2006 Chemestry of Utomotive Coatings 1

Paint Development Program
COURSE: Chemistry of Automotive Coatings
COURSE 2006 / CHEMISTRY OF AUTOMOTIVE COATINGS
9/2/02

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TABLE OF CONTENTS
2006 / CHEMISTRY OF AUTOMOTIVE COATINGS ...................................................... 1

INTRODUCTION ............................................................................................................. 1
AGENDA .........................................................................................................................3
MODULE 1: CHEMISTRY OF AUTOMOTIVE COATINGS OVERVIEW .....................1-1
LESSON 1: HISTORY OF PAINT IN THE AUTOMOTIVE INDUSTRY.............1-2
EVOLUTION OF PAINT FINISHES...................................................................1-5
LESSON 2: MATERIAL ATTRIBUTES .............................................................1-7
TOPCOAT ATTRIBUTES ..................................................................................1-8
ULTIMATE GOAL: THE IDEAL CAN OF PAINT ..............................................1-8
PERFORMANCE ATTRIBUTES .......................................................................1-9
APPEARANCE ATTRIBUTES...........................................................................1-9
PROCESSABILITY ...........................................................................................1-9
ENVIRONMENT ................................................................................................1-9
WORLD-CLASS QUALITY PAINT FINISH .....................................................1-11
LESSON 3: GM TOPCOAT VISION AND INITIATIVES .................................1-12
VISION.............................................................................................................1-13
SEVEN INITIATIVES .......................................................................................1-14
GM PAINT INITIATIVES..................................................................................1-21
LESSON 4: JACKSONVILLE STUDY ............................................................1-22
MODULE 2: PAINT CHEMISTRY ................................................................................2-1
LESSON 1: BINDERS.......................................................................................2-3
THERMOPLASTIC POLYMERS .......................................................................2-5
CELLULOSE POLYMERS ................................................................................2-6
ACRYLIC POLYMERS ......................................................................................2-6
LUCITE..............................................................................................................2-7
LATEXES ..........................................................................................................2-9
ACRYLIC POLYESTER POLYMER..................................................................2-9
THERMOSETTING POLYMERS.....................................................................2-10
DRYING OILS..................................................................................................2-11
DRIERS ...........................................................................................................2-13
ALKYDS ..........................................................................................................2-14
POLYESTER ...................................................................................................2-16
MELAMINE CROSS-LINKERS .......................................................................2-17
POLYESTER ...................................................................................................2-18
PARA-TOULANE SULFURIC ACID................................................................2-19
ACRYLIC/MELAMINE SYSTEMS ...................................................................2-20
LOW SOLID SYSTEMS ..................................................................................2-21
HIGH SOLID SYSTEMS..................................................................................2-22
ONE COMPONENT (1K) ENVIRONMENTALLY RESISTANT SYSTEMS .....2-23
EPOXY SYSTEMS ..........................................................................................2-23
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SILANE SYSTEMS ......................................................................................... 2-25

ALKOXYSILANE SYSTEM CHEMISTRY....................................................... 2-25
CARBAMATE SYSTEMS ............................................................................... 2-26
TWO COMPONENT (2K) ETCH RESISTANT SYSTEMS.............................. 2-27
2K EPOXY SYSTEMS .................................................................................... 2-27
2K POLYURETHANE SYSTEMS ................................................................... 2-27
POWDER SYSTEMS (FUTURE SYSTEMS) .................................................. 2-30
LESSON 2: PIGMENTS ................................................................................. 2-32
CHEMICAL PIGMENT CLASSIFICATION ..................................................... 2-33
TYPES OF PIGMENTS BY FUNCTION ......................................................... 2-47
METHODS OF GRINDING OR DISPERSING PIGMENTS ............................ 2-54
SHAPES OF PIGMENTS................................................................................ 2-55
PROPERTIES AFFECTED BY THE AMOUNT OF PIGMENT ....................... 2-57
CRITICAL PIGMENT VOLUME CONCENTRATION (CPVC) ........................ 2-57
PIGMENT VOLUME CONCENTRATION EFFECT
ON PAINT CHARACTERISTICS .................................................................... 2-59
PROPERTIES OF PIGMENTS ....................................................................... 2-60
CIE LAB SYSTEM .......................................................................................... 2-62
KUBELKA-MUNKS EQUATION.................................................................... 2-64
VISIBLE LIGHT SPECTRUM ......................................................................... 2-65
COLOR MIXING ............................................................................................. 2-66
COLOR DEVELOPMENT ............................................................................... 2-67
HIDING POWER ............................................................................................. 2-68
EXERCISE THREE: PIGMENT CHEMISTRY ................................................ 2-69
LESSON 3: SOLVENTS ................................................................................. 2-71
SOLVENT TYPE ............................................................................................. 2-73
HYDROCARBONS ......................................................................................... 2-73
OXYGENATED SOLVENTS ........................................................................... 2-75
CHLORINATED SOLVENTS .......................................................................... 2-76
WATER ........................................................................................................... 2-76
CLASSIFICATION OF SOLVENTS ................................................................ 2-77
TRUE SOLVENTS .......................................................................................... 2-77
DILUENTS ...................................................................................................... 2-77
LATENT SOLVENT ........................................................................................ 2-77
CLASSIFICATION BY EVAPORATION RATE............................................... 2-77
PROPERTIES OF SOLVENTS....................................................................... 2-78
GOVERNMENTAL REGULATIONS ............................................................... 2-83
REDUCTION IN THE USAGE OF HAP MATERIALS - WHY?....................... 2-84
METHODS TO MEET MACT STANDARDS ................................................... 2-84
ROAD MAP FOR PAINT SELECTION OF AN AUTOMOTIVE
PAINT FORMULATION .................................................................................. 2-85
SUMMARY OF SOLVENT REPLACEMENTS ............................................... 2-87
SOLVENT SELECTION PROGRAM .............................................................. 2-89
LESSON 4: ADDITIVES ............................................................................... 2-101
TYPES OF ADDITIVES ................................................................................ 2-102
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WETTING AND DISPENSING AGENTS.......................................................2-103

PIGMENT CHARGE ......................................................................................2-104
FLOCCULATION...........................................................................................2-105
DEFLOCCULATION......................................................................................2-106
ANTIFLOODING AND ANTIFLOATING ADDITIVES....................................2-107
CAUSES AND CORRECTION ......................................................................2-108
CATALYST AND RETARDERS ....................................................................2-110
THIXOTROPES .............................................................................................2-111
VISCOSITY....................................................................................................2-111
RHEOLOGY CONTROL (FLOW CONTROL) ADDITIVES ...........................2-112
ANTICRATERING AGENTS..........................................................................2-114
DEFOAMERS ................................................................................................2-116
UV ABSORBERS ..........................................................................................2-119
LIGHT STABILIZERS....................................................................................2-123
PRESERVATIVES.........................................................................................2-125
MODULE 3: PAINT MANUFACTURE..........................................................................3-1
LESSON 1: PAINT MANUFACTURE................................................................3-2
RESIN MANUFACTURE ...................................................................................3-4
PIGMENT DISPERSION ...................................................................................3-5
FINAL PAINT MIX .............................................................................................3-6
PARTICLE SIZE AND SHAPE ..........................................................................3-7
PRODUCTION PART APPROVAL PROCESS (PPAP)
FOR BULK MATERIALS...................................................................................3-9
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2006 / CHEMISTRY OF AUTOMOTIVE COATINGS

INTRODUCTION
Goal:
This Chemistry of Automotive Coatings course is designed to provide

the participant with an awareness of how GM develops automotive
paint coatings for their products. This course will explain the
chemistry of paint ingredients in detail, starting with what is paint.
Each layer of coating used on GM vehicles will also be discussed.
Objectives:
By the end of this course you will be able to:

Explain the GM Standard Coating Process
Describe the history of automotive paint chemistry
Describe the attributes of the ideal can of paint
Explain the seven initiatives of the paint engineering strategy
Describe the Jacksonville Study and its relevancy to Paint
Engineering
Describe the two types of binders
Explain the differences between the various thermoplastic
polymers
Define thermosetting polymers
Describe drying and curing
Compare 1K and 2K systems
Describe inorganic, organic and composite pigments
Classify organic and inorganic pigments by function
Explain how pigment physical state, particle size and shape, and
volume concentration affect coatings
Define color, color selection, physics of color, and color
development
Describe the four types of paint solvents
Classify solvents by function, evaporation rates, and properties
List the governmental regulations influencing the amount and type
of solvent used in paint formulations
Explain how wetting and dispersing agents improve pigment
Describe flooding and floating, and the methods used to correct
these problems
Define catalysts, retarders, thixotropes, and rheology control
Describe the use of defoamers, UV absorbers, light stabilizers,
and preservatives
Length:
2 Days
9/2/02

Modules:
1.
2.
3.
4.
Course Introduction (15 Minutes)

Overview of Chemistry of Automotive Coatings (3 Hours)
Paint Chemistry (7 Hours)
Paint Manufacturing (1 Hour)
Jacksonville Study (30 Minutes)
9/2/02

