WO1981000233A1

WO1981000233A1 - Clear coat/color coat finish containing an ultraviolet light stabilizer

Info

Publication number: WO1981000233A1
Application number: PCT/US1979/000540
Authority: WO
Inventors: D Chang
Original assignee: Du Pont
Priority date: 1979-07-26
Filing date: 1979-07-26
Publication date: 1981-02-05
Also published as: EP0033725A1

Abstract

A substrate that has a finish of a clear coat toplayer in firm adherence to a color coat layer that is in adherence with the substrate; wherein the clear coat consists essentially of a transparent film forming binder; the color coat consists essentially of a film forming binder and pigments; the color coat contains an ultraviolet light stabilizer and optionally, both the clear coat and the color coat contain an antioxidant and an ultraviolet light stabilizer, this finish has an excellent appearance and has excellent weatherability and durability and is particularly useful as a finish for automobiles and trucks.

Description

TITLE Clear Coat/Color Coat Finish Containing An Ultraviolet Light Stabilizer BACKGROUND OF THE INVENTION

This invention is directed towards coated substrates and in particular toward coated metal substrates that form the exterior of automobiles and trucks.

Acrylic enamel, acrylic lacquer and alkyd enamel finishes are widely used on the exterior of automobiles and trucks. It has been found that an excellent appearance along with depth of color and metallic glamour can be obtained by applying a clear or transparent coat over the conventional colored or pig ented coat. However, the weatherability and durability of these clear coats have been found to be poor since checking, cracking and flaking of the clear coat occurs after relatively short periods of exposure to outdoor weathering which gives the automo¬ bile or truck an unsightly appearance. Refinishing of these weathered clear coats is difficult and expen¬ sive since the clear coat must be sanded to remove cracked and flaked clear coat before a refinish coat can be applied.

In an effort to retard or substantially reduce checking , cracking and flaking of the clear coat conventional ultraviolet light stabilizers with and without antioxidants have been added to the clear coat . Also , a combination of a transparent pig- ment and an ultraviolet light screener~ have been added to the clear coat as suggested by LaBerge U . S . Patent 3 , 407 , 156 issued October 22 , 1968 . In each of the above cases , the durability and weatherability of the clear coat was increased only a relatively small length of time but not to the extent required for a practical automotive or truck finish.

There is need for a clear coat/color coat finish for metal substrates that will withstand long periods of weathering without failure of the finish. This invention provides a clear coat/color coat finish that has excellent weatherability and dura¬ bility as required for automobiles and trucks . SUMMARY OF THE INVENTION A -substrate having a finish of a clear coat toplayer in firm adherence to a color coat that is in adherence with the substrate ; wherein the clear coat consists essentially of a transparent film forming binder; the color coat consists essentially of a film forming binder and pigments in a weight ratio of about 1/100 to 150/100 , and the color coat contains about 0. 1-20% by weight, based on the weight of the binder of the coat, of an ultraviolet light stabilizer; optionally, the color coat and the clear coat each contain about 1-20% by weight, based on the weight of the binder of the coat, of an ultraviolet light stabilizer and about 0.1-5% by weight, based on the weight of the binder of the coat, of an antioxidant; wherein the weight ratio of ultra- violet light stabilizer to antioxidant is about 1:1 to about 50:1.

O

, Λ, wi DETAILED DESCRIPTION OF THE INVENTION

A clear coat/color coat finish for sub¬ strates has been developed in which the color coat contains an ultraviolet light stabilizer, hereinafter called U.V. stabilizer. While applicant does not wish to be held to the following theory, it is believed that U.V. stabilizer migrates from the color coat into the clear coat and provides U.V. stabilizer to the clear coat for protection against weathering. Preferably, both the clear coat and the color coat contain U.V. stabilizer and as stabilizer is lost from the clear coat due to weathering, it is replenished from the color coat. The color coat provides a reservoir for the U.V. stabilizer for the clear coat and maintains the stabilizer and antioxidant at an effective level that provides protection from weathering.

Optionally, the color coat can contain an antioxidant which also migrates to the clear coat. The antioxidant can also be used in the clear coat.

In one useful clear coat/color coat finish,both the clear coat and the color coat contain about 1-20% by weight, based on the weight of the binder of the coat of a U.V. stabilizer and about 0.1-5% by weight, based on the weight of the binder of the coat of an antioxidant. The ratio of U.V. stabilizer to antioxidant in both the color coat and clear coat is about 1:1 to about 50:1. Preferred, to form a durable finish, about 5-8% by weight of the U.V. stabilizer is used along with about 0.1-1% by weight of the antioxidant and the ratio of U.V. stabilizer to antioxidant is about 10:1. 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 0.8-1.5 mils thick. The color coat contains pigment in a pigment to binder weight ratio of about 1/100 to about 150/100. Any of the conventional pigments used in coating compositions including metallic flake pigments can be used.

The clear coat can also contain trans¬ parent 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. The coatings are usually applied to all types of substrates such as primed or unpri ed metal, plastic, rubber, flexible ethylene-propylene copolymer rubbers, flexible polyurethanes, fiber¬ glass reinforced with polyester resins and the like 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 and the like. Under some circumstances it may be desirable to apply both the color coat and clear coat in the form of a powder and upon baking coalesce the powders into a clear coat/color coat finish. Also, it may be desirable to apply the clear coat as a powder to a wet color coat and then to form a finish by baking.

O 5 Typical ultraviolet light stabilizers that are useful in this invention are as follows:

Benzophenones such as hydroxy dodecyloxy benzophenone, 2,4-dihydroxy- benzophenone, hydroxybenzophenones containing sulfonic groups, 2,4-dihydroxy-3' ,5'-ditertiary butyl benzophenone, 2,2' ,4' ,trihydroxy benzophenone esters of dicarboxylic acids, 2-hydroxy-4-acryloxyethoxy- benzophenone, aliphatic mono esters of 2,2',4-tri- hydroxy-4*alkoxybenzophenone; 2-hydroxy-4-methoxy-2'- carboxybenzophenone;

Triazoles such as 2-phenyl-4-(2¹ ,4'-di- hydroxybenzoyl)- triazoles, substituted benzotriazoles such as hydroxy-phenyltriazoles such as 2-(2*-hydroxy- 5'-methyl phenyl) benzotriazole, 2-(2'-hydroxy-phenyl) benzotriazole, 2-(2*-hydroxy-5'-oσtylphenyl) naphtho- triazole;

Triazines such as 3,5-dialkyl-4-hydroxyphenyl derivatives of triazine, sulfur containing derivatives of diallyl-4-hydroxy phenyl triazines, hydroxy phenyl- 1,3,5-triazine and such triazines containing sulfonic acid groups, aryl 1,3,5 trazines, orthohydroxyl aryl- s-triazone .

Benzoates such as dibenzoate of diphenylol propane, tertiary butyl benzoate of diphenylol pro¬ pane, nonyl phenyl benzoate, octyl phenyl benzoate, resorcinol dibenzoate.

Other ultraviolet light stabilizers that can be used include lower alkyl thiomethylene containing phenols, substi¬ tuted benzenes such as 1,3-bis-(2¹-hydroxybenzoyl) benzene, metal derivatives of 3,5-di-t-butyl-4-hy- droxy phenyl proprionic acid, asymmetrical oxalic acid diarylamides, alkylhydroxyphenyl- thioalkanoic acid esters, dialkylhydroxy-phenyl alkanoic acid esters of di and tri pentaerythritol, phenyl and naphthalene substituted oxalic acid diamides, methyl beta- (3 , 5-di-tert-butyl-4-hydroxyphenyl) -proprionate, <». ,^'-bis- (2-hydroxyphenol) -di-isopropyl-benzene, 3,5'-dibromo-2'hydroxy acetophenone, ester derivatives of 4, 4-bis (4 'hydroxyphenyl)pentanoic acid wherein there is at least one unsubstituted position ortho to the aromatic hydroxyl groups, organophosphorus sulfides such as bis (diphenyl phosphinothioyl) ono- sulfide and bis (diphenyl phosphinothioyl) disulfide, 4-benzoyl-6- (dialkyl-hydroxy-benzyl) resorcinal, bis (3-hydroxy-4-benzoyl-phenoxy) diphenyl silane, bis (3-hydroxy-4-benzoylphenoxy) dialkyl silane, 1,8- naphthalimides,^ cyano,0,$-diphenylacrylic acid deri¬ vatives, bis (2-benzoxazolyl) alkanes, bis (2-naphth- oxazolyl) alkanes, methylene malonitriles containing aryl and heterocyclic substitutes, alkylene-bis- dithic-carbamate, 4-benzoyl-3-hydroxy phenoxyethyl acrylate, 4-benzoyl-3-hydroxyphenoxy ethyl methacrylate, aryl or alkyl substituted acrylonitriles , 3-methyl-5- isopropylphenyl-6-hydroxy coumarone.

