U.S. patent application number 11/155975 was filed with the patent office on 2006-12-21 for rapid drying lacquers containing triblock copolymer for rheology control.
Invention is credited to Renee J. Kelly, Sheau-Hwa Ma.
Application Number | 20060287437 11/155975 |
Document ID | / |
Family ID | 36999994 |
Filed Date | 2006-12-21 |
United States Patent
Application |
20060287437 |
Kind Code |
A1 |
Ma; Sheau-Hwa ; et
al. |
December 21, 2006 |
Rapid drying lacquers containing triblock copolymer for rheology
control
Abstract
This invention relates to rapid drying lacquers that are
particularly useful for automotive OEM refinish applications. The
lacquer includes a novel acrylic triblock copolymer as a
replacement material for all or part of the cellulose acetate
butyrate binder component. This invention is also directed to a
process for producing coatings from the rapid drying lacquers.
These lacquers are especially useful in providing chip and humidity
resistant coatings, especially metallic effect coatings, having
excellent adhesion and down flop or metallic effect.
Inventors: |
Ma; Sheau-Hwa; (West
Chester, PA) ; Kelly; Renee J.; (Media, PA) |
Correspondence
Address: |
E I DU PONT DE NEMOURS AND COMPANY;LEGAL PATENT RECORDS CENTER
BARLEY MILL PLAZA 25/1128
4417 LANCASTER PIKE
WILMINGTON
DE
19805
US
|
Family ID: |
36999994 |
Appl. No.: |
11/155975 |
Filed: |
June 17, 2005 |
Current U.S.
Class: |
525/242 |
Current CPC
Class: |
C08L 53/00 20130101;
C08L 2666/02 20130101; C08L 2666/02 20130101; C08F 297/026
20130101; C09D 153/00 20130101; C09D 153/00 20130101; C08F 293/005
20130101; C08F 297/02 20130101; C08L 53/00 20130101 |
Class at
Publication: |
525/242 |
International
Class: |
C08F 297/02 20060101
C08F297/02 |
Claims
1. A triblock copolymer composition, wherein the block copolymer
contains a polymeric A block, a polymeric B block, and a polymeric
A' block: wherein (a) the polymeric A block is of polymerized
ethylenically unsaturated monomer(s); (b) the polymeric B block is
of a polymerized ethylenically unsaturated monomer(s); and (c) the
polymeric A' block is of polymerized ethylenically unsaturated
monomer(s); and further wherein the A and A' blocks have the same
or similar composition and the B block has a different composition
from the A and A' blocks; the A and A' blocks differ from the B
block by the presence of one or more functional groups that are
capable of interacting with each other for the formation of a
reversible network; and the functional groups are selected from at
least one of the group consisting of carboxylic acid, hydroxyl,
urea, amide, and ethylene oxide groups, and any mixtures
thereof.
2. The composition of claim 1, wherein the B block on the copolymer
is a non-functional block, essentially free of functional
groups.
3. The composition of claim 1, wherein at least 1% by weight of the
monomers used to form the A and A' blocks contain interactive
functional groups.
4. The composition of claim 1, wherein about 5 to 60% by weight of
the monomers used to form the functional blocks A and A' contain
interactive functional groups.
5. The composition of claim 1, wherein the blocks are linearly
attached to each other in the order given, each at a single
terminal point thereof.
6. The composition of claim 4, wherein the block copolymer is made
primarily from acrylic monomers.
7. The composition of claim 1, wherein the ABA' block copolymer is
prepared by a macromonmer approach using cobalt as a catalytic
chain transfer agent.
8. The composition of claim 7, wherein the block copolymer is made
primarily from acrylic or methacrylic monomers or mixtures
thereof.
9. The composition of claim 1, wherein the network-forming group
comprises at least one carboxylic acid group.
10. The composition of claim 1, wherein the ABA' block copolymer is
tapered between AB and/or BA' block.
11. A triblock copolymer composition, wherein the block copolymer
has a weight average molecular weight of about 5,000 to 200,000 and
contains a polymeric A block, a polymeric B block, and a polymeric
A' block: wherein (a) the polymeric A block is of polymerized
ethylenically unsaturated monomer(s); (b) the polymeric B block is
of a polymerized ethylenically unsaturated monomer(s); and (c) the
polymeric A' block is of polymerized ethylenically unsaturated
monomer(s); and further wherein the weight average molecular weight
of each block is at least 1,000 and the A and A' blocks have the
same or similar composition and the B block has a different
composition from the A and A' blocks; the A and A' blocks differ
from the B block by the presence of one or more functional groups
that are capable of interacting with each other for the formation
of a reversible network; and the functional groups are selected
from at least one of the group consisting of carboxylic acid,
hydroxyl, urea, amide, and ethylene oxide groups, and any mixtures
thereof.
12. The composition of claim 11, wherein the B block on the
copolymer is a non-functional block, essentially free of functional
groups.
13. The composition of claim 11, wherein at least 1% by weight of
the monomers used to form the A and A' blocks contain interactive
functional groups.
14. The composition of claim 11, wherein about 5 to 60% by weight
of the monomers used to form the functional blocks A and A' contain
interactive functional groups.
15. The composition of claim 11, wherein the blocks are linearly
attached to each other in the order given, each at a single
terminal point thereof.
16. The composition of claim 15, wherein the block copolymer is
made primarily from acrylic monomers.
17. The composition of claim 11, wherein the ABA' block copolymer
is prepared by a macromonmer approach using cobalt as a catalytic
chain transfer agent.
18. The composition of claim 17, wherein the block copolymer is
made primarily from acrylic or methacrylic monomers or mixtures
thereof.
19. The composition of claim 11, wherein the network-forming group
comprises at least one carboxylic acid group.
20. The composition of claim 11, wherein the ABA' block copolymer
is tapered between AB and/or BA' block.
Description
FIELD OF THE INVENTION
[0001] This invention relates to coating compositions and in
particular to rapid drying lacquer coating compositions that are
particularly useful for automotive refinishing.
BACKGROUND OF THE INVENTION
[0002] To refinish or repair a finish on vehicle, such as a
basecoat/clearcoat finish on automobile or truck bodies, different
fast-drying coating compositions have been developed. A number of
pigmented and clear air-dry acrylic lacquers have been used in the
past to repair basecoat/clearcoat finishes, but none meet the rapid
drying times that are desired, while also meeting today's
performance requirements, such as excellent stone-chip resistance,
humidity resistance, intercoat adhesion, and appearance.
[0003] A key concern to a refinish customer which is typically the
vehicle owner is that the coating in use has excellent durability
and weatherability and an attractive aesthetic appearance.
[0004] Another key concern of the automobile and truck refinish
industry is productivity, i.e., the ability to complete an entire
refinish operation in the least amount of time. To accomplish a
high level of productivity, any coatings applied need to have the
ability to dry at ambient or slightly elevated temperature
conditions in a relatively short period of time. The term "dry"
means that the resulting finish is physically dry to the touch in a
relatively short period of time to minimize dirt pick-up, and, in
the case of the basecoat, to allow for the application of the
subsequent clear coat.
[0005] It is also desirable to have quick drying basecoats for
additional reasons. If the applied basecoat composition layer has
not dried sufficiently before the clearcoat composition is applied,
then the application of the clearcoat will disturb the basecoat
layer and the appearance of the basecoat will be adversely
affected. For basecoats containing special effect pigments, e.g.,
flake pigments such as metallic and pearlescent flakes, the
metallic flake control and metallic appearance (or downflop) of
these basecoats will suffer due to disturbance of the flake pigment
by intermixing of the coating layers at their interface. "Downflop"
refers to a phenomenon associate with metallic effect coatings
wherein the color varies with the angle of view to provide a three
dimensional metallic effect on the surface of the vehicle.
[0006] Cost and volatile organic solvent content are further
concerns in formulating automotive refinish coating compositions.
For example, cellulose acetate butyrate (CAB) resins have been used
to shorten the dry to handle time and as rheology control additives
to enhance metallic flake control and other properties in refinish
basecoats, but coating compositions containing these CAB material
require an undesirable high amount of organic solvent. In addition,
these CAB materials are relatively expensive and require added
steps in the coatings manufacturing process. The CAB materials are
also specialty products that are not widely manufactured.
[0007] It would be advantageous, therefore, to have a lacquer
coating composition, especially a refinish basecoat lacquer, having
a short tack-free drying time at ambient temperature conditions,
good metallic flake control and appearance, that is less expensive,
that has a reduced amount of regulated emissions, and has the
ability to form a finish with excellent chip and humidity
resistance and adhesion. The novel composition of this invention
have the unique combination of properties desired.
SUMMARY OF THE INVENTION
[0008] This invention is directed to a coating composition,
especially to a lacquer coating composition, comprising a
film-forming binder and a volatile organic liquid carrier, wherein
the binder contains, preferably as a replacement for all or part of
the cellulose acetate butyrate component, a uniquely segmented
triblock copolymer. More particularly, the tri-block copolymer is
an ABA'-block copolymer, wherein the ABA' block copolymer has a
weight average molecular weight of about 5,000 to 200,000 and
contains a polymeric A block, a polymeric B block, and a polymeric
A' block; wherein:
[0009] (a) the polymeric A block is of polymerized ethylenically
unsaturated monomer(s);
[0010] (b) the polymeric B block is of a polymerized ethylenically
unsaturated monomer(s); and
[0011] (c) the polymeric A' block is of polymerized ethylenically
unsaturated monomer(s); and further wherein
[0012] the polymeric A block, polymeric B block, and polymeric A'
block of the block copolymer, are linearly attached to each other,
in the order given or in reverse order, each at a single point
thereof;
[0013] the A and A' blocks have the same or similar composition and
the B block, which is disposed between the A and A' blocks, has a
different composition from the A and A' blocks;
[0014] the A and A' blocks differ from the B block by the presence,
on the A and A' blocks, of one or more functional groups that are
capable of interacting with each other or hydrogen (H) bonding with
each other for the formation of a reversible network; and
[0015] the functional groups are selected from at least one of the
group consisting of carboxylic acid, hydroxyl, urea, amide, and
ethylene oxide groups, or mixtures of any of the above.
