U.S. patent application number 16/278770 was filed with the patent office on 2020-08-20 for adhesion promoting compositions and method of improving fuel resistance of a coated article.
This patent application is currently assigned to PPG INDUSTRIES OHIO, INC.. The applicant listed for this patent is PPG INDUSTRIES OHIO, INC.. Invention is credited to SHIRYN TYEBJEE, CHRISTOPHER A. VERARDI, HONGYING ZHOU.
Application Number | 20200263040 16/278770 |
Document ID | 20200263040 / US20200263040 |
Family ID | 1000003928029 |
Filed Date | 2020-08-20 |
Patent Application | download [pdf] |
![](/patent/app/20200263040/US20200263040A1-20200820-C00001.png)
United States Patent
Application |
20200263040 |
Kind Code |
A1 |
TYEBJEE; SHIRYN ; et
al. |
August 20, 2020 |
ADHESION PROMOTING COMPOSITIONS AND METHOD OF IMPROVING FUEL
RESISTANCE OF A COATED ARTICLE
Abstract
The present invention is directed to solventborne film-forming
compositions comprising: a) a non-chlorinated, linear polyolefin
polymer prepared from a reaction mixture comprising 0.5 to 5
percent by weight maleic anhydride based on the total weight of
monomers in the reaction mixture; b) an aminoplast: and c) a
polymer component comprising: i) an addition polymer prepared from
a reaction mixture comprising coumarone; and/or ii) an alkyd resin.
The present invention is also drawn to methods of improving fuel
resistance of a coated article, comprising: (1) applying the
solventborne film-forming composition above to a substrate to form
a coated substrate; (2) applying a curable film-forming composition
to at least a portion of the coated substrate formed in step (1) to
form a multi-layer coated substrate; and (3) heating the
multi-layer coated substrate formed in step (2) to a temperature
and for a time sufficient to cure the film-forming composition.
Inventors: |
TYEBJEE; SHIRYN; (TARENTUM,
PA) ; ZHOU; HONGYING; (ALLISON PARK, PA) ;
VERARDI; CHRISTOPHER A.; (PITTSBURGH, PA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
PPG INDUSTRIES OHIO, INC. |
CLEVELAND |
OH |
US |
|
|
Assignee: |
PPG INDUSTRIES OHIO, INC.
CLEVELAND
OH
|
Family ID: |
1000003928029 |
Appl. No.: |
16/278770 |
Filed: |
February 19, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09D 5/002 20130101;
C09D 123/30 20130101; C08J 7/042 20130101; C08J 2467/08 20130101;
C08J 2445/00 20130101; C08J 2423/30 20130101; C08J 2323/02
20130101 |
International
Class: |
C09D 5/00 20060101
C09D005/00; C09D 123/30 20060101 C09D123/30; C08J 7/04 20060101
C08J007/04 |
Claims
1. A solventborne film-forming composition comprising: a) a
non-chlorinated, linear polyolefin polymer prepared from a reaction
mixture comprising 0.5 to 5 percent by weight maleic anhydride
based on the total weight of monomers in the reaction mixture; b)
an aminoplast: and c) a polymer component comprising: i) an
addition polymer prepared from a reaction mixture comprising
coumarone; and/or ii) an alkyd resin.
2. The composition of claim 1 wherein the linear polyolefin polymer
a) is dispersed in an organic medium with a polyepoxide and a
monohydric alcohol.
3. The composition of claim 2 wherein the monohydric alcohol
comprises n-propanol, isopropanol, n-butanol, and/or
isobutanol.
4. The composition of claim 1 wherein the linear polyolefin polymer
a) is further reacted with a polyepoxide and a monohydric
alcohol.
5. The composition of claim 4 wherein the monohydric alcohol
comprises n-propanol, isopropanol, n-butanol, and/or
isobutanol.
6. The composition of claim 1 wherein the reaction mixture used to
prepare the linear polyolefin polymer a) further comprises an
ethylenically unsaturated monomer comprising at least one
(meth)acrylic monomer.
7. The composition of claim 1 wherein the aminoplast is at least
partially alkylated and wherein 10 to 35 percent of functional
groups on the aminoplast comprise imino groups.
8. The composition of claim 1 wherein the polymer component c)
comprises an addition polymer prepared from a reaction mixture
comprising coumarone, indene, and styrene.
9. The composition of claim 1 wherein the polymer component c)
comprises i) an addition polymer prepared from a reaction mixture
comprising coumarone, indene, and styrene; and ii) an alkyd
resin.
10. The composition of claim 1, further comprising a colorant.
11. The composition of claim 1, further comprising a hydroxyl
functional (meth)acrylic polymer and/or a hydroxyl functional
polyester polymer.
12. A method of improving fuel resistance of a coated article,
comprising: (1) applying a first film-forming composition to at
least a portion of a substrate to form a coated substrate, wherein
the first film-forming composition is solventborne and comprises:
a) a non-chlorinated, linear polyolefin polymer prepared from a
reaction mixture comprising 0.5 to 5 percent by weight maleic
anhydride based on the total weight of monomers in the reaction
mixture; b) an aminoplast: and c) a polymer component comprising:
i) an addition polymer prepared from a reaction mixture comprising
coumarone; and/or ii) an alkyd resin; (2) applying a second,
curable film-forming composition to at least a portion of the
coated substrate formed in step (1) to form a multi-layer coated
substrate; and (3) heating the multi-layer coated substrate formed
in step (2) to a temperature and for a time sufficient to cure the
second, curable film-forming composition; wherein the substrate
comprises an elastomeric, plastic, or composite material.
13. The method of claim 12 wherein the linear polyolefin polymer a)
is dispersed in an organic medium with a polyepoxide and a
monohydric alcohol.
14. The method of claim 13 wherein the monohydric alcohol comprises
n-propanol, isopropanol, n-butanol, and/or isobutanol.
15. The method of claim 12 wherein the linear polyolefin polymer a)
is further reacted with a polyepoxide and a monohydric alcohol.
16. The method of claim 15 wherein the monohydric alcohol comprises
n-propanol, isopropanol, n-butanol, and/or isobutanol.
17. The method of claim 12 wherein the reaction mixture used to
prepare the linear polyolefin polymer a) further comprises an
ethylenically unsaturated monomer comprising at least one
(meth)acrylic monomer.
18. The method of claim 12 wherein the aminoplast is at least
partially alkylated and wherein 10 to 35 percent of functional
groups on the aminoplast comprise imino groups.
19. The method of claim 12 wherein the polymer component c)
comprises an addition polymer prepared from a reaction mixture
comprising coumarone, indene, and styrene.
20. The method of claim 12 wherein the polymer component c)
comprises i) an addition polymer prepared from a reaction mixture
comprising coumarone, indene, and styrene; and ii) an alkyd
resin.
21. The method of claim 12, wherein the first film-forming
composition further comprises a colorant.
22. The method of claim 12, wherein the first film-forming
composition further comprises a hydroxyl functional (meth)acrylic
polymer and/or a hydroxyl functional polyester polymer.
23. The method of claim 12 wherein the multi-layer coated substrate
is heated to a temperature up to 135.degree. C. in step (3).
Description
FIELD OF THE INVENTION
[0001] The present invention relates to adhesion promoting
compositions and methods of improving fuel resistance of coated
articles.
BACKGROUND OF THE INVENTION
[0002] Polymeric materials, such as thermoplastic polyolefin (TPO)
and reaction injected molding urethane (RIM), are useful in many
applications, such as automobile parts and accessories, containers,
household appliances and other commercial items. Such polymeric
materials are often used as substrates with organic coating
compositions applied for aesthetic purposes or to protect them from
degradation when exposed to atmospheric weathering conditions such
as sunlight, moisture, heat and cold. To achieve longer lasting and
more durable parts, it is important for the coatings to be firmly
adhered to the surface of the article.
[0003] Polymeric substrates made from a variety of thermoplastic
and thermosetting materials have widely varying surface properties,
including surface tension, roughness and flexibility, which make
strong adhesion of organic coatings difficult, particularly after
aging or environmental exposure of the coated polymeric materials.
To facilitate adhesion of organic coatings to polymeric substrates,
the substrate can be pretreated using an adhesion promoter layer or
tie coat, e.g., a thin coating layer about 0.25 mils (6.35 microns)
thick, or by flame or corona pretreatment. For automotive
applications, it is important that the coating composition and/or
adhesion promoter layer is resistant to fuel damage, i.e. maintains
good adhesion of the coating to the substrate even if fuel is
accidentally spilled onto the coated substrate.