Particularly useful ultraviolet light stabilizers that can be used are hindered amines of bipiperidyl derivatives such as those in Murayama et al., U.S. Patent 4,061,616, issued December 6, 1977 column 2, line 65 through column 4 line 2 and nickel compounds such as [1-phenyl 3-methyl 4-decanoyl pyrazolate (5)]-Ni, bis- [phenyl-dithiocarbamato-] Ni (II) , and others listed in the above patent column 8, line 44 through line 55.

Typical antioxidants are as follows : tetra¬ kis alkylene (di-alkyl hydroxy aryl) alkyl ester alkanes such as tetrakis methylene 3 (3 ' , 5 ' -dibutyl-4 'hydroxy- phenyl) proprionate methane, reaction product of p- amino diphenylamine and glycidyl methacrylate, reaction product of n-hexyl-N'-phenyl-p-phenylene diamine and glycidyl methacrylate, pentaerythritol tetrakis (thio- glycolate) , trimethylol propane tris (thioglycolate) , trimethylol ethane tris (thioglycoate) , N- (4-anilino phenyl) acrylamide, N- (4-anilinophenyl) maleamic - acid,N- (4-anilinophenyl ) malei ide , alkylhydroxyphenyl groups bonded through carboalkoxy linkages to nitro- < gen atom of a heterocyclic nucleus containing an. imi- dodicarbonyl group or an imidodithiocarbonyl group, 3 , 5 di tert . butyl-4-hydroxy cinnamonitrile , ethyl 3 , 5-di tert hexyl-4-hydroxycinnamate , substituted benzyl esters of 0- ( substituted hydroxy phenyl) propionic acids , bis- (hydroxyphenyl alkylene) alkyl isocyanurate compounds , tetrakis hydroxy benzyl phosphonium halides alone or in combination with a dialkylthiodialkanoate, thiodimethylidyne tetrakis- phenols alone or in combination with a dialkyl thio- dialkanoate or phosphite or phosphonate , dihydro- ca by 1 -hydroxy phenyl aryl or alkyl phosphonites or phosphonates or phosphates or phosphites or phosphinates or phosphinites or phisphorothionates or phosphinothionates, diphenyl bis (3 , 5-ditert-butyl- -4-hydroxyphenoxy) silane , hydrocarbyl-hydroxyphenyl- dihydrocarbyldithiocarbamates such as 3 , 5 di-tert- butyl- 4 -hydroxy phenyl dimethyldithio carbamate and a ino benzyl thioether .

One preferred o iribination of ultraviolet light sta¬ bilizer and antioxidant is 2-hydroxy-4-dodecyloxy benzophenone or a substituted 2 (2 '-hydroxyphenyl) benzotriazole and tetrakis methylene 3 (3 ' , 5 ' , -dibutyl-4 ' -hydroxyphenyl) proprionate methane .

The film forming binder used in the clear coat/color coat can be from those conventional coating compositions used to finish automobiles and trucks such as solvent or water based acrylic lacquers, acrylic dispersion lacquers, solvent or water based thermo- setting acrylic enamels, polyester enamels, nonaqueous acrylic dis¬ persion enamels, alkyd resin enamels, polyurethane enamels and acrylic or polyester powder coatings. It is possible to have the binder of the clear coat different frcm the binder of the color coat. For example, a ther osetting acrylic enamel clear coat can be used with a polyester enamel color coat.

Typical acrylic lacquers that can be used are disclosed in Crissey and Lowell U . S . Patents 2 , 934 , 509 and 2,934,510 both issued on April 26, 1960, Godshalk U.S. Patent 2,860,110 issued November 11, 1958 and Zimmt U.S. Patent 3,823,205 issued July 9, 1974. The teachings of the Zimmt patent are hereby incor- porated by reference.

One preferred acrylic lacquer is a solution in which the film forming component is at least one of

(1) poly(methyl methacrylate) ,

(2) poly(ethyl methacrylate) , . (3) poly(propyl methacrylate),

(4) poly(isopropyl methacrylate),

(5) a copolymer composed only of methyl- methacrylate and at least one of an alkyl acrylate whose alkyl group con¬ tains 1 through 20 carbon atoms, an alkyl methacrylate whose alkyl group contains 2 through 18 carbon atoms, or styrene,

(6) mixtures of these, and at least one of

(1) a copolymer composed only of methyl methacrylate and an alkyl acrylate whose alkyl group contains 1 through 10 carbon atoms or an alkyl meth¬ acrylate whose alkyl group contains 4 through 18 carbon atoms, or

(2) mixtures of said copolymers; and contains an inert organic solvent for the above polymers.

One particular pref rred acrylic lacquer the film form¬ ing component is poly(methyl methacrylate) and is at least one of .

(1) a methyl methacrylate/methyl acrylate copolymer whose monomer unit weight ratio is 70/30 to 40/60 respectively.

(2) a methyl methacrylate/ethyl acrylate copolymer whose monomer unit weight ratio is 80/20- to 40/60 respectively,

(3) a methyl methacrylate/butyl acrylate copolymer whose monomer unit weight ratio is 85/15 to 65/35 respectively. (4) a methyl methacrylate/2-ethylhexyl acrylate copolymer whose monomer unit weight ratio is 90/10 to 70/30 respectively,

(5) a methyl ethacrylate/octyl methacrylate copolymer whose monomer unit weight ratio is 85/15 to 65/35 respectively, or

(6) a methyl ethacrylate/lauryl methacry¬ late copolymer whose monomer unit weight ratio is 90/10 to 75/25 respectively.

The acrylic lacquer can contain an alkyd resin and a cellulose acetate butyrate resin .

Typical acrylic dispersion lacquers that can be used are disclosed in Fryd and Lee U.S. Patent 3,660,537 issued May 2, 1972. One particularly useful acrylic dispersion lacquer has the film foπning cαrponent a graft copolymer having a backbone which is a copolymer of polymerized

(a) monomers of about 85-99. 6% , by weight , of an ester of acrylic acid or methacrylic acid;

(b) . monomers which provide potential grafting sites of about 0.2-15% , by weight , of allyl methacrylate ; and

(c) about 0.2-5% by weight of diethylamino- ethyl methacrylate , tert-butylamino- ethyl methacrylate , aminoethyl vinyl ether or di ethylaminoethyl methacry¬ late; the total of the monomers which provide potential grafting sites do not exceed 15% by weight of the total backbone , and a polymeric graft segment comprised of polymerized ironαπers of 2-ethyl hexyl acrylate, butyacrylate, 2-ethyl hexyl me-r__r_acrylate or lauryl methacrylate the graft segment ccmpri- sing about 5-80% by weight of the total graft copolymer.

One particularly useful graft copolymer used in these dispersion lacquers cαπprises methyl n_at__hacrylate/diethyl- aminoethyl methacrylate/ allyl irethacrylate/ 2-ethylhexyl acrylate in a weighs ratio of about 84.0/0.8/0..51/14.2. An aqueous dispersion lacquer composition of a binder in an aqueous medium can also be used ; the binder is comprised of

(1) a dispersed polymer of methyl methacrylate that can contain small amounts of adhesion prαnoting monomers such as diethylam__noethyl_πethacrylate and

(2) a dispersant polymer of methyl methacrylate , an alkyl acrylate or an alkyl methacrylat having 2-12 carbon atoms in the alkyl groups, and an ethylenically unsaturated carbαxylic acid such as acrylic acid or methacryliσ acid; and

(3) a graft copolymer of the above dispersed polymer and dispersant polymer and the composition contains suf¬ ficient base such as amine or aimonium hydroxide to provide a pH of about 7-11 and usually contains conventional plasticizers, pigments and other additives as are used in aqueous coating compositions .

