HIGH SOLIDS PRIMER-GUIDECOATS BASED ON T-BUTYL ACRYLATE AND STYRENE

Abstract: Coating compositions, especially useful as guide coats are produced from copolymers of t-butyl acryiate and sty­ rene which have been crosslinked, preferably with a poly­ epoxide or an etherified amine-formaldehyde resin.

Description: HIGH SOLIDS PRIMER-GUIDECOATS BASED ON T-BUTYL ACRYLATE AND STYRENE BACKGROUND OF THE INVENTION Automobile bodies and related products are generally treated with three different coatings: primer, guide coat and topcoat. The primer is usually applied by electrodeposition or dip-coating and the guide coat and topcoat spray applied. Because the guide coat is usually more highly pigmented than the primer it does not follow the substrate surface contours as closely and therefore provides a smoother surface for sanding. This sanding of the guide coat greatly improves the gloss and distinctiveness-of-image of the topcoat. Moreover, because electrodeposited primers are relatively thin and very soft before baking they are subject to damage and thus the guide coat must also provide corrosion protection to such damaged areas nearly as well as the primer. Most of the guide coats in use today are low solids solvent coatings, such as epoxy-based systems. However, due to the increasing awareness of the environmental dangers posed by solvents as well as increasing solvent costs there is dissatisfaction with such low solids systems. In addition, the guide coat compositions in use today generally employ metals, such as lead or chromium, which are environmentally unfavorable in order to protect against corrosion. It would therefore be of great use to find a high solids coating for use as a guide coat which would provide corrosion protection as well as a satisfactory surface for sanding. In addition, it would also be desirable to have a coating that would be applicable in a form which is commercially useful. It has now been surprisingly discovered that copolymers of t-butyl acrylate and styrene, which have been crosslinked by means well known to one skilled in the art, may be formulated into high solids coatings which provide a high degree of corrosion resistance to steel substrates without the need for toxic inhibitive pigments containing chromates or lead. These coatings possess a high surface hardness which renders them sandable for improved appearance and have an excellent adhesion to typical topcoats. Although coatings containing polymers comprising t-butyl acrylate and styrene (among other monomers) are disclosed in British Patents No. 1,556,456 and l,556,464, these copolymers possess high glass transition temperatures, having a Durran softening point of 90-120 C. Thus, as is apparent to one skilled in the art, these coatings must be applied as either (1) powders or (2) low-solids solutions, since high-solids coatings containing such polymers would be too highly viscous to be utile. Therefore coatings employing these polymers are comparatively uneconomical as the use of powders would necessitate the formation of relatively thick coatings (of at least about 1.5 mil) while the use of a low solids solution would require the employment of relatively large amounts of solvent. Thus, it was completely unexpected that polymers of t-butylacrylate and styrene could be produced which had comparatively low glass transition temperatures (i.e., of less than about 500C) and which would additionally possess sufficient hardness to be employed as a guide coat. * (38.1 Pom)' DESCRIPTION OF THE INVENTION This invention is directed to copolymers, and to coating compositions containing such copolymers, which provide a high degree of corrosion resistance to steel substrates and which possess a high surface hardness. These coating compositions are made up of which) comprised of: (a) from about 10 to about 90 weight percent, preferably from about 20 to about 70 weight percent, of t-butyl acrylate; (b) from about 5 to about 50 weight percent, preferably from about 10 to about 40 weight percent, of styrene; and (c) from about 1 to about 30 weight percent, preferably from about 5 to about 20 weight percent of functional comonomers containing. at least one active site, which is capable of reacting with a crosslinker such that a crosslink is produced, and (d) from 0 to about 85 weight percent, preferably from about 5 to about 50 weight percent, of other ethylenically unsaturated monomers which are capable of polymerizing with't-butyl acrylate