a laboratory scale, then by an applications
laboratory, and finally in several actual commercial applications.
3. The general conclusion from inspection of the data developed in the applications
PciCfQ 22
-------
laboratory and, especially in the commercial tests, does not indicate that any of
the oils have outstanding desirable characteristics,
3.1. Almost all applications and commercial results show a reduction in speed
of drying and the hardness of the dried films. The most disappointing
general result from these tests is that to gain VOC reductions, it is
necessary to give up so much in drying speed and hardness that the use
of vernonia oil or any of the epoxidized linseed and soybean oiis is not
practical.
4. The study of vernonia oil and partially epoxidized soybean and linseed oils, for
use as reactive diluents in architectural and industrial maintenance coatings did
not produce encouraging results.
Acknowledgment of Support and Disclaimer
This report was prepared as a result of work sponsored by the South Coast Air Quality
Management District (SCAQMD) and the U.S. Environmental Protection Agency. The
opinions, findings, conclusions, and recommendations are those of the author and do
not necessarily represent the views of the sponsors. The SCAQMD, its officers,
employees, contractors, and subcontractors make no warranty, expressed or implied,
and assume no legal liability for the information in this report, the SCAQMD has not
approved or disapproved this report, nor has the SCAQMD passed upon the accuracy
or adequacy of the information contained herein.
References
1. 1994 Air Quality Management Plan, SCAQMD, September 1994, p. ES-4.
2. 1994 Air Quality Management Plan, SCAQMD, September 1994, p. 2-1 0.
3. Rules and Regulations of the SCAQMD. Regulation XI.
4. 1994 Air Quality Management Plan, SCAQMD, September 1994, p. 1-3.
5. South Coast Air Quality Management District, Proceedings of the 3rd Annual
Technology Advancement Contractor Review Meeting, September 26 - 27,1995.
6. Dirlikov, S., Frischinger, M.S. Islam, and Lepkowski, T.J., in C.G. Gebelein (ed.),
Polymers from Biotechnology. Plenum, New York, 1990, p. 79.
7. Muturi, Patrick, Danqing, Wang, and Dirlikov Stoil, "Epoxidized Vegetable Oils as
Reactive Diluents I. Comparison of Vernonia, Epoxidized Soybean, and
Epoxidized Linseed Oils," in Progress in Organic Coatings. No. 25,1994, pg. 85-
94.
Page 23
-------
8. D4587-86, "Standard Practice for Conducting Tests on Paint and Related Coatings
and Materials Using a Fluorescent UV - Condensation Light - and Water-Exposure
Apparatus," American Society for Testing and Materials, 1916 Race St.,
Philadelphia, PA.
9. Development of Low Cost Substitutes for Vernonia Oil as Reactive Diluents with
Alkyd and Epoxy Coatings, Phase 2 Final Report, submitted by the Coatings
Research Institute, Eastern Michigan University to South Coast Air Quality
Management District(SCAQMD) under SCAQMD contract SSE93110.
10. Badou, Ignace and Dirlikov, S., "Low VOC Fast Air-Drying Alkyd Coatings. II.
Aliylic Reactive Diluents," in Polymer Material Science Engineering. 70, 1994, pg.
334-335.
11. Kuo, Chang-Pei, Chen, Zhao, Nirali, Lathia, and Dirlikov, Stoil, "Low-VOC Alkyd
Coatings Using (Meth)acrylate Reactive Diluents." American Paint and Coatings
Journal, August 15, 1994.
Page 24
-------
Low-VOC Coatings Using Reactive Diluents
Final Report
Appendix A
Technical Advisory Committee Members
Page A-l
-------
SCAQMD Low-VOC Coatings Demonstration Project
Technical Advisory Committee (TAC) Roster
September 28,1996
1. Company: Alpha Consultants
Name: David Roller Title: Consultant
Address: 1333 North Hills Drive, Upland, CA 91784-1719
Telephone: (909) 982-7225 Fax: (909) 985-2365
Project Relationship: TAC Chair
2. Company: Ameritone Paint Corp.
Name: Jack Espelage Title: President
Address: 18414 S. Santa Fe Ave., Long Beach, CA 90801
Telephone: (800) 669 - 6791 Fax:
Project Relationship: Coating Manufacturer
3. Company: Ameron Protective Coatings Division
Name: Ray Foscante Title: Vice President, General Manager
Address: 201 N. Berry Street, Brea, CA 92622-1020
Telephone: (800) 926-3766 Fax: (714) 671-5931
Project Relationship: Coating Manufacturer
4. Company: Ameron Protective Coatings Division
Name: Ida Lin Title: Senior Chemist
Address: 201 N. Berry Street, Brea, CA 92622-1020
Telephone: (714) 529 -1951 Fax: (714) 990 - 0437
Project Relationship: Coating Manufacturer
5. Company: Apex Drum Co.
Name: Jerry Flom Title: Authorized Representative
Address: 6226 Ferguson Drive, Commerce, CA 90022
Telephone: (213) 721-8994 Fax: (213) 721-1096
Project Relationship: Coating Applicator
6. Company: Cardinal Industrial Finishes
Name: Robert Sypowicz Title: Vice President Research & Development
Address: 1329 Potrero Ave, South El Monte, CA 91733
Telephone: (800) 696-5244 Fax: (818)444-0382
Project Relationship: Coating Manufacturer
7. Company: Coatings Resource Corp.
Name: Ed Laird Title: CEO
Address: 15541 Commerce Lane, Huntington Beach, CA 92649
Telephone: (714) 894-5252 Fax: (714)893-2322
Project Relationship: Coating Manufacturer
8. Company: Coatings Resource Corp.
Name: Tom Murphy Title: Chief Chemist
Address: 15541 Commerce Lane, Huntington Beach, CA 92649
Telephone: (714) 894-5252 Fax: (714)893-2322
Project Relationship: Coating Manufacturer
9. Company: Consolidated Drum Reconditioning Co.
Name: Calvin Lee Title:
Address: 1051 Union Street, Montebello, CA 90640
Telephone: (213) 887-6131 Fax: (213) 887-6526
Project Relationship: Coating Applicator
Page A-2
-------
SCAQMD Low-VOC Coatings Demonstration Project
Technical Advisory Committee (TAC) Roster
September 28,1996
10. Company: Drilube Company
Name: Mike Moone Title: Technical Director
Address: 711 W. Broadway, Glendale, CA 91204
Telephone: (818) 240 - 8144 Fax: (818)244-0846
Project Relationship: Coating Manufacturer
11. Company: Ecotek
Name: Greg Roche Title: Principal
Address: 5855 Naples Plaza, Suite 311, Long Beach, CA 90803
Telephone: (310) 433 - 3663 Fax: (310) 434 - 7193
Project Relationship: Contractor
12. Company: Frazee
Name: Marty Balow Title: VP/Technical Director
Address: 6625 Mira Mar Road, San Diego, CA 92121
Telephone: (619) 552-3261 Fax: (619)452-2897
Project Relationship: Coating Manufacturer
13. Company: Pacific Technical Consultants
Name: John Gordon Title: Consultant
Address: 25836 Sunrise Way, Loma Linda, CA 92354
Telephone: (909) 799 - 6414 Fax:
Project Relationship: Contractor
14. Company: RAM Consulting
Name: Robert McNeill Title: Consultant
Address: 9918 Foster Road, Bellflower, CA 90706
Telephone: (310) 866 - 3968 Fax:
Project Relationship: Contractor
15. Company: SCAQMD
Name: Ranji George Title: Program Supervisor, TAO
Address: 21865 E. Copley Drive, Diamond Bar, CA 91765
Telephone: (909) 396 - 3255 Fax: (909) 396 - 3252
Project Relationship: Sponsor
16. Company: Sinclair Paint
Name: Sam Bellettiere Title: Technical Director
Address: 6100 S. Garfield, Los Angeles, CA 90040
Telephone: (213) 888-8888 x8407 Fax: (213) 888-6842
Project Relationship: Coating Manufacturer
17. Company: Southern California Edison
Name: Bill La Marr Title; Program Manager
Address: 300 N. Lone Hill Ave., San Dimas, CA 91773
Telephone: (909) 394-8859 Fax: (909) 394-8922
Project Relationship: Supporter
18. Company: Technical Coatings Co.
Name: Donald Maki Title: General Manager
Address: 1000 Walsh Ave., Santa Clara, CA 95050-7410
Telephone: (408) 727-3400 Fax: (408) 727-0720
Project Relationship: Coating Manufacturer
Page A-3
-------
SCAQMD Low-VOC Coatings Demonstration Project
Technical Advisory Committee (TAG) Roster
September 28,1996
19. Company: U.S. Environmental Protection Agency
Name: Robert McCrillis Title: Project Manager
Address: 86 TW Alexander Drive MD-61, Research Triangle Park, NC 27711
Telephone: (919) 541 - 2733 Fax: (919) 541 - 2157
Project Relationship: Sponsor
20. Company: McWhorter
Name: Robert Stoner Title: Technical Director
Address: 2801 Lynwood Road, Lynwood, CA 90262
Telephone: (800) 552-0637 Fax: (310)604-0381
Project Relationship: Resin Manufacturer
21. Company: Seymour of Sycamore
Name: Robert Martin Title: Director of Research
Address: 917 Crosby Ave., Sycamore, IL 60178
Telephone: (815)895-9101 Fax: (815)895-8475
Project Relationship: Coating Manufacturer
22. Company: Sinclair Paint
Name: Arthur Lorenz Title: Chemist
Address: 6100 S. Garfield, Los Angeles, CA 90040
Telephone: (213) 888-8888 X8396 Fax: (213) 888-6842
Project Relationship: Coating Manufacturer
23. Company: Eastern Michigan University CRI
Name: John Massingill Title: Executive Director
Address: 430 W Forest, Ypsilanti, Ml 48197
Telephone: (313) 487 - 2203 Fax:
Project Relationship:
24. Company: Frazee
Name: Fernando Pedroza Title: Technical Service Manager
Address: 6625 Miramar Road, San Diego, CA 92121
Telephone: (619)276-9500x473 Fax: (619)452-2897
Project Relationship: Coating Manufacturer
25. Company: Biliheimer Consulting
Name: John Biliheimer Title: Consultant
Address: 1332 Tiger Tail Drive, Riveside, CA 92506
Telephone: (909)750-1159 Fax: (909)750-1159
Project Relationship:
26. Company: Vista Paint Company
Name: Scott Washburn Title: EH&S Director
Address: 2020 E Orangethorpe Ave, Fullerton, CA 92631
Telephone: (714) 680-3800 Fax: (714) 447-9540
Project Relationship:
Page A-4
-------
Low- VOC Coatings Using Reactive Diluents
Final Report
Appendix B
Papers Describing Commercially Available Reactive Diluents
Page B-l
-------
Factsheet 10: Tung Oil: New Uses a... Compliance for the Paint Industry
http://www.ilsr.org/ carbo/ps/facLsh 10.htm 1
Tung Oil: New Uses and Its Role in Regulatory Compliance for the
( Paint Industry
Tung oil, a vegetable oil derived from the fruit of the tung tree, has long been recognized as a high quality
natural oil for use in paints and surface coatings. During the 1940s, '50s and '60s it also represented an important
crop in the southern United States. Industrial Oil Products (Woodbury, NY) is a major importer and distributor
of vegetable oils for industrial uses. Industrial Oil Products is promoting the use of chemicals derived from
renewable agricultural materials with the introduction of TUNGSOLV 2000™. This tung oil derived product
allows the formulation of paints, coatings and printing inks with reduced solvent content
Many solvents create emissions of volatile organic compounds (VOCs), which contribute to the formation of
smog and can represent a health hazard. The EPA is currently proposing regulations to reduce the VOC content
of paints and coatings. At the same time, consumers are becoming more aware of environmental issues, and are
seeking alternative products which are more environmentally friendly and make use of renewable resources.
TUNGSOLV 2000™ allows manufacturers to formulate products which will satisfy environmental regulations
and public concern about the environment. At the same time, Industrial Oil Products' president, Blake Hanson,
is working to revive American tung oil production through the efforts of the American Tung Oil Corporation.
Tung oil is a valuable vegetable oil for paints, inks and coatings. Its penetration of porous surfaces such as wood
and paper is superior to many vegetable and petrochemical oils, making it a useful component of paints,
varnishes and inks. The chemical .properties of tung oil also make it highly suitable for coatings applications.
Tung oil is made up of compounds which have a high number of chemically reactive sites. Each of these
reactive sites is a point where chemical bonds can be formed. This bonding, called cross-linking, allows tung oil
to form durable, plastic-like films with a natural resistance to abrasion, chemicals and microorganisms such as
bacteria and fungus. Because of the viscosity, or "thickness" of tung oil is lower than the viscosity of coatings
resins, it can be used in the place of the petrochemical solvents that are usually used to thin coatings. Since it
, "dries" through chemical bonding instead of drying by evaporation, it does not contribute to
( /OCsJU-
Despite tung oil's potential as a component of paints and coatings, certain properties limit its use as a method of
reducing YOG content. While tung oil can replace some of the petrochemical solvents used to thin paints and
coatings, its viscosity is not low enough for it to serve as a major component in many coatings formulations.
Because of this, unmodified tung oil is not a sufficient solvent substitute to achieve the degree of VOC
reduction that will be necessary when more stringent VOC regulations go into effect.
The TUNGSOLV 2000™ product is a chemical modification of tung oil which allows a higher degree of
solvent replacement. Tung oil is reacted with methanol in a process called esterification. This process splits tung
oil into three separate molecules. The size of each molecule is reduced to one third the size of the original tung
oil molecule. Chemicals composed of smaller molecules tend to have lower viscosities than compounds
composed of larger molecules. Consequently, reducing the size of the tung oil molecule results in a reduction of
tung oil's viscosity. This, in combination with tung oil's natural film forming properties, make TUNGSOLV
2000™ a valuable material for solvent replacement.
The primary drawback of TUNGSOLV 2000™ is its tendency to increase the drying time for coatings
formulations. When replacing ten per cent or less of resins (by weight), the increase in dry time is slight, and
does not present a serious functional problem. At higher concentrations of 10 to 40 per cent, drying times for
coatings formulated with TUNGSOLV 2000™ are two to three times longer than drying times for conventional
coatings. Although this represents a functional limitation of TUNGSOLV 2000™, in many architectural
coatings applications these drying times are acceptable. To allow better VOC reduction in a wider variety of
applications, research is being conducted to determine an optimal blend of driers (chemicals used to accelerate
the drying of a coating) for use with TUNGSOLV 2000™ {21. This will allow higher concentrations of
^ TUNGSOLV 2000™ to be used in coatings formulations without loss of performance.
TUNGSOLV 2000™can substitute for up to forty per cent of alkyd (oil based), urethane, and acrylic resins (by
1 of 3
Page B-2
8/31/96 11:01 PM
-------
Factsheet 10: Tung Oil: New Uses a... Compliance for the Paint Industry
http://wwwJlsr.org/carbo/ps/factshlO.html
weight) in paints and varnishes. Experiments have shown that TUNGSOLV 2000™ simultaneously reduces the
VOC content and the viscosity of coatings formulations. Depending on the level of TUNGSOLV 2000™ used,
i 'he viscosity of resin mixtures was reduced by 56 to 98 per cent of the original resin viscosity. At the same time,
the VOC content of the resin formulation was reduced by 22 to 42 per cent [3J-
The value of TUNGSOLV 2000™ as a tool to reduce VOC content in coatings is being demonstrated in
products developed by the Graphic Arts Laboratory Company (Cincinnati, OH). This company has developed
varnishes with applications in printing. The use of TUNGSOLV 2000™ has allowed the formulation of
varnishes with VOC content reduced from 45 per cent to as low as five per cent and in some cases has allowed
the manufacture of varnishes that are essentially VOC free. By lowering the viscosity of coatings formulations,
TUNGSOLV 2000™Ereduces solvent use. Because it cures completely into the dried coating, it also replaces
resins. At $1.15 to 1.31 per pound, TUNGSOLV 2000™ is higher in cost than petrochemical solvents at $0.15
to 0.55 per pound, but its cost is comparable to conventional alkyd and urethane resins at $1.00 to 2.00/lb.
Overall, the formulations developed by the Graphic Arts Laboratories showed a 20 to 33 per cent increase in
cost per pound £4], Because of this, the use of TUNGSOLV 2000™ is most likely to be driven by more
stringent VOC regulations.
Expanding the uses of tung oil has economic as well as environmental benefits. At one time the tung oil was an
important agricultural commodity in the south central and south east United States. During the 1960's,
overproduction and increasing competition from foreign sources of tung oil lowered the price of tung oil, which
put a strain on farmers. Hurricane Camille, which destroyed 40,000 acres of tung orchards in 1969, dealt the
final blow to the struggling industry £5}. Recently, fluctuations in tung oil prices led Industrial Oil Products to
explore the possibility of reviving tung oil production in the United States. The American Tung Oil Corporation
was formed for this purpose. Currently, 1000 acres of tung trees have been planted in Mississippi. The
American Tung Oil Corporation plans to plant 4000 more acres within the next three years. Tung orchards are
environmentally beneficial, as tung trees have a natural resistance to disease and pests and so can be grown with
fewer chemicals. The orchards also provide habitat for wildlife, and protect the environment by eliminating
:rosion £6],
1. Hanson, Blake, "Tung Oil," Kerley News, Summer 1993, p. 2.
2. Product information provided by Industrial Oil Products and Dr. Shelby Thames.
3. Experimental data provided by D/L Laboratories. ^
4. Information provided by Graphic Aits Laboratory Company.
5. Young, Linda, "Tung Nuts Could Bring $20 Million to Stone County", Mississippi Business Journal, 14:45, December 21,1992.
6 .Information provided by Blake Hanson, American Tung Oil Corporation.
Blake Hanson, president of Industrial Oil Products, presented information on the industrial uses of tung oil at
the conference, "Industrial Uses of Biochemicals: Strategies for a Cleaner Future," held on November 29,1995.
This conference was sponsored by the Institute for Local Self-Reliance. Fact sheets 8 through 11 of the
Pollution Solutions series focus on presentations from this conference.
Factsheet Links
FS-ll FS-21 FS-31 FS-41 FS-51 FS-61 FS-71 FS-81 FS-91 FS-101 FS-111FS-121 FS-131 FS-141 FS-151 FS-161 FS-171
FS-181 FS-191 FS-201
POLLUTION SOLUTIONS is a series of fact sheets about pollution prevention strategies with biochemical
substitutes prepared by the Institute for Local Self-Reliance (ILSR). If you would like more information,
contact:
Tonathan Hamlow. Research Assistant
v David C. Pettiiohn. P.E. Senior Project Engineer
Tel: (612) 379-3815 FAX: (612) 379-3920
2 of 3
Page B-3
8/31/96 11:01 PM
-------
Factsheet 3: Biochemical Substitutions in the Paint Industry
http://www.ilsr.org/carbo/ps/factsh03.html
Biochemical Substitutions in the Paint Industry
The manufacture of paint and coatings produced over 92 million pounds of toxic chemical releases and transfers
in the Great Lakes basin during 1992. Analysis of EPA's Toxic Chemical Release Inventory (TRI) data shows
that in the paint industry, most pollution from the manufacture of paint consists of chemicals such as xylene,
toluene, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and acetone, which are used as solvents
f 11. In paint formulations, solvents provide the necessary viscosity that allows paint to be applied as a liquid.
Solvents from paint can be released to the environment from spills, as a component of paint which is discarded,
and through evaporation during the manufacturing process. Solvents are also used for the cleaning of
manufacturing equipment, which is estimated to generate more than 40 percent of waste from the manufacture
of paint [2]. After paint is applied, these solvents evaporate from the paint film, and can pose a health hazard as
well as contributing to low level ozone production and the formation of smog.
Biochemicals For Manufacturing Equipment Cleaning
The cleaning of paint manufacturing equipment is frequently carried out with toxic solvents such as MEK,
MIBK, xylene and toluene £3]. The substitution of biochemicals for these solvents produces a less toxic waste
stream.
Inland Technologies (Tacoma, WA) specializes in formulating alternative cleaning solvents tailored to meet the
cleaning needs of their clients. Many of their solvents are based on the terpene d-limonene, a powerful natural
solvent derived from the peels of citrus fruits. One such solvent, EP 921 (patent pending), is formulated to
replace MEK, MIBK and lacquer thinners for cleaning applications. EP 921 has low volatility, which reduces
fugitive emissions from cleaning processes. It contains no chemicals that are listed on the EPA 313 Toxic
Release Inventory or as Hazardous Air Pollutants (HAPs). In addition, EP 921 has extremely high solvency,
dramatically reducing the solvent waste stream for cleaning applications. One manufacturer replaced MEK with
EP 921 and reduced the volume of their solvent waste stream by 95%. This company estimated that it would
generate $9600 in savings annually from reductions in waste generation and solvent consumption [41.
Purae America (Lincolnshire, IL) manufactures the Purasolv® line of solvents. These solvents are esters of
lactic acid, which is produced by the fermentation of sugar. A variety of coatings resins, such as acrylics,
epoxics, polyesters, alkyds, nitrocellulose, and polyvinyl acetate are soluble in Purasolv solvents. Purac states
that its lactate ester solvents are low in toxicity and biodegradable, and are not listed on the EPA section 313
Toxic Release Inventory or as HAPs. Lactate ester solvents have low vapor pressure and high solvency, and so
reduce VOCs in both cleaning and formulation applications. Furthermore, these solvents are easily recycled
through distillation F51.
Biochemicals for the Formulation of High Solids Coatings
Solvent use can be reduced directly by the formulation of high solids coatings, which have reduced solvent
content. Biochemicals called diluents, which reduce the viscosity of coatings formulations, can be used to
formulate high solids coatings without a loss in performance.
Cargiil (Minneapolis, MN) manufactures the reactive diluent Dilulin™, which is derived from linseed oil. This
diluent reduces die viscosity of alkyd and urethane coatings formulations, allowing decreased solvent use. The
diluent cures into the coating, and consequently does not contribute to VOCs. It is not a HAP, and is not listed
on the EPA section 313 Toxic Release inventory. Coatings formulated with Dilulin™ have performance
comparable to conventional high solvent content formulations, with better drying times and hardness and
without the yellowing associated with coatings reformulated with linseed oil alone. Dilulin™ is compatible
with oil modified urethanes, long, medium and short oil alkyds, and other copolymer alkyds [6]. At
S0.95-S1.05/lb, its cost compares favorably to conventional alkyd and urethane resins which cost $1.00-2.00/lb.
industrial Oil Products (Woodbury, NY) produce Tungsolve 2000™, a methyl ester derivative of tung oil.
Tungsolve 2000™ acts as a solvent replacement in coatings containing oil modified resins such as alkyds and
urethanes. This reactive diluent reacts completely into the finished formulation, significantly reducing VOCs in
i of 3
Page B-4
8/31/96 10:58 PM
-------
Factsheet 3: Biochemical Substitutions in the Paint Industry
http://www.ilsr.org/carbo/ps/factsh03.html
coatings formulations. Tungsolve 2000™ contains no chemicals listed on the EPA Toxic Release Inventory or
as a HAP. At $1.15-1.31/lb, it is comparable in cost to conventional alkyd and urethane resin costs at
Sl.00-2.00/lb. In partnership with the American Tung Oil Corporation, Industrial Oil Products is working to
revive the production of tung oil in America to insure a reliable domestic supply of this versatile natural oil f71.
