WO1981000233A1 - Revetement transparent/colore contenant un element stabilisateur vis-a-vis des ultra-violets - Google Patents

Revetement transparent/colore contenant un element stabilisateur vis-a-vis des ultra-violets Download PDF

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Publication number
WO1981000233A1
WO1981000233A1 PCT/US1979/000540 US7900540W WO8100233A1 WO 1981000233 A1 WO1981000233 A1 WO 1981000233A1 US 7900540 W US7900540 W US 7900540W WO 8100233 A1 WO8100233 A1 WO 8100233A1
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WIPO (PCT)
Prior art keywords
weight
methacrylate
substrate
binder
coat
Prior art date
Application number
PCT/US1979/000540
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English (en)
Inventor
D Chang
Original Assignee
Du Pont
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Du Pont filed Critical Du Pont
Priority to PCT/US1979/000540 priority Critical patent/WO1981000233A1/fr
Publication of WO1981000233A1 publication Critical patent/WO1981000233A1/fr
Priority to EP79901288A priority patent/EP0033725A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • B05D7/532—Base coat plus clear coat type the two layers being cured or baked together, i.e. wet on wet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2201/00—Polymeric substrate or laminate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate

Definitions

  • 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.
  • 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.
  • U.V. stabilizer 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.
  • the color coat can contain an antioxidant which also migrates to the clear coat.
  • the antioxidant can also be used in the clear coat.
  • 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.
  • 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.
  • 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.
  • 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-(2 1 ,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'-o ⁇ tylphenyl) 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.
  • ultraviolet light stabilizers that can be used include lower alkyl thiomethylene containing phenols, substi ⁇ tuted benzenes such as 1,3-bis-(2 1 -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, ⁇ ».
  • 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.
  • 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
  • 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-anilinopheny
  • 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
  • One particular pref rred acrylic lacquer the film form ⁇ ing component is poly(methyl methacrylate) and is at least one of .
  • 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 fo ⁇ ning c ⁇ rponent a graft copolymer having a backbone which is a copolymer of polymerized
  • graft copolymer used in these dispersion lacquers c ⁇ prises 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
  • a dispersed polymer of methyl methacrylate that can contain small amounts of adhesion pr ⁇ noting monomers such as diethylam__noethyl_ ⁇ ethacrylate and
  • 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 the ⁇ rosetting acrylic enamels of an acrylic polymer and a crosslinker such as an alkylate _ ⁇ el__mine formaldehyde can be used such as those described in Parker
  • 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
  • thermosetting acrylic enamels can also be used. These enamels contain the following film-forming constituents :
  • 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 __ . ,j ⁇ -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
  • 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 hydr ⁇ xyl ratio of 1:0.4 to 1:1.5.
  • 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 elai ⁇ ine formaldehyde, a benzoguanamine for alde hyde. urea formaldehyde and the like.
  • One useful polyester enamel has a binder of a polymer blend of about-.
  • 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
  • thermosetting acrylic dispersion enamels Typically useful nonaqueous thermosetting acrylic dispersion enamels and process for making the same are disclosed in
  • 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
  • iron pyrophosphate and finely divided silica are particularly useful additives for both the colo coat and the clear coat.
  • 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
  • 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 .
  • Aluminum Flake Mill Base 15.48 (29.8% polymethyl metha ⁇ crylate, 12.4% aluminum flake and 57.8% 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/DEAM Solution 50% 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)
  • 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)
  • 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:
  • a clear coating A (control) is prepared by blending together the following constituents:
  • PMMA/BA Solution 50% 33.45 solids of a copolymer of 82% ethy methacrylate and 18% butyl acrylate in acetone/, toluene, 17/83 ratio
  • 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)
  • a clear coating B is prepared as follows:
  • 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.
  • 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.
  • 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-
  • 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 :
  • 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.
  • 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.
  • Example ' 1 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:
  • EXAMPLE 6 An acrylic enamel containing cellulose acetate butyrate is prepared identical to the enamel of 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)
  • 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.
  • 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.

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  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)

Abstract

Un substrat est revetu d'une couche de finition consistant en un revetement transparent qui adhere fermement a une couche de revetement colore qui elle-meme adhere au substrat. Le revetement transparent consiste essentiellement en un liant formant un film transparent; le revetement colore consiste essentiellement en un liant formant un film ainsi qu'en pigments; le revetement colore contient un element stabilisateur vis-a-vis des ultra-violets et, eventuellement le revetement transparent ainsi que le revetement colore contiennent un antioxidant ainsi qu'un element stabilisateur vis-a-vis des ultra-violets. Cette couche de finition presente un apparence, une resistance aux intemperies et une duree de vie excellentes et s'avere particulierement utile en tant que couche de finition pour les automobiles et les camions.
PCT/US1979/000540 1979-07-26 1979-07-26 Revetement transparent/colore contenant un element stabilisateur vis-a-vis des ultra-violets WO1981000233A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/US1979/000540 WO1981000233A1 (fr) 1979-07-26 1979-07-26 Revetement transparent/colore contenant un element stabilisateur vis-a-vis des ultra-violets
EP79901288A EP0033725A1 (fr) 1979-07-26 1981-02-09 Revetement transparent/colore contenant un element stabilisateur vis-a-vis des ultra-violets