AGENDA
9/2/02
Duration
Event
3 Hours
Module 1: Chemistry of Automotive Coatings

Overview
7 Hours
Module 2: Paint Chemistry
1 Hour
Module 3: Paint Manufacturing

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MODULE 1: Chemistry of Automotive Coatings Overview
MODULE 1: CHEMISTRY OF AUTOMOTIVE COATINGS OVERVIEW

Goal:
Objectives:
Time:
Lessons:
9/2/02
Provide a chemical overview of the Bill of Materials for the GM

automotive paint process
By the end of this module, you will be able to:
Describe the attributes of the ideal can of paint
Explain the seven initiatives of the paint engineering strategy
Engineering
3 Hours
1. History of Paint in the Automotive Industry (1 Hour)
2. Material Attributes (1 Hour)
3. GM Topcoat Vision and Initiatives (40 Minutes)
4. Jacksonville Study Results (20 Minutes)
1-1

LESSON 1: HISTORY OF PAINT IN THE AUTOMOTIVE INDUSTRY

Objectives:
By the end of this lesson, you will be able to:

Time:
1 Hour
1-2
9/2/02

GM STANDARD COATING PROCESS

PHOSPHATE
PRE-CLEAN
ELPO
CATHODIC
ELECTRO
DISPOSITION
PHOS
IMMERSION
SPRAY SYSTEM
STRIP
ACCUMULATOR
RINSE
SYSTEM
TRANSFER
TO FLOOR
CONVEYOR
PULL OFF
OVEN
ELPO SAND
ROBOTIC
SEAL
OPTIONAL
MANUAL
SEAL
UNDERBODY
PVC
OPTIONAL
MANUAL
SEAL
ELPO SAND
PULL OFF
OFF-LINE
REPAIR
STRIP
ACCUMULATOR
PRIMER SURFACER
BLOW-OFF
SURFACE
PREP
PRIME
SURFACER
R
BOOTH
FLASH
SAND
MOIST SAND
OVEN
PULL OFF
MANUAL
OPERATIONS
DECK
BLOW-OFF
TOP COAT
OVEN
FLASH
CLEAR COAT
HEATED
FLASH
BASE COAT
SURFACE
PREP
STRIP
ACCUMULATOR
FINESSE
GENERAL
ASSEMBLY
MISC.
OPERATIONS
OK BANK/
SEQUENCER
NOT OK
RERUN SAND
HEAVY SAND
CONFIRMATION
SPOT RERUN
FINAL LINE
PAINT
REPROCESS
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PAINT MIX
PANEL SWAP
1-3

WHAT DO YOU THINK A PAINT PROCESS

ENGINEERS JOB IS?
1. Take a few moments to write down duties and responsibilities.
1-4
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EVOLUTION OF PAINT FINISHES

Paint and painters have been an exciting part of the tapestry of
automotive history. From the days of millions of noisy black spokewheeled models chugging along our first roads and highways, to
the rich array of vehicles available today in a rainbow of colors.
This evolution spans a century in the history of man.
Initial automotive paint technology was varnish, taking after the
wooden coach and buggy painting of the era, and the natural
ingredients available. The earliest paint operations were brush
and bucket, and drying time was long and costly.
The first major topcoat technology change occurred in the early
1920s with the introduction of nitrocellulose paints. These paints
were based on natural resins and provide greater durability and
reduced drying time to help with mass productions. The polymer
chemistry industry was also starting to grow and evolve and by
1936 the first synthetic enamel paint chemistry developed and was
in use. Those enamels dried into a paint film by chemically linking
two chemical species, forming a tough finish.
The forties were a tough time for paint technology, as the industry
turned its factories to production of tanks and planes.
The fifties were a different story, and another milestone occurred
with the development of modern acrylic technology, with lacquer
literally a shining star. Great color range potentials, easy to apply
and repair, with good durability were its desirable features. GM
converted its passenger car production to acrylic lacquers. This
lacquer increased durability performance and created the
development and conversion to acrylic enamels at Ford, Chrysler,
and GM Truck.
A major drawback of early acrylic lacquer was that it went on
rather rough and needed polishing to bring out the luster.
The polishing aspect of lacquers was quickly overcome in the early
1960s with the advent of reflow lacquers. Reflow lacquer has
been a near-exclusive from GM passenger cars through the
1960s, 70s, and was the basis of MAGIC-MIRROR finish -1964 GTO. Lacquers chief product feature was the added
brilliance and attractiveness of light metallic colors.
By the late 1960s, a need arose to paint vehicles more rapidly on
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1-5

the assembly line and still achieve full film build and a quality
finish. The need to get enough paint out of the spray gun to
evenly coat the vehicle had become apparent. The development
of dispersion lacquer made it possible to have paint flow through
the gun in the required volume and then to relax and lay down flat
when baked.
The mid-1970s saw the vigorous rise of two other major issues
that were to cause a tremendous change in automotive topcoat
technology; competition, specifically foreign competition. The
Europeans and Japanese began introducing low solids (similar to
lacquers) basecoat/clearcoat enamel in the early 1970s.
Basecoat/clearcoat was quickly recognized as the premier
automotive finish for everyone to shoot at.
In the meantime, there was concern over the environment led
legislation that mandated lower solvent paints be used by the
automotive industry.
In the 1980s high solids BC/CC technology was developed and
coupled with electrostatic methods of painting to reduce the
amount of paint needed to be sprayed. U.S. Automotive
manufacturers were able to satisfy environmental concerns and
give customers outstanding BC/CC finishes on their new vehicles.
GM spent billions of dollars to make the necessary changes to
process BC/CC in the paint shops. All of GMs new models
introduced after 1982 had featured BC/CC, including the Fiero,
Beretta-Corsica, Grand Prix, Corvette, the popular Chevy Astro
Van, and the newest full size truck line from CPC Division.
BC/CC also gives rise to some new, exciting, special effect
finishes achievable by tinting one of the clearcoat passes to
produce an iridescent finish reminiscent of fine pearls.
In the 1990s, topcoats and waterborne basecoats (WBBC) are
emerging as replacements for high solids BC/CC, which promises
some further aesthetic improvements. As we look to the Twentyfirst Century, GM will be decorating cars and trucks with colored
plastics, film appliqus, and even powder paints.
1-6
9/2/02

LESSON 2: MATERIAL ATTRIBUTES

Objectives:

Describe attributes of the ideal can of paint
Time:
1 Hour
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1-7

TOPCOAT ATTRIBUTES
Gloss
Toxics
100
DOI
100
0%
Tension
20
Orange
Peel
10 Color
VOC
Spectrum
<1.0
10
10
10 Chip
Finessable
Resist.
10
0 Mar/
Low Bake
Scratch
10
0 Environ.
Recoatable
Resist.
10
Process
Latitude
5
Maint.
Free
10
100%
Gloss
Dura- Retenbility
tion
ULTIMATE GOAL: THE IDEAL CAN OF PAINT

The ideal or perfect can of paint consists of the four major attribute
classifications, which are:
1-8
Performance
Appearance
Processability
Environmental
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PERFORMANCE
Etch Resistance
Mar/Scratch
Chip Resistant
Gloss Retention
Durability
PERFORMANCE ATTRIBUTES
5 Maintenance Free
10 Durability
100% Gloss Retention
0 Environmental Resistance
0 Mar/Scratch
10 Chip Resistance
APPEARANCE ATTRIBUTES
Gloss 100%
DOI 100
Tension 20
Orange Peel 10
Color Spectrum 10
PROCESSABILITY
10 Finesse-able
10 Low Bake
10 Recoatable
10 Process Latitude
ENVIRONMENT
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Toxics 0%
VOC < 1.0
1-9

HOW DO WE DO IT?
GM is able make progress towards the ultimate goal -- the ideal
can of paint, through efforts directed at the following:
Benchmarking to worlds best -- Lexus
Continuous Improvement -- major and incremental
Surveys, etc., to monitor progress.
1-10
9/2/02

WORLD-CLASS QUALITY PAINT FINISH

We have just discussed the advances that GM has made in
material values; however, the total quality equation includes much
more than just materials. Without facilities that can produce the
product, without process controls to ensure quality, and without a
prevailing attitude within GM and the larger community that will
support these values, continuous quality improvement cannot be
realized.
In the past, most effort has been expended developing the
material, with the other four elements in the quality equation
receiving comparatively little attention. Now energy is being
refocused to produce a more comprehensive approach to systems
integration.
KEY ELEMENTS TO A WORLD-CLASS QUALITY

PAINT FINISH
FACILITIES
MATERIALS
ENVIRONMENT
(MAN)
METHODS
PROCESS
CONTROL
PDP1872P
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1-11

LESSON 3: GM TOPCOAT VISION AND INITIATIVES

Objectives:

Explain the seven initiatives of the Paint Engineering strategy.
Time:
40 Minutes.
1-12
9/2/02

VISION
To develop and implement materials that will yield a vehicle that
ages gracefully and uniformly at five years in the field with minimal
care.
During the early 90s, GM Paint Engineering formulated a paint

strategy to continue or accelerate the continuous improvement of
exterior paint systems on all North American built vehicles.
The strategy consists of seven initiatives which are shown in the
chart below.
GM TOPCOAT VISION AND SEVEN INITIATIVES