Water Based Coatings
There is a significant trend in the paints and coatings industry towards water based coatings. Water is the most
inexpensive and environmentally safe solvent available for the formulations of coatings, but traditionally it has
been ineffective for many varieties of coatings resins, and water based paints have tended towards poor
adhesion and durability [8]. Advances in technology are overcoming these limitations.
McWhorter Technologies (Minneapolis, MN) produces alkyd resins for water based coatings. Alkyd resins,
which are frequently derived from vegetable oils such as soy, linseed, and sunflower, are among the safest
available chemicals, but traditionally tend towards high solvent content in coatings formulations 191.
McWhorter manufactures water based alkyd resin dispersions that reduce solvent use by 50-80 percent and
reduce VOC emissions by a comparable amount while achieving performance equal to conventional solvent
based alkyd formulations f 101. These resins are not listed on the EPA Toxic Release Inventory or as HAPs.
Priced at about $2.60/lb, these resins cost about $ 1.30/lb more than conventional resins. However, these
biobased resins greatly reduce solvent requirements by replacing petrochemical solvents with water.
Conventional solvent based formulations require 2-3 pounds of petrochemical solvents per pound of resin. The
replacement of 2-3 pounds of solvents at $0.30-0.60/lb represents a savings of $0.60-1.80. Hence the use of
these alternative resin dispersions can save up to $0.50 per pound of resin used.
Powder Coatings
Powder coatings are applied in powder form, completely eliminating the use of solvents. Powder coatings have
high potential for eliminating solvent use and VOCs, although the high temperatures required to cure these
coatings, around 250-450 degrees Celsius, limit their use primarily to coatings for metals fill.
Elf Atochem manufactures Rilsan®, a nylon 11 resin used in metal coating applications. Nylon 11 is not listed
on the EPA Toxic Release Inventory or as a HAP. Rilsan® produces coatings with exceptional chemical and
mechanical resistance. While nylon 11 resins are relatively expensive at $4.94-$7.94/lb, tfibir markets are
growing because of their low melting point of 186 degrees Celsius (compared to greater than 200 degrees
Celsius for many resins) and superior abrasion, impact, and chemical resistance. The fact that nylon 11 resins do
not require the additional curing step required by most powder coating resins further improves the economics of
production by reducing processing time 1121.
1. U.S. EPA , 1992 Toxic Chemical Release Inventory : SIC 2851.
2. U.S. EPA, Guides to Pollution Prevention; The Paint Manufacturing Industry, EPA/625/7-90/005, Washington, DC, June
1990.
3. Ibid.
4. Product information supplied by Eric Lethe, Inland Technology Inc, Tacoma, WA.
5. Product information supplied by John Ketelaar, Purac America, Lincolnshire, EL.
6. Product information supplied by Bill Reutz, Cargill Industrial Oils Division, Minneapolis, MN.
7. Product information supplied by Blake Hanson, Industrial Oil Products, Woodbury, NY.
8. Triplet!, Tim, "Waterbomes make a splash," Industrial Paint & Powder, v. 71, January, 1995.
9. Triplett, Tim, "Resin manufacturers struggling for answers,"Industrial Paint & Powder, v. 70, November, 1994.
10. Product information supplied by Rich Johnson, McWhorter Technologies, Minneapolis, MN.
11. Ouellette, Jennifer, "Powder Coatings," Chemical Marketing Reporter, v. 246, October 10,1994.
12. Product information supplied by Craig Schmehl, Elf Atochem North America Inc, Philadelphia, PA.
Factsheet Links
ESzI! FS^j FMI EH) FSrSj FMI FS£7| EMI EMI EMffl EMU E5i!2j EH21 FS44| FS4J EMS ISbH]
FS-I8! FS-191 FS-201
Page B-5
2 of 3 8/31/96 10:58 PM
-------
Factsheet 9: Linseed Oil: New Uses... Compliance for the Paint Industry
http://www.ilsr.org/carbo/ps/factsh09.htnil
Linseed Oil: New Uses and Its Role in Regulatory Compliance for the
Paint Industry
Paints and coatings are composed of resins, pigments, various additives, and solvents. Solvents are necessary to
make coatings fluid enough to be applied, but represent an environmental concern. Most petrochemical solvents
are volatile organic compounds (VOCs) which can have an impact on air quality. Once released into the
atmosphere, VOCs can react with sunlight and contribute to the formation of ground level ozone, which in turn
contributes to the formation of smog.
Because of these effects, there have been increasing trends to reduce the solvent content of paints and coatings
through regulations. California led the way in legislation to curtail air pollution with Rule 66, which was
intended to control emissions of VOCs £0. In 1990, amendments to the Clean Air Act mandated that the EPA
study the effects of VOC emissions from consumer products and create regulations to control these emissions.
This paved the way for the development of national standards for the VOC content of consumer products such
as paints and coatings. Currently, the EPA has proposed limits for VOC content in paints and coatings to be put
into effect in 1996, with further reductions in allowable VOC content to be introduced in the year 2000 £2}. At
the same time, the National Paint and Coatings Association has developed model guidelines for VOC limits.
The reduction in VOC content suggested in these proposed regulations varies significantly based on the type of
coating. For most coatings, both proposed guidelines call for reductions in solvent use of twenty to twenty five
per cent. The EPA and representatives of the paints and coatings industry are still engaged in debate over the
specifics of VOC regulations. Despite this, the general consensus in industry is that national guidelines for VOC
content in paints and coatings are necessary.
In architectural coatings (coatings used for the maintenance of structures such as buildings and bridges), water
based coatings (i.e. latex) have replaced solvent based coatings in many applications, particularly in interior and
exterior house paints. Nevertheless, solvent based coatings will retain a major market in architectural coatings
because of functional benefits, such as superior wood penetration, adhesion, durability, and appearance. As a
result, methods of reducing solvent content in coatings formulations while maintaining functional properties are
important areas of research.
One way to lower solvent content in coatings is to use a reactive diluent. A diluent acts asJxrth a solvent and a
resin in a coatings formulation. As a solvent, it reduces the viscosity of the coatings formulation, allowing the
coating to be applied by traditional methods such as brushing, rolling or spraying. But instead of evaporating
out of the coatings formulation, the diluent dries through a chemical reaction with air called oxidation, and
becomes part of the paint film.
Linseed oil has recently been used as a diluent in paints and coatings. Linseed oil is a drying oil, a vegetable oil
which undergoes oxidation and forms a natural, plastic-like film. The reactivity of linseed oil can be improved
by the addition of metal catalysts, called driers, which promote oxidation, and by partially pre-oxidizing the
linseed oil through exposure to air. The use of linseed oil in this capacity is limited. Linseed oil has a
comparatively slow curing rate, and has a tendency to soften paint films. As a diluent it cannot reduce VOC
levels to the degree required by proposed VOC regulations while still providing the desired film properties for
many applications £3}. Dilulin™, a new linseed oil based reactive diluent manufactured by Cargill
(Minneapolis, MN), overcomes these problems.
Dilulin™ is manufactured by reacting linseed oil with a chemical called cyclopentadiene. This makes the
linseed oil more chemically reactive. Consequently, Dilulin™ undergoes chemical reactions with air more
quickly, which reduces drying times. Because it forms more chemical bonds, the films that Dilulin™ forms are
more durable than films formed by plain linseed oil. Dilulin™ also reduces the formation of compounds which
cause discoloration. Dilulin™ is compatible with resins such as alkyds and urethanes. This diluent can be used
to replace 10 to 40 per cent of the resin, by weight. The specific level of usage is determined by the functional
properties and VOC reduction required Jfcfl. Experimental formulations of 40% Dilulin™ with conventional oil
modified urethane resins showed that the addition of the diluent resulted in a reduction in viscosity and a
reduction in VOC content from 405 g/L to 310 g/L £5]. These experimental, results confirm that this diluent can
1 of 3
Page B-6
8/31/96 10:57 PM
-------
Factsheet 9: Linseed Oil: New Uses... Compliance for the Paint Industry
http://www.ilsr.oig/carbo/ps/factsh09.htinl
effectively reduce viscosity in coatings formulations while simultaneously diminishing VOC content.
Several factors must be taken into consideration in evaluating the performance of Dilulin™ in coatings
formulations. Because of the much higher solids content of coatings formulated with Dilulin™, the thickness of
the final paint film will be greater than that of a conventional coatings formulation. This has both positive and
negative effects on coating performance. The greater film thickness will give coatings formulated with
Dilulin™ better coverage and reduce the number of coats needed. However, the greater film thickness will also
extend drying times. Urethane coatings formulated with 40% Dilulin™ had drying times of around 3 hours, as
compared to less than one hour for a conventional urethane formulation. Nevertheless, drying times for coatings
formulated with Dilulin™ are acceptable for architectural applications £6]. In other functional properties, such
as the hardness of the dry film and yellowing, coatings formulated with Dilulin™ exhibit properties equal to
conventional formulations.
The economics of formulating low VOC coatings with Dilulin™ will vary considerably, depending on cost of
the resin and solvent used, as well as the degree of solvent replacement which is required by the manufacturer.
The cost of Dilulin™, $0.95-1.05 per pound, is high compared to the solvents it replaces, which cost
SO. 15-0.55Ab. The cost of Dilulin™ compares favorably to resins used in formulations: conventional alkyd and
urethane resins cost $1.00 to 2.00 per pound. Like a resin, Dilulin™ contributes to the dry paint film. The
economics of a particular coatings formulation depends on the degree of solvent displacement and the diluent's
contribution to the dry paint film. Overall, these factors translate to roughly a three to eight per cent increase in
cost per gallon [7]. The fact that coatings formulated with Dilulin™ will yield thicker paint films, resulting in
better coverage, improves the economics of using Dilulin™. It may be necessary to educate consumers, who
tend to judge coating costs in terms of volume rather than coverage, about this benefit. Currently, there is not a
strong consumer market for low VOC coatings, indicating a low level of consumer awareness of VOC issues.
Consequently, it is likely that more stringent, national VOC regulations will be necessary as an incentive for
manufacturers to adopt the use of Dilulin™.
1. Holmberg, Krister, High Solids Alkyd Resins, Marcel Dekker, New York, NY, 1987.
2. Blackburn, Lane, "VOC Regulations Change Paint Industry", Architectural Record, September 1995, p. 42.
3. op. cit. Holmberg, 1987.
4. Kodali, Dharma R., Cargill Central Research, "A New Reactive Diluent With Excellent Functional Properties to Reduce Volatile
Organic Compounds (VOC) in Solvent Borne Paints and Coatings," Paper presented at Western Coating Societies' 22nd Biennial
Symposium, San Francisco, CA February 20-22,1995.
5. Product information supplied by Cargill Inc.
6. op. cit. Kodali, 1995.
7. Product information supplied by Cargill Inc.
Bill Reutz, Department Manager of Cargill's Technical Oils Department, presented information on Cargill's
linseed oil based reactive diluent at the conference, "Industrial Uses of Biochemicals: Strategics for a Cleaner
Future," held on November 29, 1995. This conference was sponsored by the Institute for Local Self-Reliance.
Fact sheets 8 through 11 of the Pollution Solutions series focus on presentations from this conference.
Factsheet Links
FS-lt FS-21 FS-31FS-41 FS-51 FS-61 FS-71 FS-81 FS-91 FS-101 FS-111 FS-121 FS-131 FS-141 FS-151 FS-161 FS-171
FS-181 FS-191 FS-201
POLLUTION SOLUTIONS is a series of fact sheets about pollution prevention strategies with biochemical
substitutes prepared by the Institute for Local Self-Reliance (ILSR). If you would like more information,
contact:
Jonathan Hamlow. Research Assistant
David C, Pettiiohn. P.E. Senior Project Engineer
Page B-7
2 of 3 8/31/96 10:57 PM
-------
Low-VOC Coatings Using Reactive Diluents
Final Report
Appendix C
Drilube Company Test Report
Page C-J
-------
DRILUBE
Drilube Company
7U WEST BROADWAY
OLENDALE.CA 91204
(818) 240-8141
FAX (818) 244-084(5
TO: ECOTEK- ATTN5 Greg soacb
FROM; Michael A. Moone, DRILUBE Technical Director
RE; BLACK GLOSS COATING. PROJECT REPORT
DATE; 27AUG1996 FAX
FAX: 310-626-8203
We have been charged with the formulation and testing of a BLACK GLOSS -
coating for metals, utilizing a REACTIVE DILUENT, combined with an EPOXY
ESTER RESIN in a LOW V.O.C. SOLVENT system, producing a SINGLE
PACKAGE, SPRAY APPLICATION coating, with FORCE DRY CURING.
The REACTIVE DILUENT systems investigated and tested were the Shell Heloxy
Modifiers that consist of "Giycidyl Ethers" of either aliphatic or aromatic
molecules. The ultimate choice was Butyl Giycidyl Ether.
Several EPOXY ESTER RESIN systems were investigated and tested. Technical
information was available for both Jones-Dabney and Reichold products. The
(Jones-Dabney) EPI-REZ brand was selected, and was obtained through the
ACCUREZ Company (Ohio).
The LOW V.O.C. SOLVENT system selected consisted of an admixture of
existing exempted solvents; Acetone, OXSOL 100 (PCBTF), and one of the
currently available methylated siloxanes.
A number of catalysts and cross-linkers were investigated and tested. The
chemicals ultimately selected consisted of Cobalt + Manganese + Zirconium
Driers, Rare Earth Driers, and Benzyl Dimethyl Amine.
The black pigment utilized was a standard lampblack identified as Hills
Polytrend. This pigment was supplied in (what proved to be) a compatible
reactive polyester resin system.
No special effort or extra-ordinary care was taken in the intermixing of these
materials. Weighing was affected utilizing an ordinary commercial kilogram
scale accurate to 0,Q2Kg. Mixing was completed by hand stirring using an
ordinary wooden painter's stick. Each of the raw materials was added directly
Cone after the other) to a 1-gal. paint tins that was zero-tared after each
addition. The tops were affixed to the tins, which were then allowed to set
under ordinary storage conditions for a 24-hour period prior to applications.
Page C-2
-------
None of the products required "shaking", and the painter simply mixed the
contents of each tin by hand for a short period of time prior to spraying.
Ordinary low Carbon Steel (1010 or 4230) panels (4" x 6") were utilized for
spraying applications. All of the panels were solvent vapour degreased to
remove surface dirt and greases. One set of panels was used In that state.
The other three sets of panels were pretreated prior to the spray application: 1.
Heavy-duty Steel periodic reverse electroclean; 2. 120 grit sandblast; 3.
Manganese Phosphate coating.
The actual temperature range of curing was determined by finding the Technical
Definition of "Force Dry Curing" in the literature. After all of the coatings
tested were permitted to "flash" for a period of time ranging from 15 minutes
to one hour, the coating? were placed into a laboratory oven and maintained at
175° - 180°F. for one hour.
Due to the nature of the non-volatile components (every one of which, except
the Lampblack in the pigment, is in a liquid state), none of the coatings
formulated reached a "tack-free" state, however, several formulations were
noted to reach a "cotton" state after 1/2 hour.
The preliminary success of this investigation provides full indication that a
stable, durable and fairly well cured coating can be had from ordinary,
commercially available materials.
1. The formulation utilizing 12-15% w/w reactive diluent, compounded with
the normal driers, and sprayed on either the electrocleafied or lightly
sandblasted panels, yielded a highly glossy black coating, which passes
the Methyl Ethyl Ketone "Rub Test", the 3M #250 "Tape Test", and the
"Bend Test" (through a 3/8" radius).
2. The rare earth driers yield a coating that appears to be more readily
affected in the MEK Rub test, but Is otherwise identical to #1.
3. None of the several other formulations utilizing different "catalysts" or
curing agents appeared to "cure" properly, all of them remained "sticky",
were rapidly attacked in the MEK Rub test, and failed the Tape test.
4. None of the coatings applied adhered to the un-oreoared panels.
This indicates that the base metal must be fairly clean, somewhat coarse
or roughened, and free of surface dirt and oils, etc.
5. Although the phosphated panels were less glossy, they did provide a
much better surface for the coatings capable of bonding to the panels.
NOTE: All materials cured completely at 300" F. for 2 hours; additional
compounding efforts and shelf life tests need to be conducted on products.
Page C-3
-------
Appendix D
LOW VOC COATINGS
DEMONSTRATION PROJECT
CECOTEK)
ALKYDS
PROJECT CODE 1-104
¦«¦¦¦¦¦ I ¦
IIIRR ¦¦ ¦ ¦ »
!¦¦¦¦¦¦¦ ¦ i ,
¦ ¦¦¦¦¦¦¦¦ ma
¦¦¦¦¦¦¦¦ ¦¦
<¦¦¦¦¦¦¦¦¦¦¦¦¦¦*
!.¦¦¦¦¦¦¦¦¦¦¦ ¦¦ ¦ I
!*¦¦¦¦¦¦
a m ¦¦¦¦¦¦ *r
PRA
LABORATORIES, INC.
BY:
1GNACE BADOU
PRA LABORATORIES, INC.
430 West forest avenue
YPSILANTI, MICHIGAN 4&197
PHONE#: St3-468-8401
FAX#: 313-468-0065
[)-i
-------
Table of Contents
List of Figures D-iii
List of Tables .......... D-iv
1. Summary D-1
2. Raw Materials Used D-2
3. Sample Preparation and Application D-3
4. Results and Discussion D-4
4.1 White Paints D-4
4.2 Black Paints D-32
4.3 Red Oxide Primers D-55
5. Conclusions D-57
6. Suggestions for Future Work D-58
7. Detailed Recipes for Air Dry White Coatings D-59
8. Detailed Recipes for Air Dry Black Coatings D-82
9. Detailed Recipes for Air Dry Red Oxide Primers D-94
Page D-ii
-------
Figures
Air Dry White Enamels for Industrial Maintenance
Figure LI: Drying Time - Through Dry . D-10
Figure 1.2: Drying Time - Tack Free D-l 1
Figure 1.3: Dry to Touch Time D-l2
Figure 1.4: Drying Time - Set to Touch D-l3
Figure 1.5: VOC D-16
Figure 1.6: Hardness - Sward Hardness D-l8
Figure 1.7: Hardness - Pencil Hardness D-l9
Figure 1.8: Adhesion D-21
Figure 1.9: Impact Resistance - Direct Impact D-23
Figure 1.10: Impact Resistance - Reverse Impact D-24
Figure 1.11: Gloss - 20° : D-26
Figure 1.12: Gloss - 60° D-27
Figure 1.13: Solvent Resistance D-29
Air Dry Black for Industrial Maintenance
Figure 2.1: Drying Time - Set to Touch D-36
Figure 2.2: Drying Time - Dry to Touch D 37
Figure 2.3: Drying Time - Tack Free D-38
Figure 2.4: Drying Time - Through Dry D-39
Figure 2.5: VOC D-40
Figure 2.6: Hardness - Sward Hardness D-43
Figure 2.1: Hardness - Pencil Hardness D-44
Figure 2.8: Adhesion D-46
Figure 2.9: Impact Resistance - Direct Impact D-48
Figure 2.10: Impact Resistance - Reverse Impact D-49
Figure 2.11: Gloss - 20° D-50
Figure 2.12: Gloss - 60° D-51
Figure 2.13: Solvent Resistance D-53
Page D-iii
-------
Tables
White Paints:
Table 1.1: Drying Time - Set to Touch D-8
Table 1,2; Drying Time - Dry to Touch D-8
Table 1.3: Drying Time - Tack Free D-9
Table 1.4; Drying Time - Through Dry ... D-9
Table 1.5: VOC D-15
Table 1.6: Sward Hardness D-17
Table 1.7: Pencil Hardness D-17
Table 1.8: Adhesion D-20
Table 1.9: Direct Impact Resistance D-22
Table 1.10: Reverse Impact Resistance D-22
Table 1.11: Gloss - 20760° D-25
Table 1.12: MEK-Resistance D-28
Table 1.13: Salt Fog Exposure D-28
Table 1.14: Humidity Resistance D-30
Table 1.15: Gloss - 60° D-31
Black Paints;
Table 2.1: Drying Time - Set to Touch D-34
Table 2.2: Drying Time - Dry to Touch D-34
Table 2-3: Drying Time - Tack Free D-34
Table 2-4: Drying Time - Through Dry D-35
Table 2-5: VOC D-35
Table 2-6: Sward Hardness D-42
Table 2-7: Pencil Hardness D-42
Table 2-8: Adhesion D 45
Table 2.9: Direct Impact D-45
Table 2.10: Reverse Impact D-47
Table 2.11: Gloss-20760° D-47
Table 2.12: MEK-Resistance D-52
Table 2.13: Salt Fog Exposure D-52
Table 2.14: Humidity Resistance D-54
Table 2.15: Gloss 60° D-54
Red Primers:
Table 3.1: Drying Times , . . D-55
Table 3.2: Dry Film Properties D-56
Page D-iv
-------
LOW VOC COATINGS DEMONSTRATION PROJECT (ECOTEK)
Project Code #: 1043
Final Report
1. Summary:
White and black paints based on several alkyds with different drying properties and solid content
between 70% and 75% were prepared and evaluated. Dicyclopentadiene linseed (DCPD-linseed)
and 1/3 epoxidized soybean oil were used in concentrations of 20% and 30% as reactive diluents.
VOC values of 2.71b/gal (325g/l) to 31b/gal (360g/l) were obtained when 30% of the alkyd solids
weight was replaced by DCPD-linseed oil; 2.61b/gal (310g/l) to 3lb/gal (360g/l) when 20% of 1/3
epoxidized soybean oil were used and 2.4lb/gal (285g/l) to 2.71b/gal (325g/l) when 30% 1/3
epoxidized soybean oil were added. VOC of the straight alkyd formulations were between 3lb/gal
(360g/l) and 3.91b/gal (470g/l). Set to touch and dry to touch were as short as 3 minutes and as
long as 60 minutes. Tack free times were between 10 and 90 minutes and through dry times
varied between 1/2 and 8 hours. Drying time increased when reactive diluent was added. The type
and the level of the diluent affected the drying time. The longest drying times were obtained when
30% of 1/3 epoxidized soybean oil was introduced into the paint compositions. Evaluation of dry
film properties for sward and pencil hardness, adhesion, impact resistance and flexibility indicated
a dependance on the straight alkyd properties. Film performance for corrosion and humidity
resistance improved as diluent was added and aluminium driers were used. Gloss retention after
QUVB-exposure was low for samples containing vegetable oils or styrene-vinyl groups but was
high for short oil alkyd formulations. Significant loss of gloss was observed for the black samples
perhaps as a result of poor dispersion.
Red oxide primers of a phenolic resin were also prepared and tested. All drying times were under
15 minutes and VOC levels at 2.41/gal (285g/l) after addition of 30% DCPD-linseed oil, down
from 2.8lb/gal (335g/l) for the straight alkyd. The diluent did not impair the drying time but
improved the dry film properties and performance.
PageD-J
-------
2.
Raw Materials for Coatings Formulation
The following alkyds were selected based on recommendations of the contractor and the resin
producer:
57-5731: Chain stopped fast air drying short oil (recommended by ECOTEK)
57-5720; Chain stopped fast air drying short oil; (Dry faster than 57-5731 recommended by
McWhorter).
57-5747: Polysiloxane modified long oil with very good through dry and weatherbility.
57-5758: Styrene-vinyl-copolymer with excellent drying times (recommended by
McWhorter).