and styrene. The term active site refers to a location on the comonomer which is capable of reacting with the crosslinker selected such that a crosslink is produced. Among the preferred active site containing comonomers which may be employed are those which, when reacted with t-butyl acrylate and styrene will produce a copolymer possessing active carboxyl, hydroxyl, or amide group, or mixtures thereof. Illustrative of such carboxyl group producing monomers are &alpha;,ss-unsaturated carboxylic acids such as, for example, acrylic acid, methacrylic acid, a-chloroacrylic acid, itaconic acid, crotonic acid, aconitic acid, maleic acid, fumeric acid and the like. Half acid esters of the dicarboxylic acids can also be used, such as methyl hydrogen itaconate, butyl hydrogen itaconate, ethyl hydrogen maleate, and the like. Mixtures of these acids can also be used. The preferred carboxyl group producing monomers are acrylic acid and methyacrylic acid. Illustrative of active hydroxyl group producing monomers are mono- and polyhydroxyl alkyl esters of acrylic acid and methacrylic acid such as 2-hydroxyethyl acrylate and methacrylate, 2-hydroxypropyl acrylate and methacrylate, 3-hydroxypropyl acrylate and methacrylate, 2-bydroxybutyl acrylate and methacrylate, 3-hydroxybutyl acrylate and methacrylate, 4-hydroxybutyl acrylate and methacrylate, 5-hydroxyamyl acrylate and methacrylate, 6-bydroxyhexyl acrylate and methacrylate, 8-hydroxyoctyl acrylate and methacrylate, 2,3-dihydroxypropyl acrylate and methacrylate, 2,3-dihydroxybutyl acrylate and methacrylate and the like Mixtures of these hydroxyalkyl esters can also be used. The preferred hydroxyalkyl esters are hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate. Illustrative of active amide group producing monomers are monomers such as acrylamide, methacrylamide and the like. Illustrative of other ethylenically unsaturated monomers which are capable of polymerization with t-butyl acrylate and styrene, and which may be incorporated into the copolymer are acrylic esters and methacrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, sec-butyl acrylate, n-amyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, 3,5,5-trimethylhexyl acrylate, decyl acrylate, dodecyl acrylate, hexadecyl- acrylate, octadecyl acrylate, octadecenyl acrylate, n-amyl methacrylate, sec-amyl methacrylate, hexyl methacrylate, 2-ethylbutyl methacrylate, octyl methacrylate, 3,5, 5-trimethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, butoxyethyl acrylate or methacrylate or other alkoxyethyl acrylate or methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, sec-butyl methacrylate, and t-butyl methacrylate, t-amyl methacrylate, t-amyl acrylate, cyclohexyl acrylate or methacrylate, and the like; as well as other ethylenically unsaturated monomers, such as ethylene, butadiene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylonitrile, methacrylonitrile, and the like. The polymers should be produced such that they possess an average molecular weight of from about 1,000 to about 25,000, preferably of from about 3,000 to about 15,000. These polymers should possess a glass transition temperature of less than about 500C, preferably less than about 400C. Typically, the copolymers employed in the compositions of the instant invention are prepared by reacting a monomer feed mix (containing t-butyl acrylate, styrene1 a functional comonomer having at least one active site, and optionally other ethylenically unsaturated monomers) with a catalyst feed mixture at an elevated temperature. The polymers of this invention may be prepared by any standard polymerization process including free radial, anionic, etc. However, a telomerization process wherein a monomer which is a chain transfer agent such as a mercaptan is incorporated into the copolymer is preferred. Illustrative of the mercaptan chain-transfer agents which may be employed are butyl mercaptan, mercaptoacetic acid, mercaptoethanol, 3-mercapto-l,2-propanediol and 2-methyl-2-propanethyol, t-dodecyl mercaptan, phenyl mercaptan, pentaerythritol tetramercaptopropionate, octyldecyl mercaptan, tetradecyl mercaptan, and the like. The catalyst employed in the polymerization reaction is typically a free radical initiator or a redox catalyst. One can mention, as merely illustrative of suitable catalysts which can be employed, free radicals initiators such as hydrogen peroxide, peracetic acid, t-butyl hydroperoxide, di-t-butyl peroxide, dibenzoyl