[0004] Typically, adhesion promoter layers used on TPO surfaces
contain chlorinated polyolefins. Liquid adhesion promoting coating
compositions containing polyolefin diols or a blend of a saturated
polyhydroxylated polydiene polymer and a chlorinated polyolefin
have also been developed. However, chlorinated polyolefins provide
some processing limitations. For example, conventional chlorinated
polyolefins typically have no curing or crosslinking sites and
therefore must be used at high molecular weights to have a positive
effect on coating strength.
[0005] Additionally, while these known adhesion promoting
compositions are generally acceptable for commercial applications,
they tend to either have good adhesion to polymeric substrates with
poor to moderate fuel resistance; or good adhesion and good fuel
resistance but only with a small variety of polymeric substrate
types or only at high levels of chlorinated polyolefin, resulting
in high VOC. It would be desirable to provide compositions useful
as adhesion promoters and service primers for automotive topcoats
on plastic substrates, further demonstrating improved fuel
resistance, in order to meet the new demands in automotive
manufacturing such as elimination of primers.
SUMMARY OF THE INVENTION
[0006] The present invention is directed to solventborne
film-forming compositions comprising: [0007] a) a non-chlorinated,
linear polyolefin polymer prepared from a reaction mixture
comprising 0.5 to 5 percent by weight maleic anhydride based on the
total weight of monomers in the reaction mixture; and [0008] b) an
aminoplast: and [0009] c) a polymer component comprising: [0010] i)
an addition polymer prepared from a reaction mixture comprising
coumarone; and/or [0011] ii) an alkyd resin. The compositions are
useful as adhesion promoters.
[0012] The present invention is also drawn to methods of improving
fuel resistance of a coated article, comprising: [0013] (1)
applying the solventborne film-forming composition described herein
to at least a portion of a substrate to form a coated substrate;
[0014] (2) applying a curable film-forming composition to at least
a portion of the coated substrate formed in step (1) to form a
multi-layer coated substrate; and [0015] (3) heating the
multi-layer coated substrate formed in step (2) to a temperature
and for a time sufficient to cure the film-forming composition.
DETAILED DESCRIPTION OF THE INVENTION
[0016] Other than in any operating examples, or where otherwise
indicated, all numbers expressing quantities of ingredients,
reaction conditions and so forth used in the specification and
claims are to be understood as being modified in all instances by
the term "about." Accordingly, unless indicated to the contrary,
the numerical parameters set forth in the following specification
and attached claims are approximations that may vary depending upon
the desired properties to be obtained by the present invention. At
the very least, and not as an attempt to limit the application of
the doctrine of equivalents to the scope of the claims, each
numerical parameter should at least be construed in light of the
number of reported significant digits and by applying ordinary
rounding techniques.
[0017] Notwithstanding that the numerical ranges and parameters
setting forth the broad scope of the invention are approximations,
the numerical values set forth in the specific examples are
reported as precisely as possible. Any numerical value, however,
inherently contain certain errors necessarily resulting from the
standard deviation found in their respective testing
measurements.
[0018] Also, it should be understood that any numerical range
recited herein is intended to include all sub-ranges subsumed
therein. For example, a range of "1 to 10" is intended to include
all sub-ranges between (and including) the recited minimum value of
1 and the recited maximum value of 10, that is, having a minimum
value equal to or greater than 1 and a maximum value of equal to or
less than 10.
[0019] As used in this specification and the appended claims, the
articles "a," "an," and "the" include plural referents unless
expressly and unequivocally limited to one referent.
[0020] The term "curable", as used for example in connection with a
curable composition, means that the indicated composition is
polymerizable or cross linkable through functional groups, e.g., by
means that include, but are not limited to, thermal (including
ambient cure) and/or catalytic exposure.
[0021] The term "cure", "cured" or similar terms, as used in
connection with a cured or curable composition, means that at least
a portion of the polymerizable and/or crosslinkable components that
form the curable composition is polymerized and/or crosslinked.
Additionally, curing of a polymerizable composition refers to
subjecting said composition to curing conditions such as but not
limited to thermal curing, leading to the reaction of the reactive
functional groups of the composition, and resulting in
polymerization and formation of a polymerizate. When a
polymerizable composition is subjected to curing conditions,
following polymerization and after reaction of most of the reactive
end groups occurs, the rate of reaction of the remaining unreacted
reactive end groups becomes progressively slower. The polymerizable
composition can be subjected to curing conditions until it is at
least partially cured. The term "at least partially cured" means
subjecting the polymerizable composition to curing conditions,
wherein reaction of at least a portion, such as at least 10
percent, or at least 20 percent, of the reactive groups of the
composition occurs, to form a polymerizate. The polymerizable
composition can also be subjected to curing conditions such that a
substantially complete cure is attained (such as at least 70
percent, or at least 80 percent, or at least 90 percent up to 100
percent, of the reactive groups react) and wherein further curing
results in no significant further improvement in polymer
properties, such as hardness.
[0022] The various embodiments and examples of the present
invention as presented herein are each understood to be
non-limiting with respect to the scope of the invention.
[0023] The solventborne film-forming composition of the present
invention comprises a) a non-chlorinated, linear polyolefin polymer
that may be prepared from a reaction mixture comprising 0.5 to 5
percent by weight maleic anhydride, based on the total weight of
monomers in the reaction mixture. The reaction mixture used to
prepare the linear polyolefin polymer a) may further comprise
ethylene and/or propylene. Note that the phrase "and/or" when used
in a list is meant to encompass alternative embodiments including
each individual component in the list as well as any combination of
components. For example, the list "A, B, and/or C" is meant to
encompass seven separate embodiments that include A, or B, or C, or
A+B, or A+C, or B+C, or A+B+C. The polyolefin polymers may comprise
polyethylene, polypropylene, polymethylpentene, polybutene-1,
polyisobutylene, and the like. The polyolefin may also be a
copolymer of different olefinic monomers with other optional
ethylenically unsaturated monomers. The linear polyolefin polymers
often comprise polyethylene, or more often polypropylene, prepared
from a reaction mixture comprising at least 0.5 percent by weight,
or at least 1 percent by weight, or at least 2 percent by weight,
and up to 5 percent by weight, such as up to 4 percent by weight,
or up to 3 percent by weight maleic anhydride, based on the total
weight of the linear polyolefin. Examples include the linear
polyolefins TOYO-TAC, available from TOYOBO CO., LTD.
[0024] The linear polyolefin polymers may be prepared so as to have
(i) functional groups comprising ester and/or urethane groups and
(ii) reactive groups comprising hydroxyl, epoxy, and/or siloxane
groups. The reactive groups on these polyolefins may then be
further reacted with a polyfunctional material, a lactone, or a
lactide to yield a non-chlorinated, reactive polyolefin having (i)
functional groups comprising ester and/or urethane groups and (ii)
reactive groups comprising hydroxyl, epoxy, and/or siloxane
groups.
[0025] Examples of polyfunctional materials include diepoxides or
higher polyepoxides. Use of a diepoxide as a difunctional material
allows for bridging between polyolefins that contain acid
functional groups. Other polyfunctional materials are epoxy
functional alkoxysilanes such as SILQUEST.RTM. A-187, commercially
available from Momentive Performance Materials; and isocyanate
functional alkoxysilanes, such as SILQUEST.RTM. A-link 35, an
isocyanatopropyl trimethoxy silane, and SILQUEST.RTM. A-link 25, an
isocyanatopropyl triethoxy silane, both commercially available from
Momentive Performance Materials.
[0026] In certain examples of the present invention, the linear
polyolefin polymer is further reacted with a polyepoxide and a
monohydric alcohol. Examples of suitable monohydric alcohols
include n-propanol, isopropanol, n-butanol, and/or isobutanol.
[0027] In other examples of the present invention, the reaction
mixture used to prepare the linear polyolefin polymer a) further
comprises an ethylenically unsaturated monomer comprising at least
one (meth)acrylic monomer, including any of those known in the art.
The term "(meth)acrylate" is meant to encompass acrylate and/or
methacrylate molecular structures where they exist. Examples of
suitable polyolefin polymers prepared in this manner are
commercially available as AUROREN, from Nippon Paper.
[0028] Each of the linear polyolefin polymers described above may
be used individually or in any combination with each other in the
solventborne film-forming composition.
[0029] The linear polyolefin polymer a) may be present in the
solventborne film-forming composition in an amount of at least 5
percent by weight, or at least 10 percent by weight, or at least 15
percent by weight, and up to 40 percent by weight, such as up to 30
percent by weight, or up to 20 percent by weight, based on the
total weight of resin solids in the film-forming composition.