[0016] Preferably, the dissimilar B block disposed between the A'
and A' blocks is a non-functional block, essentially free of
functional groups.
[0017] The lacquer composition is most suited for use as a
pigmented basecoat lacquer in automotive refinish applications, on
top of which a transparent (clear) topcoat is applied.
[0018] While this composition is preferably used as a lacquer
coating which dries via solvent evaporation absent any substantial
crosslinking occurring, it optionally may contain a polyisocyanate
crosslinking agent for further improved film properties.
[0019] This invention is further directed to a process for
producing a coating on the surface of a substrate, such as a
vehicle body or part thereof, wherein the process comprises:
[0020] applying a layer of a lacquer coating composition on the
substrate surface, which may be previously primed or sealed or
otherwise treated, the lacquer comprising the aforesaid
composition; and
[0021] drying the layer, preferably at ambient conditions, to form
a coating on the surface of the substrate, on top of which a
clearcoat can be applied.
[0022] Also included within the scope of this invention is the
triblock copolymer composition formulated for use in the lacquer
and a substrate coated with the lacquer coating composition
disclosed herein.
DETAILED DESCRIPTION OF THE INVENTION
[0023] As used herein:
[0024] "Lacquer" means a coating composition that dries primarily
by solvent evaporation and does not require crosslinking to form a
film having the desired physical properties.
[0025] All "molecular weights" are determined by gel permeation
chromatography (GPC) using polystyrene as the standard.
[0026] "Tg" (glass transition temperature) of the polymer can be
measured by differential scanning calorimetry (DSC) or it can be
calculated as described by Fox in Bull. Amer. Physics Soc., 1, 3,
page 123 (1956).
[0027] "Acrylic polymer" means a polymer comprised of polymerized
"(meth)acrylate(s)" which mean acrylates and methacrylates,
optionally copolymerized with other ethylenically unsaturated
monomers, such as acrylamides, methacrylamides, acrylonitriles,
methacrylonitriles, and vinyl aromatics such as styrene.
[0028] The present invention is directed to a pigmented or clear
air-dry lacquer, preferably an acrylic lacquer, suited for various
coating processes, such as automotive OEM and automotive refinish.
The novel lacquer is particularly well suited for use in automotive
refinishing, particularly as a colored refinish basecoat used for
repairing or refinishing colored basecoat/clearcoat finishes on
auto and truck bodies.
[0029] Advantageously, the air-dry lacquer coating compositions
formed have excellent physical properties, such as excellent chip
and humidity resistance and intercoat adhesion, without sacrificing
desired fast dry properties at ambient temperatures and overall
appearance, such as DOI (distinctness of image) and HOB (head on
brightness).
[0030] The lacquer coating composition of this invention preferably
contains about 5 to 90% by weight, based on the weight of the
coating composition, of a film-forming binder containing an ABA'
triblock polymer, preferably an acrylic polymer, as a replacement
for all or part of the cellulose acetate butyrate (CAB) resin in
the binder and correspondingly about 10 to 95% by weight, based on
the weight of the coating composition, of a volatile organic liquid
carrier and optionally contains pigments in a pigment to binder
weight ratio of about 0.1/100 to 200/100.
ABA' Triblock Copolymer
[0031] The ABA' triblock copolymer, which also forms part of this
invention, used herein as part of the film forming binder has a
weight average molecular weight of 5,000-200,000 and preferably
about 10,000-100,000, and more preferably in a range from about
15,000-80,000.
[0032] The A and A' blocks of the ABA' block polymer have the same
or similar composition and both have at least one interactive
functional group described below.
[0033] By the "same" composition, it is meant that the A and A'
blocks are prepared from the same set of monomers, same monomer
ratios, and contain the same type interactive functional groups in
the same concentration. By "similar" composition, it is meant that
both the A and A' blocks still contain at least one interactive
functional group and serve the same network-forming function, but
the monomer set, monomer ratio, type of functional groups, and/or
concentration of functional groups may be different in each
block.
[0034] As to the B block, this block is preferably disposed between
the A and A' blocks and preferably is a non-functional block that
contains mostly polymerized non-functional monomers.
[0035] As indicated above, the A and A' blocks differ from the B
block by presence of interactive functional groups. The functional
groups used in the A and A' blocks are capable of
interacting/H-bonding with each other for the formation of a
network that is sensitive to shear force, temperature, or pH. The B
block is preferably essentially free of functional groups.
[0036] The interactive/H-bonding functional groups are preferably
selected from at least one of the following groups 1 to 6:
[0037] 1) Hydroxyl groups (e.g., primary or secondary hydroxyl)
[0038] 2) Acid groups (e.g., carboxyl groups);
[0039] 3) Urea;
[0040] 4) Amide;
[0041] 5) Ethylene Oxide; or
[0042] 6) Mixtures of any of the above.
[0043] The size of each block (or polymeric segment) will vary
depending on the final properties desired. However, each block
should be substantially linear and contain on average at least 3
units of monomers and have a number average molecular weight
greater than 300. In preferred embodiments, the number of monomers
within a single block is about 10 or more. Also in preferred
embodiments, the weight average molecular weight of each block is
at least 1,000, generally in a range from about 1,000-40,000, more
preferably from about 1,500-30,000.
[0044] The concentration of and type of interactive functional
groups on the blocks will also vary depending on the particular
attribute desired; however, the concentration of interactive groups
should be such that at least 1% to 100%, more preferably at least 5
to 60% by weight, of the monomers used to form that given block
have interactive functional groups.
[0045] In the present invention, it is particularly useful to
concentrate the interactive functional groups on the outer blocks
(or A and A' blocks), with the remaining inner block (or B block)
containing essentially no functional groups. This construction
particularly facilitates the network formation attribute desired.
By "essentially no" functional groups or "essentially free" of
functional groups, it is meant that the B block should contain less
than 1% by weight, preferably zero percent by weight, of
functionalized monomers, based on the total weight of the block
copolymer.
[0046] As will be appreciated by those skilled in the art, it may
also sometimes be desirable to have crosslinkable groups, such as
hydroxyl groups (which can serve a dual function of H-bonding and
crosslinking) or amine groups, on at least one of the blocks,
preferably the outer block(s) for potential crosslinking with other
binder components, for further improved film properties.
[0047] The ABA' triblock copolymer that can be used herein, as part
of the binder, to replace the CAB polymer can be prepared by living
polymerization methods such as anionic polymerization, group
transfer polymerization (GTP), nitroxide-mediated free radical
polymerization, atom transfer radical polymerization (ATRP), or
reversible addition-fragmentation chain transfer (RAFT)
polymerization techniques. Preferably, the polymer is prepared by
the catalytic chain transfer approach for making the triblock
copolymers of this invention.
[0048] Most of the other living polymerization approaches mentioned
above involve special and costly raw materials including special
initiating systems and high purity monomers. Some of them have to
be carried out under extreme conditions such as low moisture or low
temperature. Furthermore, some of these methods are sensitive to
the active hydrogen groups on the monomers that are key to our
invention such as the hydroxyl and carboxylic acid groups. These
groups would have to be chemically protected during the
polymerization and recovered in a subsequent step. In addition,
some of the initiating systems bring undesirable color, odor, metal
complexes, or potentially corrosive halides into the product. Extra
steps would be required to remove them. In the preferred method,
the catalyst is used at extremely low concentration and has minimum
impact on the quality of the product, and the synthesis can be
conveniently accomplished in a one-pot process.
[0049] In the catalytic chain transfer agent approach or
"macromonomer" approach, the triblock copolymers are most
conveniently prepared by a multi-step free radical polymerization
process. Such a process is taught, for example in U.S. Pat. No.
6,291,620 to Moad et al., hereby incorporated by reference in its
entirety.
[0050] In the first step of the macromonomer process, the first or
outer block A of the triblock copolymer is formed using a free
radical polymerization method wherein ethylenically unsaturated
monomers or monomer mixtures chosen for this block are polymerized
in the presence of cobalt catalytic chain transfer agents or other
transfer agents that are capable of terminating the free radical
polymer chain and forming a "macromonomer" with a terminal
polymerizable double bond in the process. The polymerization is
preferably carried out at elevated temperature in an organic
solvent or solvent blend using a conventional free radical
initiator and Co (II) or (III) chain transfer agent.
[0051] Once the first macromonomer block having the desired
molecular weight and conversion is formed, the cobalt chain
transfer agent is deactivated by adding a small amount of oxidizing
agent such as hydroperoxide. The unsaturated monomers or monomer
mixtures chosen for the next block B are then polymerized in the
presence of the first block and more initiator. This step, which
can be referred to as a macromonomer step-growth process, is
likewise carried out at elevated temperature in an organic solvent
or solvent blend using a conventional polymerization initiator.
Polymerization is continued until a macromonomer is formed of the
desired molecular weight and desired conversion of the second block
into a diblock macromonomer. The third block A' or other outer
block of the triblock copolymer is then added onto it in the same
manner to produce the triblock copolymers of this invention.
[0052] Preferred cobalt chain transfer agents are described in U.S.
Pat. No. 4,680,352 to Janowicz et al and U.S. Pat. No. 4,722,984 to
Janowicz, hereby incorporated by reference in their entirety. Most
preferred cobalt chain transfer agents are pentacyano cobaltate
(II), diaquabis(borondiflurodimethylglyoximato)cobaltate (II), and
diaquabis(borondifluorophenylglyoximato)cobaltate (II). Typically
these chain transfer agents are used at concentrations of about
2-5000 ppm based on the total weight of the monomer depending upon
the particular monomers being polymerized and the desired molecular
weight. By using such concentrations, macromonomers having the
desired molecular weight can be conveniently prepared.