A wide variety of solvent based theπrosetting acrylic enamels of an acrylic polymer and a crosslinker such as an alkylate _τel__mine formaldehyde can be used such as those described in Parker

U.S. Patent 3, 674,734 issued July 4 , 1972, Parker U.S. Patent

3, 637,546 issued January 25, 1972 and Irvin et al. U.S. Patent

3, 901,840 issued August 26, 1975.

Of particular use are the acrylic enamels containing cellulose acetate buryrate described in the aforementioned Parker ' 546 patent which is hereby incorporated by reference . These enamels comprise about 10-60% by weight of a film-forming polymer blend and a solvent for said polymer blend wherein said polymer blend consists essentially of

(1) 50-80% by weight , based on the weight of the polymer blend , of an acrylic polymer which consists essentially of 11

(a) 0-25% by weight styrene,

(b) 25-55% by weight methyl meth¬ acrylate

(c) 38-48% by weight of a soft constituent of an alkyl acrylate or an alkyl meth¬ acrylate wherein the alkyl groups have 2-12 carbon atoms;

(d) 5-20% by weight of a hydroxy containing constituent of a hydroxy alkyl methacrylate or a hydroxy alkyl acrylate wherein the alkyl groups contain 2-4 carbon atoms; and

(e) 1-5% by weight of an fiC,£-un- saturated monocarboxylic acid; wherein said acrylic polymer has a relative viscosity of 1.04-1.10 measured at 25°C. in ethylene dichloride according to ASTM D-445-46T, Method B;

(2) 5-50% by weight, based on the weight of the polymer blend, of cellulose acetate butyrate having butyryl content of about 45-55% by weight and a viscosity at 25°C. of about 1-6 seconds measured according to ASTM-D-1343-56;

(3) 5-50% by weight/ based on the weight of the polymer, of a melamine formaldehyde resin which has been at least partially reacted with an aliphatic monohydric alcohol having from 1-4 carbon atoms.

Particularly useful in these enamels are acrylic polymers of 10-18% by weight styrene, 25-30% by weight methyl methacrylate, 38-42% by weight butyl acrylate, 10-16% by weight hydroxyethyl acrylate and 1-3% by weight acrylic acid and acrylic polymers of 40-50% by weight methyl methacrylate, 40-48% by weight butyl acrylate, 6-10% by weight hydroxyethyl acrylate, 3-5% by weight acrylic acid

Aqueous thermosetting acrylic enamels can also be used. These enamels contain the following film-forming constituents :

(1) an acrylic polymer of styrene and/or methyl methacrylate , an alkyl acrylate or an alkyl methacrylate other than methyl methacrylate , a hydroxy alkyl acrylate or a hydroxy alkyl methacrylate and an ___.,jδ-unsaturated carboxylic acid wherein the polymer has an acid number of 35-150 and a car boxy 1/hydroxyl ratio of 1 : 0. 2 to 1 : 3 , and

(2) a water soluble or water dispersible alkylated melamine formaldehyde resin. Typically useful enamels of this type are disclosed in British Patent 1 , 414 , 436 granted February 25 , 1976.

Pref erred are aqueous enamels in which the acrylic polymer is of 50-60% by weight of methyl methacrylate , 30-40% by weight of butyl acrylate , 5-10% by weight of hydroxy ethyl acrylate and 4-12% by weight of acrylic acid and the polymer has an acid number of about 35-100 and a car boxy 1 to hydroxy 1 ratio o^'f 1 : 0. 3 to 1 : 1. 5. Another preferred aqueous enamel in which the acrylic polymer is of 28-32% by weight of styrene, 22-26% by weight of methyl methacrylate, 30-35% by weight of butyl acrylate, 7-9% by weight of hydroxy ethyl acrylate, 4-6% by weight of acrylic acid, and has an acid number of 30-50, and a carboxyl to hydrαxyl ratio of 1:0.4 to 1:1.5.

In one particularly preferred aqueous enamel the acrylic polymer consists essentially of 54 % methyl methacrylate , 34% butyl acrylate , 6% 2 -hydroxyethyl acrylate and 6% acrylic acid and has an acid number of about 45-50 and a carboxyl to hydroxyl ratio of about 1:0.6.

Polyester enamels can also be used. The polyesters are the reaction produolis of a polyol and a dicarboxylic acid or anhydride and are crosslinked with a conventional crosslinking age such as alkylated elaiπine formaldehyde, a benzoguanamine for alde hyde. urea formaldehyde and the like. One useful polyester enamel has a binder of a polymer blend of about-.

35-70% by weight, based on the weight of the polymer blend, of a polyester of an alkylene glycol, a triol an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid;

15-30% by weight, based on the weight of the polymer blend, of cellulose acetate butyrate and

15-35% by weight, based on the weight of the polymer blend, of an alkylated melamine formaldehyde resin.

A polyester enamel may be used as a clear coat but preferably an acrylic enamel or lacquer as described above is used as this clear coat with a polyester enamel.

A nonaqueous thermosetting acrylic disperion enamel can be used. These enamels are obtained by polymerizing a hydroxy alkyl acrylate or methacrylate in a dispersing liquid in the presence of a dispersion stabilizer and a carboxylic acid and an amine. An aminoplast resin is added to the polymer dispersion after an active solvent is added to form a solution of the acrylic polymer. One useful dispersion stabilizer is formed by a. graft copolymerizing

1. the reaction product of glycidyl methacrylate and poly(12-hydroxystearic acid) ,

2. methyl methacrylate, and

3. glycidyl methacrylate to form a copolymer pro¬ duct containing pendant epoxy groups; and b. reacting said pendant epoxy groups with etha- crylic acid.

Typically useful nonaqueous thermosetting acrylic dispersion enamels and process for making the same are disclosed in

Sullivan et al U.S. 3 ,996,667 issued June 29, 1976 which is hereby incorporated by reference.

Typical acrylic polyur ethane coating composition that can be used are disclosed in Vasta U . S . Patent 3 , 558 , 564 issued January 26 , 1971. Conventional plasticizers , pigments and other additives as are used in coating compositions can be incorporated into the color coat or clear coat as required . The compositions can be reduced with conventional solvents , if solvent based compositions , for application such as spraying. If the compositions are aqueous based, then water or water solvent mixtures can be us

Two particularly useful additives for both the colo coat and the clear coat are iron pyrophosphate and finely divided silica. Up to about 10% by weight and generally about 0.1-10% by weight based on the weight of the binder, of iron pyrophosphate can be used. Up to about 15% by weight, and generally about 0.5- 15% by weight, based on the weight of the binder, of finely divided silica can be used. Iron pyrophosphate and the silica improved overall durability and performance of the finish of this inventio

In particular , iron pyrophosphate is a useful additive which provides a synergistic effect of the U .V. stabilizer and antioxidant . Compo¬ sitions containing the above three constituents have a suprisingly longer period of outdoor weatherability before failure occurs . The longer period is more than the cummulative effect that would be expected of the combination of the three constituents . The following examples illustrate the invention . All parts and percentages are on a weight basis unless otherwise specified .