[0030] In certain examples of the present invention, the linear
polyolefin polymer a) may be dispersed in an organic medium with a
polyepoxide and a monohydric alcohol. Suitable organic media
include xylene, AROMATIC 100 (CAS No. 64742-95-6, a blend of
C.sub.9-10 dialkyl- and trialkylbenzenes, available from
ExxonMobil), cyclohexane, and butyl acetate. The polyepoxide may be
a di- or higher polyepoxide; for example, a diepoxide, such as
EPONEX 1510, commercially available from Hexion, can be used.
Examples of suitable monohydric alcohols include any of those
disclosed above. In this example, the polyepoxide may be present in
the solventborne film-forming composition in an amount of at least
0.01 percent by weight, or at least 0.10 percent by weight, or at
least 0.50 percent by weight, and up to 10.00 percent by weight,
such as up to 5.00 percent by weight, or up to 1.00 percent by
weight, based on the total weight of resin solids in the
film-forming composition. The monohydric alcohol may be present in
the solventborne film-forming composition in an amount of at least
0.10 percent by weight, or at least 1.00 percent by weight, or at
least 5.00 percent by weight, and up to 20.00 percent by weight,
such as up to 16.00 percent by weight, or up to 8.00 percent by
weight, based on the total weight of resin solids in the
film-forming composition.
[0031] The solventborne film-forming composition of the present
invention further comprises b) an aminoplast. Useful aminoplast
resins are addition products of formaldehyde with an amino- or
amido-group carrying substance. Condensation products obtained from
the reaction of alcohols and formaldehyde with melamine, urea or
benzoguanamine are most common. While the aldehyde employed is most
often formaldehyde, other similar condensation products can be made
from other aldehydes, such as acetaldehyde, crotonaldehyde,
acrolein, benzaldehyde, furfural, glyoxal and the like.
[0032] The aminoplast resins often contain methylol or similar
alkylol groups, and in most instances at least a portion of these
alkylol groups are etherified by reaction with an alcohol. Any
monohydric alcohol can be employed for this purpose, including
methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol,
as well as benzyl alcohol and other aromatic alcohols, cyclic
alcohols such as cyclohexanol, monoethers of glycols, and
halogen-substituted or other substituted alcohols such as
3-chloropropanol and butoxyethanol. Many aminoplast resins are
partially alkylated with methanol or butanol. Carbamoyl triazines
of the formula C.sub.3N.sub.3(NHCOXR).sub.3 where X is nitrogen,
oxygen or carbon and R is a lower alkyl group having from one to
twelve carbon atoms or mixtures of lower alkyl groups, such as
methyl, ethyl, propyl, butyl, n-octyl, and 2-ethylhexyl, are also
suitable. Such compounds and their preparation are described in
detail in U.S. Pat. No. 5,084,541 (column 2, line 50 through column
7, line 63) incorporated by reference in pertinent part herein.
[0033] Imino groups and amino groups on an aminoplast resin arise
from the incomplete reaction of the aldehyde with the amine.
Aminoplast resins are characterized as low-imino if the imino
content is less than about 10%; that is, if less than about 10% of
the functional groups on the resin consist of imino or amino groups
as determined by NMR analysis. Commonly, low-imino aminoplast
resins contain less than 5% imino content. On the other hand, if
the imino content of an aminoplast resin is greater than about 10%,
it can be characterized as high-imino. More commonly, the imino
content of a high imino resin is 15% or higher. Commercial high
imino melamine resins, for example, are available with up to about
35% imino content. Typically the aminoplast is at least partially
alkylated and 10 to 35 percent, usually 15 to 35 percent, of
functional groups on the aminoplast comprise imino groups. A
particularly useful aminoplast is CYMEL 1158, available from
Allnex.
[0034] The aminoplast b) may be present in the solventborne
film-forming composition in an amount of at least 5 percent by
weight, or at least 7 percent by weight, or at least 10 percent by
weight, and up to 20 percent by weight, such as up to 17 percent by
weight, or up to 15 percent by weight, based on the total weight of
resin solids in the film-forming composition.
[0035] The solventborne film-forming composition of the present
invention further comprises c) a polymer component comprising i) an
addition polymer prepared from a reaction mixture comprising
coumarone; and/or ii) an alkyd resin. The addition polymer i) is
usually prepared from a reaction mixture comprising coumarone and
indene, and often additionally styrene. Such addition polymers are
commercially available from Nitto Chemical as Coumarone V-120S and
from Neville Chemical CO. as CUMAR 130. Suitable alkyd resins may
be prepared in a known manner by condensation of polyhydric
alcohols and polycarboxylic acids including fatty acids. Suitable
polyhydric alcohols include, but are not limited to, ethylene
glycol, propylene glycol, butylene glycol, 1,6-hexylene glycol,
neopentyl glycol, diethylene glycol, glycerol, trimethylol propane,
and pentaerythritol. Suitable polycarboxylic acids include, but are
not limited to, succinic acid, adipic acid, azelaic acid, sebacic
acid, maleic acid, fumaric acid, phthalic acid, tetrahydrophthalic
acid, hexahydrophthalic acid, and trimellitic acid, as well as
fatty acids, for example, those derived from linseed oil, soya bean
oil, tall oil, dehydrated castor oil, or tung oil. Besides the
polycarboxylic acids mentioned above, functional equivalents of the
acids such as anhydrides where they exist or lower alkyl esters of
the acids such as the methyl esters may be used. A particularly
suitable alkyd resin is illustrated in the Examples below. Often,
both i) and ii) are present in the polymer component c). The weight
ratio of the linear polyolefin polymer a) to the polymer component
c) in the curable film-forming composition may range from 5:95 to
40:60.
[0036] Often the solventborne film-forming composition of the
present invention further comprises a hydroxyl functional
(meth)acrylic polymer and/or a hydroxyl functional polyester
polymer. By "polymer" is meant a polymer including homopolymers and
copolymers, and oligomers. Useful hydroxyl functional ethylenically
unsaturated monomers used to prepare the (meth)acrylic polymer
include hydroxyalkyl (meth)acrylates, typically having 2 to 4
carbon atoms in the hydroxyalkyl group, such as hydroxyethyl
(meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl
(meth)acrylate, hydroxy functional adducts of caprolactone and
hydroxyalkyl (meth)acrylates, as well as the beta-hydroxy ester
functional monomers described below.
[0037] Beta-hydroxy ester functional monomers can be prepared from
ethylenically unsaturated, epoxy functional monomers and carboxylic
acids having from about 13 to about 20 carbon atoms, or from
ethylenically unsaturated acid functional monomers and epoxy
compounds containing at least 5 carbon atoms which are not
polymerizable with the ethylenically unsaturated acid functional
monomer.
[0038] Useful ethylenically unsaturated, epoxy functional monomers
used to prepare the beta-hydroxy ester functional monomers include,
but are not limited to, glycidyl (meth)acrylate, allyl glycidyl
ether, methallyl glycidyl ether, 1:1 (molar) adducts of
ethylenically unsaturated monoisocyanates with hydroxy functional
monoepoxides such as glycidol, and glycidyl esters of polymerizable
polycarboxylic acids such as maleic acid. Glycidyl (meth)acrylate
is preferred. Examples of carboxylic acids include, but are not
limited to, saturated monocarboxylic acids such as isostearic acid
and aromatic unsaturated carboxylic acids.
[0039] Useful ethylenically unsaturated acid functional monomers
used to prepare the beta-hydroxy ester functional monomers include
monocarboxylic acids such as acrylic acid, methacrylic acid,
crotonic acid; dicarboxylic acids such as itaconic acid, maleic
acid and fumaric acid; and monoesters of dicarboxylic acids such as
monobutyl maleate and monobutyl itaconate. These acid functional
monomers may also be used in the reaction mixture to prepare the
first film-forming polymer, providing acid functional reactive
groups thereto. The ethylenically unsaturated acid functional
monomer and epoxy compound are typically reacted in a 1:1
equivalent ratio. The epoxy compound does not contain ethylenic
unsaturation that would participate in free radical-initiated
polymerization with the unsaturated acid functional monomer. Useful
epoxy compounds include 1,2-pentene oxide, styrene oxide and
glycidyl esters or ethers, usually containing from 7 to 30 carbon
atoms, such as butyl glycidyl ether, octyl glycidyl ether, phenyl
glycidyl ether and para-(tertiary butyl) phenyl glycidyl ether.