EOL
REPAIR
FINISHED
SYSTEMS AND
VEHICLE
FIELD
PROTECTIVE
MATERIALS
SYSTEMS/
MATERIALS
WATERBORNE
BASECOATS
IMPROVED
PAINT ON
PARTS STRATEGY
CHIP
RESISTANT
MATERIAL &
PROCESS
ETCH
RESISTANCE
CLEARCOAT
SCRATCH
AND MAR
RESISTANCE
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1-13

SEVEN INITIATIVES
INITIATIVE ONE: ETCH RESISTANT CLEARCOATS
The vision includes seven initiatives. An important part of the
vision is Initiative One, which is :
Etch Resistant Clearcoats

Continued implementation of clearcoats resistant to
environmental etching and water spotting.
Ultimate conversion to 2K Urethane or 1K equivalents.
Environmentally Resistant Clearcoats
1-14
Environmental damage developed into the major customer

dissatisfier in the mid-1980s.
All topcoats etch or pit when exposed to severe environmental
conditions and contaminants.
Most spotting occurs on dark colors under summer conditions.
New clearcoats have been developed and are being
implemented; spotting has been significantly reduced along
with customer complaints.
GM has led the way in implementation of both one and twocomponent clearcoats, with minimal impact on production
schedules.
These new clearcoats also have improved general durability
attributes.
Extensive accelerated tests and ongoing outdoor exposure (to
failure) have shown excellent robustness, which is being
confirmed in service.
9/2/02

INITIATIVE TWO: WATERBORNE BASECOATS

(WBBC)
Initiative Two is:
Waterborne Basecoats
Implement current technologies as funding is available.
Incremental improvements to higher solids and better
processability.
We are migrating to WBBC at other GM plants:
Greenfield sites are replaced and renovated; or regulations
mandate
Current plants:
Orion, Wentzville, Ramos, Wilmington, Oklahoma City,
Oshawa Truck, Saturn, Moraine, Hamtramck,
Lansing/Grand River, and Silao
Next plants:
Lordstown, Oshawa 1&2
WBBC offers improved (low solids) appearance, especially on

verticals, and reduced VOC emissions.
Its been introduced on most of our luxury cars for appearance
enhancement, and is a key part of our emissions strategy for
the future.
WBBC is being gradually introduced world-wide:
9/2/02
Excellent test and field history since early 1980s

Other emissions driven topcoat developments are:
Waterborne clearcoat -- led by Opel
Powder clearcoat -- led by GM and LEPC (Low Emission
Paint Commission)
1-15

INITIATIVE THREE: SOURCES OF SCRATCH AND

MAR DAMAGE
Scratch and Mar Resistance

Understanding mechanism
Develop test and measuring methods
Development of new materials
Sources of scratch and mar damage include:
Car washing
In-plant finessing and polishing
Stylus-type impact, such as fingernails or keys
Other materials, such as those carried in the box of a truck
Environment -- shrubs, sand, shopping carts
Scratch and Mar Testing Methods

The following statements describe scratch and mar testing
methods:
Tests used have either dry or wet abrasion

Damage is measured instrumentally as:
Gloss loss
Haze
Whitening (Delta L)
Optical imaging
Scratch and Mar tests

The following are typical scratch and mar tests:
1-16
Lab tests
Bench top carwash machine
Outdoor tests
Field trials conducted with panels mounted on top of car
9/2/02

INITIATIVE FOUR: FLEXIBLE PAINTS AND PAINT ON

PARTS STRATEGY
9/2/02
Flexible Paints and Paint on Parts System

Upgrade appearance, durability, and etch resistance to
OEM body levels
Upgrade appearance, durability and etch resistance to match

body topcoat performance
Identify current substrate/topcoat systems
Initiate color match program for secondary suppliers
Implement pigment durability testing
Establish durability baseline from audit of current systems
Validate etch resistance in annual Jacksonville Study
Improve topcoat processabiliy

Lower bake products
Expanded bake windows
Define, validate, and expand film build ranges
Understand interactions of topcoat/substrate

UV screened migration into substrate
Flexibility vs. etch resistance
Topcoat durability over steel vs. plastic
Create a paint on parts strategy

Rewrite APOS System and testing
Rewrite MATSPEC
Roll-out to:
GM organizations
Paint suppliers
Tier I and II suppliers
1-17

INITIATIVE FIVE: END-OF-LINE REPAIR SYSTEMS
End of Line Repair Systems

Upgrade durability and etch resistance to OEM levels
Better processability -- color match, bake, waterborne
Strategies for End of Line Repair Systems are:
Evaluate and approve upgraded aftermarket materials for

dealer use on GM warranty claims
Joint program -- STG and GM Paint Engineering
Develop, test, and approve materials that protect the finished

vehicle
Transportation damage
In-plant mutilations
Environmental storage damage
Export protection
Rail dust
Intensive programs -- all suppliers

Upgrade durability and etch resistance to OEM levels
Better processability -- bake, color match, waterborne
Major factors
Repair philosophy
Panel replacement
Spot repair capability
Color match -- OEM basecoat, if possible
Refinish technologies
Urethane facilities/people
Reduced bake
Room temperature cure, post cure
Little/no heat shielding
Sanding requirements
Emissions
1-18
9/2/02

INITIATIVE SIX: PROTECT THE FINISHED VEHICLE
Develop, test, and approve materials that protect the finished

vehicle
Transportation damage
In-plant mutilations
Environmental storage damage
Export protection
Rail dust
Best Practice Committee Meeting Outcomes
GMs situation is different from that of Ford, Toyota, or other

automakers.
Transit coating is specified only for export.
No cost/benefit case has been developed for transit film.
Committee and Quality Directors endorsed this selective caseby-case approach.
Service Management Committee MEETING
An approach was endorsed and someone assigned to

coordinate activity.
Coordination between GM Paint and Service and Logistics was
established to identify and evaluate dealers who have high
warranty utilization.
GM Quality Best Practices Team
9/2/02
The current data indicates that a general release of protective

(plant installed) paint coating is not justified for the domestic
market.
Specific high paint warranty dealerships should be investigated
on a case-by-case basis for consideration of transit coating.
Anti-mutilation films are a platform/plant call, but must be
removed prior to shipping, if not approved by GM Paint.
1-19

INITIATIVE SEVEN: CHIP RESISTANCE PROGRAM
Chip Resistant material and process

Provide enhanced chip resistance of topcoat systems
through engineering and chemistry.
Competitive assessment through surveys and field studies.
Evaluate effectiveness of external augmentation systems,
such as tapes and deflectors, or shields.
Chemistry issues relative to chip resistance are being

evaluated. These issues include:
New 4356 specification that provides high orange peel
coatings in low visibility areas
Innovative augmentation coatings under development, such
as urethanes
Engineering is trying to influence:

Design of vehicle
Cladding, in lieu of paint, in high impact areas
Augmentation
PB of colors
Colors not approved for production when modification is
deemed not possible
Use color keyed and color specified primer surfacer when
and where possible
Develop a truck tough system that places emphasis on chip

performance and scratch and mar resistance.
We have reviewed with you the GM Topcoat Vision and each of

the Seven Initiatives. Turn to the next page for a summary.
1-20
9/2/02

GM PAINT INITIATIVES
INITIATIVE
Etch Resistance Clearcoats
GOALS
Continue implementation of clearcoats
resistant to environmental etching and water
spotting.
Ultimate conversion to 2K Urethane or 1K
equivalents.
Waterborne Basecoats
Implement current technologies as funding is

available.
Incremental improvements to higher solids
and increased processability.
Scratch and Mar Resistance
Understanding mechanism.
Develop test and measuring methods.
Development of new materials.
Flexible Paint and Paint of Parts System
Upgrade appearance, durability, and etch

resistance to OEM body levels.
Develop, Test, and Approve Materials

That Protect the Finished Vehicle
Transportation damage.
In-plant mutilations.
Environmental storage damage.
Export protection.
Rail dust.
Chip Resistant Materials and Processes
9/2/02
Benchmark competitors by surveys and studies.
1-21

LESSON 4: JACKSONVILLE STUDY

Objectives:
By the end of this lesson you will be able to:
Time:

Engineering
20 Minutes.
Notes:
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9/2/02

COURSE: Chemistry Of Automotive Coatings
MODULE 2: Paint Chemistry
MODULE 2: PAINT CHEMISTRY

Goal:
To provide an increased awareness of the chemical input

to the paint process
Objectives:
By the end of this module, you will be able to:

Explain the differences between the various
thermoplastic polymers
Explain how pigment physical state, particle size and
shape, and volume concentration affect coatings
development
Describe the four types of paint solvents
Classify solvents by function, evaporation rates, and
properties
List the governmental regulations influencing the
amount and type of solvent used in paint formulations
Explain how wetting and dispersing agents improve
pigment
Describe flooding and floating, and the methods used to
correct these problems
Define catalysts, retarders, thixotropes, and rheology
control
Describe the use of defoamers, UV absorbers, light
stabilizers, and preservatives
Time:
7 Hours
Lessons:
1.
2.
3.
4.
9/2/02
Binders (2 Hours)
Introduction to Pigments (2 Hours)
Solvents (1 Hours)
Additives (2 Hours)
2-1

2-2
9/2/02

LESSON 1: BINDERS
Objectives:

Explain the differences between the various thermoplastic
polymers
Time:
2 Hours
9/2/02
2-3

BINDERS
The binder is the most important component of a paint. A binder
is either: the liquid resinous part of a paint that holds all of the
paints constituents into a continuous system, or it is the main film
former.
The resinous material in binders is made up of polymers. A
polymer is a chain linkage of many repeating individual chemical
structures called monomers. The solvent-thinned polymers are
termed binders.
Polymers are categorized into two main types:
Thermoplastic polymers
2-4
Thermoset polymers
9/2/02

THERMOPLASTIC POLYMERS
Thermoplastic polymers have high molecular weight, long chain
polymers with few, if any, chemical bonds acting as cross-links
between the chains. Such polymers, when heated normally
become soft and more fluid. See the illustration below.
Coatings made with thermoplastic binders are called lacquers.
Following are the thermoplastic binders that will be discussed:
Cellulose Polymers
Acrylic Polymers
Lucite
Latexes
THERMOPLASTIC BINDERS
Polymer chains,
as in elastomers,
and thermoplastics
cross links
9/2/02
2-5

CELLULOSE POLYMERS
Cellulose is a natural product obtained from wood pulp. Esters of
cellulose:
L-nitrocellulose was used as binders in earlier days.

