HIGHLY WEATHERABLE COATINGS

Abstract: Copolymers which are comprised of from about 10 to about 90 weight percent t-butyl acrylate, and which possess a glass transition temperature of less than about 50 °C, are formulated into crosslinked coating compositions which possess unexpectedly superior weathering resistance.

Description: HIGHLY WEATHERABLE COATINCS any coatings are used on surfaces which are employed in an outdoor environmeDt. Such coatings are exposed to sunlight, moisture and the like under a variety of temperarure conditions and must therefore be able to withstand such changes in climate. Among the preferred veatherable coatings are those based on acrylic polymers. However, after long exposures of time even these coatings will suffer deterioration at a pace which is dependent upon the geographical area involved. As a result, several additives have been incorporated into coating formulations to slov down the degradative process Among the more commonly employed additives are those which protect against ultraviolet radiation and hydrolytic attack. Hovever, incorporation of such additives increases the cost of producing weatherable coatings. Thus it would be desirable to produce a highly veatherable coating which did not require the presence of such, expensive additives. In addition, many of the weatherable coatings heretofore employed utilize relatively large amounts of volatile organic solvents. With the rising price of energy, as vell as the increased appreciation of the deleterious effects of organic solvents on the environment, it would be desirable to produce a- weatherable coating which employed only s minimal amount of volatile organic solvent. Among the compositions which have been developed in response to such need for highly weatberable coatings are those disclosed in British Patents No. 1,556,436, and 1,536,464 which contain copolymer: consisting of 50-75 weight percent t-butyl acrylate; 5-30 weight percent styrenes vinyltoluene or methyl methacrylate; and 4-20 weight percent of acrylonitrile. However, these copolymers, which are cured by crosslinking with an aliphatic dicarboxylic acid, possess high glass transition temperatures as they have a Durran softening point of 9Q-120gC. 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 vould te too highly viscous to be utile. Therefore coatings employing these polymers are compsratively uneconomical as the use of povders would necessitate the formation of relatively thick 38 urn - coatings (of at least about 1.5 mil) vhereas a lov solids solution would require the use of relatively large amounts of solvent. Thus, it was completely upexpected that polymers of t-butyl acrylate could be produced which had comparatively lov glass transition temperatures i.e. of less than about 50 C) and which when formulated into coating compositions vould possess desirable veatherable properties Moreover, because of such low glass transition temperatures, coatings employing these novel polymers may be employed in a high solids solution form thus permitting economical use of both the polymers and organic solvent. DESCRIPTION OF THE INVENTION This invention is directed to polymers vhich, vhen formulated into coating compositions, demonstrate a high degree of outdoor veatherability. These polymers are lov molecular weight copolymers having a glass transition temperature of less than about 50'C which are comprised of: : (a) from 10 to 90 weight percent, preferably of from 20 veight percent or units derived thereof to 70 weight percent, t-butyl acrylate/ (b) from 1 to 30 weight percent, preferably of from 5 to about 20 weight percent, of a functional comonomer containing or units derived thereof at least one active crosslinking sit; and (c) from 0 to 85 weight percent, preferably of from 5 to 60 weight percent of other ethylenically unsaturated monomers which are capable of polymerizing with t-butyl acrylate or units derived thereof. The term active crosslinking site refers to a location on the comonomer which is capable of reacting with the crosslinker employed such that a crosslinkage is produced. Among the preferred functional comonomers which may be employed are those vhich, when reacted with t-butyl acrylate will produce a copolymer possessing an active carboxyl group, hydroxyl group, and/or amide