EXAMPLE 1 The following constituents are blended together to form a paint A (control) :

^{Pθrtiθn λ} Parts by Weight

Acetone 9 30

Alkyd resin solution 9.53

⁽85% solids alkyd resin of ethylene glycol/phthalic anhydride/coconut oil having Portion 1 (cont'd.) a hydroxy1 No. of about 20 and an acid No. of about 8- 10 in toluene and having a Gardner Holdt viscosity of about 3 measured at 25°C)

Portion 2

Aluminum Flake Mill Base 15.48 (29.8% polymethyl metha¬ crylate, 12.4% aluminum flake and 57.8% solvent mixture of toluene and acetone)

Blue Mill Base 3.39 (10% "Monastral" blue flake, 16% polymethyl methacrylate, 74% solvent mixture of toluene and acetone)

Carbon Black Mill Base 0.33 (6% carbon black pigment, 24% polymethyl methacrylate, 70% solvent mixture of toluene, acetone, ethylene glycol monoether acetate, butyl acetate)

Green Mill Base 0.36 (8.33% "Monastral" green pigment, 21.11% polymethyl- methacrylate, 70.66 solvent mixture of toluene/acetone/ xylene) Portion 3

Silicone solution (4% silicone 0.03 SF69 in xylene)

PMMA Solution (40% solids 2.70 of polymethyl methacrylate ratio of 70/30)

PMMA/DEAM Solution (40% solids 4.04 of a copolymer of 99% methyl methacrylate and 1% diethyl- aminoethyl methacrylate in acetone/toluene, 27/73 ratio)

PMMA/BA Solution (40% solids 20.02 of a copolymer of 85% methyl methacrylate and 15% butyl acrylate in acetone/toluene, 17/83 ratio) PBA Solution (50% solids 0.20 polybutylacrylate in xylene)

Portion 3

CAB Solution (25% solids 12.98 cellulose acetate butyrate having a 37% butyryl con¬ tent 2 second viscosity in toluene/acetone, 70/30 ratio)

CAB Solution II (15% solids 21.64 cellulose acetate butyrate having a 38% butyryl content and a 20 second viscosity in toluene/acetone, 70/30 ratio)

Total 100.00

Portion 1 is charged into a mixing vessel and mixed for 10 minutes, portion 2 is added and mixed for 10 minutes and then portion 3 is added and mixed for 20 minutes to form Paint A. Paint A has a weight solids content of 32.41% and a binder conten of 30.8% by weight.

Paint B is prepared as follows:

Paint A(prepared above) 50.000

U.V. Stabilizer (2-hydroxy-4- 0.880 dodecyloxy benzophenone) AntioxidantCtetrakis methylene 0.088 3 (3' ,5^*-dibutyl-4'-hydroxy¬ phenyl)proprionate methane]

Total 50.968 The above constituents are mixed together for 15 minutes to form paint B.

A clear coating A (control) is prepared by blending together the following constituents:

Parts by Weight Toluene 2.92

Acetone 11.60

Ethylene glycol monobutyl ether 4.72 acetate Alkyd rc_=ιn solution (90% solids 5.60 in toluene of an alkyd resin of adipic acid, neopentyl glycol/ benzoic acid having a Gardner Holdt Viscosity measured at 25°C at the above solids of U-W)

Silicone Solution (described above) 0.03

PMMA Solution (described above) 14.81

PMMA/DEAM Solution 8.22 (described above)

PMMA/BA Solution (40% 33.45 solids of a copolymer of 82% ethy methacrylate and 18% butyl acrylate in acetone/, toluene, 17/83 ratio)

PBA Solution (described above) 0.20

CAB Solution (25% solids of 18.45 cellulose acetate butyrate having a 37% butyryl content and a 2 second viscosity in acetone/ethylene glycol mono- butylether acetate, ratio 94/6)

Total 100.00 The above constituents are blended together to form a clear coating composition having a binder solids content of 32.35%.

A clear coating B is prepared as follows:

Parts by Weight

Clear coating A(prepared above) 50.000

U.V. Stabilizer(described 0.410 above)

Antioxidant(described above) 0.041

Total 50.451 Paint A (control) and Paint B are reduced to a spray viscosity of 47.5 seconds measured at 25°C with a No. 1 Fisher Cup with a paint thinner of acetone/toluene/xylene ratio of 22.5/43.5/34. The reduced paints are each sprayed onto separate -phos- phatized steel panels and allowed to air dry for 10 minutes.

Clear coat A (control) and Clear coat B are similarly reduced to a spray viscosity and Clear coat A (control) is sprayed onto the paint A (control) coated panel and clear coat B is sprayed onto the paint B coated panel. Each is allowed to air dry 10 minutes and then baked for 10 minutes at 82°C and 30 minutes at 155°C. The clear coat on each of the panels is about 1.3 mils thick and the paint is about 1.0 mils thick.

Each of the panels are then exposed to a Q.U.V. "Weather-O-Meter" that uses a SF40 Westing- house ultraviolet lamp and has the following cycles: 8 hours ultraviolet exposure at 68°C and 4 hours at 100% relative humidity at 55°C.

The gloss of each of the panels is measured at 20°C after given exposure times and checking of the clear coat is noted. The results are as follows:

Exposure Data

Gloss Measured

Time Expo- at 20° surehrs.) 100 200 340

Clear Coat A/ 75 73 70 52^■

Color Coat A (control)

Clear Coat B/ 83 81 81 78

Color Coat B

Gloss measured

Time Expor at 20° sure(hrs.) 400 600 730 800

Clear Coat A/ 46 F I L E D

Color Coat A (Control) Clear Coat B/ 78 71 69* 66

Color Coat B

* Checked The results show that the control checked after 340 hours and failed after 600 hours while clear coat B/color coat B which contains an anti¬ oxidant and U.V. stabilizer checked at 730 hours exposure. From these data, it can be expected that clear coat/color coat systems of acrylic solution lacquer that contain an antioxidant and a U.V. stabilizer will have an outdoor durability of about twice that of the same lacquer that does not contain an antioxidant and a U.V. stabilizer. EXAMPLE 2

An acrylic dispersion lacquer is prepared according to the teachings of Example 1 of U.S. Patent 3,660,537, issued May 2, 1972. A Paint C (control) is prepared using the same mill bases as used in Example 1 above and Paint D is prepared which is identical to Paint C except the same U.V. stabilizer and antioxidant are added as in Example 1 for Paint B in the same amounts.

A Clear Coating C (control) is prepared from the acrylic dispersion lacquer and a Clear Coat D is prepared which is identical to Coating C except the same U.V. stabilizer and antioxidant are added as in Example 1 for Clear Coating B in the same amounts. Paints C (control) and D are reduced to a spray viscosity and each is sprayed onto separate phosphatized steel panels and allowed to air dry for 10 minutes.

Clear Coats C (control) and D are reduced to a spray viscosity. Clear Coat C (control) is sprayed onto Paint C (control) coated panel. Clear Coat D is sprayed onto Paint D coated panel. Each panel is dried and baked as in Example 1. The clear coat on each of the panels is about 1.3 mils thick, and the paint on each of the panels is about 1.0 mils thick.

The panels are then exposed to a "Weather-O-

Meter" as in Example 1. The gloss of each of the panels is measured at 20° after given exposure times and checking of the clear coat is noted. The results are as follows:

EXPOSURE DATA

Gloss Measured At 20°

Time Exposure

(hrs.) 0 150 280 400 550 750 900 1000

Clear Coat C/ 74 62 51* 40 15 — FAILED — Color Coat C (control)

Clear Coat D/ 77 75 68 60 56 53* 48 35 Color Coat D

* Checked

The results show that the control checked after 280 hours and failed after 550 hours while Clear Coat D/Color Coat D, which contains an antioxidant and a U.V. stabilizer checked at 750 hours exposure. From these data, it can be expected that clear coat/color coat systems of acrylic dispersion lacquer that contain an antioxidant and a U.V. stabilizer will have an outdoor durability of more than twice that of the same lacquer that does not contain an antioxidant and a U.V. stabilizer.

EXAMPLE 3 A polyester solution is prepared in which the polyester is the reaction product of an alkylene glycol, a triol, an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid and contains cellulose acetate butyrate and an alkylated melamine formaldehyde crosslinking agent. A Paint E (control) is prepared therefrom using the same pigmentation as used in Example 1 and Paint F is prepared which is identical to Paint E except a U.V. stabilizer of a substituted 2 (2,-hydroxyphenyl) benzotriazole and an antioxidant described in Example 1 are added in the same amounts as in Example 1 for Paint B.

