WO2015033624A1 - Coating composition and coated article - Google Patents

Coating composition and coated article Download PDF

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Publication number
WO2015033624A1
WO2015033624A1 PCT/JP2014/063893 JP2014063893W WO2015033624A1 WO 2015033624 A1 WO2015033624 A1 WO 2015033624A1 JP 2014063893 W JP2014063893 W JP 2014063893W WO 2015033624 A1 WO2015033624 A1 WO 2015033624A1
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WIPO (PCT)
Prior art keywords
hydroxyl group
coating composition
mass
coating
resin
Prior art date
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PCT/JP2014/063893
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French (fr)
Japanese (ja)
Inventor
正人 中水
Original Assignee
関西ペイント株式会社
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Publication date
Application filed by 関西ペイント株式会社 filed Critical 関西ペイント株式会社
Priority to CN201480049628.9A priority Critical patent/CN105658747B/en
Priority to JP2014550954A priority patent/JP5692481B1/en
Publication of WO2015033624A1 publication Critical patent/WO2015033624A1/en

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    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
    • C08G18/4615—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen
    • C08G18/4638—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C08G18/4661—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
    • 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
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret 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
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate 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
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C08G2101/00—Manufacture of cellular products

Definitions

  • the present invention relates to a coating composition and a coated article that can form a coating film having excellent scratch resistance, hardness, appearance, adhesion, and chemical resistance to a plastic substrate.
  • plastic base materials such as ABS resin, polypropylene, urethane resin, and polycarbonate resin have been used for various industrial products such as communication devices, home appliances, and automobile parts.
  • industrial products are required to have scratch resistance, hardness, appearance, adhesion, chemical resistance, and the like.
  • the first layer is coated with multiple types of paints with different functions, such as the paint with excellent adhesion to the substrate and the second layer with excellent scratch resistance of the substrate.
  • paints with different functions
  • chemical resistance in particular, skin containing ultraviolet absorbers, preservatives, and emulsifiers such as liquid foundations, makeup bases, concealers, sunscreens, cosmetics such as cosmetics, emulsions and hand creams.
  • composition for external use Even if the composition for external use is left on the surface of the coating film, it does not cause poor coating adhesion, decrease in appearance, or decrease in hardness (hereinafter abbreviated as “resistance to a composition containing an ultraviolet absorber”). There is a need for it.
  • Patent Document 1 discloses a clear coating composition containing a hydroxyl group-containing acrylic resin and a polyfunctional isocyanate compound as a paint excellent in scratch resistance and acid resistance, wherein the hydroxyl group-containing acrylic resin is at least part of a monomer.
  • a hydroxyl group-containing acrylic resin obtained using a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 4 to 9 carbon atoms wherein at least a part of the polyfunctional isocyanate compound is an isocyanurate type isocyanate compound
  • Soft seg of origin A clear coating composition for automobiles, wherein the proportion of the tip portion is 4.5% by mass or less and the resulting cured coating film has a dynamic glass transition temperature in the range of 30 to 60 ° C.
  • a composition is disclosed.
  • the paint is mainly suitable for a metal substrate, and adhesion to a plastic substrate in a 1-coating 1-baking process and resistance to a composition containing an ultraviolet absorber are not sufficient.
  • the hydroxyl value is 80 to 220 mgKOH / g
  • the glass transition temperature is ⁇ 50 ° C. or higher and lower than 0 ° C.
  • a coating composition comprising a resin (B) and a crosslinking agent (C) comprising a polyisocyanate compound as essential components, wherein the content ratio of the hydroxyl group-containing resin (A) and the hydroxyl group-containing resin (B) is a resin solid Isocyanate having a mass ratio of 95/5 to 50/50 and a functional group of the crosslinking agent (C) for the total hydroxyl groups of the hydroxyl group-containing resin (A) and the hydroxyl group-containing resin (B) Content of coating composition is disclosed, wherein the molar ratio of NCO / OH is 0.5 to 1.5.
  • the paint is mainly suitable for a metal substrate, and adhesion to a plastic substrate in a 1-coat 1-bake coating process and resistance to a composition containing an ultraviolet absorber are not sufficient.
  • Patent Document 3 discloses a self-restoring coating composition containing a lactone-modified acrylic resin and a polycarbonate diol. Although the said coating resin composition is excellent in the abrasion resistance to the ABS board in the 1 coat 1 baking process, the tolerance with respect to the composition containing a ultraviolet absorber etc. is not enough.
  • Patent Document 4 discloses that a polyisocyanate compound (A) having an isocyanate group equivalent in the range of 100 to 280 g / eq and an average glass transition temperature (Tg) of ⁇ 55 ° C. or more and less than ⁇ 9 ° C. And an acrylic polyol (B) having an average functional group number of 4 to 20 and a number average molecular weight (Mn) in the range of 3000 to 15000, the ratio of both [the number of moles of isocyanate groups in the polyisocyanate compound] ] / [The number of moles of hydroxyl groups in the acrylic polyol (B)] is contained in such a ratio that it is in the range of 0.75 to 1.5.
  • the said coating resin composition is excellent in the scratch resistance to the ABS board in a 1 coat 1 baking coating process, and base-material adhesiveness, the tolerance with respect to the composition containing a ultraviolet absorber etc. is not enough.
  • Patent Document 5 discloses a polyisocyanate compound (A) having an isocyanate group equivalent of 100 to 280 g / eq, an average Tg of ⁇ 50 to ⁇ 10 ° C., and an average number of functional groups of hydroxyl groups per molecule of 4 to Polyester polyol (B) having a number average molecular weight (Mn) in the range of 1000 to 3000 and a ratio of the two [molar number of isocyanate groups in the polyisocyanate compound] / [polyester polyol (B)
  • a coating resin composition is disclosed, which is contained in such a ratio that the number of moles of the hydroxyl group in the range of 0.75 to 1.5.
  • the coating resin composition is excellent in scratch resistance and substrate adhesion to an ABS plate in a 1-coat 1-bake coating process, but is not sufficiently resistant to a composition containing an ultraviolet absorber or the like.