peroxide, benzoyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2,5-dimethyl-2,5-bis-(hydroperoxy) hexane, perbenzoic acid, t-butyl peroxypivalate, t-butyl peracetate, azo-bis-isobutylonitrile, ammonium persulfate, potassium persulfate, sodium perphosphate, potassium perphosphate, isopropyl peroxycarbonate, and the like; and redox catalyst systems such as sodium persulfate-sodium formaldehyde sulfoxylate, cumene hydroperoxide-sodium metabisulfite, hydrogen peroxide-ascorbic acid, sulfur dioxide-ammonium persulphate, and the like. The catalysts are employed in the usual catalytically effective concentrations which are known to those skilled in the art of polymerization. The polymerization is typically carried out in the presence of an organic solvent which will not interfere with the polymerization reaction. Illustrative of the solvents which may be employed are ethoxyethyl acetate, methylene chloride, ethanol, iso-propanol, n-propanol, n-butanol, iso-butanol, tert,-butanol; the methyl, ethyl, propyl or butyl esters of acetic acid; acetone, methyl ethyl ketone, benzene, toluene and the like. The reaction may be carried out at a temperature of from about 50 C to about 1600C, with a preferred temperature of from about 90 C to about 1300e, The reaction may be performed at sub- or superatmospheric pressures, with atmospheric pressure being preferred. Reaction time is not critical and may vary from less than several hours to several days or more depending upon the reaction batch size, pressure, temperature, etc. selected. The coating compositions of this invention comprise mixtures of (1) the novel t-butyl acrylate/styrene/functional monomer/(optionally other ethylenically unsaturated monomer) copolymer of the instant invention, (2) a suitable crosslinker and (3) suitable additives that are known to one skilled in the art of coating formulations. Illustrative of such additives are pigments and fillers, such as titanium dioxide, and the like; flow and leveling aids such as silcone surfactants, fluorocarbon based surfactants and the like; pigment dispersants; etc. These coating compositions may be blended by means well known to one skilled in the art. The novel compositions of this invention may be formulated into high solids coatings, i.e., as much as 75 weight percent or higher, although this figure may vary in accordance with the solvent selected, the viscosity desired, application temperature, etc. The crosslinkers which may be employed will vary with the type of functional crosslinking sites on the copolymer copolymer employed. Thus, for copolymers containing active hydroxyl groups crosslinkers including polyepoxides (such as cycloaliphatic epoxides and diglycidyl epoxides), polyfunctional isocyanates, etherated amino-formaldehyde resins, etc. and mixtures thereof may be employed. For copolymers containing active carboxyl groups crosslinkers including including polyepoxides (such as cycloaliphatic epoxides and diglycidyl epoxides), aziridines, carbodiimides, etherated amino-formaldehyde resins, etc. and mixtures thereof may be employed. For copolymers containing active amide groups, crosslinkers including polyfunctional isocyanates, polyepoxides (such as cycloaliphatic epoxides and diglycidyl epoxides), etherated amino-formaldehyde resins, etc. and mixtures thereof may be employed. For copolymers which contain mixtures of active hydroxyl carboxyl and/or amide groups, mixtures of suitable crosslinkers may be utilized. preferred crosslinkers include polyepoxides and etherated amino-formaldehyde resins, as these crosslinkers are reactive with active hydroxyl, carboxyl and amide groups. Illustrative of the polyfunctional isocyanates which may be employed for copolymers containing active hydroxyl and/or amide sites are 3,5,5-trimethyl-1-isocyanatomethyl-cyclohexane, (di(2-isocyanatoethyl)-bicyclo(2.2.1) hept-5-ene-2, 1-dicarboxylate, 2,4tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, dianisidine diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, the m- and p-xylylene diisocyanates, tetramethylene d.iisocyanate, dicyclohexyl- 4,4'-methane diisocyanate, cyclohexane l,4-diisocyan'ate, 1,5-naphthylene diisocyanate, 4,4'-diisocyanate diphenyl ether, 2,4,6-triisocyanate toluene, 4,4',4"-triisocyanate triphenyl methane, diphenylene-4, 4-diisocyanate, the polymethylene polypbenylisocyanates and the like. Illustrative of the polyepoxides which may be employed are the cycloaliphatic epoxides which are