Commonly used glycidyl esters include those of the structure:
##STR00001##
where R is a hydrocarbon radical containing from about 4 to about
26 carbon atoms. Usually, R is a branched hydrocarbon group having
from about 5 to about 10 carbon atoms, such as neopentyl,
neoheptanyl or neodecanyl. Suitable glycidyl esters of carboxylic
acids include CARDURA E and glycidyl esters of VERSATIC ACID 911
and, each of which is commercially available from Shell Chemical
Co.
[0040] One or more other polymerizable ethylenically unsaturated
monomers may be included in the reaction mixture that may be used
to prepare the hydroxyl functional (meth)acrylic polymer. Useful
alkyl esters of acrylic acid or methacrylic acid include aliphatic
alkyl esters containing from 1 to 30, and preferably 4 to 18 carbon
atoms in the alkyl group. Non-limiting examples include methyl
(meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate.
Suitable other copolymerizable ethylenically unsaturated monomers
include vinyl aromatic compounds such as styrene and vinyl toluene;
nitriles such as acrylonitrile and methacrylonitrile; vinyl and
vinylidene halides such as vinyl chloride and vinylidene fluoride
and vinyl esters such as vinyl acetate.
[0041] A particularly suitable hydroxyl functional (meth)acrylic
polymer may be prepared as demonstrated in the Examples below. The
hydroxyl functional (meth)acrylic polymer may be prepared using
known addition polymerization techniques, such as organic solution
polymerization techniques, in particular from the afore-mentioned
reaction mixtures.
[0042] Hydroxyl functional polyester polymers may also or
alternatively be used. Such polymers may be prepared in a known
manner by condensation of polyhydric alcohols and polycarboxylic
acids. Suitable polyhydric alcohols include, but are not limited
to, ethylene glycol, propylene glycol, butylene glycol,
1,6-hexylene glycol, neopentyl glycol, diethylene glycol, glycerol,
trimethylol propane, and pentaerythritol. Suitable polycarboxylic
acids include, but are not limited to, succinic acid, adipic acid,
azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic
acid, tetrahydrophthalic acid, hexahydrophthalic acid, and
trimellitic acid. Besides the polycarboxylic acids mentioned above,
functional equivalents of the acids such as anhydrides where they
exist or lower alkyl esters of the acids such as the methyl esters
may be used. The polyhydric alcohol is used in stoichiometric
excess relative to the polycarboxylic acid to ensure hydroxyl fucnt
groups on the resultant polyester polymer.
[0043] When used, the hydroxyl functional (meth)acrylic and/or
polyester polymer is present in the solventborne film-forming
composition in an amount of at least 5 percent by weight, or at
least 8 percent by weight, or at least 11 percent by weight, and up
to 16 percent by weight, such as up to 20 percent by weight, or up
to 23 percent by weight, based on the total weight of resin solids
in the film-forming composition.
[0044] The solventborne film-forming compositions of the present
invention may be curable when the hydroxyl functional (meth)acrylic
and/or polyester polymer is present and/or when the polyolefin
polymer a) contains reactive functional groups that may react with
the aminoplast. Curing may be desirable when the composition is
used as a service primer to prevent damage to the resulting coating
during subsequent shipping. However, it is not necessary to cure
the composition (i.e., subject it to its own cure regimen) when it
is used as a coating immediately prior to application of any
subsequent coating layers. Curing may occur when the subsequently
applied layers are subjected to curing conditions. The film-forming
compositions may further contain a catalyst to facilitate any
desired cure. Typical catalysts include phenyl acid phosphate and
sulfonic acid functional catalysts such as dodecylbenzene sulfonic
acid (DDBSA) and the like. Alternatively, the film-forming
compositions may be essentially free of a catalyst. As used
throughout this specification, including the claims, by
"essentially free" is meant that a compound is not intentionally
present in the composition; and if a compound is present in the
composition, it is present incidentally in an amount less than 0.1
percent by weight, usually less than trace amounts.
[0045] The solventborne film-forming compositions of the present
invention can also include a colorant. As used herein, the term
"colorant" means any substance that imparts color and/or other
opacity and/or other visual effect to the composition. The colorant
can be added to the coating in any suitable form, such as discrete
particles, dispersions, solutions and/or flakes. A single colorant
or a mixture of two or more colorants can be used in the coatings
of the present invention.
[0046] Example colorants include pigments, dyes and tints, such as
those used in the paint industry and/or listed in the Dry Color
Manufacturers Association (DCMA), as well as special effect
compositions. A colorant may include, for example, a finely divided
solid powder that is insoluble but wettable under the conditions of
use. A colorant can be organic or inorganic and can be agglomerated
or non-agglomerated. Colorants can be incorporated into the
coatings by grinding or simple mixing. Colorants can be
incorporated by grinding into the coating by use of a grind
vehicle, such as an acrylic grind vehicle, the use of which will be
familiar to one skilled in the art.
[0047] Example pigments and/or pigment compositions include, but
are not limited to, carbazole dioxazine crude pigment, azo,
monoazo, disazo, naphthol AS, salt type (lakes), benzimidazolone,
condensation, metal complex, isoindolinone, isoindoline and
polycyclic phthalocyanine, quinacridone, perylene, perinone,
diketopyrrolo pyrrole, thioindigo, anthraquinone, indanthrone,
anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone,
dioxazine, triarylcarbonium, quinophthalone pigments, diketo
pyrrolo pyrrole red ("DPPBO red"), titanium dioxide, carbon black
and mixtures thereof. The terms "pigment" and "colored filler" can
be used interchangeably.
[0048] Example dyes include, but are not limited to, those that are
solvent and/or aqueous based such as acid dyes, azoic dyes, basic
dyes, direct dyes, disperse dyes, reactive dyes, solvent dyes,
sulfur dyes, mordant dyes, for example, bismuth vanadate,
anthraquinone, perylene, aluminum, quinacridone, thiazole,
thiazine, azo, indigoid, nitro, nitroso, oxazine, phthalocyanine,
quinoline, stilbene, and triphenyl methane.
[0049] Example tints include, but are not limited to, pigments
dispersed in water-based or water miscible carriers such as
AQUA-CHEM 896 commercially available from Degussa, Inc., CHARISMA
COLORANTS and MAXITONER INDUSTRIAL COLORANTS commercially available
from Accurate Dispersions division of Eastman Chemical, Inc.
[0050] In particular examples of the present invention, the
solventborne film-forming composition further comprises a pigment
colorant such as carbon black and/or TiO.sub.2. In general, the
colorant can be present in the coating composition in any amount
sufficient to impart the desired property, visual and/or color
effect. The colorant may comprise from 1 to 90 weight percent of
the present compositions, such as from 3 to 40 weight percent or 5
to 35 weight percent, with weight percent based on the total weight
of the compositions.
[0051] The solventborne film-forming compositions of the present
invention are particularly useful as adhesion promoters for
subsequently applied coating compositions on industrial substrates.
In accordance with the present invention, the compositions of the
present invention may be used in a method of improving fuel
resistance of a coated article, such as a vehicular component. By
"improving fuel resistance" is meant fuel resistance of a coated
article increases when subjected to the fuel resistance test as
described in footnote 22 of Table 5 below. Coated articles
demonstrate improved fuel resistance when coated with the
compositions of the present invention using the method of the
present invention, compared to articles coated with similar
compositions that do not contain an aminoplast. The method
comprises: (1) applying a first film-forming composition to at
least a portion of a substrate to form a coated substrate, wherein
the first film-forming composition comprises any of the
solventborne film-forming compositions described above; (2)
applying a second, curable film-forming composition to at least a
portion of the coated substrate formed in step (1) to form a
multi-layer coated substrate; and (3) heating the multi-layer
coated substrate formed in step (2) to a temperature and for a time
sufficient to cure the second, curable film-forming
composition.
[0052] The method of the present invention is particularly useful
for elastomeric, plastic, or composite substrates such as those
that are found on motor vehicles and used as vehicle components
such as wheels, bumpers, fenders, hoods, doors, panels, etc. These
vehicle parts may be formed from any of the common thermoplastic or
thermosetting synthetic materials, including thermoplastic olefins
such as polyethylene and polypropylene, thermoplastic urethane,
polycarbonate, thermosetting sheet molding compound,
reaction-injection molding compound, acrylonitrile-based materials,
nylon, and the like. By "composite" is meant any substrate
comprising a resinous matrix such as one or more of polypropylene,
polybutylene terephthalate, polystyrene, polyaniline, polypyrrole,
polyepoxide, poly(methyl methacrylate), polyurethane, and
polycarbonate, reinforced with fibers typically oriented as
strands, multi-ply yarns, woven sheets, or braids, and comprising
at least one of stainless steel fibers, copper fibers, nickel
fibers, silver fibers, aluminum fibers, glass fibers, and carbon
fibers. The film-forming composition is applied to at least one
surface of the substrate. A substrate may have one continuous
surface, or two or more surfaces such as two opposing surfaces.