A Clear Coating E (control) is prepared from an acrylic solution lacquer (described in Example 1), and a Clear Coat F is prepared which is identical to Coating E except the above U.V. stabilizer and anti¬ oxidant are added in the same amounts as in Example 1 for Clear Coating B.

Paints E (control) and F are reduced to a spray viscosity. Clear Coat E (control) is sprayed onto Paint E (control) coated panel. Clear Coat F is sprayed onto Paint F coated panel. Each panel is - dried and baked as in Example 1. The clear coat on each of the panels is about 1.5 mil thick, and the paint on each of the panels is about 0.7 mil thick. The panels are then exposed to a "Weather-O-

Meter" as in Example 1. The gloss of each of the panels is measured at 20° after given exposure times and checking of the clear coat is noted. The results are as follows: EXPOSURE DATA

Gloss Measured At 20°

Time Exposure

(hrs.) 0 450 600 800 950 1900 2200 2500 3000

Clear Coat E/ 75 62 59 45 13* — FAILED Color Coat E (control)

Clear Coat F/ 95 90 91 90 90 89 87* 65 26 Color Coat F

* Checked

The results show that the control checked after 950 hours and failed after 950 hours while Clear Coat F/Color Coat F, which contains an antioxidant and a U.V. stabilizer checked at 2200 hours exposure. Fro these data, it can be expected that clear coat/color coat systems of clear acrylic solution lacquer/polyest color coat that contain an antioxidant and a U.V. stabilizer will have an outdoor durability of more tha twice that of the same system that does not contain an antioxidant and a U.V. stabilizer.

EXAMPLE 4 An aqueous acrylic dispersion is prepared according to the teachings of Example 1 of British Patent 1,414,436, granted February 25, 1976. A Paint (control) is prepared using a light blue metallic mill base and Paint H is prepared which is identical to Paint G except a U.V. stabilizer of 2-hydroxy-4-methox 2-carboxybenzophenone and an antioxidant described in Example 1 are added in the same amounts as in Example 1 for Paint B.

A Clear Coating G (control) is prepared from the aqueous acrylic dispersion, and a Clear Coat H is prepared which is identical to Coating G except the above U.V. stabilizer and antioxidant are added in the same amounts as in Example 1 for Clear Coating B.

Paints G (control) and H are reduced to a spray viscosity and each is sprayed onto separate phosphatized steel panels and allowe to air dry for 10 minutes.

Clear Coats G (control) and H are reduced to a spray viscosity. Clear Coat G (control) is sprayed onto Paint G (control) coated panel. Clear Coat H is sprayed onto a Paint H coated panel. Each panel is dried and baked as in Example 1. The clear coat on each of the panels is about 1.2 mils thick, and the paint on each of the panels is about 0.8 mils thick. The panels are then exposed to a "Weather-O- Meter" as in Example 1. The gloss of each of the panels is measured at 20° after given exposure times and checking of the clear coat is noted . The results are as follows :

EXPOSURE DATA Gloss Measured At 20°

Time Exposure (hrs . ) 0 400 800 1200 1400 -1800 2200 . 2600 ^" .2800

Clear Coat G/ 90 81 67 39 21 FAILED Color Coat G (control)

Clear Coat H/ 80 81 77 73 71 68 58 28 16 Color Coat H (distorted)

The results show that the control failed after 1400 hours while Clear Coat H/Color Coat H, which contains an antioxidant and a U.V. stabilizer distorted after 2200 hours exposure. From these data, it can be^' expected that clear coat/color coat systems of an aqueous acrylic dispersion enamel that contains an antioxidant and a U.V. stabilizer will have an outdoor durability substantially better than that of the same enamel that does not contain an antioxidant and a U.V. stabilizer.

EXAMPLE 5

An acrylic enamel containing cellulose acetate butyrate is prepared according to the teachings of U.S. Patent 3,637,546, issued June 25, 1972. A Paint I (control) is prepared using the same pigmenta^¬ tion as used in Example 1, and Paint J is prepared which is identical to Paint I except a U.V. stabilizer of a substituted 2(2,hydroxyphenyl) benzotriazole and an anti¬ oxidant identified in Example 1 are added in the same amounts as in Example 1 for Paint B.

A Clear Coating I (control) is prepared from the above acrylic enamel containing cellulose acetate butyrate, and a Clear Coat J is prepared which is identical to Coating I except that the U.V. stabilizer and antioxidant are added as above in the same amounts as in Example 1 for Clear Coating B.

About 0.3% by weight, based on the weight of the binder, of iron pyrophosphate is included in each of the above paints and clear coats.

Paints I (control) and J are reduced to a spray viscosity and each is sprayed onto separate phosphatized steel panels and allowed to air dry for 10 minutes.

Clear Coats I (control) and J are reduced to a spray viscosity. Clear Coat I (control) is sprayed onto Paint I (control) coated panel. Clear Coat J is sprayed onto Paint J coated panel. Each panel is dried and baked as in Example 1. The clear coat on each of the panels is about 1.0 mil thick, and the paint on each of the panels is about 1.0 mil thick.

The panels are then exposed to a "Weather-O- Meter" as in Example^' 1. The gloss of each of the panels is measured at 20° after given exposure times and checking of the clear coat is noted. The results are as follows:

EXPOSURE DATA

Gloss Measured At 20^c

Time Exposure (hrs.) 500 1000 1500 2100 3000 4000

Clear Coat 1/ 82 74 68 62 40 — FAILED ~

Color Coat I (blis¬

(control) tered)

Clear Coat J/ 88 88 85 85 84 82 70 Color Coat J

EXPOSURE DATA, Cont. Gloss Measured At 20°

Time Exposure (hrs.) 4800 5000 5250

Clear Coat 1/ FAILED Color Coat I (control) 25

Clear Coat J/ 68 66 63 Color Coat J (checked)

The results show that the control failed after 2100 hours while Clear Coat J/Color Coat J, which contains an antioxidant and a U.V. stabilizer checked after 5250 hours exposure. From these data, it can be expected that clear coat/color coat systems of an acrylic enamel that contain iron pyrophosphate, an antioxidant and a U.V. stabilizer will have a substan- tially longer period of outdoor durability than that of the same acrylic enamel that contains iron pyrophos¬ phate but does not contain an antioxidant and a U.V. stabilizer.

EXAMPLE 6 An acrylic enamel containing cellulose acetate butyrate is prepared identical to the enamel of Example 5.

The following paints are prepared from the acrylic enamel using the same pigmentation as used in Example 1:

%, Based on Binder, %, Based on Binder, U.V. Stabilizer Antioxidant

Paint K 0 0

Paint M 3.6 0

Paint N 8.3 0

Paint 0 3.6 0.27

The following clear coats are prepared from the acrylic enamel:

%, Based on Binder, %, Based on Binder,

U.V. Stabilizer Antioxidant

Clear Coat K 0 0

Clear Coat L 6.3 0

Clear Coat M 3.6 0

Clear Coat 0 3.6 0.27

The U.V. stabilizer and antioxidant used in ^:the above paints and clear coats are identified in Example 5.

Paints K, M, N and O are each reduced to a spray viscosity and are each sprayed onto separate phosphatized steel panels and allowed to dry for 10 minutes.

Clear coats K, L, M and 0 are each reduced to a spray viscosity and sprayed to form the following finishes on the panels: Clear Coat K/Paint K (control)

Clear Coat L/Paint K Clear Coat M/Paint M Clear Coat K/Paint N Clear Coat O/Paint O. Each panel is dried and baked as in

Example 1. The clear coat on each of the panels is about 1.0 mil thick, and the paint on each of the panels is about 1.0 mil thick.

