NZ235893A - Coating composition containing an acrylic polymer, containing glycidyl and acetoacetoxy groups, and an amino ester acrylic polymer - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £35893 23589 Priority Dafe<s): USpecif jeation FUed: 30.".IOu..5rj[Q.. V. \0)..fZ/0.c.rj.b.i.j.lL^ '".i&iiCStton £M(*: . t'JJ. jouj-.-J'j ').J; 50 OCT 199" ■ r^CElVED Patents Form No. 5 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION COATING COMPOSITION OF AN ACRYLIC POLYMER CONTAINING GLYCIDYL GROUPS AND ACETOACETOXY GROUPS AND AN AMINO ESTER ACRYLIC POLYMER WE, E.I. DU PONT DE NEMOURS AND COMPANY, a corporation under the laws of the State of Delaware, U.S.A. of 10th & Market Streets, Wilmington, Delaware, U.S.A. hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statements (followed by page la) W'.x^ 235893 lo 3 This invention is related to a coating composition and in particular to a coating composition that cures rapidly at ambient temperatures to form a 10 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 15 cure at ambient temperatures and provide finishes with good physical properties such as gloss, hardness, weatherability, good adhesion, chip resistance and the like. Typical useful compositions are shown in DenHartog et al US 4,525,521 issued June 25, 1985? 20 however, it would be very desirable if these compositions would have a faster initial curing rate without a sacrifice of any of the other very acceptable properties of the compositions. Other useful compositions are shown in Crawley et al 25 US 4,131,571 issued Dec. 26, 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. These compositions contain isocyanate 30 compounds to achieve curing and excellent properties. It would be desirable to provide an ambient temperature curing composition that has a rapid initial curing rate, excellent physical properties, acceptable "pot life" and does not contain an PAT ENT OF-'f- -5 NOV 1991 RECEIVED <5> 235893 isocyanate compound.

The novel composition of this invention has a rapid initial cure rate, i.e., crosslinks quickly at ambient temperatures and provides excellent initial 5 properties such as moisture and tape marking resistance, has an acceptable pot life, forms a finish with excellent durability and has the other properties that are necessary for exterior finishes for automobiles and trucks and does not contain an 10 isocyanate compound.

This invention provides a coating composition containing about 20-80% by weight of a binder and 80-20% by 15 weight of a solvent for the binder, wherein the binder comprises about: A. 60-80% by weight, based on the weight of the binder, of an acrylic polymer A comprising polymerized moncroers of methyl 20 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 pendent from 25 the carbon-carbon atoms of the polymer backbone aminoester groups of the formula 0 II -C-O-R-NH where R is an alkylene group having 2-3 carbon atoms; or hydroxy aminoester groups of the formula N.2. i-'A; C: ^5 NOV 1991 - • - -• / a 235B93 0 NH.

II I 2 ■C-O-CH,-C-CH,-OH or 2 | 2 H 0 1 OH I -C-O-CH,-C-CH,-NH_ and 2 i 2 2 H groups' of the formula OH H Jml -CH-CH2-NR- or HNR. OH I 1 I -CH CH. a , where R is an alkyl group of 1-8 carbon atoms; and ) •25 B. 20-40% by weight, based on the weight of the binder, of an acrylic crosslinking polymer B comprising polymerized monomers of -at least 3% by weight, based on the weight of the crosslinking polymer, of a glycidyl constituent selected from the group of glycidyl methacrylate and glycidyl acrylate, and at least 5% by weight of an alkyl acrylate or methacrylate having a pendent group of the formula and the remainder of the monomers are 0 0 II » -0-C-CH-C-CH selected from the group of alkyl methacrylate and alkyl acrylate each N.L. rr\ 1 c-NT OFFICE -5 NOV M r> 235893 having 1-12 carbon atoms in the alkyl group ? wherein polymers A and B each have a weight average molecular weight of about 5,000-40,000 determined by 5 gel permeation chromatography using polymethyl methacrylate as a standard.