group. If desired, mixtures of active carboxyl group producing monomers, active hydroxyl group producing monomers and/or active amide producing group monomers may be employed. Illustrative of such carboxyl group producing monomers are alpha-unsaturated carboxylic acids such as, for example, acrylic acid, methacrylic acid, a -ch lo roa cry 1 ic 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 methylhydrogen itaconate, butyl hydrogen itaconate, ethyl hydrogen maleate, and the like. Mixtures of these acids can also be used. The preferred active carboxyl group producing monomers are acrylic acid and methyacrylic acid. Illustrative of active hydroxyl group producing monomers are monohydroxy- and polyhydroxy asters of acrylic acid and methyacrylic acid, such as, for example, 2-hydroxyethyl acrylate and methacrylate, 2-hydroxypropyl acrylate and methacrylate, 3-hydroxypropyl acrylate and methacrylate, 2-hydroxybutyl acrylate and methacrylate, 3-hydroxybutyl acrylate and methacrylate, 4-hydroxybutyl acrylate and methacrylate, 5=hydroxyamyl acrylate and methacrylate, 6-hydroxyhexyl acrylate, and methacrylate, 8-hydroxyoctyl acrylate and methacrylate, 2,3-dihydroxypropyl acrylate and methacrylate; 2,3-dihydroxybutyl acrylate and methacrylate, and the like. Hixtures 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. In addition to the t-butyl acrylate and functional comonomer components, the copolymer may additionally contain other ethylenically unsaturated monomers which are capable of copolymerization vith t-butyl acrylate. These comonomers may be added to the polymerization mixture to achieve desired effects well knovn to one skilled in the art However, it is desirable that the incorporation of these monomers not raise the glass transition temperature of the resultant copolymer above about 509C so that such copolymers produced may be employed in high solids coating compositions. Exemplary of such ethylenically unsaturated monomers are acrylic esters and methacrylic esters such as for example 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-trimethyihexyl 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 methacrylatec, methylmethacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, t-amyl methacrylate, t-amyl acrylate, cyclohexyl acrylate or methacrylate, and the like; as well as other q , B-ethylenically unsaturated monomers such as styrene, ethylene, butadiene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylonitrile, methacrylonitrile, and the like. The copolymers of this invention may be prepared by any standard polymerization process including free radical, anionic, etc. Hovever, a telornerization process wherein a mercaptan is employed as the chain transfer agent is preferred. Illustrative of the mercaptan chain-transfer agents which may be employed are butyl mercaptan, mercaptoacetic acid, mercaptoethanol, 3-mercapvo-1,2-propanediol and 2-methyl-2-propane thiol, t-dodecyl mercaptan, phenyl mercaptan, pentaerythritoi tertramercaptopropionate, octyldecyl mercaptan, tetradecyl mercaptan, and the like. Typically, the copolymers of the instant invention are prepared by reacting monomer feed mix (containing t-butyl acrylate, a functional comonomer having at least one active crosslinking site, and optionally other reactive monomers) with a catalyst feed mixture pt an elevated temperature in the presence of an organic solvent. The catalyst employed is typically a free radical initiator or a redox catalyst. One can mention, as merely illustrative of suitable catalysts which can be employed, free radical 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-isobutyronitrile, ammonium persulfate, sodium persulfate, potassium persuifate, sodium perphosphate, potassium perphosphate, isopropyl peroxycrbonate, and the like; and redox catalyst systems such as sodium persulfate-sodium formaldehyde sulfoxylate, cumene hydroperoxide-sodium me-tabisulfite, hydrogen peroxide-ascorbic acid, sulfur dioxide-ammonium persulphate, and the like; etc.. The catalysts are employed in the usual catalytically effectiçe concentrations which are known to those skilled in the art of polymerization. Typically, the polymerization process vill require the use of a solvent. The solvents which may be employed are thost organic solvents which vill not interfere