Cellulose acetate butyrate (C.A.B.) is the ester of cellulose with
acetic and butyric acids. It is used today in small amounts for
rheology control.
ACRYLIC POLYMERS
These polymers are made by polymerizing esters of acrylic acid or
methacrylic acid, which are also referred to as monomers.
ACRYLIC ACID AND METHACRYLIC ACID
H
CH2 = C
CH2 = C
COOH
ACRYLIC ACID
2-6
CH3
COOH
METHACRYLIC ACID
9/2/02

LUCITE
Lucite is a polymer made from methyl methacrylate. This is a
very hard polymer, as shown in the illustration below.
LUCITE
CH2
CH3
CH3
CH2
CH2
COOCH3 COOCH3 COOCH3

PDP3261P
9/2/02
2-7

The polymer can be made softer and more flexible by

using larger or branched groups to form the esters.
Different functional groups are introduced in the polymer
backbone by using the appropriate monomer.
Hydroxyl group introduced by using the following :
CH3
I
CH2 = C
I
COOCH2-CH2OH
2-8
Acrylic lacquers form very hard, brittle films and must be

plasticized (internal or external plasticizers can be used).
Lacquers do not cross-link. Upon heating, the solvents
evaporate and the polymers uncurl and flatten out to form the
film.
Lacquers can also be sent through a second oven at a
very high temperature. This will make them reflow and form
a smooth, glossy continuous film and drive out the residual
solvent.
Lacquers were used at GM until the mid-eighties.
Initially solutional lacquers were used which were replaced
by dispersion lacquers to comply with environmental
regulations.
9/2/02

LATEXES
Latexes are polymer dispersions in water.
They are high molecular weight acrylic polymers dispersed in
water.
Latexes can also can be cross-linked with cross-linkers, such
as melamines.
Waterborne basecoats are usually latexes.
ACRYLIC POLYESTER POLYMER

Acrylic Polyester
~ 63%
R1
CH3
I
CH2 - C
I
H3COOC
~ 20%
CH - CH2
I
~ 10%
~ 2%
~ 5%
H
I
CH2 - C
I
H9C4OOC
CH3
I
CH2 - C
I
HOOC
CH3
I
CH2 - C
I
HO(H2C)2O
R2
N
MMA
(Methyl methacrylate)
Styrene
BA
(Butyl acrylate)
MAA
(Methacrylic acid)
Note:
1 free OH for
each mole HEMA
R1, R2 = CH3, H
N = ~100
HEMA
(Hydroxyethyl
methacrylate
PDP162
9/2/02
2-9

Thermoplastic Systems
Nitro cellulose
Solution lacquer
17% dispersion lacquer
24% dispersion lacquer
THERMOSETTING POLYMERS
Thermosetting polymers are normally made from relatively low
molecular weight, usually semi-fluid substances which, when
heated, become highly cross-linked; thereby, forming hard,
infusible, and insoluble products having a three-dimensional
space network of bonds interconnecting the polymer chains.
Thermoset polymers are also known as enamels.
THERMOSETTING POLYMERS
heat
Un-cross-linked polymer
2-10
Highly cross-linked
polymer (heavy lines
represent cross-links)
9/2/02

DRYING OILS
The following are drying oils:
9/2/02
Esters of glycerol and fatty acids

Curing or drying by the uptake of oxygen
Reaction catalyzed by organic-metallic compounds called
driers
The oxidative reaction takes place at the double bond.
The more double bonds in the oil, the faster is the cure.
Oils with fatty acids with conjugated double bonds react faster
than oils with non-conjugated double bonds.
The oils are divided into classes by the degree of drying. They
can undergo:
Drying oils which form a film at normal temperature.
Semi-drying oils which need heat to form a film.
Non-drying oils which do not form a film and remain tacky.
Mechanism of Drying
Uptake of oxygen and formation of hydroperoxides and
peroxides.
These peroxides are relatively stable, but can decompose
to give free radicals.
2-11

CROSS-LINKING OF OIL MOLECULES

X X
X
X
X
Glyerol
Fatty acid
2-12
Combination of free radicals
X Potential free radical site
9/2/02

DRIERS
Driers are:
9/2/02
Driers are organo-metallic compounds that catalyze the

drying reaction; they are also referred to as metal soaps.
Cobalt and manganese catalyst compounds are the most
popular. They catalyze by:
Uptake of oxygen
Decomposition of peroxides to free radicals
Secondary driers, such as lead, zirconium, calcium, and
cerium compounds (only catalyze uptake of oxygen).
Lead is highly toxic and is not used today.
Driers are used in qualities less than 1% of the total formula.
2-13

ALKYDS
CH3(CH2)10COOH
HO CH2
I
H3C - C - CH3OH
I
HO CH2
CH3(CH2)10COOH
HO CH2
HOOC
I
H3C - C - CH2OH
I
H2C - OH
Lauric acid
(coconut oil acid)
Trimethylolethane
H
O
O
C
H
O
O
C
Note:
2 free OH shown,
with a small excess
phthalic acid, there
can be further free
COOH.
N = 12 - 16
-o-phthalic acid
ALKYDS
2-14
Alkyd resins may contain acids and alcohols, in addition to

oils to improve film-forming capability.
The alcohols and acids usually have multiple functional
groups to obtain branching. Branching can be controlled by
selecting the right acid/alcohol functionality ratio. Example of
an alcohol and/or acid used in alkyds is given on the next
page:
9/2/02

ALCOHOL AND/OR ACID

O
II
C
O
CH2 - OH
I
CH2 - OH
Ethylene Glycol
9/2/02
C
II
O
Phthalic Anhydride
Alkyds need not be made from oils.

Non-drying oils have a plasticizing effect on the film.
A drying alkyd will dry faster than an oil because of the
higher functionality of the molecule and its greater size.
Alkyd can be made lacquer-like by modification with
styrene and/or methacrylate polymer resins.
Two mechanisms by which alkyds dry
Lacquer type dry
Oxygen uptake
Property of alkyds depends on chemical formulation and
building blocks used to make them.
Alkyds are used for air-dry products, such as
Refinish automotive paints
Household paints
Stoving finishes are alkyds cured by heat. These are more
recently used for automotive primers.
Curing mechanism involves cross-linkers.
2-15

POLYESTER
Polyester resins are made from bifunctional alcohols and acids.

Resins formed have excess alcohol group on it (-OH) are
called polyols; this is also referred to as having pendant alcohol
groups on the back.
The curing mechanisms is by cross-linking with melamine
cross-linkers. The melamine reacts with the alcohol groups on
the polymer backbone.
POLYOL
OH
OH
OH
Pendant alcohol groups on the backbone.
2-16
9/2/02

MELAMINE CROSS-LINKERS
N
H2N
N
ROH2C
NH2
1. CH2O
ROH2C
2. ROH
N
N
CH2OR
Catalyst
NH2
CH2OR
N
ROH2C
Melamine
CH2OR
Amino cross-linking agents can have the following variety of reactive groups:
CH2OR
CH2OR
CH2OR
X-N
X-N
\
X-N
\
CH2OR
CH2OH
X-N
\
CH2OH
\
H
H
3
R = CH3, C2H5, C4H9, etc.

X= urea, melamine, benzoguanamine moiety
Relative Reactivity of Groups

- NH
INCREASE
- NCH2OH
- NCH2OR
9/2/02
2-17

POLYESTER
Curing mechanism replaces the alkyl-groups (R-groups), which

are either the methyl, ethyl, or butyl group with the polymer.
Curing also involves the reaction of melamine groups, with
the acid and amide group on the resin.
The melamine molecule forms cross-links between two
polyester molecules.
ACRYLIC / MELAMINE CHEMISTRY
OH
0
CH2
HO
CH2
OH
N
CH2
CH2
N
OH
PDP1863P
2-18
CH2
CH2
OH
9/2/02

Each melamine molecule has six reactive groups on it.

