EP0067989A1 - Vernis acrylique a thermoprise utilise contre les intemperies par addition d'un stabilisateur contre la lumiere ultraviolette - Google Patents

Vernis acrylique a thermoprise utilise contre les intemperies par addition d'un stabilisateur contre la lumiere ultraviolette

Info

Publication number
EP0067989A1
EP0067989A1 EP19810901404 EP81901404A EP0067989A1 EP 0067989 A1 EP0067989 A1 EP 0067989A1 EP 19810901404 EP19810901404 EP 19810901404 EP 81901404 A EP81901404 A EP 81901404A EP 0067989 A1 EP0067989 A1 EP 0067989A1
Authority
EP
European Patent Office
Prior art keywords
weight
composition according
ultraviolet light
coating
light stabilizer
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP19810901404
Other languages
German (de)
English (en)
Inventor
Jacques Marie Louis Berghmans
Jan Michel Bernard Switten
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0067989A1 publication Critical patent/EP0067989A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/32—Modified amine-aldehyde condensates

Definitions

  • This invention relates to coating compositions and to coated articles having a color coat overlaid with a clear coat.
  • it is directed toward thermosetting acrylic enamels containing ultraviolet light stabilizers, which enamels give a high quality weather resistant coating, especially useful for coating the exterior of automobile and truck bodies.
  • the enamels are prepared as disclosed in United States Patent 3,622,651 - Vasta issued November 23, 1971, incorporated herein by reference.
  • the addition of one or more ultraviolet light stabilizers serves to diminish the degradation effects of the ultraviolet radiation in the sunlight.
  • the enamels also contain one or more antioxidants.
  • Sunlight is composed of electromagnetic radiation with energy in the infrared, visible, and ultraviolet portions of the spectrum.
  • the energy may be partially or wholly absorbed by the coating.
  • the energy absorbed initiates a photochemical reaction which causes discoloration and/or physical failure of the coating.
  • Pigimented surface coatings also suffer from ultraviolet degradation.
  • the inclusion of an ultraviolet light stabilizer can increase the useful life of both clear and pigmented coatings. Ultraviolet light stabilizers protect the coatings by absorbing the destructive, high energyultraviolet rays and converting such energy into nondestructive heat energy.
  • Antioxidants are useful in preventing the oxidation of polymers, or for inhibiting oxidation already begun by oxygen, air, ozone, or oxidizing agents of many types.
  • the rate of thermal oxidation of the polymeric systems used in coating compositions is normally rather slow, i.e., a reaction that occurs over weeks, months, or years under ordinary conditions. However, even though the reaction is often slow, pronounced effects may be readily observable very early in the degradation reaction. Furthermore, more rapid oxidative degradation occurs in the presence of ultraviolet radiant energy.
  • Antioxidants can assist ultraviolet light stabilizers in effectively retarding this degradation.
  • Thermosetting acrylic enamel finishes are widely used on the exterior of automobiles and trucks.
  • Ultraviolet light stabilizers have traditionally been used only in those coating compositions which are utilized as topcoats. The problem with this procedure has been the tendency of the stabilizers to leach out of the topcoat and escape into the atmosphere, leaving the topcoat susceptible to weathering.
  • the composition of this invention containing ultraviolet light stabilizer and, optionally, antioxidant, has a preferred utility of being used as a clear coat/color coat finish and particularly as the clear coat of such a finish. It is theorized that the ultraviolet light stabilizer will migrate from the color coat into the clear coat, thereby protecting the clear coat against weathering.
  • the preferred finish is one in which both the clear coat and the color coat contain as additives one or more ultraviolet light stabilizers and one or more antioxidants. Some of the additives will be consumed from the clear surface through leaching, evaporation, and photochemical reaction. A high concentration of additives in the color coat will serve as a reservoir and replenish the lost additives through diffusion from the color coat to the clear coat.
  • Thermosetting acrylic enamels prepared according to the teachings of United States Patent 3,622,651 - Vasta can be used to provide clear coats of increased flexibility and durability.
  • Substrates are coated with first a color coat then a clear coat containg thermosetting acrylic enamels prepared according to the teachings of united States Patent 3,622,651 - Vasta and at least one ultraviolet light stabilizer.
  • the invention also provides a liquid coating composition consisting essentially of solvents and (a) 95-50%, byweight, of a polymer having a backbone of polymerized ethylenically unsaturated monomers and having ester groups attached directly to its backbone, said ester groups comprising about 10 to 75 percent of the total weight of the polymer and consisting essentially of Ester Group (A) 0-C-O-P ⁇ -OH and Ester Group (B) selected from the group consisting of
