CA2034557A1 - Coating compositions of acrylic polymers containing reactive groups and an epoxy organosilane - Google Patents

Abstract

A coating composition which cures at ambient temperatures and contains 20-80% by weight of a binder and 80-20% by weight of a solvent for the binder, wherein the binder contains about:
A. an acrylic polymer A of polymerized monomers of methyl methacrylate and monomers of styrene, alkyl methacrylate and/or alkyl acrylate each having 2-12 carbon atoms in the alkyl group and said polymer having pending from the polymer backbone aminoester groups, hydroxy aminoester groups or hydroxyamine groups, B. an acrylic crosslinking polymer B of polymerized monomers of at least 3% by weight, based on the weight of the crosslinking polymer, of a glycidyl constituent of glycidyl methacrylate or acrylate and the remainder of the monomers are alkyl methacrylate an acrylate each having 1-'2 carbon atoms in the alkyl group and optionally contains at least 3% by weight, based on the weight of the crosslinking polymer, of an alkyl methacrylate or acrylate having a pendent group of the formula ;
C. an organosilane compound having an epoxy group;
the composition is useful as an exterior finish for automobiles and trucks and for repairing and finishes of automobiles and trucks.

Description

i~3~ 7 F~.- 0 3 2 3 ~a~
COATING COMPOSITION OF ACRYLIC POLYMERS CONTAINING
P~EACq`IVE GROUPS AND AN EPOXY ORGANOSII~NE

BACKGROUND OF THE INVEMTION
This invention is related to a coating composition and in particular to a coating composition that cures rapidly at ambient temperatures to form a finish with improved initial properties such as moisture resistance and tape marking resistance.
There are a number of coating compositions available for finishing and repairing of the exterior finish of automobiles and trucks. These compositions cure at ambient temperatures and provide finishes with l~ good physical properties such as gloss, hardness, weatherability, good adhesion, chip resistance and the like. Typical useful compositions are shown in Den Hartog et al US 4,525,521 issued June 25, 1985;
however, it would be very desirable if these 2~ compositions would ha~e a faster initial curing rate without a sacrifice of any of the other ~ery acceptable properties of the compositions. Other useful compositions which contain isocyanates are shown in Crawley et al US 4,131,571 issued Dec. 26, 25 1978, Miller US 4,020,216 issued Apr. 26, 1977, Miller US 3,844,993 issued Oct. 29, 1974, Miller US 3,789,037 issued Jan. 29, 1974 and Vasta US 3,558,564 issued Jan. 26, 1971. It would be desirable to provide an ambient temperature curing composition that has a rapid initial curing rate along with an acceptable ~pot lifen that forms an automotive quality finish on curing an~ does not cont~in an isocyanate compoundO
The novel composition of this invention has a rapid initial cure rate, i.e., crosslinks quickly at ambient temperatures to provide ~xcellent initial properties such as moisture and tape marking .

'~

, 2 ~3~5'7 reC-'stance, has an acceptable pot life, forms a finish that has acceptable flexiblity and outdoor durability and has the other properties that are necessary for exterior finishes ~or automobiles and trucXs and does not contain an isocyanate compound.

~UMMARY OF THE INVENTION
- A coating composition containing about 20-80~ by weight of a binder and 80-20~ by weight of a solvent for the binder, wherein the binder contains about:
A. 40-78% by weight, based on the weight of the binder, of an acrylic polymer A
of polymerized monomers of methyl methacrylate and monomers selected from the group of styrene, alkyl methacrylate and alkyl acrylate each having 2-12 carbon atoms in the alkyl group and the polymer has pending from the carbon-carbon atoms of the polymer backbone aminoester groups of the formula o il 2~ -C-O-R-NH2 where R is an alkylene group having 2-3 carbon atoms: or hydroxy aminoester groups of the formula Il I
-C-0-CH2-C-CH2-0H or i H

:: . . .
,~
.

2C~557 Il I
-c-o-cH2-c-cH2-N~2 or I
H
groups of the formula OH H

-C~-CH2-NRl or HNRl OH

lS
where Rl is an alkyl group of 1-8 carbon atoms; and B. 20-40% ~y weight, based on the weigh of the binder, of an acrylic crosslinking polymer B of polymerized monomers of at least 3% by weight, based on the weight of the crosslinking polymer, of a glycidyl constituent selected ~rom the group of glycidyl methacrylate and glycidyl acrylate, and the remainder of the monomers are selected from the group of alkyl methacrylate and alkyl acrylate each having 1-12 carbon atoms in the alkyl group and optionally contains at least 3% by weight, based on the weight of the crosslinking polymer, ~f an alkyl acrylate or methacrylate having a pendent grQup of the formula , 4 ~3~i7 o o Il 11 -O-C-CH2-C-CH3; and C. 2 40% by weight, based on the weight of the binder, of an organosilane compound . containing an spoxy group:
wherein polymers A' and B each have a wei~ht averaye molecular weight of about 5,000-40,000 determined by gel permeation chromatography using polymethyl methacrylate as a standard.