  • Patent Document 6 discloses a coating composition capable of forming on the surface of various substrates a self-healing coating film in which the generated scratches disappear in a short time, and has a hydroxyl value of 40 to 80 mgKOH / g and a glass transition temperature.
  • the coating composition is excellent in self-restoration and adhesion in a 1-coat 1-bake coating process, but is not sufficiently resistant to a composition containing an ultraviolet absorber or the like.
  • Patent Document 7 describes chemical resistance, for example, a lotion used to prevent sunburn, and the surface of the acrylic resin film does not become rough even if it is exposed to a high temperature for a long time with the hand cream attached, and it is suitable for a deep-drawn molded product.
  • the film surface does not crack, and has a surface hardness, and has a carboxyl group and a hydroxyl group, and has a solid content acid value of 15 to 150 mgKOH / g and a glass transition temperature.
  • a curable resin composition for a thermoforming film characterized by a content that reacts with 80 mg KOH / g is disclosed.
  • the curable resin composition for thermoforming film is not sufficient in adhesion to the ABS plate and scratch resistance in the 1-coat 1-bake coating process.
  • the present invention has been made in consideration of these points, and contains excellent scratch resistance, hardness, appearance, adhesion, ultraviolet absorbers and the like for a plastic substrate in a 1-coat 1-bake coating process. It is an object of the present invention to provide a coating composition and a coated article capable of forming a coating film having resistance to the composition.
  • the present inventor includes a main agent containing a specific hydroxyl group-containing acrylic resin and a hydroxyl group-containing polyester resin, and a curing agent containing a specific polyisocyanate compound, It has been found that the above problems can be solved by using a coating composition having a glass transition temperature of 20 to 60 ° C. of the obtained coating film, and the present invention has been completed.
  • the present invention provides the following coating composition and an article obtained by coating the coating composition.
  • the present invention relates to the following (1) to (5).
  • a coating composition comprising a main ingredient containing a hydroxyl group-containing acrylic resin (A) and a hydroxyl group-containing polyester resin (B), and a curing agent containing a polyisocyanate compound (C),
  • the hydroxyl group-containing acrylic resin (A) has a hydroxyl value of 100 to 200 mgKOH / g and a glass transition temperature of less than ⁇ 20 ° C.
  • Methyl methacrylate (a1) 15 to 35% by mass, 5-30% by mass of polymerizable unsaturated monomer (a2) having a hydroxyalkyl group having 4 to 9 carbon atoms, and 35-80% by mass of other polymerizable unsaturated monomer (a3) Is a hydroxyl group-containing acrylic resin obtained by reacting Polyhydric alcohol and polybasic acid having a hydroxyl value of 50 to 200 mg KOH / g and a number average molecular weight of 2,000 to 20,000 and containing a cyclic polyol compound (b1) having a nurate structure
  • the polyisocyanate compound (C) is at least one selected from the group consisting of a biuret group-containing polyisocyanate compound and an allophanate group-containing polyisocyanate compound;
  • the coating composition of the present invention has excellent scratch resistance, hardness, appearance, adhesion, and resistance to a composition containing an ultraviolet absorber, etc., for a plastic substrate in a 1-coat 1-bake coating process.
  • a coating film can be formed.
  • weight means “weight”.
  • the coating composition of the present invention contains a main agent containing a hydroxyl group-containing acrylic resin (A) and a hydroxyl group-containing polyester resin (B) and a curing agent containing a polyisocyanate compound (C).
  • the hydroxyl group-containing acrylic resin (A) refers to an acrylic resin containing a hydroxyl group in the molecule.
  • the hydroxyl group-containing acrylic resin (A) is a polymerizable unsaturated monomer such as methyl methacrylate (a1), a polymerizable unsaturated monomer (a2) having a hydroxyalkyl group having 4 to 9 carbon atoms, and other polymerizable unsaturated monomers. It can be synthesized by copolymerizing (a3) by a conventional method.
  • Examples of the polymerizable unsaturated monomer (a2) having a hydroxyalkyl group having 4 to 9 carbon atoms include 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 7 -Hydroxyheptyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 7-methyl-8-hydroxyoctyl (meth) acrylate, 2-methyl-8-hydroxyoctyl (meth) acrylate, 9-hydroxynonyl (meth) An acrylate etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively.
  • polymerizable unsaturated monomer (a2) having a hydroxyalkyl group having 4 to 9 carbon atoms from the viewpoint of excellent scratch resistance, appearance, adhesion and resistance to a composition containing an ultraviolet absorber, among others, 4-hydroxybutyl (meth) acrylate and 6-hydroxyhexyl (meth) acrylate are particularly preferred.
  • Examples of other polymerizable unsaturated monomers (a3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, Monoesterified product of polyhydric alcohol such as polypropylene glycol (meth) acrylate and (meth) acrylic acid, compound obtained by ring-opening polymerization of ⁇ -caprolactone to monoesterified product of polyhydric alcohol and (meth) acrylic acid, etc.
  • the other polymerizable unsaturated monomer (a3) from the viewpoint of obtaining a coating film excellent in resistance to a composition containing scratch resistance, hardness, appearance, adhesion, and an ultraviolet absorber, the carbon number of 4 to It is preferable to contain a hydroxyl group-containing polymerizable unsaturated monomer other than the polymerizable unsaturated monomer having 9 hydroxyalkyl groups, and an alkyl ester of (meth) acrylic acid.
  • 2-hydroxyethyl (meth) acrylate is particularly preferable as the hydroxyl group-containing polymerizable unsaturated monomer other than the polymerizable unsaturated monomer having a hydroxyalkyl group having 4 to 9 carbon atoms.
  • alkyl ester of (meth) acrylic acid a polymerizable unsaturated monomer having 4 to 8 carbon atoms in the alkyl portion is particularly preferable.
  • the scratch resistance, hardness, appearance, and adhesion of the resulting coating film are preferred.
  • n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are particularly preferred from the viewpoint of resistance to a composition containing an ultraviolet absorber and the like.