The coating composition contains about -80% by weight of a film forming binder and 80-20% by weight of solvent for the binder. The binder is a blend of about 60-80% by weight of acrylic polymer A and 20-40% of acrylic crosslinking polymer B. The 15 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 20 binder weight ratio of about 1:100 to 200:100 can be used.

Both acrylic polymer A and acrylic ^ crosslinking polymer B have a weight average molecular weight of about 5,000-40,000 and a number average 25 molecular weight of about 2,000-15,000. Molecular weight is determined by gel permeation chromatography using polymethyl methacrylate as the standard. ^ One method for preparing the acrylic polymer A is to polymerize monomers of methyl 30 methacrylate, alkyl methacrylate, alkyl acrylate or mixtures thereof, each having 2-12 carbon atoms in the 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 35 resulting polymer are reacted with an alkylene imine r -5 NOV 1991 T' V 235 8 preferably in a molar ratio of about 1:1 to form pendent amino ester groups from the backbone of the ^ polymer.

The polymerization of the monomers to form 5 the acrylic polymer A is carried out by conventional techniques in which the monomers, solvents and polymerization catalysts are charged into a ^ polymerization vessel and reacted at about 50-175C for about 0.5-6 hours to form the polymer. 10 Typical solvents used are toluene, xylene, ethyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethanol, isopropanol and other aliphatic, cycloaliphatic and aromatic hydrocarbon esters, ethers, ketones and alcohols as are 15 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% 20 styrene and 10-15% by weight methacrylic acid. The carboxyl groups of the polymer are post reacted with ^ an alkylene imine such as propylene imine, preferably \ -J in a 1:1 molar ratio, to a provide amino ester groups pendent from the carbon-carbon polymer backbone of the 25 formula 0 M - C-O-R—NH- & where R is an alkylene group having 2-3 carbon atoms.

Other useful acrylic polymers are the 30 aformentioned acrylic polymers except that the aminoester group is replaced by hydroxy aminoester groups of the formula 235 0 NH_ II I 2 -c-o-ch2-ch—ch2-oh ^ ' 0 OH II I -c-o-ch2-ch-ch2-nh2 Such polymers are disclosed in DenHartog et al. U.S. Patent 4,525,521 issued June 25, 1985 which is hereby i --y incorporated by reference.

Another useful type of acrylic polymer are the aforementioned acrylic polymers except that the aminoester group is replaced with groups of the formula oh h 1 1 1 -CH-CH2-N-R or HNR. OH I 1 I -CH CH2 1 where R 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 at ^ least 5% by weight of an alkyl methacrylate or acrylate having 1-4 carbon atoms in the alkyl group and pendent groups of the formula 0 0 II II -o-c-ch2-c-ch3 and the remainder of the monomers are alkyl methacrylate, alkyl acrylate or mixtures thereof where 35 the alkyl group contains 1-12 carbon atoms. 6 2358 7 Acetoacetoxy ethyl methacrylate or acetpacetoxyethyl acrylate are typically useful and preferred monomers that contain the aforementioned pendent group.

The acrylic 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 ketene such as 2,2,6 trimethyl-4H-l,3 dioxin-4- one may also be used.

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, 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.

The following are examples of preferred acrylic crosslinking polymers: 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 methacrylate.

Other useful acrylic crosslinking are as follows: % glycidyl methacrylate/40% butyl xnethacrylate/30% acetoacetoxy ethyl methacrylate, 3% glycidyl methacrylate/40% butyl methacrylate/57% acetoacetoxy ethyl methacrylate.

The aforementioned percentages are weight percentages. 2358 8 It was found that when only acetoacetoxy ethyl methacrylate or acrylate was used in the acrylic crosslinking polymer, the "pot life" of the composition was unacceptably short and finishes of the composition had unacceptable moisture and acid resistance after application and curing. With only the presence of the glycidyl component, the coatings early cure properties (24 hours cure at ambient temperatures) needed to be improved e.g. hardness tape print resistance and moisture resistance. By balancing the amount of acetoacetoxy ethyl methacrylate or acrylate and the glycidyl component in the crosslinking polymer, a composition was formed that had an adequate *pot life" and provided a finish that had excellent durability, weatherability, . hardness, tape print resistance, appearance properties such as gloss and distinctness of image and had acceptable yellowing performance.

