CA2228940C - Multicoat paint system, process for its preparation, and nonaqueous topcoat suitable therefore - Google Patents
Multicoat paint system, process for its preparation, and nonaqueous topcoat suitable therefore Download PDFInfo
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- CA2228940C CA2228940C CA002228940A CA2228940A CA2228940C CA 2228940 C CA2228940 C CA 2228940C CA 002228940 A CA002228940 A CA 002228940A CA 2228940 A CA2228940 A CA 2228940A CA 2228940 C CA2228940 C CA 2228940C
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- hydroxy
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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
- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
-
- 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
- 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
- B05D7/24—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 for applying particular liquids or other fluent materials
- B05D7/26—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 for applying particular liquids or other fluent materials synthetic lacquers or varnishes
-
- 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
- B05D7/56—Three layers or more
- B05D7/57—Three layers or more the last layer being a clear coat
- B05D7/572—Three layers or more the last layer being a clear coat all layers being cured or baked together
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
- C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31928—Ester, halide or nitrile of addition polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon
Abstract
The present invention relates to a process for producing a multicoat paint system, in which (1) an optionally pigmented basecoat is applied to a substrate surface, (2) a polymer film is formed from the basecoat film applied in stage (1), (3) one or more further coating films are applied optionally thereto, (4) then a nonaqueous topcoat is applied which comprises A) a hydroxy-functional polyacrylate resin, B) as crosslinking agent tris(alkoxycarbonylamino)- triazine and C) optionally further crosslinking agents, such as blocked isocyanates, which are different from the tris(alkoxycarbonylamino)triazine, and/or amino resins, and subsequently (5) the coating films are baked together, where in that [sic] the polyacrylate resin comprises secondary OH groups.
Description
29018-11(S) Multicoat paint system, process for its preparation, and nonaqueous topcoat suitable therefor The present invention relates to a multicoat paint system and to a process for producing it. The invention also relates to nonaqueous coating materials suitable for the multicoat paint system and for the~process for producing it.
The art describes a process for producing a two-coat paint system, in which (1) a pigmented basecoat is applied to the substrate surface (2) a polymer film is formed from the basecoat applied in stage (1) (3) a nonaqueous transparent topcoat is applied to the basecoat film thus obtained, and then (4) basecoat film and topcoat film are baked together.
The invention also relates to nonaqueous coating materials suitable for this process.
The above-described basecoat/clearcoat process is employed in particular for producing multicoat paint systems, especially metallic finishes on car bodies (cf. e.g. US-A-3,639,147 and EP-A-38 127).
t Using the basecoat/clearcoat process it is possible to produce finishes which, in comparison to one-coat topcoat systems, feature an improved rendering of the effect and feature the possibility of producing paint systems with bright and cleaner shades.
The basecoat applied first in stage (1), depending on the nature, amount and spatial orientation of the pigments employed, determines the shade and, if appropriate, the effect (e. g. metallic or pearlescent effect) of the paint system.
In stage (2) of the process, in an evaporation phase, at least some of the organic solvents and/or of the water is removed from the basecoat film applied in stage (1). Atop this pre-dried but unbaked basecoat film there is applied, in stage (3), a nonaqueous transparent topcoat (wet-on-wet technique) and then, in stage (4), basecoat film and topcoat film are baked together_ The transparent topcoat applied in stage (3) imparts gloss and fullness to the two-coat paint system and protects the pigmented paint film applied in stage (1) against chemical and physical attack.
Using the process under discussion it is possible to obtain high-quality two-coat paint systems only when the transparent topcoat applied in stage (3) does not inter-fere with the basecoat applied in stages (1) and (2) in r such a way that there is impairment of the optical effect (e.g. clouding). On the other hand, the composition of the transparent topcoat must be such that it adheres well to the basecoat film following the baking process con-s ducted in stage (4). Further important properties which the transparent topcoat film obtained after the baking process must have are high transparency, good gloss and good mechanical properties, such as hardness, scratch resistance and elasticity. The transparent topcoat film obtained after the baking process is required not least to have high resistance to climatic effects (e. g. tem perature fluctuations, moisture in the form of water vapor, rain, dew, attack by radiation etc.) and to attack by acids or other chemicals, such as organic solvents, for example.
Furthermore, the transparent topcoats applied in stage (3) should have a very low content of organic solvents, and good stability on storage.
JP-A-2-242867 describes a basecoat/clearcoat process in stage (3) of which nonaqueous transparent topcoats are applied which comprise (A) a hydroxyl-containing synthetic resin, (B) an amino resin and (C) a blocked polyisocyanate, where components (B) and (C) are to be selected such that the temperature at which a chemical reaction ensues between (A) and (C) is not more than 20°C
below and not more than 50°C above the temperature at which a chemical reaction ensues between (A) and (B).
r Blocking agents specified for preparing component (C) are: volatile compounds of low molecular mass containing active hydrogen atoms, such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, benzyl alcohol, ethylene glycol monoethyl ether and other aliphatic or aromatic monoalcohols, dimethyl- or diethylaminoethanol and other hydroxyl-containing tertiary amines, acetone oxime, methyl ethyl ketone oxime and other oximes, acetylacetone, acetoacetates, malonates and other com-pounds containing active methylene groups, e-caprolactam and other lactams, and phenol. Blocking agents preferably employed are aliphatic monoalcohols, oximes and capro-lactams.
The transparent topcoats described in JP-A-2-242867 give rise to paint systems which, especially in terms of their resistance to organic solvents and acids, gloss, trans-parency and resistance to yellowing, are to be improved.
DE-B-26 39 491 describes nonaqueous coating materials which comprise a hydroxyl-containing polyester resin and/or alkyd resin, hexamethylene diisocyanate blocked with an alkyl acetoacetate and/or 2,2,4 trimethylhexa-methylene [sic] diisocyanate blocked with an alkyl aceto-acetate, and an amino resin. These coating materials can also be employed as transparent topcoats in the sector of automotive finishing. The finishes obtained with these coating systems, especially when heightened baking temperatures and/or prolonged baking times are employed, 29018-11(S) . ' _ 5 _ undergo yellowing and are to be improved especially in terms of their resistance to acids and organic solvents and in terms of their scratch resistance.
The properties of the coating materials can be improved by the use of specific crosslinking agents. Mention should be made here in particular of the tris(alkoxy-carbonylamino)triazines and derivatives thereof that are known from US-A 5084541, 4939213, 5288865, 4710542 and from the EP Applications 0565774, 0541966, 0604922 and EP-B 0245700. Coating materials of this kind feature an especially good chemical resistance, which is evident in particular in the good results of outdoor weathering in Jacksonville, Florida. The tight crosslinking of such formulations, however, has the disadvantage of increased sensitivity toward moisture stresses, which is manifested in blushing of the coating films after such stresses.
The object of the present invention is now to provide a process for producing a multicoat paint system, in which:
(1) an optionally pigmented basecoat is applied to a substrate surface, (2) a polymer film is formed from the basecoat film applied in stage (1), (3) one or more further coating films are applied optionally thereto, (4) then a nonaqueous topcoat is applied which comprises 29018-11 (S) A) a hydroxy-functional polyacrylate resin, B) as crosslinking agent tris(alkoxycarbonylamino)-triazine and C) optionally further crosslinking agents, such as blocked isocyanates, which are different from the tris(alkoxycarbonylamino)triazine, and/or amino resins, and subsequently (5) the coating films are baked together, which leads to coating films having good results both in the case of outdoor weathering in Jacksonville and in the case of moisture stresses.
This object is achieved by the polyacrylate resin com-prising secondary OH groups.
The present invention accordingly provides as well a multicoat paint system comprising (1) one coat of a polymer film of an optionally pigmented basecoat which has been applied to a substrate surface, (2) optionally one or more coating films applied thereto, (3) one coat of a nonaqueous topcoat which comprises A) a hydroxy-functional polyacrylate resin, B) as crosslinking agent tris(alkoxycarbonylamino)-29018-11(S) triazine and C) optionally further crosslinking ageats, such as blocked isocyanates, which are different from the tris(alkoxycarbonylamino)triazine, and/or amino resins, and subsequently (4) the coating films are baked together, c h a r a c t a r i z a d in that the polyacrylate resin comprises secondary OH groups.
I0 A further subject of the invention is a nonac_ueous coating material comprising A) a hydroxy-functional polyaczylate resin, B) as crosslinking agent tris(alkoxycarbonylamino)-triazine and C) optionally further crosslinking agents, such as blocked isocyanates, which are different from the tris(alkoxycarbonylamino)triazine, and/or amino resins, c h a r a c t a r i z a d in that the polyacrylate resin (A) comprises secondary OH groups.
The invention also relates, finally, to the use of the specified nonaqueous coating material for producing transparent topcoats and to the use oz the multicoat paint system for coating car bodies.
29018-11(S) - 7a -According to one aspect of the present invention, there is provided a process for producing a multicoat paint system, comprising (1) applying a basecoat to a substrate surface, (2) forming a polymer film from the basecoat applied in stage (1), (3) applying to the polymer film a nonaqueous topcoat comprising (A) a hydroxy-functional polyacrylate resin comprising secondary OH groups, (B) as crosslinking agent tris(alkoxycarbonylamino)triazine and (C) optionally further crosslinking agents, and (4) baking together the nonaqueous topcoat applied to the polymer film.