[0053] To make distinct blocks, the growth of each block needs to
occur to high conversion. Conversions are determined by size
exclusion chromatography (SEC) via integration of polymer to
monomer peak. For UV detection, the polymer response factor must be
determined for each polymer/monomer polymerization mixture. Typical
conversions can be 50% to 100% for each block. Intermediate
conversion can lead to block copolymers with a transitioning (or
tapering) segment where the monomer composition gradually changes
to that of the following block as the addition of the monomer or
monomer mixture of the next block continues. This may affect
polymer properties such as phase separation, thermal behavior and
mechanical modulus and can be intentionally exploited to drive
properties for specific applications. This may be achieved by
intentionally terminating the polymerization when a desired level
of conversion (e.g., >80%) is reached by stopping the addition
of the initiators or immediately starting the addition of the
monomer or monomer mixture of the next block along with the
initiator.
[0054] Typical solvents that can be used to form the triblock
copolymer are alcohols, such as methanol, ethanol, n-propanol, and
isopropanol; ketones, such as acetone, butanone, pentanone, and
hexanone; alkyl esters of acetic, propionic, and butyric acids,
such as ethyl acetate, butyl acetate, and amyl acetate; ethers,
such as tetrahydrofuran, diethyl ether, and ethylene glycol and
polyethylene glycol monoalkyl and dialkyl ethers such as
cellosolves and carbitols; and, glycols such as ethylene glycol and
propylene glycol; and mixtures thereof.
[0055] Any of the commonly used azo or peroxide type polymerization
initiators can be used for preparation of the macromonomer or the
triblock copolymer provided it has solubility in the solution of
the solvents and the monomer mixture, and has an appropriate half
life at the temperature of polymerization. "Appropriate half life"
as used herein is a half-life of about 10 minutes to 4 hours. Most
preferred are azo type initiators such as
2,2'-azobis(isobutyronitrile), 2,2'-azobis
(2,4-dimethylvaleronitrile), 2,2'-azobis(methylbutyronitrile), and
1,1'-azobis(cyanocyclohexane). Examples of peroxy based initiators
are benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate,
t-butyl peroctoate which may also be used, provided they do not
adversely react with the chain transfer agents under the reaction
conditions for macromonomers.
[0056] Any of the conventional acrylic monomers and optionally
other ethylenically unsaturated monomers or monomer mixtures can be
used to form the individual A, B and A' blocks of the triblock
copolymer of this invention. Depending on the preparation methods,
certain monomers or monomer mixtures will work better than the
others. For the preferred method of preparation for this invention,
the "macromonomer" approach, methacrylate monomers must be used.
Specifically, each individual block must contain at least 70 mole
percent of a methacrylate monomer or methacrylate monomer mixtures.
More preferred is a composition containing at least 90 mole percent
of a methacrylate monomer or methacrylate monomer mixtures. The
other comonomers may be of the type of acrylate, acrylamide,
methacrylamide, vinyl aromatics such as styrene, and vinyl
esters.
[0057] For example, monomers that may be polymerized using the
methods of this invention include at least one monomer selected
from the group consisting of unsubstituted or substituted alkyl
acrylates, such as those having 1-20 carbon atoms in the alkyl
group, alkyl methacrylate such as those having 1-20 carbon atoms in
the alkyl group, cycloaliphatic acrylates, cycloaliphatic
methacrylates, aryl acrylates, aryl methacrylates, other
ethylenically unsaturated monomers such as acrylonitriles,
methacrylonitriles, acrylamides, methacrylamides,
N-alkylacrylamides, N-alkylmethacrylamides, N,N-dialkylacrylamides,
N,N-dialkylmethacrylamides, vinyl aromatics such as styrene, and
combinations thereof. Functionalized versions of these monomers and
their relative concentrations are especially useful in
differentiating the blocks, as will be discussed further
hereinbelow.
[0058] In the present invention, as mentioned above, preferably the
two outer blocks, A and A', contain a functional group, referred to
herein as an interactive or H-bonding group, for network formation
and better metallic flake control. This group will lead to the
formation of a network that is connected by physical forces and is
sensitive to shear force, temperature, or pH. This type of system
is useful for its rheological properties such as the thixotropic
behavior and parallel metallic flake orientation. Groups capable of
hydrogen bonding in particular, which will be discussed further
hereinbelow, may be advantageously employed for this purpose.
[0059] This group will vary depending on the nature of the other
binder components present in the lacquer coating; however,
carboxylic acid and other acid groups as are listed below are
generally preferred.
[0060] Specific monomers or comonomers that have no special
functional groups and may be used in this invention include various
non-functional acrylic monomers such as methyl methacrylate, ethyl
methacrylate, propyl methacrylate (all isomers), butyl methacrylate
(all isomers), 2-ethylhexyl methacrylate; isobornyl methacrylate,
methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate
(all isomers), butyl acrylate (all isomers), 2-ethylhexyl acrylate,
isobornyl acrylate, acrylonitrile, etc, and optionally other
ethylenically unsaturated monomers, e.g., vinyl aromatics such as
styrene, alpha-methyl styrene, t-butyl styrene, and vinyl toluene,
etc.
[0061] To introduce interactive/H-bonding primary or secondary
hydroxyl groups into the triblock copolymer, hydroxyl functional
acrylic monomers can be used. Examples of hydroxyl functional
acrylic monomers include hydroxyl alkyl(meth)acrylates having 1-10
atoms in the alkyl group such as 2-hydroxyethyl methacrylate
(primary), hydroxypropyl methacrylate (all isomers, primary and
secondary), hydroxybutyl methacrylate (all isomers, primary and
secondary), 2-hydroxyethyl acrylate (primary), hydroxypropyl
acrylate (all isomers, primary and secondary), hydroxybutyl
acrylate (all isomers, primary and secondary), other hydroxy alkyl
acrylates and methacrylates, and the like.
[0062] To introduce interactive/H-bonding acid groups into the
triblock copolymer at the appropriate blocks, acid-functional
monomers can be used. Carboxylic acid functional monomers are
generally preferred for better compatibility with other binder
components in the lacquer coating composition. The most commonly
used carboxyl acid group containing monomers are methacrylic acid
and acrylic acid. Others include beta-carboxyethyl acrylate, vinyl
benzoic acid (all isomers), alpha-methylvinyl benzoic acid (all
isomers), and the diacids such as maleic acid, fumaric acid,
itaconic acid, and their anhydride form that can be hydrolyzed to
the carboxylic acid groups after the polymers are made. Of course,
a low level of other types of acid groups, such as sulfonic acid or
phosphoric acid may be used.
[0063] Useful amide functional monomers which can be used to
introduce interactive/H-bonding amide groups into the polymer
include acrylamides and methacrylamides and other vinyl monomers
containing either a cyclic or acyclic amide group.
[0064] Examples of acrylamide or methacrylamide monomers are
represented by the formula ##STR1##
[0065] where R.sup.1 and R.sup.2 are each independently selected
from the group consisting of hydrogen, alkyl group, aryl group,
arylalkyl group, and alkylaryl group having 1 to 20 carbon atoms,
and optionally containing one or more substituents that do not
interfere with the polymerization process. Such substituents may
include alkyl, hydroxy, amino, ester, acid, acyloxy, amide,
nitrile, halogen, alkoxy, etc. Useful examples include
methacrylamides such as N-methylmethacrylamide,
N-ethylmethacrylamide, N-octylmethacrylamide,
N-dodecylmethacrylamide, N-(isobutoxymethyl)methacrylamide,
N-phenylmethacrylamide, N-benzylmethacrylamide,
N,N-dimethylmethacrylamide, and the like; and acrylamides such as
N-methyl acrylamide, N-ethylacrylamide, N-t-butylacrylamide,
N-(isobutoxymethyl)acrylamide, N,N-dimethylacrylamide,
N,N-diethylacrylamide, N,N-dibutyl acrylamide, and the like.
[0066] Examples of vinyl monomers that can be used to introduce
cyclic amide groups into the copolymer include acrylic,
methacrylic, acrylamide, methacrylamide, and some other vinyl
monomers. The acrylic, methacrylic, acrylamide and methacrylamide
monomers are represented by formula ##STR2##
[0067] where Y is O or N, R.sup.3 is selected from the group
consisting of alkyl group, aryl group, arylalkyl group, and
alkylaryl group having 1 to 20 carbon atoms and may contain
substituents which do not interfere with polymerization such as
hydroxy, amino, ester, acid, acyloxy, amide, nitrile, halogen,
alkoxy, etc., R.sup.4 does not exist when Y is O but when Y is N,
R.sup.4 is selected from the group consisting of hydrogen, alkyl
group, aryl group, arylalkyl group, and alkylaryl group having 1 to
20 carbon atoms and may contain substituents which do not interfere
with polymerization such as hydroxy, amino, ester, acid, acyloxy,
amide, nitrile, halogen, alkoxy, etc., and Z is a radical center
connected to structure (1) or (2) below.
[0068] Other vinyl monomers which can also be used to introduce the
interactive cyclic amide groups are represented by formula
##STR3##
[0069] where R.sup.5 is selected from the group consisting of alkyl
group, aryl group, arylalkyl group, and alkylaryl group having 0 to
20 carbon atoms and may contain substituents which do not interfere
with polymerization such as hydroxy, amino, ester, acid, acyloxy,
amide, nitrile, halogen, alkoxy, etc., and Z is a radical center
connected to structure (1) or (2) below. The most useful example is
N-vinyl-2-pyrrolidinone.
[0070] Structures (1) and (2), respectively, are represented by
##STR4##
[0071] where n=3-7, preferably 3-5, m=0-3, X is a substituent on
the cyclic structure and may be selected from the group consisting
of alkyl group, aryl group, arylalkyl group, alkylaryl group, and
heterocyclic group having 1 to 20 carbon atoms, and may contain
substituents which do not interfere with polymerization such as
hydroxy, amino, ester, acid, acyloxy, amide, nitrile, halogen,
alkoxy, etc., R is selected from the group consisting of hydrogen,
alkyl group, aryl group, arylalkyl group, and alkylaryl group
having 1 to 20 carbon atoms, and may contain substituents which do
not interfere with polymerization such as hydroxy, amino, ester,
acid, acyloxy, amide, nitrile, halogen, alkoxy, etc., and Z is a
radical center connected to the vinyl monomer structures referenced
above. Examples of the heterocyclic group include triazole,
triazine, imidazole, piperazine, pyridine, pyrimidine, and the
like.