DETAI LED DES CRI PTI ON OF THE INVENTI ON
The coating composition contains about 20-80~ by weight of a film forming binder and 80-20%
by weight of sol~ent for the binder. The binder is a blend of about 40-78~ by weight of acrylic polymer ~, 20-40% of acrylic crosslinking pol~mer B and 2-40% by weight of and organosilane oompound having an expoxy group. The composition can be used as a clear finish without pigments or only lightly pigmented while retaining its clear characteristics or can be pigmented and used as a conventional monofinish or as the color coat of a color coat/clear coat finish.
Typically, a pigment to binder weight ratio of about 1:100 to 200:100 can be used.
Both acrylic polymer A and acrylic crosslinXing polymer B have a weight average molecular weight of about 5,000-40,000 and a number average molecular weight of about 2,000-15,000. Molecular weight is determined by gel permeation chromakography using polymethyl methacrylate as the standard.
On~ method ~or preparing the acrylic pol~mer A is to polymerize monomers of methyl methacrylate, alkyl ~ethacrylate, alkyl acrylate or mixtures thereof, each having 2-12 carbon ato~s in the '' ~03~55~7 alkyl group, and methacrylic acid or acrylic acid.
Styrene also can be used in amounts of about 50% by weight of the polymer. The carboxyl groups of the resulting pol~mer are reacted with an alkylene imine S preferably in a molar ratio of about 1:1 to form pendent amino ester groups from the backbone of the poiy~ler.
The polymeri7ation of the monomers to form the acrylic polymer A is carried out by conventional techniques in which the monomers, solvents and polymerization catalysts are charged into a polymeri~ation vessel and reacted at about 50-175C
for about 0.5-6 hours to form the polymer.
Typical solvents used are toluene, xylene, e~hyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethanol, isopropanol and other aliphatic, cycloaliphatic and aromatic hydrocarbon esters, ethers, ketones and alcohols as are conventionally used.
One preferred acrylic polymer contains about 20-30% by weight methyl methacrylate, 25-35% by weight of an alkyl methacrylate having 4-12 carbon atoms in the alkyl group such as butyl methacrylate, 30-40%
styrene and 10-15% by weight methacrylic acid. The ~arboxyl groups of the polymer are post reacted with an alkylene imine such as propylene imine, preferably in a 1:1 molar ratio, to a provide amino ester groups pendent from the carbon-carbon polymer backbone of the formula Il where R is an alXylene group having 2-3 carbon atoms.
Other useful ~crylic polymers are the aformentioned acrylic polymers except that khe 6 ;~3~;i57 aminoester group is replaced by hydroxy aminoester groups of the formula 11 l o OH
Il I

Such polymers are disclosed in DenHartog et al. U.S.
Patent 4,52S,521 issued June 25, 19~5 which is hereby incorporated by reference.
- 1~ Another useful type of acrylic poly~er are the aforementioned acrylic poiymers except that the aminoester group is replaced with groups of ~he formula OH H

-CH-CH2-N-R1 or ~S -CH - CH2 where Rl is an alkyl group of 1 8 carbon atoms. Such polymers are disclosed in Snow U.S. Patent 4,785,054 issued November 15, 1988 which is hereby incorporated by reference.
The acrylic crosslinking polymer B is composed of polymerized monomers of at least 3~ by weight of a glycidyl constituent which is either glycidyl methacrylate or glycidyl acrylate and the remainder of the monomers are alkyl methacrylate, alkyl acrylate or mixtures thereof where the alkyl :: 6 ' ~ .

7 ~03~5~

group contains 1-12 carbon atoms and ~ptionally contains at least 3% by weight of an alkyl methacrylate or acrylate having 1-4 carbon atoms in ~ the ~l~yl group and pendent groups of the formula o O
Il 11 -O-C-CH2-C-CH3.
Useful acrylic crosslinking polymers are composed of polymerized monomers of about 3-80% by weight, based on the weight of the polymer, of glycidyl methacrylate or acrylate, 20-97% by weight, based on the weight of the polymer of an alkyl methacrylate having 1-12 carbon atoms, preferably 4-12 carbon atoms, in the alkyl group such as butyl methacrylate.
Other useful acrylic crosslinking p~l~mers are composed of polymerized monomers of about 3-80% by weight, based on the weight of the polymer, of glycidyl methacrylate or acrylate, 15-40% by weight, based on the weight of the polymer, of an alkyl methacrylate having 1-12 carbon atoms, preferably 4-12 carbon atoms, in the alkyl group such as butyl methacrylate and 3-57~ by weight, based on the weight of the polymer, of acetoacetoxy ethyl methacrylate or ~5 acrylate.
The following are an examples of preferred acrylic crosslinking polymers:
60% glycidyl methacrylate/40% butyl methacrylate, 45% glycidyl methacrylate/40% butyl methacrylate/15%
acetoacetoxy ethyl methacrylate, 50% glycidyl methacrylate/40% butyl methacrylate/10% acetoacetoxy ethyl methacrylate, 55% glycidyl methacrylate/40%
butyl methacrylate/5% acetoacetoxy ethyl ~ethacrylate.
Other useful crosslinXing polymers are as follows: 30% glycidyl methacrylate/40~ ~utyl methacrylate/30% acetoacetoxy ethyl methacrylate, 8 ~3'1~