According to another aspect of the present invention, there is provided a process for producing a multicoat paint system, comprising (1) applying a basecoat to a substrate surface, (2) forming a polymer film from the basecoat applied in stage (1), (3) applying to the polymer film a one-component nonaqueous topcoat comprising (A) a hydroxy-functional polyacrylate resin comprising secondary OH groups, (B) as crosslinking agent tris(alkoxycarbonyl-amino)triazine and (C) optionally further crosslinking agents, and (4) baking together the one-component nonaqueous topcoat applied to the polymer film.
According to still another aspect of the present invention, there is provided a multicoat paint system comprising (1) a polymer film of a basecoat applied to a substrate surface, and (2) a nonaqueous topcoat applied to the polymer film, the nonaqueous topcoat comprising (A) a hydroxy-functional polyacrylate resin comprising secondary OH groups, (B) a crosslinking agent comprising tris(alkoxycarbonylamino)triazine and (C) optionally further crosslinking agents.
According to yet another aspect of the present invention, there is provided a nonaqueous coating material 29018-11(S) - 7b -comprising (A) a hydroxy-functional polyacrylate resin comprising secondary OH groups, and (B) a crosslinking agent comprising tris(alkoxycarbonylamino)triazine.
According to a further aspect of the present invention, there is provided a one-component nonaqueous coating composition comprising (A) a hydroxy-functional polyacrylate resin comprising secondary OH groups, (B) a crosslinking agent comprising tris(alkoxycarbonylamino)-triazine and (C) optionally further crosslinking agents.
The multicoat paint systems produced by the process of - g -the invention feature high hardness, high gloss, good adhesion between basecoat film and topcoat film, good topcoat holdout, good scratch resistance and good resis-tance to climatic effects, organic solvents and acids, and also high resistance to yellowing (especially to yellowing which occurs as a consequence of high baking temperatures and/or as a consequence of long baking times). These good properties are obtained even when different basecoats are used. The transparent topcoats employed in accordance with the invention are also notable for high stability on storage and can also be processed readily with a low content (e.g. less than 50~
by weight) of organic solvents. In particular, the coating materials of the invention feature good resis-tance to the specific weathering effects in Jacksonville exposure and low sensitivity toward moisture stress.
Consequently, the otherwise observed blushing of the coating films is not noted in the case of the present invention.
In stage (1) of the process of the invention it is possible in principle to employ all pigmented basecoats which are suitable for producing two-coat paint systems.
Such basecoats are well known to the skilled worker.
It is possible to employ both water-dilutable basecoats and basecoats based on organic solvents. Suitable base-coats are described, for example, in US-A-3,639,147, DE-A-33 33 072, DE-A-38 14 853, GB-A-2 012 191, US-A-3,953,644, EP-A-260 447, DE-A-39 03 804, _ _ g _ EP-A-320 552, DE-A-36 28 124, US-A-4,719,132, EP-A-297 576, EP-A-69 936, EP-A-89 497, EP-A-195 931, EP-A-228 003 and DE-A-28 18 100. These patent documents are also a source of further information on the basecoat/
clearcoat technique under discussion.
In stage (2) of the process of the invention, in an evaporation phase, the solvents and/or the water are removed from the basecoat applied in stage (1). The basecoat film can also be baked. This is, however, disadvantageous on economic grounds since then two or more baking operations are required to produce the multicoat paint system instead of one baking operation.
In stage (3) of the process of the invention it is preferred to employ transparent nonaqueous coating materials.
Hydroxyl-containing polyacrylate resins are well known.
Examples of such resins and their preparation are described, for example, in JP-A-2-24 28 67, DE-B-26 39 491 and in the patent documents specified on ~O maa'F? F in linac '~'I i-n ~~ f~ir~l - _ r __~ _- . .__ ~ ~___.._.. ~ ~ ,-~. _. .. ,, .~ , In the process of the invention it is preferred as component (A) to employ polyacrylate resins which have hydroxyl numbers of from 40 to 240, preferably from 60 to 210 and, with very particular preference, from 100 to 200, acid numbers of from 0 to 35, preferably from 0 to 23 and, with very particular preference, from 3.9 to I5.5, glass transition temperatures of from -35 to +70°C, preferably from -20 to +40°C and, with very particular preference, from -20 to +15°C and number-average molecu-lar weights of from 1500 to 30,000, preferably from 2000 to 15,000 and, with very particular preference, from 2500 to 5000.
As component (A) it is particularly preferred to employ polyacrylate resins which can be prepared by reacting (a) from 10 to 92, preferably from 20 to 70o by weight of an alkyl or cycloalkyl acrylate or of an alkyl or cycloalkyl methacrylate having 1 to 18, preferably 4 to 13 carbon atoms in the alkyl or cycloalkyl radical, or mixtures of such monomers (b) from 8 to 60, preferably from 12.5 to 51~ by weight of a hydroxyalkyl acrylate or of a hydroxylalkyl [sic? methacrylate having 2 to 4 carbon atoms in the hydroxyalkyl radical, or mixtures of such monomers, where the overall amount of the hydroxy-functional acrylates or methacrylates is combined from 10 to 90% by weight, preferably from 20 to 80 [lacuna]
hydroxy-functional acrylates or methacrylates having primary OH groups and from 90 to 10~ by weight, preferably from 20 to 80o by weight, of hydroxy-functional acrylates or methacrylates having secon-dary OH groups, (c) from 0.0 to 5_0, preferably from 0.0 to 3.0~ by 29018-11(S) ' ~ - 11 -weight of acrylic acid or methacrylic acid, or mixtures of these monomers, and (d) from 0 to 50, preferably from 0 to 40% by weight of ethylenically unsaturated monomers which are dif-ferent from but copolymerizable with (a), (b) and (c), or mixtures of such monomers.
Very particular preference is given to polyacrylate resins which can be prepared by reacting (a) from 20 to 60~ by weight of an alkyl or cycloalkyl acrylate or of an alkyl or cycloalkyl methacrylate having 1 to 18, preferably 4 to 13 carbon atoms in the alkyl or cycloalkyl radical, or mixtures of such monomers (b) from 20 to 41% by weight of a hydroxyalkyl acrylate or of a hydroxyalkyl methacrylate having 2 to 4 carbon atoms in the hydroxyalkyl radical, or mixtures of such monomers, where the overall amount of the hydroxy-functional acrylates or methacrylates is combined from 25 to 50% by weight of hydroxy-functional acrylates or methacrylates having primary OH groups and from 75 to 50% by weight of hydroxy-functional acrylates or methacrylates having secon-dart' OH groups, (c) from 0.5 to 2% by weight of acrylic acid or meth-acrylic acid, or mixtures of these monomers, and (d) from 0 to 30% by weight of ethylenically unsaturated monomers which are different from but copolymeri-zable with (a), (b) and (c), or mixtures of such monomers.
Examples of (a) components are:
methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl and 2-ethylhexyl acrylate and methacrylate and also cyclohexyl acrylate and cyclohexyl methacrylate.
Examples of (b) components having primary OH groups are:
2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate and the adducts thereof with E-caprolactone [sic];
examples of (b) components having secondary OH groups are:
2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate and the adducts of acrylic acid and methacrylic acid with the glycidyl ester of Versatic acid.
Examples of (d) components are:
vinylaromatic compounds, such as, for example, styrene, vinyltoluene, a-methylstyrene, a-ethylstyrene, ring-substituted di-ethylstyrenes, isopropylstyrene, butyl-styrenes and methoxystyrenes; vinyl ethers, such as, for example, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether, and vinyl esters, such as, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate and the vinyl ester of 2-methyl-2-ethylheptanoic acid.
The hydroxyl number and the acid number of the poly acrylate resins can be controlled by the skilled worker without problems by way of the amount of component (b) and (c), respectively, that is employed.
The glass transition temperature of the polyacrylate resin is determined by the nature and amount of the monomers employed. The monomers can be selected by the skilled worker with the aid of the following formula, by means of which it is possible to calculate approximately the glass transition temperature of polyacrylate resins:
I ~ n~x W
n TG n = 1 TGn TG - glass transition temperature of the polyacrylate resin x - number of different monomers copolymerized in the polyacrylate resin.
Wn - proportion by weight of the nth monomer Tin - glass transition temperature of the homopolymer of the nth monomer_ Measures for controlling the molecular weight (e. g.
selection of appropriate polymerization initiators, use of chain transfer agents, etc.) belong to the expert knowledge of the averagely skilled worker and need not be . CA 02228940 1998-02-06 elucidated further here.
As component (A) it is also possible to employ mixtures of the described polyacrylate resins with other synthetic resins. Examples are polyester resins or alkyd resins which can be prepared by reacting (a) a cycloaliphatic or aliphatic polycarboxylic acid or a mixture of such polycarboxylic acids (,Ci) an aliphatic or cycloaliphatic polyol having more than two hydroxyl groups in the molecule, or a mixture of such polyols ('y) an aliphatic or cycloaliphatic diol or a mixture of such diols and (b) an aliphatic linear or branched saturated mono-carboxylic acid or a mixture of such monocarboxylic acids in a molar ratio of (a) : (,(i) : ('y) : (b) -1.0:0.2 - 1.3:0.0 - 1.1:0.0 - 1.4, preferably 1.0:0.5 - 1.2:0.0 - 0.6:0.2 - 0.9 to form a polyester resin or alkyd resin.
Examples of component (a) are: hexahydrophthalic acid, 1,4-cyclohexanedicarboxylic acid, endomethylenetetra-hydrophthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
29fl18-11 (S) Examples of component (~) are: pentaerytrritol, tri-methylolpropane, trimethylolethane and glycerol.