57-4368: Polyurethane modified long oil with very good through dry and corrosion and
humidity resistance (recommended by McWhorter).
All alkyds were provided by McWhorter.
Reactive Diluents
Dicyclopentadiene modified linseed oil produced by Cargill and 1/3 epoxidized soybean oil from
Atochem were used.
Driers
XP208, a 6% solution of aluminium chelate from Manchem.
Cobalt-CEM-ALL as 12% solution from OMG
Zirconium-CEM-ALL as 12% and 24% solution from OMG
Calcium-CEM-ALL as 10% solution from OMG
Maganese-CEM-ALL as 12% solution from OMG
Activ-8 as 38% solution of 1,10 phenanthroline from Vanderbilt.
Additives
Exkin#2, a anti-skinning agent (Huls)
Byk 300, Byk 301, for slip and mar resistance (BYK-Chemie)
Nuoperse 657, dispersing agant (Huls)
Bentone SD-1, rheological modifier (Rheox)
Page D-2
-------
3, Sample Preparation and Application
The paints were prepared by using the formulations in the Tables outlined. FW#1 to 28 for the
whites, FB#1 to 16 for the blacks and R#1 to 4 for the red primers.
The manufacturer's suggested formulations were used, adjusted if necessary, and modified with
the introduction of diluent. Each paint sample was based on its own formulation . The paint
sample was then applied in the same sequence as prepared, first over glass for drying time
determination, then over untreated cold rolled steel for performance testing. The wet paints were
applied with No.36 or No.42 bar to give a wet film thickness about 3mils and dry film thickness
about Imil. Five panels for each paint were drawn down and left to air dry for 7 to 10 days before
testing.
Testing Procedure
Set to touch, dry to touch, tack free and through dry were determined according to ASTM
D1640-83. A B-K-drying recorder was used to determine the through dry. Film thickness was
measured with Elcometer -300 digital thickness gauge.
Paint characteristics and dry film properties were determined with the following tests:
Weight per gallon (ASTM D1475), Non Volatile by Weight (ASTM D2369), VOC (ASTM
D3960-87), Pencil Hardness (ASTM D3363-74), Sward Hardness (ASTM D2134-66),
Crosshatch Adhesion (ASTM D3359-90), Impact Resistance (ASTM D2794), Package Stability
(ASTM D1849-80), Gloss (D523), QUV Weathering (D4587), Humidity Resistance (D2247 and
D714), Salt Fog Exposure (B117), Viscosity was measured with Brookfield, ICI Cone & Plate,
Krebs-Stormer and Ford Cup #4.
Page D-3
-------
4. Results and Discussion
White and black paints and red oxide primers containing 30% dicyclopentadiene-linseed, 20% and
30% 1/3 epoxidized soybean oil were formulated, applied, air dried, tested and compared with
samples based on straight alkyd formulations.
4.1. White Paints
4.1.1. Sample Compositions
All paint samples were based on the producer suggested formulations for topcoats. Samples were
prepared and a drier combination consisting of calcium, zirconium, cobalt and active-8 were used.
Samples with the same compositions but containing cobalt and aluminium as driers were also
prepared and tested. The straight alkyd formulations with the Ca/Zr/Co/Activ-8 were used as
control. All other samples contained Al/Co as drier.
28 white paint samples (each with its own modified formulation ) were evaluated.
Samples based on 57-5731
Formula #W1 to W5 were based on short oil alkyd 57-5731 with reportedly fast set to touch, dry
to touch and tack free. FW#1 was the reference sample (control) and contained the
Ca/Zr/Co/Activ-8 as drier (FW#1). FW#2 was a similar sample but contained cobalt and
aluminium. FW#3 contained 30% DCPD-linseed oil, FW#4 30% 1/3 epoxidized soybean oil and
FW#5 20% 1/3 epoxidized soybean oil. Except for FW#1, all samples contained cobalt and
aluminium as drier. (See pages D-59 to D-62 for detailed recipes.)
Samples based on 57-5720
FW#6 to FW#10 were based on short oil alkyd 57-5720. It is a chained stopped short oil with
properties similar to those of 57-5731 but dried faster.
FW#6 was the straight formulation containing Ca/Zr/Co/Activ-8 as drier. It was the reference
sample (control). FW#7 had the same composition but aluminium and cobalt was used as drier.
FW#8, FW#9 and FW#10 contained 30% DCPD-linseed, 30% and 20% 1/3 epoxidized soybean
oil respectively. (See pages D-63 to D-66 for detailed recipes.)
Samples based on 57-5747
FW#11 to FW#15 contained long oil silicone alkyd 57-5747. FW#11 was the reference sample
(control) and contained Ca/Zr/Co/Activ-8 like the control samples described above. FW#12 was
the straight alkyd formulation with Al/Co-drier, and FW#13, FW#14 and FW#15 contained 30%
DCPD-linseed, 30% and 20% 1/3 epoxidized soybean oil respectively. (See pages D-67 to D-71
for detailed recipes.)
PageD-4
-------
Samples based on 57-5758
Samples FW#16 to FW#19 were formulated with 57-5758, a styrene-vinyl-copolymer which has
reportedly a very short drying time. FW#16 was the control and contained cobalt and activ-8 as
the only driers, FW#17 the straight alkyd formulation with Al/Co-drier, FW#18 and FW#19
contained 30% DCPD-linseed and 20% 1/3 epoxidized soybean oil respectively. (See pages D-72
to D-74 for detailed recipes.)
Samples based on 57-4368
FW#20 to FW#23 were based on long oil urethane alkyd 57-4368. The control sample was
FW#20, FW#21 the straight alkyd with Al/Co-drier; FW#22 30% DCPD-linseed; and FW#23
20% 1/3 epoxidized soybean oil. (See pages D-75 to D-77 for detailed recipes.)
Samples based on Blend of 57-5758/57-4368
Samples FW#24 to FW#28 consisted of a blend of 57-5758 and 57-4368. 57-5758 was used for
grinding and 57-4368 in the letdown. FW#24 was the reference sample with Ca/Zr/Co/Activ-8 as
drier. FW#25 was the straight alkyd formulation with Al/Co as drier, FW#26 contained 30%
DCPD-linseed, FW#27 and FW#28 30% and 20% 1/3 epoxidized soybean oil respctively.
(See pages D-78 to D-81 for detailed recipes.)
The Formulas , sample compositions and wet paint properties are summarized in the Tables
outlined. Formulations were calculated by determining the PVC and the solid volume
compositions and then the total volume, the total weight and the solid weight. ICI viscosity was
adjusted to about 2 poises by adding solvent.
4.1.2. Drvine Time
Set to touch time for the straight alkyd formulations was under 10 minutes except for the samples
based on the silicone alkyd 57-5747 where values of 10 and 15 minutes were obtained. Addition
of reactive diluents affected the set to touch time of the samples.
Dry to touch was longer, especially when reactive diluents were added. Samples based on short
oils 5731 and 5720, the long oil urethane alkyd 4368 and the blend 5758/4368 dried tack free
within 45 minutes. Those based on long oil silicone 57-5747 dried within 60 minutes and the
samples containing the styrenated alkyd 5758 needed about 90 minutes to dry tack free when
diluent was added. Depending on the type of alkyd, variations were observed in the through
drying times. Through dry was relatively long for both straight and diluent containing
formulations of the short oils 5731 and 5720.
Drying conditions: Temperature was between 75°F and 85°F and relative humidity varied from
37% to 70% but was most of the time below 50%.
Set to touch, dry to touch tack free and through dry times are summarized in Table 1.1 to 1.4 and
Figure 1.1 to 1.4.
Page D-5
i '
-------
Samples based on 57-5731
Set to touch time was within 10 minutes for all samples, dry to touch time increased to 20
minutes. Tack free was very good except for the sample containing 30% DCPD-linseed oil which
dried within 45 minutes. Through dry for the straight formulations could be reduced by replacing
the Ca/Zr/Co/Activ-8 drier by Al/Co-drier. Addition of vegetable oil derivatives increased through
dry to 5 hours.
Samples based on 57-5720
Addition of reactive diluents increased set to touch to about 20 minutes when 30% DCPD-iinseed
or 20% 1/3 epoxidized soybean oil were added and 30 minutes when 30% 1/3 epoxidized were
added. Dry to touch was similar to the values of 57-5731. Tack free for all samples based on short
oil alkyd 5720 was very good (less than 30 minutes) but through dry was relatively long for the
samples containing reactive diluents (6 to 8 hours). Through dry for the straight formulation could
be reduced by using aluminium and cobalt intead of Ca/Co/Zr/Activ-8 as drier.
Samples based on 57-5747
57-5747 is a long oil alkyd with relatively long drying times. Set to touch for the samples were
within 20 minutes except for the sample containing 30% epoxidized soybean oil . Dry to touch
was longer but not over 40 minutes. Variation in the drying conditions affected particulary the
tack free time for the samples based on the silicone alkyd: Under good drying conditions (50% or
less relative humidity and temperature about 75°F or more) 15 to 45 minutes were measured for
the straight formulations and about 60 minutes when 30% DCPD-linseed or 30% 1/3 epoxidized
soybean oil were added. But at higher humidity and temperatures below 70°F much longer tack
free time was observed. No discrepency was observed during recording of through dry time. All
values were consistently below 4 hours.
Samples based on 57-5758
The straight formulations of the styrene-vinyl-copolymers were among the fastest drying.
However, introduction of the diluents into the formulations significantly increased the drying time
as shown in Figure 1.1. Set to touch changed from less than 10 minutes for the straight
formulations to 30 and 40 minutes after addition of 30% DCPD-linseed or 20% 1/3 epoxidized
soybean oil. Dry to touch increased from less than 10 minutes to 40 or 60 minutes. Tack free was
also relatively long for the samples containing vegetable oils while in absence of oil the samples
dried tack free in less than 10 minutes. Loss of gloss that could indicate incompatibility was not
observed. Less discrepancy was observed in through dry for the samples formulated with this
alkyd and relatively short times were recorded.
PageD-6
-------
Samples based on 57-4368
Set to touch for the straight formulations of long oil urethane alkyd 57-4368 was among the
shortest but in contrast to the styrene-vinyl-copolymer, addition of DCPD-linseed and 1/3
epoxidized soybean oil increased only moderately the drying time. Dry to touch was good.
Samples with 30% DCPD-linseed and 20% 1/3 epoxidized soybean oil dried within 30 minutes.
Tack free time was less than 45 minutes. The alkyd appeared to be more compatible with the
diluents (high content of vegetable oil). Some of the shortest through drying times were recorded
for the samples formulated with this alkyd, especially when reactive diluents were added.
Samples based on Blend of 57-5758/4368
Despite incompatibility which was observed through loss of gloss, set to touch times of
formulations based on the blend of the the styrene-vinyl-copolymer 5758 and the long oil urethane
alkyd 4368 were among the shortest, especially when reactive diluents were added. Dry to touch
was longer but did not exceed 45 minutes. Tack free was very short for the straight formulations
(10 minutes), but increased to 30 and 45 minutes after addition of 20% 1/3 epoxidized soybean
and 30% DCPD-linseed oil respectively. 60 minutes tack free was observed when 30% 1/3
epoxidized soybean oil was added. Through dry was as fast as for the samples based on 5758 or
4368.
General Comments
Short oil alkyds (5731 and 5720) and the styrene-vinyl-copolymer exhibited very short set to
touch, dry to touch and tack free times in their straight formulations while greater values were
obtained for the samples based on the long oil alkyds (5747, 4368 and the blend of 5758/4368).
No great difference due to the use of a particular drier was observed.
Addition of diluents led to an increase of tack free times. Samples formulated with 5758, 5747
were the most affected with values reaching 60 and 90 minutes respectively.
Through dry was longer for the samples based on the short oil alkyds 5731 and 5720, especially
when diluent was added. Through dry were less than 3 hours for all other samples.
Samples based on the short oil alkyds could be recommended for end use when tack free less than
45 minutes is required and through dry above 8 hours is not a great concern. Samples formulated
with the urethane alkyd 4368 and its blend with 5758 could also be recommended because of the
the tack free time below 60 minutes and their excellent through dry (less than 3 hours).
Tack free and through dry were generally reduced when 30% DCPD-linseed or 20% 1/3
epoxidized soybean oil was used in place of 30% 1/3 epoxidized soybean oil.
PageD-7
-------
Table 1.1: Drying Time for White Paints; Set to Touch (mm)
Alkyd 5731 5720 5747 5758 4368 5758/4368
Control
7
5
10
3
3
3
Straight Alkyd (Co/Al)
7
5
15
5
5
5
30% DCPD-linseed oil
10
15
20
40
20
10
30% Epoxidized Soybean oil
10
20
30
-
-
20
20% Epoxidized Soybean oil
10
15
15
30
15
10
Table 1.2: Drying Time for White Paints; Dry to Touch (min)
Alkyd 5731 5720 5747 5758 4368 5758/4368
Control
10
10
15
5
10
5
Straight Alkyd (Co/Al)
10
10
20
5 •
10
5
30% DCPD-linseed oil
20
20
30
60
30
30
30% Epoxidized Soybean oil 20
30
40
-
-
45
20% Epoxidized Soybean oil 15
15
20
45
20
20
Page D-S
-------
Table 1.3: Drying Time for White Paints; Tack Free (min)
Alkyd 5731
5720
5747
5758
4368
5758/4368
Control 10
10
25
10
20
10
Straight Alkyd (Co/Al) 15
15
30
10
20
10
30% DCPD-linsecd oil 30
20
60
90
45
45
30% Epoxidized Soybean oil 40
25
60
-
-
60
20% Epoxidized Soybean oil 20
20
40
60
30
30
Table 1.4: Drvins Time for White Paints; Through Dry (h)
Alkyd 5731
5720
5747
5758
4368
5758/4368
Control 3
6
3
1
1.5
1
Straight Alkyd (Co/Al) 2
1.5
2
0.5
1
0.5
30% DCPD-linseed oil 5
7
2
2
2
2
30% Epoxidized Soybean oil 5
8
3
-
-
3
20% Epoxidized Soybean oil 4
6
2
2
1
1.5
Page D-9
-------
Figure 1.1
AIR DRY WHITE ENAMELS FOR INDUSTRIAL MAINTENANCE
Drying Time
Through Dry (h)
*0
OJ
"9
a
M
O
Bar code relationship:
top-to-bottom in key = left-to-right
in graph.
ALKYDS
1: 5731 (Short Oil) 4: 5758 (Styrene/Vinyl)
2: 5720 (Short Oil) 5; 4368 (Long Oil Urethane)
3: 5747 (Long OH Silicone) 6: Blend of 4368/5758
-------
Figure 1.2
AIR DRY WHITE ENAMELS FOR INDUSTRIAL MAINTENANCE
Drying Time
Tack Free (min)
I?
0)
©
tJ
i
M
M
120
100
Bar code relationship:
top-to-bottom in key = left-to-right
in graph.
1: 5731 (Short Oil) 4: 5758 (Styrene/VInyl)
2: 5720 (Short Oil) 5: 4368 (Long Oil Urethane)
3: 5747 (Long Oil Silicone) 6: Blend of 4368/5758
-------
Figure 1.3
AIR DRY WHITE ENAMELS FOR INDUSTRIAL MAINTENANCE
Dry to Touch Time
Dry to Touch (min)
3 4
ALKYDS
Bar code relationship:
top-to-bottom in key = left-to-right
in graph.
1: 5731 (Short Oil) 4: 5758 (Styrene/Vlnyl)
2: 5720 (Short Oil) 5: 4368 (Long Oil Urethane)
3: 5747 (Long Oil Silicone) 6; Blend of 4368/5758
-------
Figure 1.4
AIR DRY WHITE ENAMELS FOR INDUSTRIAL MAINTENANCE
Drying Time
Set to Touch (min)
Bar code relationship:
tup-to-bottom in key = left-to-right
in graph.
1: 5731 (Short Oil) 4: 5758 (Styrene/Vlnyl)
2: 5720 (Short Oil) 5: 4368 (Long Oil Urethane)
3: 5747 (Long Oil Silicone) 6: Blend of 4368/5758
-------
4.1.3 VOC
VOC levels of the straight formulations were as high as 3.9 lb/gal (470 g/i) and as low as 3.21b/gal
(385 g/1). VOC could be reduced to as low as 2.41b/gal (285 g/1). Initial investigations have
indicated that further reduction in VOC by increasing the diluent content over 30% could
adversely affect drying time, film performance, and properties such as hardness and humidity
resistance. Significant reduction in VOC was obtained when 30% of the alkyd solid weight was
replaced by 1/3 epoxidized soybean oil. 1/3 epoxidized soybean oil was chosen among all
vegetable oil derivatives because it had less adverse effects on the coatings performance when
added in concentrations up to 30%. DCPD-linseed oil provided better coating properties,
especially for dry time and hardness but had a higher density (8.61b/gal). Since VOC and density
are related to each other, the lower the density the lower the VOC of the paint. All VOC data are
summarized in Table 1.5 and Figure 1.5.
Samples Based on 57-5731
VOC of the straight formulations was about 3.61b/gal (395g/l). Addition of 30% DCPD-linseed
reduced it to 2.81b/gal (335g/1), 20% 1/3 epoxidized soybean oil to 2.91b/gal (350g/l) and 30% 1/3
epoxidized soybean oil to 2.61b/gal (310g/l).
Samples Based on 57-5720
The straight formulations had a much higher VOC than the formulations of 5731, 3.61b/gal
(430g/l). A reduction to 3lb/gal (360g/l), 2.91b/gal (350g/l) and 2,71bs/gal (325g/l) was obtained
as 30% DCPD-linseed, 20% and 30% 1/3 epoxidized soybean oil were added respectively.
Samples Based on 57-5747
Initial VOC was 3.21b/gal (385g/l) then reduced to 2.71b/gal (325g/l) with 30% DCPD-linseed and
20% 1/3 epoxidized soybean oil, and to 2.41b/gal (285g/l) with 30% 1/3 epoxidized soybean oil.
Samples Based on 57-5758
VOC was about 2.71b/gal (325g/1) when diluent was added, down from 3.21b/gal (385g/l) for the
straight formulations.
Samples Based on 57-4368
The straight formulations had the highest VOC, 3.91b/gal (470g/l). It was reduced to 3 .1 lb/gal
(370g/l) and 3.01b/gal (360g/l) with 20% 1/3 epoxidized soybean and 30% DCPD-linseed oil
respectively.
Samples Based on the Blend of 5758/4368
The straight formulations had a VOC of 3 .31b/gal (395g/l). Substitution of the solid resin weight
with 30% DCPD-linseed oil reduced the value to 2.71b/gal (325g/l), 20% 1/3 epoxidized soybean
oil to 2.61b/gal (310g/l) and 30% 1/3 epoxidized soybean oil to 2.41b/gal (290g/l).
Page D-14
-------
Table 1.5: White Paints; VOC (g/1)
Alkyd 5731 5720 5747 5758 4368 5758/4368
Control
395
430
385
385
470
395
Straight Alkyd (Co/Al)
395
430
385
385
455
395
30% DCPD-linseed oil
335
360
325
325
370
325
30% Epoxidized Soybean oil
310
325
385
-
-
285
20% Epoxidized Soybean oil
350
350
335
335
360
310
4.1.4 Film Performance
Sward Hardness
The samples were left to air dry for about 7 to 10 days under normal conditions (relative humidity
below 50% and temperature above 78°F). As a result, sward hardness was in average over 25
rocks. This is an indication that the surface drying process was complete. Nevertheless, values
below 20 rocks were obtained for the samples containing 30% 1/3 epoxidized soybean oil. The
straight formulations with 5731, 5720 and 5758 had the shortest tack free times, and also had the
highest hardness. Samples based on the long oil silicone alkyd 5747 exhibited high values, perhaps
because of the presence of polysilane and siloxane derivatives which are known to provide hard
surfaces to coatings. Samples containing DCPD-linseed oil also dried hard on the surface. High
sward hardness values were also observed for the samples with 20% 1/3 epoxidized soybean oil.
The data are summarized in Table 1.6 and in Figure 1.6.
Page D-J5
-------
Figure 1.5
AIR DRY WHITE ENAMELS FOR INDUSTRIAL MAINTENANCE
VOC
VOC (lb/gal)
4.5
Bcontrol
Hst.AlkydECo/AI-Drler)
Bho% OCPD-L!nae«d
¦ 30% Esboll
¦ 20% Esboll
Bar code relationship:
top-to-bottom in key = left-to-right
in graph.
1: 5731 (Short Oil) 4: 5758 (Styrene/Vinyl)
2: 5720 (Short Oil) 5: 4368 (Long Oil Urethane)
3: 5747 (Long Oil Silicone) 6: Blend of 4368/5758
-------
Table 1.6: White Paints; Sward Hardness
Alkyd 5731 5720 5747 5758 4368 5758/4368
Control
28
31
33
35
27
28
Straight Alkyd (Co/Al)
32
33
32
34
28
27
30% DCPD-linseed oil
22
27
17
25
24
29
30% Epoxidized Soybean oil 20
27
14
-
-
15
20% Epoxidized Soybean oil 25
28
20
25
25
27
Pencil Hardness
Relatively good hardness was obtained for most of the samples. Straight formulations and samples
containing DCPD-linseed oil had pencil hardness of about HB. The styrenated alkyd 5758 and its
blend with 4368 exhibited values of about F and H. In all eases addition of 30% 1/3 epoxidized
soybean oil reduced the hardness. Data are summarized in Table 1.7 and Figure 1.7.
Table 1.7: White Paints; Pencil Hardness
Alkyd 5731 5720 5747 5758 4368 5758/4368
Control
HB
HB
UD
no
HB
B
F
Straight Alkyd (Co/Al)
HB
HB
HB
F
HB
H
30% DCPD-Linseed oil
HB
HB
HB
HB
B
HB
30% Epoxidized Soybean oil 4B
3B
B
-
-
2B
20% Epoxidized Soybean oil 2B
2B
HB
HB
HB
HB
Page D-17
-------
Figure 1.6
AIR DRY WHITE ENAMELS FOR INDUSTRIAL MAINTENANCE
Hardness
Sward Hardness (rocks)
Bar code relationship:
top-to-bottom in key = left-to-right
in graph.
1: 5731 (Short Oil) 4: 5758 (Styrene/Vinyl)
2: 5720 (Short OH) 5: 4368 (Long Oil Urethane)
3: 5747 (Long Oil Silicone) 6: Blend of 4368/575B
-------
Figure 1J7
AIR DRY WHITE ENAMELS FOR INDUSTRIAL MAINTENANCE
Hardness
Pencil (-6=6B,-2=2B,-1 =B,1 =HB,2=F,3=H)
JtJ
Ul
9
<0
tJ
i
h»
vo
Bar code relationship:
top-to-bottom in key - left-to-right
in graph.