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PCT/US1979/000540 WO1981000233A1 (fr) 1979-07-26 1979-07-26 Revetement transparent/colore contenant un element stabilisateur vis-a-vis des ultra-violets
WOUS79/00540 1979-07-26

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WO1981000233A1 true WO1981000233A1 (fr) 1981-02-05

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4746194A (en) * 1984-07-17 1988-05-24 Peter Rasmussen Method of mounting an end portion of an optical fibre in an optical fibre connector
EP0285071A2 (fr) * 1987-03-27 1988-10-05 Avery International Corporation Procédé de peinture par transfert à sec et produit obtenu
WO1989006598A1 (fr) * 1988-01-25 1989-07-27 E.I. Du Pont De Nemours And Company Structure composite en polyolefine thermoplastique
GB2225737A (en) * 1988-11-07 1990-06-13 Ats Leichtmetallraeder Gmbh Fa Corrosion protection methods
US5707697A (en) * 1987-03-27 1998-01-13 Avery Dennison Corporation Dry paint transfer product having high DOI automotive paint coat
US5725712A (en) * 1987-03-27 1998-03-10 Avery Dennison Corporation Dry paint transfer process for making high DOI automotive body panels
US9475954B2 (en) 2014-12-24 2016-10-25 Hyundai Motor Company High-hardness clear coating material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2919259A (en) * 1956-08-22 1959-12-29 Ralph A Naylor Light stabilized polyvinyl chloride compositions
US3134752A (en) * 1961-12-21 1964-05-26 American Cyanamid Co Polystyrene color stabilized with trialkyl phenol and a benzophenone
US3639147A (en) * 1968-09-30 1972-02-01 Celanese Coatings Co Article having multilayer coating and process for producing same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2919259A (en) * 1956-08-22 1959-12-29 Ralph A Naylor Light stabilized polyvinyl chloride compositions
US3134752A (en) * 1961-12-21 1964-05-26 American Cyanamid Co Polystyrene color stabilized with trialkyl phenol and a benzophenone
US3639147A (en) * 1968-09-30 1972-02-01 Celanese Coatings Co Article having multilayer coating and process for producing same

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4746194A (en) * 1984-07-17 1988-05-24 Peter Rasmussen Method of mounting an end portion of an optical fibre in an optical fibre connector
US6835267B1 (en) 1987-03-27 2004-12-28 Avery Dennison Corporation Dry paint transfer process and product
US6649003B1 (en) 1987-03-27 2003-11-18 Avery Dennison Corporation Dry paint transfer lamination process for making high DOI automotive body panels
EP0285071A3 (en) * 1987-03-27 1988-11-30 Avery International Corporation Dry paint transfer process and product
US6984280B2 (en) 1987-03-27 2006-01-10 Avery Dennison Coporation Dry paint transfer process for making deep-draw high doi automotive body panels
US6966962B2 (en) 1987-03-27 2005-11-22 Avery Dennison Corporation Dry paint transfer-lamination process for making high DOI automotive body panels
AU628785B2 (en) * 1987-03-27 1992-09-24 Avery Dennison Corporation Exterior automotive dry paint transfer process and product
WO1988007416A1 (fr) * 1987-03-27 1988-10-06 Avery International Corporation Procede de transfert de peinture seche et produit obtenu
US5916643A (en) * 1987-03-27 1999-06-29 Avery Dennison Corporation Dry paint transfer-laminated body panels having deep-draw high DOI automotive paint coat
US5707697A (en) * 1987-03-27 1998-01-13 Avery Dennison Corporation Dry paint transfer product having high DOI automotive paint coat
US6579397B1 (en) 1987-03-27 2003-06-17 Avery Dennison Corporation Dry paint transfer process for making deep draw high DOI automotive body panels
US5725712A (en) * 1987-03-27 1998-03-10 Avery Dennison Corporation Dry paint transfer process for making high DOI automotive body panels
EP0285071A2 (fr) * 1987-03-27 1988-10-05 Avery International Corporation Procédé de peinture par transfert à sec et produit obtenu
WO1989006598A1 (fr) * 1988-01-25 1989-07-27 E.I. Du Pont De Nemours And Company Structure composite en polyolefine thermoplastique
GB2225737A (en) * 1988-11-07 1990-06-13 Ats Leichtmetallraeder Gmbh Fa Corrosion protection methods
US9475954B2 (en) 2014-12-24 2016-10-25 Hyundai Motor Company High-hardness clear coating material

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