vith the polymerization reaction. These solvents are vell known to one skilled in the art. Illustrative of such solvents are ethoxyethy' 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. In general, the polymerization reaction is carried out at a temperature of from about 50 C to about 1600C, vith a preferred temperature of from about 900C to about 1300C. However, this range will vary depending upon the particular catalyst or catalyst system selected. Reaction pressure may vary from subatmospheric to superatmospheric with atmospheric pressure being preferred. Reaction time is not critical and may vary from hours to days depending upon the reaction batch size, pressure, temperature,. etc. selected. The coating compositions of this invention comprise mixtures of (1) the novel t-butyl acryla te/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 ;n the art of coating formulations. Illustrative of such additives are pigments and fillers, such an 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 vell 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, the application temperature selected, etc. The crosslinkers which may be employed will vary with the type of functional crosslinking sites which are present on the copolymer selected. Thus, for copolymers containing active hydroxyl groups crosslinkers including polyepoxides (such as cycloaliphatic epoxides snd- diglycidyl epoxides), polyfunctional isocyanates, etherated amino-formaldehyde resins, etc. and mixtures thereof may be employed. For copolymers containing active carboxyl groups crosslinkers 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 resins1 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-isocyanato-3-isocyanatomethyl-cyclohexane, di(2-isocyanatoethyl)-bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylate, 2,4-tÏlylene diisocyanate, 2,6-tolylene diisocyanate, 4,4' -diphenylmethane diisocyanate, dianisidine diisocyanate, hexamethylene diisocyanate, the m- and p-xylylene diisocyanates, te tramethylene diisocyanate, dicyclohexyl4,4'-methane diisocyanate, cyclohexane1,4-diisocyanate, l,5-naphthylene diisocyanate, 4,4'-diisocyanate diphenyl ether, 2,4,6-tri isocyanste toluene, 4,4µ,4"-triisocyanate triphenyl methane, diphenylene-4,4-diisocyanate, the polymethylene polyphenylisocyanates and the like. Typical representatives of the polyepoxide crosslinkers which may be employed are the cycloaliphatic epoxides 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 7s line 38 of No. 3,027,357), including 3.4-epoxycyclohexyl- methyl-314-epoxycyclohexane carboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, bis(2,3-epoxy cyclopentyl)-ether, vinyl cyclohexene dioxide, 2-(3,4-epoxycyclohexyl)-5,5-spiro-(2,3 epoxycyclohexane)-m-dioxane, bis(3,4 epoxycyclohexylmethylzadipate, endo- and exo-dicyclopentadiene diepoxide, limonene diepoxide, and the like. Illustrative of the amino-formaldehyde resins which are useful are hexaki smethoxymethylmelamine, dimethylol ethylene urea, tetramethylol acetylene didres, tris methoxymethylmelamine, the methyl, butyl, isobutyl ethers of mel amine-formaldehyde adducts and the like; the methyl, butyl, isobutyl ethers of benzoguanamine-formaldehyde; tetra-alkyl glycoluril and the like, etc. In general, the amount of crosslinker employed 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 vith the particular functional monomer and crosslinker combination selected, and will be known to one skilled in the art. Frequently, the crosslinking reaction will require the use of a catalyst. The amounts and types of catalyst needed, if any, are dependent upon the particular active site/crosslinker combination selected and vill be vell known to one skilled in the art. Thus, for example, when aminoformaldehyde resins are employed as 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 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, etc. can be used. This crosslinking reaction may be performed at reaction conditions well known to one skilled in the art. Typically, temperatures of from 1100C to 2000C are employed. Crosslinking reaction time is not critical and vill vary in accordance with the conditions, reactants, etc. selected. EXAMPLES The folloving 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 cotelomer having a weight ratio of 