[0072] Useful urea functional monomers which can be used to
introduce interactive/H-bonding urea groups into the polymer
include acrylates methacrylates, acrylamides, methacrylamides and
other vinyl monomers containing either a cyclic or a linear/acyclic
urea group.
[0073] The urea containing acrylic, methacrylic, acrylamide, and
methacrylamide monomers are represented by the general formula of
##STR5##
[0074] where Y, R.sup.3 and R.sup.4 are as described above, and Z'
is a radical center connected to structure (3) below for a linear
or acyclic urea group, or (4) or (5) below for a cyclic urea
group.
[0075] Other vinyl monomers which can also be used to introduce
either acyclic or cyclic urea group are represented by the general
formula of ##STR6##
[0076] where R.sup.5 is as described above, and Z' is a radical
center connected to structure (3) below for a linear or acyclic
urea group, or (4) or (5) for a cyclic urea group.
[0077] Structure (3), (4), and (5), respectively, are represented
by ##STR7##
[0078] where n=0-5, preferably 2-5, m=0-3, X is a substituent on
the cyclic structure and may be selected from the group consisting
of alkyl group, aryl group, arylalkyl group, alkylaryl group, and
heterocyclic group having 1 to 20 carbon atoms, and may contain
substituents which do not interfere with polymerization such as
hydroxy, amino, ester, acid, acyloxy, amide, nitrile, halogen,
alkoxy, etc., each R is independently selected from the group
consisting of hydrogen, alkyl group, aryl group, arylalkyl group,
alkylaryl group, and heterocyclic group having 1 to 20 carbon
atoms, and may contain substituents which do not interfere with
polymerization such as hydroxy, amino, ester, acid, acyloxy, amide,
nitrile, halogen, alkoxy, etc., and Z' is a radical center
connected to the vinyl monomer structures referenced above.
Examples of the heterocyclic group include triazole, triazine,
imidazole, piperazine, pyridine, pyrimidine, and the like. The
cyclic urea structure may also contain other heteroatoms such as O,
S, N(R), or groups such as C(O), S(O).sub.2 or unsaturated double
bonds, especially when n is 0 or 1. Examples of such structures
include urazole, uracil, cytosine, and thymine.
[0079] Typical examples of ethylenically unsaturated urea
containing monomers are described in U.S. Pat. Nos. 5,030,726 and
5,045,616, hereby incorporated by reference. Preferred monomers of
this type are the acrylate, methacrylate, acrylamide or
methacrylamide derivatives of 2-hydroxyethylene urea (HEEU), or
2-aminoethylethylene urea (AEEU). The most preferred monomers of
this type that are commercially available include
N-(2-methacryloyloxyethyl)ethylene urea and
methacrylamidoethylethylene urea. Other examples of urea containing
monomers can be obtained by reacting an ethylenically unsaturated
monomer having an isocyanato group such as dimethyl
m-isopropenylbenzyl isocyanate (m-TMI) or 2-isocyanatoethyl
methacrylate (ICEMA) with a hydroxyl or amino compound having a
linear or a cyclic urea group such as HEEU or AEEU. In these
examples the urea group is linked to the monomer through a urethane
or another urea group.
[0080] The ethylene oxide groups are capable of hydrogen-bonding
with other functional groups that are also desirable for the
polymer of this invention such as carboxylic acid. They can be
conveniently introduced with the monomers of the general formula of
CH.sub.2.dbd.C(R.sup.6)(C(O)OX.sub.n(CH.sub.2CH.sub.2O).sub.m)--R.sup.7
[0081] wherein n=0 or 1; when n=1, X is an akyl, aryl, or alkaryl
diradical connecting group of 1-10 carbon atoms; m=2-100, R.sup.6
is H or CH.sub.3, and R.sup.7 is an alkyl group of 1-10 carbon
atoms. Useful examples of such comonomers include
2-(2-methoxyethoxy)ethyl acrylate, 2-(2-methoxyethoxy)ethyl
methacrylate, ethoxytriethyleneglycol methacrylate, methoxy
polyethyleneglycol (molecular weight of 200-100) monomethacrylate,
polyethyleneglycol (molecular weight 200-1000)
monomethacrylate.
[0082] As indicated above, the choice of monomers and monomer
mixtures for each block, the block size, overall ratios of monomers
used to form the blocks, and molecular weights, and nature of each
block will vary so as to provide the particular attribute desired
for a particular application.
[0083] In one preferred embodiment, the ABA' block polymer contains
in the A-block: methacrylic acid/2-hydroxyethyl methacrylate/ethoxy
triethyleneglycol methacrylate (MAA/HEMA/ETEGMA); B-block: methyl
methacrylate/butyl methacrylate (MMA/BMA); and A'-block: methyl
methacrylate/butyl methacrylate/2-hydroxyethyl
methacrylate/methacrylic acid (MMA/BMA/HEMA/MAA).
[0084] It should be understood that the polymer can be made
starting from either end. For instance, an A'BA (reverse of ABA')
block polymer also can be formed and is part of this invention. In
forming a A'BA block polymer, the A' block is first made using the
same procedure as above and then the monomers for the B block are
added and after the B block is formed the monomers for the A block
are added and polymerized.
[0085] The novel coating composition of the present invention
generally contains as part of the binder, in the range of about 1
to 80% by weight, preferably about 5 to 60%, and even more
preferably in the range of about 10 to 40% by weight of this CAB
replacement polymer, all weight percentages being based on the
total weight of the binder.
Other Binder Materials
[0086] In addition to the triblock copolymer described above, the
coating composition can also include, as part of the binder, 0 to
98% by weight, preferably in the range of 20 to 95%, and even more
preferably from 30 to 90% by weight of an acrylic polymer,
polyester, alkyd resin, acrylic alkyd resin, cellulose acetate
butyrate, an iminated acrylic polymer, ethylene vinyl acetate
co-polymer, nitrocellulose, plasticizer or a combination thereof,
all weight percentages being based on the total weight of the
binder.
[0087] Useful acrylic polymers are conventionally polymerized from
a monomer mixture that can include one or more of the following
monomers: an alkyl acrylate; an alkyl methacrylate; a hydroxy alkyl
acrylate, a hydroxy alkyl methacrylate; acrylic acid; methacrylic
acid; styrene; alkyl amino alkyl acrylate; and alkyl amino alkyl
methacrylate, and mixtures thereof; and one or more of the
following drying oils: vinyl oxazoline drying oil esters of linseed
oil fatty acids, tall oil fatty acids, and tung oil fatty
acids.
[0088] Suitable iminiated acrylic polymers can be obtained by
reacting acrylic polymers having carboxyl groups with propylene
imine.
[0089] Useful polyesters include the esterification product of an
aliphatic or aromatic dicarboxylic acid, a polyol, a diol, an
aromatic or aliphatic cyclic anhydride and a cyclic alcohol. One
such polyester is the esterification product of adipic acid,
trimethylol propane, hexanediol, hexahydrophathalic anhydride and
cyclohexane dimethylol.
[0090] Other polyesters that are useful in the present invention
are branched copolyester polyols. One particularly preferred
branched polyester polyol is the esterification product of
dimethylolpropionic acid, pentaerythritol and epsilon-caprolactone.
These branched copolyester polyols and the preparation thereof are
further described in WO 03/070843 published Aug. 28, 2003, which is
hereby incorporated by reference.
[0091] Suitable cellulose acetate butyrates, which may still be
used, if desired, are supplied by Eastman Chemical Co., Kingsport,
Tenn. under the trade names CAB-381-20 and CAB-531-1. These
materials may be used in an amount of 0.1 to 20% by weight based on
the weight of the binder. Preferably, however, the lacquers of this
invention are free or essentially free of these materials,
especially the high molecular weight, high hydroxyl number CAB
resins like CAB-381-20.
[0092] A suitable ethylene-vinyl acetate co-polymer (wax) is
supplied by Honeywell Specialty Chemicals--Wax and Additives,
Morristown, N.J., under the trade name A-C 405 (T) Ethylene-Vinyl
Acetate Copolymer.
[0093] Suitable nitrocellulose resins preferably have a viscosity
of about 1/2-6 seconds. Preferably, a blend of nitrocellulose
resins is used. Optionally, the lacquer can contain ester gum and
castor oil.
[0094] Suitable alkyd resins are the esterification products of a
drying oil fatty acid, such as linseed oil and tall oil fatty acid,
dehydrated castor oil, a polyhydric alcohol, a dicarboxylic acid
and an aromatic monocarboxylic acid. One preferred alkyd resin is a
reaction product of an acrylic polymer and an alkyd resin.
[0095] Suitable plasticizers include butyl benzyl phthalate,
dibutyl phthalate, triphenyl phosphate, 2-ethylhexylbenzyl
phthalate, dicyclohexyl phthalate, diallyl toluene phthalate,
dibenzyl phthalate, butylcyclohexyl phthalate, mixed benzoic acid
and fatty oil acid esters of pentaerythritol, poly(propylene
adipate)dibenzoate, diethylene glycol dibenzoate,
tetrabutylthiodisuccinate, butyl phthalyl butyl glycolate,
acetyltributyl citrate, dibenzyl sebacate, tricresyl phosphate,
toluene ethyl sulfonamide, the di-2-ethyl hexyl ester of
hexamethylene diphthalate, and di(methyl cyclohexyl)phthalate. One
preferred plasticizer of this group is butyl benzyl phthalate.
[0096] If desired, the lacquer can include metallic driers,
chelating agents, or a combination thereof. Suitable organometallic
driers include cobalt naphthenate, copper naphthenate, lead
tallate, calcium naphthenate, iron naphthenate, lithium
naphthenate, lead naphthenate, nickel octoate, zirconium octoate,
cobalt octaoate, iron octoate, zinc octoate, and alkyl tin
dilaurates, such as dibutyl tin dilaurate. Suitable chelating
agents include aluminum monoisopropoxide monoversatate,
aluminum(monoiospropyl)phthalate, aluminum diethoxyethoxide
monoversatate, aluminum trisecondary butoxide, aluminum
diisopropoxide monoacetacetic ester chelate and aluminum
isopropoxide.