described in U.S. Patents No. 3,027,357, NO. 2,890,194 and No. 2,890,197 (especially column 7, line 11 to column 7, line 38 of NO. 3,027,357), including 3,4-epoxycyclomethylhexylmethyl-3,4-epoxycyclohexane carboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, bis(2,3-epoxycyclopentyl)ether, vinyl cyclohexene dioxide, 2-(3,4-epoxycyclohexyl)- 5, 5-spiro- (2,3-epoxycyclohexane)-m-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, endo- and exo-dicyclopentadiene diepoxide, limonene diepoxide, and the like. illustrative of the amino-formaldehyde resins which are a r z u useful are hexabismethoxymethyl- melamine, dimethylol ethylene urea, tetramethylol acetylene diurea, tris methoxymethylmelamine, various methyl, butyl, isobutyl ethers of melamine-formaldehyde adducts, various methyl, butyl, isobutyl ethers of benzoguanamineformaldehyde and the like. In general, the amount of crosslinker will be dependent on the equivalent weight of the crosslinker used, the inherent flexibility of the crosslinker used, the reactivity of the crosslinker with itself, and the degree of hardness/softness or flexibility desired in the final coating. These amounts will vary with the particular functional monomer and crosslinker combination selected and will be known to one skilled in the art. The catalyst employed in the crosslinking reaction, if indeed a catalyst is required for the given active site/crosslinker combination, will vary in accordance with the particular active site/crosslinker combination chosen. The amounts and types of catalysts necessary will be well known to one skilled in the art. Thus, for example with etherated amine-formaldehyde resin crosslinkers catalysts such as p-toluene sulfonic acid, naphthalene sulfonic acid, phosphoric acid, dinonyl naphthalene disulfonic acid, or the stannous salt of trifluoromethane sulfonic acid and the like can be used. With cycloaliphatic epoxides catalysts such as stannous octanoate, dibutyltin dilaurate, triflic acid, the reaction product of triflic acid and stannous oxide, diethyl ammonium triflate, and the like can be used. Although particularly useful as guidecoats, the compositions of the instant invention may also be used on any surface in which their sanding and/or anticorrosive properties may be taken advantage of. EXAMPLES The following examples are intended to further illustrate the invention and are not intended to limit the scope of the invention in any manner. Example 1 A t-butyl acrylate/styrene/n-butyl acrylate/2-hydroxyethyl acrylate cotelomer was prepared for use in a coating formultion in the following manner. Two feed mixtures were prepared from the following ingredients. Monomer Feed Mixture Catalyst Feeding Mixture Styrene l20g VAZO-52* 10g t-Butyl Acrylate 267g 2-Ethoxyethyl Acetate 113g n-Butyl Acrylate 138g 2-Hydroxyethyl acrylate 75g t-dodecyl mercaptan 18g 2-Ethoxyethyl acetate 43g *VAZO-52 = 2, 2' -azobis (2,4-dimethylvaleronitrile) The cotelomerization was carried out in a 2-liter resin kettle equipped witn a stirrer, reflex condenser, temperature controller, separate monomer and catalyst feed lines controlled with volumetric displacement pumps, and a sampling tube. The kettle was charged with 44g. of ethoxyethyl acetate and heated to 1100C, Then the catalyst feed was started. Ten minutes later the monomer feed was started. After 173 minutes all of the monomer mixture had been fed to the reactor, and the catalyst feed was completed after another 12 minutes. During the feed period the temperature was maintained between 105QC and 1240C, The reaction mixture was then cooked out for an additional 114 minutes at ll3-ll40C at which time the heat was turned off. The solution of cotelomer in 2-ethyoxyethyl acetate was allowed to cool to room temperature and then the 800 grams of a golden-yellow colored solution of cotelomer had a Ubbelohde viscosity of 1860 cks at 300C and a glass transition temperature of 50C as measured by a differential scanning calorimeter. Comparative Experiment A A t-butyl acrylate/ethyl acrylate/acrylic acid cotelomer was prepared for use in a coating formatulation in the following manner. Two feed mixtures were prepared from the following ingredients. Monomer Feed Mixture Catalyst Feeding Mixture t-Butyl acrylate 360g VAZO-52 10g Ethyl acrylate 150g Ethoxyethyl acetate 113g Acrylic acid' 90g 2-Ethoxyethyl acetate 43g t-Dodecyl mercaptan 18g The cotelomerization was carried out in a 2-liter, glass resin kettle equipped with a