  • (meth) acrylate means acrylate or methacrylate
  • (meth) acrylic acid means acrylic acid or methacrylic acid
  • (Meth) acryloyl means acryloyl or methacryloyl
  • (meth) acrylamide means acrylamide or methacrylamide.
  • the proportions of methyl methacrylate (a1), polymerizable unsaturated monomer (a2) having a hydroxyalkyl group having 4 to 9 carbon atoms, and other polymerizable unsaturated monomer (a3) used in the monomer component are determined as follows. From the viewpoint of scratch resistance, hardness, appearance, adhesion, and resistance to a composition containing an ultraviolet absorber, etc., the total mass of monomer components (polymerizable unsaturated monomers (a1) to (a3)) is used as a basis. Is within the following range.
  • Methyl methacrylate (a1) 15 to 35% by mass, preferably 20 to 30% by mass, more preferably 22 to 27% by mass
  • the copolymerization of the polymerizable unsaturated monomers (a1) to (a3) is preferably a solution polymerization method.
  • a mixture of a polymerizable unsaturated monomer and a radical polymerization initiator is dissolved in an organic solvent.
  • a method may be mentioned in which the polymerization is carried out by dispersing and heating at about 80 ° C. to about 200 ° C. with stirring for about 1 to 10 hours.
  • the hydroxyl group-containing acrylic resin (A) has a hydroxyl value of 100 to 200 mgKOH / g, preferably 105 to 170 mgKOH / g, more preferably 110 to 150 mgKOH / g, and a glass transition temperature of less than ⁇ 20 ° C., preferably ⁇ A hydroxyl group-containing acrylic resin having a temperature of less than 23 ° C., more preferably less than ⁇ 25 ° C.
  • the hydroxyl value of the hydroxyl group-containing acrylic resin (A) is 100 mgKOH / g or more, the resistance to a composition containing an ultraviolet absorber is good, and when it is 200 mgKOH / g or less, the resulting coating film has good scratch resistance. This is preferable.
  • the glass transition temperature exceeds ⁇ 20 ° C., the scratch resistance and hardness of the coating film may be inferior.
  • W1, W2,... Wn are mass fractions of the respective monomers
  • T1, T2... Tn are glass transition temperatures Tg (K) of the homopolymers of the respective monomers.
  • the glass transition temperature of the homopolymer of each monomer is described in POLYMERHANDBOOKFourth Edition, J. MoI. Brandrup, E .; h. Immergut, E .; A.
  • the glass transition temperature of a monomer not described in this document which is a value according to Grulk ed. (1999), was synthesized such that the monomer homopolymer had a weight average molecular weight of about 50,000, and its glass transition. The value when the temperature is measured by differential scanning thermal analysis is used.
  • the hydroxyl group-containing acrylic resin (A) has a weight average molecular weight of 5,000 to 33,000 in view of scratch resistance, hardness, appearance, adhesion, and resistance to a composition containing an ultraviolet absorber, The range is preferably 8,000 to 30,000.
  • the weight average molecular weight and the number average molecular weight are the retention time (retention capacity) measured using a gel permeation chromatograph (GPC), and the retention time of standard polystyrene with a known molecular weight measured under the same conditions ( It is a value obtained by converting to the molecular weight of polystyrene by (retention capacity).
  • the content of the hydroxyl group-containing acrylic resin (A) is preferably 10 to 80 parts by mass, more preferably 55 to 75 parts by mass, based on the total resin solid content in the main agent. It is suitable from the viewpoint of scratch resistance, hardness, appearance, adhesion, resistance to a composition containing an ultraviolet absorber and the like of the resulting coating film within the above range.
  • the hydroxyl group-containing polyester resin (B) can be generally obtained by esterifying a polyhydric alcohol and a polybasic acid with an excess of hydroxyl groups by a method known per se.
  • the polyhydric alcohol is a compound having two or more hydroxyl groups in one molecule
  • the polybasic acid is a compound having two or more carboxyl groups in one molecule.
  • the hydroxyl group-containing polyester resin (B) contains a cyclic polyol compound (b1) having a nurate structure as a polyhydric alcohol.
  • Examples of the cyclic polyol compound (b1) having a nurate structure include tris (hydroxyalkyl) isocyanurate such as tris (hydroxyethyl) isocyanurate, tris (hydroxypropyl) isocyanurate and tris (hydroxybutyl) isocyanurate, the tris ⁇ -caprolactone modified form of (hydroxyalkyl) isocyanurate, tris (hydroxyethyl) isocyanurate, diol compound and dicarboxylic acid, and the hydroxyl group in tris (hydroxyethyl) isocyanurate and diol compound is converted to a carboxyl group in dicarboxylic acid.
  • tris (hydroxyalkyl) isocyanurate such as tris (hydroxyethyl) isocyanurate, tris (hydroxypropyl) isocyanurate and tris (hydroxybutyl) isocyanurate
  • These can be used alone or in combination of two or more.
  • tris (2-hydroxyethyl) isocyanurate and ⁇ -caprolactone-modified products of tris (2-hydroxyethyl) isocyanurate from the viewpoint of resistance of the resulting coating film to a composition containing an ultraviolet absorber or the like. Is preferred, and tris (2-hydroxyethyl) isocyanurate is more preferred.
  • polyhydric alcohol other than the component (b1) examples include ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, and 1,3-butane.
  • the content ratio of the cyclic polyol compound (b1) having a nurate structure in the hydroxyl group-containing polyester resin (B) is based on the total amount of alcohol components from the viewpoint of resistance to a composition containing an ultraviolet absorber or the like of the obtained coating film. As a result, it is preferably in the range of 1 to 75 mol%, more preferably in the range of 10 to 60 mol%. When the content ratio of the cyclic polyol compound (b1) having a nurate structure is within the above range, resistance to a composition containing an ultraviolet absorber or the like is improved.
  • polybasic acid examples include aromatic polybasic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, diphenylmethane-4,4′-dicarboxylic acid, and anhydrides thereof; Hexahydroisophthalic acid, hexahydroterephthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid and other alicyclic dicarboxylic acids and their anhydrides; adipic acid, sebacic acid, suberic acid, succinic acid, glutaric acid, maleic acid, chloroformate Aliphatic polybasic acids such as acids, fumaric acid, dodecanedioic acid, pimelic acid, azelaic acid, itaconic acid, citraconic acid and dimer acid and their anhydrides; lower alkyl esters such as methyl esters and ethyl
  • the introduction of a hydroxyl group can be performed, for example, by using a polyhydric alcohol having 3 or more hydroxyl groups in one molecule.