Examples of component ('y) are: ethylene glycol, diethy-lene glycol, propylene glycol, neopentyl glycol, 2-methyl-2-propylpropane-1,3-diol, 2-ethyl-2-butylpropane-1,3-diol, 2,2,4-trimethylpentane-1,5-diol, 2,2,5-trimethylhexane-1,6-diol, neopentyl glycol hydroxy-pivalate and dimethylolcyclohexane.
Examples of component (b) are: 2-ethylhexanoic acid, lauric acid, isooctanoic acid, isononanoic acid and monocarboxylic acid mixtures which are obtained from coconut oil or palm kernel oil.
The preparation of hydroxyl-bearing .polyester resins and/or alkyd resins is described, for example, in Ullmanns Encyklopadie der technischen Chemie, third edition, 14th volume, Urban & Schwarzenberg, Munich, Berlin 1863, pages 80 to 89 and pages 99 to 105, and in the books: Resines Alkydes-Polyesters by ~ J. Bourry, Paris, Dunod publishers 1952, Alkyd Resins by C.R. Martens, Reinhold Publishing Corporation. New York 1961 and Alkyd Resin Technology by T.C. Patton, Interscience Publishers 1962.
As component (B) use is made of tris(alkoxycarbonyl-amino)triazines in accordance with US-A 4 939 213, US-A 5 084 541 and EP 0 624 577. Derivatives of these compounds can also be employed.
The tris(alkoxycarbonylamino)triazines and derivatives thereof can, in accordance with the invention, also be employed in a mixture with conventional crosslinking agents (component C). Blocked polyisocyanates different from the tris(alkoxycarbonylamino)triazines are particu-larly suitable here. It is also possible to employ amino resins, for example melamines.
In principle it is possible to employ any amino resin which is suitable for transparent topcoats, or a mixture of such amino resins.
Resins of this kind are well known to the skilled worker and are marketed by many companies as sales products.
Amino resins are condensation products of aldehydes, especially formaldehyde, with, for example, ureas, melamine, guanamine and benzoguanamine. The amino resins include alcohol groups, preferably methylol groups, all or some of which have generally been etherified with alcohols.
As component (C) it is preferred to employ melamine-formaldehyde resins which have been etherified with lower alcohols, especially with methanol or butanol.
Particular preference is given to the use as component (B) of melamine-formaldehyde resins which have been etherified with lower alcohols, especially with methanol and/or butanol, and which on statistical average per triazine ring still comprise from 0.1 to 0.25 hydrogen atoms attached to nitrogen atoms.
The topcoats employed in accordance with the invention may also comprise as component (C) a blocked polyiso-cyanate or a mixture of blocked polyisocyanates.
In principle, all polyisocyanates which can be employed in the paints sector can be employed to prepare component (C). It is preferred, however, to employ polyisocyanates whose isocyanate groups are attached to aliphatic or cycloaliphatic radicals. Examples of such polyisocyanates are hexamethylene diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, dicyclohexylmethane diisocyanate and 1,3-bis(2-isocyanatoprop-2-yl)benzene (TMXDI) and also adducts of these polyisocyanates with polyols, especially low molecular mass polyols, such as trimethylolpropane, for example, and polyisocyanates which are derived from these polyisocyanates and contain isocyanurate groups and/or biuret groups.
It is particularly preferred as polyisocyanates to employ hexamethylene diisocyanate and isophorone diisocyanate, polyisocyanates derived from these diisocyanates contain-ing isocyanurate or biuret groups and preferably includ-ing more than two isocyanate groups in the molecule, and also reaction products of hexamethylene diisocyanate and isophorone diisocyanate, or of a mixture of hexamethylene diisocyanate and isophorone diisocyanate, with 0.3 - 0.5 _ 1g _ equivalents of a low molecular mass polyol having a molecular weight of from 62 to 500, preferably from 104 to 204, especially a triol, such as trimethylolpropane, for example.
As blocking agents it is possible to employ dialkyl malonates or a mixture of dialkyl malonates.
Examples of dialkyl malonates that can be employed are dialkylmalonates having from 1 to 6 carbon atoms in each of the alkyl radicals, such as dimethyl malonate and diethyl malonate, for example, preference being given to the employment of diethyl malonate.
It is possible, furthermore, to employ other blocking agents containing active methylene groups, and oximes, and also mixtures of these blocking agents.
Examples are: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or dodacyl aceto-acetate, acetone oxime, methyl ethyl ketoxime, acetyl-acetone, formal doxime, acetaldoxime, benzophenoxime, acetoxime and diisobutyl ketoxime.
The components (A), (B) and (C) are generally employed, in the transparent topcoats that are employed in accor-dance with the invention, in amounts such that component (A) is present in an amount of from 20 to 80, preferably from 30 to 60°s by weight, component (B) in an amount of from 1 to 50, preferably from 5 to 35~ by weight and component (C) in an amount of from 0 to 50, preferably from 0 to 35% by weight, the percentages by weight for (A) + (B) + (C) being = 100 % by weight and being based on the solids content of the component (A) , (B) and (C) .
The transparent topcoats employed in accordance with the invention preferably comprise no pigments or only trans-parent pigments. As organic solvents, the topcoats comprise customary organic solvents which are conven-tional for the preparation of coating materials. The topcoats may, in addition, include further conventional additives, such as light stabilizers, leveling assis-tams, etc.
The multicoat paint systems produced using the topcoats that are employed in accordance with the invention feature the advantageous properties especially when they have been baked under the baking conditions currently employed in the production-line (OEM) finishing of cars (30 minutes at 130°C or 20 minutes at 140°C).
The invention is elucidated further in the examples which follow. All amounts and percentages, unless expressly stated otherwise, are to be understood as figures by weight.
Acrylate resin A (according to the invention) Into a laboratory reactor having a useful volume of 4 1 and fitted with two dropping funnels for the monomer mixture and initiator solution, respectively, a nitrogen inlet pipe, thermometer and reflux condenser there are weighed 731 g of a fraction of aromatic hydrocarbons having a boiling range of 158 to 172°C. The solvent is heated to 140°C. On reaching 140°C, a monomer mixture comprising 458 g of ethylhexyl methacrylate, 183 g of n-butyl methacrylate, 214 g of styrene, 183 of 2-hydroxy-ethyl acrylate, 458 g of 2-hydroxypropyl methacrylate and 31 g of acrylic acid is metered into the reactor at a uniform rate over the course of 4 hours, and an initiator solution of 153 g of t-butyl perethylhexanoate in 92 g of the described aromatic solvent is metered into the reactor at a uniform rate over the course of 4.5 hours.
The metered addition of the monomer mixture and of the initiator solution is begun simultaneously. After the end of the metered addition of the initiator, the reaction mixture is held at 140°C for two hours more and then cooled. The resulting polymer solution has a solids con-tent of 65% (determined in a convection oven at 130°C for 1 h), an acid number of 17 and a viscosity of 24.5 dPas (measured on a 60~ strength dilution of the polymer solution in the described aromatic solvent, using an ICI
plate-cone viscometer at 23°C).
Acrylate resin B (comparative example) Into a laboratory reactor having a useful volume of 4 1 and fitted with two dropping funnels for the monomer mixture and initiator solution, respectively, a nitrogen inlet pipe, thermometer and reflux condenser there are weighed 731 g of a fraction of aromatic hydrocarbons having a boiling range of 158 to 172°C. The solvent is heated to 140°C. On reaching 140°C, a monomer mixture comprising 763 g of ethylhexyl methacrylate, 122 g of n-butyl methacrylate, 214 g of styrene, 397 g of 4-hydroxybutyl acrylate and 31 g of acrylic acid is metered into the reactor at a uniform rate over the course of 4 hours, and an initiator solution of 153 g of t-butyl perethylhexanoate in 92 g of the described l0 aromatic solvent is metered into the reactor at a uniform rate over the course of 4.5 hours. The metered addition of the monomer mixture and of the initiator solution is begun simultaneously. After the end of the metered addition of the initiator, the reaction mixture is held at 140°C for two hours more and then cooled. The result-ing polymer solution has a solids content of 65~ (deter-mined in a convection oven at 130°C for 1 h), an acid number of 17 and a viscosity of 3.8 dPas (measured on a 60% strength dilution of the polymer solution in the described aromatic solvent, using an ICI plate-cone viscometer at 23°C).
Acrylate resin C (comparative example) Into a laboratory reactor having a useful volume of 4 1 and fitted with two dropping funnels for the monomer mixture and initiator solution, respectively, a nitrogen inlet pipe, thermometer and reflux condenser there are weighed 731 g of a fraction of aromatic hydrocarbons having a boiling range of 158 to 172°C. The solvent is heated to 140°C: On reaching 140°C, a monomer mixture comprising 546 g of ethylhexyl methacrylate, 183 g of n-butyl methacrylate, 214 g of styrene, 552 g of 2-hydroxyethyl acrylate and 31 g of acrylic acid is metered into the reactor at a uniform rate over the course of 4 hours, and an initiator solution of 153 g of t-butyl perethylhexanoate in 92 g of the described aromatic solvent is metered into the reactor at a uniform rate over the course of 4.5 hours. The metered addition of the monomer mixture and of the initiator solution is begun simultaneously. After the end of the metered addition of the initiator, the reaction mixture is held at 140°C for two hours more and then cooled. The result-ing polymer solution has a solids content of 650 (deter-mined in a convection oven at 130°C for 1 h), an acid number of 19 and a viscosity of 19 dPas (measured on a 60~ strength dilution of the polymer solution in the described aromatic solvent, using an ICI plate-cone viscometer at 23°C).