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.

About 0.1-4% by weight, based on the weight of the binder, of a catalyst can be added to the coating composition. Typical catalysts are resorcinol, resorcinol monobenzoate, boron trifluoride amine complex, phenol, para methoxy phenol, parahydroxy methyl benzoate and hydroquinone. 8 235 893 9 As mentioned before, the composition can contain pigments. These pigments can be introduced into the composition by first forming a mill base with the acrylic polymer utilized in the composition or with other compatible polymers or polymer dispersants by conventional techniques, such as sand-grinding, ball milling, attritor grinding, two roll milling to disperse the pigments. The mill base is blended with the film-forming constituents 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 other organic pigments and dyes.

To improve weatherability of finishes of the coating composition about 0.1-5%, by weight, based on the weight of the binder, of an ultraviolet light stabilizer or a combination of ultraviolet light stabilizers can be added. Typically useful ultra-violet light stabilizers are disclosed hereinafter.

The coating composition of this invention can be applied over a variety of substrates, such as metal, glass, plastic, reinforced plastic and the like, by any of the conventional application methods, such as spraying, electro-static spraying, 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, D 235 89 the composition is utilized at a high solids content which keeps air pollution at a minimum level.

The coatings are usually dried at ambient temperatures and are tack free after about 1-4 hours 5 and fully cured after about 4-7 days. The coatings can be baked at relatively low temperatures of about 65°—140°C. 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 10 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 15 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 coating has good adhesion 20 to substrates of all types, is hard and resistant to weathering, solvents, alkali, scratches and the like. ~\ These characteristics make the composition v particularly useful as a finish for automobiles, trucks, airplanes, railroad equipment and for the 25 repair of finishes of trucks and automobiles.

Another aspect of this invention is to ^ utilize the composition as a clear coat/color coat finish for substrates. In this finish, a clear coat top layer is in firm adherence to a color coat layer 30 that is in adherence with a substrate. The clear coat is a transparent film of the coating composition of this invention and the color coat is the coating composition of this invention and contains pigments in a pigment-to-binder ratio of about 1/100 to 150/100 35 and other additives. 235893 11 The thickness of the fully cured color coat and clear coat can vary. Generally, the color coat is about 0.4-1.5 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 pigments 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 pigment-to-binder weight ratio of about 1/100 to 10/100 are inorganic siliceous pigments, such as silica pigments. These pigments 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: Benzophenones such as hydroxy dodecyloxy benzophenone, 2,4 dihydroxybenzophenone, hydroxybenzophenones containing sulfonic groups and the like.

Triazoles such as 2-phenyl-4-(2',4'-dihydryoxylbenzoyl)-triazoles, substituted benzotriazoles such 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-l,3,5-triazine and the like. 11 235 893 12 Benzoates such as dibenzoate of diphenylol propane, tertiary butyl benzoate of diphenylol propiane, and the like.

Other ultraviolet light stabilizers that can be used include lower alkyl thiomethylene containing phenols, substituted benzenes such as 1,3-bis(2'-hydroxybenzoyl)benzene, metal derivatives of 3,5-di-t-buty1-4-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 weight ratio of about 1:1. The combination is used in an amount of about 1-4% by weight, based on the weight of the binder. One preferred benzotriazole is "Tinuvin" 328,2-(2 hydroxy-3,5-ditertiary amyl-phenol)-2H-benzotriazole and a preferred hindered amine is "Tinuvin" 292, bis(l,2,2,6,6-pentamethyl-4 piperidinyl)sebacate. Another preferred hindered amine is "Tinuvin" 770, di[4(2,2,6,6 tetramethyl piperdinyl)]sebacate.

The clear coat/color coat finish is applied by conventional spraying techniques and preferably the clear coat is applied to the color coat while the color coat is still 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. 12 X 235 8,9 3 13 -J J ,5 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.