ALKYDS
1: 5731 (Short Oil) 4: S758 (Styrene/Vinyl)
2: 5720 (Short Oil) 5: 4368 (Long OH Urethane)
3: 5747 (Long Oil Silicone) 6: Blend of 4368/5758
-------
Adhesion
The straight formulations of the short oil alkyds 5731 and 5720 and the styrenated alkyd 5758 had
exhibited relatively poor adhesion ( 2B and 3B). Introduction of the diluent had improved
adhesion but not enough to provide coatings with no failure. All samples based on the silicone
alkyd 5747 had adhesion values of about 4B. Samples based on the urethane alkyd 4368 and its
blend with 5758 exhibited adhesion values of 5B when reactive diluents were added (Table 1.8
and Figure 1.8)
Table 1.8: White Paints; Adhesion
Alkyd 5731 5720 5747 5758 4368 5758/4368
Control
3B
3B
4B
3B
4B
4B
Straight Alkyd (Co/Al)
2B
3B
4B
3B
4B
4B
30% DCPD-linseed oil
4B
2B
4B
4B
5B
5B
30% Epoxidized Soybean oil 4B
3B
4B
-
-
5B
20% Epoxidized Soybean oil 4B
3B
4B
4B
5B
5B
Impact Resistance
Except the formulations based on the urethane alkyd 4368 and its blend with 5758, all samples
exhibited generally very low impact resistance; an indication of poor flexibility. Addition of
diluent, especially 1/3 epoxidized soybean oil improved both direct and the more severe reverse
impact resistance as summarized in Table 1.9 and 1.10, and in Figure 1.9 and 1.10.
Page D-20
-------
Figure 1.8
AIR DRY WHITE ENAMELS FOR INDUSTRIAL MAINTENANCE
Adhesion
Adhesion (B)
Bar code relationship:
top-to-bottom in key = left-to-right
in graph.
1: 5731 (Short Oil) 4: 5758 (Styrene/Vinyl)
2: 5720 (Short Oil) 5: 4368 (Long Oil Urethane)
3: 5747 (Long Oil Silicone) 6: Blend of 4368/5758
-------
Table 1.9: White Paints; Direct Impact Resistance (in-ib)
Alkyd 5731 5720 5747 5758 4368 5758/4368
Control
10
10
10
10
160
80
Straight Alkyd (Co/Al)
10
10
20
10
160
100
30% DCPD-linseed oil
100
30
70
20
160
160
30% Epoxidized Soybean oil
160
50
160
-
-
160
20% Epoxidized Soybean oil
160
20
150
20
160
160
Table 1.10: White Paints; Reverse Impact Resistance (in-lb)
Alkyd 5731 5720 5747 5753 4368 5758/4368
Control
10
10
10
15
160
20
Straight Alkyd (Co/Al)
10
10
20
5
160
160
30% DCPD-linseed oil
60
20
40
5
160
160
30% Epoxidized Soybean oil
140
30
160
-
-
160
20% Epoxidized Soybean oil
100
20
140
80
160
160
Page D-22
-------
Figure 1.9
AIR DRY WHITE ENAMELS FOR INDUSTRIAL MAINTENANCE
Impact Resistance
Direct Impact Resistance (in-lb)
I?
1
t)
i
t-0
1*3
Bar code relationship:
top-to-bottom in key - left-to-right
in graph.
1: 5731 (Short Oil) 4: 5758 (Styrene/Vlnyl)
2: 5720 (Short Oil) 5: 4368 (Long Oil Urethane)
3; 5747 (Long Oil Silicone) 6: Blend of 4368/5758
-------
Figure 1.10
AIR DRY WHITE ENAMELS FOR INDUSTRIAL MAINTENANCE
Impact Resistance
Reverse Impact Resistance (in-Ib)
u
(D
t»
I
•tk
100
I Control
lst,AIHyd(Co/Al-Drlar)
130% DCPD-Llnssod
130% Esboil
120% Esboil
Bar code relationship:
top-to-bottom in key = left-to-right
in graph.
1; 5731 (Short Oil) 4: 5758 (Styrene/Vinyl)
2: 5720 (Short Oil) 5: 4368 (Long Oil Urethane)
3: 5747 (Long Oil Silicone) 6: Blend of 4368/5758
-------
Gloss
Gloss was measured at 20° and 60°. All values obtained indicated that the samples were high
gloss enamels. Gloss at 20° was above 75 and at 60° above 85. However, the samples prepared by
blending the styrene-vinyl-copolymers 57-5758 with the long oil urethane alkyd 57-4368 exhibited
very low gloss indicating a possible incompatibility. Addition of reactive diluents could help
overcome the incompatibility and raise the gloss at 60° above 60. Data are summerized in
Table' 1,11 and Figure 1.11 and 1.12.
Table 1.11: White Paints; Gloss (20°/60°)
Alkyd 5731 5720 5747 5758 4368 5758/4368
Control
75/88
64/87
73/85
66/93
75/88
5/25
Straight Alkyd (Co/Al)
67/86
65/88
75/84
68/94
77/90
7/30
30% DCPD-linseed oil
77/87
65/86
70/83
80/93
80/89
12/55
30% Epoxidized Soybean oil
76/89
68/87
73/82
-
-
30/72
20% Epoxidized Soybean oil
75/86
67/88
70/83
85/93
83/90
25/65
MEK-Resistance
The greatest failure was observed for the formulations based on the styrene-vinyl-copolymer. The
urethane alkyd formulations exhibited better resistance when exposed to MEK. Addition of 30%
1/3 epoxidized soybean oil seemed to reduce the solvent resistance. Results are presented in
Table 1.12 and Figure 1.13.
Page D-25
-------
Figure 1.11
AIR DRY WHITE ENAMELS FOR INDUSTRIAL MAINTENANCE
Gloss
&
0
1
to
Bar code relationship:
top-to-bottom in key = left-to-right
in graph.
ALKYDS
1: 5731 (Short Oil)
2: 5720 (Short Oil)
3: 5747 (Long Oil Silicone)
4; 5758 (Styrene/Vlnyl)
5: 4368 (Long Oil Urethane)
6: Blend of 4368/5758
-------
Figure 1.12
AIR DRY WHITE ENAMELS FOR INDUSTRIAL MAINTENANCE
Gloss
to
I
d
i
to
Gloss (60°)
/I
ALKYDS
Bar code relationship:
lop-to-bottom in key = left-to-right
in graph.
1: 5731 (Short OH) 4: 5758 (Styrene/Vinyl)
2: 5720 (Short Oil) 5: 4368 (Long Oil Urethane)
3: 5747 (Long Oil Silicone) 6: Blend of 4368/5758
-------
Table 1.12: White Paints; MEK-Resistance (Double Rub)
Alkyd 5731 5720 5747 5758 4368 5758/4368
Control
10
20
20
6
20
14
Straight Alkyd (Co/Al)
15
22
20
7
23
16
30% DCPD-linseed oil
15
20
15
12
30
26
30% Epoxidized Soybean oil
7
12
16
-
-
10
20% Epoxidized Soybean oil
11
15
17
10
28
25
Salt Fog Exposure
Data obtained from several literature sources indicated that results from salt fog exposure do not
correlate well with real environment conditions. Reproducibility has also proven to be not reliable.
Nonetheless, the test results gave good indications on the coating performance.
Formulations based on the short oil alkyds 5720 and 5731, the long oil urethane alkyd 4368 and
its blend with the styrenated alkyd 5758 have shown good corrosion resistance. Rating for scribed
and unscribed samples after 10 days exposure was very high. Samples prepared from the silicone
alkyd 5747 performed very poorly ( Table 1.13).
Extensive damage was observed on the surface of all samples after 3 weeks exposure.
Table 1.13: White Paints; Salt Fog Exposure,(10 days Exposure)
Rating for Scribed/Unscribed Panels
Alkyd 5731 5720 5747 5758 4368 5758/4368
Control
10/10
10/10
1/3
6/8
10/9
10/9
Straight Alkyd (Co/Al)
10/10
10/10
3/3
7/8
10/10
10/10
30% DCPD-linseed oil
9/8
8/8
4/5
7/6
9/8
9/9
30% Epoxidized Soybean oil
10/10
10/9
5/5
-
-
10/10
20% Epoxidized Soybean oil
10/10
10/10
4/3
8/9
9/8
10/10
Page D-28
-------
Figure 1.13
AIR DRY WHITE ENAMELS FOR INDUSTRIAL MAINTENANCE
Solvent Resistance
MEK Resistance (Double Rubs)
to
CD
to
to
ALKYDS
1; 5731 (Short Oil)
2: 5720 (Short Oil)
3: 5747 (Long Oil Silicone)
Bar code relationship:
top-to-bottom in key = left to right
in graph.
4: 5758 (Styrene/Vinyl)
5: 4368 (Long Oil Urethane)
6: Blend of 4368/5758
-------
Humidity Resistance
The Cleveland Humidity Cabinet Exposure has proven to be a more severe test for corrosion than
Salt Fog Exposure. Reproducibility of test results has also been good.
Except the formulations of silicone alkyd 5747, all samples exhibited very good humidity
resistance. Samples based on short oil alkyds 5731 and 5720, the long oil urethane alkyd 4368,
and the blend of 5758/4368 have performed very well. Aluminium driers seemed to improve the
film integrity and reduce film permeability. The best results surprisingly were obtained from the
samples containing 1/3 epoxidized soybean oil. The use of high amounts of epoxidized oil as
reactive diluent had been a concern because of the possibility of not reacting completely when air
dried only. Results are presented in Table 1.14.
Table 1.14: White Paints; Humidity Resistance (10 Days Exposure)
Blister Rating
Alkyd 5731 5720 5747 5758 4368 5758/4368
Control
6,D
6,D
6,D
6,MD
6,D
6,D
Straight Alkyd (Co/Al)
8,D
8,D
6,D
6,F
6,D
8,D
30% DCPD-linseed oil
2,F
4,M
4,M
8,D
8,D
9?D
30% Epoxidized Soybean oil
8,D
8,M
4,M
-
-
10
20% Epoxidized Soybean oil
8,D
8,D
4,M
8,D
8,D
10
OUV-Exposure
Gloss (60°) was measured after 14 days exposure to UVB light in the QUV Accelerated
Weathering Cabinet. Gloss retention was relatively high for the samples based on short oil alkyds
5731 and 5720 and silicone alkyd 5747 (Table 1.15). Loss of gloss was significant for the samples
based on 5758, 4368 and the blend 5758/4368. The latter exhibited an initial low gloss due to a
possible incompatibility discussed above. Short oil alkyds have less unsaturation than long oil,
therefore, they could show less degradation in presence of UV. The presence of polysiloxanes in
silicone alkyd 5747 increased its resistance to UV. Styrene-vinyl-copolymers are not known to be
UV resistant without additives. The further loss of gloss of the samples based on the blend of
4368/5758 could result from the presence of different UV degradable groups such as unsaturated
vegetable oils (linseed and soybean) and UV unstable vinyl and styrene. Results are presented in
Table 1.15.
Page D-36
-------
Table 1.15: White Paints; Gloss (60°) Initial/2 Weeks Exposure
Alkyd 5731 5720 5747 5758 4368 5758/4368
Control
88/67
87/65
85/70
93/14
88/47
25/3
Straight Alkyd (Co/Al)
86/44
88/45
84/76
94/16
90/45
30/4
30% DCPD-linseed oil
87/58
86/32
83/57
93/40
89/23
55/5
30% Epoxidized Soybean oil
89/84
87/61
82/72
-
-
72/3.5
20% Epoxidized Soybean oil
86/82
88/66
83/75
93/30
90/30
65/5
General Comments
Formulations based on short oil alkyds 5731 and 5720 and the styrene-vinyl-copolymer exhibited
good sward and pencil hardness. Impact resistance was relatively low. As a result, the coatings
showed poor flexibility that could impair adhesion. Addition of diluents reduced the pencil
hardness but improved impact resistance and adhesion. Samples based on the long oil silicone
alkyd 5747, long oil urethane alkyd 4368 and the blend of 4368 and 5758 exhibited veiy good
impact resistance, adhesion pencil and sward hardness. Straight formulations of 5747 tended to be
brittle but the addition of 1/3 epoxidized soybean oil increased flexibility.
All samples could be characterized as high gloss enamels with values in the upper 80's for gloss at
60°. A significant loss of gloss was observed for the straight formulations prepared from the blend
of the styrenated alkyd 5758 and the long oil urethane 4368, Gloss did improve as diluent was
added.
Coating performance for corrosion, humidity and UV-resistance were very good for the samples
based on on short oil alkyds 5731 and 5720. Addition of diluents improved humidity resistance.
Formulations prepared with the long oil urethane alkyd 4368, the styrenated alkyd and the blend
5758/4368 performed very good in salt fog and humidity cabinets. However, UV resistance was
low, perhaps because of the presence of unsaturated vegetable oils and UV sensitive styrene and
vinyl groups.
Page D-31
-------
4.2
Black Paints
4.2.1 Sample Compositions
Black formulations of the following alkyds were prepared and evaluated:
Short oil chain stopped 57-5731
Short oil chain stopped 57-5720
Long oil silicone alkyd 57-5747
Blend of styrene-vinyl-copolymer 57-5758 and long oil urethane alkyd 57-4368
All systems have been evaluated in white and discussed above.
Two straight formulations containing different driers were prepared for each alkyd:
A drier combination consisting of calcium, zirconium, cobalt and activ-8 was used in the first
formula which was also used as the reference sample (control). The second straight formulation
contained aluminium and cobalt.
Samples containing reactive diluents were also prepared by replacing 30% of the alkyd solid
weight by DCPD-linseed or 1/3 epoxidized soybean oil Aluminium and cobalt were used as
driers. The formulations are described and summarized below.
Samples based on 57-5731
FB#1 was the straight formulation containing Co/Ca/Zr/Activ-8 as drier. It was also the reference
sample.
FB#2 had a similar composition but aluminium and cobalt were used as driers.
FB#3 contained 30% DCPD-linseed and FB#4 30% 1/3 epoxidized soybean oil.
(See pages D-82 to D-84 for detailed recipes )
Samples based on 57-5720
FB#5 was the control and contained Co/Ca/Zr/Activ-8. FB#6 was similar but with aluminium and
cobalt as driers, FB#7 contained 30% DCPD-linseed and FB#8 30 of 1/3 epoxidized soybean oil.
(See pages D-85 to D-87 for detailed recipes.)
Samples based on 57-5747
FB#9 was the control, FB#!0 contained aluminium and cobalt driers, FB#11 30% DCPD-linseed
and FB#12 30% of 1/3 epoxidized soybean oil. (See pages D-88 to D-90 for detailed recipes.)
Samples based on Blend of 5758/4368
FB#13 was the reference sample, FB#14 was the straight formulation with aluminium and cobalt
as driers, FB#15 contained 30% DCPD-linseed and FB#16 30% of 1/3 epoxidized soybean oil.
(See pages D-91 to D-93 for detailed recipes.)
Page D-32
-------
4.2.2
Despite variations observed during recording, the drying conditions were good. Relative humidity
was about 50% or below. The temperature was sometimes around 70° but generally above 78°F.
Set to touch, dry to touch, tack free and through dry were determined according to testing
procedures specified in ASTM. All data are summarized in Tables 2.1 to 2.4 and in Figures 2.1 to
2.4.
Samples based on 57-5731
Set to touch was minimal for both straight formulations (5 minutes). Addition of diluents
increased the drying time as illustrated in Figure 2.1. 20 minutes was obtained for the sample
containing 30% 1/3 epoxidized soybean oil. Dry to touch, tack free and through dry were also
affected in the same way. Addition of 30% DCPD-linseed oil increased the dry to touch to 30
minutes, tack free to 45 minutes and through dry to about 5 hours. Longer times were recorded
when 30% of 1/3 epoxidized soybean oil was added.
Samples based on 57-5720
The drying behavior of the formulations based on this alkyd was similar to that of the 5731.
However, set to touch, dry to touch and tack free were shorter. Through dry was relatively long
for all samples especially for the straight formulations.
Samples based on 57-5747
Slow drying was characteristic for these alkyd formulations. Tack free was very long especially
for the samples containing diluent, 2 hours for DCPD-linseed oil and 4 hours for 1/3 epoxidized
soybean oil.
Samples based on Blend of 5758/4368
Despite loss of gloss indicating incompatibility, drying times for these formulations were relatively
short especially when DCPD-linseed or 1/3 epoxidized oil was added.
General Comments
Drying behavior of the black paints was similar to that of the white samples. Set to touch, dry to
touch and tack free for the straight alkyd formulations was less than 40 minutes. Samples from
5747 had the longest times. Addition of DCPD-linseed and 1/3 epoxidized soybean oil increased
the drying time in some cases significantly.
Page D-33
-------
Table 2.1: Drying Time for Black Paints; Set to Touch (min)
Alkyd 5731 5720 5747 5758/4368
Control 5 3 10 5
Straight Alkyd (Co/Al) 5 5 10 5
30% DCPD-linseed oil 15 10 30 10
30% 1/3 Epoxidized Soybean oil 20 20 45 20
Table 2.2: Drying Time for Black Paints; Dry to Touch (min)
Alkyd 5731 5720 5747 5758/4368
Control 10 5 20 10
Straight Alkyd (Co/Al) 10 5 20 10
30% DCPD-linseed oil 30 15 40 20
30% Epoxidized Soybean oil 60 30 60 45
Table 2.3: Drying Time for Black Paints; Tack Free (min)
Alkyd 5731 5720 5747 5758/4368
Control 15 10 40 20
Straight Alkyd (Co/Al) 15 10 40 20
30% DCPD-linseed oil 45 30 120 60
30% Epoxidized Soybean oil 90 45 240 120
Page D-34
-------
Table 2.4: Drying Time for Black Paints; Through Dry (h)
Alkyd 5731 5720 5747 5758/4368
Control
3.5
7
2
1.5
Straight Alkyd (Co/Al)
3
6
1.5
1
30% DCPD-linseed oil
4.5
6.5
3
2.5
30% Epoxidized Soybean oil 6.5
8
4
4
4.2.3 VOC
The lowest VOC was obtained with 30% of 1/3 epoxidized soybean oil: 2.1 lb/gal (250g/l) to
2.3lb/gal (275g/l). and 2.41b/gal (285g/l) to 2.71b/gal (325g/l) were achieved with 30% DCPD-
linseed oil The initial VOC for the straight formulations was between 31b/gal (360g/l) and
3 21b/gal (385g/l). Results are presented in Table 2.5 and Figure 2,5.
Table 2,5: Black Paints; VOC (g/1)
Alkyd 5731 5720 5747 5758/4368
Control
360
380
360
370
Straight AJkyd (Co/Al)
360
380
360
370
30% DCPD-linseed oil
300
325
290
300
30% 1/3 Epoxidized Soybean oil
265
275
250
260
Page D-35
-------
Figure 2.1
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Drying Time
&>
ffi
to
i
to
ov
100
80
60
40
20
Set to Touch (min)
I Control
St.Alkyd{Co/AI-Drier)
30% DCPD-Linseed
30% Esboll
ALKYDS
Bar code relationship:
iop-to-botiom in key = left-to-right
in graph.
1: 5731 (Short Oil)
2: 5720 (Short Oil)
3: 5747 (Long Oil Silicone)
6: Blend of 4368/5758
-------
Figure 2,2
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Drying Time
ft!
3
o
r
la
120
100
80
60
40
20
Dry to Touch (min)
/!
Control
St.Alkyd(Co/AI-Drier)
30% DCPD-Llriseed
30% Esboil
J ill J
Bar code relationship:
top-to-bottom in key = left-to-right
in graph.
ALKYDS
1: 5731 (Short Oil)
2: 5720 (Short Oil)
3: 5747 (Long OH Silicone)
6: Blend of 4368/5758
-------
Figure 2.3
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Drying Time
Tack Free (min)
0)
i
fct
i
U)
CD
SI Control
¦ St.Alkyd(Co/Al-Drier)
¦ 30% DCPD-Linseed
I 30% Esboi!
2 3
ALKYDS
Bar code relationship:
top-to-bottom in key = left-to-right
in graph.
1: 5731 (Short Oil)
2: 5720 (Short Oil)
3; 5747 (Long Oil Silicone)
6: Blend of 4368/5758
-------
Figure 2.4
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Drying Time
Through Dry (h)
Bar code relationship:
lop-to-bottom in bey = left-to-right
in graph.
1: 5731 (Short Oil)
2: 5720 (Short Oil)
3: 5747 (Long Oil Silicone)
6; Blend of 4368/5758
-------
Figure 2.5
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
VOC
VOC (lb/gal)
2 3
ALKYDS
Bar code relationship:
lop-to-bottom in key = lefl-to-right
in graph.
1: 5731 (Short Oil)
2; 5720 (Short Oil)
3: 5747 (Long Oil Silicone)
6: Blend of 4368/5758
-------
i rnt_ - _ ^ ...^1 1-. "L. -"i i_ »
(Tnxs page intentionally oianjc)
Page D-41
-------
4,2.4 Film Performance
Performance tests for hardness, adhesion, impact resistance, gloss, corrosion, humidity and UV-
light resistance were conducted for all samples. Results are summarized in the Tables and Figures
outlined below.
Sward Hardness
Sward hardness was about 20 rocks for most of the samples, 30 rocks for the straight
formulations of 5731 and between 10 and 15 rocks for the samples containing 30% of 1/3
epoxidized soybean oil. Results are presented in Table 2.6 and Figure 2.6.
Table 2.6: Black Paints; Sward Hardness (rocks)
Alkyd 5731 5720 5747 5758/4368
Control
32
20
20
20
Straight Alkyd (Co/Al)
30
22
21
19
30% DCPD-linseed oil
17
19
19
20
30% Epoxidized Soybean oil 10
12
15
10
Pencil Hardness
Pencil Hardness was similar to the values of the white paints. All samples containing 1/3
epoxidized soybean oil were softer. Results are presented in Table 2,7 and Figure 2.7.
Table 2.7: Black Paints; Pencil Hardness
Alkyd
5731
5720
5747
5758/4368
Control
HB
HB
F
F
Straight Alkyd (Co/Al)
HB
HB
HB
HB
30% DCPD-linseed oil
HB
HB
HB
B
30% Epoxidized Soybean oil B
B
2B
2B
Page D-42
-------
Figure 2.6
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Hardness
Sward Hardness (rocks)
1?
0)
"9
fD
itt
Bar code relationship:
top-to-bottom in key = left-to-right
in graph.
1: 5731 (Short Oil) 3: 5747 (Long Oil Silicone)
2: 5720 (Short Oil) 6; Blend of 4368/5758
-------
Figure 2.7
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Hardness
Pencil Hardness (-6——B, 1 —• HB, 2—F)
ALKYDS
1: 5731 {Short Oil)
2: 5720 (Short Oil)
3; 5747 (Long Oil Silicone)
6: Blend of 4368/5758
Bar code relationship:
lop-to-bottom in key = left-to-right
in graph.
-------
Adhesion
Adhesion was very good for all samples except the straight formulations of short oil alkyd 5720
which exhibited relatively poor adhesion. Results are presented in Table 2.8 and Figure 2.8.
Table 2.8: Black Paints; Adhesion
Alkyd 5731 5720 5747 5758/4368
Control
5B
2B
5B
5B
Straight Alkyd (Co/Al)
5B
3B
5B
5B
30% DCPD-linseed oil
5B
5B
5B
5B
30% F.poxidized Soybean oil 5B
5B
5B
5B
Impact Resistance
Low impact values were obtained for the straight formulations of the short oils 5731 and 5720.
Addition of diluent increased both direct and reverse impact to 160 in-lb. Results are presented in
Table 2.9 and 2.10 and Figure 2.9 and 2.10.
Table 2.9: Black Paints; Direct Impact (in-!b)
Alkyd 5731 5720 5747 5758/4368
Control
60
80
160
160
Straight Alkyd (Co/Al)
80
90
160
160
30% DCPD-linseed oil
160
160
160
160
30% Epoxidized Soybean oil 160
160
160
160
Page D-45
-------
Figure 2.8
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Adhesion
Adhesion (B)
Bar code relationship:
top-to-bottom in hey = left-to-right
in graph.