3% glycidyl methacrylate/40% butyl methacrylate/57%
acetoacet~xy ethyl methacrylate.
The aforementioned percentages are weight - percentagesO
Acetoacetoxy ethyl methacrylate or acrylate are typically useful and preferred monomers that ront~in the a~orementioned pendent group of the crosslinking polymer.
The pendent group of the crosslinking polymer can also be formed by preparing a hydroxyl containing acrylic polymer and reacting the hydroxyl groups of the polymer with a diketene or with an alkylate of acetoacetic acid such as methyl acetoacetate or t-butyl aceto acetate. A blocked 15 ketene such as 2,2,6, trimethyl-4H-1,3 dioxin-4-one may also be used.
It was found that when a crosslinking polymer was used that contained the aforemened pendent group and was combined with an epoxy functional organosilane compound, finishes were formed that cured more rapidly and had improved solvent resistance in comparison to finishes ~ormed with crosslinking polymers that did not contain the pendent group.
Typical alkyl methacrylate and alkyl acrylate monomers that are used to prepare the aforementioned polymers are ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, ethyl hexyl methacrylate, nonyl methacrylate, decyl methacrylate, lauryl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, pentyl acrylate, hexyl acrylate, ethyl hexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate and the like.
The organo Gilane compound containing an epoxy group is represented by the formula:

.

;~034SS7 (R2~b Rl-Si- (oR3) a - wherein Rl is an organic group having an epoxy group, R2 is hydrogen, a hydrocarbon group having 1-6 carbon atoms b is an integer o~ 0 2, R3 is a hydrocarbon group having 1-5 carbon atoms or an alkoxyalkyl group, a is an inteqer of 1-3. Typical silanes are as follows:
glycidoxymethyl trimethoxysilane, glycidoxymethyl triethoxysilane, glycidoxyethyl triethoxysilane, glycidoxypropyl trimethoxysilane, glycidoxypropyl triethoxysilane, glycidoxypropyl tri(methoxyethoxy)silane, glycidoxypropyl triacetoxysilane, glycidoxybutyl trimethoxysilane, glycidoxymethyl dimethoxysilane, glydidoxymethyl(ethyl)dimethoxysilane, glycidoxymethyl(dimethyl)methoxysilane, glycidoxyethyl(ethyl)dimethoxysilane, glycidoxypropyl(ethyl)dimethoxysilane, glycidoxybutyl(methyl)dimethoxysilane, glycidylmethyl trimethoxysilane, ylycidylmethyl triethoxysilane, glycidylethyl triethoxysilane, glycidylpropyl triethoxysilane, glycicylbutyl triethoxysilane, 3,4-epoxycy~lohexylmethyl trimethoxysilane, 3,4-epoxycyclohexylethyl trimethoxysilane, 3,4 epoxycyclohexylpropyl trimethoxysilane, 3,4-epoxycyclohexylbutyl trimethoxysilane.
Preferred silanes are glycidoxypropyl trimethoxysilane and beta-~3,4-epoxycyclohexyl~ethyl trimethoxysilane since these silanes form finishes of excellent guality, durability and weatherability.

~ [)3~5~7 About 0.1~4% by weight, based on th~ weight of the binder, of a catalyst can be added to the coating composition. Typical catalysts are resorcinol, resorcinol ~onobenzoate, boron trifluoride amine complex, phenol, para methoxy phenol, parahydroxy methyl benzoate,hydroquinone, and alkyl rEtal laurate cataly~ts such as dibutyl tin dilaurate and the like. A metal laurate catalyst can be combined with one of the other ca~alysts to further enhance cure rate.
As mentioned before, the composition can contain pigments. These pigments can be introduced into the composition by first forming a mill base with acrylic polymer A utilized in the composition or with other compatible polymers or polymer dispersants by conventional techniques, such as sand-grinding, ball milling, attritor qrinding, two roll milling to disperse the pigments. The mill base is blended with the film-forming constituents as shown in the following Examples.
Any of the conventional pigments used in coating compositions can be utilized in the composition such as the following: metallic oxides, such as titanium dioxide, zinc oxide, iron oxide and the like, metal hydroxide, metal flakes such as aluminum flake, 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 3~ other organic pigments and dyes.
To improve weatherability of finishes of the coating compo~ition about 0.1-5%, by weight, based on the weight of the binder, of an ultraviolet liqht stabilizer or a combination of ulraviolet light stabilizers can be added. Typically useful 3~57 ultra-violet light stabilizers are disclosed hereinafter.
The coatin~ compositi~n of this invention can be applied over a variety of substrates, such as ~etal, glass, plastic, reinf~rced plastic and the like, by any of the conventional application methods, su_~ as spraying, electro-static ~praying, dipping, brushing, flow-coating and the like. The viscosity of the composition can be adjusted for any of these methods by adding solvents if necessary. Generally, the composition is utilized at a high solids content which keeps air pollution at ~ minimum level.
The coatings are usually dried at ambient temperatures and are tack free after about 1-4 hours and fully cured after a~out 4-7 days. The coatings can be baked at relatively low temperatures of about 65-140C. for about 15 minutes-2 hours. The resulting coating is about 0.1-5 mils thick but for most uses, a 1-3 mil thick coating is used. One technique that is used to insure that there will be no popping or cratering of the coating is to allow the solvents to flash off for at least 2 minutes before a second coating is sprayed on or otherwise applied, then waiting about 2-10 minutes before baking the 2~ coating to allow any residual solvents to flash off if the coating is to be baked. The resulting coating has good gloss and can be rubbed or polished with conventional techniques to improve the smoothness, appearance and gloss. The coatin~ has good adhesion to substrates of all types, is hard and resistant to weathering, solvents, alkali, scratches and the like.
These characteristics make the composition particul~rly useful as a ~inish for automobiles, trucks, airplanes, railxGad equipment and Por the repair of finishes of trucXs and automobiles.