EXAMPLE 1 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 bv Weight Portion 1 Butyl acetate 959.53 Toluene 367.08 Isopropanol 641.24 Butyl methacrylate monomer (BMA) 127.22 Portion 2 Butyl methacrylate monomer 817.23 Methyl methacrylate monomer (MMA) 755.55 Styrene monomer (S) 1066.42 Methacrylic acid monomer (MAA) 329.93 Portion 3 2,2'-Azobis(methylbutyronitrile) 97.58 Toluene 295.06 Portion 4 Methacrylic acid monomer 48.81 Toluene 148.69 Portion 5 2,2'-Azobis(methylbutyronitrile) 1.17 Toluene 12.77 Portion 6 Butyl acetate 2160.71 Portion 7 Propylene imine Total 251.01 8080.00 j 13 235893 14 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 period 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 been 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. Portion 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 to 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 polymer has a composition of about 24% methyl methacrylate, 30% butyl methacrylate, 34% styrene and 12% methacrylic acid postiminated with propylene imine. The resulting polymer has an acid no. of about 2, a number average molecular weight of about 6,800 and a weight average molecular weight of about 10,600.

Four crosslinking polymer solutions were prepared. The polymer of crosslinking polymer solution 1 did not contain acetoacetoxy ethyl methacrylate (AAEM) and is the control. Crosslinking polymer solutions 2,3 and 4 contained acetoacetoxy ethyl methacrylate in the following amounts of 15%, 10% and 5% as shown in the following table: 14 Vtt&w, 235 O Crosslinking Polymer % BMA % GMA % AAEM .1 40 60 0 ■J> 2 40 45 15 3 40 50 10 4 40 55 5 Crosslinking polymer solution 1 was prepared by charging the following ingredients into a reaction vessel equipped as above: Parts bv weight 1 Portion 1 Butyl acetate 1489.26 Toluene 255.11 Ethyl acetate 413.87 Portion 2 Glycidyl methacrylate monomer (GMA) 2331.23 Butyl methacrylate monomer (BMA) 1554.08 Portion 3 Butyl acetate 560.34 2,2'-Azobis(methylbutyronitrile) 186.78 Portion 4 Butyl acetate 143.22 2,2'-Azobis(methylbutyronitrile) 47.74 Portion 5 Butyl acetate 102 0.01 .

Propylene glycol monomethyl acetate 483.20 Total 8484.84 Portion 1 was charged into a reaction vessel and heated to its reflux temperature of about 110-112C. Portions 2 and 3 are each premixed and simultaneously added to the reaction vessel with constant stirring over a 2 hour period while maintaining the resulting reaction mixture at its reflux temperature. Immediately after portions 2 and 3 were added, Portion 4 was added over a 30 minute period and the reaction mixture was held at its reflux r> 235 8 16 7) 3 3 temperature for an additional 30 minutes. Portion 5 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 1.037-1.039. The composition of the polymers was 40% butyl methacrylate and 60% glycidyl methacrylate and had a number average molecular weight of about 2410 and a weight average molecular weight of about 5250.

Crosslinking polymer solution 2 was prepared by charging the following constituents into a reaction vessel described above: Portion 1 Butyl acetate Toluene Ethyl acetate Portion 2 Parts bv Weight 745.00 128.00 207.00 875.00 777.00 291.00 280.00 93.00 72.00 24.00 Glycidyl methacrylate monomer Butyl methacrylate monomer Acetoacetoxy ethyl methacrylate monomer Butyl acetate 2,2'-Azobis(methylbutyronitrile) Portion 3 Butyl acetate 2,2'-Azobis(methylbutyronitrile) 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. Portion 2 was premixed and added at a uniform rate over a 2 hour period while maintaining the reaction mixture at its reflux temperature. Immediately after portion 2 was completely added, Portion 3 was added over a 30 minute 16 235 0 17 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 Gardner Holdt viscosity of about A. The composition of the polymers is 40% butyl methacrylate, 45% glycidyl methacrylate and 15% acetoacetoxy ethyl methacrylate and had a number 10 average molecular weight of about 1,976 and a weight average molecular weight of about 5,303.