[0053] The compositions may be applied to the substrate by one or
more of a number of methods including spraying, dipping/immersion,
brushing, or flow coating, but they are most often applied by
spraying. The usual spray techniques and equipment for air spraying
and electrostatic spraying and either manual or automatic methods
can be used. The coating layer typically has a dry film thickness
of 0.1-1 mils (2.5-25.4 microns), often 0.2-0.4 mils (5-10
microns).
[0054] The film-forming compositions can be applied directly to the
surface of a substrate to form a coated substrate or onto or under
a primer coat or other coating as an adhesion promoter. They are
also useful as service primers; i.e., a primer applied to an
automotive body part that is sold to an automotive refinish/repair
shop for subsequent painting.
[0055] Multiple coating layers such as a colored base coat, a
monocoat that may or may not be colored, and/or a clear coat may be
applied to the coated substrate as a second, curable film-forming
composition after application of the solventborne film-forming
composition of the present invention. Thus these layers may
comprise multiple, different coatings serving different
purposes.
[0056] After applying the second, curable film-forming composition
on the coated substrate to form a multi-layer coated substrate, the
multi-layer coated substrate can be heated to a temperature and for
a time sufficient to cure at least the second film-forming
composition; for example, by allowing it to stand at ambient
temperature, or a combination of ambient temperature cure and
baking, or by baking alone. Ambient temperature usually ranges from
60 to 90.degree. F. (15.6 to 32.2.degree. C.), such as a typical
room temperature, 72.degree. F. (22.2.degree. C.). The composition
of the present invention may be cured at ambient temperature
typically in a period ranging from about 24 hours to about 36
hours. If ambient temperature and baking are utilized in
combination, the composition is often allowed to stand ("flash")
for a period of from about 2 minutes to about 120 minutes at a
temperature ranging from ambient to 175.degree. F. (79.4.degree.
C.), followed by baking at a temperature up to about 275.degree. F.
(135.degree. C.), usually 180.degree. F. (82.degree. C.) or
250.degree. F. (176.degree. C.) for a period of time ranging from
about 20 minutes to about 1.5 hour. A heated cure of the
film-forming composition of the present invention is particularly
useful when it is used as a service primer, although the
composition does not need to cure; an ambient flash is often
sufficient. For plastic substrates that are heat-sensitive and may
deform at high temperatures, the curable film-forming compositions
may be curable at temperatures from ambient to 90.degree. C., such
as from ambient to 80.degree. C.
[0057] After application of the second curable film-forming
composition to the coated substrate and upon curing, the coated
article demonstrates fuel resistance, measured as demonstrated in
the Examples below.
[0058] The methods of the present invention are particularly
suitable for the improving fuel resistance on a component of a
vehicle. Such vehicles may include landcraft such as cars, trucks,
sport utility vehicles, motorcycles; watercraft such as boats,
ships and submarines; aircraft such as airplanes and helicopters;
construction vehicles; and military vehicles, for example tanks and
Humvees.
[0059] The methods of the present invention are also suitable for
improving fuel resistance on a component of an autonomous vehicle.
Many vehicles in use today, including autonomous vehicles, utilize
transmitters and sensors to send and receive signals for various
purposes. It is vital for the continued accurate and safe operation
of such vehicles that these signals, which are typically
electromagnetic radiation in the form of radio waves, do not get
impeded in any way. Coated substrates covering the transmitters and
sensors must allow for transmission of the signals therethrough.
Improving fuel resistance by using the methods of the present
invention is particularly beneficial.
[0060] Each of the embodiments and characteristics described above,
and combinations thereof, may be said to be encompassed by the
present invention. For example, the present invention is thus drawn
to the following nonlimiting aspects:
1. A solventborne film-forming composition comprising: a) a
non-chlorinated, linear polyolefin polymer prepared from a reaction
mixture comprising 0.5 to 5 percent by weight maleic anhydride
based on the total weight of monomers in the reaction mixture; b)
an aminoplast: and c) a polymer component comprising: [0061] i) an
addition polymer prepared from a reaction mixture comprising
coumarone; and/or [0062] ii) an alkyd resin. 2. The composition
according to aspect 1 wherein the linear polyolefin polymer a) is
dispersed in an organic medium with a polyepoxide and a monohydric
alcohol. 3. The composition according to aspect 2 wherein the
monohydric alcohol comprises n-propanol, isopropanol, n-butanol,
and/or isobutanol. 4. The composition according to any of aspects 1
to 3 wherein the linear polyolefin polymer a) is further reacted
with a polyepoxide and a monohydric alcohol. 5. The composition
according to aspect 4 wherein the monohydric alcohol comprises
n-propanol, isopropanol, n-butanol, and/or isobutanol. 6. The
composition according to any of aspects 1 to 5 wherein the reaction
mixture used to prepare the linear polyolefin polymer a) further
comprises an ethylenically unsaturated monomer comprising at least
one (meth)acrylic monomer. 7. The composition according to any of
aspects 1 to 6 wherein the aminoplast is at least partially
alkylated and wherein 10 to 35 percent of functional groups on the
aminoplast comprise imino groups. 8. The composition according to
any of aspects 1 to 7 wherein the polymer component c) comprises an
addition polymer prepared from a reaction mixture comprising
coumarone, indene, and styrene. 9. The composition according to any
of aspects 1 to 8 wherein the polymer component c) comprises i) an
addition polymer prepared from a reaction mixture comprising
coumarone, indene, and styrene; and ii) an alkyd resin. 10. The
composition according to any of aspects 1 to 9, further comprising
a colorant such as carbon black and/or TiO.sub.2. 11. The
composition according to any of aspects 1 to 10, further comprising
a hydroxyl functional (meth)acrylic polymer and/or a hydroxyl
functional polyester polymer. 12. A method of improving fuel
resistance of a coated article, comprising: (1) applying a first
film-forming composition to at least a portion of a substrate to
form a coated substrate, wherein the first film-forming composition
comprises the composition according to any of aspects 1 to 11; (2)
applying a second, curable film-forming composition to at least a
portion of the coated substrate formed in step (1) to form a
multi-layer coated substrate; and (3) heating the multi-layer
coated substrate formed in step (2) to a temperature and for a time
sufficient to cure the second, curable film-forming composition;
wherein the substrate comprises an elastomeric, plastic, or
composite material. 13. The method according to aspect 12 wherein
the multi-layer coated substrate is heated to a temperature up to
135.degree. C. in step (3).
[0063] The following examples are intended to illustrate various
embodiments of the invention, and should not be construed as
limiting the invention in any way.
EXAMPLES
[0064] The following working examples are intended to further
describe the invention. It is understood that the invention
described in this specification is not necessarily limited to the
examples described in this section. Note that for all measurements,
the IR spectrometer used was a ThermoScientific Nicolet iS5 FT-IR.
Acid number was determined via titration using a Metrohm 888
Titrando and a homogeneous sample solution of tetrahydrofuran (THF)
with methanolic potassium hydroxide solution (0.1 N).
Example A: Preparation of Alkyd Resin Solution
[0065] An Alkyd resin solution was prepared from the following
charges:
TABLE-US-00001 Ingredients Parts by weight (g) Charge #1 NOURACID
.RTM. SE45 .sup.1 1126.2 Crotonic acid .sup.2 299.2 Pentaerythritol
.sup.3 502.8 Phthalic anhydride .sup.4 422.4 DBTO .sup.5 4.18
Charge #2 Xylene 46.2 Charge #3 Xylene 968.9 .sup.1 NOURACID SE 45
is soybean oil fatty acid and commercially available from Oleon.
.sup.2 Crotonic acid is commercially available from Clariant
Corporation. .sup.3 Pentaerythritol is commercially available from
Clariant Corporation. .sup.4 Phthalic anhydride is commercially
available from BASF. .sup.5 DBTO is dibutyl tin oxide and
commercially available from Arkema Inc.