  • a monobasic acid, an oil component (including this fatty acid) and the like may be used as necessary.
  • the monobasic acid include benzoic acid and t-butylbenzoic acid.
  • the oil component include castor oil, dehydrated castor oil, safflower oil, soybean oil, linseed oil, tall oil, coconut oil, and the like. These fatty acids etc. are mentioned, These can be used 1 type or 2 or more types.
  • the polyester resin may be modified with an epoxy compound such as butyl glycidyl ether, alkylphenyl glycidyl ether, or neodecanoic acid glycidyl ester, if necessary.
  • an epoxy compound such as butyl glycidyl ether, alkylphenyl glycidyl ether, or neodecanoic acid glycidyl ester, if necessary.
  • the hydroxyl group-containing polyester resin (B) has a hydroxyl value of 50 to 200 mgKOH from the viewpoint of scratch resistance, hardness, appearance, adhesion, resistance to a composition containing an ultraviolet absorber, etc. / G, preferably 50 to 150 g KOH / g, number average molecular weight 2,000 to 20,000, preferably 2,000 to 15,000.
  • the content of the hydroxyl group-containing polyester resin (B) is determined from the viewpoint of the scratch resistance, hardness, appearance, adhesion, resistance to the composition containing an ultraviolet absorber, etc. Is preferably 20 to 90 parts by mass, more preferably 25 to 45 parts by mass.
  • the main agent of the present invention comprises a hydroxyl group-containing acrylic resin (A) and a hydroxyl group-containing polyester resin (B) as essential components, and further includes a hydroxyl group-containing urethane resin, a phenol resin, a polycarbonate resin, and an epoxy resin as necessary.
  • a resin component can be contained.
  • the curing agent used in the present invention contains a polyisocyanate compound (C).
  • the polyisocyanate compound (C) contains at least one selected from the group consisting of an allophanate group-containing polyisocyanate compound and a biuret group-containing polyisocyanate compound as an essential component.
  • the allophanate group-containing polyisocyanate compound is a compound obtained by subjecting a polyisocyanate selected from an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate and the like to an allophanate reaction by a known method.
  • the biuret group-containing polyisocyanate compound is a compound obtained by subjecting a polyisocyanate selected from an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate and the like to a biuret reaction by a known method.
  • aliphatic polyisocyanate examples include diisocyanates (for example, trimethylene diisocyanate, 1,2-propylene diisocyanate, tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, hexamethylene.
  • diisocyanates for example, trimethylene diisocyanate, 1,2-propylene diisocyanate, tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, hexamethylene.
  • Diisocyanates pentamethylene diisocyanates, C2-16 alkane diisocyanates such as 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate), polyisocyanates (eg lysine) Ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanate DOO methyl octane, 1,3,6-triisocyanato hexane, C6-20 alkanes triisocyanates such as 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyl octane) and the like.
  • C2-16 alkane diisocyanates such as 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyana
  • alicyclic polyisocyanate examples include diisocyanates (for example, 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate.
  • diisocyanates for example, 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate.
  • aromatic polyisocyanate examples include diisocyanates (for example, 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ⁇ , ⁇ ′-diisocyanato-1,4-diethylbenzene, 1,3- or 1,4- Bis (1-isocyanato-1-methylethyl) benzene (common name: tetramethylxylylene diisocyanate) or a mixture thereof, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate 2,4'- or 4,4'-diphenylmethane diisocyanate or mixtures thereof, 2,4- or 2,6-tolylene diisocyanate or mixtures thereof, 4,4'-toluidine diisocyanate, 4,4'-diph Phenyl ether diisocyanate), polyisocyanates
  • a biuret group-containing polyisocyanate compound or an allophanate group-containing polyisocyanate compound of an aliphatic polyisocyanate contains the scratch resistance, hardness, appearance, adhesion, ultraviolet absorber and the like of the resulting coating film. Can be preferably used from the standpoint of resistance to the like.
  • the coating film from which hexamethylene diisocyanate can be used can be preferably used in terms of scratch resistance, hardness, appearance, adhesion, resistance to a composition containing an ultraviolet absorber, and the like.
  • the polyisocyanate compound (C) can contain a polyisocyanate compound other than the allophanate group-containing polyisocyanate compound and / or the biuret group-containing polyisocyanate compound as necessary.
  • aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, lysine diisocyanate; isocyanurate cycloadducts, uretdione type adducts of these aliphatic polyisocyanates; isophorone diisocyanate, 4,4 ′ -Alicyclic diisocyanates such as methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4- or -2,6-diisocyanate; isocyanurate cycloadducts of these alicyclic diisocyanates; xylylene diisocyanate, tetramethylxylylene diisocyanate Isocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyan
  • the amount of the polyisocyanate compound (C) used is generally such that the isocyanate group (NCO) contained in the polyisocyanate compound (C) is an equivalent ratio of NCO / OH with respect to the hydroxyl group (OH) in the main agent. It is appropriate to select it within a range of 2.0, preferably 0.8 to 1.5.
  • a coating used in the field of ordinary coatings such as an organic solvent, a curing catalyst, a pigment, a pigment dispersant, a leveling agent, an ultraviolet absorber, a light stabilizer, and a plasticizer.
  • Additives can be combined in the main agent and / or curing agent in an appropriate combination.
  • the organic solvent is not particularly limited, and for example, usual paint solvents such as hydrocarbon, ester, ether, alcohol, and ketone can be used.
  • curing catalyst examples include tin octylate, dibutyltin di (2-ethylhexanoate), dioctyltin di (2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, and dioctyl.