60/25/15 of t-butyl acrylate/ethyl acrylate/acrylic acid was prepared for use in a coating formulation in the following manner. Two feed mixtures vere prepared from the following ingredients: Monomer Feed Mixture Catalyst Feed Mixture t-Butyl acrylate 360 g. VAZO-52* 10 g. Ethyl acrylate 150 g. 2-Ethoxyethyl 113 g. acetate Acrylic acid 90 g. 2-Ethoxyethyl 43 g. acetate t-Dodecyl mercaptan 18 g. *VAZO-52 n 2,2'-azobis(2,4-dimethylvaleronitrile) The cotelomerization vas carried out in a 2later, glass resin kettle equipped vith 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 1170C. Then the catalyst feed was started. Ten minutes later the monomer feed vas 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 vas complete. During this time the temperature vas maintained at 1.10 to 124-C. The reaction mixture vas then cooked out for another 58 minutes at 113-114'C at which time the heat was turned off. The solution of cotelomer in 2-ethoxyethyl acetate vas allowed to cool to room temperature and then 800 grams of a golden-yellov colored solution vere collected as a residue product. Duplicate analyses indicated that the solution contained 74.3 weight percent of the cotelomer. The solution of cotelomer had a Brookfield viscosity of @ 13,000-14,000 cps 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. The cotelomer formed had a glass transition temperature of llC, as measured by a differential scanning calorimeter. Example 2 In a similar manner to that described in Example 1, a cotelomer having a weight ratio of 60/25/15 of t-butyl acrylate/isopropyl acrylate/acrylic acid was prepared for ut in a coating formulation. The reactants employed were as follows: Monomer Catalyst Kettle Feed Feed Charge Mixture Mixture 2-Ethoxy- 44 g. t-Butyl 360 g. VAZ0-52 10 g. ethyl acrylate acetate i-Propyl 150 g. 2-Ethoxy- 113 g. acrylate ethyl acetate Acrylic acid 90 g. 2-Ethoxy ethyl 43 g. acetate t-Dodecyl- 18 g. mercaptan The kettle charge was heated to 116'C and then the catalyst feed was started. Ten minutes later the monomer feed vas begun. After 183 minutes, all of the monomer mixture had been fed to the reactor; and 17 minutes later the feeding of the catalyst mixture was complete. During this time, the temperature was maintained at 113 to 1200C. The reaction mixture was then cooked out for an additional 48-minute period after which the heat was turned off. The solution of cotelomer in 2-ethoxyethyl acetate was allowed to cool to room temperature and then 803 grams of the light yellow colored solution were collected as r residue product. Replicate analysis indicated the total solids in the solution were 74.1X and 74.or by weight. The solution of cotelomer had a Brookfitld viscosity of about 11,500 mPa. S cps at room temperature. It had a weight average molecular weight of 8,500 s determined by gel permeation chromatography using a calibration based on polystyrene. The cotelomer produced possessed a glass transition temperature of 13 C, as determined by a differential scanning calorimeter. Example 3 In a manner similar to that described in Example 1, a cotelomer having a weight ratio of 44.4/20/23/12.5 of t-butyl acrylate/styrene/n-butyl acrylate/2-hydroxyethyl acrylate was prepared for use in a coating formulation. The reactants employed vere as follovs: Honomer Feed Hixture Catalyst Feed Mixture Styrene 120 g. VAZO-52 10 g. t-Butyl Acrylate 267 g. Ethyoxyethyl Acetate 113 g. n-Butyl Acrylate 138 g. 2-Hydroxyethyl acrylate 75 g. t-dodecyl mercaptan 18 g Ethoxyethyl acetate 43 g. The cotelomeri:ation- was carried out in a 2-liter, resin kettle equipped with a stirrer, reflux condenser, temperature controller, separate monomer and catalyst feed lines controlled with FI pump, and a sampling tube. The kettle was charged vith 44 g. of ethoxyethyl acetate and heated to llD-C. 