ALKYDS
1: 5731 (Short Oil)
2: 5720 (Short Oil)
3: 5747 (Long Oil Silicone)
6; Blend of 4368/5758
-------
Table 2.10: Black Paints; Reverse Impact (in-lb)
Alkyd 5731 5720 5747 5758/4368
Control
20
20
160
160
Straight Alkyd (Co/Al)
30
30
160
160
30% DCPD-linseed oil
160
160
160
160
30% Epoxidized Soybean oil 160
160
160
160
Gloss
Gloss again was high but somewhat lower for the black compared to the white paints. Dispersion
of the carbon black with a high speed disk impeller was difficult and particles were visible in the
black paints applied on CRS despite filtration. As a result, gloss was reduced. Loss of gloss due to
incompatibility was observed for the samples prepared from the blend of styrene-vinyl-copolymer
57-5758 and long oil urethane alkyd 57-4368. However, introduction of DCPD-linseed and 1/3
epoxidized soybean oil helped increase gloss and reduce incompatibility (Table 2,11 and Figure
2.1 land 2.12).
Table 2.11: Black Paints; Gloss (20°/60°)
Alkyd 5731 5720 5747 5758/4368
Control
55/83
48/88
47/80
16/62
Straight Alkyd (Co/Al)
55/85
50/90
48/84
15/65
30% DCPD-linseed oil
52/82
64/80
54/85
61/86
30% Epoxidized Soybean oil 59/79
67/85
55/87
63/88
Page D-47
-------
Figure 2,9
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Impact Resistance
!p
tu
ID
t)
1
to
Direct Impact Resistance (in-lb)
IB Control
¦ St.Alkyd(Co/AI-Drier)
¦ 30% DCPD-Linseed
¦ 30% Esboil
Bar code relationship:
top-to-bottom in key = left-to-right
in graph.
1: 5731 (Short Oil)
2: 5720 (Short Oil)
3: 5747 (Long Oil Silicone)
6: Blend of 4368/5758
-------
Figure 2.10
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
|mr\ar*t Rocictnnrko
III I l\#wl W It Cm I (vt#
Reverse Impact Resistance (in-lb)
oj
i
250
200
Control
St. Alky d{Co/AI-Drier)
30% DCPD-Linseed
30% Esboll
2 3
ALKYDS
Bar code relationship:
top-to-bottom in key = left-to-right
in graph.
1: 5731 (Short Oil)
2: 5720 (Short Oil)
3; 5747 (Long Oil Silicone)
6: Blend of 4368/5758
-------
Figure 2.11
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Gloss
Gloss (20°)
5s
$
£
Bar code relationship:
top-to-bottom in key = left-to-right
in graph.
ALKYDS
1: 5731 (Short OH)
2: 5720 (Short OH)
3; 5747 (Long Oil Silicone)
6: Blend of 4368/5758
-------
Figure 2.12
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Gloss
Gloss (60°)
120
110
100
Control
St.Alkyd(Co/AI-Drier)
30% DCPD-Linseed
30% Esboil
Bar code relationship:
(op-to-bottom in key = left-to-right
in graph.
ALKYDS
1: 5731 (Short Oil)
2: 5720 (Short Oil)
3: 5747 (Long Oil Silicone)
6; Blend Of 4368/5758
-------
MEK-Resi stance
Samples based on the short oil alkyds 5731 and 5720 showed the least MEK-resistance.
Formulations based on the blend 5758/4368 exhibited higher values. Results are presented in
Table 2.12 and Figure 2.13.
Table 2.12: Black Paints; MEK-Resistance (Double Rub)
Alkyd 5731 5720 5747 5758/4368
Control
12
25
27
35
Straight Alkyd (Co/Al)
15
27
26
34
30% DCPD-linseed oil
11
15
18
33
30% Epoxidized Soybean oil 10
12
11
30
Salt Foe Exposure
Good ratings were obtained for all samples except those based on silicone alkyd 57-5747 for
which lower values were found. Results are presented in Table 2.13.
Table 2.13; Black Paints; Salt Fog Exposure (10 days)
Rating for Scribed/Unscribed Panels
Alkyd 5731 5720 5747 5758/4368
Control
10/10
10/8
9/7
10/8
Straight Alkyd (Co/Al)
10/10
10/9
9/7
10/8
30% DCPD-linseed oil
8/9
10/8
7/6
10/8
30% Epoxidized Soybean oil 9/9
10/9
7/5
8/6
Page D-52
-------
Figure 2.13
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Solvent Resistance
MEK Resistance (double rubs)
50
40
30
20
10
Jz
mil.
Si Control
K5 St.Alkyd(Co/AI-Drier)
HI 30% DCPD-Linseed
H 30% Esboll
2 3
ALKYDS
Bar code relationship:
top-to-bottom in key = left-to-right
in graph.
1: 5731 (Short Oil)
2: 5720 (Short Oil)
3: 5747 (Long OH Silicone)
6: Blend of 4368/5758
-------
Table 2.14: Black Paints; Humidity Resistance (10 Days Exposure)
Blister Rating
Alkyd 5731 5720 5747 5758/4368
Control
6,D
4,M
4,D
8,D
Straight Alkyd (Co/Al)
8,D
8.M
4,M
8,D
30% DCPD-linseed oil
8,D
8JD
4,M
6,D
30% Epoxidized Soybean oil 8,F
8,D
4,MD
9,D
OlJV-Weathering
Gloss (60°) was measured after 14 days exposure to UVB light in the QUV Accelerated
Weathering Cabinet. Unlike the white samples, gloss retention was very low for all samples. This
could be attributed to chalking resulting from the use of unstabilized black pigment. Carbon black
is known to absorb UV-light, but when it is not stabilized it could initiate a radical
photodegradation of the binder that leads to a loss of gloss. Unlike carbon black, most titanium
dioxide pigments are treated with aluminium, silica or zirconium derivatives that reduces or
inhibits any photoactivity. Results are presented in Table 2.15.
Table 2.15: Black Paints; Gloss 60° (Initial/2 Weeks Exposure)
Alkyd
5731
5720
5747
5758/4368
Control
83/11
88/5
80/4
62/4
Straight Alkyd (Co/Al)
85/12
90/5
84/3
65/16
30% DCPD-linseed oil
82/19
80/7
85/6
86/13
30% Epoxidized Soybean oil 79/23
85/6
87/5
88/21
Page D-54
-------
4.3 Red Oxide Primers
Red primers of Rezimac 2810X1 IS, a phenolic/rosin alkyd were formulated and tested. Four
samples were prepared by using the producer's suggested formulations. R#1 was the straight
formulation and contained calcium/cobalt/maganese/zirconium/activ-8 as drier. It was also the
reference sample (control). R#2 had a similar composition but aluminium and cobalt were used as
driers. 30% of the alkyd solid weight was replaced by DCPD-linseed oil in both straight
formulations to give R#3 and RM, (See pages D-97 to D-94 for detailed recipes.)
4.3.1 Drying Time
Set to touch, dry to touch, tack free and through dry were very short for all four samples. Set to
touch, dry to touch and tack free were less than 5 minutes and through dry did not exceed 15
minutes. However, a print free about 6 hours was recorded for the sample containing 30%
DCPD-linseed oil and aluminium/cobalt drier (R#4). Results are presented in Table 3.1.
Table 3.1: Red Primers; Drying Times (min)
R#1
R#2
R#3
R#4
Set to Touch
<3
<3
<3
<3
Dry to Touch
<3
<3
<3
<3
Tack Free
<5
<5
<5
<5
Through Dry
<15
<15
<15
<15
Print Free
<5
<5
<5
240
page D-55
-------
4.3.2 Film properties and Performance
VOC could be reduced to 2.41b/gal (285g/l) from the initial 2.91b/gal (350g/l) when 30% DCPD-
linseed oil were added to the straight formulations. Sward hardness was above 20 rocks and
pencil hardness about 2H. Adhesion and impact resistance were low for the straight formulations
but improved as reactive diluent was introduced. Film performance for corrosion and humidity
resistance improved when aluminium driers were used in place of calcium, zirconium, maganese
and activ-8. No blistering was observed for the samples containing cobalt and aluminium drier
(R#2 and R#4) whereas a rating of #6, dense was obtained for R#1 and R#3, Results are presented
in Table 3.2.
Table 3.2: Red Primers; Dry Film Properties
R#1
R#2
R#3
R#4
VOC (lb/gal)
2.9
2.9
2.4
2.5
Thickness
1.2
1.0
1.1
1.2
Gloss (20760°)
2.3/18.2
1.2/10
11/48
3.6/25
Sward Hardness
23
20
20
23
Pencil Hardness
2H
2H
3H
2H
Adhesion
OB
IB
3B
4B
Impact Strength (D)
5
60
160
160
Impact Strength (R)
5
20
160
160
MEK-Double Rub
10
10
11
11
Salt Fog Exposure
Scribed/Unscribed
10/9
10/10
10/9
10/10
Humidity Resistance
Blister Rating
#6,D
10
#6,D
10
Page D-56
-------
5. Conclusions
Dicyclopentadiene-linseed and 1/3 epoxidized soybean oil could be used to reduce the VOC and
improve performance of white and black formulations based on alkyds for industrial maintenance
end use.
Up to 30% diluent could be used to obtain fast air drying coatings with good performance and
decrease VOC to 2.4 lb/gal (285g/l). VOC of straight formulations was as high as 3,91b/gal
(470g/l).
30% DCPD-linseed and 20% of 1/3 epoxidized soybean oil modification affected the samples in
the same way. Set to touch was less than 20 minutes, dry to touch less than 45 minutes, tack free
within an hour and through dry as high as 8 hours depending on the type of alkyd. Short oil
formulations air dried tack free the fastest while through dry was among the longest.
Modification with 30% of 1/3 epoxidized soybean oil significantly increased the drying time while
reducing VOC in most cases.
Dry films when tested after 7 to 10 days air dry for pencil and sward hardness, adhesion, impact
resistance, solvent, corrosion and humidity resistance showed good performance. Short oil alkyd
formulations exhibited good hardness but poor impact resistance and flexibility, especially in
straight formulations while long oil alkyd samples were more flexible but softer.
Despite viscosity increases observed when used at levels above 0.1% metal concentration,
aluminium driers could improve notably through dry and film performance for humidity and
corrosion resistance. Potlife was not affected but package stability could be a problem. No
adverse effects was observed below that concentration. Selective influence of the aluminium drier
on the type of alkyd was reported by the manufacturer. Short oil alkyds such as 57-5731 and 57-
5720 and the styrene-vinyl-copolymer have shown problems with package stability when more
than 0.1% Al, 1% Ca or 0.1% Zr was used as drier.
All white and black paints tested could be characterized as high gloss topcoats with gloss (60°)
above 85. However, gloss retention after UV-exposure was high for the white formulations while
a huge loss of gloss was observed for the black paints. This was probably due to the lack of
photostability of the carbon black.
Loss of gloss that might indicate incompatibility was observed when straight formulations were
prepared from a blend of long oil urethane alkyd (57-4368) and a styrene-vinyl-copolymer (57-
5758), addition of diluents could reduce the incompatibility.
The use of alumium driers was necessary to improve the dry film properties and performance for
adhesion, impact resistance, corrosion and humidity resistance of red oxide primers formulated
with Rczimac 2810 XHS, a phenolic /rosin alkyd. No adverse effect was noted. Addition of 30%
DCPD-linseed oil did not affect drying times or film performance but reduced VOC to 2.41b/gal
(285g/l).
Page D-57
-------
6. Suggestions for Future Work
In the first part of this work, the evaluation of clear coats and white paints for architectural end
use was reported. It demonstrated that clearcoats, top coats and primers with good film
performance could be formulated at VOC levels as low as l.Blb/gal (200g/l) by using epoxidized
oils, and DCPD-linseed oil as reactive diluents. Because of long drying times, force dry was
necessary.
In the second part, white and black topcoats and red oxide primers for industrial maintenance
were evaluated. The results indicated that fast air drying coatings with good performance and
VOC as low as 2.41b/gal (285g/l) could be formulated by using 1/3 epoxidized soybean and
DCPD-linseed oil.
Therefore, it was demonstrated that dicyclopentadiene-linseed and epoxidized vegetable oils with
different degrees of epoxidation could be used as reactive diluents to reduce the VOC of different
alkyds for architectural and industrial maintenance end uses, and improve performance in some
cases.
Future work could be concentrated on the use of epoxidized vegetable oils, especially folly
epoxidized soybean oil in combination with aluminium driers in baking systems based on short oil
alkyds to replace melamine-formaldehyde as crosslinker. Compatibility should not be a problem
and coatings with very good performance for corrosion humidity and solvent resistance should be
possible.
Fully epoxidized soybean oil could also be use to reduce VOC of polysiloxane coatings where
methanol resulting from polycondensation is a big problem. In presence of fully epoxidized oil
methanol could react with the epoxy groups to form glycidyl ether derivatives. However,
incompatibility problems could occur when oils with lower degrees of epoxidation such as 1/3 or
2/3 epoxidized soybean oil are used.
Furthermore, a possible use of epoxidized vegetable oils in coatings for trade sales could be
explored.
Page D-58
-------
7.0 Detailed Recipes for Air Dry White Coatings
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #W1: Short Oil Alkyd 5731; Drier 1: Co/Ca/Zr/Activ-8
Formula #W2: Drier 2: Al/Co
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Soli
MIAK
36.5
0
6.77
5.4
0
57-5731
238.8
179.1
8.8
27.1
19
Byk 301
0.92
0.46
8.08
0.11
0.04
Aerosil R972
4.1
4.1
18.4
0.2
0.23
TiPure 900
366.6
366.6
33.3
11
11
Grind to Hegman 7.7 with High Speed Disk Disperser
57-5731
264
198
8.8
30
21
12% Co
1.9
1.2
8.3
0.2
0.07
XP208
18.9
13.2
8.3
2.3
1.5
Butyl Carbitol
2.7
0
8.16
0.3
0
MIAK
157.9
0
6.77
23.4
0
Total
1092.3
762.7
100.01
52.84
Weight Solid %
71.2
WPG (lb/gal)
10.9
PVC
0.21
ICI (poise)
2.2
Stormer (KU)
66
Ford Cup,#4
70
VOC (lb/gal)
3.2
Alkyd wt. Fr.
0.75
Alkyd vol. Fr.
0.7
Volume Factor
0.99990001
Page D-59
-------
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #W3: Short Alkyd 5731 and 30% DCPD- Linseed
Raw Material
Total Weight Weight Solid
WPG
Total Vol.
Vol. Soli
MIAK
36.5
0
6.77
5.4
0
57-5731
238.8
179,1
8.8
27.1
19
Byk 301
0.92
0.46
8.08
0.1
0.04
Aerosil R972
4.1
4.1
18.4
0.2
0.23
TiPure 900
416.6
416.6
33.3
12.5
12.5
Grind to Hegman 7.7 with High Speed Disk Disperser
57-5731
144.5
108.4
8.8
16.4
11.5
DCPD-Linseed
123.2
123.2
8.6
14.3
14.3
12% Co
1.9
1.2
8.3
0.2
0.07
XP208
18.9
13.2
8.3
2.3
1.5
Butyl Carbitol
2.7
0
8.16
0.3
0
MIAK
142.4
0
6.77
21.2
0
Total
1130.5
846.3
100
59.14
Weight Solid % 78.8
WPG (ib/ga!) 11.2
PVC 0.21
1CI (poise) 2.1
Stormer (KU) 68
Ford Cup,#4 70
VOC (ib/gal) 2.8
Alkyd wt. Fr. 0.75
Alkyd vol. Fr. 0.7
Volume Factor 1
Page D-60
-------
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #W4: Short Alkyd 5731 and 30% 1/3 Epoxidized Soybean
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Soli
MIAK
36.5
0
6.77
5.4
0
57-5731
238.8
179.1
8.8
27.1
19
Byk 301
0.92
0.46
8.08
0.11
0.04
Aerosil R972
4.1
4.1
18.4
0.22
0.23
TiPure 900
433.3
433.3
33.3
13
13
Grind to Hegman 7.7 with High Speed Disk Disperser
57-5731
144.6
108.4
8.8
16.4
11.5
1/3 Esboil
123.2
123.2
7.9
15.6
15.6
12% Co
1.9
1.2
8.3
0.23
0.07
XP208
18.9
13.2
8.3
2.3
1.5
Butyl Carbitol
2.7
0
8.16
0.33
0
MIAK
130.7
0
6.77
19.31
0
Total
1135.62
862.96
100
60.94
Weight Solid %
83.4
WPG (lb/gal)
11.3
PVC
0.21
ICI (poise)
2.1
Stormer (KU)
68
Ford Cup,#4
70
VOC (lb/gal)
2.6
Alkyd wt. Fr. 0.75
Alkyd vol. Fr. 0.7
Volume Factor 1
Page D-61
-------
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #W5: Short Oil Alkyd 5731 and 20% Epoxidized Soybean
Raw Material Total Weight Weight Solid WPG Total Vol. Vol. Solid
MIAK
36.5
0
6.77
5.4
0
57-5731
238.8
179.1
8.8
27.1
19
Byk 301
0.92
0.46
8.08
0.11
0.04
Aerosil R972
4.1
4.1
18.4
0.22
0.23
TiPure 900
416.6
416.6
33.3
12.5
12.5
Grind to Hegman 7.7 with High Speed Disk Disperser
57-5731
188.6
141.4
8.8
21.4
15
1/3 ESBoil
80.1
80.1
7.9
10.1
10.1
12% Co
1.9
1.2
8.3
0.2
0.07
XP208
18.9
13.2
8.3
2.3
1.5
Butyl Carbitoi
2.7
0
8.16
0.3
0
MIAK
136.9
0
6.77
20.4
0
Total
1126.02
836.16
100.03
58.44
Weight Solid %
80.2
WPG (ib/gal)
11.2
PVC
0.21
ICI (poise)
2.4
Stormer (KU)
71
Ford Cup,#4
72
VOC (Ib/gal)
2.9
Alkyd wt. Fr.
Alkyd vol. Fr.
Volume Factor
0.75
0.7
0.99970009
Page D-62
t ••
-------
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #W6: Short Oil Alkyd 5720; Drier 1: Co/Ca/Zr/Activ-8
Formula #W7: Drier 2: Al/Co
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Solid
MIAK
36.5
0
6.77
5.4
0
57-5720
234.8
176.1
8.65
27.1
19
Byk 301
0.92
0.46
8.08
0.11
0.04
Aerosil R972
4.1
4.1
18.4
0.23
0.23
TiPure 900
366.6
366.6
33.3
11
11
Grind to Hegman 7.7 with High
Speed Disk Disperser
57-5720
259.5
194.6
8.65
30
21
12% Co
1.9
1.2
8.3
0.23
0.07
XP208
18.9
13.2
8.3
2.3
1.5
Butyl Carbitol
2.7
0
8.16
0.33
0
MIAK
157.7
0
6.77
23.3
0
Total
1083.62
756.26
100
52.84
Weight Solid % 71.2
WPG (lb/gal) 10.7
PVC 0.21
IC! (poise) 2
Stormer (KU) 72
Ford Cup,#4 68
VOC (lb/gal) 3.6
Alkyd wt. Fr. 0.75
Alkyd vol. Fr. 0.7
Volume Factor 1
Page D-63
-------
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #W8: Short Alkyd 5720 and 30% DCPD- Linseed
Raw Material
Total Weight
Weight Solid
WPG
Total Vol,
Vol. Sol
MIAK
36.5
0
6.77
5.4
0
57-5720
234.8
176.1
8.65
27.1
19
Byk 301
0.92
0.46
8.08
0.11
0.04
Aerosit R972
4.1
4.1
18.4
0.22
0.23
TiPure 900
416.3
416.3
33.3
12.5
12.5
Grind to Hegman 7.7 with High Speed Disk Disperser
57-5720
142.1
106.6
8.65
16.4
11.5
DCPD-Linseed
121.2
121.2
8.6
14.1
14.1
12% Co
1.9
1.2
8.3
0.23
0.07
XP208
18.9
13.2
8.3
2.3
1.5
Butyl Carbitol
2.7
0
8.16
0.33
0
MIAK
144.3
0
6.77
21.31
0
Total
1123.72
839.16
100
58.94
Weight Solid %
78.8
WPG (lb/gal)
10.5
PVC
0.21
ICI (poise)
2.3
Stormer (KU)
70
Ford Cup,#4
75
VOC (lb/gal)
3.1
Alkyd wt. Fr. 0.75
Alkyd vol. Fr. 0.7
Volume Factor 1
Page D-64
-------
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #W9: Short Alkyd 5720 and 30% 1/3 Epoxidized Soybean
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Soli
MIAK
36.5
0
6.77
5.4
0
57-5720
234.8
176.1
8.65
27.1
19
Byk 301
0.92
0.46
8.08
0.11
0.04
Aerosil R972
4.1
4.1
18.4
0.22
0.23
TiPure 900
433.3
433.3
33.3
13
13
Grind to Hegman 7.7 with High Speed Disk Disperser
57-5720
142.1
106.6
8.65
16.4
11.5
1/3 Esboil
121.1
121.1
7.9
15.3
15.3
12% Co
1.9
1.2
8.3
0.23
0.07
XP208
18.9
13.2
8.3
2.3
1.5
Butyl Carbitol
2.7
0
8.16
0.33
0
MIAK
132.7
0
6.77
19.61
0
Total
1129.02
856.06
100
60.64
Weight Solid %
81.3
WPG (lb/gal)
10.7
PVC
0.21
ICI (poise)
2.3
Stormer (KU)
71
Ford Cup,#4
76
VOC (lb/gal)
2.8
Alkyd wt. Fr. 0.75
Alkyd vol. Fr. 0.7
Volume Factor 1
Page D-65
-------
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #W10: Short Oil Alkyd 5720 and 20% Epoxidized Soybean
Raw Material Total Weight Weight Solid WPG Total Vol. Vol. Solid
MIAK
36.5
0
6.77
5.4
0
57-5720
234.8
176.1
8.65
27.1
19
Byk 301
0.92
0.46
8.08
0.11
0.04
Aerosil R972
4.1
4.1
18.4
0.22
0.23
TiPure 900
383.3
383.3
33.3
11.5
11.5
Grind to Hegman 7.7 with High Speed Disk Disperser
57-5720
154.5
115.8
8.65
17.8
12.5
1/3 ESBoil
73
73
7.9
9.2
9.2
12% Co
1.9
1.2
8.3
0.23
0.07
XP208
18.9
13.2
8.3
2.3
1.5
Butyl Carbitol
2.7
0
8.16
0.33
0
MIAK
175.3
0
6.77
25.9
0
Total
1085.92
767.16
100.09
54.04
Weight Solid % 77.5
WPG (lb/gal) 10.2
PVC 0.21
ICI (poise) 2
Stormer (KU) 65
Ford Cup,#4 68
VOC (lb/gal) 3
Alkyd wt. Fr. 0.75
Alkyd vol. Fr. 0.7
Volume Factor 0.999100809
Page D-66
-------
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #W11: Long Oil Silicone Alkyd; Drier 1:Ca/Co/Zr/Activ-8
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Solid
MIAK
13.6
0
6.77
2.01
0
57-5747
274
179.6
8.7
31.5
15.35
Byk 300
0.81
0.39
8.1
0.1
0.03
TiPure 706
290
290
33.33
8.7
8.7
Grind to Hegman 7.7 with High Speed Disk Disperser
57-5747
182.6
119.7
8.7
21
10.23
12% Co
2.8
1.8
8.3
0.33
0.1
12% Zr
13.4
5.9
8.1
1.66
0.5
10% Ca
21
11.13
8.4
2.5
1
Activ-8
1.6
0.6
7.9
0.2
0.06
Exkin #2
0.9
0
7.7
0.12
0
MIAK
215.8
0
6.77
31.9
0
Total
1016.51
609.12
100.02
35.97
Weight Solid %
69.6
WPG (lb/gal)
10.3
PVC
0.24
ICI (poise)
2.2
Stomer (KU)
70
Ford Cup,#4
85
VOC (lb/gal)
3.2
Alkyd wt. Fr. 0.6555
Alkyd vol. Fr. 0.4873
Volume Factor 0.99980004
Page D-67
-------
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #W12: Long Oil Silicone Alkyd; Drier 2: Al/Co
Raw Material
Total Weight
Weight Solid WPG Total Vol.