Table 1 i Acrylate Acrylate Acrylate i resin A resin B resin C
EHMAl~ 458 763 546 I
nBMA2~ 183 122 183 Styrene 214 214 214 2-HEA3~ 183 --- 552 4-HBA4> ___ 397 ___ HPMAS~ 458 __- _-_ AA6~ 31 31 31 TBPEH'~ 153 153 153 l~ 2-ethylhexyl methacrylate n-butyl methacrylate 2-hydroxyethyl acrylate 4-hydroxybutyl acrylate 2-hydroxypropyl methacrylate 6~ acrylic acid '~ tert-butyl perethylhexanoate Prenarina the clearcoats The clearcoats are prepared by weighing out the poly acrylate resin solutions, then adding the amounts indi sated in Tab. 2 of triazine crosslinker, solvent, UV
adsorber [sic], free-radical scavenger and leveling agent, with stirring, and carrying out thorough incor-poration by stirring. The resulting coating materials are if appropriate adjusted, for application, to a viscosity of 23 sec (measured with a DIN 4 cup at 20°C) using xylene.
Table 2 Clearcoat A Clearcoat 8 Clearcoat C
Acrylate resin A 55.0 --- ---Acrylate resin B --- 62.4 ---Acrylate resin C --- --- 55.0 Triazine crosslinkerl~ 28.2 18.5 28.2 UV absorbera~ 0.8 0.9 0.8 Free-radical scavenger's1.0 1.1 1.0 Leveling agent4~ 1.5 1.7 1.5 Petroleum spirit 180/2106.0 6.8 6.0 Xylene 2.5 2.8 2.5 Solvesso 150 7.1 6.0 6.0 Blushings~ no no yes Jacksonville rating6~ 3.5 10 4 l~ triazine crosslinkeras per 4939312, 5054541 (Cytec) US US
commercial UV absorb ers of benzotriazolclass the " commercial free-rad ical scavenger on a sterically based hindered amine " commercial leveling agent based on a polydimethylsiloxane 2 5~ blushing after moisture (240 h/40C,1008 rel. atmos-0 stress pheric humidity) 6' metal panel exposurein Jacksonville, Florida;
rating 1 (good) - 10 (poor)
The art describes a process for producing a two-coat paint system, in which (1) a pigmented basecoat is applied to the substrate surface (2) a polymer film is formed from the basecoat applied in stage (1) (3) a nonaqueous transparent topcoat is applied to the basecoat film thus obtained, and then (4) basecoat film and topcoat film are baked together.
The invention also relates to nonaqueous coating materials suitable for this process.
The above-described basecoat/clearcoat process is employed in particular for producing multicoat paint systems, especially metallic finishes on car bodies (cf. e.g. US-A-3,639,147 and EP-A-38 127).
t Using the basecoat/clearcoat process it is possible to produce finishes which, in comparison to one-coat topcoat systems, feature an improved rendering of the effect and feature the possibility of producing paint systems with bright and cleaner shades.
The basecoat applied first in stage (1), depending on the nature, amount and spatial orientation of the pigments employed, determines the shade and, if appropriate, the effect (e. g. metallic or pearlescent effect) of the paint system.
In stage (2) of the process, in an evaporation phase, at least some of the organic solvents and/or of the water is removed from the basecoat film applied in stage (1). Atop this pre-dried but unbaked basecoat film there is applied, in stage (3), a nonaqueous transparent topcoat (wet-on-wet technique) and then, in stage (4), basecoat film and topcoat film are baked together_ The transparent topcoat applied in stage (3) imparts gloss and fullness to the two-coat paint system and protects the pigmented paint film applied in stage (1) against chemical and physical attack.
Using the process under discussion it is possible to obtain high-quality two-coat paint systems only when the transparent topcoat applied in stage (3) does not inter-fere with the basecoat applied in stages (1) and (2) in r such a way that there is impairment of the optical effect (e.g. clouding). On the other hand, the composition of the transparent topcoat must be such that it adheres well to the basecoat film following the baking process con-s ducted in stage (4). Further important properties which the transparent topcoat film obtained after the baking process must have are high transparency, good gloss and good mechanical properties, such as hardness, scratch resistance and elasticity. The transparent topcoat film obtained after the baking process is required not least to have high resistance to climatic effects (e. g. tem perature fluctuations, moisture in the form of water vapor, rain, dew, attack by radiation etc.) and to attack by acids or other chemicals, such as organic solvents, for example.
Furthermore, the transparent topcoats applied in stage (3) should have a very low content of organic solvents, and good stability on storage.
JP-A-2-242867 describes a basecoat/clearcoat process in stage (3) of which nonaqueous transparent topcoats are applied which comprise (A) a hydroxyl-containing synthetic resin, (B) an amino resin and (C) a blocked polyisocyanate, where components (B) and (C) are to be selected such that the temperature at which a chemical reaction ensues between (A) and (C) is not more than 20°C
below and not more than 50°C above the temperature at which a chemical reaction ensues between (A) and (B).
r Blocking agents specified for preparing component (C) are: volatile compounds of low molecular mass containing active hydrogen atoms, such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, benzyl alcohol, ethylene glycol monoethyl ether and other aliphatic or aromatic monoalcohols, dimethyl- or diethylaminoethanol and other hydroxyl-containing tertiary amines, acetone oxime, methyl ethyl ketone oxime and other oximes, acetylacetone, acetoacetates, malonates and other com-pounds containing active methylene groups, e-caprolactam and other lactams, and phenol. Blocking agents preferably employed are aliphatic monoalcohols, oximes and capro-lactams.
The transparent topcoats described in JP-A-2-242867 give rise to paint systems which, especially in terms of their resistance to organic solvents and acids, gloss, trans-parency and resistance to yellowing, are to be improved.
DE-B-26 39 491 describes nonaqueous coating materials which comprise a hydroxyl-containing polyester resin and/or alkyd resin, hexamethylene diisocyanate blocked with an alkyl acetoacetate and/or 2,2,4 trimethylhexa-methylene [sic] diisocyanate blocked with an alkyl aceto-acetate, and an amino resin. These coating materials can also be employed as transparent topcoats in the sector of automotive finishing. The finishes obtained with these coating systems, especially when heightened baking temperatures and/or prolonged baking times are employed, 29018-11(S) . ' _ 5 _ undergo yellowing and are to be improved especially in terms of their resistance to acids and organic solvents and in terms of their scratch resistance.
The properties of the coating materials can be improved by the use of specific crosslinking agents. Mention should be made here in particular of the tris(alkoxy-carbonylamino)triazines and derivatives thereof that are known from US-A 5084541, 4939213, 5288865, 4710542 and from the EP Applications 0565774, 0541966, 0604922 and EP-B 0245700. Coating materials of this kind feature an especially good chemical resistance, which is evident in particular in the good results of outdoor weathering in Jacksonville, Florida. The tight crosslinking of such formulations, however, has the disadvantage of increased sensitivity toward moisture stresses, which is manifested in blushing of the coating films after such stresses.
The object of the present invention is now to provide a process for producing a multicoat paint system, in which:
(1) an optionally pigmented basecoat is applied to a substrate surface, (2) a polymer film is formed from the basecoat film applied in stage (1), (3) one or more further coating films are applied optionally thereto, (4) then a nonaqueous topcoat is applied which comprises 29018-11 (S) A) a hydroxy-functional polyacrylate resin, B) as crosslinking agent tris(alkoxycarbonylamino)-triazine and C) optionally further crosslinking agents, such as blocked isocyanates, which are different from the tris(alkoxycarbonylamino)triazine, and/or amino resins, and subsequently (5) the coating films are baked together, which leads to coating films having good results both in the case of outdoor weathering in Jacksonville and in the case of moisture stresses.
This object is achieved by the polyacrylate resin com-prising secondary OH groups.
The present invention accordingly provides as well a multicoat paint system comprising (1) one coat of a polymer film of an optionally pigmented basecoat which has been applied to a substrate surface, (2) optionally one or more coating films applied thereto, (3) one coat of a nonaqueous topcoat which comprises A) a hydroxy-functional polyacrylate resin, B) as crosslinking agent tris(alkoxycarbonylamino)-29018-11(S) triazine and C) optionally further crosslinking ageats, such as blocked isocyanates, which are different from the tris(alkoxycarbonylamino)triazine, and/or amino resins, and subsequently (4) the coating films are baked together, c h a r a c t a r i z a d in that the polyacrylate resin comprises secondary OH groups.
I0 A further subject of the invention is a nonac_ueous coating material comprising A) a hydroxy-functional polyaczylate resin, B) as crosslinking agent tris(alkoxycarbonylamino)-triazine and C) optionally further crosslinking agents, such as blocked isocyanates, which are different from the tris(alkoxycarbonylamino)triazine, and/or amino resins, c h a r a c t a r i z a d in that the polyacrylate resin (A) comprises secondary OH groups.
The invention also relates, finally, to the use of the specified nonaqueous coating material for producing transparent topcoats and to the use oz the multicoat paint system for coating car bodies.
29018-11(S) - 7a -According to one aspect of the present invention, there is provided a process for producing a multicoat paint system, comprising (1) applying a basecoat to a substrate surface, (2) forming a polymer film from the basecoat applied in stage (1), (3) applying to the polymer film a nonaqueous topcoat comprising (A) a hydroxy-functional polyacrylate resin comprising secondary OH groups, (B) as crosslinking agent tris(alkoxycarbonylamino)triazine and (C) optionally further crosslinking agents, and (4) baking together the nonaqueous topcoat applied to the polymer film.