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 vas completed after another 12 minutes. During the feed period the temperature was maintained between 105 C and 124'C. The reaction mixture was then cooked out for an additional 114 minutes at 113-114'C at which time the heat was turned off. The solution of cotelomer in 2-ethoxyethyl acetate was allowed to cool to room temperature and then 800 grams of a golden-yellov colored solution were collected as a residue product. Duplicate analysis indicated that the solution contained 70.95 by weight of the cotelomer. The solution of cotelomer had a mPa.s Ubbelohde viscosity of 1860 cks at 30 C and a glass transition temperature of 5'C as measured by a differential scanning calorimeter. Example 4 In a manner similar to that described in Example 1 a t-butyl acrylate/ethyl acrylate/2-hydroxyethyl acrylate cotelomer was prepared using the folloving ingredients: Monomer Feed Hixture Catalyst Feed Hixture t-butyl acrylate 360-g. VAZO-52 10 g. ethyl acrylate 167 g. 2-ethoxyethyl Acetate 113 g. 2-hydroxyethyl acrylate 75 g. Rettle Charge 2-ethoxyethyl acetate 43 g. 2-ethoxyethyl 44 g. t-dodecyl mercaptan 18 g. acetate The cotelomer produced possessed a glass transition temperature of lOaC as measured by a differential scanning calorimeter. Comparative Experiment A In a manner similar to that described in Example 1 a cotelomer having a weight ratio of 42.5/42.5/15 of styrcne/ethyl acrylete/acrylic acid was prepared using the following ingredients: Monomer Feed Mixture Catalyst Feed Hixture Styrene 255 g. VAZO-52 10 g. Ethyl Acrylate 255 g. 2-ethoxyethyl acetate 113 g. Acrylic acid 90 g. Kettle Charge 2-ethoxyethyl acetate 43 g. 2-ethoxyethyl t-dodecyl mercaptan 18 g. acetate 44 g. Comparative Experiment B In a manner similar to that described in Example 1 a cotelomer having a weight ratio of 42.51-45/12.5 of styrene/ethyl acrylate/2-hydroxyethyl acrylate was prepared, using the folloving ingredients: Monomer Feed Mixture Catalyst Feed Mixture Styrene 255 g. VAZO-52 s 10g. Ethyl Acrylate 270 g. 2-ethoxyethyl acetate 113g. 2-hydroxyethyl acrylate 75 g. - Kettle Charge 2-ethoxyethyl acetate 43 g. @ 2-ethoxyethyl Mercaptoacetic acid 24.4 g. acetate 44 g; The cotelomer produced possessed a glass transition temperature of 13'C as measured by a differential scanning calorimeter. Comparative Experiment C In a manner similar to that described in Example 1, a cotelomer having a weight ratio of 21.6/27.9/37.1/13.5 of styrene/methyl methacrylate/ n-butyl acrylate/2-hydroxyethyl acrylate was prepared using the folloving ingredients: Monomer Feed Mixture Catalyst Feed Mixture Styrene 129.6 g. VAZO-52 10 g. Hethyl methacrylate 167.4 g. 2-etboxyethyl acetate 113 g. n-butyl acrylate 220.6 g. 2-hydroxyethyl Kettle Charge acrylate 81 g. 2-ethoxyethyl 2-ethoxyethyl 44 g acetate 43 g. acetate t-dodecyl mercaptan 18 g. The cotelomer produced possessed a glass transition temperature of 17"C as measured by a differential scanning calorimeter. Example 5 A two-package, high solids coating of the cotelomer prepared and described in Example 1 was prepared in the folloving manner. A pigment grind vas prepared by adding the following list of ingredients to a ball mill- and grinding overnight. Pigment Grind Ex. 1 Cotelomer Solution (74.32 Solids) 150 g. TiO2 137.7 g. Silicone Surfactantl 0.98 g. 2-Ethoxyethyl Acetate 50 g. 1 Silicone Surfactant L-5410tM (Union Carbide) a commercially available surfactant After grinding, the pigment was removed, the ball mill was vashed vith 25 grams of 2-ethoxyethyl acetate (which was added to the grind), and the mixture of grind and wash was stored. To make up the paint formulation for spraying, the following ingredients vere combined: Paint Formulation Pigment Grind @ 150 g. ERL-4221 * 35.2 g. 2-Ethoxyethyl Acetate 34 g. Stannous Octanoate 0.21 g. *ERL-4221 - 3,4- epoxycyclohexylmethyl-3,4- epoxycyclohexane carboxylate (Union Carbide) This fomulation, which contained 62.9 weight percent total solids and had a Zahn Cup 82 viscosity of 23.3 seconds, was then air sprayed onto steel panels using a conventional. suction-feed 177 C spray gun and cured in a forced-air oven at 350'F for 20 minutes. These panels were then tested for their general coating properties, salt spray resistance, detergent resistance and accelerated outdoor light/humidity exposure resistance. These tests were conducted as follows: Knoop Hardness Number -- The indentation hardness of the films was determined with a Tukon Hardness Tester equipped with a 25-gram load. ASTH D1474-68, Method A Crosshatch Adhesion -- Films are scribed with razor blades in r crosshatch design. A measure of coating adhesion is obtained by firmly applying high tack tape and pulling off rapidly. The percent coating retained on the substrate