  • Organic metals such as tin oxide, dibutyltin fatty acid salt, lead 2-ethylhexanoate, zinc octylate, zinc naphthenate, fatty acid zinc, cobalt naphthenate, calcium octylate, copper naphthenate, tetra (2-ethylhexyl) titanate
  • urethane curing catalysts such as tertiary amines and phosphoric acid compounds, if necessary.
  • the amount of the curing catalyst used is usually 0.001 to 2 parts by mass, preferably 0.01 to 100 parts by mass of the resin solid content in the coating composition.
  • the range of ⁇ 1 part by mass is appropriate.
  • the pigment examples include titanium oxide, zinc white, carbon black, cadmium red, molybdenum red, chromium yellow, chromium oxide, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, selenium pigment, Color pigments such as perylene pigments; body pigments such as talc, clay, kaolin, barita, barium sulfate, barium carbonate, calcium carbonate, alumina white; metallic pigments such as aluminum powder, mica powder, mica powder coated with titanium oxide, etc. Can be mentioned. These can be used alone or in combination of two or more.
  • the amount of the pigment is preferably an amount that does not hinder the transparency of the resulting coating film.
  • it is preferably in the range of 0.1 to 20 parts by weight, more preferably in the range of 0.3 to 10 parts by weight, based on 100 parts by weight of the solid content in the coating composition. More preferably, it is in the range of 5 to 5 parts by mass.
  • the blending amount of the pigment is usually 1 to 200 based on 100 parts by mass of the solid content in the coating composition. It is preferably in the range of parts by mass, more preferably in the range of 2 to 100 parts by mass, and still more preferably in the range of 5 to 50 parts by mass.
  • ultraviolet absorber conventionally known ones can be used, and examples thereof include ultraviolet absorbers such as benzotriazole absorbers, triazine absorbers, salicylic acid derivative absorbers, and benzophenone absorbers. These can be used alone or in combination of two or more.
  • the blending amount of the ultraviolet absorber is in the range of 0.1 to 10 parts by mass based on 100 parts by mass of the solid content in the coating composition. It is preferably within the range of 0.2 to 5 parts by mass, and more preferably within the range of 0.3 to 2 parts by mass.
  • light stabilizer conventionally known light stabilizers can be used, and examples thereof include hindered amine light stabilizers.
  • the blending amount of the light stabilizer is in the range of 0.1 to 10 parts by mass based on 100 parts by mass of the solid content in the matte coating composition. Preferably, it is within the range of 0.2 to 5 parts by mass, and more preferably within the range of 0.3 to 2 parts by mass.
  • a coated article can be obtained by painting the coating composition on the surface of a plastic substrate.
  • the plastic substrate is not particularly limited.
  • a polyolefin-based resin represented by polyethylene, polypropylene, etc .
  • Thermoplastic polyester resins such as (PC / PBT) resin
  • Styrenic resins such as acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene-acrylate (ASA) resin
  • Other polymethyl methacrylate resin acrylic Resin, vinylidene chloride, polyamide resin, polyphenylene ether resin, polyoxymethylene resin, polyurethane resin, epoxy resin, etc.
  • materials surface such as a hybrid resin and fiber reinforced plastic (Fiber-Reinforced Plastics). These material surfaces may be subjected to a degreasing treatment or a surface treatment as needed. Furthermore, after forming an undercoat film on the plastic substrate surface, the coating composition of the present invention may be applied.
  • the method for applying the coating composition of the present invention is not particularly limited.
  • it can be applied by air spray, airless spray, rotary atomizing coater, dip coating, brush or the like.
  • the coating film of the coating composition of the present invention can usually have a cured film thickness of usually 3 to 100 ⁇ m, preferably 3 to 50 ⁇ m.
  • the heating conditions are not particularly limited, but it can be carried out by holding at 50 to 100 ° C., preferably 50 to 90 ° C. for 10 to 90 minutes.
  • the heating condition is preferably maintained at 50 to 80 ° C. for 10 to 90 minutes, for example, when an ABS resin is used.
  • the coating film obtained by the coating composition of the present invention has a glass transition temperature of 20 in terms of scratch resistance, hardness, appearance, adhesion and resistance to a composition containing an ultraviolet absorber and the like. -60 ° C, preferably 30-55 ° C, more preferably 35-50 ° C.
  • the glass transition temperature is obtained by using a dynamic viscoelasticity measuring apparatus as a measurement sample, and forming a 25 ⁇ m-thick coating film that has been heat-cured at 80 ° C. for 30 minutes into a strip-shaped free film (0.5 cm ⁇ 2 cm).
  • FT Rheospectra DVE-V4 (trade name, manufactured by Rheology) can be used.
  • the coating film obtained by the coating composition of the present invention has a molecular weight between crosslinks of 300 to 300 after curing from the viewpoints of scratch resistance, hardness, appearance, adhesion and resistance to a composition containing an ultraviolet absorber and the like. It is preferably 1000, more preferably 350 to 900, and still more preferably 400 to 800.
  • the molecular weight between crosslinks is a theoretical calculated value obtained by applying the glass transition temperature value of the coating film measured by the above method to the following rubber viscoelastic theoretical formula such as Flory.
  • Part and % represent “part by mass” and “% by mass”, respectively.
  • the film thickness of a coating film is based on a cured coating film.
  • the obtained hydroxyl group-containing acrylic resin (A-1) solution was a uniform transparent solution having a solid content of 55%.
  • the weight average molecular weight of the acrylic resin was about 21,000, the hydroxyl value was 113 mgKOH / g, and the glass transition temperature was ⁇ 29 ° C.
  • Production Examples 2 to 19 In the above Production Example 1, the same operations as in Production Example 1 were conducted except that the monomer mixture had the composition shown in Table 1, and the hydroxyl group-containing acrylic resins (A-2) to (A-19) having a solid content of 55% were obtained. ) A solution was obtained. Table 1 shows the weight average molecular weight, hydroxyl value, and glass transition temperature of each hydroxyl group-containing acrylic resin obtained.
  • polyester resin (B-1) had a number average molecular weight of 2,200 and a hydroxyl value of 106 mgKOH / g.