[0066] Charge 1 was added to a 5 L 4-necked flask equipped with a
motor driven stainless steel stir blade, glycol recovery column, a
water-cooled condenser, and a heating mantle with a thermometer
connected through a temperature feedback control. The reactor
contents were heated to 215.degree. C. and water removed until the
acid value was 28.about.30 mg KOH/g. Then, the glycol recovery
column was replaced with a Dean-Stark trap filled with xylene and
charge 2 was added into reaction vessel. Water was azeotropically
removed until the acid value was less than 10.0 mg KOH/g. The
resulting alkyd resin was diluted with charge 3 to afford a
solution with solid weight percent of 70% measured for one hour at
110.degree. C., an acid value of 4 to 9 mg KOH/g, and a Gardner
viscosity of E to G.
Example B: Preparation of Alkyd Acrylic Resin in Xylene
Solution
[0067] An Alkyd acrylic resin in xylene solution was prepared from
the following charges:
TABLE-US-00002 Ingredients Parts by weight Charge #1 Xylene 50.82
T-Butyl perbenzoate .sup.1 17.64 Charge #2 Example A (Alkyd resin
solution) 2736.09 Styrene 845.67 Methyl methacrylate 423.99
2-Ethylhexyl acrylate 139.23 Acrylonitrile 157.29 Charge #3 Xylene
1170.12 Charge #4 Xylene 273.21 T-Butyl perbenzoate 9.03 Charge #5
Xylene 1095.0 Charge #6 Xylene 295.0 .sup.1 T-Butyl perbenzoate is
commercially available from Akzo Nobel Chemicals.
[0068] A 12 liter, 4-necked flask equipped with a motor driven
stainless steel stir blade, additional funnel, thermocouple,
condenser, and a nitrogen blanket was charged with charge 1, 2, and
3. The reactor contents were heated to 125.degree. C. slowly.
External reactor cooling was applied when the reactor contents
temperature reached 110.degree. C. to control the resulting
exotherm to less than 130.degree. C. The reactor contents were
stirred for one hours at 124.about.127.degree. C. Then charge 4 was
added over 180 minutes, the additional funnel rinsed with charge 5
and the reactor contents stirred for another 90 minutes. Then the
reactor contents were cooled to 115.degree. C. and 14 inches of
vacuum was applied to distill 1482 g solvent. Charge 5 and 6 were
added to the reactor to afford a product with 55.8 weight percent
solid content (measured for one hour at 110.degree. C.), an acid
value of 2 to 5 KOH/g, a Gardner viscosity of U to W, and free
acrylonitrile content of less than 50 ppm.
Example C: Preparation of Alkyd Acrylic Resin in Aromatic 100
Solution
[0069] An Alkyd acrylic resin in Aromatic 100 solution was prepared
from the following charges:
TABLE-US-00003 Ingredients Parts by weight Charge #1 Example B
(Alkyd Acrylic 2940.0 resin in xylene solution) Charge #2 Aromatic
100 1309.9
[0070] Charge 1 was added to a 5 L 4-necked flask equipped with a
motor driven stainless steel stir blade, a condenser with
distillation adaptors, a nitrogen blanket, and a heating mantle
with a thermometer connected through a temperature feedback control
device. The reaction mixture was heated to 145.degree. C. and
vacuum was applied to distill 1286 g solvent. When distillation was
completed, the vacuum and heat were off. Charge 2 was added through
additional funnel over 20 minutes to afford a product with 56.11
weight percent solid content (measured for one hour at 110.degree.
C.), and a Gardner viscosity of Z.
Example D: Preparation of Polyolefin Solution
[0071] A polyolefin solution was prepared from the following
charges:
TABLE-US-00004 Ingredients Parts by weight (g) Charge #1 AROMATIC
100 2313.70 Charge #2 EPONEX 1510.sup.1 3.08 AROMATIC 100 24.95
Charge #3 TOYOBO PMA-KE.sup.2 496.92 Charge #4 Cyclohexane 696.82
Charge #5 Cyclohexane 226.30 Isopropanol 84.61 .sup.1EPONEX 1510 is
a diepoxide and commercially available from Hexion Specialty
Chemicals. .sup.2TOYOBO PMA-KE is an anhydride functional
polyolefin and commercially available from Toyobo.
[0072] Charge 1 was added to a 5 L 4-necked flask equipped with a
motor driven stainless steel stir blade, a water-cooled condenser,
a nitrogen blanket, and a heating mantle with a thermometer
connected through a temperature feedback control device. The
reaction mixture was heated to 40.degree. C. At 40.degree. C.,
charge 2 was added and held for 15 minutes followed by addition of
Charge 3. The reaction mixture was heated to 80.degree. C. and held
at 80.degree. C. until beads were dissolved. The reaction mixture
was cooled to 60.degree. C. At 60.degree. C., charge 4 was added
into reaction mixture and held until it incorporated. Charge 5 was
premixed and added into reaction mixture and held until it
incorporated. The reaction product was poured out through 5-micron
nylon mesh filter bag. The solids content of polyolefin dispersion
was 13.5%.
Example E: Preparation of Coumarone Solution
[0073] A Coumarone resin solution was prepared from the following
charges:
TABLE-US-00005 Ingredients Parts by weight Charge #1 Coumarone
V-120S.sup.1 2018.00 AROMATIC 100 1009.00 Cyclohexane 1009.00
.sup.1Coumarone V-120S is commercially available from Nitto
Chemical.
[0074] Charge 1 was added to a 12 L 4-necked flask equipped with a
motor driven stainless steel stir blade, a water-cooled condenser,
a nitrogen blanket, and a heating mantle with a thermometer
connected through a temperature feedback control device. The
reaction mixture was heated to 40.degree. C. and held at 40.degree.
C. for 1 hour. Then reaction mixture was heat to 60.degree. C. and
held until it incorporated. The reaction product was cooled to
40.degree. C. poured out through 5-micron nylon mesh filter bag.
The solids content of polyolefin dispersion was 53.9%.
Example F: Preparation of Polyolefin Solution
[0075] A polyolefin solution was prepared from the following
charges:
TABLE-US-00006 Ingredients Parts by weight (g) Charge #1 AROMATIC
100 2313.70 Charge #2 EPONEX 1510.sup.1 3.08 AROMATIC 100 24.95
Charge #3 TOYOBO PMA-LE.sup.2 496.92 Charge #4 Cyclohexane 696.82
Charge #5 Cyclohexane 226.30 Isopropanol 84.61 .sup.1Eponex 1510 is
commercially available from Hexion Specialty Chemicals.
.sup.2Toyobo PMA-LE is an anhydride functional polyolefin and
commercially available from Toyobo.
[0076] Charge 1 was added to a 5 L 4-necked flask equipped with a
motor driven stainless steel stir blade, a water-cooled condenser,
a nitrogen blanket, and a heating mantle with a thermometer
connected through a temperature feedback control device. The
reaction mixture was heated to 40.degree. C. At 40.degree. C.,
charge 2 was added and held for 15 minutes followed by addition of
Charge 3. The reaction mixture was heated to 80.degree. C. and held
at 80.degree. C. until beads were dissolved. The reaction mixture
was cooled to 60.degree. C. At 60.degree. C., charge 4 was added
into reaction mixture and held until it incorporated. Charge 5 was
premixed and added into reaction mixture and held until it
incorporated. The reaction product was poured out through 5-micron
nylon mesh filter bag. The solids content of polyolefin dispersion
was 13.2%.
Example G: Preparation of Polyester Modified Polyolefin
[0077] A polyester modified polyolefin solution was prepared from
the following charges:
TABLE-US-00007 Ingredients Parts by weight Charge #1 TOYOBO
PMA-LE.sup.1 200.00 AROMATIC 150 600.00 Butyl Acetate 150.00 Charge
#2 EPONEX 1510.sup.2 75.40 AROMATIC 150 20.00 Charge #3 Butanol
71.23 Charge #4 ARMEEN DMCD .sup.3 1.83 AROMATIC 150 1.49 Charge #5
Cyclohexane 248.60 .sup.1TOYOBO PMA-LE is an anhydride functional
polyolefin and commercially available from Toyobo. .sup.2EPONEX
1510 is commercially available from Hexion Specialty Chemicals.
.sup.3 ARMEEN DMCD (0.5%) is dimethyl cocoamine and commercially
available from Akzo Nobel Chemicals.
[0078] Charge 1 was added to a 2 L 4-necked flask equipped with a
motor driven stainless steel stir blade, a water-cooled condenser,
a nitrogen blanket, and a heating mantle with a thermometer
connected through a temperature feedback control device. The
reaction mixture was heated to 100.degree. C. At 100.degree. C.,
charge 2 was added and held for 15 minutes. After holding, charge 3
was added and held for 15 minutes. The reaction mixture was stirred
at 100.degree. C. until anhydride peaks were gone as measured by
IR. Charge 4 was added into reaction mixture and held at
100.degree. C. until acid value is less than 4. The reaction
product was cooled to 60.degree. C. by adding charge #5 and poured
out through 5-micron nylon mesh filter bag. The solids content of
polyolefin resin was 21.18%.