All reactive groups react; usually, only three react.
The reaction is catalyzed by acid.
Reaction temperature can be lowered using an acid
catalyst.
An acid catalyst can be external or internal.
Internal catalyst would be any carboxyl groups (-COOH) on
the backbone.
An external catalyst can be a catalyst like para-toluene
sulphonic acid.
PARA-TOULANE SULPHONIC ACID

ORGANIC ACID
p - TOLUENE SULPHONIC ACID
SO3H
O
-C-OH
CH3
PDP220a
During cross-linking the melamine molecule can also selfcondense.
9/2/02
2-19

SELF-CONDENSATION OF MELAMINE
X-N-CH2 OR + ROCH2-N-X
X-N-CH2-O-CH2-N-X + H2O + ROH

ETHER BRIDGE
X-N-CH2OR + RO CH2-N-X
X-N-CH2-N-X + CH2O + H2O + ROH

METHYLENE BRIDGE
R = CH3, C2H5, C4H9, etc

X = MELAMINE, MOIETY
A high degree of self-condensation is undesirable.

Self-condensation can make the paint moisture-sensitive
and brittle.
Polyester resins are used today for automotive primers and
basecoats.
ACRYLIC/MELAMINE SYSTEMS
2-20
Acrylic/melamine systems are made by making acrylic

polymers that have hydroxyl (-OH) and acid (-COOH) groups
on the backbone.
Acrylic polymer is cross-linked with melamines, to form a
network.
This chemistry is used today for some basecoat/clearcoat
systems.
These systems are prone to environmental damage. These
acrylic/melamine clearcoats are being replaced by more
environmentally resistant systems.
Acrylic/Melamine chemistry is used for automotive solvent
borne basecoats.
9/2/02

LOW SOLID SYSTEMS

Characteristics of Low Solid Systems are:
These are high molecular weight polymers. High molecular

weight acrylic polymers are cross-linked with polymeric
melamines.
Due to high molecular weight, these polymers are very
viscous; their viscosity has to be adjusted during application
to obtain films with good appearance.
The control of polymer molecular weight during the
manufacture process, needs less cross-linking to obtain good
properties.
The performance of low solid systems depend on the paint
supplied by the manufacturer.
LOW SOLIDS
OH
M
OH
OH
M
OH
M
OH
M
OH
PDP271
9/2/02
2-21

HIGH SOLID SYSTEMS
High solid systems have low solvent content to meet the

EPA, VOC regulations.
These are low molecular weight acrylic polymers with
hydroxyl (-OH) and acid (-COOH) groups on the backbone,
cross-linked with monomeric melamines.
The viscosity of those polymers is much lower and they
can be formulated into higher solid systems of reasonable
viscosity that can be sprayed to provide film with good
appearance.
These systems have to undergo a high degree of crosslinking to form a network with good film properties.
The performance of these systems is very dependent on the
process of film-formation, during the painting process in the
assembly plant.
HIGH SOLIDS
OH
M
OH
M
OH
OH
OH
OH
OH
M
OH
M
OH
OH
OH
OH
OH
OH
OH
M
OH
PDP271A
2-22
9/2/02

ONE COMPONENT (1K) ENVIRONMENTALLY

RESISTANT SYSTEMS
EPOXY/ACID SYSTEMS
Epoxy/Acid Systems are acrylic resins with epoxy groups on the
backbone that have reacted with polyester resins with acid groups
to form ester linkages.
Characteristics of the Epoxy / Acid System
The reaction is brought about by heat.

One component epoxy systems are of a higher molecular
weight than two component epoxy systems.
These systems are resistant to environmental damage.
It is an addition chemistry.
EPOXY ACID REACTION

O
R - CH - CH2 + RC - OH
O
9/2/02
O
R - CH - CH2 - O - C - R
OH
2-23

EPOXY / ACID CHEMISTRY

C=O C=O
OH
OH
C=O C=O
O
+
O
2-24
OH
CH2
O
CH-OH
9/2/02

SILANE SYSTEMS
The silane systems are formed by reacting two silicone resins

which form the following bond.
l
l
- Si - O - Si l
l
This bond is very stable, making silane paint systems

resistant to environmental degradation.
Silane systems are also cross-linked with melamine crosslinker.
It is a condensation chemistry.
ALKOXYSILANE SYSTEM CHEMISTRY

OCH3
I
SI
I
OCH3
OH
I
SI
I
OH
OH
I
SI
I
OH
H2O
OCH3
Organotin
OH
- H2O
Advantages
Excellent environmental damage resistance
Good mar and scratch resistance
Low toxicity
9/2/02
OH
+ 3 CH3OH
OH
I
SI
I
O
I
SI
I
OH
I
SI
I
O
I
SI
I
Disadvantages
High cost
Brittle prone to cracking
High shrinkage
Moisture sensitive
2-25

CARBAMATE SYSTEMS
Carbamate binders are formed by reacting carbamate acrylic
resins with melamine crosslinkers. Urethane linkages are formed
for this network. This is a novel way to produce urethane linkages
without using toxic ingredients.
The reaction is catalyzed with a strong acid.

Carbamate systems are etch and scratch resistant.
The are also chemically resistant.
CARBAMATE SYSTEM
Carbamate-functional
polymeric acrylic resin
R-O
Melamine
crosslinker
O
N
O-C-NH2
+
R
P
R
O
O-C-NH
urethane
+ HOR
Carbamate-Melamine reaction
2-26
9/2/02

TWO COMPONENT (2K) ETCH RESISTANT SYSTEMS

The following are two examples of 2K etch resistant systems:
2K Epoxy/acid systems
2K polyurethane systems
2K EPOXY/ACID SYSTEMS
2K Epoxy/Acid systems are acrylic epoxy resins, reacted with
polyester resins containing acid groups.
The reaction takes place at a lower temperature because it is

catalyzed.
The two components have to be kept separate because some
reactions can take place at room temperature, and gel the
paint.
The polymers are of a lower molecular weight than 1K epoxy
systems.
The two components are metered in and mixed at the gun
before spraying.
2K POLYURETHANE SYSTEMS
9/2/02
Polyurethane systems are formed by reacting acrylic polyols

with polyisocyanates. Urethane linkages are formed.
Reaction can take place at room temperature.
The urethane bond (shown below) is very stable.
O
The isocyanate cross-linker and the acrylic polyol are kept

separate and metered to the spray gun and mixed just before
spraying.
Urethane groups are resistant to acid hydrolysis, therefore,
polyurethane paints are resistant to environmental damage.
Urethanes have good durability and appearance.
2-27

CHEMICAL REACTION MECHANISM OF 2K

POLYURETHANE SYSTEMS
OH
N=C=O
+
O=C=N
N=C=O
HO
OH
Room Temperature
Polyurethane
2-28
9/2/02

The etch resistance of a paint is influenced by its chemistry. The

rate of etching is presented in the table below for different bond
types. Etching and etch mechanics will be discussed in detail in
PDP 2030.
RATE OF ETCHING AND CHEMICAL BOND TYPE

RATE OF ETCHING AND CHEMICAL BOND TYPE
TYPE OF CROSSLINK
STRUCTURE
RATE OF ETCHING
ETHER
I
I
-C-O-CI
I
Fast/Medium
ESTER
0
II
I
-C-O-CI
Medium/Slow
URETHANE
I
I
-C-N-C-O-CI I II
HO
Slow
SILOXANE
I
I
-Si-O-SiI
I
Very Slow
HYDROCARBON
I I
-C-C
I I
Extremely Slow
12/5/01
1
Thermoset System
1K
Polyester
Acrylic/melamine
Epoxy/acid
Silane
Carbamate
9/2/02
2K
Epoxy/acid
Polyurethane
2-29

POWDER SYSTEMS (FUTURE SYSTEMS)
Powder clearcoats and primers are being developed to meet

future environmental regulations.
These systems have no solvent.
The paint is made, solvent evaporates, and the residue is
pulverized into smaller particles.
Powder systems are sprayed as solids.
Powder systems wrap around the edges and have a high
transfer efficiency.
The paint particles fuse together when heated to form a
uniform film.
Powder primers are being used in some GM plants and can
be either acrylics or polyesters.
Powder clearcoats of urethane and epoxy chemistry are
being developed for use with waterborne basecoats.
POWDER SYSTEMS
2-30
9/2/02

BINDERS
PAINT FILM FORMER
THERMOPLASTIC
THERMOSET
Nitrocellulose
1K Systems
2K Systems
Solution Lacquer
Drying Oils
Epoxy/Acid
17% Dispersion Lacquer
Alkyd
Urethane
24% Dispersion Lacquer
Polyester
Acrylic/Melamine
Epoxy/Acid
Silane
Carbamate
9/2/02
2-31

LESSON 2: PIGMENTS
Objectives:

Explain how pigment physical state, particle size and shape, and
volume concentration affect coatings
development
Time:
2 Hours
2-32
9/2/02

PIGMENTS
Pigments are tiny solid particles dispersed in the binder, that are
used to enhance the appearance of a product by providing color
and/or improving the physical properties of the paint film.
Pigments are colored, black, white, or fluorescent. They are
particulate organic and inorganic solids, and usually insoluble.
They are physically and chemically unaffected by the vehicle, or
substrate in which they are incorporated. They alter appearance
by selective absorption and/or by scattering of light.
CHEMICAL PIGMENT CLASSIFICATION
9/2/02
Inorganic Pigments
Organic Pigments
Inorganic/Organic Composite Pigments
2-33