  • Ester Group (3) is from about 1:1.5 to 1:2.5;
  • R 1 is a saturated hydrocarbon radical containing
  • R 2 is selected from the group consisting of alkylene, vinylene, aromatic carbocyclic and heteroradicals
  • R 3 is selected from the group consisting of a saturated aliphatic hydrocarbon radical having one to 26 carbon atoms and an ethylenically unsaturated aliphatic hydrocarbon radical having 12 to 18 carbon atoms; (b) 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; and (c) at least one ultraviolet light stabilizer.
  • These enamels preferably contain about 1-20% by weight, based on the weight of the filmforming constituents, of ultraviolet light stabilizer.
  • they also contain about 0.1-5% by weight of antioxidant, wherein the weight ratio of ultraviolet light stabilizer to antioxidant is about 1:1 to about 50:1. More preferably, about 5-8% by weight of ultraviolet light stabilizer is used, optionally with about 0.1-1% by weight of antioxidant, wherein the weight ratio of ultraviolet light stabilizer to antioxidant is about 10:1.
  • the specified percentages of ultraviolet light stabilizer or antioxidant may be obtained by combining two or more ultraviolet light stabilizers or two or more antioxidants as well as by utilizing such additives singularly.
  • the acrylic polymer is prepared by conventional polymerization techniques in which the monomer constituents are blended with solvents and a polymerization catalyst and heated to 75-150°C. for about 2-6 hours to form a polymer that has a relative viscosity of about 1.04-1.10 and preferably about 1.06-1.09.
  • Typical solvents and diluents which are used to prepare the acrylic polymer and the coating composition of this invention are toluene, xylene, butyl acetate, acetone, methyl isobutyl ketone, methyl ethyl ketone, butyl alcohol, and other aliphatic, cycloaliphatic and aromatic hydrocarbons, esters, ethers, ketones, and alcohols, such as are conventionally used in coating compositions.
  • a polymerization catalyst is used to prepare the acrylic polymer.
  • Typical catalysts are di-t-butyl peroxide, cumene hydroperoxide, azobisisobutyronitrile and the like.
  • Typical ultraviolet light stabilizers which are useful in this, invention are as follows:
  • Benzophenones such as hydroxydodecycloxybenzophenone, 2,4-dihydroxybenzophenone, hydroxybenzophenones containing sulfonic acid groups, 2,4- dihydroxy-3',5'-di-t-butylbenzophenone, 2,2',4'- trihydroxybenzophenone esters of dicarboxylic acids, 2-hydroxy-4-acryloxyethoxybenzophenone, aliphatic monoesters of 2,2',4-t ihydroxy-4'-alkoxybenzophenone, 2- hydroxy-4-methoxy-2'-carboxybenzophenone;
  • Triazoles such as 2-phenyl-4-(2'-4'-dihydroxybenzoyl) triazoles, substituted benzotriazoles such as hydroxyphenyltriazoles such as 2-(2'-hydroxy-5'- methylphenyl)benzotriazole, 2-(2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-octylphenyl) naphthotriazole; Triazines such as 3,5-dialkyl-4-hydroxyphenyl derivatives of triazine, sulfur-containing derivatives of diallyl-4-hydroxyphenyltriazines, hydroxyphenyl1,3,5-triazines and such triazines containing sulfonic acid groups, aryl-1,3,5-triazines, orthohydroxyaryl-s- triazine;
  • Benzoates such as dibenzoate of diphenylolpropane, t-butyl benzoate of diphenylolpropane, nonyl ph ⁇ nyl benzoate, octyl phenyl benzoate, resorcinol dibenzoate.
  • ultraviolet light stabilizers that can be used include lower alkyl thiomethylene-containing phenols, substituted benzenes such as 1,3-bis(2' hydroxybenzoyl) benzene, metal derivatives of 3,5,-di-tbutyl-4-hydroxyphenylpro ⁇ ionic acid, asymmetrical oxalic acid diarylamides, alkylhydroxyphenylthioalkanoic acid esters, dialkylhydroxyphenylalkanoic acid esters of di- and tri- pentaerythritol, phenyl- and naphthlenesubstituted oxalic acid diamides, methyl- ⁇ -(3,5-di-1butyl-4-hydroxyphenyl)propionate, ⁇ , ⁇ '-bis(2-hydroxy phenyl) diisopropylbenzene, 3,5'-dibromo-2'-hydroxy- acetophenone, ester derivatives of 4,4-bis(4'-hydroxyphen
  • ultraviolet light stabilizers that can be used are hindered amines of bipiperidyl derivatives such as those disclosed 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-decanoylpyrazolate
  • Typical antioxidants are as follows: tetrakisalkylene dialkylhydroxyaryl alkyl ester alkanes such as tetrakismethylene-3-(3',5'-dibutyl-4'-hydroxyphenyl) propionate methane, the reaction product of p-aminodiphenylamine and glycidyl methacrylate, the reaction product of n-hexyl-N'-phenyl-p-phenylene diamine and glycidyl methacrylate, pentaerythritol tetrakis (thioglycolate), trimetlxylolpropane tris (thioglycolauc, trimethylolethane tris(thioglycolate), N-(4-anilinophenyl) acrylamide, N-(4-anilinophenyl)maleamic acid, N-(4-anilinophenyl)maleimide, alkylhydroxy
  • Plasticizers can be used in the novel coating composition of this invention in amounts of up to 20% by weight of the film-forming material. Preferably, about 3-8% by weight of a plasticizer is used.