  • Production Examples 21 to 28 In the above Production Example 20, the same operation as in Production Example 20 was performed except that the mixture of the monomer and the polymerization initiator was changed to the composition shown in Table 2, and the hydroxyl group-containing polyester resin (B-2) having a solid content of 50% was obtained. (B-9) A solution was obtained. Table 2 shows the number average molecular weight and hydroxyl value of each hydroxyl group-containing polyester resin obtained.
  • Table 3 shows the solid content, and (C-1) to (C-3) in Table 3 are as follows.
  • the black pigments shown in Table 3 were blended in advance with 1 part of a dispersant (“Solspers 37500”, trade name, manufactured by Lubrizol).
  • the L15 ° value is measured using a variable angle color difference meter “MA68II” (trade name, manufactured by X-rite), and the L in the direction of the light receiving angle of 15 degrees with respect to the direction in which light is incident in the direction perpendicular to the scratches.
  • the value (this is referred to as L15 ° value) was read and the difference ⁇ L15 ° before and after the test was calculated. The case where ⁇ L15 ° exceeds 30 is rejected.
  • Pencil hardness Implemented according to JIS K 5600-5-4 (1999). The pencil lead was applied at an angle of about 45 ° with respect to the coating surface of each test coating plate, and the pencil was moved forward at a uniform speed by about 10 mm while pressing firmly against the coating surface so as not to break the core. This operation was repeated 5 times at different locations, and the hardness symbol of the hardest pencil that did not leave a pencil lead mark on the coating film was defined as pencil hardness.
  • Adhesiveness Cut lines were made with a cutter so as to reach the substrate on the coating film surface of each test coating plate, and 100 squares having a size of 2 mm ⁇ 2 mm were made. Subsequently, a cellophane pressure-sensitive adhesive tape and a cloth pressure-sensitive adhesive tape were adhered to the coating surface, and the number of cells remaining after the film was rapidly peeled off at 20 ° C. was evaluated according to the following criteria. .
  • A The number of cells remaining when the cellophane adhesive tape was peeled off was 100, and the number of cells remaining when the cloth adhesive tape was peeled off was 100.
  • ⁇ The number of squares in which the coating film remains when the cellophane adhesive tape is peeled off, and the square in which the coating film remains when the cloth adhesive tape is peeled off The number is 99 or less.
  • X The number of cells remaining when the cellophane adhesive tape is peeled is 99 or less, and the film remains when the cloth adhesive tape is peeled off. The number of squares is 99 or less

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Abstract

The purpose of the present invention is to provide: a coating composition which can form, on plastic bases, a coating film excellent in terms of scratch resistance, hardness, appearance, adhesion, and chemical resistance; and a coated article. This coating composition comprises: a main ingredient comprising a specific hydroxylated acrylic resin (A) and a specific hydroxylated polyester resin (B); and a hardener comprising a specific polyisocyanate compound (C). The coating composition gives a coating film having a glass transition temperature of 20-60°C.

Description

塗料組成物及び塗装物品Coating composition and coated article
　本発明は、プラスチック基材に対して優れた耐擦り傷性、硬度、外観、付着性及び耐薬品性を有する塗膜を形成することができる塗料組成物及び塗装物品に関する。 The present invention relates to a coating composition and a coated article that can form a coating film having excellent scratch resistance, hardness, appearance, adhesion, and chemical resistance to a plastic substrate.
　近年、通信機器、家電製品、自動車用部品などの各種工業製品にＡＢＳ樹脂、ポリプロピレン、ウレタン樹脂、ポリカーボネート樹脂等のプラスチック基材が用いられている。かかる工業製品には耐擦り傷性、硬度、外観、付着性、耐薬品性などが求められる。 In recent years, plastic base materials such as ABS resin, polypropylene, urethane resin, and polycarbonate resin have been used for various industrial products such as communication devices, home appliances, and automobile parts. Such industrial products are required to have scratch resistance, hardness, appearance, adhesion, chemical resistance, and the like.
　種々の工業製品には、第一層目は基材への付着性に優れる塗料、第二層目は基材の耐擦り傷性に優れる塗料といったように、機能の異なる複数種の塗料を塗り重ねて複層塗膜を形成させる工業製品もあるが、なかには、一種類の塗料による１コート１ベーク（１回塗装１回焼付け）の塗装工程において付着性と各種塗膜性能とを成立させることが求められる工業製品もあり、課題としては１コート１ベークが求められる方が難しい。また、耐薬品性としては、近年特に、液状ファンデーション、化粧下地、コンシーラー、日焼け止め剤、美容液、乳液、ハンドクリームなどの化粧料のような、紫外線吸収剤、防腐剤及び乳化剤を含有する皮膚外用組成物が塗膜面に付着したまま放置されても塗膜の付着不良、外観低下及び硬度低下等が発生しないこと（以下、「紫外線吸収剤等を含有する組成物に対する耐性」と略記することがある）が求められている。 For various industrial products, the first layer is coated with multiple types of paints with different functions, such as the paint with excellent adhesion to the substrate and the second layer with excellent scratch resistance of the substrate. There are industrial products that can form multi-layer coatings, but in some cases, it is possible to establish adhesion and various coating film performances in the coating process of one coat and one bake (one coating and one baking) with one type of paint. Some industrial products are required, and it is more difficult to find one coat and one bake as a problem. As chemical resistance, in particular, skin containing ultraviolet absorbers, preservatives, and emulsifiers such as liquid foundations, makeup bases, concealers, sunscreens, cosmetics such as cosmetics, emulsions and hand creams. Even if the composition for external use is left on the surface of the coating film, it does not cause poor coating adhesion, decrease in appearance, or decrease in hardness (hereinafter abbreviated as “resistance to a composition containing an ultraviolet absorber”). There is a need for it.