According to another aspect of the present invention, there is provided a process for producing a multicoat paint system, comprising (1) applying a basecoat to a substrate surface, (2) forming a polymer film from the basecoat applied in stage (1), (3) applying to the polymer film a one-component nonaqueous topcoat comprising (A) a hydroxy-functional polyacrylate resin comprising secondary OH groups, (B) as crosslinking agent tris(alkoxycarbonyl-amino)triazine and (C) optionally further crosslinking agents, and (4) baking together the one-component nonaqueous topcoat applied to the polymer film.
According to still another aspect of the present invention, there is provided a multicoat paint system comprising (1) a polymer film of a basecoat applied to a substrate surface, and (2) a nonaqueous topcoat applied to the polymer film, the nonaqueous topcoat comprising (A) a hydroxy-functional polyacrylate resin comprising secondary OH groups, (B) a crosslinking agent comprising tris(alkoxycarbonylamino)triazine and (C) optionally further crosslinking agents.
According to yet another aspect of the present invention, there is provided a nonaqueous coating material 29018-11(S) - 7b -comprising (A) a hydroxy-functional polyacrylate resin comprising secondary OH groups, and (B) a crosslinking agent comprising tris(alkoxycarbonylamino)triazine.
According to a further aspect of the present invention, there is provided a one-component nonaqueous coating composition comprising (A) a hydroxy-functional polyacrylate resin comprising secondary OH groups, (B) a crosslinking agent comprising tris(alkoxycarbonylamino)-triazine and (C) optionally further crosslinking agents.
The multicoat paint systems produced by the process of - g -the invention feature high hardness, high gloss, good adhesion between basecoat film and topcoat film, good topcoat holdout, good scratch resistance and good resis-tance to climatic effects, organic solvents and acids, and also high resistance to yellowing (especially to yellowing which occurs as a consequence of high baking temperatures and/or as a consequence of long baking times). These good properties are obtained even when different basecoats are used. The transparent topcoats employed in accordance with the invention are also notable for high stability on storage and can also be processed readily with a low content (e.g. less than 50~
by weight) of organic solvents. In particular, the coating materials of the invention feature good resis-tance to the specific weathering effects in Jacksonville exposure and low sensitivity toward moisture stress.
Consequently, the otherwise observed blushing of the coating films is not noted in the case of the present invention.
In stage (1) of the process of the invention it is possible in principle to employ all pigmented basecoats which are suitable for producing two-coat paint systems.
Such basecoats are well known to the skilled worker.
It is possible to employ both water-dilutable basecoats and basecoats based on organic solvents. Suitable base-coats are described, for example, in US-A-3,639,147, DE-A-33 33 072, DE-A-38 14 853, GB-A-2 012 191, US-A-3,953,644, EP-A-260 447, DE-A-39 03 804, _ _ g _ EP-A-320 552, DE-A-36 28 124, US-A-4,719,132, EP-A-297 576, EP-A-69 936, EP-A-89 497, EP-A-195 931, EP-A-228 003 and DE-A-28 18 100. These patent documents are also a source of further information on the basecoat/
clearcoat technique under discussion.
In stage (2) of the process of the invention, in an evaporation phase, the solvents and/or the water are removed from the basecoat applied in stage (1). The basecoat film can also be baked. This is, however, disadvantageous on economic grounds since then two or more baking operations are required to produce the multicoat paint system instead of one baking operation.
In stage (3) of the process of the invention it is preferred to employ transparent nonaqueous coating materials.
Hydroxyl-containing polyacrylate resins are well known.
Examples of such resins and their preparation are described, for example, in JP-A-2-24 28 67, DE-B-26 39 491 and in the patent documents specified on ~O maa'F? F in linac '~'I i-n ~~ f~ir~l - _ r __~ _- . .__ ~ ~___.._.. ~ ~ ,-~. _. .. ,, .~ , In the process of the invention it is preferred as component (A) to employ polyacrylate resins which have hydroxyl numbers of from 40 to 240, preferably from 60 to 210 and, with very particular preference, from 100 to 200, acid numbers of from 0 to 35, preferably from 0 to 23 and, with very particular preference, from 3.9 to I5.5, glass transition temperatures of from -35 to +70°C, preferably from -20 to +40°C and, with very particular preference, from -20 to +15°C and number-average molecu-lar weights of from 1500 to 30,000, preferably from 2000 to 15,000 and, with very particular preference, from 2500 to 5000.
As component (A) it is particularly preferred to employ polyacrylate resins which can be prepared by reacting (a) from 10 to 92, preferably from 20 to 70o by weight of an alkyl or cycloalkyl acrylate or of an alkyl or cycloalkyl methacrylate having 1 to 18, preferably 4 to 13 carbon atoms in the alkyl or cycloalkyl radical, or mixtures of such monomers (b) from 8 to 60, preferably from 12.5 to 51~ by weight of a hydroxyalkyl acrylate or of a hydroxylalkyl [sic? methacrylate having 2 to 4 carbon atoms in the hydroxyalkyl radical, or mixtures of such monomers, where the overall amount of the hydroxy-functional acrylates or methacrylates is combined from 10 to 90% by weight, preferably from 20 to 80 [lacuna]
hydroxy-functional acrylates or methacrylates having primary OH groups and from 90 to 10~ by weight, preferably from 20 to 80o by weight, of hydroxy-functional acrylates or methacrylates having secon-dary OH groups, (c) from 0.0 to 5_0, preferably from 0.0 to 3.0~ by 29018-11(S) ' ~ - 11 -weight of acrylic acid or methacrylic acid, or mixtures of these monomers, and (d) from 0 to 50, preferably from 0 to 40% by weight of ethylenically unsaturated monomers which are dif-ferent from but copolymerizable with (a), (b) and (c), or mixtures of such monomers.
Very particular preference is given to polyacrylate resins which can be prepared by reacting (a) from 20 to 60~ by weight of an alkyl or cycloalkyl acrylate or of an alkyl or cycloalkyl methacrylate having 1 to 18, preferably 4 to 13 carbon atoms in the alkyl or cycloalkyl radical, or mixtures of such monomers (b) from 20 to 41% by weight of a hydroxyalkyl acrylate or of a hydroxyalkyl methacrylate having 2 to 4 carbon atoms in the hydroxyalkyl radical, or mixtures of such monomers, where the overall amount of the hydroxy-functional acrylates or methacrylates is combined from 25 to 50% by weight of hydroxy-functional acrylates or methacrylates having primary OH groups and from 75 to 50% by weight of hydroxy-functional acrylates or methacrylates having secon-dart' OH groups, (c) from 0.5 to 2% by weight of acrylic acid or meth-acrylic acid, or mixtures of these monomers, and (d) from 0 to 30% by weight of ethylenically unsaturated monomers which are different from but copolymeri-zable with (a), (b) and (c), or mixtures of such monomers.
Examples of (a) components are:
methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl and 2-ethylhexyl acrylate and methacrylate and also cyclohexyl acrylate and cyclohexyl methacrylate.
Examples of (b) components having primary OH groups are:
2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate and the adducts thereof with E-caprolactone [sic];
examples of (b) components having secondary OH groups are:
2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate and the adducts of acrylic acid and methacrylic acid with the glycidyl ester of Versatic acid.
Examples of (d) components are:
vinylaromatic compounds, such as, for example, styrene, vinyltoluene, a-methylstyrene, a-ethylstyrene, ring-substituted di-ethylstyrenes, isopropylstyrene, butyl-styrenes and methoxystyrenes; vinyl ethers, such as, for example, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether, and vinyl esters, such as, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate and the vinyl ester of 2-methyl-2-ethylheptanoic acid.
The hydroxyl number and the acid number of the poly acrylate resins can be controlled by the skilled worker without problems by way of the amount of component (b) and (c), respectively, that is employed.
The glass transition temperature of the polyacrylate resin is determined by the nature and amount of the monomers employed. The monomers can be selected by the skilled worker with the aid of the following formula, by means of which it is possible to calculate approximately the glass transition temperature of polyacrylate resins:
I ~ n~x W
n TG n = 1 TGn TG - glass transition temperature of the polyacrylate resin x - number of different monomers copolymerized in the polyacrylate resin.
Wn - proportion by weight of the nth monomer Tin - glass transition temperature of the homopolymer of the nth monomer_ Measures for controlling the molecular weight (e. g.
selection of appropriate polymerization initiators, use of chain transfer agents, etc.) belong to the expert knowledge of the averagely skilled worker and need not be . CA 02228940 1998-02-06 elucidated further here.
As component (A) it is also possible to employ mixtures of the described polyacrylate resins with other synthetic resins. Examples are polyester resins or alkyd resins which can be prepared by reacting (a) a cycloaliphatic or aliphatic polycarboxylic acid or a mixture of such polycarboxylic acids (,Ci) an aliphatic or cycloaliphatic polyol having more than two hydroxyl groups in the molecule, or a mixture of such polyols ('y) an aliphatic or cycloaliphatic diol or a mixture of such diols and (b) an aliphatic linear or branched saturated mono-carboxylic acid or a mixture of such monocarboxylic acids in a molar ratio of (a) : (,(i) : ('y) : (b) -1.0:0.2 - 1.3:0.0 - 1.1:0.0 - 1.4, preferably 1.0:0.5 - 1.2:0.0 - 0.6:0.2 - 0.9 to form a polyester resin or alkyd resin.