[0097] If the lacquer is to be used as a clearcoat for the exterior
of automobiles and trucks, about 0.1 to 5% by weight, based on the
weight of the total weight of the binder, of an ultraviolet light
stabilizer or a combination of ultraviolet light stabilizers and
absorbers can be added to improve the weatherability of the
composition. These stabilizers include ultraviolet light absorbers,
screeners, quenchers and specific hindered amine light stabilizers.
Also, about 0.1 to 5% by weight, based on the total weight of the
binder, of an antioxidant can be added. Most of the foregoing
stabilizers are supplied by Ciba Specialty Chemicals, Tarrytown,
N.Y.
[0098] Additional details of the foregoing additives are provided
in U.S. Pat. Nos. 3,585,160, 4,242,243, 4,692,481, and US Re
31,309, which are hereby incorporated by reference.
Pigments
[0099] If desired, the novel composition can be pigmented to form a
colored mono coat, basecoat, primer or primer surfacer. Generally,
pigments are used in a pigment to binder weight ratio (P/B) of
0.1/100 to 200/100; preferably, for base coats in a P/B of 1/100 to
50/100. If used as primer or primer surfacer higher levels of
pigment are used, e.g., 50/100 to 200/100. The pigments can be
added using conventional techniques, such as sand-grinding, ball
milling, attritor grinding, two roll milling to disperse the
pigments. The mill base is blended with the film-forming
constituents.
[0100] Any of the conventional pigments used in coating
compositions can be utilized in the composition such as the
following: metallic oxides, metal hydroxide, metal flakes,
chromates, such as lead chromate, sulfides, sulfates, carbonates,
carbon black, silica, talc, china clay, phthalocyanine blues and
greens, organo reds, organo maroons, pearlescent pigments and other
organic pigments and dyes. If desired, chromate-free pigments, such
as barium metaborate, zinc phosphate, aluminum triphosphate and
mixtures thereof, can also be used.
[0101] Suitable flake pigments include bright aluminum flake,
extremely fine aluminum flake, medium particle size aluminum flake,
and bright medium coarse aluminum flake; mica flake coated with
titanium dioxide pigment also known as pearl pigments. Suitable
colored pigments include titanium dioxide, zinc oxide, iron oxide,
carbon black, mono azo red toner, red iron oxide, quinacridone
maroon, transparent red oxide, dioxazine carbazole violet, iron
blue, indanthrone blue, chrome titanate, titanium yellow, mono azo
permanent orange, ferrite yellow, mono azo benzimidazolone yellow,
transparent yellow oxide, isoindoline yellow,
tetrachloroisoindoline yellow, anthanthrone orange, lead chromate
yellow, phthalocyanine green, quinacridone red, perylene maroon,
quinacridone violet, pre-darkened chrome yellow, thio-indigo red,
transparent red oxide chip, molybdate orange, and molybdate orange
red.
Liquid Carrier
[0102] The lacquer of the present invention can further, and
typically does, contain at least one volatile organic solvent as
the liquid carrier to disperse and/or dilute the above ingredients
and form a coating composition having the desired properties. The
solvent or solvent blends are typically selected from the group
consisting of aromatic hydrocarbons, such as, petroleum naphtha or
xylenes; ketones, such as, methyl amyl ketone, methyl isobutyl
ketone, methyl ethyl ketone or acetone; esters, such as butyl
acetate or hexyl acetate; glycol ether esters, such as, propylene
glycol monomethyl ether acetate; and alcohols, such as isopropanol
and butanol. The amount of organic solvent added depends upon the
desired solids level, desired rheological (e.g., spray) properties,
as well as the desired amount of VOC of the lacquer.
[0103] The total solids level of the coating of the present
invention can vary in the range of from 5 to 95%, preferably in the
range of from 7 to 80% and more preferably in the range of from 10
to 60%, all percentages being based on the total weight of the
coating composition.
Optional Crosslinking Component
[0104] If the novel composition is used as a clear coating
composition, a crosslinking component is generally known to provide
the improved level of durability and weatherability required for
automotive and truck topcoats. Typically, polyisocyanates are used
as the crosslinking agents. Suitable polyisocyanate has on average
2 to 10, alternately 2.5 to 8 and further alternately 3 to 8
isocyanate functionalities. Typically the coating composition has,
in the binder, a ratio of isocyanate groups on the polyisocyanate
in the crosslinking component to crosslinkable groups (e.g.,
hydroxyl and/or amine groups) of the branched acrylic polymer
ranges from 0.25/1 to 3/1, alternately from 0.8/1 to 2/1, further
alternately from 1/1 to 1.8/1.
[0105] Examples of suitable polyisocyanates include any of the
conventionally used aromatic, aliphatic or cycloaliphatic di-, tri-
or tetra-isocyanates, including polyisocyanates having isocyanurate
structural units, such as, the isocyanurate of hexamethylene
diisocyanate and isocyanurate of isophorone diisocyanate; the
adduct of 2 molecules of a diisocyanate, such as, hexamethylene
diisocyanate; uretidiones of hexamethylene diisocyanate;
uretidiones of isophorone diisocyanate or isophorone diisocyanate;
isocyanurate of meta-tetramethylxylylene diisocyanate; and a diol
such as, ethylene glycol.
[0106] Polyisocyanates functional adducts having isocyanaurate
structural units can also be used, for example, the adduct of 2
molecules of a diisocyanate, such as, hexamethylene diisocyanate or
isophorone diisocyanate, and a diol such as ethylene glycol; the
adduct of 3 molecules of hexamethylene diisocyanate and 1 molecule
of water (available under the trademark Desmodure.RTM. N from Bayer
Corporation of Pittsburgh, Pa.); the adduct of 1 molecule of
trimethylol propane and 3 molecules of toluene diisocyanate
(available under the trademark Desmodur.RTM. L from Bayer
Corporation ); the adduct of 1 molecule of trimethylol propane and
3 molecules of isophorone diisocyanate or compounds, such as
1,3,5-triisocyanato benzene and 2,4,6-triisocyanatotoluene; and the
adduct of 1 molecule of pentaerythritol and 4 molecules of toluene
diisocyanate.
[0107] The coating composition containing a crosslinking component
preferably includes one or more catalysts to enhance crosslinking
of the components on curing. Generally, the coating composition
includes in the range of from 0.01 to 5% by weight, based on the
total weight of the binder.
[0108] Suitable catalysts for polyisocyanate can include one or
more tin compounds, tertiary amines or a combination thereof.
Suitable tin compounds include dibutyl tin dilaurate, dibutyl tin
diacetate, stannous octoate, and dibutyl tin oxide. Dibutyl tin
dilaurate is preferred. Suitable tertiary amines include
triethylene diamine. One commercially available catalyst that can
be used is Fastcat.RTM. 4202 dibutyl tin dilaurate sold by
Elf-Atochem North America, Inc. Philadelphia, Pa. Carboxylic acids,
such as acetic acid, may be used in conjunction with the above
catalysts to improve the viscosity stability of two component
coatings.
Application
[0109] In use, a layer of the novel composition is typically
applied to a substrate by conventional techniques, such as,
spraying, electrostatic spraying, roller coating, dipping or
brushing. Spraying and electrostatic spraying are preferred
application methods. When used as a pigmented coating composition,
e.g., as a basecoat or a pigmented top coat, the coating thickness
can range from 10 to 85 micrometers, preferably from 12 to 50
micrometers and when used as a primer, the coating thickness can
range from 10 to 200 micrometers, preferably from 12 to 100
micrometers. When used as a clear coating, the thickness is in the
range of from 25 micrometers to 100 micrometers. The coating
composition can be dried at ambient temperatures or can be dried
upon application for about 2 to 60 minutes at elevated drying
temperatures ranging from about 50.degree. C. to 100.degree. C.
[0110] In a typical clearcoat/basecoat application, a layer of
conventional clear coating composition is applied over the basecoat
of the novel composition of this invention by the above
conventional techniques, such as, spraying or electrostatic
spraying. Generally, a layer of the basecoat is flashed for 1
minute to two hours under ambient or elevated temperatures before
the application of the clear coating composition or dried at
elevated temperatures shown above. Suitable clear coating
compositions can include two-pack isocyanate crosslinked
compositions, such as 72200S ChromaPremier.RTM. Productive Clear
blended with an activator, such as 12305S ChromaPremier.RTM.
Activator, or 3480S Low VOC Clear composition activated with 194S
Imron Select.RTM. Activator. Isocyanate free crosslinked clear
coating compositions, such as 1780S Iso-Free Clearcoat activated
with 1782S Converter and blended with 1775S Mid-Temp Reducer are
also suitable. Suitable clear lacquers can include 480S Low VOC
Ready to Spray Clear composition. All the foregoing clear coating
compositions are supplied by DuPont (E.I. Dupont de Nemours and
Company, Wilmington, Del.).
[0111] If the coating composition of the present invention contains
a crosslinking agent, such as a polyisocyanate, the coating
composition can be supplied in the form of a two-pack coating
composition in which the first-pack includes the branched acrylic
polymer and the second pack includes the crosslinking component,
e.g., a polyisocyanate. Generally, the first and the second packs
are stored in separate containers and mixed before use. The
containers are preferably sealed air tight to prevent degradation
during storage. The mixing may be done, for example, in a mixing
nozzle or in a container. When the crosslinking component contains,
e.g., a polyisocyanate, the curing step can take place under
ambient conditions, or if desired, it can take place at elevated
baking temperatures.