12 ~ S~7 Another aspect o~ this invention is to utilize the composition as a clear coat/color coat finish for substra~es~ In this finish, a clear coat top layer is in firm adherence to a color coat layer that is in adherence with a ~ubstrate. The clear coat is a transparent film of the coating composition of this invention and the col~r coat is the coating composition of khis invention and contains pigments in a pigment~to-binder ratio of about 1/100 to lS0/100 and other additives. Other compatible color coats can be used with the clear coating composition of this invention.
The thickness of the fully cured color coat and clear coat can vary. Generally, the color coat is about 0.4-l.S mils thick and preferably 0.6-1.0 mils thick and the clear coat is about 0.5-6.0 mils thick and preferably 0.8-2.0 mils thick. Any of the aforementioned conventional pigments can be used in the color coat including metallic flake pigment~ can be used. The clear coat can also contain transparent pigments, i.e., pigments having the same or similar refractive index as the binder of the clear coat and are of a small particle size of about 0.015-50 microns. Typical pigments that can be used in a ?5 pigment-to-binder weight ratio of about 1/100 to 10/100 are inorganic siliceous pigments, such as silica pigments. These piqments have a refractive index of about 1.4-1.6.
To form a durable finish, the clear coat and optionally, the color coat contain about 0.1-5% by weight based on the weight of the binder, of an ultraviolet light stabilizer. Typical ultraviolet light stabilizers that are useful are as follows:
8enzophenones ~uch as hydroxy dodecyloxy benzophenone, 2,4 dihydroxybenzophenone, 2~3~57 hydroxybenzophenones containing sulfonic groups and the like~
Triazoles suoh as 2-phenyl-4-(2',4'-dihydryoxylbenzoyl)-triazoles, substituted S benzotriazoles ~uch as hydroxy-phenyltriazoles and the like.
Triazines such as 3,5-dialkyl 4-hydroxyphenyl derivatives of triazine, sulfur containing derivatives of diallyl-4-hydroxy phenyl triazines, hydroxy phenyl-1,3,5-triazine and the like.
Benzoates such as dibenzoate of diphenylol propane, tertiary butyl ben~oate of diphenylol propane, and the like.
Other ultraviolet li~ht stabiliæers that can be used include lower alkyl thiomethylene containing phen~ls, substituted benzenes such as 1,3-bis(2'-hydroxybenzoyl)benzene, metal derivatives of 3,5-di-t-butyl-4-hydroxy phenyl propianic acid, asymmetrical oxalic acid, diarylamides, alkylhydroxy-phenyl-thioalkanoic acid ester and the like.
Particularly useful ultraviolet light stabilizers that can be used are hindered amines of bipiperidyl derivatives such as those in Murayama et al., U.S. Pat. No. 4,061,616, issued Dec. 6, 1977.
One preferred combination of ultraviolet light stabilizer is a benzotriazole and a hindered amine light stabilizer and is preferably used in a weignt ratio of about 1:1. The combination is used in an amount of about 1-4% by weig~t, based on the weight of the binder. One preferred benzotriazole is ~Tinuvin~ 328,2-(2 hydroxy-3,5-ditertiary amyl-phen~ 2H-ben~otriazole and a preferred hindered amine is ~Tinuvin~ 292, bis(l,2,2,6,6-pentamethyl-4 piperidinyl~sebacate. Another pre~erred hindered ~4 ~203~557 amine is ~Tinuvin~ 770, di~4(2,2,6,6 tetramethyl piperdinyl)~sebacate.
The clear coat/color coat finish is applied - by conventional spraying t~chniques and preferably the clear coat is applied to the color coat while the color coat is ~till wet. Other conventional application techniques can be used such as brushing, roller coating, electrostatic spraying the the like.
The finish is then dried at ambient temperatures or can be used as indicated above.
The following Examples illustrate the invention. All parts and percentages are on a weight -basis unless otherwise indicated. Molecular weights are determined by gel permeation chromatography using polymethyl methacrylate as the standard.