Examples of component (a) are: hexahydrophthalic acid, 1,4-cyclohexanedicarboxylic acid, endomethylenetetra-hydrophthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
29fl18-11 (S) Examples of component (~) are: pentaerytrritol, tri-methylolpropane, trimethylolethane and glycerol.
Examples of component ('y) are: ethylene glycol, diethy-lene glycol, propylene glycol, neopentyl glycol, 2-methyl-2-propylpropane-1,3-diol, 2-ethyl-2-butylpropane-1,3-diol, 2,2,4-trimethylpentane-1,5-diol, 2,2,5-trimethylhexane-1,6-diol, neopentyl glycol hydroxy-pivalate and dimethylolcyclohexane.
Examples of component (b) are: 2-ethylhexanoic acid, lauric acid, isooctanoic acid, isononanoic acid and monocarboxylic acid mixtures which are obtained from coconut oil or palm kernel oil.
The preparation of hydroxyl-bearing .polyester resins and/or alkyd resins is described, for example, in Ullmanns Encyklopadie der technischen Chemie, third edition, 14th volume, Urban & Schwarzenberg, Munich, Berlin 1863, pages 80 to 89 and pages 99 to 105, and in the books: Resines Alkydes-Polyesters by ~ J. Bourry, Paris, Dunod publishers 1952, Alkyd Resins by C.R. Martens, Reinhold Publishing Corporation. New York 1961 and Alkyd Resin Technology by T.C. Patton, Interscience Publishers 1962.
As component (B) use is made of tris(alkoxycarbonyl-amino)triazines in accordance with US-A 4 939 213, US-A 5 084 541 and EP 0 624 577. Derivatives of these compounds can also be employed.
The tris(alkoxycarbonylamino)triazines and derivatives thereof can, in accordance with the invention, also be employed in a mixture with conventional crosslinking agents (component C). Blocked polyisocyanates different from the tris(alkoxycarbonylamino)triazines are particu-larly suitable here. It is also possible to employ amino resins, for example melamines.
In principle it is possible to employ any amino resin which is suitable for transparent topcoats, or a mixture of such amino resins.
Resins of this kind are well known to the skilled worker and are marketed by many companies as sales products.
Amino resins are condensation products of aldehydes, especially formaldehyde, with, for example, ureas, melamine, guanamine and benzoguanamine. The amino resins include alcohol groups, preferably methylol groups, all or some of which have generally been etherified with alcohols.
As component (C) it is preferred to employ melamine-formaldehyde resins which have been etherified with lower alcohols, especially with methanol or butanol.
Particular preference is given to the use as component (B) of melamine-formaldehyde resins which have been etherified with lower alcohols, especially with methanol and/or butanol, and which on statistical average per triazine ring still comprise from 0.1 to 0.25 hydrogen atoms attached to nitrogen atoms.
The topcoats employed in accordance with the invention may also comprise as component (C) a blocked polyiso-cyanate or a mixture of blocked polyisocyanates.
In principle, all polyisocyanates which can be employed in the paints sector can be employed to prepare component (C). It is preferred, however, to employ polyisocyanates whose isocyanate groups are attached to aliphatic or cycloaliphatic radicals. Examples of such polyisocyanates are hexamethylene diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, dicyclohexylmethane diisocyanate and 1,3-bis(2-isocyanatoprop-2-yl)benzene (TMXDI) and also adducts of these polyisocyanates with polyols, especially low molecular mass polyols, such as trimethylolpropane, for example, and polyisocyanates which are derived from these polyisocyanates and contain isocyanurate groups and/or biuret groups.
It is particularly preferred as polyisocyanates to employ hexamethylene diisocyanate and isophorone diisocyanate, polyisocyanates derived from these diisocyanates contain-ing isocyanurate or biuret groups and preferably includ-ing more than two isocyanate groups in the molecule, and also reaction products of hexamethylene diisocyanate and isophorone diisocyanate, or of a mixture of hexamethylene diisocyanate and isophorone diisocyanate, with 0.3 - 0.5 _ 1g _ equivalents of a low molecular mass polyol having a molecular weight of from 62 to 500, preferably from 104 to 204, especially a triol, such as trimethylolpropane, for example.
As blocking agents it is possible to employ dialkyl malonates or a mixture of dialkyl malonates.
Examples of dialkyl malonates that can be employed are dialkylmalonates having from 1 to 6 carbon atoms in each of the alkyl radicals, such as dimethyl malonate and diethyl malonate, for example, preference being given to the employment of diethyl malonate.
It is possible, furthermore, to employ other blocking agents containing active methylene groups, and oximes, and also mixtures of these blocking agents.
Examples are: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or dodacyl aceto-acetate, acetone oxime, methyl ethyl ketoxime, acetyl-acetone, formal doxime, acetaldoxime, benzophenoxime, acetoxime and diisobutyl ketoxime.
The components (A), (B) and (C) are generally employed, in the transparent topcoats that are employed in accor-dance with the invention, in amounts such that component (A) is present in an amount of from 20 to 80, preferably from 30 to 60°s by weight, component (B) in an amount of from 1 to 50, preferably from 5 to 35~ by weight and component (C) in an amount of from 0 to 50, preferably from 0 to 35% by weight, the percentages by weight for (A) + (B) + (C) being = 100 % by weight and being based on the solids content of the component (A) , (B) and (C) .
The transparent topcoats employed in accordance with the invention preferably comprise no pigments or only trans-parent pigments. As organic solvents, the topcoats comprise customary organic solvents which are conven-tional for the preparation of coating materials. The topcoats may, in addition, include further conventional additives, such as light stabilizers, leveling assis-tams, etc.
The multicoat paint systems produced using the topcoats that are employed in accordance with the invention feature the advantageous properties especially when they have been baked under the baking conditions currently employed in the production-line (OEM) finishing of cars (30 minutes at 130°C or 20 minutes at 140°C).
The invention is elucidated further in the examples which follow. All amounts and percentages, unless expressly stated otherwise, are to be understood as figures by weight.
Acrylate resin A (according to the invention) Into a laboratory reactor having a useful volume of 4 1 and fitted with two dropping funnels for the monomer mixture and initiator solution, respectively, a nitrogen inlet pipe, thermometer and reflux condenser there are weighed 731 g of a fraction of aromatic hydrocarbons having a boiling range of 158 to 172°C. The solvent is heated to 140°C. On reaching 140°C, a monomer mixture comprising 458 g of ethylhexyl methacrylate, 183 g of n-butyl methacrylate, 214 g of styrene, 183 of 2-hydroxy-ethyl acrylate, 458 g of 2-hydroxypropyl methacrylate and 31 g of acrylic acid is metered into the reactor at a uniform rate over the course of 4 hours, and an initiator solution of 153 g of t-butyl perethylhexanoate in 92 g of the described aromatic solvent is metered into the reactor at a uniform rate over the course of 4.5 hours.
The metered addition of the monomer mixture and of the initiator solution is begun simultaneously. After the end of the metered addition of the initiator, the reaction mixture is held at 140°C for two hours more and then cooled. The resulting polymer solution has a solids con-tent of 65% (determined in a convection oven at 130°C for 1 h), an acid number of 17 and a viscosity of 24.5 dPas (measured on a 60~ strength dilution of the polymer solution in the described aromatic solvent, using an ICI
plate-cone viscometer at 23°C).
Acrylate resin B (comparative example) Into a laboratory reactor having a useful volume of 4 1 and fitted with two dropping funnels for the monomer mixture and initiator solution, respectively, a nitrogen inlet pipe, thermometer and reflux condenser there are weighed 731 g of a fraction of aromatic hydrocarbons having a boiling range of 158 to 172°C. The solvent is heated to 140°C. On reaching 140°C, a monomer mixture comprising 763 g of ethylhexyl methacrylate, 122 g of n-butyl methacrylate, 214 g of styrene, 397 g of 4-hydroxybutyl acrylate and 31 g of acrylic acid is metered into the reactor at a uniform rate over the course of 4 hours, and an initiator solution of 153 g of t-butyl perethylhexanoate in 92 g of the described l0 aromatic solvent is metered into the reactor at a uniform rate over the course of 4.5 hours. The metered addition of the monomer mixture and of the initiator solution is begun simultaneously. After the end of the metered addition of the initiator, the reaction mixture is held at 140°C for two hours more and then cooled. The result-ing polymer solution has a solids content of 65~ (deter-mined in a convection oven at 130°C for 1 h), an acid number of 17 and a viscosity of 3.8 dPas (measured on a 60% strength dilution of the polymer solution in the described aromatic solvent, using an ICI plate-cone viscometer at 23°C).
Acrylate resin C (comparative example) Into a laboratory reactor having a useful volume of 4 1 and fitted with two dropping funnels for the monomer mixture and initiator solution, respectively, a nitrogen inlet pipe, thermometer and reflux condenser there are weighed 731 g of a fraction of aromatic hydrocarbons having a boiling range of 158 to 172°C. The solvent is heated to 140°C: On reaching 140°C, a monomer mixture comprising 546 g of ethylhexyl methacrylate, 183 g of n-butyl methacrylate, 214 g of styrene, 552 g of 2-hydroxyethyl acrylate and 31 g of acrylic acid is metered into the reactor at a uniform rate over the course of 4 hours, and an initiator solution of 153 g of t-butyl perethylhexanoate in 92 g of the described aromatic solvent is metered into the reactor at a uniform rate over the course of 4.5 hours. The metered addition of the monomer mixture and of the initiator solution is begun simultaneously. After the end of the metered addition of the initiator, the reaction mixture is held at 140°C for two hours more and then cooled. The result-ing polymer solution has a solids content of 650 (deter-mined in a convection oven at 130°C for 1 h), an acid number of 19 and a viscosity of 19 dPas (measured on a 60~ strength dilution of the polymer solution in the described aromatic solvent, using an ICI plate-cone viscometer at 23°C).