is recorded. Face and Reverse Impact -- Panels were impacted by a falling weight with a hemi-spherical tip. Indentations were examined and recorded as the mKg highest lnch-pounos welch did not cracK tne trim. ASTM D2794-69. Methyl Ethyl Ketone Rubs -- The films were rubbed manually with methyl ethyl ketone soaked cheese or off until the metal panel was exposed or until 100 back and forth cycles were reached The film appearance was given a 1-5 rating with 1 - no charge. Salt SDray -- Continuous exposure to 55 C salt fog at 94 + 2 F. Panels were exposed either at 15e to vertical or hung vertically. Scribed metal 152 305 panel was 6" x 12". ASTM B117-57T Detergent Resistance -- Coated panels were immersed in 1.5 percent Tide solution maintained at 74 C 165 F. ASTM D2248-73 Accelerated Outdoor Light/Humidity Exposure -- ASTH-G-53-77; QUV cabinet exposure (cyclic ultraviolet testing cabinet) cycle: 4 hours light 60 C (FS-40 UV lamps) at 140 F followed by 4 hours 46 C condensation (distilled vater) at 115 F. The test results are given in Tables I, II, III, and IV. Example 6 A two-package, high solids coating of the cotelomer prepared and described in Example 2 was prepared in the same manner as described in Example 5. The ingredients used are as follows. Pigment Grind Ex. 2 Cotelomer Solution (74X Solids) 150 g. TIO2 135.7 g. Silicone Surfactant L-5410TM 0.97 g. 2-Ethoxyethanol Acetate 50 g. Ball Mill Wath 2-Ethoxyethanol Acetate 25 g. Paint Formulation Pigment Grind 150 g. ERL-4221 34.4 g. 2-Ethoxyethanol Acetate 30 g. Stannous Octanoate 0.20 g. This paint formulation, which contained 63.7% total solids and had a-Zahn Cup &num;2 viscosity of 23.5 seconds, was then air sprayed onto steel panels using a conventional, suction-feed spray gun and 177 C cured in a forced-air oven at 3500F for 20 minutes. The panels were tested as described in Example 8. The test results are given in Tables I, II, III, and IV. Comparative Experiment D For comparision purposes, a two-package, high solids coating was prepared from a commercial, acrylic oligomer Acryloid AT-71 (Rohm and Haas Co.). This oligomer had a weight average molecular weight of 25,900 as measured by gel permeation chromatography using a calibration based on polystyrene. The coating was prepared in the same manner as described in Example 8 from the folloving ingredients. Pigment Grind Acryloid AT-71 (50X solids) 200 g. TiO2 113 g. Silicone Surfactant L-5410- 0.B1 g. 2-Ethoxyethyl Acetate 50 g. Paint Formulation Pigment Grind 150 g. ERL-4221 25.33 g. 2-Ethoxyethyl Acetate 4.3 g. Stannous Octanoate 0.17 g. - This paint formulation, which contained 51.8% total solids and had a Zahn Cup & viscosity of 23.5 seconds, was then air sprayed onto steel panels using a conventional. suction-feed spray gun and 0C cured in a forced-air oven at 350 F for 20 minutes. The panels vere then tested as described in Example The test results are given in Tables I, II, III and IV. TABLE I GENERAL PROPERTIES OF COATINGS BEFORE ACCELERATED AGING TESTS Example Property 5 6 D Knoop Hardness 18.9 16.9 17.9 Crosshatch Adhesion, % Lose O 0 0 Gardner Impact, (in.lbs.)mkg Direct (28) 0,322 (26) 0,299 (30) 0,345 Reverse ( 1) 0,0115 ( 1) 0,115 ( 2) 0,0230 MEK Rubs* 1 2+ 3+ * Coating subjected to 100 MEK (methyl ethyl ketone) doulbe rubs. Then film was rated with the following code: 1 = no change, 2 = scratched, 3 = gloss loss. A plus sign (+) indicates a greater degree of change than and a minus sign (-) a lesser degree of change than is usually attributed to a given rating. TABLE II - RESULTS OF SALT SPRAY* TESTING OF COATINGS Example 5 6 D Exposure Time Blisters/Creep Blisters/Creep Blisters/Creep 288 Hrs. 9/0 9/0 9/0 432 Hrs. 6/0 8/0 5/0 1056 Hrs. ** 7/0 ** 1224 Hrs. --- 7/0.25 in * ASTM-B-117-73 Test. Continuous exposure to 5 % salt fog at 94 + 2 OF (34,5 + 1 OC). Blister size rating on a 10 to 0 scale: 10 = no change, 9 = fine, 5 = medium, 1 = large. Creep measured in inches ** Test discontinued after 432 hrs. which was considered the failure point. TABLE III RESULTS OF DETERGENT* TESTING OF COATINGS Example 5 6 D Blisters **/ Blisters**/ Blisters**/ Exposure Time Hardness Hardness Hardness 30 Hrs. 9F/H 9VF/H 8F/H 78 Hrs. 6F/H 8F/H 6MD/F 94 Hrs. 6F/H 7F/H 6MD/2B 150 Hrs. 5F/H 5F/3B 174 Hrs. 4F/F * ASTM-D-2248-73, 1.5% Tide solution