The panels of Clear Coat L and Paint K in which the Clear Coat L contains 6.3% U.V. absorber had a discoloration or^" tne clear coat, and the clear coat is softer than the clear coat on the other panels. The discoloration and softness are attributed to the hiσh U.V. stabilizer content of the Clear Coat L. The panels are then exposed to a "Weather-

O-Meter" as in Example 1. The gloss of each of the panels is measured at 20° after given exposure times and checking of the clear coat is noted. The results are as__follows:

EXPOSURE DATA Gloss Measured At 20°

Time Exposure (hrs . ) 0 167 330 659 988 1153 1480 1642 1855 Clear Coat K/ 82 84 89 83 82 75 39* — Failed — Paint K (control)

Clear Coat / 81 82 88 88 82 87 84 87 91 Paint K

Clear Coat M/ 86 86 89 90 93 92 88 94 98 Paint M Clear Coat K/ 87 87 88 89 91 91 84 93 95 Paint N

Clear Coat 0/ 84 86 87 89 89 91 86 93 94 Paint 0

EXPOSURE DATA, Cont.

Time Exposure (hrs . ) 2044 2328 3011 3222 3900 4500 5300

Clear Coat K/ E D Paint K (control)

Clear Coat L/ 88 80 82 84 82 82* 58* Paint K

Clear Coat M/ 88 87 93 94 93 84* 30* Paint M

Clear Coat K/ 87 84 93 94 79* 46* Paint N

Clear Coat 0/ 93 90 96 88 62* Paint 0

* Checked

The above results show that the control which did not contain U .V. stabilizer and antioxidant checked at 1480 hours exposure and failed thereafter . The panel having a finish of Clear Coat L which contained a relatively large quantity of U .V . stabilizer and Paint K which did not contain U . V. stabilizer or antioxidant checked at 4500 hours ; however, the finish was unacceptable for color and softness of the clear coat . The other panels had an acceptable appearance and hardness. The panel having a finish of Clear Coat M and Paint M in which both the clear coat and the color coat contained U.V. stabilizer checked at 4500 hours. The panel having a finish of a Clear Coat K with no U.V. stabilizer and Paint N with a large amount of U.V. stabilizer checked at 3900 hours and failed after 4500 hours. The panel having a finish of a Clear Coat O and Paint 0 which both contained U.V. stabilizer and antioxidant checked at 3900 hours and failed at 4500 hours. From these results, it can be expected that clear coat/color coat finishes that contain U.V. stabilizers alone or in combination with antioxidants can be expected to have a substantially longer period of outdoor durability than the same finishes without U.V. stabilizer and antioxidant. Also, the U.V. stabilizer need not be in the clear coat to be effective, but can be only in the color coat as shown by the panel having Clear Coat K and Paint N since the U.V. stabilizer migrates into the clear coat.

EXAMPLE 7

An acrylic nonaqueous dispersion enamel is prepared according to the teachings of U.S. Patent 3,966,667, issued June 29, 1976. A Paint P (control) is prepared using the same pigmentation as used in Example 1 and Paint Q is prepared which is identical to Paint P except a U.V. stabilizer of a substituted 2(2,hydroxyphenol) benzotriazole and antioxidant described in Example 1 are added in the same amounts as in Example 1 for Paint B.

A Clear Coat P (control) is prepared from the nonaqueous dispersion enamel, and a Clear Coat Q is prepared which is identical to Coating P except the above U.V. stabilizer and antioxidant are added in the same amounts as in Example 1 for Clear Coating B. To Clear Coat Q, 3.2% by weight, based 29 on the weight of the binder, of finely divided silica and 2% by weight, based on the weight of the binder, of iron pyrophosphate are added.

Paints P (control) and Q are reduced to a spray viscosity and each is sprayed onto separate phosphatized steel panels and allowed to air dry for 10 minutes.

Clear Coats P (control) and Q are reduced to a spray viscosity. Clear Coat P (control) is sprayed onto Paint P (control) coated panel. Clear Coat Q is sprayed onto Paint Q coated panel. Each panel is dried and baked as in Example 1. The clear coat on each of the panels is about 1.0 mil thick, and the paint on each of the panels is about 1.0 mil thick.

The panels are then exposed to a "Weater-O- Meter" as in Example 1. The gloss of each of the panels is measured at 20° after given exposure times and checking of the clear coat is noted. The results are as follows:

EXPOSURE DATA

Gloss Measured At 20°

Time Exposure

(hrs.) 0 500 1000 1500 2000 2200 2500 3000

Clear Coat P/ 85 86 82 85 85 82** 82 79

Color Coat P (control)

Clear Coat Q/ 85 82* 42 15 12 83* 23 93*

Color Coat Q

* Polished with standard automotive polish to restore gloss^■ ** Checked The results show that the control checked after 2200 hours, while Clear Coat Q/Color Coat Q, which contains an antioxidant and a U.V. stabilizer, did not check even after 3000 hours exposure. Clear Coat Q/Color Coat Q lost gloss at a more rapid rate than the control but the gloss was restored by polishing. From these data, it can be expected that clear coat/ color coat system of a nonaqueous acrylic dispersion enamel that contains an antioxidant and a U.V. stabilizer and the above additives will have an outdoor durability greater than that of the same enamel that does not contain an antioxidant and a stabilizer.

Claims

1. A substrate having a finish of a clear coat top layer in firm adherence to a color coat layer in adherence with the substrate; wherein the clear coat consists essentially of a transparent film forming binder; the color coat consists essentially of a film forming binder and pigments in a pigment to binder weight ratio of about 1/100 to 150/100; and the color coat contains about 0.1-20% by weight, based on the weight of the binder, of an ultraviolet light stabilizer.

2. The substrate of claim 1 in which the color coat is about 0.4-1.5 mils thick and the clear coat is about 0.5-5.0 mils thick.

3. The substrate of claim 1 in which both the color coat and the clear coat each contain an ultra¬ violet light stabilizer.

4. The substrate of claim 1 in which both the color coat and the clear coat each contain about 1-20% by weight, based on the weight of the binder, of an ultraviolet light stabilizer and about 0.1-5% by weight, based on the weight of the binder, of an antioxidant; wherein the weight ratio of ultraviolet light stabilizer to antioxidant is 1:1 to about 50:1. 5. .The. substrate of claim 4 in_._ which the ultraviolet light stabilizer is a benzopheno or a substituted benzotriazole type stabilizer.

6. The substrate of claim 4 in which the antioxidant is an alkylene (dialkyl hydroxy aryl) ester alkane.

1. ' The substrate of claim 4 in which the binder of the clear coat and the color coat is an acrylic polymer or a mixture of acrylic polymers. 8. The substrate of claim 7 in which the binder of the clear coat and the color coat consists essentially of

(A) at least one of

(1) poly(methyl methacrylate) , (2) poly(ethyl methacrylate) ,

(3) poly(propyl methacrylate),

(4) poly(isopropyl methacrylate),

(5) a copolymer consisting of methyl methacrylate and at least one of an alkyl acrylate whose alkyl group contains 1 through 20 carbon atoms, an alkyl methacrylate whose alkyl group contains 2 through 18 carbon atoms, or styrene,

(6) mixtures of these, and

(B) at least one of

(1) a copolymer consisting of methyl methacrylate and an alkyl acrylate whose alkyl group con¬ tains 1 through 10 carbon atoms or an alkyl methacrylate whose alkyl group contains 4 through 18 carbon atoms, or

(2) mixtures of said copolymers. 9• The substrate of claim 8 in which the binder of the clear coat and the color coat consists essentially of (A) poly(methyl methacrylate)" and _f (B) at least one of

(1) a methyl methacrylate/methyl acrylate copolymer whose monomer unit weight ratio is 70/30 to 40/60 respectively, (2) a methyl methacrylate/ethyl acrylate copolymer whose monomer unit weight ratio is 80/20 to 40/60 respectively,

(3) a methyl methacrylate/butyl acrylate copolymer whose monomer unit weight ratio is 85/15 to 65/35 respectively,

(4) a methyl methacrylate/2-ethyl- hexyl acrylate copolymer whose monomer unit weight ratio is 90/10 to 70/30 respectively,

(5) a methyl methacrylate/octyl methacrylate copolymer whose monomer unit weight ratio is 85/15 to 65/35 respectively, or

(6) a methyl methacry1ate/1auryl methacrylate copolymer whose monomer unit weight ratio is 90/10 to 75/25 respectively. ]0. The substrate of claim 9 in which the binder contains in addition to the acrylic polymer an alkyd resin and cellulose acetate buty¬ rate.