Vol. Solid
MIAK
13.6
0 6.77 2.01
0
57-5747
274
179.6 8.7 31.5
15.35
Byk 300
0.81
0.39 8.1 0.1
0.03
TiPure 900
290
290 33.33 8.7
8.7
Grind to Hegman 7.7 with High Speed Disk Disperser
57-5747
182.6
119.7 8.7 21
10.23
12% Co
2.8
1.8 8.3 0.33
0.1
XP208
18.9
13.2 8.3 2.3
1.5
MIAK
230.8
0 6.77 34.1
0
Total
1013.51
604.69 100.04
35.91
Weight Solid,%
WPG (lb/gal)
10.1
PVC
0.24
ICI (poise)
2.3
Stormer (KU)
67
Ford Cup,#4
80
VOC (lb/gal)
3.3
Alkyd wt. Fr.
0.6555
Alkyd vol. Fr.
0.4873
Volume Factor 0.99960016
Page D-68
-------
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #W13: Long Oil Silicone Alkyd and 30% DCPD-Linseed
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Soli
MIAK
13.6
0
6.77
2.01
0
57-5747
274
179.6
8.7
31.5
15.35
Byk 300
0.81
0.39
8.1
0.1
0.03
TiPure 900
416.6
416.6
33.33
12.5
12.5
Grind to Hegman 7.7 with High Speed Disk Disperser
57-5747
160.7
105.3
8.7
18.5
9
DCPD-Linseed
122.1
122.1
8.6
14.2
14.2
12% Co
1.9
1.2
8.3
0.23
0.07
XP208
18.9
13.2
8.3
2.3
1.5
MIAK
126.7
0
6.77
18.7
0
Total
1135.31
838.39
100.04
52.65
Weight Solid %
76.1
WPG (lb/gal)
11.1
PVC
0.24
ICI (poise)
2.1
Stormer (KU)
65
Ford Cup,#4
70
VOC (lb/gal)
2.9
Aikyd wt. Fr. 0.6555
Alkyd vol. Fr. 0.4873
Volume Factor 0.99960016
Page D-69
-------
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #W14: Long Oil Silicone Alkyd and 30% Epoxidized Soybean
Raw Material Total Weight Weight Solid WPG Total Vol. Vol. Solid
MIAK 13.6 0 6,77 2.01 0
57-5747 274 179.6 8.7 31.5 15.35
Byk 300
0.81
0,39
8.1
0.1
0.03
TiPure 900
430
430
33.33
12.9
12.9
Grind to Hegman 7.7 with High Speed Disk Disperser
57-5747
160.7
105.3
8.7
18.5
9
1/3 ESBoil
122.1
122.1
7.9
15.5
15.5
12% Co
1.9
1.2
8.3
0.23
0.07
XP208
18.9
13.2
8.3
2.3
1.5
MIAK
115.5
0
6.77
17
0
Total
1137.51
851.79
100.04
54.35
Weight Solid % 74.5
WPG (lb/gal) 10.9
PVC 0.24
ICI (poise) 2.2
Stormer (KU) 67
Ford Cup,#4 78
VOC (lb/gal) 2.7
Alkyd wt. Ft. 0.6555
Alkyd vol. Fr. 0.4873
Volume Factor 0.99960016
Page D-70
-------
AiR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #W15:
Long Oil Silicone Alkyd and 20% Epoxidized Soybean
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Soli
MIAK
13.6
0
6.77
2.01
0
57-5747
274
179.6
8.7
31.5
15.35
Byk 300
0.81
0.38
8.1
0.1
0.03
TiPure 900
420
420
33.33
12.6
12.6
Grind to Hegman 7.7 with High
Speed Disk Disperser
57-5747
219.6
143.9
8.7
25.2
12.3
1/3 ESBoil
80.9
80.9
7.9
10.2
10.2
12% Co
1.9
1.2
8.3
0.23
0.07
XP208
18.9
13.2
8.3
2.3
1.5
MIAK
107.4
0
6.77
15.86
0
Total
1137.11
839.18
100
52.05
Weight Solid %
73.1
WPG (lb/gal)
11.2
PVC
0.24
ICI (poise)
2.5
Stormer (KU)
70
Ford Cup,#4
85
VOC (lb/gal)
2.9
Alkyd wt. Fr.
0.6555
Alkyd vol. Fr.
0.4873
Volume Factor
1
Page D-7I
-------
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #W16: Styrene-Vinyl Alkyd 5758; Drier 1: Co/Active-8
Formula #W17:Drier 2: Co/AI
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Soli
MIAK
31.8
0
6.77
4.7
0
57-5758
322.2
241.7
8.14
39.6
27.91
Byk 300
0.92
0.46
8.08
0.11
0.04
TiPure 900
330
330
33.33
9.9
9.9
Grind to Hegman 7.7 with High Speed Disk Disperser
57-5758
226.9
170.2
8.14
27.9
19.65
12% Co
1.9
1.2
8.3
0,23
0.07
XP208
12.6
8.8
8.3
1.5
1
DAc-OH
39.8
0
7.8
5.11
0
MIAK
74.5
0
6.77
11
0
Total
1040.62
752.36
100.05
58.57
Weight Solid %
68.4
WPG (lb/gal)
10.2
PVC
0.17
ICi (poise)
1.8
Stormer (KU)
58
Ford Cup,#4
49
VOC (lb/gal)
3.2
Alkyd wt. Fr.
Alkyd vol. Fr.
Volume Factor
0.75
0.705
0.99950025
Page D-72
-------
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #W18: Styrene-Vinyl Alkyd 5758 and 30% DCPD-Linseed
Raw Material
Total Weight
Weight Solid
WPG
Total Vol,
Vol. Solid
MIAK
31.8
0
6.77
4.7
0
57-5758
322.2
241.7
8.14
39.6
27.91
Byk 300
0.92
0.46
8.08
0.11
0.04
TiPure 900
366.6
366.6
33.33
11
11
Grind to Hegman 7.7 with High Speed Disk Disperser
57-5758
92.4
69.3
8.14
11.3
8
LSO-DCPD
133.3
133.3
8.2
16.3
16.3
12% Co
1.9
1.2
8.3
0.23
0.07
XP208
12.6
8.8
8.3
1.5
1
DAc-OH
23.4
0
7.8
3
0
MIAK
83.3
0
6.77
12.3
0
Total
1068.42
821.36
100.04
64.32
Weight Solid %
73.8
WPG (lb/gal)
10.5
PVC
0.17
ICI (poise)
1.9
Stormer (KU)
60
Ford Cup,#4
55
Alkyd wt. Fr. 0.75
Alkyd vol. Fr. 0.705
Volume Factor 0.99960016
Page D-73
-------
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #W19: Styrene-Vinyl Alkyd 5758 and 20% Epoxidized Soybean
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Soli
MIAK
31.8
0
6.77
4.7
0
57-5758
322.2
241.7
8.14
39.6
27.91
Byk 300
0.92
0.46
8.08
0.11
0.04
TiPure 900
366.6
366.6
33.33
11
11
Grind to Hegman 7.7 with High Speed Disk Disperser
57-5758
150.1
112.6
8.14
18.4
13
Esboil
88.6
88.6
7.9
11.2
11.2
12% Co
1.9
1.2
8.3
0.23
0.07
XP208
12.6
8.8
8.3
1.51
1
DAc-OH
23.4
0
7.8
3
0
MIAK
69.4
0
6.77
10.25
0
Total
1067.52
819.96
100
64.22
Weight Solid %
74.2
WPG (lb/gal)
10.6
PVC
0.17
ICI (poise)
2
Stormer (KU)
62
Ford Cup,#4
58
VOC (lb/gal)
3.1
Alkyd wt. Fr.
0.75
Alkyd vol. Fr.
0.705
Volume Factor
1
Page D-74
-------
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #W20; Long Oil Urethane Alkyd 4368; Drier 1 ;Co/Zr/Ca/Activ-8
Formula #W21: Drier 2; Al/Co
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Solid
n-BuAc
11.5
0
7.35
1.57
0
57-4368
194
135.8
8.14
23.8
15.97
Byk 300
0.8
0.4
8.08
0.1
0.035
TiPure 900
266.6
266.6
33.33
8
8
Grind to Hegman 7.7 with High Speed Disk Disperser
57-4368
291.9
204.4
8.14
35.8
24.03
12% Co
1.9
1.2
8.3
0.23
0.07
XP208
12.6
8.8
8.3
1.51
1
n-BuAc
213.1
0
7.35
29
0
Total
992.4
617.2
100.01
49.105
A/eight Solid %
60.9
WPG (lb/gal)
9.9
PVC
0.16
ICI (poise)
1.8
Stormer (KU)
61
Ford Cup, #4
50
VOC (lb/gal
3.9
Alkyd wt. Fr.
0.7
Alkyd vol. Fr. 0.67
Volume Factor 0.99990001
Page D-75
-------
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #22: Long Oil Urethane Alkyd 4368 and 30% DCPD-Linseed
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Solid
n-BuAc
22.05
0
7.35
3
0
57-4368
218,7
153.1
8.14
26.9
18
Byk 300
0.8
0.4
8.08
0.1
0.035
TiPure 900
333.3
333.3
33.33
10
10
Grind to Hegman 7.7 with High Speed Disk Disperser
57-4368
212.6
148.8
8.14
26.1
17.5
LSO-DCPD
129.4
129.4
8.6
15
15
12% Co
1.9
1.2
8.3
0.23
0.07
XP208
12.6
8.8
8.3
1.51
1
n-BuAc
126.4
0
7.35
17.2
0
Total
1057.75
775
100.04
61.605
Weight Solid % 68.6
WPG (lb/gal) 10.3
PVC 0.16
ICl (poise) 1.9
Stormer (KU) 61
Ford Cup,#4 50
VOC (lb/gal) 3.2
Alkyd wt. Fr.
Alkyd vol. Fr.
Volume Factor
0.7
0.67
0.99960016
Page D-76
-------
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #23: Long Oil Urethane Alkyd 4368 and 20% 1/3 Epoxidized Soybean
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Solid
n-BuAc
22.05
0
7.35
3
0
57-4368
218.7
153.1
8.14
26.9
18
Byk 300
0.8
0.4
8.08
0.1
0.035
TiPure 900
333.3
333.3
33.33
10
10
Grind to Hegman 7.7 with High Speed Disk Dispenser
57-4368
255.1
178.6
8.14
31.3
21
1/3 Esboil
82.9
82.9
7.9
10.5
10.5
12% Co
1.9
1.2
8.3
0.23
0.07
XP208
12.6
8.8
8.3
1.51
1
n-BuAc
121.3
0
7.35
16.5
0
Total
1048.65
758.3
100.04
60.605
Weight Solid %
68.6
WPG (lb/gal)
10.3
PVC
0.16
ICI (poise)
2
Stormer (KU)
62
Ford Cup,#4
53
VOC (lb/gal)
3.3
Alkyd wt. Fr.
0.7
Alkyd vol. Fr.
0.67
Volume Factor
0.99960016
Page D-77
-------
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #W24: Blend of 5758/4368; Drier 1: Co/Zr/Activ-8
Formula #W25: Drier 2; AI/Co
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Solid
MIAK
10.6
0
6.77
1.57
0
57-5758
184.4
138.3
8.14
22.6
15.97
Byk 300
0.8
0.4
8.08
0.1
0.035
TiPure 900
266.6
266.6
33.33
8
8
Grind to Hegman 7.7 with High Speed Disk Disperser
57-4368
291.9
204.4
8.14
35.9
24.03
12% Co
1.9
1.2
8.3
0.23
0.07
XP208
12.6
8.8
8.3
1.51
1
MIAK
67.7
6.77
10
n-BuAc
147.7
0
7.35
20.1
0
Total
984.2
619.7
100.01
49.105
Weight Solid % 68.5
WPG (lb/gal) 9.9
PVC 0.16
ICI (poise) 1.8
Stormer (KU) 60
Ford Cup,#4 55
VOC (lb/gal) 3.3
Alkyd wt. Fr.
Alkyd vol. Fr.
Volume Factor
0.75
0.705
0.99990001
Page D-78
-------
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #W26: Blend 5758/4368 and 30% DCPD-Linseed
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Solid
MIAK
13.5
0
6.77
2
0
57-5758
207.8
155.9
8.14
25.5
18
Byk 300
0.4
0.4
8.08
0.1
0.035
TiPure 900
326.6
326.6
33.33
9.8
9.8
Grind to Hegman 7.7 with High Speed Disk Disperser
57-4368
196
137.1
8.2
23.9
16
LSO-DCPD
125.6
125.6
8.2
15.3
15.3
12% Co
1.9
1.2
8.3
0.23
0.07
XP208
12.6
8.8
8.3
1.51
1
MIAK
6.77
8
n-BuAc
100.7
0
7.35
13.7
0
Total
985.1
755.6
100.04
60.205
i/Veight Solid %
68.4
WPG (lb/gal)
10
PVC
0.16
ICI (poise)
1.8
Stormer (KU)
60
Ford Cup,#4
64
VOC (lb/gal)
2.7
Alkyd wt. Fr.
0.75
Alkyd vol. Fr.
0.705
Volume Factor 0.99960016
Page D-79
-------
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #W27: Blend of 57S8/4368 and 30% 1/3 Epoxidlzed Soybean
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Solid
MIAK
13.5
0
6.77
2
0
57-5758
207.9
155.9
8.14
25.5
18
Byk 300
0.8
0.4
8.08
0.1
0.035
TiPure 900
353.3
353.3
33.33
10.6
10.6
Grind to Hegman 7.7 with High Speed Disk Disperser
57-4368
226.4
158.5
8.2
27.6
18.5
1/3 Esboil
134.7
134.7
7.9
17.1
17.1
12% Co
1.9
1.2
8.3
0.23
0.07
XP208
12.6
8.8
8.3
1.51
1
MIAK
54.16
6.77
8
n-BuAc
54.1
0
7.35
7.36
0
Total
1059.36
812.8
100
65.305
Weight Solid % 71.5
WPG (lb/gal) 10.5
PVC 0.16
iCI (poise) 1.7
Stormer (KU) 65
Ford Cup,#4 65
VOC (lb/gal) 2.4
Alkyd wt. Fr. 0.75
Alkyd vol. Fr. 0.705
Volume Factor 1
Page D-80
-------
AIR DRY WHITE FOR INDUSTRIAL MAINTENANCE
Formula #W28: Blend of 5758/4368 and 20% 1/3 Epoxidized Soybean
Raw Materia!
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Soli
MIAK
13.5
0
6.77
2
0
57-5758
207.8
155.8
8.14
25.5
18
Byk 300
0.8
0.4
8.08
0.1
0.035
TiPure 900
320
320
33.33
9.6
9.6
Grind to Hegman 7.7 with High Speed Disk Disperser
57-4368
244.8
171.3
8.2
29.8
20
1/3 Esboit
81.8
81.8
7.9
10.4
10.4
12% Co
1.9
1.2
8.3
0.23
0.07
XP208
12.6
8.8
8.3
1.51
1
MIAK
64.3
6.77
9.5
n-BuAc
83.79
0
7.35
11.4
0
Total
1031.29
739.3
100.04
59.105
Weight Solid %
74.1
WPG (lb/gal)
10.4
PVC
0.16
ICI (poise)
1.9
Stormer (KU)
68
Ford Cup,#4
66
VOC (lb/gal)
2.8
Alkyd wt. Fr.
0.75
Alkyd vol. Fr.
0.705
Volume Factor
0.99960016
Page D-81
-------
8.0 Detailed Recipes for Air Dry Black Coatings
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Formula # B1: Short Oil Alkyd 5731; Drier: Co/Zr/Activ-8
Formula #B2: Drier Al/Co
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Solid
MIAK
47.7
0
6.77
7.04
0
57-5731
192
144
8.8
21.8
15.27
Byk 300
2.2
1.1
7.8
0.28
0.1
Special Black 4
11.4
11.4
15
0.76
0.76
Supercoat
153
153
22.5
6.8
6.8
Grind to Hegman 6.0 with High Speed Disk Disperser
57-5731
350.7
263.1
8.8
39.8
27.9
MIBK
104.52
6.7
15.6
12% Co
2.8
1.8
8.3
0.33
0.1
12% Zr
8.7
3.8
8.1
1.07
0.32
Activ-8
2.1
0.8
7.9
0.27
0.08
Exkin #2
2.1
0
7.7
0.27
0
Butyl Carbitol
3.3
0
8.16
0.4
0
MIAK
37.9
0
6.77
5.6
0
Total
918.42
579
100.02
51.33
Weight Solid %
66.9
WPG (lb/gal)
9.2
PVC
0.15
ICI (poise)
2
Stormer (KU)
61
Ford Cup,#4
54
VOC (lb/gal) 3.1
Alkyd wt. Fr. 0.75
Alkyd vol. Fr. 0.7
Volume Factor 0.99980004
Page D-82
-------
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
nmula #B3; Short Oil Alkyd 5731 and 30% Epoxidized Soybean
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Sol
MIAK
47.7
0
6.77
7.04
0
57-5731
204.5
153.4
8.8
23.2
16.27
Byk 300
2.2
1.1
7.8
0.28
0.1
Special Black 4
14.3
14.3
15
0.95
0.95
Supercoat
191.3
191.3
22.5
8.5
8.5
Grind to Hegman 6.0 with High Speed Disk Disperser
57-5731
232.6
174.4
8.8
26.4
18.5
1/3 Esboil
140.5
140.5
7.9
17.8
17.8
MIBK
60.3
6.7
9
12% Co
4.1
2.7
8.3
0.5
0.15
XP208
12.6
8.8
8.3
1.51
1
Butyl Carbitol
4.1
0
8.16
0.5
0
MIAK
30.5
0
6.77
4.5
0
Total
944.7
686.5
100.18
63.27
Weight Solid%
70.9
WPG (lb/gal)
9.2
PVC
0.15
ICI (poise)
1.8
Stormer (KU)
64
Ford Cup,#4
67
VOC (lb/gal)
2.2
Alkyd wt. Fr.
0.75
Alkyd vol. Fr.
0.7
Volume Factor 0.998203234
Page D-S3
-------
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Formula #B4: Short Oil Alkyd 5731 and 30% DCPD- Linseed
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Sol
MIAK
47.7
0
6.77
7.04
0
57-5731
204.5
153.4
8.8
23.2
16.27
Byk 300
2.2
1.1
7.8
0.28
0.1
Special Black 4
14.25
14.3
15
0.95
0.95
Supercoat
191.25
191.3
22.5
8.5
8.5
Grind to Hegman 6.0 with High Speed Disk Disperser
57-5731
232.5
174.4
8.8
26.4
18.5
DCPD-LSOIL
140.5
140.5
8.6
16.3
16.3
MIBK
72.4
6.7
10.8
12% Co
2.8
1.8
8.3
0.33
0.1
XP208
12.6
8.8
8.3
1.51
1
Butyl Carbitol
4.1
0
8.16
0.5
0
MIAK
28.5
0
6.77
4.2
0
Total
953.3
685.6
100.01
61.72
Weight Solid %
68.7
WPG (lb/gal)
9.2
PVC
0.15
ICI (poise)
1.7
Stormer (KU)
62
Ford Cup, #4
58
VOC (lb/gal)
2.6
Alkyd wt. Fr.
0.75
Alkyd vol. Fr.
0.7
Volume Factor
0.99990001
Page D-84
-------
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Formula #5: Short Oil Alkyd 5720; Drier 1: Co/Zr/Activ-8
Formula #6: Drier 2; Al/Co
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Soli
MIAK
47.7
0
6.77
7.04
0
57-5720
197.1
147.8
8.65
22.8
15.27
Byk 300
2.2
1.1
7.8
0.28
0.1
Special Black 4
11.4
11.4
15
0.76
0.76
Supercoat
153
153
22.5
6.8
6.8
Grind to Hegman 6.0 with High Speed Disk Disperser
57-5720
340
254.8
8.65
39.3
26.32
MIBK
105.2
6.7
15.7
12% Co
2.8
1.8
8.3
0.33
0.1
XP208
12.6
8.8
8.3
1.51
1
MIAK
37.2
0
6.77
5.5
0
Total
909.2
578.7
100.02
50.35
Weight Solid %
63.3
WPG (lb/gal)
9.03
PVC
0.15
ICI (poise)
Stormer (KU)
Ford Cup,#4
1.8
61
66
VOC (Ib/ga!)
3.3
Alkyd wt. Fr.
Alkyd vol. Fr.
Volume Factor
0.75
0.67
0.99980004
Page D-85
-------
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Formula #B7: Short Oil Alkyd 5720 and 30% DCPD-Linseed
Raw Material Total Weight Weight Solid WPG Total Vol. Vol. Solid
MIAK
47.7
0 6.77 7.04
0
r "i
57-5720
208.5
156.4 8.65 24.1
16.15
i I
Byk 300
2.2
1.1 7.8 0.28
0.1
Special Black 4
13.5
13.5 15 0.9
0.9
r *
Supercoat
182.25
182.3 22.5 8.1
8.1
i f
Grind to Hegman 6.0 with High Speed Disk Dispenser
i I
57-5720
226
169.5 8.65 26.1
17.5
f—1
DCPD-LSOIL
139.7
139.7 8.6 16.2
16.2
; I
MIBK
71.8
6.7 10.71
12% Co
4.1
2.7 8.3 0.5
0.15
n
XP208
12.6
8.8 8.3 1.51
1
^ *
MIAK
31.1
0 6.77 4.6
0
i <
Total
939.45
674 100.04
60.1
Weight Solid %
66.4
WPG (lb/gal)
9.02
5 •
PVC
0.15
ICI (poise)
1.6
Stormer (KU)
63
Ford Cup,#4
60
VOC (lb/gal)
2.8
? I
tr
Alkyd wt Fr.
0.75
Alkyd vol. Fr.