stirrer, reflux condenser, temperature controller, separate monomer and catalyst feed lines, and a sampling tube in the following manner. Forty-four grams of 2-ethoxyethyl acetate (kettle charge) were charged to the reactor and heated to 117 C. Then the catalyst feed was started. Ten minutes later the monomer feed was started. After 175 minutes, all of the monomer mixture had been fed to the reactor; and 15 minutes later the feeding of the catalyst mixture was complete. During this time the temperature was maintained at 110 to 1240C. The reaction mixture was then cooked out for another 58 minutes at 113-1l40C at which time the heat was turned off. The solution of cotelomer in, 2-ethyoxyethanol acetate was allowed to cool to room temperature and then 800 grams of a golden-yellow colored solution were collected as a residue product. Duplicate analyses indicated that the solution contained 74.3% of the cotelomer. The solution of cotelomer had a mPa. 5) Brookfield viscosity of about 13,000-14,000 B at room temperature. It had a weight average molecular weight of 10,000 as determined by gel permeation chromatography using a calibration based on polystyrene. Example 2 A t-butyl acrylate/i-propyl acrylate/styrene/2-hydroxyethyl acrylate cotelomer was prepared in a manner similar to Example 1. The feed mixtures were prepared from the following ingredients: Monomer Feed Mixture Styrene 85.4g. t-butyl Acrylate 36.3g. i-propyl Acrylate 252g. 2-hydroxyethyl Acrylate 53.4g. 5-dodecyl mercaptan 12.8g. 2-ethoxyethyl Acetate 24.6g. Catalyst Feed Mixture VAZO-52 7.1 g. 2-ethoxyethyl acetate 8b.4 g. Kettle Charge 2-ethoxyethyl 31.3 g. acetate The residue product, 71.88 solids, had a Ubbelohde viscosity of 2631*6 cks and a glass transition temperature of 0 C. Example 3 A stable, one-package, high solids guide coat was prepared with the cotelomer resin described in Example 1. A pigment grind was prepared by adding the following list of ingredients to a ball mill and grinding overnight to give a fineness of grind of > 7 on a Hegman g Xge. PIGMENT GRIND Ex. 1 cotelomer solution 200 g. (70.95% total solids) Rutile TiO2 42.6 g. Barium sulfate 200.8 g. Aluminum silicate ' - 156.8 g. Attapulgite clay # 4.16 g. Carbon black - 1.79 g. After grinding, the pigment grind was removed, the ball mill was washed with 33 g. of 2-ethoxyethyl acetate which was added to the grind. The paint formulation was made of the following ingredients. GUIDE COAT FORMULATION PIGMENT GRIND 150 g. etherated amine-formaldehyde , 11.3 g. 2-ethoxyethyl acetate 2.75 g. *Cymel 325TM, American Cyanamid, a commercially available product This formulation contained 65.88 solids and had a 2 Zahn Cup viscosity of 25.8 sec. The coating was applied by conventional air spray techniques onto 3" x 9" 20 gauge unpolished Parker steel test panels pretreated with a corrosion prohibiting pretreatment, Bonderite EP-1/P-6OTM Parker. The lower half of the panel had been sanded to bare metal prior to application of the guide coat. The panels were baked for 30 minutes at 1600C in a forced air oven to give a dry film thickness of a. 2-1.4 mils) 30.5 - 35.6 clam. The guide-coated panels were sanded to the thickness showing in Table II, below, and top coated with a topcoat which consisted of 55 weight percent DuPont Lucite Acrylic Lacquer White Wald -3967 and 45 weight percent 3840 STD Red Acrylic Thinner (Grow Group, Inc.) (both of which are commercially available products). The thickness of the topcoat applied is listed in Table II. Comparative Experiment B A two-package, high solids coating of the cotelomer prepared and described in Comparative Experiment A was prepared in the same manner as described in Example 3 The ingredients used were as follows: Pigment Grind Exp. A Cotelomer solution 75 g. (74.3%total solids) Rutile titanium dioxide 20.6 g. Barium sulfate . 