Table 1 i Acrylate Acrylate Acrylate i resin A resin B resin C
EHMAl~ 458 763 546 I
nBMA2~ 183 122 183 Styrene 214 214 214 2-HEA3~ 183 --- 552 4-HBA4> ___ 397 ___ HPMAS~ 458 __- _-_ AA6~ 31 31 31 TBPEH'~ 153 153 153 l~ 2-ethylhexyl methacrylate n-butyl methacrylate 2-hydroxyethyl acrylate 4-hydroxybutyl acrylate 2-hydroxypropyl methacrylate 6~ acrylic acid '~ tert-butyl perethylhexanoate Prenarina the clearcoats The clearcoats are prepared by weighing out the poly acrylate resin solutions, then adding the amounts indi sated in Tab. 2 of triazine crosslinker, solvent, UV
adsorber [sic], free-radical scavenger and leveling agent, with stirring, and carrying out thorough incor-poration by stirring. The resulting coating materials are if appropriate adjusted, for application, to a viscosity of 23 sec (measured with a DIN 4 cup at 20°C) using xylene.
Table 2 Clearcoat A Clearcoat 8 Clearcoat C
Acrylate resin A 55.0 --- ---Acrylate resin B --- 62.4 ---Acrylate resin C --- --- 55.0 Triazine crosslinkerl~ 28.2 18.5 28.2 UV absorbera~ 0.8 0.9 0.8 Free-radical scavenger's1.0 1.1 1.0 Leveling agent4~ 1.5 1.7 1.5 Petroleum spirit 180/2106.0 6.8 6.0 Xylene 2.5 2.8 2.5 Solvesso 150 7.1 6.0 6.0 Blushings~ no no yes Jacksonville rating6~ 3.5 10 4 l~ triazine crosslinkeras per 4939312, 5054541 (Cytec) US US
commercial UV absorb ers of benzotriazolclass the " commercial free-rad ical scavenger on a sterically based hindered amine " commercial leveling agent based on a polydimethylsiloxane 2 5~ blushing after moisture (240 h/40C,1008 rel. atmos-0 stress pheric humidity) 6' metal panel exposurein Jacksonville, Florida;
rating 1 (good) - 10 (poor)
Claims (15)
1. ~A process for producing a multicoat paint system, comprising (1) applying a basecoat to a substrate surface, (2) forming a polymer film from the basecoat applied in stage (1), (3) applying to the polymer film a nonaqueous topcoat comprising A) a hydroxy-functional polyacrylate resin comprising secondary OH groups, B) as crosslinking agent tris(alkoxycarbonylamino)triazine and C) optionally further crosslinking agents, and (4) baking together the nonaqueous topcoat applied to the polymer film.
2. A process for producing a multicoat paint system, comprising (1) applying a basecoat to a substrate surface, (2) forming a polymer film from the basecoat applied in stage (1), (3) applying to the polymer film a one-component nonaqueous topcoat comprising A) a hydroxy-functional polyacrylate resin comprising secondary OH groups, B) as crosslinking agent tris(alkoxycarbonylamino)triazine and C) optionally further crosslinking agents, and (4) baking together the one-component nonaqueous topcoat applied to the polymer film.
3. ~The process of claim 1 or 2, wherein the basecoat is pigmented.
4. ~The process of any one of claims 1 to 3, wherein one or more further coatings are applied to the polymer film formed from the basecoat.
5. ~The process of any one of claims 1 to 4, wherein the substrate is a car body.
6. ~A multicoat paint system comprising (1) a polymer film of a basecoat applied to a substrate surface, and (2) a nonaqueous topcoat applied to the polymer film, the nonaqueous topcoat comprising A) a hydroxy-functional polyacrylate resin comprising secondary OH groups, B) a crosslinking agent comprising tris(alkoxycarbonylamino)triazine and C) optionally further cross linking agents.
7. ~A nonaqueous coating material comprising A) a hydroxy-functional polyacrylate resin comprising secondary OH groups, and B) a crosslinking agent comprising tris(alkoxycarbonylamino)triazine.
8. ~The nonaqueous coating material of claim 7, which is transparent.
9. ~The nonaqueous coating material of claim 7 or 8, comprising the polyacrylate resin having a hydroxyl number of from 40 to 200, an acid number of from 0 to 35, a glass transition temperature of from -35 to +70°C, and a number-average molecular weight of from 1,500 to 30,000.
10. ~The nonaqueous coating material of claim 7 or 8, comprising the polyacrylate resin having a hydroxyl number of from 60 to 210, an acid number of from 0 to 23, a glass transition temperature of from -20 to +40°C and a number-average molecular weight of from 2,000 to 15,000.
11. The nonaqueous coating material of any one of claims 7 to 10, further comprising C) further crosslinking agents.
12. The nonaqueous coating material of claim 11, wherein C) the further crosslinking agents are selected from the group consisting of blocked isocyanates which are different from the tris(alkoxycarbonylamino)triazine, an amino resin, and mixtures thereof.
13. The nonaqueous coating material of claim 7, comprising A) a hydroxy-functional polyacrylate resin comprising (a) from 10 to 92% by weight of a monomer selected from the group consisting of an alkyl or cycloalkyl acrylate having 1 to 18 carbon atoms in the alkyl or cycloalkyl radical, an alkyl or cycloalkyl methacrylate having 1 to 18 carbon atoms in the alkyl or cycloalkyl radical, and mixtures of such monomers, (b) from 8 to 60% by weight of a mixture of hydroxy-functional acrylates or hydroxy-functional methacrylates having 2 to 4 carbon atoms in the hydroxyalkyl radical, wherein the mixture comprises from 10 to 90% by weight of hydroxy-functional acrylates or hydroxy-functional methacrylates having primary OH groups and from 90 to 10% by weight of hydroxy-functional acrylates or hydroxy-functional methacrylates having secondary OH groups, (c) from 0 to 5% by weight of acrylic acid or methacrylic acid, or mixtures of these monomers, and (d) from 0 to 50% by weight of ethylenically unsaturated monomers which are different from but copolymerizable with (a), (b) and (c), or mixtures of such monomers.
14. The nonaqueous coating material of claim 13, comprising A) a hydroxy-functional polyacrylate resin comprising (a) from 20 to 60% by weight of a monomer selected from the group consisting of an alkyl or cycloalkyl acrylate having 4 to 13 carbon atoms in the alkyl or cycloalkyl radical, an alkyl or cycloalkyl methacrylate having 4 to 13 carbon atoms in the alkyl or cycloalkyl radical, and mixtures of such monomers, (b) from 20 to 41% by weight of a mixture of hydroxy-functional acrylates or hydroxy-functional methacrylates having 2 to 4 carbon atoms in the hydroxyalkyl radical, wherein the mixture comprises from 25 to 50% by weight of hydroxy-functional acrylates or hydroxy-functional methacrylates having primary OH groups and from 75 to 50% by weight of hydroxy-functional acrylates or hydroxy-functional methacrylates having secondary OH groups, (c) from 0.5 to 2% by weight of acrylic acid or methacrylic acid, or mixtures of these monomers, and (d) from 0 to 30% by weight of ethylenically unsaturated monomers which are different from but copolymerizable with (a), (b) and (c), or mixtures of such monomers.