Crosslinking polymer solutions 3 and 4 were prepared using the above procedure and constituents except the monomer amounts were adjusted to provide 15 the following compositions: Crosslinking polymer solution 3 - polymer solids 46%, Gardner Holdt viscosity -A, polymer composition 4 0% butyl methacrylate, 50% glycidyl methacrylate, 10% acetoacetoxy ethyl methacrylate; 20 number average molecular weight - 2,650, weight average molecular weight 5,502.

Crosslinking polymer solution 4 - polymer solids 46%, Gardner Holdt viscosity -A, polymer composition 40% butyl methacrylate, 55% glycidyl 25 methacrylate, 5% acetoacetoxy ethyl methacrylate; number average molecular weight - 2,577, weight average molecular weight 5,377. ^ A Clear Polymer Solution was prepared by blending the following constituents: 30 Parts bv Weight Acrylic polymers A solution (prepared 456.51 above) Isopropanol 9.86 Propylene glycol monoethyl ether acetate 31.86 35 Hydrocarbon solvent 10.50 ~\ t J 17 235 8 n 18 Mineral spirits (aromatic controlled) 10.61 UV Stabilizer ("Tinuvin" 328) 2.72 ^ HALS light stabilizer ("Tinuvin" 292) 2.72 ' * Flow control agent ("Acrylon" MFPF from Synthron) 0.39 Slip agent (BYK 325) 0.53 Non-Aqueous Dispersion Rheology Control Agent 12.85 Total 538.55 A Solution was prepared by blending the following constituents: Parts bv Weight Propylene glycol monoethyl ether acetate 30.78 Hydrocarbon solvent 26.69 Ethyl 3-ethoxy propionate 59.56 Butyl Cellosolve Acetate 1.12 Catalyst solution (p-hydroxymethyl benzoate) 7.74 Total 125.89 Clear coating compositions 1,2,3 and 4 were each prepared by mixing 67.38 parts of the above prepared Clear Polymer Solution, 15.78 parts of the J above Solution and 16.84 parts of the respective Crosslinking Polymer Solutions 1,2,3, and 4 together. 25 Each clear coating composition was sprayed onto separate primed steel panel coated with an acrylic lacquer pigmented finish and then cured for about 168 ^ hours at room temperature. In each case, the resulting clear finish was about 2 mils thick. Each panel was 30 tested for tape print resistance and for water spot resistance.

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 35 removed one hour after it was applied and then 1 hour 18 o 235 893 19 after the tape was removed, the finish was inspected for printing resulting from the tape. The time at which no printing from the tape was noted is shown below.

In the water spot resistance test, three drops of distilled waster were applied every 4 hours after application of the finish and the water was allowed to evaporate. After the water evaporated the panel was inspected for distortion of the finish. The 10 time at which no distortion from water was noted is shown below.

Test Tape Print Water Spot Resistance (l) Resistance (2) Coating Comp. 1 (control) 16 hours 20 hours Coating Comp. 2 (15% AAEM) 8 m 8 - Coating Comp. 3 (10% AAEM) 12 " 12 » Coating Comp. 4 ( 5% AAEM) 16 * 12 ";(1) Time in hours when tape did not imprint finish. 20 (2) 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 and were acceptable for an automotive quality finish. 19 9 ^ R po 3 L. ■/ ->

Claims (16)

WHAT WE CLAIM IS;