0.67
f ^
Volume Factor
0.99960016
% a
Page D-86
-------
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Formula #B8: Short Oil Alkyd 5720 and 30% Epoxidized Soybean
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Solid
MIAK
47 j
0
6.77
7.04
0
57-5720
208.5
156.4
8.65
24.1
16.15
Byk 300
2.2
1.1
7.8
0.28
0.1
Special Black 4
13.5
13.5
15
0.9
0.9
Supercoat
182.25
182.3
22.5
8.1
8.1
Grind to Hegman 6.0 with High Speed Disk Disperser
57-5720
225.9
169.4
8.65
26.1
17.5
Esboil
139.6
139.6
7.9
17.7
17.7
MIBK
65
6.7
9.7
12% Co
4.1
2.7
8.3
0.5
0.15
XP208
12.6
8.8
8.3
1.51
1
MIAK
27.5
0
6 77
4.07
0
Total
928.85
673.8
100
61.6
Weight Solid % 65.3
WPG (lb/gal) 8.95
PVC 0.15
ICI (poise) 2
Stormer (KU) 68
Ford Cup,#4 72
VOC (lb/gal) 2.3
Alkyd wt. Fr. 0.75
Alkyd vol. Fr. 0.67
Volume Factor 1
Page D-87
-------
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Formula #9; Long Oil Silicone Alkyd 5747; Drier 1: Co/Zr/Activ-8
Formula #10: Drier 2; Al/Co
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Solid
MIAK
47.7
0
6.77
7.04
0
57-5747
177.1
141.7
8.7
20.36
15.27
Byk 300
2.2
1.1
7.8
0.28
0.1
Special Black 4
11.4
11.4
15
0.76
0.76
Supercoat
153
153
22.5
6.8
6.8
Grind to Hegman 6.0 with High Speed Disk Disperser
57-5747
323.6
258.9
8.7
37.2
27.9
MIBK
125.4
6.7
18.7
12% Co
2.8
1.8
8.3
0.33
0.1
XP208
12.6
8.8
8.3
1.5
1
MIAK
48
0
6.77
7.2
0
Total
903.8
576.7
100.17
51.93
Weight Solid %
64.5
WPG
9.05
PVC
0.15
ICI (poise)
1.7
Stormer (KU)
63
Ford Cup,#4
58
Alkyd wt. Fr.
0.8
Alkyd vol. Fr.
0.75
Volume Factor
0.998302885
Page D-88
-------
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Formula #B11: Alkyd 5747 and 30% DCPD-Linseed
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Solid
MIAK
47.7
0
6.77
7.04
0
57-5747
188.7
151
8.7
21.7
16.27
Byk 300
2.2
1.1
7.8
0.28
0.1
Special Black 4
14.25
14.3
15
0.95
0.95
Supercoat
191.25
191.3
22.5
8.5
8.5
Grind to Hegman 6.0 with High Speed Disk Disperser
57-5747
214.89
171.7
8.7
24.7
18.5
DCPD-LSOIL
138.3
138.3
8.6
16.1
16.1
MIBK
88.9
6.7
13.3
12% Co
4.15
2.7
8.3
0.5
0.15
XP208
12.6
8.8
8.3
1.5
1
MIAK
37.2
0
6.77
5.5
0
Total
940.14
679.2
100.07
61.57
Weight Solid%
70.5
WPG (lb/gal)
9.1
PVC
0.15
ICl (poise)
1.9
Stormer (KU)
68
Ford Cup,#4
70
VOC (lb/gal)
2.4
Alkyd wt. Fr.
0.8
Alkyd vol. Fr.
0.75
Volume Factor
0.99930049
Page D-89
-------
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Formula #B12: Alkyd 5747 and 30% Esboil
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Solid
MIAK
47.7
0
6.77
7.04
0
57-5747
188.7
151
8.7
21.7
16.27
Byk 300
2.2
1.1
7.8
0.28
0.1
Special Black 4
14.25
14.3
15
0.95
0.95
Supercoat
191.25
191,3
22.5
8.5
8.5
Grind to Hegman 6.0 with High Speed Disk Disperser
57-5747
214.89
171.7
8.7
24.7
18.5
Esboil
138.3
138.3
7.9
17.5
17.5
MJBK
81.7
6.7
12.2
12% Co
4.1
2.7
8.3
0.5
0.15
XP208
12.6
8.8
8.3
1.5
1
MIAK
35
0
6.77
5.15
0
Total
930.69
679.2
100.02
62.97
Weight Solid%
69.2
WPG (lb/gal)
8.9
PVC
0.15
ICI (poise)
1.8
Stormer (KU)
67
Ford Cup,#4
67
VOC (lb/gal)
2.1
Alkyd wt. Fr.
0.8
Alkyd vol. Fr.
0.75
Volume Factor
0.99980004
Page D-90
-------
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Formula #B13: Blend of 5758/4368 ; Drier 1: Co/Zr/Activ-8
Formula #14: Drier 2; Ai/Co
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Solid
MIAK
47.7
0
6.77
7.04
0
57-5758
176.3
132.2
8.14
21.6
15.27
Byk 300
2.2
1.1
7.8
0.28
0.1
Special Black 4
11.4
11.4
15
0.76
0.76
Supercoat
153
153
22.5
6.8
6.8
Grind to Hegman 6.0 with High Speed Disk Disperser
57-4368
341.5
239.05
8.2
41.65
27.9
MIBK
97.1
6.7
14.5
12% Co
2.8
1.8
8.3
0.33
0.1
XP208
12.6
8.8
8.3
1.5
1
MIAK
38
0
6.77
5.6
0
Total
882.6
547.35
100.06
51.93
Weight Solid % 61
WPG (lb/gal) 8.6
PVC 0.14
ICI (poise) 1.6
Stormer (KU) 58
Ford Cup,#4 53
VOC (lb/gal) 3.2
Alkyd wt. Fr.
Alkyd vol. Fr.
Volume Factor
0.75
0.705
0.99940036
Page D-91
-------
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Formula #B15: Blend of 5758/4368 and 30% DCPD-Linseed
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Sol
MIAK
47.7
0
6.77
7.04
0
57-5758
196.2
147.1
8.14
24.1
17
Byk 300
2,2
1.1
7.8
0.28
0.1
Special Black 4
12.75
12.8
15
0.85
0.85
Supercoat
172.2
172.2
22.5
7.65
7.65
Grind to Hegman 6.0 with High Speed Disk Dispenser
57-4368
208.3
145.8
8.2
25.4
17
DCPD-LSOIL
125.5
125.5
8.6
14.6
14.6
MIBK
84.4
6.7
12.6
12% Co
4.1
2.7
8.3
0.5
0.15
XP208
12.6
8.8
8.3
1.5
1
MIAK
37.2
0
6.77
5.5
0
Total
903.15
616
100.02
58.35
Weight Solid %
66.5
WPG (lb/gal)
8.7
PVC
0.14
ICI (poise)
1.7
Stormer (KU)
62
Ford Cup,#4
64
VOC (lb/gal)
2.6
Alkyd wt. Fr.
0.75
Alkyd vol. Fr.
0.705
Volume Factor
0.99980004
Page D-92
-------
AIR DRY BLACK FOR INDUSTRIAL MAINTENANCE
Formula #B16: Blend of 5758/4368 and 30% 1/3 Epoxidized Soybean
Raw Material
Total Weight
Weight Solid
WPG
Total Vol. Vol. Soli
MIAK
47.7
0
6.77
7.04
0
57-5758
196.2
147.1
8.14
24.1
17
Byk 300
2.2
1.1
7.8
0.28
0.1
Special Black 4
12.75
12.8
15
0.85
0.85
Supercoat
172.2
172.2
22.5
7.65
7.65
Grind to Hegman 6.0 with High Speed Disk Disperser
57-4368
201.9
141.3
8.2
24.62
16.5
1/3 Esboil
123.6
123.6
7.9
15.5
15.5
MIBK
82.4
6.7
12.3
12% Co
4.1
2.7
8.3
0.5
0.15
XP208
12.5
8.75
8.3
1.5
1
MIAK
38.6
0
6.77
5.7
0
Total
894.15
609.55
100.04
58.75
Weight Solid %
67.6
WPG (lb/gal)
8.6
PVC
0.14
ICI (poise)
1.8
Stormer (KU)
64
Ford Cup,#4
68
VOC (lb/gal)
2.4
Alkyd wt. Fr.
0.75
Alkyd vol. Fr.
0.705
Volume Factor
0.99960016
Page D-93
-------
9.0 Detailed Recipes for Air Pry Red Oxide Primers
AIR DRY RED OXIDE PRIMER FOR INDUSTRIAL MAINTENANCE
Formula #R1: Phenolic resin Rezimac 2810; Drier: Ca/Co/Mn/Zr/Activ-8
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Solid
Rezimac 2810
292.3
222.2
8.78
33.33
23
Nuosperse 657
2.3
1.6
7.85
0.29
0.19
10% Ca
1.85
0.92
8.4
0.22
0.1
Bentone SD-1
1.5
1.5
12.5
0.12
0.12
Toluene
50.8
0
7.26
7
0
VM&P Naphta
27.5
0
6.12
4.5
0
SZP 391
45
45
25
1.8
1.8
Red Fe203 4097
122.4
122.4
40.8
3
3
Gammasperse 80
339
339
22.6
15
15
Butyl acetate
44.1
0
7.35
6
0
Grind to Hegman 5; Temp; 90°F to 150°F
with HS-Disperser
Rezimac 2810
76.4
58.1
8.78
8.7
6
Xylene
13.3
0
7.4
1.8
0
Nytal 300 Mag Si
59.25
59.25
23.7
2.5
2.5
12% Co
1.2
0.8
8.2
0.15
0.06
12% Mn
1.28
0.8
8.5
0.15
0.06
24% Zr
3.2
2.8
10.6
0.3
0.22
Exxkin #2
3.1
0
7.65
0.4
0
MPK
100
0
6.74
14.8
0
Add under Agitation
Total
1184.48
854.37
100.06
52.05
Weight Solid % 75.4
WPG (lb/gal) 12
PVC 0.43
ICI (poise) 1.6
Stormer (KU) 63
Ford Cup,#4 40
Alkyd wt, Fr.
Alkyd vol. Fr.
Volume Factor
0.76
0.69
0.99940036
Page D-94
-------
AIR DRY RED OXIDE PRIMER FOR INDUSTRIAL MAINTENANCE
Formula #R3: Phenolic resin rezimac 2810; 30% DCPD Linseed; Drier: Ca/Co/Mn/Zr/Activ-8
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Solid
Rezimac 2810
235.4
178.9
8.78
26.81
18.5
Nuosperse 657
2.3
1.6
7.85
0.29
0.19
10% Ca
1.85
0.92
8.4
0.22
0.1
Bentone SD-1
1.5
1.5
12.5
0.12
0.12
Toluene
41.4
0
7.26
5.7
0
VM&P Naphta
20.8
0
6.12
3.4
0
SZP 391
50
50
25
2
2
Red Fe02 4097
134.65
134.65
40.8
3.3
3.3
Gammasperse 80
372.9
372.9
22.6
16.5
16.5
Butyl acetate
34.5
0
7.35
4.7
0
Grind to Hegman 5; Temp: 90° F to 150°F with HS-Disperser
Rezimac 2810
76.4
58.1
8.78
8.7
6
DCPD-Lsoil
101.6
101.6
8.6
11.8
11.8
Xylene
11.8
0
7.4
1.6
0
Nytal 300 Mag Si
78.2
78.2
23.7
3.3
3.3
12% Co
1.2
0.8
8.2
0.15
0.06
12% Mn
1.3
0.8
8.5
0.15
0.06
24% Zr
3.3
2.8
10.6
0.31
0.22
Exkin #2
3.1
0
7.65
0.4
0
MPK
71.5
0
6.74
10.6
0
Add under Agitation
Total
1243.7
982.77
100.05
62.15
Weight Solid %
80.4
WPG (lb/gal)
12.3
PVC
0.4
ICI (poise)
1.8
Stormer (KU)
67
Ford Cup,#4
55
Alkyd wt. Fr.
0.76
Alkyd vol. Fr,
0.69
Page D-95
-------
AIR DRY RED OXIDE PRIMER FOR INDUSTRIAL MAINTENANCE
Formula #R2: Phenolic resin Rezimac 2810; Drier: Al/Co
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Solid
Rezimac 2810
318.1
241.7
8.78
36.23
25
Nuosperse 657
2.3
1.6
7.85
0.29
0.19
Bentone SD-1
1.5
1.5
12.5
0.12
0.12
Toluene
41.4
0
7.26
5.7
0
VM&P Naphta
20.8
0
6.12
3.4
0
SZP 391
50
50
25
2
2
Red Fe02 4097
134.65
134.65
40.8
3.3
3.3
Gammasperse 80
372.9
372.9
22.6
16.5
16.5
Butyl acetate
riA
0
7.35
4.7
0
Grind to Hegman 5; Temp: 90°F to 150°
F with HS-Disperser
Rezimac 2810
96.6
73.4
8.78
11
7.6
Xylene
11.8
0
7.4
1.6
0
Nytal 300 Mag Si
78.2
78.2
23.7
3.3
3.3
12% Co
1.2
0.8
8.2
0.15
0.06
XP208
12.6
8.8
8.3
1.5
1
MPK
69
0
6.74
10.23
0
Add under Agitation
Total
1245.595
963,55
100.02
59.07
Weight Solid %
75.9
WPG (lb/gal)
12.14
PVC
0.42
ICI (poise)
2.2
Stormer (KU)
65
Ford Cup,#4
50
VOC (lb/gal)
2.9
Alkyd wt. Fr.
0.76
Alkyd vol. Fr.
0.69
Volume Factor
0.99980004
Page D-96
-------
AIR DRY RED OXIDE PRIMER FOR INDUSTRIAL MAINTENANCE
Formula #R4:Phenolic Resin Rezimac 2810; 30% DCPD- Linseed; Drier: A/Co
Raw Material
Total Weight
Weight Solid
WPG
Total Vol.
Vol. Solid
Rezimac 2810
235.3
178.8
8.78
26.8
18.5
Nuosperse 657
2.3
1.6
7.85
0.29
0.19
Bentone SD-1
1.5
1.5
12.5
0.12
0.12
Toluene
41.4
0
7.26
5.7
0
VM&P Naphta
20.8
0
6.12
3.4
0
SZP 391
50
50
25
2
2
Red Fe02 4097
134.65
134.65
40.8
3.3
3.3
Gammasperse 80
372.9
372.9
22.6
16.5
16.5
Butyl acetate
34.2
0
7.35
4.65
0
Grind to Hegman 5; Temp: 90°F to 150°F with HS-Disperser
Rezimac 2810
76.4
58.1
8.78
8.7
6
DCPD-Lsoil
101.5
101.5
8.6
11.8
11.8
Xylene
11.8
0
7.4
1.6
0
Nytal 300 Mag Si
78.2
78.2
23.7
3.3
3.3
12% Co
1.2
0.8
8.2
0.15
0.06
XP208
12.5
8.75
8.3
1.5
1
MPK
70
0
6.74
10.2
0
Add under Agitation
Total
1244.65
986.8
100.01
62.77
Weight Solid %
78.7
WPG (lb/gal)
12.1
PVC
0.4
ICI (poise)
2.5
Stormer (KU)
67
Ford Cup,#4
55
VOC (lb/gal)
2.5
Alkyd wt. Fr.
Alkyd vol. Fr.
Volume Factor
0.76
0.69
0.99990001
Page D-97
-------
Appendix E
LOW VOC COATINGS
DEMONSTRATION PROJECT
(ECOTEK)
PROJECT CODE 1-1043
¦
*¦¦¦¦¦¦¦¦¦¦ ¦
<¦¦¦¦¦¦¦ ¦ I
¦¦¦¦¦¦¦¦a 11ci
¦¦¦¦¦¦¦¦ ¦¦ ¦¦k
JB¦¦¦¦¦¦¦¦¦¦¦¦¦¦
<¦¦¦¦¦¦¦¦¦¦¦¦¦¦*
«¦¦¦¦¦¦¦¦¦¦¦¦¦*
•¦¦¦¦¦!¦¦¦¦¦¦¦•
i it¦¦¦¦¦¦¦¦ ¦ ¦¦ »
!<¦¦¦¦¦¦¦¦¦¦>
LABORATORIES, INC.
BV:
1QNACE BADOU
PEA LABORATORIES, INC.
430 WfeST FOREST AYfeNUE
YPSILAOTI, MICHIGAN 4619?
PHONE#: 313-463-3401
FAX#: 813-463-0065
EPOXIES
¦
% SbJ ¦
¦I rf ¦ ¦¦ ¦ ¦ ¦ ¦
I ¦ ¦ ¦ ¦ ¦¦ ¦ ¦
-------
Table of Contents
List of Tables E-iii
1. Objective E-1
2. Summary E-1
3. Raw Materials for Resin Preparation and Coatings Formulation E-2
4. Resin Preparation E-2
4.1 Shell Advancement Procedure E-2
4.2 Advancement Procedure Proposed by CRI E-2
4.3 Alternative Advancement Procedure for Fully Epoxidized Linseed Oil E-3
5. Sample Preparation and Application E-3
6. Results and Discussion E-4
6.1 Advancement of Epoxy Resins with Epoxidized Vegetable Oils E-4
6.2 Paint Compositions E-5
6.3 Dry Time E-5
6.4 Potlife E-6
6.5 VOC E-7
6.6 Film Performance E-7
7. Conclusions E-11
8. Detailed Recipes for Air Dry Red Oxide Epoxy Primers .................. E-12
Page E-ii
-------
Tables
Table 1:
Resin Properties and Synthesis Conditions
.. . . , E-4
Table 2;
Drying Time for Red Primers
E-6
Table 3:
Potiife
E-7
Table 4:
VOC
E-7
Epoxy Red
Primers:
Table 5:
Sward Hardness
E-8
Table 6:
Pencil Hardness
E-8
Table 7:
Adhesion
.E-8
Table 8;
Direct Impact
E-9
Table 9:
Reverse Impact
E-9
Table 10:
MEK Resistance
E-9
Table 11:
Humidity Cabinet
Table 12:
Salt Fog Cabinet
E-10
Page E-iii
-------
LOW VOC COATINGS DEMONSTRATION PROJECT
ECOTEK
Project Code #: 1043
Epoxy Red Iron Oxide Primers
1. Objective:
Identify VOC reduction capabilities of vegetable oil reactive diluents in epoxy coatings based on a
technology from Coatings Research Institute.
2. Summary:
Red iron oxide primers of six epoxy resins formulations were prepared and tested. These six
formulations were based on modifications to a blend of high and low molecular weight Bisphenol
A epoxy resins. Two of the formulations were prepared by adding 20% and 30% respectively of
fiiEy epoxidized linseed oil to the blend of epoxy resins. The other four formulations were
prepared by advancing the molecular weight of a single low molecular weight epoxy resin with
either epoxidized linseed oil or vernonia oil. Depending on the degree of advancement, resins with
different epoxy equivalent weights were obtained. Red iron oxide primers of these six modified
epoxy coatings were compared with that of the primer from the unmodified epoxy blend.
The VOC of the straight formulation was 260g/l and could be reduced to 140 and 120g/l when
20% and 30% fully epoxidized linseed oil were added. However, drying times were increased.
Formulations based on the advanced resins gave higher VOC (260 to 330g/l), but drying times
were decreased. Hardness, adhesion, impact, corrosion and humidity resistance were good for all
formulations.
Page E-l
-------
3. Raw Materials for Resin Preparation and Coatings Formulation
Resins
The following resins were used based on initial studies at the Coatings Research Institute:
DER 660-80 (Dow Chemical), is a Bisphenol A epoxy resin with an epoxide equivalent weight
about 500 and 80% solid content.
EPON 828 (Shell) and DER 331 are Bisphenol A type epoxy resins with 100% solid content and
an epoxide equivalent weight of 190.
Vernonia oil is a natural saturated epoxidized oil with an epoxide equivalent weight of 430
(Shell).
Fully epoxidized linseed oil is an unsaturated epoxidized oil with an epoxide equivalent weight of
176.
Additives
Triphenyl phosphite is an antioxidant (Aldrich)
Ethyl triphenylphosphonium acetate is a catalyst for epoxide etherification reactions.
Sodium carbonate was used as catalyst.
Nuoperse 657, dispersing agent (Hiils)
A&T Atomite, calcium carbonate
Vantalc 6H, magnesium silicate
Harcros 6057, red iron oxide
4. Resin Preparation
4.1 Shell Advancement Procedure
To a suitable reactor were added 150 parts of vernonia oil with an epoxide equivalent weight of
432, 223 parts of the diglycidyl ether of Bisphenol A (DER 331 or EPON 828) having an epoxide
equivalent weight of 190, 127 parts Bisphenol A, 5 parts of phosphite antioxidants (triphenyl
phosphite) and 0.38 part of ethyl triphenylphosphonium acetate. Heat, agitation and nitrogen
sparge were applied. The temperature was raised to 200°C (390°F) and held at this temperature
for 3 hours and 30 minutes. The epoxide equivalent weight of the reaction mass was 1086. Then
214 parts of methyl n-propyl ketone (MPK) were added to reduced the solid content to 70
percent. The viscosity at 70 percent solids was 390 centipoises.
4.2 Advancement Procedure Proposed by CRI
To a suitable reactor were added 184 parts of fully epoxidized linseed oil with an epoxide
equivalent weight of 176, 230 parts of the diglycidyl ether of Bisphenol A (DER 331 or EPON
828) having an epoxide equivalent weight of 190, 127 parts Bisphenol A, and 5 parts of sodium
carbonate as catalyst. Heat, agitation and nitrogen sparge were applied. The temperature was
raised to 160°C (320°F) and held at tMs temperature for 1 hour and 30 minutes. The epoxide
equivalent weight of the reaction mass was 442. Then 125 parts of xylene were added to reduce
the solid content to 80 percent. The viscosity at 70 percent solids was 300 centipoises.
PageE-2
-------
4.3 Alternative Advancement Procedure for Fully Epoxidized Linseed oil.
To a suitable reactor were added 184 parts of fully epoxidized linseed oil with an epoxide
equivalent weight of 176, 230 parts of the diglycidyl ether of Bisphenol A (DER 331 or EPON
828) having an epoxide equivalent weight of 190, 127 parts Bisphenol A and 5 parts phosphite
antioxidant (triphenyl phosphite). Heat, agitation and nitrogen sparge were applied. The
temperature was raised to 220°C (430°F) and held at this temperature for 1 hour. The epoxide
equivalent weight of the reaction mass was 580. Then 198 parts of methyl n-propyl ketone (MPK)
were added to reduce the solid content to 72 percent. The viscosity at 72 percent solids was 580
centipoises.
5. Sample Preparation and Application
The paints were prepared by using the formulations in the Tables outlined, EP#0 to #6. EP#0 was
used as control. The paint samples were applied in the same sequence as prepared, first over glass
for drying time determination, then over untreated cold rolled steel for performance testing. The
wet paints were applied with No.42 bar to give a wet film thickness of about 3mils and dry film
thickness of about lmil. Ten panels for each paint were drawn down, Five were force dried at
90°C for one hour and left to air dry with the remaining five panels for 4 to7 days before testing.
Testing Procedure
Set to touch, dry to touch, tack free and through dry were determined according to ASTM
D1640-83. A B-K-drying recorder was used to determine the through dry. Film thickness was
measured with Elcometer -300 digital thickness gauge.
Paint characteristics and dry film properties were determined with the following tests:
Weight per gallon (ASTM D1475), Non Volatile by Weight (ASTM D2369), VOC (ASTM
D3960-87), Pencil Hardness (ASTM D3363-74), Sward Hardness (ASTM D2134-66),
Crosshatch Adhesion (ASTM D33 59-90), Impact Resistance (ASTM D2794), Package Stability
(ASTM D1849-80), Gloss (D523), QUV Weathering (D4587), Humidity Resistance (D2247 and
D714), Salt Fog Exposure (B117), Viscosity was measured with Brookfield, ICI Cone & Plate,
Krebs-Stormer. Epoxy equivalent weight and epoxy content were determined according to ASTM
1652.