Acrylic polymer A solution was prepared by charging the following constituents into a reaction vessel equipped with a heating mantle, reflux condenser, thermometer and stirrer:
Parts by Wei~ht Portion 1 Butyl acetate 959.53 Toluene 367.08 Isopropanol 641.24 Butyl methacrylate monomer (BMA) 127.22 Portion 2 Butyl methacrylate monomer817.23 Methyl methacrylate monomer (MMA) 7S5.55 Styrene monomer (S) 1066.42 Methacrylic acid monomer (MAA) 329.93 portion 3 2,2r-Azobis(methylbutyronitrile) 97~58 Toluene 295.06 .

2~3~5~7 Portion 4 Methacrylic acid monomer 48.81 Toluene 148.69 Portion 5 5 2,2'-Azobi~(methylbutyronitrile)1.17 Toluene 12.77 PGrtion 6 Butyl acetate 2160.71 Portion 7 Propylen imine 251.01 Total 8080.00 Portion 1 is charged into the reaction vessel and mixed and the resulting mixture is heated to its reflux temperature of about 90C. Portion 2 is premixed and slowly added at a uniform rate over a 90 minute p~riod to the reaction vessel while maintaining the mixture at its reflux temperature. Portion 3 is premixed and fed into the reaction vessel simultaneously with Portion 2 over the same time period. Immediately after Portions 2 and 3 have bee~
added Portion 4 is added over a 45 minute period while holding the reaction mixture at its reflux temperature and then holding the reaction mixture at its reflux temperature for an additional 30 minutes. ~ortion 5 is added and then the reaction mixture is held at its reflux temperature for 45 minutes. Portion 6 is added and the reaction mixture is cooled to 60C and then Portion 7 is added and the reaction mixture is heated t~ its reflux temperature and held at this temperature until and acid no. of 2 is reached.
The resulting polymer solution has a polymer weight solids content of about 42%, a Gardner Holdt viscosity at 25C of about C +1/2 to D ~1/2. The polyme~ has a composition of about 24% ~ethyl methacrylate, 30% butyl methacrylate, 34~ ~tyrene and 12% methacrylic acid postiminated with propylene 16 z~3~

imine. The resulting polymer has an acid no. o~ about 2, a number average molecular weight of about 6,800 and a wei~ht average molecular weight of about 10,600.
- ~ Crosslinking polymer solution 1 was prepared by charging the following constituents into a reaction vessel described above:
Parts bv Wei~ht Portion l Butyl acetate 745.00 Toluene 128.00 Ethyl acetate 207.00 Portion 2 Glycidyl methacrylate monomer 1166.00 Butyl methacrylate monomer777.00 Butyl acetate 280.00 2,2'-Azobis(methylbutyronitrile) 93.00 Portion 3 Butyl acetate 72.00 2,2'-Azobis(methylbutyronitrile) 24.00 Portion 4 Butyl acetate ` 510.00 Propylene glycol monomethyl acetate 242.00 Total 4244.00 Portion 1 was charged into the reaction vessel and heated to its reflux temperature of about 110-112~C. Portion 2 was premixed and added at a uniform rate over a 2 hour period while maintaining the reaction mixture at its reflux temperature.
I~med~ately after portion 2 was completely added, Portion 3 was added over a 30 minute period and then the reaction mixture was held at its reflux temperature for an additional 30 minutes. Portion 4 was added and the reaction mixture was cooled to room temperature.
The resulting polymer solution had a polymer solids of about 46%. and a relative viscosity of about :

~7 1.037-1.039. The composition o~ the polymers is 40%
butyl methacrylate, and 60% glycidyl ~ethacrylatP and had a number average ~olecular weight ~f about 2,410 and a weight average molecular weight of about 53250.
A Clear Polymer Solution was prepared by blending the following constituents Parts by Weiqht Acrylic polymers A solution (prepared 456.51 above) 10 Isopropanol 9.86 Propylene ~lycol monoethyl ether acetate 31.86 Hydrocarbon solvent 10.50 Mineral spirits (aromatic controlled) 10.61 W Stabilizer (~Tinuvin~ 328) 2.72 15 HALS light stabilizer ("Tinuvinn 292) 2.72 Flow control agent ("Acrylon" MFPF from Synthron) 0.39 Slip agent (BYK 325) 0.53 Non-Agueous Dispersion Rheology Control Agent 12.85 Total 538.55 : A Thinner Solution was prepared by blending the following constituents:
Parts bY Wei~ht ~5 Propylene glycol monoethyl ether acetate 30.78 Hydrocarbon solvent 26.69 Ethyl 3-ethoxy propionate 59.5S
Butyl Cellosolve Acetate 1.12 Catalyst solution (p-hydroxymethyl benzoate) 7.74 Total 125.89 A silane solution was prepared by blending toqether the following constituents:

.. .... - . i :

2~3~557 Parts by Weiqht Glycidoxypropyl trimethoxysilane 90.91 Dibutyltin dilaurate 9.09 Total 100.00 Clear coating cGmpositions 1-3 were formulated as follows. Clear c~ating composition 1 does not oontain silane and is considered the control.
Clear coating compositions 2 and 3 each contained respectively 10~ and 20% by weightl based on the weight of the binder of the composition, of silane.
Clear coating composition 1 was prepared by blending the following constituents together:
Parts by Weiqht Clear Polymer Solution (prepared abo~e) 67.38 15 Thinner Solution (prepared above) 15.78 Crosslinker Polymer Solution i (prepared 16.84 above) Total 100.00 Clear coating composition 2 was prepared by blending the following constituents together:
Parts bv Wei~ht Clear Polymer Solution (prepared Above) 65.08 Thinner Solution (prepared above~ 15.24 Crosslinker Polymer Solution 1 (prepared 16.26 ~5 above) Silane solution (prepared above) 3.42 Total 100.00 Clear coating composition 3 was prepared by blending the following constituents toge~her:
Parts bv Weiqht Clear Polymer Solution (prepared above) 62.92 Thinner Solution (prepared above) 14.74 Crosslinker Polymer Solution 1 (prepared 15.73 above) 35 Silane solution (prepared above)6.61 Total lOO.Oo : ' :

Z~3~5~7 Clear coating comp~si~ions 1,2 and 3 were sprayed onto separate primed steel panels coated with an acrylic lacquer pigmented ~inish and then cured at - room temperature. In each case, the resulting clear finish was about 2 mils thick. Each panel was~tested for tape print resistance and for water spot ~esistance.
In the tape print resistance test masking tape was applied every 4 hours during a period of 8-24 hours after application of the finish. The tape was removed one hour after it was applied and then 1 hour after the tape was removed, the finish was inspected for printing resulting ~rom the tape. The time at which no printing from the tape was noted is shown below.
In the water spot resistance test7 three drops of distilled waster ~ere applied every 4 h~urs after application of the finish and the water was allowed to evaporate. After the water evaporated the panel was inspected for distortion o~ the finish. The time at which no distortion from water was noted is shown below.
Test Tape Print Water Spot Resistance (1) Resistance (2) Coating Comp. 1 (control) 16 hours 20 hours Coating Comp. 2 (10% silane) 8 ~ 8 n Coating Comp. 3 (20% silane) ~ ~ 8 ~ i,ne in hours when tape did not imprint finish.
t2) Time in hours when water did not spot finish.
Other properties of the each of the finishes were tested such as gloss, distinctness of image, durability, chemical resistance and adhesion after 1~8 hours of uring at room temperature and were acceptable for an automotive quality finish.

~3~557 Crosslinking polymer solution 2 was prepared by charging the $oll~wing constituents into a reaction vessel described above:
Parts by Weiqht Portion l ~utyi acetate 745.00 10 Toluene 12B.00 Ethyl acetate 207.00 Portion 2 Glycidyl methacrylate monomer 875.00 Butyl methacrylate monomer777.00 Acetoacetoxy ethyl methacrylate monomer 291.00 Butyl acetate 280.00 2,2'-Azobis(methylbutyronitrile)93.00 Portion 3 Butyl acetate 72.00 2,2' Azobis(methylbutyronitrile) 24.00 Portion 4 Butyl acetate 510.00 Propylene ~lycol monomethyl acetate 242~00 Total 4244.00 Portion 1 was charged into the reaction vessel and heated to its reflux temperature of about 110-112. Portion 2 was premixed and added at a uniform rate over a 2 hour period while ~aintaining the reaction mixtu-e at its reflux temperature.
Immediately after portion 2 was completsly added, Portion 3 was added over a 30 minute period and then the reaction mixture was held at its reflux temperature for an additional 30 minutes. Portion 4 was added and the reaction mixture was cooled to room te~perature.
The resulting polymer ~olution had a polymer ~olids of about 46%. and a relative viscosity of about 1.037-1.039. The composition of the polymers is 40%

': , :