　例えば特許文献１には耐傷性と耐酸性に優れた塗料として、水酸基含有アクリル樹脂と多官能イソシアネート化合物とを含有するクリヤー塗料組成物であって、前記水酸基含有アクリル樹脂が、少なくとも一部のモノマーとして炭素数４～９のヒドロキシアルキル基を有するヒドロキシアルキル（メタ）アクリレートを用いて得た水酸基含有アクリル樹脂であり、前記多官能イソシアネート化合物のうちの少なくとも一部がイソシアヌレート型イソシアネート化合物であり、特定のソフトセグメント部を、前記水酸基含有アクリル樹脂及び多官能イソシアネート化合物の固形分全量に対して２５～５０質量％有し、前記水酸基含有アクリル樹脂及び多官能イソシアネート化合物の固形分全量に対するラクトン含有モノマー由来のソフトセグメント部の割合を４．５質量％以下とし、かつ、得られる硬化塗膜の動的ガラス転移温度が３０～６０℃の範囲となるように調製されていることを特徴とする自動車用クリヤー塗料組成物が開示されている。 For example, Patent Document 1 discloses a clear coating composition containing a hydroxyl group-containing acrylic resin and a polyfunctional isocyanate compound as a paint excellent in scratch resistance and acid resistance, wherein the hydroxyl group-containing acrylic resin is at least part of a monomer. As a hydroxyl group-containing acrylic resin obtained using a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 4 to 9 carbon atoms, wherein at least a part of the polyfunctional isocyanate compound is an isocyanurate type isocyanate compound, A lactone-containing monomer having a specific soft segment portion in an amount of 25 to 50% by mass based on the total solid content of the hydroxyl group-containing acrylic resin and polyfunctional isocyanate compound, and based on the total solid content of the hydroxyl group-containing acrylic resin and polyfunctional isocyanate compound Soft seg of origin A clear coating composition for automobiles, wherein the proportion of the tip portion is 4.5% by mass or less and the resulting cured coating film has a dynamic glass transition temperature in the range of 30 to 60 ° C. A composition is disclosed.
　しかしながら当該塗料は主に金属基材に適したものとなっており、プラスチック基材に対する１コート１ベーク塗装工程での付着性及び紫外線吸収剤等を含有する組成物に対する耐性は十分ではない。 However, the paint is mainly suitable for a metal substrate, and adhesion to a plastic substrate in a 1-coating 1-baking process and resistance to a composition containing an ultraviolet absorber are not sufficient.
　特許文献２には耐洗車傷性、耐酸性、耐候性に優れた塗料として、水酸基価が８０～２２０ｍｇＫＯＨ／ｇであり、ガラス転移温度が－５０℃以上、かつ０℃未満であって、４－ヒドロキシブチル（メタ）アクリレートに由来する単位を２５～５５質量％含有する水酸基含有樹脂（Ａ）、水酸基価が８０～２２０ｍｇＫＯＨ／ｇであって、ガラス転移温度が０～５０℃である水酸基含有樹脂（Ｂ）、及びポリイソシアネート化合物から成る架橋剤（Ｃ）とを必須成分とする塗料組成物であって、水酸基含有樹脂（Ａ）と水酸基含有樹脂（Ｂ）との含有割合が、樹脂固形分質量比で、９５／５～５０／５０であり、かつ、水酸基含有樹脂（Ａ）および水酸基含有樹脂（Ｂ）の合計の水酸基に対する架橋剤（Ｃ）の官能基であるイソシアネート基の含有割合が、ＮＣＯ／ＯＨのモル比で０．５～１．５であることを特徴とする塗料組成物が開示されている。 In Patent Document 2, as a paint excellent in car washing scratch resistance, acid resistance and weather resistance, the hydroxyl value is 80 to 220 mgKOH / g, the glass transition temperature is −50 ° C. or higher and lower than 0 ° C. A hydroxyl group-containing resin (A) containing 25 to 55% by mass of units derived from hydroxybutyl (meth) acrylate, a hydroxyl group value having a hydroxyl value of 80 to 220 mgKOH / g and a glass transition temperature of 0 to 50 ° C. A coating composition comprising a resin (B) and a crosslinking agent (C) comprising a polyisocyanate compound as essential components, wherein the content ratio of the hydroxyl group-containing resin (A) and the hydroxyl group-containing resin (B) is a resin solid Isocyanate having a mass ratio of 95/5 to 50/50 and a functional group of the crosslinking agent (C) for the total hydroxyl groups of the hydroxyl group-containing resin (A) and the hydroxyl group-containing resin (B) Content of coating composition is disclosed, wherein the molar ratio of NCO / OH is 0.5 to 1.5.
　しかしながら当該塗料は主に金属基材に適したものとなっており、プラスチック基材に対する１コート１ベーク塗装工程での付着性、紫外線吸収剤等を含有する組成物に対する耐性は十分ではない。 However, the paint is mainly suitable for a metal substrate, and adhesion to a plastic substrate in a 1-coat 1-bake coating process and resistance to a composition containing an ultraviolet absorber are not sufficient.
　特許文献３には、ラクトン変性アクリル樹脂とポリカーボネートジオールを含有することを特徴とする自己復元塗料組成物が開示されている。当該コーティング樹脂組成物は１コート１ベーク塗装工程でのＡＢＳ板への耐擦傷性に優れているが、紫外線吸収剤等を含有する組成物に対する耐性は十分ではない。 Patent Document 3 discloses a self-restoring coating composition containing a lactone-modified acrylic resin and a polycarbonate diol. Although the said coating resin composition is excellent in the abrasion resistance to the ABS board in the 1 coat 1 baking process, the tolerance with respect to the composition containing a ultraviolet absorber etc. is not enough.