INORGANIC PIGMENTS
Earth Pigments
Mineral Pigments
Synthetic Inorganic Pigments
Metallic Pigments
Mica Pearl Pigments
White
Black
EARTH PIGMENTS
These are naturally occurring minerals with some organic matter.
When heated, they can be dehydrated. They are not important in
automotive applications because improved synthetic versions are
now available. They show water and lightfastness and are
grouped as:
Ochres
These are iron oxides that vary in color from various shades of
yellow to red.
Sienna
Vary in color from yellow brown to reddish orange. They are
also oxides of iron.
Umber
Color varies from greenish brown to dark brown, due to
manganese dioxide (MnO2). They are also oxides of iron.
Green Earth
Green earth is not currently used as a pigment in paint.
2-34
9/2/02

MINERAL PIGMENTS
Mineral pigments are used as extender pigments. These
pigments have low refractive indices and tinting strengths
which make them relatively transparent in the dry paint film. They
are either white or weakly colored, due to impurities. These are
naturally occurring compounds that are replaced by synthetic
compounds. Talc, mica, and bentonite are used in automotive
paint.
Some examples are:
Barytes
Baryte is a mineral that is primarily barium sulfate (BaSo4). It is
resistant to acid and alkali and is used in primers and chemical
resistant paints.
Blanc Fixe
This mineral is a precipitated barium sulfate. Particles are
crypto-crystalline and they are softer than barytes.
Calcium Carbonate
The pigment can be natural or precipitated form. They are
widely used in house paints, inexpensive, and available in a
variety of sizes. Because of water sensitivity, they are not often
used in automotive paints.
Dolomite
This mineral is calcium magnesium carbonate. Dolomite is an
inexpensive extender with good wetting and dispersing
properties with no serious effect on gloss.
Ca Mg(CO3)2
Silica
These minerals exist in three forms: quartz, crypto-crystalline,
and crystalline form. Silica is used because it improves the
wear resistance properties used in rubbing compounds.
Diatomaceous Earth
This mineral is siliceous material made of skeletons of marine
organisms. It has a flattening (deglossing) effect on the film and
provides mechanical reinforcement.
9/2/02
2-35

China clay
This mineral is a hydrated aluminum silicate (Al2O3 2SiO22H2O),
free of iron and sand. China clay forms a plastic thixotropic mass
that has a tendency to form a three-dimensional flocculate,
which creates soft filers with a reduced water resistance.
Magnesium Silicate
This mineral is also called talc. Pure talc is hydrated magnesium
silicate, providing good sanding properties and moisture
resistance to primer films.
(3Mg04SiO2 H20)
Mica
This mineral is potassium aluminum silicate. After coating with
metal oxides, it is used as a flake in topcoats to provide a certain
type of glamour. It will be discussed under Effect Pigments.
(K203Al2036Si022H20)
Calcium Silicate
This mineral is used in semi-gloss house paints. CaSi03 has a
flattening effect.
Bentonite
This mineral has a general formula Al2O3 4 SiO2 2H2O. It is a
thixotrope.
2-36
9/2/02

SYNTHETIC INORGANIC PIGMENTS

These pigments are compounds of lead, iron, cadmium, cobalt,
zinc, and chromium. Compounds that are used are sulphate,
chromates, and molybolates. These heavy metals are toxic and,
except for oxides of iron and bismuth vanadate are not used
today. They vary in color from yellow, red, red-brown or green
and blue, except for the iron oxides.
These inorganic pigments have been replaced by organic
pigments because of better color and strength. The chromate
pigments also provide good anti-corrosive properties, but
because of environmental regulations they have been replaced by
zinc oxide.
METALLIC PIGMENTS
The use of metallic pigment flakes for special effects are covered
in the Effect Pigments section.
9/2/02
2-37

WHITE PIGMENTS
White pigments can be oxides of titanium, lead, or zinc.
Titanium Dioxide (TiO2) is being used widely today because it has
a high refractive index and very good hiding quality. It exists in
two crystalline forms, anatase and rutile. The rutile form is being
used in topcoats because it is more stable then the anatase form.
The anatase form is less desirable because it shows more
chalking.
TiO2 reacts with atmospheric oxygen which causes chalking.
Sometimes a surface treatment is applied to the pigment to make
it less reactive, but this increases the cost of the pigment.
BLACK PIGMENTS
Black pigments are produced by burning hydrocarbons, natural
gas, or oil under controlled conditions so that they do not pollute
the environment.
Previously, lamp, channel, and bone blacks were available.
Black pigments have a mass tone of blue or brown (if seen

straight on)
The finer the pigment, the better the hiding and tinting
strength (only a small amount of pigment is required for
hiding)
Blacks have a small P/B ratio and a good gravel rating
Ferrous oxide is a naturally occurring black mineral. It has poor

color and strength when compared to carbon black.
2-38
9/2/02

ORGANIC PIGMENTS
Organic pigments produce color by absorption of specific
wavelengths of light. All pigments contain a characteristic
grouping and arrangement called chromophore that determines
the color of the molecule. Chromophores in organic compounds
are unsaturated or heterocyclic groups and can absorb light. The
presence of auxochrome chemical groups can enhance the color
or shift the hue.
9/2/02
Examples of chromophore chemical groups are: -N=N>C=C< >C=O >C=S -phenyl -N=O or -NO2.
Examples of auxochrome chemical groups are: -OH, -NH2,

-NHR, and -NR2.
2-39

ORGANIC PIGMENTS
Metalcomplex
Pigments
AZO-Pigments
MONOAZO
DISAZO
Phthalocyanin
Monoarylide
Pyrazolon
Azomethine
beta-Naphthol
Naphthol AS
Polycyclic
Pigments
blue
Chinophthalone
yellow
Anthraquinone
yellow/
green shade
Flavantrone
Isoindoline
Benzimidazolone
yellow /
red shade
Pyranthrone
Perinone
Diketo-PyrroloPyrrol
Quinacridone
orange
red /
yellow shade
red /
blue shade
Perylene
Thioindigo
Dioxazine
Indanthrone
R1-N=N-R2
2-40
R1-N=N-R3-N=N-R2
Me-R
violet
blue /
red shade
9/2/02

The three organic pigment classes are:
Pigment dyestuffs are colored insoluble organic compounds

used as pigments, without any special treatment.
Toner pigments are water-soluble acid or basic dyes which

are converted to pigments on precipitation with metallic salts.
Lakes are derived from water-soluble dyes by means of

precipitation in the presence of an inorganic base. The base
is an integral part of the pigment. Al(OH)3 (alumina) is the
base used today. Lakes are inferior in chemical resistance
to toners and dyestuffs.
GROUPS OF ORGANIC PIGMENTS

Group I Basic Class
Group II Insoluble Azo Class
Group III Soluble Azo Class
Group IV Condensation Acid Class
Group V Vat Class
Group VI Phthalocyanines Class
Group VIII Miscellaneous Class
9/2/02
2-41

CHEMICAL GROUPS OF ORGANIC PIGMENTS

Group I Basic Class
Group I organic pigments are formed from basic dyes containing
diphenyl and triphenyl groups and substituted amino groups,
as auxochromes. They have great tinting strength and
brilliance, but lack lightfastness.
Group II Insoluble Azo Class
Group II insoluble azo organic pigments have good hiding
power, durability, and colorfastness in mass tones. They wet
and disperse readily in organic solvents. Some are durable
enough for automotive use.
Group III (precipitates) Soluble Azo Class
Group III soluble azo organic pigments, with acid groups that have
been precipitated as Ba, Ca, Fe, Cu and Mn salts, and are
resistant to bleeding in lacquers and enamels. They show
lightfastness only in mass tones and are not adequate for
outdoor exposure.
Group IV Condensation Acid Class
Group IV condensation acid organic pigments are water-soluble
dyestuffs that have been precipitated as metallic salts. Due to its
inferior light resistance, this class in not used in automotive
paints but is used in the production of printing inks.
Group V Vat Class
Group V are dyes that are converted to pigments. They are very
expensive and have only limited use in automotive paints.
2-42
9/2/02

Group VI Phthalocyanines Class

Group VI phthalocyanines organic pigments have excellent light
resistance and high-tinting strength. This class has a chelated
Cu atom. Phthalocyanines exist in both blue and green shades.
This is dependent on the amount of halogen substitution of the
hydrogen atoms on the outer rings; such as:
4 chlorines = blue
8 chlorines = blue/green
10-12 chlorines or bromines = yellow
They are widely used in automotive paints. The following
molecule is a phthalocyanine blue. The progressive addition of
halogen groups shifts the hue from reddish-blue to green.
PHTHALOCYANINE BLUE MOLECULE

Cl
N
C
C -N
N
N -C
Cu
C =N
N
N -C
C
N
9/2/02
2-43

Group VII Miscellaneous Class

Group VII miscellaneous organic pigments are quinacridone and
perylene groups. They are synthetic organic pigments with high
brilliance and colorfastness, and are often used in automotive
paints.
2-44
9/2/02