Example H: Preparation of Higher Solid Polyolefin Solution
[0079] A higher solid polyolefin solution was prepared from the
following charges:
TABLE-US-00008 Ingredients Parts by weight (g) Charge #1 Butyl
acetate 293.20 Charge #2 EPONEX 1510.sup.1 1.54 Butyl acetate 4.97
Charge #3 TOYOBO PMA-LE.sup.2 248.46 Charge #4 Cyclohexane 496.92
Charge #5 Cyclohexane 198.80 Isopropanol 42.31 .sup.1EPONEX 1510 is
commercially available from Hexion Specialty Chemicals.
.sup.2TOYOBO PMA-LE is an anhydride functional polyolefin and
commercially available from Toyobo.
[0080] Charge 1 was added to a 2 L 4-necked flask equipped with a
motor driven stainless steel stir blade, a water-cooled condenser,
a nitrogen blanket, and a heating mantle with a thermometer
connected through a temperature feedback control device. The
reaction mixture was heated to 40.degree. C. At 40.degree. C.,
charge 2 was added and held for 15 minutes followed by addition of
Charge 3. The reaction mixture was heated to 80.degree. C. and held
at 80.degree. C. until beads were dissolved. The reaction mixture
was cooled to 60.degree. C. At 60.degree. C., charge 4 was added
into reaction mixture and held until it incorporated. Charge 5 was
premixed and added into reaction mixture and held until it
incorporated. The reaction product was poured out through 5-micron
nylon mesh filter bag. The solids content of polyolefin dispersion
was 19.3%.
Example I: Preparation of an Anhydride and Acrylic Modified
Polyolefin Solution
[0081] An anhydride and acrylic modified polyolefin solution was
prepared from the following charges:
TABLE-US-00009 Ingredients Parts by weight (g) Charge #1 AROMATIC
100 462.70 Charge #2 EPONEX 1510.sup.1 0.62 AROMATIC 100 4.99
Charge #3 AUROREN S-5297S.sup.2 99.38 Charge #4 Cyclohexane 139.36
Charge #5 Cyclohexane 45.30 Isopropanol 16.92 .sup.1EPONEX 1510 is
commercially available from Hexion Specialty Chemicals.
.sup.2AUROREN S-5297S is an anhydride and acrylic modified
polyolefin and commercially available from Nippon Paper Group.
[0082] Charge 1 was added to a 1 L 4-necked flask equipped with a
motor driven stainless steel stir blade, a water-cooled condenser,
a nitrogen blanket, and a heating mantle with a thermometer
connected through a temperature feedback control device. The
reaction mixture was heated to 40.degree. C. At 40.degree. C.,
charge 2 was added and held for 15 minutes followed by addition of
Charge 3. The reaction mixture was heated to 80.degree. C. and held
at 80.degree. C. until beads were dissolved. The reaction mixture
was cooled to 60.degree. C. At 60.degree. C., charge 4 was added
into reaction mixture and held until it incorporated. Charge 5 was
premixed and added into reaction mixture and held until it
incorporated. The reaction product was poured out through 5-micron
nylon mesh filter bag. The solids content of polyolefin dispersion
was 13.7%.
Example J: Preparation of Acrylic Resin
[0083] An acrylic resin was prepared in a 300 mL continuous stir
tank reactor (CSTR) system from the components listed in the table
below.
TABLE-US-00010 Ingredients Parts by weight (g) Charge #1
Hydroxypropyl acrylate.sup.1 2320.0 Styrene 1160.0 Butyl acrylate
1102.0 Butyl methacrylate 1073.0 Acrylic acid 116.0 Methyl
methacrylate 29.0 Di-t-amyl peroxide.sup.1 58.0 Charge #2 Di-t-amyl
peroxide 58.0 .sup.1Hydroxypropyl acrylate is commercially
available from BASF. .sup.2 Di-t-amyl peroxide is commercially
available from Arkema INC.
[0084] The CSTR was charged with 300 mL of Dowanol PM. The charge 1
were weighed and stirred for 15 minutes at an agitation rate
sufficient to provide good mixing, then charged to a feed tank
while the reactor system was heating up to the reaction temperature
(226.degree. C.). Collection of the resulting acrylic resin was
begun 15 minutes after the feed was started and continued for 25
minutes. The neat resin was continuously transferred to flash tank
where charge 2 was added as a chaser initiator. The flash tank was
maintained under pressure at the temperature around 195.degree. C.
(not exceed to 200.degree. C.). The resulting material was thinned
with a solvent mixture of aromatic 100 and Dowanol PM acetate
(weight ratio is 40:60) to a weight percent solid content of 67%
(measured for one hour at 110.degree. C.). The final resin was a
viscous liquid with a Mw of 8557, a Mn of 2079, and PDI of 4.1.
[0085] The weight average molecular weight was determined by Gel
Permeation Chromatography using a Waters 2695 separation module
with a Waters 410 differential refractometer (RI detector) and
polystyrene standards. Tetrahydrofuran (THF) was used as the eluent
at a flow rate of 1 ml min.sup.-1, and two PL Gel Mixed C columns
were used for separation
Film Forming Compositions:
Unpigmented Adhesion Promoters:
[0086] Compositions for Examples 1 and 2 according to the present
invention are listed below in Table 1. The amounts listed are the
total parts by weight in grams. Each component was mixed
sequentially with agitation.
TABLE-US-00011 TABLE 1 Parts by weight of Component Ingredient
Example 1 Example 2 SOLVESSO 100 .sup.1 160.39 160.39 HARDLEN
PMA-KE PO.sup.2 238.10 238.10 Alkyd acrylic resin.sup.3 107.46 --
Coumarone V120S.sup.4 -- 117.24 KRATON G1726X Thermoplastic
rubber.sup.5 22.44 22.44 Cyclohexane.sup.6 160.39 160.39 CYMEL
1158.sup.7 14.59 14.59 Isopropyl alcohol.sup.8 20.69 20.69 DC200
Silicone Solution.sup.9 0.04 0.04 CYCAT 600.sup.10 2.06 2.06 Phenyl
acid phosphate.sup.11 0.11 0.11 EFKA PL 5651 NF.sup.12 1.08 1.08
Total 727.34 737.13 .sup.1 Solvent commercially from Exxon Mobil
Corporation. .sup.2Synthesis example D .sup.3Alkvd acrylic resin:
Synthesis example C .sup.4Synthesis example E .sup.5Resin solution
containing 25% KRATON G1726X, commercially available from Kraton
Polymers, AND 75% SOLVESSO 100, available from Exxon Mobil
Corporation. .sup.6Solvent commercially available from Brenntag.
.sup.7High-imino melamine commercially available from Allnex.
.sup.8Solvent commercially available from Dow Chemical.
.sup.9Additive solution containing ANDISIL SF100 commercially
available from AB Specialty Silicones LLC. .sup.10Catalyst
commercially available from Allnex. .sup.11Catalyst commercially
available from Islechem LLC. .sup.12Additive commercially available
from BASF.
Pigmented Adhesion Promoters:
[0087] Compositions for Pigment Pastes 1-4 are listed below in
Table 2. The amounts listed are the total parts by weight in grams.
Ingredients of the grind except the methyl n-amyl ketone are added
sequentially together and mixed with a Cowles blade before entering
the mill. A mill is used to grind the mixture to a Hegman of 7.25.
The methyl n-amyl ketone is added at the end as a mill wash.
TABLE-US-00012 TABLE 2 Parts by weight of Component Pigment Pigment
Pigment Pigment Ingredient Paste 1 Paste 2 Paste 3 Paste 4 SOLVESSO
100 .sup.1 46.42 46.42 27.66 26.48 SOLVESSO 150 .sup.1 8.77 8.77
5.23 8.77 Alkyd acrylic resin .sup.3 58.17 58.17 -- 58.17 Coumarone
V120S.sup.4 -- -- 60.55 -- KRATON G1726X Thermoplastic 22.44 22.44
22.44 22.44 rubber.sup.5 PRINTEX XE 2-B.sup.13 7.67 7.67 7.67 7.67
VM&P Naptha.sup.14 34.98 34.98 20.85 34.98 White tint.sup.15
126.78 25.78 25.78 126.78 Methyl N-amyl ketone.sup.16 36.04 36.04
-- 36.04 Total 341.27 240.25 170.17 321.34 .sup.1 Solvent
commercially from Exxon Mobil Corporation. .sup.3 Alkyd acrylic
resin: Synthesis example C .sup.4Synthesis example E .sup.5Resin
solution containing 25% KRATON G1726X, commercially available from
Kraton Polymers, AND 75% SOLVESSO 100, available from Exxon Mobil
Corporation. .sup.13Carbon black available from Orion Engineered
Carbons. .sup.14Solvent available from Ashland Inc. .sup.15Titanium
dioxide pigment paste dispersion of 64.25% titanium dioxide pigment
available from The Chemours Company LLC, 11.24% alkyd (Synthesis
example B), 23.53% SOLVESSO 100 (available from Exxon Mobil
Corporation) and 0.98% xylene. .sup.16Solvent available from Dow
Chemical Co.