11. The substrate of claim 10 in which the ultraviolet light stabilizer is hydroxy dodeσyloxy benzophenone and the antioxidant is tetrakis methy¬ lene 3(3* ,5 ' -dibutyl-4 '-hydroxyphenol) proprionate methane.

12. The substrate of claim η in which the acrylic polymer ±έ a graft copolymer consis¬ ting essentially of a backbone copolymer of polymerized

(a) monomers of about 85-99.6%, by weight based on the weight of the backbone, of an alkyl ester of acrylic acid or methacrylic acid; (b) monomers which provide potential grafting sites of about 0.2-15%, by weight based on the weight of the backbone, of allyl methacrylate; and

(c) about 0.2-5% by weighty based on the weight of the backbone, of diethyl- aminoethyl methacrylate, tert-butyl- amino ethyl methacrylate, aminoethyl- vinyl ether or dimethylaminoethyl methacrylate; the total of the monomers which provide potential grafting sites do not exceed 15% by weight of the tota backbone, and a polymeric graft segment comprised of polymerized monomers of 2-ethyl hexyl acrylate, buty- acrylate, 2-ethyl hexyl methacrylate or lauryl metha- crylate, the graft segment comprising about 5-80% by weight of the total graft copolymer.

13. The substrate of claim 12 in which the acrylic polymer consists essentially, of a back¬ bone of polymerized monomers of methyl methacrylate, diethyl- aminoethyl methacrylate, allyl methacrylate and a graft segmentof polymerized monomers of 2-ethylhexylacrylate or butyl acrylate.

14. The substrate of claim 13 in which the ultraviolet light stabilizer is hydroxy dodecyloxy benzophenone and the antioxidant is tetrakis methy- lene 3(3' ,5'-dibuty1-4 'hydroxyphenyl) proprionate methane.

15. The substrate of claim 7 in which the binder of the clear coat and the color coat consists essentially of a polymer blend of (1) a polymer of methyl methacrylate and

(2) a polymer of methyl methacrylate, an alkyl acrylate or an alkyl metha¬ crylate having 2-12 carbon atoms in alkyl groups and an ethylenically unsaturated carboxylic acid and (3) a graft copolymer of (1) and (2) above. 16. The substrate of claim 4 in which the binder of the clear coat and the color coat is an acrylic polymer crosslinked with an alkylated melamine formaldehyde resin. j η _m The substrate of claim 4 in which the binder of the clear coat and the color coat is an acrylic polymer and contains cellulose acetate butyrate and crosslinked with an alkylated melamine formaldehyde resin.

18. The substrate of claim 17 in which the binder of the clear coat and the color coat consists essentially of

(1) 50-30% by weight, based on the binder of an acrylic polymer which consists essentially of

(a) 0-25% by weight styrene,

(b) 25-55% by weight methyl methacrylate,

(c) 38-48% by weight of a soft constituent selected from the group consisting of an alkyl acrylate and an alkyl methacrylate wherein the alkyl groups contain 2-12 carbon atoms;

(d) 5-20% by weight of hydroxy containing constituent selected from the group con¬ sisting of a hydroxy alkyl methacrylate and ahydroxy alkyl acrylate wherein the alkyl groups•^■ contain 2-4 carbon atoms; and (e) 1-5% by weight of an et,β- unsaturated monocarboxylie acid; wherein said acrylic polymer has a relative viscosity of 1.04-1.10 measured at 25°C in ethylene dichloride according to ASTM . D-445-46T, Method B;

(2) 5-50% by weight, based on the weight of the binder, of cellu lose acetate butyrate having butyryl content of about 45- 55% by weight and a viscosity at 25 C. of about 1-6 seconds measured according to ASTM-D- 1343-56; and

(3) 5-50% by weight based on the weight of the binder of a melamine formaldehyde resin which has been at least partially reacted with an aliphatic monohydric alcohol having from 1-4 carbon atoms.

19. The substrate of claim 18 in which the acrylic polymer consists essentially of 10- 18% by weight styrene, 25-30% by weight methyl metha¬ crylate, 38-42% by weight butyl acrylate, 10-16% by weight hydroxyethyl acrylate and 1-3% by weight acrylic acid.

20.. The substrate of claim 18 in which the acrylic polymer consists essentially of

40-50% by weight methyl methacrylate, 40-48% by weight butyl acrylate, 6-10% by weight hydroxyethyl acrylate, 3-5% by weight acrylic acid.

21. The substrate of claim 18 in which the ultraviolet light stabilizer is a 2(2,- hydroxy phenyl) benzotriazole and the antioxidant is tetrakis methylene 3 (3 ' ,5'-dibutyl-4 '-hydroxy phenyl)- proprionate methane.

22. The substrate of claim 4 con¬ taining up to 10% by weight, based on the weight of the binder, of iron pyrophosphate.

23. The substrate of claim 4 con¬ taining up to 15% by weight, based on the weight of the binder of finely divided silica. 24. The substrate of claim 4 con¬ taining about 0.1-10% by weight, based on the weight of the binder of iron pyrophosphate and about 0.5-15% by weight, based on the weight of the binder, of finely ^• divided silica.

25. The substrate of claim 4 in which the binder of the color coat and the clear coat consists essentially of

(1) an acrylic polymer of methyl ' methacrylate, an alkyl acrylate or an alkyl methacrylate other than methyl methacrylate, a hydroxy alkyl acrylate or a hydroxy alkyl methacrylate and an <_JB -unsaturated carboxylic acid wherein the polymer has an acid number of 35-150 and a carboxyl/hydroxy ratio of 1:0.2 to 1:3; and

(2) crosslinked with alkylated melamine formaldehyde resin.

26. The substrate of claim 25 in which the acrylic polymer consists essentially of 50-60% by weight of methyl methacrylate, 30-40% by weight of butyl acrylate, 5-10% by weight of hydroxy ethyl acrylate and 4-12% by weight of acrylic acid and the polymer has an acid number of about 35-100 and a carboxyl to hydroxyl ratio of 1:0.3 to 1:1.5.

27. The substrate of claim 25 in which the acrylic polymer consists essentially of 28-32% by weight of styrene, 22-26% by weight of methyl methacrylate, 30-35% by weight of butyl acrylate, 7-9% by weight of hydroxy ethyl acrylate, 4-6% by weight of acrylic acid, and has an acid number of 30-50, and a carboxyl to hydroxyl ratio of 1:0.4 to l.:1.5.

28. The substrate of claim 25 in which the acrylic polymer consists essentially of 54% methyl methacrylate, 34% butyl acrylate, 6% 2-hydroxy- Claim 28 cont'd ethyl acrylate and 6% acrylic acid and has an acid number of about 45-50 and a carboxyl to hydroxyl ratio of about 1:0.6. ⁵ 7.9 . The substrate of claim 25 in which the ultraviolet light stabilizer is 2-hydroxy-4-methoxy-2'- carboxy benzophenone or hydroxy phenyl benzotriazole.

30. The substrate of claim 4 in which the binder of the color coat consists essentiall

10 of a polymer formed by polymerizing a hydroxy alkyl acrylate or methacrylate in the presence of a dis¬ persion stabilizer.

31. The substrate of claim 30 in which the dispersion stabilizer is formed by

15 a. polymerizing

1. the reaction product of glycidyl methacrylate and poly(12-hydroxystearic acid),

2. methyl methacrylate, and on

3. glycidyl methacrylate to form a copolymer product containing pendant epoxy groups; and b. reacting said pendant epoxy groups with methacrylic acid.

25 32. The substrate of claim 31 in which the ultraviolet light stabilizer is a substi¬ tuted 2(2-hydroxy phenol) benzotriazole and the antioxidant is tetrakis methylene 3 (3* ,5* ,-dibutyl- 4'-hydroxyphenyl) proprionate methane.