97 g. Aluminum silicate 75.8 g Attapulgite clay 1.96 g. Carbon black 0.79 g. 2-ethoxyethyl acetate 100 g. Paint Formulation Pigment Grind 200 g. ERL-4221* 22.9 g. Stannous octanoate 0.13 g. 2 ethoxyethyl acetate 19 g. *ERL-4221 = 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclo hexane carboxylate This paint formulation, which contained 65.58 total solids and had a t2 Zahn Cup viscosity of 26.7 seconds, was then air sprayed onto Bonderite EP-1/P-60 Parker test panels as described in Example 3 and cured in a forced air oven at 1600C for 30 minutes. The panels were then sanded and topcoated as described in Example 3 above Example 4 A one package, high solids guide coat was prepared from the cotelomer described in Example 2 in the same manner as described in Example 3. The ingredients used were as follows: Pigment grind Ex. 3 cotelomer solution 100 g. (71.8% total solids) Rutile titanium dioxide 21.6 g. Barium sulfate 101.5 g. Aluminum silicate 79.3 g. Attapulgite clay 2.1 g. Carbon black 0.9 g. 2-ethoxyethyl acetate 100 g. paint Formulation Pigment grind, 70.6% Total solids 150 g. 2-ethoxyethyl acetate 18 g. etherated amine-formaldebyde* 11.4 g. *Cymel 325TM This paint formulation, which contained 65.4% total solids and had a &num;2 Zahn Cup viscosity of 26.5 seconds, was then air sprayed onto Bonderite EP-1/P-60 Parker-test panels as described in Example 3 and they were cured in a forced-air oven at 160 C for 30 minutes. The panels were then sanded and topcoated as described in Example 3, above. Comparative Experiment C In order to compare the coatings of the instant invention against a commercially employed guidecoat, Inmont &num;2 was sprayed on test panels as described in Example 3. The panels were then heat cured, sanded and topcoated as described in Ei1e 3 above. The formulation of Examples 3 and 4 and of Comparative Example B and C were tested for their utility as guide coats by the following means: Salt Spray ASTM-B117-57T This test was conducted briefly as follows: Panels were scribed from top to bottom corner and subjected to continuous exposure of 5 percent salt fog at(94 + 2 Ft. After exposure for a given interval of time the coating was scratched along the scribe to remove any loosely bound coating and rated for Scribe, Field and Blush according to the rating system shown in Table I. A higher rating number indicated better performance. Scribe (S) indicated the extent of rusting along the scribe line, Field (F) indicates the face rusting on the panel, and Blush (B) gives the extent of delamination of the coating along the scribe. The difference between S and B is that while the former represents the delamination of the filr.l over the rusted area, the latter represents the delamination over the rusted as well as the non-rusted area. * 34.4 + 1.1 C TABLE I SALT SPRAY RATING SYSTEM FOR CORROSION RESISTANCE EVALUATION (a): Scribe and Blush Scribe Blush Measurement of Measurement of Failure Rating Failure (Rusted Area) (Rusted + Non-Rusted Area) Number From the Scribe From the Scribe in. mm in. mm 10 0 o . o o 9 1/64 0.4 1/64 0.4 8 1/32 0.8 1/32 0.8 7 1/16 1.6 1/16 1.6 6 1/8 3.2 1/8 3.2 5 3/16 4.8 3/16 4.8 4 1/4 6.4 1/4 6.4 3 3/8 9.5 3/8 9.5 2 1/2 12.7 1/2 12.7 1 5/8 15.9 5/8 15.9 0 I or more 20 or more 1 or more 20 or more (b): : FIELD RATING - FACE STING (RATING) OF AREA OTHER THAN SCRIBE AND BLUSH) Rating Description and Number Percent Failure 10 No failure 9 1% failure 8 2% failure or blister 7 5% failure, blister or haze 6 7-10% failure, blister or haze 5 7-10% failure, with spots 4 11-25% failure 3 26-40% failure 2 41-59% failure 1 60-75% failure 0 75-100% failure Rating: 10 = Perfect, 1 = Poor TABLE II SALT SPRAY TESTING OF LUCITE ACRYLIC LAQUER OVER GUIDE COATINGS RATINGS GUIDE THICKNESS PORTIONÚ COATING GUIDE TOPCOAT OF PANEL 168 HOURS 336 HOURS SCRIBE FIELD BLUSH SCRIBE FIELD BLUSH (mils) m (mils) m 3 (0.7) 17.8 (1.5) 38.1 Top 10 10 10 - - 3 (0.7) 17.8 (1.5) 38.1 Bottom 10 10 6 - - 4 (0.8) 20.3 (1.9) 48.3 Top 10 10 10 10 10 10 4 (0.8) 20.3 (1.9) 48.3 Bottom 10 10 5.5 10 10 5 B (0.8) 20.3 (2.3) 58.4 Top 10 10 10 9 10 8 B (0.8) 20.3 (2.3) 58.4 Bottom 10 10 0 9 10 0 C (0.8) 20.3 (2.2) 55.9 Top 8 10 8.5 8 10 8 C (0.8) 20.3 (2.2) 55.9 Bottom 8 10 4 8 10 2 1 Bonderite EP-1/P-60 treated Parker test panels, bottom half of panel sanded to bare steel prior to guide coat application. - Not tested. The data in Table II clearly indicates the superiority of the compositions of the instant invention as these compositions provide enhanced protection against delamination vis-a-vis commercially used guide coats and those not containing styrene. This is most clearly evidenced by the Blush tests of the bottom half of the panels Because the steel on the bottom half of the panels does not contain any anti-corrosive treatment, this test section corresponds to those areas of an automobile body where the primer has been damaged and where, therefore, the guide coat must provide protection against corrosion.Thus the compositions of the instant invention possess characteristics which make them particularly useful as guide coats.