SYNTHETIC ORGANIC PIGMENTS

A. Quinacridone
O
II
C
H
N
H
N
C
II
O
R = CH3 or Cl
When R = H the color is red or violet depending

on spherical molecular formula R = -CH3 or CL gives magenta.
B. Perylene
O
II
C
O
II
C
R-N
N-R
C
II
O
C
II
O
R = CH3
Note: R = -CH3 gives maroon

R = -H gives violet
9/2/02
2-45

DIFFERENCE BETWEEN INORGANIC AND ORGANIC PIGMENTS

In general the following are attributes of inorganic and organic pigments:
Inorganic Pigments
Insoluble (non-bleeding) in organic

solvents
High-specific gravity
Superior-heat resistance
Less costly per pound
Low-tinting strength
Opaque
High hiding power
Low intensity (color and brightness)
Larger particle size
2-46
Organic Pigments
Some have a tendency to bleed

(dissolve) in organic solvents
Lower-specific gravity
Low-heat resistance
High cost per pound
High-tinting strength
High transparency
Low hiding power
High intensity (color and brightness)
Smaller particle size
9/2/02

TYPES OF PIGMENTS BY FUNCTION

Organic and inorganic pigments can be classified by function as
given below:
Colored pigments
Extender pigments
Effect pigments
COLORED PIGMENTS
Color pigments can be organic or inorganic and are selected from
the pigments discussed above to formulate specific colors.
9/2/02
2-47

EXTENDER PIGMENTS
Extender pigments are mainly inorganic mineral pigments. They
have low tinting strength and are in primers, as a filler to increase
the pigment to binder ratio (P/B). They provide:
Sandability
Low tinting strength
Moisture resistance
Bulk
Decreased cost
Increased mechanical strength
2-48
9/2/02

EFFECT PIGMENTS
Effect pigments are used to formulate glamorous color. Some
examples of these are:
9/2/02
Aluminum flake (white sparkle effect)

99.3% - 99.9% pure aluminum
Color effect will depend on the size of the flake
Earlier corn flake types were susceptible to degradation in
circulation (bending and breaking)
Newer silver dollar shapes are smoother and thicker and
therefore non-degrading
When aluminum is used for waterborne basecoats, it is
treated to prevent the reaction with water which produces
hydrogen (passivated)
Inexpensive
Mica flake with metal oxide surface treatment (white or colored

sparkle effect)
Hard flake of potassium aluminum silicate
Introduced in the 1970s
Sheet layer of silicate mineral platelets
Treated with oxides for color
Color is a consequence of light reflected at surface and
boundaries of the different layers
Also adds pearlescent effect to paint
Enhances durability
Is translucent
Does not provide good-hiding power
Expensive
2-49

ADSORPTION COLOR DEPENDS ON OXIDE COLOR

AND THICKNESS
Fe2O3
Mica
Fe2O3
Bronze
2-50
Russet
9/2/02

9/2/02
Colored Aluminum
Pigments with an aluminum core that have metal oxide
deposited on the surface that imparts colors (colored
sparkle effect)
Obtained by polymerizing resin in the presence of pigment
and aluminum (pigment attached to surface of aluminum)
Flake has a bronze look that imparts a gold color/sparkle
Yellow strips but blue released for production
They provide good-hiding properties
Expensive
Titanates
Micronized TiO2 (to 1/10 of size of TiO2)
Creates double color effect
The effect produces a gold look on the face, with bluish
effect on the side (double color effect)
Scatters blue light, transmits yellow light
Transparent
Graphitans
Fine graphite or carbon particles (gray flop).
Scatter light on the side tone
Provide a new kind of effect by giving a bluish gray side
tone (smoky look)
Xirallic System
Fe2O3 core with Fe2O3 and TiO2 selectively reflecting layers
System is in great demand
One color styled for Corvette
Glamorous colors with a sparkle
Glass Flakes
Manufactured from clear and amber colored beer bottle
glass
Provide unusual sparkle due to large size particles
Japanese are studying these pigments
Colors when styled are beautiful
Had production problems with settling
When flakes are adjusted for manufacture, colors did not
look as attractive
System not productionized
2-51

ALUMINUM TREATED WITH OXIDES
Palicrom
Fe2O3 crystals deposited on aluminum
Color controlled by thickness of Fe2O3
Color varies from pale gold to violet
Does not bleed because no resin is used to attach pigment
to aluminum
Excellent Florida durability
Variocrom
Aluminum layered with SiO2 and Fe2O3
Color obtained by varying the layer thickness
Color depends on the angle of view
Produced by vapor deposition
Could have a Fe2O3 core
Has 2 year Florida durability
Expensive
Being tested at GM for productionization
VARIOCROM
Color variable Pigments CVP

Selectively reflecting
Fe2o3
Spacer layer
SiO2
Al (totally reflecting)
Thickness
320 - 350 nm
380 - 400 nm
410 - 420 nm
430 - 440 nm
2-52
face angle color
grazing angle color
greenish gold
red
violet
weak copper
reddish grey
gold
green
red
9/2/02

Chroma Flair
Produced by vapor deposition of MgF2 and Fe2O3 on
aluminum foil
Foil is cut into flakes
Has open edges with aluminum exposed
Can cause gassing in waterborne coatings
Color controlled by thickness of MgF2 layer
Color varies from gold to green
PIGMENT PHYSICAL STATES

Pigments are tiny solid particles used to enhance the appearance
by providing color and/or improve the physical (functional)
properties of the paint film.
In solid form, as before processing, they exit as agglomerates
which:
9/2/02
Are a collection of primary particles strongly bonded to one

another
Have to be mechanically broken down into primary particles to
maximize tinting strength and obtain uniform color, by
grinding or shearing by the dispersing process.
In liquid form, they can be either deflocculated or flocculated,
depending on the ability of the other ingredients (resins,
solvents) to wet the pigment surface and stabilize the particles.
2-53

METHODS OF GRINDING OR DISPERSING

PIGMENTS
Grinding or dispersing a pigment consist of the following:
Wetting
Displacing adsorbed contaminants, such as air and water
Covering the pigment with a binder ; the degree of wetting
affects the gloss and hiding power by affecting the degree
of stabilization
Breaking
Van Der Waals attractive forces holds primary particles
together as aggregates or agglomerates
Mechanical energy is required to break these down to
primary particles
Certain solvents with high-cohesive energy densities are
used to assist the break up of agglomerates.
Stabilization of dispersion by controlling the interfacial forces
Dispersions have to be stabilized so that particles do not
recombine
Particles can collide and form aggregates
Gravity causes sedimentation, which can change quantity of
particles
Resins and surface active agents prevent the dispersed
pigment particles from recombining.
Dispersed Pigments
Clustered Pigments
Strong film
Excellent-hiding power
Thoroughly blended
Uniform color
Weak-tensile strength
Limited-hiding ability
Poorly mixed paint
Non-uniform color
Substrate
2-54
9/2/02

SHAPES OF PIGMENTS
PARTICLE SIZE
There is an ideal particle diameter for the maximum scattering of
light at interfaces, which is approximately equal to the wavelength
of the light in the particle. As a rough guide, the optimum diameter
is approximately half the wavelength of the light in air, about
2.2-0.4
m. Below this size, the particle loses scattering power.
Particle size distribution is usually approximated as a bell shaped
curve. After the particles have been dispersed, the opaque
pigments, organic or inorganic, will be approximately 0.5m in
diameter. Transparent pigments, organic or inorganic, are .05
m
in diameter. Flake ranges from 5.0-40.0m.
COLORED PIGMENTS SIZE
9/2/02
2-55

PARTICLE SHAPE
Particle shapes are:
Spherical
Cubical -- some organic pigments
Nodular irregular shape TiO2, lithopone, white Pb
Acicular -- needle shaped particles ZnO, tend to reinforce film
Laminar -- leaf-like, may also reinforce film or reflect secular
light (mirror-like)
Particle shape affects pigment packing, thus affecting hiding

power and the direction of light reflection, thus affecting color/twotone.
Rod-shaped particles can reinforce paint films, like iron bars in
concrete, or they may tend to poke through the surface
reducing gloss. Such rough surfaces may help the next coat to
stick more easily, so this type of pigment could be useful in an
undercoat.
Plate-shaped particles tend to overlap one another as tiles on a
roof, making it more difficult for water to penetrate the film.
They can also reflect light like tiny mirrors.
Aluminum and mica pigments have laminar shapes with irregular
edges.
2-56
9/2/02

PROPERTIES AFFECTED BY THE AMOUNT OF

PIGMENT
Hiding
Flow*
Gloss and appearance
Cure response (if pigment interacts with curing catalyst in
paint)
Mechanical properties (adhesion, chip-resistance)
Weatherfastness
Humidity-resistance
Cost
* Flow is impacted by aspect ratio, which is the ratio of width to

length. The smaller the ratio the more needle like the particle. A
small aspect (needle shape) reduces flow; large aspect (round
shape) improves flow
CRITICAL PIGMENT VOLUME CONCENTRATION

(CPVC)
Critical Pigment Volume Concentration (CPVC) is the
maximum amount of pigment wettable by the binder, without
leaving voids between particles.
Decreasing or increasing the amount of pigment in a binderpigment dispersion, will bring striking changes in the paint film
properties. These changes can be graphed and will produce
characteristic curves for each property. Each graph of pigment-tovolume concentration versus a particular paint film property, will
show a distinctive change of direction at the CPVC.
The CPVC is the transition point above or below which substantial
differences in the appearance and behavior of a paint film will be
encountered. Pigment volume concentration is calculated as
follows:
9/2/02
2-57