[0088] The Pigment Pastes 1-4 were used in Examples 3-11.
Compositions for Examples 3-11 are listed below in Tables 3-4.
(Note that Example 8 is comparative; the composition does not
contain an aminoplast.) The amounts listed are the total parts by
weight in grams. Each component was mixed sequentially with
agitation.
TABLE-US-00013 TABLE 3 Parts by weight of Component Ingredient
Example 3 Example 4 Example 5 Example 6 Pigment Paste 1 341.27 --
-- -- Pigment Paste 2 -- 240.25 -- -- Pigment Paste 3 -- -- 170.17
-- Pigment Paste 4 -- -- -- 321.34 TOYO-TAC PMA-KE 238.10 -- -- --
PO.sup.2 TOYO-TAC PMA-LE -- 151.17 151.17 -- PO.sup.17 Modified
PMA-LE PO.sup.18 -- -- -- 97.23 White tint.sup.15 -- 101.01 101.01
-- SOLVESSO 100 .sup.1 87.68 87.68 87.68 107.62 Cyclohexane.sup.6
87.68 87.68 87.68 87.68 Coumarone V120S.sup.4 25.28 45.28 45.28 42
CYMEL 1158.sup.7 14.59 14.59 14.59 14.59 Isopropyl alcohol.sup.8
20.69 20.69 20.69 20.69 DC200 Silicone 0.04 0.04 0.04 0.04
Solution.sup.9 CYCAT 600.sup.10 2.06 2.06 2.06 2.06 Phenyl acid
0.11 0.11 0.11 0.11 phosphate.sup.11 EFKA PL 5651 NF.sup.12 1.08
1.08 1.08 1.08 Total 700.72 751.64 681.56 694.43
TABLE-US-00014 TABLE 4 Parts by weight of Component Example 8
Ingredient Example 7 (Comparative) Example 9 Example 10 Example 11
Pigment Paste 4 321.34 321.34 321.34 321.34 321.34 TOYO-TAC PMA-LE
103.52 103.52 103.52 -- -- PO.sup.19 AUROREN S-5297S.sup.20 -- --
-- 145.56 145.56 SOLVESSO 100 .sup.1 107.62 107.62 107.62 107.62
107.62 Cyclohexane.sup.6 87.68 87.68 87.68 87.68 87.68 Coumarone
V120S.sup.4 42 63.12 38.29 42 -- Acrylic resin.sup.21 -- -- 12.45
-- -- Alkyd acrylic .sup.3 -- -- -- -- 41.5 CYMEL 1158.sup.7 14.59
-- 6.41 14.59 14.59 Isopropyl alcohol.sup.8 20.69 20.69 20.69 20.69
20.69 DC200 Silicone 0.04 0.04 0.04 0.04 0.04 Solution.sup.9 CYCAT
600.sup.10 2.06 2.06 2.06 2.06 2.06 Phenyl acid 0.11 0.11 0.11 0.11
0.11 phosphate.sup.11 EFKA PL 5651 NF.sup.12 1.08 1.08 1.08 1.08
1.08 Total 700.72 707.25 701.29 742.76 742.26 .sup.1 Solvent
commercially from Exxon Mobil Corporation. .sup.2 Synthesis example
D .sup.3 Synthesis example C .sup.4Synthesis example E
.sup.6Solvent commercially available from Brenntag. .sup.7Melamine
commercially available from Allnex. .sup.8Solvent commercially
available from Dow Chemical. .sup.9Additive solution containing
ANDISIL SF100 commercially available from AB Specialty Silicones
LLC. .sup.10Catalyst commercially available from Allnex.
.sup.11Catalyst commercially available from Islechem LLC.
.sup.12Additive commercially available from BASF. .sup.15 Titanium
dioxide pigment paste dispersion of 64.25% titanium dioxide pigment
available from The Chemours Company LLC, 11.24% alkyd (Synthesis
example B), 23.53% SOLVESSO 100 (available from Exxon Mobil
Corporation) and 0.98% xylene. .sup.17 Synthesis example F .sup.18
Synthesis example G .sup.19Synthesis example H .sup.20Synthesis
example I .sup.21Synthesis example J
[0089] Coatings were applied to Lyondell Basell Hifax TRC779X
(4''.times.12''.times.0.118'') thermoplastic olefin (TPO) panels,
available from Standard Plaque Inc.
[0090] For Examples 1-5, LBC408YB, an orange metallic solventborne
basecoat and TKU2000CS 2K isocyanate clearcoat, both available from
PPG, were applied over the adhesion promoters. Adhesion promoter,
basecoat and clearcoat were applied wet-on-wet-on-wet via hand
spray application targeting dry film thicknesses of 5-10, 16-20 and
38-46 microns respectively. All flashes between coating layers and
before the cure oven were untimed at ambient conditions. The system
was baked for 35 minutes at 180.degree. F. (82.degree. C.) in a
horizontal position.
[0091] For Examples 6-11, LBC8555B, a black pigmented solventborne
basecoat and TKU2000CS 2K isocyanate clearcoat, both available from
PPG, were applied over the adhesion promoters. Adhesion promoter,
basecoat and clearcoat were applied wet-on-wet-on-wet via automated
spray applied targeting dry film thicknesses of 5-10, 16-20 and
38-46 microns respectively. Adhesion promoter was applied in one
coat with a 4-minute ambient flash before basecoat application. The
basecoat was applied in two coats with 60-second ambient flash
between coats and a 4-minute ambient flash before clearcoat.
Clearcoat was sprayed in 2 coats with a 60-second ambient flash
between coats and a 7-minute ambient flash before entering the cure
oven. The system was baked for 35 minutes at 180.degree. F.
(82.degree. C.) in a vertical position. A coating system without
adhesion promoter was sprayed as a negative control.
[0092] Coated panels were allowed to rest under ambient conditions
for at least 3 days before testing. Panels were tested for
resistance to delamination in a fuel soak test. Results follow in
Table 5.
TABLE-US-00015 TABLE 5 Adhesion Promoter Fuel Resistance.sup.22
(minutes) Example 1 32 Example 2 29 Example 3 60 Example 4 60
Example 5 32 Example 6 60 Example 7 60 Example 8 7 Example 9 60
Example 10 60 Example 11 60 None 2 .sup.22Coated panels were cut
into three 1'' .times. 4'' pieces for each coating system to be
tested for fuel resistance. Cut edges were covered using Nichiban
LP-24 tape available from Alliance Rubber Co. An "X" was cut into
the coating layers on one end of each panel and that end was
submersed in a synthetic fuel blend (formulation in Table 6).
Panels were timed from the time they were submerged in the fuel
until the time the coating started to lift from the "X." The time
at which the coating lifted from the substrate was recorded as the
time to fail. The times to fail for the three panels for each
coating system were averaged, rounded to the nearest whole value
and listed as Fuel Resistance;, higher times indicate better fuel
resistance. Test specifications for a "pass" rating require at
least 15 minutes in the fuel soak before lifting of the coating
from the substrate is observed.
TABLE-US-00016 TABLE 6 Synthetic Fuel formulation Parts by weight
of Ingredient Component 2,2,4-trimethylpentane.sup.23 25.35
Toluene.sup.24 42.25 di-isobutylene.sup.23 12.68 Ethanol SDA-3A 200
4.22 PROOF.sup.25 Methanol.sup.24 15.00 Deionized water 0.50 Total
100.00 .sup.23Solvent commercially available from Fisher
Scientific. .sup.24Solvent commercially available from Ashland Inc.
.sup.25Solvent commercially available from Brenntag.
[0093] Whereas particular embodiments of this invention have been
described above for purposes of illustration, it will be evident to
those skilled in the art that numerous variations of the details of
the present invention may be made without departing from the scope
of the invention as defined in the appended claims.
* * * * *