at 165 F (74 C). ** ASTM-D-714-56; Blister size rating on a 10 to 0 scale: 10 = no change, 9 = fine, 5-= medium, 1 = large; Frequence rating: F =few, M = moderate, D = dense (V = very). *** Test discontinued at previous time which was considered as the failure point. TABLE IV ACCELERATED OUTDOOR LIGHT/HUMIDITY EXPOSURE TESTING WITH QUV TESTING APPARATUS 200 Gloss** Exposure Time Ex. 5 Ex. 6 Ex. D O (initial) 72 69 74 272 Hrs. 70 (97%) 72 (104%) 70 (95%) 488 Hrs. 66 (92%) 64 ( 93%) 57 (77%) 680 Hrs. 66 (92%) 57 ( 83%) 38 (51%) 1016 Hrs. 60 (83%) 43 ( 62%) ** 1352 Hrs. 60 (83%) 38 ( 55%) -1520 Hrs. 48 (67%) 24 ( 35%) -1688 Hrs. 45 (63%) ** -1856 Hrs. 39 (54%) -- -2024 Hrs. 37 (51%) -- . - * Number in parentheses are % gloss retention relative to the initial value. All values given are the average of five measurements. ** Test discontinued after previously stated time was considered to be the failure time. The above results indicate that the coatings of this invention possess unexpectedly superior weatherable properties relative to commercial acrylic-based coatings which do not contain t-butyl acrylate. This is shown most clearly by cxamination of Tables III and IV wherein the coatings of this invention displayed enhanced detergent and ultrs-violet light resistance. Example 7 A one-package, high solids coating of the cotelomer prepared and described in Example 3 was prepared in the folloving manner. A pigment grind was prepared by adding the folloving list of ingredients to a ball mill and grinding to a fineness of grind of > 7 on a Hegman scale. Pigment Grind Example 3 cotelomer solution (72.7X solids) 47.0g. TiO2 39.0g. - Disperse Aid &num;1TN (Daniels Products) 2. lug. Propoxy propanol 22.7g. TN To this grind was added 14.6 g. of Cymel 325 , a commercially available melamine-formaldehyde resin, American Cyanamid, and the mill was rolled for one more hour. The coating vas reduced with 27g. of propoxy propanol to give a 57.6X weight solids system with a {2 Zahn Cup viscosity of 24 second. This coating was spray applied as described in Example 5. Examples B and 8(A) and Comparative Experiments E, F, F(A) and G Using a pigment grind similar to that employed in Example 5, high solids coatings were prepared utilizing the cotelomern produced in Example 4 (Examples 8 and 8(A)) and in Comparative Experiments A (Comparative Experiment E), B (Comparative Experiments F and F(A)) and C (Comparative Experiment G) respectively. These cotelomers were crosslinked utilizing the crosslinkers shown in Table V, belov. These coatings were the spray applied to panels as described in Example 5. In order to test the effects of long-term outdoor exposure on these coatings, as vell as those produced in Examples 5, 6 and 7, panels were sent to Miami, Florida. Here the panels were placed outdoors facing south, while tilted at a 450 angle. The panels were le-ft in this position and exposed to the elements for the periods indicated in Table V, below. The panels vere examined for their 60 gloss, color and chalk. Chalk ratings are based upon photographs appearing in Exposure Standards Manual, Federation of Societies for Paint Technology. Color is rated on a 10-0 scale by visual observation, employing the folloving scale: 10 - No change 9 - Very slight 8 - Slight 6 - Definite 4 - Mediuim 2 - Bad 0 Very bad The results of such testing are shown in Table V below: TABLE V 45 SOUTH, FLORIDA OUTDOOR EXPOSURE DATA After 12 Mo. Crosslink Initial Exposure After 24 Mo. Exposure Example Agent 60 Gloss 60 Gloss Color 60 Gloss Color Chalk %Gloss Retention 5 ERL-4221 76 64 9 21 9 9.5 28 6 ERL-4221 73 63 10 19 9 9.5 26 7 Resin 3 85 78 9 * * * 8 Resin 1 83 73 9 63 9 10 76 8(A) Resin 2 72 61 9 46 9 10 64 E ERL-4221 85 64 10 11 9 8 13 F Resin 1 90 80 10 34 9 9.5 38 F(A) Resin 2 85 9 9 0 9 8 0 G Resin 3 11 3 9 * * * ERL-4221 = 3,4-epoxycycloxylmethyl-3,4-epoxycyclohexane carboxylate Reisin 1 = hexakismethoxymethyl melamine Resin 2 = tetrabutoxymethyl glycoluril Resin 3 = Cymel TM 325, American Cyanamid, a commercially availble etherated melamine formaldehyde resin * = test results not available. The above data indicates that the coating compositions of the instant invention will resist weathering in a superior fashion to coating compositions employing copolymers not containing t-butyl acrylate.