  • Functional polymeric plasticizers which react with the constituents in the coating composition can be used, such as epoxidized soya bean oil, oil-free and oil-modified alkyIs and polyesters, such as polyorthophthalate esters, polyalkylene adipate esters or polyarylene adipate esters. Volatile non-functional monomeric plasticizers can also be used.
  • the enamel contains pigment in the amount of 0.1-20.0% pigment volume concentration. Preferably, a pigment volume concentration of about 0.3-6.0% is used.
  • the enamel may contain one or more transparent pigments , i . e . , pigments having the same or similar refractive index as the binder of the clear coat with a small particle size of about 0.015-50 microns.
  • iron pyrophosphate and finely divided silica are particularly useful additives for both the color coat and clear coat.
  • iron pyrophosphate and finely divided silica Up to about 10% by weight of iron pyrophosphate and up to about 15% by weight of silica, based on the weight of the film-forming constituents, can be used.
  • the addition of iron pyrophosphate and silica will improve the overall durability and performance of the finish.
  • iron pyrophosphate creates a synergistic effect with ultraviolet light stabilizers and antioxidants, yielding a period of outdoor weatherability surpassing that which would cumulatively be expected from a combination of the three types of additives .
  • Thermosetting acrylic enamels prepared in the manner described and containing about 1-20% by weight, and preferably about 5-8% by weight, based on the weight of the film-forming constituents, of ultraviolet light stabilizer prove particularly useful in clear coat/color coat finishes.
  • Such enamels may also contain about 0.1-5% by weight, and preferably about 0.1-1% by weight, of antioxidant. Where an antioxidant is used, the weight ratio of ultraviolet light stabilizer to antioxidant ranges from about 1:1 to about 50:1 and is preferably about 10:1.
  • novel coating compositions of this invention can be applied to a variety of substrates, e.g., metal, wood, glass, and plastics such as polypropylene, styrene, and copolymers of styrene, by any of the usual application methods, e.g., spraying, electrostatic spraying, dipping, brushing, flow coating, and the like.
  • the coating composition is applied over a suitably primed metal substrate.
  • These coatings can be air dried or can be baked to minimize the drying period.
  • the resulting coating is about 1-5 mils thick, preferably 1-3 mils thick, and can be rubbed or polished in accordance with conventional techniques, if desired, to improve smoothness or apparent gloss or both.
  • the coating preferably is cured at about 125-175oC. for about 15-30 minutes.
  • conventional catalyst to the novel composition, the curing temperature can be reduced to 80-110°C.
  • Typical catalysts that can be used are butyl acid phosphate, paratoluene sulfonic acid and the like.
  • EXAMPLE A steel substrate is coated with a chip-resistant primer and a primer surfacer which is sanded as appropriate to obtain the desired finish. Then the base coat or color coat is sprayed thereon, to a thickness of 15 ⁇ m and allowed to dry a few minutes until it is dry to the touch. Than the clear coat is sprayed on to a dry film thickness of 40-45 ⁇ m, let stand for 10 minutes, then baked 20 minutes at 130oC.
  • compositions known in the art can be used for the chip resistant primer and the primer surface. Although the same is true for the color coat, preferably it is made by blending the following ingredients by known techniques and reacting them at reflux:
  • Wax 6.84 The color coat is reduced 70-100% with butylacetate to facilitate spraying.
  • the clear coat includes an acrylate resin by blending the following ingredients and reacting them by heating I to reflux, about 650°C, then adding II and refluxing for 8 hours.
  • the acrylate resin at 60% solids is then blended with melamine and solvents as follows:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La capacite de resistance aux intemperies et la longevite des finis derives de vernis acryliques a thermoprise peuvent etre sensiblement ameliorees en ajoutant au vernis, avant de l'appliquer un ou plusieurs stabilisateurs a la lumiere ultraviolette et, eventuellement un ou plusieurs anti-oxydants. La flexibilite et la longevite d'une couche transparente dans un systeme de revetement en couleur/transparent peuvent etre ameliorees en utilisant une resine acrylique contenant un anhydride phtalique que l'on fait reagir avec un ester de glycidyle.
EP19810901404 1980-12-31 1980-12-31 Vernis acrylique a thermoprise utilise contre les intemperies par addition d'un stabilisateur contre la lumiere ultraviolette Withdrawn EP0067989A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1980/001756 WO1982002397A1 (fr) 1980-12-31 1980-12-31 Vernis acrylique a thermoprise utilise contre les intemperies par addition d'un stabilisateur contre la lumiere ultraviolette