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 comprises: 5 A. 60-80% by weight, based on the weight of the binder, of an acrylic polymer A •comprising polymerized monomers of methyl methacrylate and 10 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 pendent 15 from the carbon-carbon atoms of the polymer backbone reactive groups selected from the group consisting of aminoester groups of the formula 0 II 20 -C-0-R-NH2 where R is an alkylene group.having 2-3 carbon atoms-, hydroxyamino ester groups of the formula 0 NH- il I 2 25 -C-O-CH,-C-CH,-OH or 2 | 2 H 0 OH 11 1 , -C-O-CH,-C-CH,-NH, and 2 J 2 2 H 30 groups of the formula OH H 1 I 1 -CH-CH2-NR or HNR. OH I 1 I 3 5 -CH CH JFRCE 20 .5 NOV 1991 RECEIVED 21 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 5 "-comprising 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, at least 5% by weight of an alkyl acrylate or alkyl methacrylate having a pendent group of the formula 0 0 II II -0-C-CH2-C-CH3 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; wherein said polymers A and B each have a weight average molecular weight of 5,000-40,000 determined by gel permeation chromatography using polymethyl methacrylate as a standard.

2. The coating composition of claim 1 in which the acrylic polymer A 'comprises 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 pendent from the carbon-carbon atoms of 235893 O 22 the polymer backbone reactive aminoester groups of the formula 0 II -C-0-R-NH2 5 where R is an alkylene group having 2-3 carbon atoms.

3. The coating composition of claim 2 in which the acrylic polymer A comprises . 20-30% by weight, based on the acrylic polymer, of methyl methacrylate, 30-40% by weight,' based on the . . 10 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 15 polymer reacted with an alkylene imine to provide said amino ester groups.

4. The coating composition of claim 1 in which the acrylic polymer A comprises polymerized monomers of methyl methacrylate and' 20 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 J polymer having pendent from the carbon-carbon atoms of the polymer backbone hydroxyamino ester groups of the 25 formula 0 NH, ii I 2 -C-O-CH-CH-CH-OH or 0 OH H I 3 0 -C-0-CH2-CH-CH2-NH2. .

-5. The coating composition of claim 1 in which the acrylic polymer A comprises polymerized monomers of methyl methacrylate and 35 monomers selected from the group consisting of PATENT OFFICE 22 -5 NOV 1991 23 styrene, alkyl methacrylate and alkyl acrylate, having 2-12 carbon atoms in the alkyl group and polymer having pendent from the backbone groups formula OH H I I i -CH-CH2-NRX or HNR. OH -CH—hs. 1 . where R is an alkyl group of 1-8 carbon atoms.

6. The coating composition of any one of claims 1 to 5 in which the acrylic crosslinking .polymer B comprises 3-80% by weight, based on the weight of the acrylic crosslinking polymer, of glycidyl methacrylate or glycidyl acrylate, 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 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 0 0 II II -0-C-CH2-C-CH3«

7. The coating composition of any one of claims 2 to 5 in which the acrylic crosslinking" polymer B comprises 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. each said of the 24

8. The coating composition of any one of claims 1 to 7 containing 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 trifluoride amine complex, phenol,-para methoxy phenol, and parahydroxymethyl benzoate.

9. The coating composition of any one of claims 1 8 containing 0.1-5% by weight, based on the weight of the binder, of ultraviolet light stabilizer.

10. The coating composition of claim 1 in which the binder comprises: 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 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 A. acrylic polymer A which comprises . 20-30% by weight, based 0 M —C-0-R—NH2 where R is an alkylene group having 2-3 carbon atoms; and B. acrylic crosslinking polymer B which comprises . 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, 24 235893 25 of alkyl methacrylate having 4-12 carbons in the alkyl group and 5-57% by weight, based on the weight of the acrylic crosslinking polymer, of acetoacetoxy ethyl methacrylate.

11. The coating composition of any one of claims 1 to 10 containing pigments in a pigment-to-binder weight ratio of 1:100 to 200:100.

12. A coating composition according to claim 1 and substantially as described in this specification with reference to the example.

13. A substrate coated with a dried layer of the composition of any one of claims 1 to 12.

14. The coated substrate of claim 13 in which the substrate is a metal.

15. The coated substrate of claim 13 in which the substrate is a plastic.

16. A substrate coated with a dried layer of a pigmented composition and having a second dried clear layer of the coating composition of any one of claims 1 to 10 and 12 in superimposed adherence thereto. E.fl. DU PONT DE NEMOURS AND COMPANY 25