15. A one-component nonaqueous coating composition comprising A) a hydroxy-functional polyacrylate resin comprising secondary OH groups, B) a crosslinking agent comprising tris(alkoxycarbonylamino)triazine and C) optionally further crosslinking agents.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19622878A DE19622878A1 (en) | 1996-06-07 | 1996-06-07 | Multi-layer painting, process for its production and suitable non-aqueous top coat |
| DE19622878.6 | 1996-06-07 | ||
| PCT/EP1997/002677 WO1997047700A1 (en) | 1996-06-07 | 1997-05-26 | Multi-layered paint spraying, process for achieving same, and a suitable, non-aqueous finishing coat |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2228940A1 CA2228940A1 (en) | 1997-12-18 |
| CA2228940C true CA2228940C (en) | 2004-05-18 |
Family
ID=7796386
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002228940A Expired - Fee Related CA2228940C (en) | 1996-06-07 | 1997-05-26 | Multicoat paint system, process for its preparation, and nonaqueous topcoat suitable therefore |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5981080A (en) |
| EP (2) | EP0843706B1 (en) |
| JP (1) | JP4285772B2 (en) |
| KR (1) | KR100493844B1 (en) |
| CN (1) | CN1197473A (en) |
| AT (1) | ATE301171T1 (en) |
| BR (1) | BR9702319A (en) |
| CA (1) | CA2228940C (en) |
| DE (2) | DE19622878A1 (en) |
| ES (1) | ES2247630T3 (en) |
| MX (1) | MX9801076A (en) |
| WO (1) | WO1997047700A1 (en) |
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|---|---|---|---|---|
| JP3491450B2 (en) * | 1996-07-12 | 2004-01-26 | 日本油脂Ｂａｓｆコーティングス株式会社 | Thermosetting coating composition |
| WO1998027134A1 (en) * | 1996-12-18 | 1998-06-25 | Basf Coatings Ag | Coating agent and method for producing same |
| US5980993A (en) * | 1996-12-20 | 1999-11-09 | Ppg Industries Ohio, Inc. | Method for applying a color-plus-clear composite coating to a substrate |
| US5965670A (en) * | 1997-12-24 | 1999-10-12 | Ppg Industries Ohio, Inc. | Curable-film forming compositions having improved mar and acid etch resistance |
| US6300422B1 (en) | 1999-08-25 | 2001-10-09 | Lilly Industries, Inc. | Tris(alkoxycarbonylamino)triazine crosslinked waterborne coating system |
| US7445816B2 (en) * | 1999-11-15 | 2008-11-04 | Ppg Industries Ohio, Inc. | Method and apparatus for coating a substrate |
| DE10040223C2 (en) * | 2000-08-17 | 2002-12-05 | Basf Coatings Ag | Structurally viscous, powder clearcoat slurry free of organic solvents and external emulsifiers, process for their preparation and their use |
| JP2002080781A (en) * | 2000-09-11 | 2002-03-19 | Nippon Yushi Basf Coatings Kk | Thermosetting coating material composition |
| US20040175551A1 (en) * | 2003-03-04 | 2004-09-09 | Ford Motor Company | Wet-on-wet two-tone painting |
| CA2461835A1 (en) * | 2003-03-28 | 2004-09-28 | Kansai Paint Co., Ltd. | Paint film forming method |
| WO2004094515A1 (en) * | 2003-04-24 | 2004-11-04 | Nuplex Resins B.V. | Coating composition |
| US20100163423A1 (en) | 2008-12-29 | 2010-07-01 | Basf Corporation | Electrocoat composition and process replacing phosphate pretreatment |
| CN102272243A (en) | 2008-12-29 | 2011-12-07 | 巴斯夫涂料有限公司 | Electrocoat composition and process replacing phosphate pretreatment |
| US8153733B2 (en) | 2008-12-29 | 2012-04-10 | Basf Coatings Gmbh | Electrocoat compositions with amine ligand |
| WO2012115691A1 (en) | 2011-02-22 | 2012-08-30 | Basf Coatings Gmbh | Electrocoat coating with low gloss |
| CN103946321B (en) * | 2011-11-17 | 2016-08-24 | 巴斯夫涂料有限公司 | Comprise the coating of diglyceride and the purposes in multilamellar paint thereof |
| US20150267315A1 (en) | 2012-11-09 | 2015-09-24 | Basf Coatings Gmbh | Method For Improving Coating Cure For Article Coated In Phosphate-Contaminated Electrocoat Coating Composition And Electrocoat Coating Composition |
| CN105442797A (en) * | 2015-12-07 | 2016-03-30 | 无锡捷阳节能科技股份有限公司 | UV interior wall decorative sheet |
| JP6869753B2 (en) * | 2016-03-09 | 2021-05-12 | 関西ペイント株式会社 | High solid content paint composition |
| CN110872372B (en) * | 2019-11-29 | 2021-08-03 | 鞍山润德精细化工有限公司 | Six-functional-group acrylic polyurethane containing triazine ring and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4397989A (en) * | 1982-02-08 | 1983-08-09 | E. I. Du Pont De Nemours & Co. | High solids coating composition of an acrylic polymer a polyester polyol and an alkylated melamine crosslinking agent |
| DE3322037A1 (en) * | 1983-06-18 | 1984-12-20 | Basf Farben + Fasern Ag, 2000 Hamburg | COATING SIZE, ESPECIALLY FOR THE PRODUCTION OF A TRANSPARENT TOP LAYER |
| US4720405A (en) * | 1985-12-13 | 1988-01-19 | Ppg Industries, Inc. | Method of providing a substrate with a flexible multilayer coating |
| US4710542A (en) * | 1986-05-16 | 1987-12-01 | American Cyanamid Company | Alkylcarbamylmethylated amino-triazine crosslinking agents and curable compositions containing the same |
| DE3731652A1 (en) * | 1987-09-19 | 1989-04-06 | Basf Lacke & Farben | CONTAINER BASED ON AN ACRYLATE COPOLYMERATE WITH HYDROXYL, CARBOXYL AND TERTIAER AMINOGRUPPES, PROCESS FOR PREPARING THE CONVEYOR AND ITS USE |
| US5084541A (en) * | 1988-12-19 | 1992-01-28 | American Cyanamid Company | Triazine crosslinking agents and curable compositions |
| US4939213A (en) * | 1988-12-19 | 1990-07-03 | American Cyanamid Company | Triazine crosslinking agents and curable compositions containing the same |
| US5380816A (en) * | 1989-05-11 | 1995-01-10 | Sullivan; Carl J. | Linear polyester diols based on isophthalic acid and 2-methyl-1,3-propanediol for thermoset coating compositions |
| DE4204518A1 (en) * | 1992-02-15 | 1993-08-19 | Basf Lacke & Farben | METHOD FOR PRODUCING A TWO-LAYER PAINTING AND NON-AQUEOUS VARNISHES SUITABLE FOR THIS METHOD |
| US5503935A (en) | 1992-05-11 | 1996-04-02 | General Electric Company | Heat curable primerless silicone hardcoat compositions, and thermoplastic composites |
| US5574103A (en) * | 1992-12-29 | 1996-11-12 | Cytec Technology Corp. | Aminoresin based coatings containing 1,3,5-triazine tris-carbamate co-crosslinkers |
| DE4310414A1 (en) * | 1993-03-31 | 1994-10-06 | Basf Lacke & Farben | Process for producing a two-coat top coat on a substrate surface |
| DE4317861C1 (en) * | 1993-05-28 | 1994-11-24 | Herberts Gmbh | Process for multi-layer coating of substrates and application of the process |
| DE4407409A1 (en) * | 1994-03-05 | 1995-09-07 | Basf Lacke & Farben | Coating compositions based on a hydroxyl-containing polyacrylate resin and its use in processes for producing a multicoat paint system |
| ES2130609T3 (en) | 1994-04-29 | 1999-07-01 | Ppg Industries Inc | HARDENABLE FLEXIBLE FILM FORMING COMPOSITIONS WITH AMINOPLASTS, FORMING FILMS THAT RESIST TO ACID ATTACK. |
| JP3017539B2 (en) | 1995-05-01 | 2000-03-13 | ピーピージー インダストリーズ オハイオ， インコーポレイテッド | Curable compositions, composite coatings and processes for imparting improved damage and abrasion resistance |
| DE19529124C1 (en) | 1995-08-08 | 1996-11-21 | Herberts Gmbh | Acid-resistant coating material, pref. clear top-coat for cars |
| DE69633927T2 (en) * | 1995-08-30 | 2005-11-24 | Cytec Technology Corp., Wilmington | Compositions containing 1,3,5-triazine carbamates and epoxy compounds |
| US5741880A (en) * | 1996-05-10 | 1998-04-21 | The Sherwin-Williams Company | Clearcoating compositions |
| AU718471B2 (en) | 1997-02-21 | 2000-04-13 | Ppg Industries Ohio, Inc. | Photochromic polyurethane coating and articles having such a coating |
-
1996
- 1996-06-07 DE DE19622878A patent/DE19622878A1/en not_active Withdrawn
-
1997
- 1997-05-26 US US09/011,389 patent/US5981080A/en not_active Expired - Lifetime
- 1997-05-26 EP EP97925944A patent/EP0843706B1/en not_active Revoked
- 1997-05-26 DE DE59712381T patent/DE59712381D1/en not_active Expired - Lifetime
- 1997-05-26 AT AT97925944T patent/ATE301171T1/en not_active IP Right Cessation
- 1997-05-26 EP EP02016458.8A patent/EP1254934B1/en not_active Revoked
- 1997-05-26 CN CN97190896A patent/CN1197473A/en active Pending
- 1997-05-26 CA CA002228940A patent/CA2228940C/en not_active Expired - Fee Related
- 1997-05-26 WO PCT/EP1997/002677 patent/WO1997047700A1/en active IP Right Grant
- 1997-05-26 BR BR9702319A patent/BR9702319A/en not_active IP Right Cessation
- 1997-05-26 KR KR10-1998-0700928A patent/KR100493844B1/en not_active IP Right Cessation
- 1997-05-26 JP JP50111398A patent/JP4285772B2/en not_active Expired - Fee Related
- 1997-05-26 ES ES97925944T patent/ES2247630T3/en not_active Expired - Lifetime
-
1998
- 1998-02-09 MX MX9801076A patent/MX9801076A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0843706B1 (en) | 2005-08-03 |
| EP1254934B1 (en) | 2015-08-19 |
| DE59712381D1 (en) | 2005-09-08 |
| KR100493844B1 (en) | 2005-12-21 |
| EP1254934A3 (en) | 2002-11-27 |
| ATE301171T1 (en) | 2005-08-15 |
| WO1997047700A1 (en) | 1997-12-18 |
| BR9702319A (en) | 1999-03-09 |
| MX9801076A (en) | 1998-11-30 |
| CA2228940A1 (en) | 1997-12-18 |
| CN1197473A (en) | 1998-10-28 |
| US5981080A (en) | 1999-11-09 |
| KR19990036260A (en) | 1999-05-25 |
| EP0843706A1 (en) | 1998-05-27 |
| JP4285772B2 (en) | 2009-06-24 |
| EP1254934A2 (en) | 2002-11-06 |
| JPH11511073A (en) | 1999-09-28 |
| ES2247630T3 (en) | 2006-03-01 |
| DE19622878A1 (en) | 1997-12-11 |
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