Publications (1)

Publication Number Publication Date
EP0067989A1 true EP0067989A1 (fr) 1983-01-05

Family

ID=22154716

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19810901404 Withdrawn EP0067989A1 (fr) 1980-12-31 1980-12-31 Vernis acrylique a thermoprise utilise contre les intemperies par addition d'un stabilisateur contre la lumiere ultraviolette

Country Status (2)

Country Link
EP (1) EP0067989A1 (fr)
WO (1) WO1982002397A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6036565A (ja) * 1983-08-09 1985-02-25 Asahi Glass Co Ltd 被覆用硬化性樹脂組成物
EP0180548B1 (fr) * 1984-11-01 1989-06-28 Ciba-Geigy Ag Revêtements stabilisés contre l'action de la lumière

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3407156A (en) * 1964-06-03 1968-10-22 Du Pont Weatherable transparent coating composition for wood substrates
US3823205A (en) * 1965-11-22 1974-07-09 Du Pont Lacquers based on acrylic polymer blends
US3622651A (en) * 1969-12-01 1971-11-23 Du Pont Novel polymer having pendent ester groups for low temperature bake coatings
JPS5224286A (en) * 1975-06-30 1977-02-23 Toyoda Gosei Co Ltd Metallized article having a metallic thin film on its surface
US4208465A (en) * 1978-05-03 1980-06-17 E. I. Du Pont De Nemours And Company Clear coat/color coat finish containing an antioxidant and an ultraviolet light stabilizer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8202397A1 *

Also Published As

Publication number Publication date
WO1982002397A1 (fr) 1982-07-22

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