Claims: 1. A copolymer having a glass transition temperature of less than about 500C comprising: (a) from 10 to 90 weight percent t-butyl acrylate units; (b) from 1 to 30 weight percent of units derived from a functional comonomer containing at least one active crosslinking site; and (c) from 0 to 85 weight percent of units derived from other ethylenically unsaturated monomers which are capable of polymerizing with t-butyl acrylate. 2. The copolymer of claim 1 wherein t-butyl acrylate units are present in an amount of from 20 weight percent to 70 weight percent. 3. The copolymer of claim 1 or 2 wherein the functional comonomer units are present in an amount of from 5 to 20 weight percent. 4. The copolymer of claim 1 to 3 wherein the functional comonomer units, component (b), are derived from acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and mixtures thereof. 5. The copolymer of claim 1 to 4 wherein the ethylenically unsaturated monomer units, component (c), are present in an amount of from 5 to 60 weight percent. 6. A copolymer of claim 1 to 5 comprising: (a) from 20 to 70 weight percent t-butyl acrylate units; (b) from 5 to 20 weight percent of units derived from one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and mixtures thereof, and (c) from 5 to 60 weight percent of units derived from other ethylenically unsaturated monomers which are capable of polymerizing with t-butyl acrylate. 7. A coating composition comprised of the copolymer of claim 1 to 6 wherein the weight.percentages of components (a), (b) and (c) are based upon the total weight of the copolymer; and a suitable crosslinker. 8. The coating composition of claim 7 wherein the crosslinker is a polyepoxide or an etherified aminoformaldehyde resin. 9. The coating composition of claim 8 wherein the polyepoxide is a cycloaliphatic epoxide or a diglycidyl epoxide. PATENT CLAIMS FOR AUSTRIA 1. A process for producing a copolymer having a glass transition temperature of less than about 5O0C comprising: (a) from 10 to 90 weight percent t-butyl acrylate units; (b) from 1 to 30 weight percent of units derived from a functional comonomer containing at least one active crosslinking site; and (c) from 0 to 85 weight percent of units derived from other ethylenically unsaturated monomers which are capable of polymerizing with t-butyl acrylate by any standard polymerization process of the monomers. 2. The process of claim 1 wherein the polymerization takes place in the presence of a catalyst, and an organic solvent at an elevated temperature. 3. The process of claim 1 or 2 for producing a copolymer comprising: (a) from 20 to 70 weight percent t-butyl acrylate units; (b) from 5 to 20 weight percent of units derived from one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and mixtures thereof, and (c) from 5 to 60 weight percent of units derived from other ethylenically unsaturated monomers which are capable of polymerizing with t-butyl acrylate. 4. The process of claim 1 to 3 for producing a copolymer wherein the functional comonomer units, component (b), are derived from acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and mixtures thereof. 5. A coating composition comprised of the copolymer - produced according to process of claim 1 to 4 - and a suitable crosslinker. 6. The coating composition of claim 4 wherein the crosslinker is a polyepoxide or an etherified aminoformaldehyde resin. 7. The coating composition of claim 5 wherein the polyepoxide is a cycloaliphatic epoxide or a diglycidyl epoxide.

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