[0112] For a two pack coating composition, the two packs are mixed
just prior to use or 5 to 30 minutes before use to form a potmix. A
layer of the potmix is typically applied to a substrate by the
above conventional techniques. If used as a clear coating, a layer
is applied over a metal substrate, such as, automotive body, which
is often pre-coated with other coating layers, such as, an
electrocoat primer, primer surfacer and a basecoat. The two-pack
coating composition may be dried and cured at ambient temperatures
or may be baked upon application for 10 to 60 minutes at baking
temperatures ranging from 80.degree. C. to 160.degree. C. The
mixture can also contain pigments and can be applied as a mono coat
or a basecoat layer over a primed substrate or as a primer
layer.
[0113] The coating composition of the present invention is suitable
for providing coatings on variety of substrates. Typical
substrates, which may or may not be previously primed or sealed,
for applying the coating composition of the present invention
include automobile bodies, any and all items manufactured and
painted by automobile sub-suppliers, frame rails, commercial trucks
and truck bodies, including but not limited to beverage bottles,
utility bodies, ready mix concrete delivery vehicle bodies, waste
hauling vehicle bodies, and fire and emergency vehicle bodies, as
well as any potential attachments or components to such truck
bodies, buses, farm and construction equipment, truck caps and
covers, commercial trailers, consumer trailers, recreational
vehicles, including but not limited to, motor homes, campers,
conversion vans, vans, pleasure vehicles, pleasure craft snow
mobiles, all terrain vehicles, personal watercraft, motorcycles,
bicycles, boats, and aircraft. The substrate further includes
industrial and commercial new construction and maintenance thereof;
cement and wood floors; walls of commercial and residential
structures, such office buildings and homes; amusement park
equipment; concrete surfaces, such as parking lots and drive ways;
asphalt and concrete road surface, wood substrates, marine
surfaces; outdoor structures, such as bridges, towers; coil
coating; railroad cars; printed circuit boards; machinery; OEM
tools; signage; fiberglass structures; sporting goods; golf balls;
and sporting equipment.
[0114] The novel compositions of this invention are also suitable
as clear or pigmented coatings in industrial and maintenance
coating applications.
[0115] These and other features and advantages of the present
invention will be more readily understood, by those of ordinary
skill in the art from the following examples. In the examples, all
parts and percentages are on a weight basis unless otherwise
noted.
EXAMPLES
[0116] The following ABA' triblock copolymer were prepared from the
following macromonomers and then used to form lacquer coating
compositions.
Example 1
Preparation of MAA/HEMA/ETEGMA Macromonomer, 60/20/20% by
Weight
[0117] This example illustrates the preparation of a macromonomer
with carboxyl groups, primary hydroxyl groups, and polyethylene
oxide groups that are capable of forming hydrogen bonds and can be
used to form the A block (outer block) of a triblock copolymer of
this invention. A 5-liter flask was equipped with a thermometer,
stirrer, additional funnels, heating mantel, reflux condenser and a
means of maintaining a nitrogen blanket over the reactants. The
flask was held under nitrogen positive pressure and the following
ingredients were employed. TABLE-US-00001 Weight (gram) Portion 1
Methyl ethyl ketone 850.0 Isopropanol 990.0 Portion 2
Diaquabis(borondifluorodiphenyl 0.48 glyoximato)cobaltate (II),
Co(DPG-BF.sub.2) Acetone 106.4 Portion 3
2,2'-Azobis(methylbutyronitrile) (Vazo .RTM. 21.6 67 by DuPont Co.,
Wilmington, DE) Methyl ethyl ketone 260.0 Portion 4 Methacrylic
acid (MAA) 720.0 2-Hydroxyethyl methacrylate (HEMA) 240.0 Ethoxy
triethyleneglycol methacrylate (ETEGMA) 240.0 Total 3428.48
[0118] Portion 1 mixture was charged to the flask and the mixture
was heated to reflux temperature and refluxed for about 20 minutes.
Portion 2 was prepared by dissolving the cobalt catalyst
completely. Portion 3 was added to Portion 2 and agitated to
dissolve the initiator. The mixture of Portion 2 and Portion 3 was
fed to the flask over 210 minutes while Portion 4 was
simultaneously fed to the flask over 180 minutes, and the reaction
mixture was held at reflux temperature throughout the course of
additions. Reflux was continued for another 1.5 hours and the
solution was cooled to room temperature and filled out.
[0119] The resulting macromonomer solution was a light yellow clear
polymer solution and had a solid content of about 36.2% and a
Gardner-Holtz viscosity of P. The macromonomer had a 6,390 Mw and
3,805 Mn after the carboxyl groups were protected by methyl groups
to facilitate the GPC analysis.
Example 2
Preparation of an AB Diblock Macromonomer BMA/MMA//MAA/HEMA/ETEGMA,
45/30/15/5/5% by Weight
[0120] This example shows the preparation of a diblock macromonomer
where the B block (center block) has no specific functional groups
and the A block (one of the terminal block) contains carboxyl
groups, primary hydroxyl groups, and polyethylene oxide groups from
the macromonomer prepared above.
[0121] A 5-liter flask was equipped as in Example 1. The flask was
held under nitrogen positive pressure and the following ingredients
were employed. TABLE-US-00002 Weight (gram) Portion 1 Macromonomer
of Example 1 1257.15 Isopropanol 614.8 Portion 2 Methyl
methacrylate (MMA) 528.0 Butyl methacrylate (BMA) 792.0 Portion 3
t-Butyl peroctoate (Elf Atochem North 28.0 America, Inc.,
Philadelphia, PA) Ethyl acetate 300.0 Total 3519.95
[0122] Portion 1 mixture was charged to the flask and the mixture
was heated to reflux temperature and refluxed for about 10 minutes.
Portion 2 was added over 3 hours and Portion 3 was simultaneously
added over 3.5 hours while the reaction mixture was held at reflux
temperature. The reaction mixture was refluxed for another 1.5
hours.
[0123] After cooling, the resulting macromonomer solution was a
clear polymer solution and had a solid content of about 51.3% and a
Gardner-Holtz viscosity of Y+1/2. The macromonomer had a 20,027 Mw
and 8,578 Mn after the carboxyl groups were protected by methyl
groups to facilitate the GPC analysis.
Example 3
Preparation of an ABA' Triblock Copolymer
[0124] This example shows the preparation of an ABA' triblock
copolymer of this invention containing carboxyl groups, and primary
hydroxyl groups on both the A and A' blocks, no specific functional
groups on the center B block, specifically methyl
methacrylate-co-butyl methacrylate-co-2-hydroxyethyl
methacrylate-co-methacrylic acid-b-butyl methacrylate-co-methyl
methacrylate-b-methacrylic acid-co-hydroxyethyl
methacrylate-co-ethoxytriethyleneglycol methacrylate,
32/22/7/4//15.75/10.51/5.25/1.75/1.75% by weight, from a
macromonomer prepared above.
[0125] A 12-liter flask was equipped as in Example 1. The flask was
held under nitrogen positive pressure and the following ingredients
were employed. TABLE-US-00003 Weight (gram) Portion 1 Macromonomer
of Example 2 2350.0 Ethyl acetate 960.0 Portion 2 Methyl
methacrlate (MMA) 1075.0 Butyl methacrylate (BMA) 740.0
2-Hydroxyethyl methacrylate (HEMA) 236.0 Methacrylic acid 135.0
Portion 3 t-Butyl peroctoate (Elf Atochem North 45.0 America, Inc.,
Philadelphia, PA) Ethyl acetate 1066.0 Portion 4 t-Butyl peroctoate
(Elf Atochem North 4.6 America, Inc., Philadelphia, PA) Ethyl
acetate 107.0 Portion 5 Butyl acetate 283.0 Total 7001.6
[0126] Portion 1 mixture was charged to the flask and the mixture
was heated to reflux temperature and refluxed for about 10 minutes.
Portion 2 and 3 were simultaneously added over 3 hours while the
reaction mixture was held at reflux temperature. The reaction
mixture was refluxed for 30 minutes. Portion 4 was added over 5
minutes, and the reaction mixture was refluxed for another 2 hours.
Portion 5 was added toward the end of the reflux.
[0127] After cooling, the resulting ABA' triblock copolymer
solution was slightly hazy and had a solid content of about 50.2%
and a Gardner-Holtz viscosity of Z1. The triblock copolymer had a
relatively narrow distribution of molecular weight with 28,146 Mw
and 12,176 Mn, and a very high Tg of 110 C measured by Differential
Scanning Calorimetry.
Example 4
Preparation of an ABA' Triblock Copolymer
[0128] This example shows the preparation of an ABA' triblock
copolymer of this invention containing urea groups, primary
hydroxyl groups, and polyethylene oxide groups on one terminal
block, and carboxyl groups and primary hydroxyl groups on the
other, and no specific functional groups on the center B block,
specifically methyl
methacrylate-co-N-(2-methacryloyloxyethyl)ethylene urea-co-butyl
methacrylate-co-hydroxyethyl methacrylate-g-butyl
methacrylate-co-methyl methacrylate-b-methacrylic
acid-co-hydroxyethyl methacrylate-co-ethoxytriethyleneglycol
methacrylate, 33/4/20/8//5.75/10.50//5.25/1.75/1.75% by weight,
from a macromonomer prepared above.
[0129] A 12-liter flask was equipped as in Example 1. The flask was
held under nitrogen positive pressure and the following ingredients
were employed. TABLE-US-00004 Weight (gram) Portion 1 Macromonomer
of Example 2 2579.85 Isopropanol 1471.5 Portion 2 Methyl
methacrylate (MMA) 773.96 Butyl methacrylate (BMA) 737.10 Rohamere
6844-0 (25% N-(2- 589.68 methacryloyloxyethyl)ethylene urea in MMA,
Rohm Tech Inc., Maiden, MA) 2-Hydroxyethyl methacrylate (HMEA)
294.84 Portion 3 t-Butyl peroctoate (Elf Atochem North 46.00
America, Inc., Philadelphia, PA) Ethyl acetate 980.0 Portion 4
t-Butyl peroctoate (Elf Atochem North 4.6 America, Inc.,
Philadelphia, PA) Ethyl acetate 98.0 Portion 5 t-Butyl peroctoate
(Elf Atochem North 4.6 America, Inc., Philadelphia, PA) Ethyl
acetate 98.0 Total 7678.13
[0130] Portion 1 mixture was charged to the flask and the mixture
was heated to reflux temperature and refluxed for about 10 minutes.