Page E-3
-------
6
Results and Discussion
6.1 Advancement of Epoxy Resins with Epoxidized Vegetable Oils
The procedure consisted of reacting a low molecular weight Bisphenol A epoxy resin, an
epoxidized vegetable oil and Bisphenol A in presence or absence of a suitable catalyst and
antioxidants at temperatures above 150°C. The simultanous incorporation of flexible vegetable oil
segments and rigid Bisphenol A units could give fast air drying and low VOC resins with good
physical properties and performance. Four resins were synthesized using different advancement
procedures.
In the first procedure vernonia oil was used as the vegetable oil and ethyl triphenyl phosphonium
acetate as catalyst. Phosphite antioxidants were added to reduce color. Vernonia oil is a unique
vegetable oil that contains about 2.5 epoxy groups per molecule and has no unsaturation. The
relatively low epoxy content and the absence of oxidizing double bonds allow to advance resins
having epoxy equivalent weights as high as 1300. The advancement is part of a procedure
invented by Elmore et al. (Shell patent 5,227,453) to synthesize vernonia oil modified epoxy
esters. According to the inventors, the procedure could not be used for other epoxidized
vegetable oils such as fully epoxidized linseed or soybean oil because of the risk of gellation. In
addition to the relatively high epoxy content (up to nine epoxy group per molecule), epoxidized
linseed and soybean oil contain light oxidizable linoleic and linolenic residues succeptible to
polymerization under the conditions the advancement was done (at temperature about 200°C).
In the second procedure fully epoxidized linseed or soybean oil were used. Lower temperatures
and less active catalysts were required. Sodium carbonate was used as catalyst and the reaction
temperature did not exceed 160°C (320°F). The epoxy equivalent weight of the resin was 442.
When no catalyst was added the temperature was raised to 220°C and the epoxy equivalent
weight was 580. Table 1 shows synthesis conditions and resin properties.
Table 1: Resin Properties and Synthesis Conditions
Adv. Resin 1 Adv.Resin 2 Adv. Resin 3 Adv. Resin 4
Temperature (°C)
Catalyst
Epoxidized Oil
Reaction Time (h)
EEW of the Mixture
EEW of the Resin
Brookfield (#3, lOOrpm)
Weight per gallon (lb/gal)
Weight Solid,%
Volume Solid,%
VOC (g/1)
1.5
221
442
520
8.8
80
80
230
160
Carbonate
linseed
none
linseed
1
221
580
590
8.4
72
65
270
MPK
220
3.5
330
1086
570
8.3
70
65
310
MPK
200
ETPPA
vernonia
4.5
330
1300
390
8.3
70
63
300
MPK
200
ETPPA
vernonia
Solvent
Xylenes
EEW: Epoxy equivalent weight MPK: Methyl n-propyl ketone
Page E-4
-------
6.2 Paint Compositions
All paints were formulated as red iron oxide primers with similar compositions having a PVC
about 24%, Six different binders were used.
EP#0 was the straight formulation based only on DER-660 and EPON 828. DER 660-80 is an
80% solid high molecular weight Bisphenol A resin with an epoxy equivalent weight of about
500. EPON 828 is a 100% solid low molecular weight resin and has an epoxy equivalent weight
of about 190. The weight ratio of DER-660:Epon 828 used in the straight formulation was 3:1.
EP#1 was prepared by replacing 20% of the total weight of the binder by folly epoxidized linseed
oil. The epoxy equivalent weight of fully epoxidized linseed oil is 176. EP#2 had a similar
composition but the epoxidized linseed oil content was 30%. EP#3 was prepared with advanced
resin-1, EP#4 with advanced resin-2, EP#5 with advanced resin-3 and EP#6 with advanced resin-
4. The sample compositions are summarized in the Tables outlined. The pigments were dispersed
in the epoxy resins (Component A) and EPOTUF 37-601, a polyamide amine with an amine
hydrogen equivalent weight of 84.6 that was added as crosslinker (Component B). The mixture
was left one hour at room temperature before application. (See pages E-12 to E-17 for detailed recipes.)
6.3 Drying Time
Set to touch time for the advanced resins formulations was less than 10 minutes but over 2 hours
for the samples blended with 20% and 30% fully epoxidized linseed oil (EP#1 and EP#2). A time
of 26 minutes was found for EP#0, the straight formulation based on DER 660 and EPON 828
that was used as control. Dry to touch was about 45 minutes for EP#0 but less than 5 minutes for
the advanced formulations based on vernonia oil (EP#5 and EP#6) and both had relatively low
epoxide content and high epoxy equivalent weight (EEW); 1086 for advanced resin-3 and 1300
for advanced resin-4. Dry to touch was 10 minutes for EP#4, 15 minutes for EP#3, 45 minutes for
EP#0 and over 2 hours for EP#1 and EP#2. Tack free was the shortest for EP#6 (10 minutes),
EP#5 dried tack free in 15 minutes, EP#4 in 20 minutes and EP#3 in 30 minutes. The samples
blended with folly epoxidized linseed oil had the longest tack free time; 5 hours for EP#1 and 6
hours for EP#2 while the straight formulation EP#0 had a tack free time of about 2 hours.
Through dry was relatively short for the advanced formulations but it increased as the epoxy
equivalent weight decreased (4 to 8 hours). The formulations containing 20 and 30% of folly
epoxidized linseed oil dried relatively long. Fully epoxidized linseed oil still contained unsaturated
groups such as linoleic and linolenic which air dry rapidly in the presence of metal driers like
cobalt octoate. Since no drier was added to the paints, an autoxidative crosslinking was very
slow. As a result, set to touch, dry to touch and tack free were longer than for the straight
formulation EP#0. Through dry was about 10 hours for the three samples EP#0, EP#1 and EP#2.
Page E-5
-------
General Comments
The drying times of the advanced resin formulations depended on the epoxy equivalent weight.
EP#6 dried through in 3 hours and tack free in 10 minutes. Its epoxy equivalent weight was 1300.
EP#5 had an EEW of 1086, and dried tack free in 15 minutes. Through dry was 5 hours. EP#3
and #4 which were based on resins advanced with linseed oil and had a tack free time of 30 and
20 minutes while through dry was 10 and 8 hours respectively. The EEW was 442 for EP#3 and
580 for EP#4. The advancement increased not only the molecular weight but also the number of
rigid Bisphenol A units in the resins. These two facts could have helped reduce tack free and
through dry times. The two samples based on blends with fully epoxidized linseed oil (EP#1 and
EP#2) had the longest drying times perhaps because of the low epoxy equivalent weight and the
presence of unsaturation. Surface dry, expressed in set to touch, dry to touch and tack free, was
shorter for the straight formulation EP#0.
Table 2: Drying Time for Red Primers
Sample ID EP#0 EP#1 EP#2 EP#3 EP#4 EP#5 EP#6
Set to Touch (min)
25
120
150
10
5
5
3
Dry to Touch (min)
45
180
240
15
10
5
5
Tack Free (min)
120
250
300
30
20
15
10
Through Dry (h)
10
8
10
10
8
5
3
6.4 Potlife
The samples exhibited different potlives. After mixing component A and B, solvent was added to
adjust the initial ICI viscosity to about 2 poises. ICI was then measured after 1 hour, 6 hours and
24 hours. The results are summarized in Table 3.
The samples blended with fully epoxidized linseed oil (EP#1 and EP#2) exhibited the shortest
potlife. The straight formulation EP#0 had a somewhat longer potlife. Increased potlife was
observed for the advanced formulations. The samples with the highest epoxy equivalent weight
exhibited the longest potlife.
Page E~6
-------
Table 3: Potlife
Sample ID _ EP#0 EP#1EP#2 JEP#3 EP#4 _ EP#5 EP#6_
Initial ICI (poise)
ICI after lh (poise)
ICI after 6 hours (poise)
ICI after 24 hours (poise)
2.3
2.1
2.0
1.8
2.1
2.0
2.0
3.2
6.0
6.6
4.4
2.2
2.0
2.0
6.5
8.0
>10
5.8
4.0
2.5
2.0
>10
>10
>10
8.0
6.0
5.0
2.8
6.5 VOC
VOC levels for the advanced formulations were very high, especially when the epoxy equivalent
weight increased. EP#6 with an EEW of 1300 had a VOC about 330g/l while a value of 260g/l
was found for EP#3 which had an EEW of 442. The samples blended with fully epoxidized
linseed oil exhibited the lowest VOC, 140g/l for EP#1 which contained 20% and 120g/l for EP#2
which contained 30% folly epoxidized linseed oil. VOC of the straight formulation EP#0 was
260g/l. Addition of 20% and 30% of fully epoxidized linseed oil reduced it to 140g/l and 120g/l
respectively. The data are summarized in Table 4
Table 4: VOC
SampleID~ " " " "EP#o"~EP#l EP#2 EP#3 ET#4 EP#5~"1p#6 "
VOC (g/1) - 260 140 120 260 310 300 330
VOC (lb/gal) - 2.2 1.2 1.0 2.2 2.6 2.5 2.8
6.6 Film Performance
Sward Hardness
Two panels were prepared for each sample. The first panel was force dried for 1 hour at 90°C
then left to air dry with the second for about 5 to 7 days under normal conditions (relative
humidity below 50% and temperature above 78°F). Sward hardness was between 15 and 30
rocks. This is an indication that the surface drying process was complete. No significant difference
was observed between force and air dried samples (Table 5). The samples blended with fully
epoxidized linseed oil exhibited the highest values, perhaps because of the higher crosslinking
density due to the initial high concentration of functional groups. A dependency of the epoxy
equivalent weight on sward hardness could not be observed probably because of a decrease in
epoxide groups that led to an increase in rigid Bisphenol A units. Both contributed to the surface
hardness.
Page E-7
-------
Table 5: Epoxy Red Primers; Sward Hardness (rock)
Sample ID EP#0 EP#1 EP#2 EP#3 EP#4 EP#5 EP#6
Air Dry 28 27 30 18 18 20 15
Force Dry 24 30 28 17 18 15 19
Pencil Hardness
Pencil hardness decreased with the degree of advancement; The samples with the highest epoxy
equivalent weight (EP#5 and F.P#6) also had the lowest pencil hardness. Apparently, an increase
in the epoxy equivalent weight led to a decrease in available functional groups, thus a lower
crosslinking density. No difference was observed for force and air dried samples based on
advanced resins. The samples blended with folly epoxidized linseed oil exhibited the highest pencil
hardness resulting from a higher crosslinking density (Table 6).
Table 6: Epoxy Red Primers; Pencil Hardness
"SampleID ' ~ EP#0~ljp#l" EP#2 EP#3 EP#4 EP#5 EP#6~
Air Dry 5H 4H 3H H 5H HB 2B
Force Dry 4H 5H 4H 2H 5H HB B
Adhesion
Crosshatch adhesion to CRS was excellent for all samples.
Table 7: Epoxy Red Primers; Adhesion
"sampiero
Air Dry 5B 5B 5B 5B 5B 5B 5B
Force Dry 5B 5B 5B 5B 5B 5B 5B
Page ICS
-------
Impact Resistance
Except EP#6, all samples exhibited excellent direct and reverse impact resistance (Table 8 and 9).
EP#6 had the highest epoxy equivalent weight and the concentration of rigid Bisphenol A units
was relatively high. As a result, the coatings tended to be brittle.
Tabic 8: Epoxy Red Primers; Direct Impact (iii-Ib)
Sample ID
EP#0 EP#1 EP#2 EP#3 EP#4 EP#5 EP#6
Air Dry
Force Dry
160 160 160 160 160 160 140
160 160 160 160 160 160 50
Table 9: Epoxy Red Primers; Reverse Impact (in-lb)
Sample ID
EP#0 EP#1 EP#2 EP#3 EP#4 EP#5 EP#6
Air Dry
160 160 160 160 160 160 130
MEK Resistance
Resistance to MEK was significantly lower for the advanced formulations than for the samples
based on the blend with fully epoxidized linseed oil. The relatively low crosslinking density and
the presence of unpolar aromatic and aliphatic glycidyl ether derivatives led to a good solubility of
the advanced samples in organic solvent such as methyl ethyl ketone. The samples based on the
blend with fully epoxidized linseed oil exhibited high MEK resistance due to the high crosslinking
density and a lower film permeability, especially when force diy (Table 10).
Table 10: Epoxy Red Primers; MEK resistance (Double Rub)
Sample ID EP#0 EP#1 EP#2 EP#3 EP#4 EP#5 EP#6
Air Dry 60 90 100 25 20 5 4
Force Dry 30 >200 >200 35 25 7 7
Page E-9
-------
Humidity Resistance
Humidity resistance was excellent. No blistering was observed after 21 days exposure to a
Cleveland Humidity Cabinet for most of the samples. However, the paints formulated with the
resins advanced with folly epoxidized linseed oil exhibited a few small blisters with a rating of #9.
Table 11: Epoxy Red Primers; Humidity Cabinet, 21 days Exposure,
Blister Rating
SampfelD " ' ~ EP^1bP#1"~EP#2-EP#3 ' ™
Air Dry none none #9,F #9,F none none none
Force Dry none none #9,F #9,F none none none
Corrosion Resistance
No significant damage was observed for the samples after 5 days exposure to the Salt Fog
Cabinet. However, few blisters with a rating of #8 were observed around the scribed areas for all
samples after 10 days exposure. Only a slight rust formation was observed.
Table 12: Epoxy Red Primers; Salt Fog Cabinet 10 days Exposure
Rating for Scribed/unscribed Panels
Sample ID
EP#0 EP#1 EP#2 EP#3 EP#4 EP#5 EP#6
Air Dry
Force Dry
9/9 9/10 8/9 10/8 9/8 9/8 10/8
9/9 9/9 9/9 9/8 8/8 9/8 10/8
Page E-10
-------
7. Conclusions
VOC reduction was successful only with the vehicles from the blending of fully epoxidized linseed
oil with Bisphenol A epoxy resins. The drying times, however, were significantly increased;
through dry was similar to the bisphenol A resins alone.
The advancement procedures did not allow for VOC reduction in primer formulations. However,
this approach provided some opportunity for improved properties of primer formulations using
these vehicles.
The significant reduction in VOC (from 260 g/1 to 120-140 g/1) using a 20%-3Q% blend of fully
epoxidized linseed oil with Bisphenol A epoxy resins offers a real opportunity for this technology.
The significant increase in drying time for set-to-touch, and for tack-free are serious
shortcomings; however, it may be possible to over come this shortcoming through the exploration
of new or novel drier systems. Another area to explore would be an attempt to use other low
VOC resins that provide early "snap-dry" as a blending agent with these vehicles.
The advancement technology for vernonia oil appears to be self-limiting, since the Bisphenol A
epoxy groups react with themselves faster than with the epoxy from vernonia oil, leaving a blend
of high molecular weight Bisphenol A and a plasticizer (unreacted epoxidized vernonia oil). The
advancement technology for fully epoxidized linseed oil is limited by the presence of unsaturation,
which limits how high a temperature can be used for advancement to high epoxy equivalent
weight. Often, gellation occurs prior to achievement of an EEW sufficient for good properties.
Research into improved advancement techniques might provide vehicles that can offer reasonably
lower VOC's, while still keeping the excellent performance properties.
Page E-11
-------
8.0 De^i led Recipes for Air Drv Red OxidQ Epoxy Primers
Formula EP#1: Red Oxide Epoxy Primer
Blend Containing 20% Epoxidized Linseed Oil
Raw Material
Component A
MIBK
Total Weight Weight Solid WPG Total Vol. Vol. Solid EEW
88,4
6.8
13
3/3 Elsoil
72.2
72.2
8.6
8.4
8.4
Nuosperse 657
2.26
1.58
7.85
0.29
0.19
Dissolve
Heucophos ZBZ
75
75
30
2-5
2.5
Sicorin RZ
6.2
6.2
20.85
0.3
0.3
RO-4097
204
204
40.8
5
5
Vantalc 6H
103,05
103.05
22.9
4.5
4.5
T+WAtomite
112.5
112.5
22.5
5
5
Grind to Hegman 5 with HS-Disperser
DER 660-80
240
192
9.6
25
20
EPON 828
97
97
9.7
10
10
MIBK 87.5
Component B
Epotuf 37-601 110.4
110.4
6.8
8.4
12.87
13.2
Total
Weight Solid %
Average WPG
PVC {%)
VOC
ICI (poise)
Stormer (KU)
Mix thoroughly
1198.51 973.93
90.5
11.98
24.6
1.2
2.1
70
Alkyd wt Fr. 0.8
Alkyd vol. Fr. 0.8
176
500
190
13.2
100.06 69.09
Page E-J2
-------
1
HI
1
n
h
F
P
Formula EP#2: Red Oxide Epoxy Primer
Blend with 30% 3/3 EpoxJdized Linseed Oil
Raw Material Total Weight Weight Solid WPG
Component A
Total Vof. Vol. Solid EEW
MIBK
88,4
6.8
13
3/3 Elsoil
111.5
111.5
8.6
13
13
Nuosperse 657
2.3
1.61
7.85
0.29
0.19
Dissolve
Heucophos ZBZ
75
75
30
2.5
2.5
Sicorin RZ
6,26
6.26
20.85
0.3
0.3
RO-4097
204
204
40.8
5
5
Vantalc 6N
103.05
103.05
22.9
4.5
4.5
T+W Atomite
112.5
112.5
22.5
5
5
Grind to Hegman 5 with HS
-Oisperser
DER 660-80
216
172.8
9.6
22.5
18
EPON 828
87.3
87.3
9.7
9
9
MIBK
71.4
6.8
10.5
Comoonent B
Epotuf 37-601
121.7
121.7
8.4
14.5
14.5
Mix thoroughly
Total
1199.41
995.72
100.09
71.99
Weight Solid %
90.7
WPG (lb/gal)
11.83
PVC {%}
23.6
VOC (lb/gal)
1
ICI (poise)
2
Stormer (KU)
75
AlKyd wt. Fr.
0.8
Alkyd vol. Fr,
0.8
176
500
190
Page Fs-13
-------
Formula EP#3: Red Oxide Epoxy Primer
Advanced Resin #1 with Epoxy Equivalent Weight: 442
Raw Material Total Weight Weight Solid WPG Total Vol. Vol. Solid EEW
Component A
MIBK 88,4 6.8 13
Adv. Restn-1 125.3 100.24 8.8 14,6 11.68 442
Nuosperse 657 2.3 1.61 7.85 0.29 0.19
Dissolve
Heucophos ZBZ 60 60 30 2 2
Sicorin RZ 4.2 4.2 20.85 0.2 0.2
RG-4097 224.4 224.4 40.8 5.5 5.5
Vantalc 6H 68.7 68.7 22.9 3 3
T+WAtomite 124 124 22.5 5.5 5.5
Grind to Hegman 5 with HS-Disperser
Adv. Res'm-1 313.3 250.6 8.8 35.6 28.5 442
MIBK 84 6.8 12.31
Component B
Epotuf 37-601 67.2 67.2 8.4 8 8
Mix thoroughly
Total 1161.8 900.95 100 64.57
Weight Solid % 81.1
WPG (lb/gal) 11.4
VOC (lb/gal) 2.2
PVC (%) 24,8
ICI (poise) 1.8
Stormer (KU) 65
AJkyd wt. Fr. 0.8
Alkyd vol. Fr. 0.8
Page E-14
-------
Formula EP#4: Red Oxide Primer;
Advanced Resfn-2 with Epoxy Equivalent Weight: 580
Raw Material
Total Weight Weight Solid
WPG
Total Vol.
Vol. Solid
Comoonent A
MIBK
88.4
6,8
13
Adv. Resin-2
120
86.4
8,5
13,95
9.07
Nuosperse 657
2.3
1,6
7.85
0.29
0.19
Dissolve
Heucophos 2BZ
60
60
30
2
2
Sicorin RZ
4.2
4.2
20.85
0.2
0.2
RO-4097
204
204
40.8
5
5
Vantalc 6H
57.3
57.3
22.9
2.5
2.5
T+W Atomite
99
99
22.5
4.4
4,4
Grind to Hegrnan 5 with HS-Disperser
Adv. Resin-2
333.5
240.12
8.5
39.23
25.5
MIBK
94
6.8
13.8
Comoonent B
Epotuf 37-601
47.6
47.6
8.4
5.67
5.67
Mix thoroughly
Total
1110.3
800.22
100.04
54.53
Weight Solid %
76.7
WPG
11.4
VOC(!b/gal)
2.6
PVG{%)
25.5
ICi (poise)
6.8
Stormer (KU)
88
AJkyd wt Fr.
0J2
580
580
Alkyd vol. Fr.
0.65
Page E-I5
-------
Formula EP#5: Red Oxide Epoxy Primer;
Advanced Resin #3 with Epoxy Equivalent Weight: 1086
Raw Material Total Weight Weight Solid WPG Total Vol. Vol. Solid EEW
Component A
MIBK
83.7
6.8
123
Adv. Resin-3
128
89.6
8.2
14.88
9.67
Nuosperse 657
2.3
1.61
7.85
0.29
0.19
Dissolve
Heucophos ZBZ
60
60
30
2
2
Sicorin RZ
4.2
4.2
20.85
0.2
0.2
RO-4097
204
204
40,8 .
5
5
Vantalc 6H
45.8
45.8
22.9
2
2
T+W Atomite
101.25
101.25
22.5
4.5
4.5
Grind to Hegman 5 with H$-Disperser
Adv. Resin-3
365.8
256.06
8,2
44.62
29
MIBK
75
6.8
11.01
Component B
Epotuf 37-601
26.9
26.9
8.4
3.2
3.2
Mix thoroughly
Total
1096.95
789.42
100
55.76
Weight Solid %
WPG
10.97
VOC(ib/gal)
2.5
PVC{%)
24.2
ICI (poise)
2
Stormer (KU)
71
Alkyd wt. Fr.
0.7
Aikyd vol. Fr. 0.65
Page E-16
-------
Formula EP#6: Red Oxide Epoxy Primer;
Advanced Resin #4 with Epoxy Equivalent Weight: 1300
Raw Material
Total Weight Weight Solid
WPG
Tote! Vol.
Vol. Solid
Comoonent A
MIBK
83
6.8
12.2
Adv. Resin-4
129.1 90.37
8,3
15.01
9.46
Nuosperse 657
2.3 1.61
7.85
0.29
0.19
Dissolve
Heucophos Z6Z
60 60
30
2
2
Sicorin RZ
4.2 4.2
20.85
0.2
0.2
RO-4097
204 204
40.8
5
5
Vantalc 6H
45.8 45.8
22.9
2
2
T+W Atomite
101.25 101.25
22.5
4.5
4.5
Grind to Hegman 5 with HS-Disperser
Adv. Resin-4
369 258.3
8,3
44.44
28
MIBK
80
6.8
11.7
Comoonent B
Epotuf 37-601
22.7 22.7
8.4
2.7
2.7
Mix thoroughly
Total
1101.35 788.23
100.04
54.05
Weight Solid %
74.7
WPG (Ib/gai)
11
VOC (fb/gal)
2.8
PVC(%)
25
ICI (poise)
2
Stormer (KU)
68
Alkyd wt Fr,
0.7
Alkyd vol. Fr.
0.63
1300
1300
Page E-17
TOTAL P.08
------- |