21 203flLS57 butyl methacrylate, 60% glycidyl methacrylate and 15%
acetoacetoxy ethyl methacrylate and had a number average molecular weight of about 1,976 a~d a weight average molecular weight of about 5,303.
Clear coating compositions 4 and 5 were prepared using the same constituents and amounts as in Example 1 except Crosslinking Polymer Solution 2 tprepared above) was substituted for Crosslinking Polymer Solution 1. Clear coating compositions 1, 4 and 5 each were sprayed onto ~eparate primed ~teel panels coated with an acrylic lacquer pigmented basecoat finish and then cured at room temperature. In each case, the resulting clear finish was about 2 mils thick. Each panel was tested for rerepair lift.
Rerepair lift is tested by sanding through an area of the coating to the substrate below the basecoat and lifting is checked at specified times after the panels were sprayed. The panels were sanded in such a way to produce a smooth feather-edge. These panels were then resprayed to hiding with the above basecoat. A 0-5 rating scale is used to describe the - lift; O represents no lift and 5 represents ~evere lifting over both sanded and unsanded areas of the panel. The data is shown below.
1 Day 4 Davs 7 DaYs 14 Davs Coating comp. 1 (control) 2 3 2 Coating comp. 4 (10% silane) 1 1 0 0 C~ating comp. 5 (20% silane) 1 0 O O
Other properties of the each of the finishes were tested such as gloss, distinctness of image, durability, chemical resistance and adhesion after 168 hours of curing and were acceptable for an automotive quality finish.

Claims (21)

1. A coating composition comprising 20-80%
by weight of a binder and 80-20% by weight of a solvent for the binder, wherein the binder consists essentially of about:
A. 40-78% by weight, based on the weight of the binder, of an acrylic polymer A
consisting essentially of polymerized monomers of methyl methacrylate and monomers selected from the group consisting of styrene, alkyl methacrylate and alkyl acrylate each having 2-12 carbon atoms in the alkyl group and said polymer having pending from the carbon-carbon atoms of the polymer backbone reactive groups selected from the group consisting of aminoester groups of the formula where R is an alkylene group having 2-3 carbon atoms, hydroxyamino ester groups of the formula or or groups of the formula or where R1 is an alkyl group of 1-8 carbon atoms; and B. 20-40% by weight, based on the weight of the binder, of an acrylic crosslinking polymer B consisting essentially of polymerized monomers of at least 3% by weight, based on the weight of the crosslinking polymer, of a glycidyl constituent selected from the group consisting of glycidyl methacrylate and glycidyl acrylate, and the remainder of the monomers being selected from the group consisting of alkyl methacrylate and alkyl acrylate each having 1-12 carbon atoms in the alkyl groups and optionally contains at least 3% by weight, based on the weight of the crosslinking polymer, of an alkyl acrylate or methacrylate having a pendent group of the formula ; and C. 2-40% by weight, based on the weight of the binder, of an organosilane compound containing an epoxy group;
wherein said polymers A and B each have a weight average molecular weight of about 5,000-40,000 determined by gel permeation chromatography using polymethyl methacrylate as a standard.

2. The coating composition of claim 1 containing pigments in a pigment-to-binder weight ratio of 1:100 to 200:100.

3. The coating composition of claim 1 in which the organosilane consists of a compound of the formula wherein R1 is an organic group having an epoxy group, R2 is hydrogen, a hydrocarbon group having 1-6 carbon atoms b is an integer of 0-2, R3 is a hydrocarbon group having 1-5 carbon atoms or an alkoxyalkyl group, a is an integer of 1-3.

4. The coating composition of claim 3 wherein the organosilane is selected from the group consisting of glycidoxypropyl trimethoxysilane and beta-(3,4-epoxy cyclohexyl)ethyl trimethoxysilane.

5. The coating composition of claim 3 in which the acrylic polymer A consists essentially of polymerized monomers of methyl methacrylate and monomers selected from the group consisting of styrene, alkyl methacrylate and alkyl acrylate, each having 2-12 carbon atoms in the alkyl group and said polymer having pending from the carbon-carbon atoms of the polymer backbone reactive aminoester groups of the formula where R is an alkylene group having 2-3 carbon atoms.

6. The coating composition of claim 5 in which the acrylic polymer A consists essentially of about 20-30% by weight, based on the acrylic polymer, of methyl methacrylate 30-40% by weight, based on the weight of the acrylic polymer, of styrene, 25-35% by weight, based on the weight of the acrylic polymer, of an alkyl methacrylate having 4 12 carbon atoms in the alkyl group and 10-15% by weight, based on the weight of the acrylic polymer, of methacrylic acid: said polymer reacted with an alkylene imine to provide said amino ester groups.

7. The coating composition of claim 3 in which the acrylic polymer A consists essentially of polymerized monomers of methyl methacrylate and monomers selected from the group consisting of styrene, alkyl methacrylate and alkyl acrylate, each having 2-12 carbon atoms in the alkyl group and said polymer having pending from the carbon-carbon atoms of the polymer backbone hydroxyamino ester groups of the formula or .

8. The coating composition of claim 3 in which the acrylic polymer A consists essentially of polymerized monomers of methyl methacrylate and monomers selected from the group consisting of styrene, alkyl methacrylate and alkyl acrylate, each having 2-12 carbon atoms in the alkyl group and said polymer having pending from the backbone groups of the formula or where R1 is an alkyl group of 1-8 carbon atoms.

9. The coating composition of claim 3 in which the acrylic crosslinking polymer B consists essentially of about 3-80% by weight, based on the weight of the acrylic crosslinking polymer, of glycidyl methacrylate, or glycidyl acrylate and 20-97%
by weight, based on the weight of the acrylic crosslinking polymer, of an alkyl methacrylate having 1-12 carbon atoms in the alkyl group.