Portion 2 and 3 were simultaneously added over 3 hours while the
reaction mixture was held at reflux temperature. The reaction
mixture was refluxed for 30 minutes. Portion 4 was added over 5
minutes, and the reaction mixture was refluxed for another 30
minutes. Portion 5 was added over 5 minutes and the reaction
mixture was refluxed for 2 hours. After cooling, the resulting
triblock copolymer solution was slightly hazy and had a solid
content of about 47.5% and a Gardner-Holtz viscosity of Z+1/2. The
triblock copolymer had a 30,291 Mw and 13,288 Mn, and a Tg of 84.6
C measured by Differential Scanning Calorimetry.
Example 5
Preparation of an ABA' Triblock Copolymer
[0131] This example shows the preparation of an ABA' triblock
copolymer of this invention containing carboxyl groups, primary
hydroxyl groups, and polyehtylene oxide groups on one terminal
block, and hydroxyl and additional polar acetoacetate groups on the
other, no specific functional groups on the center B block,
specifically methyl methacrylate-co-butyl
methacrylate-co-2-hydroxyethyl methacrylate-co-2-acetoacetoxyethyl
methacrylate-b-butyl methacrylate-co-methyl
methacrylate-b-methacrylic acid-co-hydroxyethyl
methacrylate-co-ethoxytriethyleneglycol methacrylate,
33/16/8/8/115.75/10.5/15.25/1.75/1.75% by weight, from a
macromonomer prepared above.
[0132] A 5-liter flask was equipped as in Example 1. The flask was
held under nitrogen positive pressure and the following ingredients
were employed. TABLE-US-00005 Weight (gram) Portion 1 Macromonomer
of Example 2 1176.0 Ethyl acetate 533.0 Portion 2 Methyl
methacrlate (MMA) 554.4 Butyl methacrylate (BMA) 268.8
2-Hydroxyethyl methacrylate (HEMA) 134.4 2-acetoactoxyethyl
methacrylate (AAEM) 134.4 Portion 3 t-Butyl peroctoate (Elf Atochem
North 20.0 America, Inc., Philadelphia, PA) Ethyl acetate 445.0
Portion 4 t-Butyl peroctoate (Elf Atochem North 2.0 America, Inc.,
Philadelphia, PA) Ethyl acetate 45.0 Portion 5 t-Butyl peroctoate
(Elf Atochem North 2.0 America, Inc., Philadelphia, PA) Ethyl
acetate 45.0 Total 3360.0
[0133] The procedure of Example 4 was repeated. After cooling, the
resulting ABA' triblock copolymer solution was slightly hazy and
had a solid content of about 51.5% and a Gardner-Holtz viscosity of
Z1. The triblock copolymer had a relatively narrow distribution of
molecular weight with 29,472 Mw and 13,063 Mn, and a very high Tg
of 110 C measured by Differential Scanning Calorimetry.
Example 6
Preparation of an ABA' Triblock Copolymer
[0134] This example shows the preparation of an ABA' triblock
copolymer of this invention containing carboxyl groups, primary
hydroxyl groups, and polyethylene oxide groups on one terminal
block and the primary hydroxyl groups only on the other, no
specific functional groups on the center B block, specifically
methyl methacrylate-co-butyl methacrylate-co-2-hydroxyethyl
methacrylate-b-butyl methacrylate-co-methyl
methacrylate-b-methacrylic acid-co-hydroxyethyl
methacrylate-co-ethoxytriethyleneglycol methacrylate,
34/23/8//15.75/10.5//5.25/1.75/1.75% by weight, from a macromonomer
prepared above.
[0135] A 5-liter flask was equipped as in Example 1. The flask was
held under nitrogen positive pressure and the following ingredients
were employed. TABLE-US-00006 Weight (gram) Portion 1 Macromonomer
of Example 2 1146.6 Isopropanol 596.2 Portion 2 Methyl methacrlate
(MMA) 556.92 Butyl methacrylate (BMA) 376.74 2-Hydroxyethyl
methacrylate (HEMA) 131.04 Portion 3 t-Butyl peroctoate (Elf
Atochem North 20.0 America, Inc., Philadelphia, PA) Ethyl acetate
530.0 Portion 4 t-Butyl peroctoate (Elf Atochem North 2.0 America,
Inc., Philadelphia, PA) Ethyl acetate 53.0 Total 3412.5
[0136] Portion 1 mixture was charged to the flask and the mixture
was heated to reflux temperature and refluxed for about 10 minutes.
Portion 2 and 3 were simultaneously added over 3 hours while the
reaction mixture was held at reflux temperature. The reaction
mixture was refluxed for 30 minutes. Portion 4 was added over 5
minutes, and the reaction mixture was refluxed for another 2 hours.
After cooling, the resulting ABA' triblock copolymer solution was
slightly hazy and had a solid content of about 47.1% and a
Gardner-Holtz viscosity of Y. The triblock copolymer had a
relatively narrow distribution of molecular weight with 28,679 Mw
and 12,546 Mn, and a very high Tg of 76.8 C measured by
Differential Scanning Calorimetry.
Paint Examples
Paint Examples BC2 to 5, BC7 to 0 and Comparative Examples BC1,
BC6
[0137] The following air-drying lacquer basecoats were prepared
from the following pre-blends and then tested.
[0138] The following pre-blends were made on an air mixer, adding
the cellulose acetate butyrate, if employed, slowly with vigorous
mixing:
[0139] Solvent Blend A TABLE-US-00007 Ingredient Wt (grams) n-butyl
acetate 10241.14 methyl n-amyl ketone 4389.06 Total 14630.20
[0140] CAB Solution B TABLE-US-00008 Ingredient Wt (grams) Solvent
Blend A 433.37 Eastman Chemical Company CAB 381-20 76.48 Total
509.85
[0141] The ingredients were blended together on an air mixer
(basecoats BC2 to BC5 use triblock acrylic copolymers of Example 3
to 6 as gram for gram solid replacements for the solid CAB in the
comparative Example BC1 while BC7 to BC10 replace both the CAB and
the conventional random acrylic resin in the comparative Example
BC1 with the triblock acrylic copolymers of Example 3 to 6 on a
solid gram for gram basis) to form the silver metallic basecoats
BC1 to BC10: TABLE-US-00009 Batch Batch Batch Batch Batch
Ingredient (g) BC1 (g) BC2 (g) BC3 (g) BC4 (g) BC5 DuPont .TM.
444.55 219.97 220.17 220.30 220.49 MasterTint 894J CAB Solution B
230.11 0.00 0.00 0.00 0.00 random acrylic 114.71 56.76 56.81 56.84
56.89 copolymer* triblock copolymer 0.00 34.02 0.00 0.00 0.00 of
Example 3 triblock copolymer 0.00 0.00 35.99 0.00 0.00 of Example 4
triblock copolymer 0.00 0.00 0.00 33.22 0.00 of Example 5 triblock
copolymer 0.00 0.00 0.00 0.00 36.35 of Example 6 wax dispersion **
384.42 190.21 190.39 190.50 190.66 Solvent Blend A 226.20 199.04
196.64 199.14 195.61 Total 1399.99 700.00 700.00 700.00 700.00
Batch Batch Batch Batch Batch Description (g) BC6 (g) BC7 (g) BC8
(g) BC9 (g) BC10 DuPont .TM. 441.28 218.64 219.24 219.61 220.17
MasterTint 894J CAB Solution B 0.00 0.00 0.00 0.00 0.00 random
acrylic 171.36 0.00 0.00 0.00 0.00 copolymer* triblock copolymer
0.00 100.79 0.00 0.00 0.00 of Example 3 triblock copolymer 0.00
0.00 106.82 0.00 0.00 of Example 4 triblock copolymer 0.00 0.00
0.00 98.69 0.00 of Example 5 triblock copolymer 0.00 0.00 0.00 0.00
108.19 of Example 6 wax dispersion ** 381.60 189.07 189.59 189.91
190.39 Solvent Blend A 405.76 191.49 184.35 191.79 181.24 Total
1400.00 699.99 700.00 700.00 699.99 Table Footnotes *A random
acrylic copolymer sty/mma/ibma/hema (15/20/45/20 by weight) at
59.6% wt solids in 85/15 by wt xylene/methyl ethyl ketone (85/15)
mixture was prepared with the standard free radical polymerization
procedure. ** Wax & Additives AC .RTM. 405-T is a ethylene
vinyl acetate copolymer dispersion at 5.986% by wt. in a
42.43/57.57 blend by weight of xylene/n-butyl acetate, manufactured
by Honeywell Specialty Chemicals.
[0142] The silver basecoats were sprayed per the application
instructions used for DuPont.TM. ChromaPremier.RTM. Basecoat
specified in the DuPont ChromaSystem Tech Manual. The basecoats
were sprayed to hiding over Ecoat panels (ACT cold rolled steel
04.times.12.times.032 panels coated with Powercron 590) which were
scuffed with a 3M.TM. Scotch-Brite.TM. 7777 Imperial.TM. Paint Prep
Scuff Pad then wiped with DuPont First Klean 3900S.TM. and next
coated with DuPont.TM. ChromaPremier.RTM. 42440.TM./42475.TM.S.TM.
2K Premier Sealer as per the instructions in the DuPont
ChromaSystem Tech Manual.
[0143] The basecoats were then clearcoated with DuPont.TM.
ChromaClear.RTM. V-7500S.TM. Multi-Use as per the instructions in
the DuPont ChromaSystem Tech Manual. Basecoat/clearcoat panels were
flashed and then baked in a 140.degree. F. oven for 30 minutes.
Topcoated panels were allowed to air dry for an additional 7 days
prior to testing.