30 33. The substrate of claim 4 in which the binder of the color coat is a blend of a polyester of a polyol and a dicarboxylic acid and a crosslinking agent and the binder of the clear coat is an acrylic polymer. 5 34. The substrate of claim 33 in which the binder of the color coat is a blend consisting Claim 34 cont'd essentially of

35-70% by weight, based on the weight of the blend, of a polyester of alkylene 5 glycol/a triol/aromatic dicarboxylic acid/aliphatic dicarboxylic acid.

15-30% by weight, based on the weight of the polymer blend, of cellulose acetate butyrate and 10 15-35% by weight, based on the weight of the polymer blend, of an alkylated melamine formaldehyde resin and the binder of the clear coat is an acrylic resin.

35. The substrate of claim 34 in

15 which the ultraviolet light stabilizer is a substituted 2 (2,hydroxyphenol) benzotriazole.

36. A process for finishing a sub¬ strate which comprises:

^'(1) applying a color coat layer

20 to the substrate wherein the color coat consists essentially of a liquid carrier and a film forming binder and pigments in a pigment to binder ratio of about 1/100 to about 150/100; and

25 (2) applying a clear coat layer directly to the color coat layer wherein the clear coat consists essentially of a ^' liquid carrier and a film forming binder; and wherein the color coat contains

³⁰ about 0.1-20% by weight, based on the weight of the binder, of an ultraviolet light stabilizer.

(3) drying the above applied layers to form a finish on the _,_c substrate. 37. The process of claim 36 in which the resulting color coat is about 0.4-1.5 mils thick and the clear coat is about 0.5-5.0 mils thick.

38. The process of claim 37 in which both 5 the color coat and the clear coat each contain about

1-20%, by weight, based on the weight of the binder, of an ultraviolet light stabilizer and about 0.1-5% by weight, based on the weight of the binder, of an anti¬ oxidant; wherein the weight ratio of ultraviolet light 0 stabilizer to antioxidant is 1:1 to about 50:1.

39. The process of claim 38 in which the color coat and clear are an acrylic lacquer in which the binder consists essentially of

(A) at least one of 5 (1) poly(methyl methacrylate),

(2) poly(ethyl methacrylate) , (3) - poly(propyl methacrylate) ,

(4) poly(isopropyl methacrylate),

(5) a copolymer composed only of n methyl methacrylate and at least one of an alkyl acrylate whose alkyl group contains 1 through 20 carbon atoms, an alkyl methacrylate whose alkyl group contains 2 through 18 carbon atoms, or styrene, 5 (6) mixtures of these, and (B) at least one of

(1) a copolymer composed only of methyl methacrylate and an alkyl acrylate whose alkyl group con¬ tains 1 through 10 carbon atoms or an alkyl methacrylate whose 0 alkyl group contains 4 through 18 carbon atoms, or

(2) mixtures of said copolymers; and containing an inert organic sol¬ vent for (A) and (B) .

5 40. The process of claim 38 in which the color coat and the clear coat are solvent based acrylic dispersion lacquers in which the binder con¬ sists essentially of a graft copolymer having

5 (A) a backbone which is a copolymer comprised of polymerized

(a) monomers of about 85-99.6% by weight, of an alkyl ester of acrylic acid or methacrylie acid;

10 (b) monomers which provide potential grafting sites of about 0.2-15% by weight, of allyl methacrylate; and monomers of about

(c) 0.2-5% by weight.of diethyl- ,. aminoethyl methacrylate, tert- butylaminoethyl methacrylate, aminoethylvinyl ether or di- methylaminoethyl methacrylate; the total of the monomers which provide potential grafting sites not exceeding

2o 15% by weight of the total backbone, and

(B) a polymeric graft segment comprised of polymerized monomers of 2- ethyl hexyl acrylate, butylacrylate, 2-ethylhexyl methacrylate or lauryl methacrylate, the graft segment comprising from 5-80% by 25 __-_" weight of the total graft copolymer.

41. The process of claim 40 in which the graft copolymer has a backbone which is a copolymer comprised of polymerized monomers of methyl metha¬ crylate , allyl methacrylate and diethylaminoethyl

30 methacrylate, and graft segments which are a co¬ polymer comprised of polymerized monomers of 2-ethyl hexyl acrylate or butyl acrylate.

42. The process of claim 38 in which the color coat and the clear coat are aqueous acrylic 35 dispersions in which the binder consists essentially Claim 42 cont'd

(1) a dispersed polymer A of methyl methacrylate and small amounts of an adhesion promoting monomer and

(2) a dispersant polymer B of methyl methacrylate, an alkyl acrylate or an alkyl methacrylate and an ethylenically unsaturated car- boxylic acid;

(3) a graft copolymer of the dis- ₀ persed polymer A and dispersant polymer B and the lacquer con¬ tains sufficient base to provide a pH of about 7-11.

43. The process of claim 38 in which the color coat and clear coat are aqueous acrylic 5 dispersion in which the binder consists essentially of

(1) an acrylic polymer of methyl methacrylate, an alkyl acrylate or an alkyl methacrylate other than methyl methacrylate, a _Q hydroxy alkyl acrylate or a hydroxy alkyl methacrylate and an α,β-unsaturated carboxylic acid wherein the polymer has an acid number of 35-150 and a carboxyl/hydroxyl ratio of 1:0.2 to 1:3; and

(2) a water soluble or water dispersi ble alkylated melamine formal¬ dehyde resin and contains suf¬ ficient base to provide a pH of about 7-11.

44. The process of claim 38 in which the color coat and the clear coat are a thermosetting nonaqueous dispersion of a polymer formed by poly¬ merizing a hydroxy alkyl acrylate or methacrylate in a liquid in the presence- of a dispersion stabilizer.

45. The process of claim 44 in which the dispersion stabilizer is formed by a. polymerizing

1. the reaction product of glycidyl methacrylate and poly(12-hydroxystearic acid). Claim 45 cont'd

2. methyl methacrylate, and

46. The process of claim 38 in which the color coat and clear coat are a thermosetting acrylic enamel comprising 10-60% by weight of a film-forming binder and a solvent for said binder wherein said binder consists essentially of

(1) 50-80% by weight, based on the weight of the binder, of an acrylic polymer which consists essentially of (a) 0-25% by weight styrene,

(b) 25-55% by weight methyl methacrylate,

(c) 38-48% by weight of a soft constituent selected from the group consisting of an alkyl acrylate and an alkyl meth¬ acrylate wherein the alkyl groups contain 2-12 carbon atoms;

(d) 5-20% by weight of a hydroxy containing constituent selected from the group consisting of a hydroxy alkyl methacrylate and a hydroxy alkyl acrylate wherein the alkyl group contain 2-4 carbon atoms; and

(e) 1-5% by weight of an Cf,/3-u satu¬ rated monocarboxylic acid; wherein said acrylic polymer has a relative viscosity of 1.04-1.10 measured at 25°C in ethylene di- chloride according to ASTM D-445-46T, Method B; •

(2) 5-50% by weight, based on the weight of the binder, of cellulose acetate butyrate having butyryl content of about 45-55% by weight and a viscosity at 25°C. of about 1-6 seconds measured according to ASTM-D-1343-56; and Claim 46 cont'd

(3) 5-50% by weight based on the weight o the binder, of a melamine formalde¬ hyde resin which has been at least partially reacted with an aliphatic monohydric alcohol having from 1-4 carbon atoms.

47. The process of claim 38 in which the enamel contains about 0.1-10% by weight, based on the weight of the binder of iron pryophosphate and 0.5- 15% by weight, based on the weight of the binder, of finely divided silica.

48. The process of claim 38 in which the color coat is a composition of comprising about 10-50% by weight, of a blend of a polyester of a polyol and a dicarboxylic acid and a crosslinking agent and the clear coat is an acrylic lacquer.

49- The substrate of claim 2 in which the substrate is metal.

50. The substrate of claim 2 in which the substrate is a ferrous metal. 5i The substrate of claim 2 in which the substrate is a flexible material.

52. The substrate of claim 51 in which the substrate is a flexible plastic.

53. The substrate of claim 51 in which the substrate is a flexible hydrocarbon rubber.

54. The substrate of claim 51 in which the flexible material is a polyurethane.