Claims: WHAT IS CLAIMED IS: 1. A copolymer possessing a glass transition temperature of less than about 500C which is comprised of: (a) from about 10 to about 90 weight percent of t-butyl-acrylate; (b) from about 5 to about 50 weight percent of styrene; (c) from about 1 to about 30 weight percent of a functional comonomer containing at least one active crosslinking site which is capable of reacting with a crosslinker such that a crosslink is produced; and (d) from about 0 to about 85 weight percent of other ethylenically unsaturated monomers which are capable of polymerizing with t-butyl acrylate and styrene, wherein the weight percent of components (a) through (d) are based on the total weight of the copolymer- 2. The copolymer of claim 1 wherein t-butyl acrylate is present in an amount of from about 20 to about 70 weight percent. 3 or 2 The copolymer of claim 1 wherein styrene is present in an amount of from about 10 to about 40 weight percent. of any one to 3 4. The copolymerofclaimsl wherein the functional monomer is present in an amount of from about 5 to about 20 weight percent. any one to 5. The copolymer of any one of claims to 4 wherein the ethylenically unsaturated monomer, component (d), is present in an amount of from about 5 to about 50 weight percent. of any one to 5 6. The copolymer of claims 1 wherein the functional monomer is one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and mixtures thereof. 7. A coating composition made up of: (1) a copolymer of any one of claims 1 to 6, (2) a suitable crosslinker; and (3) suitable additives. 8 The coating composition of claim 7 wherein the crosslinker, component (2), is an etherified amino-formaldehyde resin. 9. The coating composition of claim 7 wherein the crosslinker, component (2), is a polyepox ide. 10. The coating composition of claim 9 wherein the polyepoxide is a cycloaliphatic epoxide or a diglycidyl epoxide Claims for Austria 1. A process for preparing a copolymer possessing a glass transition temperature of, less than about 500C which is comprised of: (a) from about 10 to about 90 weight percent of t-butyl-acrylate; (b) from about 5 to about 50 weight percent of styrene; (c) from about 1 to about 30 weight percent of a functional comonomer containing at least one active crosslinking site which is capable of reacting with a crosslinker such that a crosslink is produced; and (d) from about 0 to about 85 weight percent of other ethylenically unsaturated monomers which are capable of polymerizing with t-butyl acrylate and styrene wherein the weight percent of components (a) through (d) are based on the total weight of the copolymer, by polymerizing a monomer feed comprising t-butylacrylate,styrene, a functional comonomer containing at least one active crosslinking site which is capable of reacting with a crosslinker such that a crosslink is produced; and optionally other ethylenically unsaturated monomers which are capable of polymerizing with t-butyl acrylate and styrene, in the presence of a catalyst and in the presence of an organic solvent. 2. The process according to claim 1 for producing a copolymer wherein t-butyl acrylate is present in an amount of from about 20 to about 70 weight percent. 3. The process according to claim 1 or 2 for producing a copolymer wherein st-yrene is present in an amount of from about 10 to about 40 weight per cent. 4. The process according to any one of claims 1 to 3 for producing a copolymer wherein the functional monomer is present in an amount of from about 5 to about 20 weight percent. S The process according to any one of claims 1 to 4 for producing a copolymer wherein the ethylenically unsaturated monomer, component (d), is present in an amount of from about 5 to about 50 weight percent. 6. The process according to any one of claims 1 to 5 for producing a copolymer wherein the functional monomer is one of acrylic acid,methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and mixtures thereof. 7. The use of the copolymer as produced according to any one of claims 1 to 6 in a coating composition made up of (1) the copolymer, (2) a suitable crosslinker; and (3) suitable additives. 8. The use according to claim 7 wherein the crosslinker, component (2), is an etherified amino-formaldehyde resin. 9. The use according to claim 7 wherein the crosslinker, component (2), is a polyepoxide. 10. The use according to claim 9 wherein the polyepoxide is a cylcoaliphatic epoxide or a diglycidyl epoxide.

Inventors: KOLESKE, JOSEPH VICTOR, SHERWIN, MAYNARD ARTHUR
Applicants: UNION CARBIDE CORPORATION
Application year: 1983
Main classification: C08F220
IPC codes: C09D133, C08L63, C08F212, C08F220, C08G18, C08F20, C08L61