CRITICAL PIGMENT VOLUME CONCENTRATION

(CPVC)
PVC =
P/B =
X 100
Volume of Pigment
Volume of Pigment + Volume of Binder
Weight of Pigment
Weight of Binder
X 100
A: Binder
Under pigmented.
B: Pigment
Fully pigmented.
(CPVC)
C: Voids
Over pigmented.
P/B ranges:
White 80-100
Red 40
Black 3-4
Silver 8-15
Pigment Volume Concentration (PVC) range under 20 PVC
Mica <25
Pearl <15
PVC is a more accurate indicator of the physical affect of

pigment on mechanical properties than P/B, since pigment
densities vary widely.
PVC of a paint will depend on the polymer and pigments used in
the formulation and desired properties required from that paint.
Some properties depend on PVC and others on P/B. The most
useful ratio is specified for a given property.
2-58
9/2/02

When the pigment loading in a paint is high, pigment particles can

protrude from the applied paint film, thereby creating a rough
surface that scatters light, giving a low gloss. A low pigment
concentration can leave a smooth paint film, resulting in a high
gloss film.
PIGMENT CONCENTRATION
HIGH GLOSS
LOW PVC
HIGH PVC
LOW GLOSS
Substrate
Pigment volume concentration of a coating will depend on the

polymer and pigments used in the formulation. The PVC at which
a paint is formulated is selected, depending on the properties
required from that paint system.
9/2/02
2-59

PIGMENT VOLUME CONCENTRATION EFFECT ON PAINT CHARACTERISTICS

CPVC
High
Gloss
* Pe
Low
bility
rmea
T
le S
ensi
th
treng
Low
High
* Permeability to gas and water

PDP216
2-60
9/2/02

PROPERTIES OF PIGMENTS
Color properties:
Hue
Intensity (color and brightness)
Strength and transparency
Rheology:
Good flow
Gloss
Dispersibility:
Ease of grinding
Durability:
Resistance to light and weather effects
Chemical resistance
Application (robustness)
Resistance to flocculation and wet color drift
Resistance to migration and solvent bleed
Humidity resistance
Circulation stability
COLOR
Color selection
Physics of color
Color development
COLOR SELECTIONS
Color selections for automobiles are made as follows:
9/2/02
Selected by stylist based on color trends

Marketing strategy of GM for a vehicle
Cost consistent with platform targets
Workability consistent with production capability
2-61

PHYSICS OF COLOR
The color of an object depends on how the object reflects,
absorbs, and scatters light. In engineering terms, this is described
by using the red, green, blue, yellow, white, and black color terms
to measure and define each color.
When light falls on an object it can be:
Reflected
Scattered
Absorbed
A -- Reflected at the surface

B -- Reflected by pigment
C -- Absorbed by pigment
D -- Refracted by pigment
E -- Reflected by substrate
LIGHT FALLING ON A SURFACE

A
2-62
B E
9/2/02

The science of color is an integration of the sciences of physics,

mathematics, and psychology.
CIE LAB SYSTEM

The CIE Lab system is used for automotive color and represents
the three-dimensional uniform color space that is used to describe
a color:
The L,a,b scale is used to describe this space and it is
weighted for sensitivity of the eye
0.3 units of difference of the L,a, or b axis is a barely
perceptible difference by the human eye
9/2/02
2-63

CIE L,A,B COLOR SOLID
2-64
9/2/02

KUBELKA-MUNKS EQUATION
Mathematically, a color can be described by the Kubelka-Munks
equation.
2
K/S = (1-R) /2R

S=coefficient of scattering
K=coefficient of absorption
R=reflectance at infinite thickness
Colors are measured by using photoelectric instruments. Some
are:
9/2/02
Spectrophotometer measures the reflectance of light over the

different wavelengths of visible light. (Reflectance depends on
scattering and absorption). It is complex and more expensive
than a colorimeter.
Colorimeter measures color the way the eye sees it. In terms
of red/green/yellow components, usually through colored filters.
It is less precise than a spectrophotometer.
2-65

VISIBLE LIGHT SPECTRUM

Wavelength is usually measured in nanometers.
Visible light is made of electromagnetic waves present in sunlight,
that can be detected by the human eye.
Visible light spectrum
A display of the colors that make up a beam of white light
Each color band represents a very small range of wavelengths.
HOW WE SEE COLOR

Inside a
spectrometer
White
screen
Face-on view
Visible light
spectrum
Red
Orange
Yellow
Green
Blue
Light shone
on sheet with
central slit.
Achromatic lens (see
chromatic aberration)
2-66
Prism*.
Different wavelengths*
refracted by different
amounts, causing
dispersion of white light.
Indigo
Violet
9/2/02

PHYSICS OF VISIBLE LIGHT SPECTRUM

Unique colors can be produced by mixing of basic colors in two
ways:
Color mixing -- additive color

Color mixing -- subtractive color
COLOR MIXING
ADDITIVE COLOR
By shining two lights of two different colors onto a white surface
and filtering out the lights, a third color (a mixture of the two) is
seen by the eye. This is additive mixing, or color mixing by
addition. If the proper set of three additive primary colors is mixed
in the proper proportions, the result is white. This is the principle
used to produce color on a TV set screen.
SUBTRACTIVE COLOR
By shining a white light onto a pure color filter, only light of the
same color (range of wavelengths) as the filter passes through
(the other colors are absorbed). This is subtractive mixing or color
mixing by subtraction. If the proper set of three primary colors is
mixed in the proper proportions, the result is black. The color on
an automobile is the result of subtractive color mixing. The
pigments in the paint absorb all other color ranges, only the color
of light as the pigment gets reflected.
9/2/02
2-67

COLOR DEVELOPMENT
The color development for new automobile colors takes place as
follows:
2-68
Colors are developed by the blending of single pigment tints

(dispersion). According to specific rules to ensure durability,
workability, and color.
Colors can be matched visually by a shader with color
training.
Colors can also be matched instrumentally for large batches
(1000 gallons or more), but final match is checked by humans
to ensure accuracy.
9/2/02

HIDING POWER
Hiding power of a pigment measures its ability to hide or
obliterate the color or pattern of the substrate on which it is
applied.
When a film is applied over a black and white substrate, the eye
will not be able to differentiate between the white and black
backgrounds when the ratio of the light reflected by the black and
white substrates is at least 0.98 i.e., Rb/Rw 0.98
Rb = reflection over black substrate
Rw = reflection over white substrate
9/2/02
2-69

EXERCISE THREE: PIGMENT CHEMISTRY
2-70
9/2/02

2006 Chemestry of Utomotive Coatings 1

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Paint Development Program

COURSE: Chemistry of Automotive Coatings

COURSE 2006 / CHEMISTRY OF AUTOMOTIVE COATINGS

Paint Development Program

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Paint Development Program

2006 / CHEMISTRY OF AUTOMOTIVE COATINGS ...................................................... 1

Paint Development Program

SILANE SYSTEMS ......................................................................................... 2-25

Paint Development Program

WETTING AND DISPENSING AGENTS.......................................................2-103

Paint Development Program

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Paint Development Program

2006 / CHEMISTRY OF AUTOMOTIVE COATINGS

This Chemistry of Automotive Coatings course is designed to provide

By the end of this course you will be able to:

Paint Development Program

Course Introduction (15 Minutes)

Paint Development Program

Module 1: Chemistry of Automotive Coatings

Module 2: Paint Chemistry

Module 3: Paint Manufacturing

Paint Development Program

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Paint Development Program

MODULE 1: CHEMISTRY OF AUTOMOTIVE COATINGS OVERVIEW

Provide a chemical overview of the Bill of Materials for the GM

Paint Development Program

LESSON 1: HISTORY OF PAINT IN THE AUTOMOTIVE INDUSTRY

By the end of this lesson, you will be able to:

Paint Development Program

GM STANDARD COATING PROCESS

Paint Development Program

WHAT DO YOU THINK A PAINT PROCESS

Paint Development Program

EVOLUTION OF PAINT FINISHES

Paint Development Program

Paint Development Program

LESSON 2: MATERIAL ATTRIBUTES

By the end of this lesson, you will be able to:

Paint Development Program

ULTIMATE GOAL: THE IDEAL CAN OF PAINT

Paint Development Program

Paint Development Program

Paint Development Program

WORLD-CLASS QUALITY PAINT FINISH

KEY ELEMENTS TO A WORLD-CLASS QUALITY

Paint Development Program

LESSON 3: GM TOPCOAT VISION AND INITIATIVES

By the end of this lesson, you will be able to:

Paint Development Program

During the early 90s, GM Paint Engineering formulated a paint

GM TOPCOAT VISION AND SEVEN INITIATIVES

Paint Development Program

Etch Resistant Clearcoats

Environmentally Resistant Clearcoats

Environmental damage developed into the major customer

Paint Development Program

INITIATIVE TWO: WATERBORNE BASECOATS

WBBC offers improved (low solids) appearance, especially on

WBBC is being gradually introduced world-wide:

Excellent test and field history since early 1980s

Paint Development Program