[0144] Below are the color readings on basecoat alone panels
recorded by a DuPont ChromaVision Custom Color MA 100B meter
manufactured by X-Rite, Inc. of Grandville, Mich. (flop values via
calculation): TABLE-US-00010 Near Near Near Flat Flat Flat High
High High Basecoat Spec L Spec A Spec B L A B L A B Flop BC1 153.51
3.03 9.45 49.29 0.98 3.42 34.34 -0.7 -1.12 18.99 BC2 150.92 2.9
6.29 58.67 0.72 2.38 38.2 -0.65 -0.99 15.37 BC3 149.49 2.89 5.98
59.31 0.69 2.22 39.67 -0.68 -1 14.79 BC4 150.6 2.89 6.22 59.09 0.72
2.26 38.84 -0.68 -1.11 15.13 BC5 151.82 2.98 7.22 57.07 0.88 2.69
37.42 -0.65 -0.96 16.00 BC6 151.56 2.97 6.98 57.8 0.76 2.51 38.09
-0.66 -0.96 15.68 BC7 154.83 2.65 9.32 50.8 1.03 3.52 36.3 -0.66
-1.11 18.39 BC8 155.51 2.28 9.18 50.48 1.02 3.59 35.9 -0.69 -1.05
18.68 BC9 154.36 2.87 9.49 51.67 1 3.57 36.45 -0.67 -1.17 18.02
BC10 153.84 2.95 9.63 49.64 1.05 3.39 35.74 -0.66 -1.06 18.69
[0145] None of the triblock copolymers performed as well for color
using a gram for gram replacement for CAB. However, when the
triblock acrylic copolymers of this invention were used as the main
component of the binder in the absence of CAB (BC7 to 10), these
panels gave color very comparable to that of the Comparative
Example BC1 with CAB. It was also clear that the conventional
random acrylic resin as a main binder component in the Comparative
Example BC6 did not fair well for color (especially flop) vs. the
Comparative Example BC1 containing CAB.
[0146] Below are the color readings on basecoat/clearcoat panels
recorded by the same instrument: TABLE-US-00011 Near Near Near Flat
Flat Flat High High High Basecoat Spec L Spec A Spec B L A B L A B
Flop BC1 148.68 3.86 9.33 51.3 0.92 3.14 33.63 -0.66 -1.01 17.65
BC2 137.89 1.54 2.92 65.84 0.25 0.85 36.63 -0.76 -1.22 12.36 BC3
133.64 1.21 2.47 66.98 0.16 0.64 37.36 -0.8 -1.37 11.51 BC4 136.62
1.41 2.74 66.26 0.19 0.81 37.25 -0.82 -1.46 12.03 BC5 135.99 1.31
2.41 66.79 0.15 0.6 36.96 -0.79 -1.34 11.91 BC6 134.22 1.26 2.58
67.25 0.21 0.97 36.97 -0.79 -1.17 11.60 BC7 145.46 2.78 6.03 57.08
0.6 1.86 34.97 -0.72 -1.16 15.39 BC8 144.68 2.61 6.09 57.35 0.63
2.15 34.88 -0.7 -1.1 15.22 BC9 145.99 2.76 6.17 57.13 0.6 1.96
35.05 -0.71 -1.07 15.45 BC10 145.21 2.48 5.41 58.93 0.55 1.62 35.21
-0.72 -1.14 14.90
[0147] Below are the color readings comparing the color of the
basecoat alone panels vs. those of the basecoat/clearcoat (the
delta of basecoat alone readings minus the basecoat/clearcoat
readings indicates the approximate amount of strike-in caused by
clearcoating the panels): TABLE-US-00012 delta delta delta Near
Near Near delta delta delta delta delta delta Base- Spec Spec Spec
Flat Flat Flat High High High coat L A B L A B L A B BC1 4.83 -0.83
0.12 -2.01 0.06 0.28 0.71 -0.04 -0.11 BC2 13.03 1.36 3.37 -7.17
0.47 1.53 1.57 0.11 0.23 BC3 15.85 1.68 3.51 -7.67 0.53 1.58 2.31
0.12 0.37 BC4 13.98 1.48 3.48 -7.17 0.53 1.45 1.59 0.14 0.35 BC5
15.83 1.67 4.81 -9.72 0.73 2.09 0.46 0.14 0.38 BC6 17.34 1.71 4.4
-9.45 0.55 1.54 1.12 0.13 0.21 BC7 9.37 -0.13 3.29 -6.28 0.43 1.66
1.33 0.06 0.05 BC8 10.83 -0.33 3.09 -6.87 0.39 1.44 1.02 0.01 0.05
BC9 8.37 0.11 3.32 -5.46 0.4 1.61 1.4 0.04 -0.1 BC10 8.63 0.47 4.22
-9.29 0.5 1.77 0.53 0.06 0.08
[0148] In addition to the observations made on the basecoat alone
panels, the delta readings indicate that none of the triblock
copolymers as a gram for gram replacement for CAB provided the
strike-in resistance of CAB (BC1 with CAB vs. BC2 to BC5). However,
when the triblock copolymers of this invention were present as the
main binder component in the absence of CAB (BC7 to BC10), the
strike-in resistance was comparable to that of the basecoat
containing CAB (BC1). Again, when the conventional random acrylic
resin was the main binder component without CAB (BC6), the
strike-in resistance was very poor.
[0149] The tables below show the results of "Dry Chip" gravelometer
testing per ASTM-D-3170-87 using a 55 degree panel angle, with
panels and stones kept in the freezer for a minimum of two hours
prior to chipping. Each basecoat/clearcoat shows a rating and locus
of failure using 1 pint or 3 pints of stones. The results of "Wet
Chip" gravelometer testing per ASTM-D-3170-87 using a 55 degree
panel angle, with panels and stones kept in the freezer for a
minimum of two hours prior to chipping, are also included. For the
"wet chip" gravelometer testing the panels were exposed in a
humidity cabinet per ASTM-D-2247-92 at 100% relative humidity for
96 hours after they were air dried for 7 days after the 140.degree.
F..times.30 minute bake. TABLE-US-00013 BC1 BC2 BC3 BC4 BC5 Dry
Chip - After 1 week AD: Gravelometer 55 deg - frozen panels
Locus/Failure 1 pint stones 0 delam 6 BB 6 BB 5 BB 5 BB 3 pints
stones 0 delam 4 BB 2 BB 2 BB 1 BB Wet Chip - After 1 wk AD + 96
hours in Humidity Cabinet: Gravelometer 55 deg - frozen panels
Locus/Failure 1 pint stones 0 delam 5 BB 5 BB 5 BB 5 BB 3 pints
stones 0 delam 2 BB 2 BB 3 BB 1 BB Table Footnotes BB = failure
between layers of basecoat delam = clean clearcoat delamination
from the basecoat (no basecoat adheres to clearcoat)
[0150] The Comparative Example BC1 containing CAB showed severe
clearcoat delamination while none of the replacement resins of this
invention displayed this deficiency (BC2 to BC5). TABLE-US-00014
BC6 BC7 BC8 BC9 BC10 Dry Chip - After 1 week AD: Gravelometer 55
deg - frozen panels Locus/Failure 1 pint stones 5 BB 5 BB 5 BB 5 BB
5 BB 3 pints stones 0 delam 2 BB/SE 2 BB/SE 3 BB 3 BB/SE Wet chip -
After 1 wk AD + 96 hours in Humidity Cabinet: Gravelometer 55 deg -
frozen panels Locus/Failure 1 pint stones 5 BB 5 BB 5 BB 5 BB 5 BB
3 pints stones 0 delam 4 BB/SE 3 BB/SE 4 BB 2 BB Table Footnotes BB
= failure between layers of basecoat delam = clean clearcoat
delamination from the basecoat (no basecoat adheres to clearcoat)
SE = failure between sealer and Ecoat
[0151] Use of the triblock copolymers of Example 3 to 6 of this
invention in BC7 to BC10 eliminated the clearcoat delamination seen
when using the conventional random acrylic copolymer alone in the
Comparative Example BC6.
[0152] The table below shows the results of humidity cabinet
testing after 96 hours exposure (ASTM D2247-92 testing water
resistance of coatings in 100% relative humidity)--X-hatch
adhesion, grid hatch adhesion, and blistering per ASTM D3359-92A
(measuring adhesion by tape test) and ASTM D714-87 (blistering):
TABLE-US-00015 BC1 BC2 BC3 BC4 BC5 X hatch: Initial 0 delam 5 BB 6
BB 6 BB 8 BB Wet 0 delam 1 BB 1 BB 0 BB 0 BB 24 hrs. recovery 0
delam 1 BB 0 BB 0 BB 1 BB Grid: Initial 0 delam 0 BB 0 BB 0 BB 0 BB
Wet 0 delam 0 BB 0 BB 2 BB 1 BB 24 hrs. recovery 0 delam 0 BB 0 BB
0 BB 0 BB Blistering 10 10 10 10 10 Table Footnotes BB = failure
between layers of basecoat delam = clean clearcoat delamination
from the basecoat (no basecoat adheres to clearcoat)
[0153] TABLE-US-00016 BC6 BC7 BC8 BC9 BC10 X hatch: Initial 7 BB 8
BB 9 BB 6 BB 9 BB Wet 0 BB 0 BB 6 BB 4 BB 5 BB 24 hrs. recovery 2
BB 7 BB 7 BB 8 BB 5 BB Grid: Initial 0 BB 0 BB 0 BB 0 BB 0 BB Wet 1
BB 0 BB 0 BB 0 BB 1 BB 24 hrs. recovery 0 BB 0 BB 1 BB 0 BB 0 BB
Blistering 10 10 10 10 10 Table Footnotes BB = failure between
layers of basecoat
[0154] The Comparative Example BC1 containing CAB displayed severe
clearcoat delamination while none of the basecoats having the
replacement resins of this invention BC2 through BC5 and BC7
through BC10 on a gram for gram solid replacement basis for CAB or
a total replacement of CAB and the conventional random acrylic
resin did.
[0155] Various modifications, alterations, additions or
substitutions of the compositions and processes of this invention
will be apparent to those skilled in the art without departing from
the spirit and scope of this invention. This invention is not
limited by the illustrative embodiments set forth herein, but
rather is defined by the following claims.
* * * * *