10. The coating composition of claims 6, 7 or 8 in which the acrylic crosslinking polymer 8 consists essentially of about 3-80% by weight based on the weight of the acrylic crosslinking polymer, of glycidyl methacrylate, and 20-97% by weight, based on the weight of the acrylic crosslinking polymer, of an alkyl methacrylate having 4-12 carbon atoms in the alkyl group.

11. The coating composition of claim 3 in which the acrylic crosslinking polymer B consists essentially of about 3-80% by weight, based on the weight of the acrylic crosslinking polymer, of glycidyl methacrylate, or glycidyl acrylate and 15-40%
by weight, based on the weight of the acrylic crosslinking polymer, of an alkyl methacrylate having 1-12 carbon atoms in the alkyl group and about 3-57%
by weight, based on the weight of the acrylic crosslinking polymer of an alkyl methacrylate or alkyl acrylate each having 1-4 carbon atoms in the alkyl group and each having a pendent group of the formula

12. The coating composition of claims 6, 7 or 8 in which the acrylic crosslinking polymer B
consists essentially of about 3-80% by weight, based on the weight of the acrylic crosslinking polymer, of glycidyl methacrylate, 15-40% by weight, based on the weight of the acrylic crosslinking polymer, of an alkyl methacrylate having 4-12 carbon atoms in the alkyl group and 3-57% by weight, based on the weight of the acrylic crosslinking polymer, of acetoacetoxy ethyl methacrylate.

13. The coating composition of claim 1 containing about 0.1-4% by weight, based on the weight of the binder, of a catalyst selected from the group consisting of resorcinol, resorcinol monobenzoate, boron trifuloride amine complex, phenol, para methoxy phenol, parahydroxymethyl benzoate or alkyl tin dilaurate.

14. The coating composition of claim 1 containing 0.1 5% by weight, based on the weight of the binder, of ultraviolet light stabilizer.

15. The coating composition of claim 2 in which the binder consists essentially of about A. acrylic polymer A consists essentially of about 20-30% by weight, based on the acrylic polymer, of methyl methacrylate, 30-40% by weight, based on the weight of the acrylic polymer, of styrene, 25-35% by weight, based on the weight of the acrylic polymer, of alkyl methacrylate methacrylate having 4-12 carbon atoms in the alkyl group and 10-15% by weight, based on the weight of the acrylic polymer, of methacrylic acid; said polymer reacted with an alkylene imine to provide amino ester groups pendent from the carbon-carbon polymer backbone of the formula ?-O-R-NH2 where R is an alkylene group having 2-3 carbon atoms; and B. acrylic crosslinking polymer B
consists essentially of about 3-80% by weight, based on the weight of the acrylic crosslinking polymer, of glycidyl methacrylate, and 20-97% by weight, based on the weight of the acrylic crosslinking polymer, of alkyl methacrylate having 4-12 carbons in the alkyl group;
C. an organosilane selected from the group consisting of glycidoxypropyl trimethoxysilane and beta-(3,4-epoxy cyclohexyl) ethyl trimethoxysilane.

16. The coating composition of claim 2 in which the binder consists essentially of about A. acrylic polymer A consists essentially of about 20-30% by weight, based on the acrylic polymer, of methyl methacrylate, 30-40% by weight, based on the weight of the acrylic polymer, of styrene, 25-35% by weight, based on the weight of the acrylic polymer, of alkyl methacrylate methacrylate having 4-12 carbon atoms in the alkyl group and 10-15% by weight, based on the weight of the acrylic polymer, of methacrylic acid; said polymer reacted with an alkylene imine to provide amino ester groups pendent from the carbon-carbon polymer backbone of the formula -?-O-R-NH2 where R is an alkylene group having 2-3 carbon atoms; and B. acrylic crosslinking polymer B
consists essentially of about 3-80% by weight based on the weight of the acrylic crosslinking polymer, of glycidyl methacrylate, 15-40% by weight, based on the weight of the acrylic crosslinking polymer, of an alkyl methacrylate having 4-12 carbon atoms in the alkyl group and 3-57% by weight, based on the weight of the acrylic crosslinking polymer, of acetoacetoxy ethyl methacrylate.
C. an organosilane selected from the group consisting of glycidoxypropyl trimethoxysilane and beta-(3,4-epoxy cyclohexyl) ethyl trimethoxysilane.

17. A substrate coated with a dried layer of the composition of claim 1.

18. The coated substrate of claim 17 in which the substrate is a metal.

19. The coated substrate of claim 17 in which the substrate is a plastic

20. A substrate coated with a dried layer of a pigmented composition and having a second dried clear layer of the coating composition of claim 1 in superimposed adherence thereto.

21. A substrate coated with a dried layer of composition of claim 1 containing pigment in pigment to binder weight ratio of about 1:100 to 200:100 and having a second dried clear layer of the coating composition of claim 1 in superimposed adherence thereto.