　特許文献４にはイソシアネート基当量が１００～２８０ｇ／ｅｑの範囲であるポリイソシアネート化合物（Ａ）と、平均ガラス転移温度（Ｔｇ）が－５５℃以上－９℃未満であり、１分子あたりの水酸基の平均官能基数が４～２０であり、かつ、数平均分子量（Ｍｎ）が３０００～１５０００の範囲であるアクリル系ポリオール（Ｂ）とを、両者の比率［ポリイソシアネート化合物中のイソシアネート基のモル数］／［アクリル系ポリオール（Ｂ）中の水酸基のモル数］が０．７５～１．５の範囲となるような割合で含有することを特徴とするコーティング樹脂組成物が開示されている。当該コーティング樹脂組成物は１コート１ベーク塗装工程でのＡＢＳ板への耐傷性、及び基材密着性に優れているが、紫外線吸収剤等を含有する組成物に対する耐性は十分ではない。 Patent Document 4 discloses that a polyisocyanate compound (A) having an isocyanate group equivalent in the range of 100 to 280 g / eq and an average glass transition temperature (Tg) of −55 ° C. or more and less than −9 ° C. And an acrylic polyol (B) having an average functional group number of 4 to 20 and a number average molecular weight (Mn) in the range of 3000 to 15000, the ratio of both [the number of moles of isocyanate groups in the polyisocyanate compound] ] / [The number of moles of hydroxyl groups in the acrylic polyol (B)] is contained in such a ratio that it is in the range of 0.75 to 1.5. Although the said coating resin composition is excellent in the scratch resistance to the ABS board in a 1 coat 1 baking coating process, and base-material adhesiveness, the tolerance with respect to the composition containing a ultraviolet absorber etc. is not enough.
　特許文献５にはイソシアネート基当量が１００～２８０ｇ／ｅｑの範囲であるポリイソシアネート化合物（Ａ）と、平均Ｔｇが－５０～－１０℃であり、１分子あたりの水酸基の平均官能基数が４～２０であり、かつ、数平均分子量（Ｍｎ）が１０００～３０００の範囲であるポリエステルポリオール（Ｂ）とを、両者の比率［ポリイソシアネート化合物中のイソシアネート基のモル数］／［ポリエステルポリオール（Ｂ）中の水酸基のモル数］が０．７５～１．５の範囲となるような割合で含有することを特徴とするコーティング樹脂組成物が開示されている。当該コーティング樹脂組成物は１コート１ベーク塗装工程でのＡＢＳ板への耐傷性及び基材密着性に優れているが、紫外線吸収剤等を含有する組成物に対する耐性は十分ではない。 Patent Document 5 discloses a polyisocyanate compound (A) having an isocyanate group equivalent of 100 to 280 g / eq, an average Tg of −50 to −10 ° C., and an average number of functional groups of hydroxyl groups per molecule of 4 to Polyester polyol (B) having a number average molecular weight (Mn) in the range of 1000 to 3000 and a ratio of the two [molar number of isocyanate groups in the polyisocyanate compound] / [polyester polyol (B) A coating resin composition is disclosed, which is contained in such a ratio that the number of moles of the hydroxyl group in the range of 0.75 to 1.5. The coating resin composition is excellent in scratch resistance and substrate adhesion to an ABS plate in a 1-coat 1-bake coating process, but is not sufficiently resistant to a composition containing an ultraviolet absorber or the like.
　特許文献６には生じた傷が短時間に消失する自己修復性の塗膜を各種基材の表面に形成できる塗料組成物として、水酸基価が４０～８０ｍｇＫＯＨ／ｇであり、かつガラス転移温度が－４０～－１０℃であるポリエステルポリオール（Ａ）、および水酸基価が３５～６５ｍｇＫＯＨ／ｇであり、かつガラス転移温度が５０～７０℃であるポリエステルポリオール（Ｂ）、ならびに脂肪族ジイソシアネートの三量体（Ｃ）を含有し、かつ、（Ａ）成分と（Ｂ）成分の使用重量比〔（Ａ）／（Ｂ）〕が４５／５５～８５／１５であり、かつ、（Ａ）成分と（Ｂ）成分の水酸基の合計モル数（ＯＨ）と（Ｃ）成分のイソシアネート基のモル数（ＮＣＯ）との比〔ＮＣＯ／ＯＨ〕が０．８～２である塗料組成物が開示されている。しかし当該塗料組成物は１コート１ベーク塗装工程での自己修復性及び密着性に優れているが、紫外線吸収剤等を含有する組成物に対する耐性は十分ではない。 Patent Document 6 discloses a coating composition capable of forming on the surface of various substrates a self-healing coating film in which the generated scratches disappear in a short time, and has a hydroxyl value of 40 to 80 mgKOH / g and a glass transition temperature. Trimer of polyester polyol (A) having a temperature of −40 to −10 ° C., polyester polyol (B) having a hydroxyl value of 35 to 65 mgKOH / g and a glass transition temperature of 50 to 70 ° C., and aliphatic diisocyanate Body (C), the weight ratio [(A) / (B)] used between the component (A) and the component (B) is 45/55 to 85/15, and the component (A) Disclosed is a coating composition wherein the ratio [NCO / OH] of the total number of moles of hydroxyl groups (OH) of component (B) to the number of moles of isocyanate groups (NCO) of component (C) is 0.8-2. Yes. However, the coating composition is excellent in self-restoration and adhesion in a 1-coat 1-bake coating process, but is not sufficiently resistant to a composition containing an ultraviolet absorber or the like.
　特許文献７には耐薬品性、例えば、日焼け防止に用いるローション、ハンドクリームが付着したまま高温下で長時間曝されてもアクリル樹脂フィルム表面が荒れることなく、また、深絞り形状の成形品に成形した場合フィルム表面に割れが発生することがなく、且つ、表面硬度を備えた熱成形用フィルムとして、カルボキシル基と水酸基を有し、固形分酸価が１５～１５０ｍｇＫＯＨ／ｇでありガラス転移温度が７０～１４０℃であるビニル系重合体（Ａ）と、ポリイソシアネート化合物（Ｂ）を含有し、ポリイソシアネート化合物（Ｂ）の含有量がビニル系重合体（Ａ）の固形分水酸基価２～８０ｍｇＫＯＨ／ｇと反応する含有量であることを特徴とする熱成形用フィルム向け硬化性樹脂組成物が開示されている。しかし当該熱成型用フィルム向け硬化性樹脂組成物は１コート１ベーク塗装工程でのＡＢＳ板への付着性及び耐擦り傷性が十分ではない。 Patent Document 7 describes chemical resistance, for example, a lotion used to prevent sunburn, and the surface of the acrylic resin film does not become rough even if it is exposed to a high temperature for a long time with the hand cream attached, and it is suitable for a deep-drawn molded product. When molded, the film surface does not crack, and has a surface hardness, and has a carboxyl group and a hydroxyl group, and has a solid content acid value of 15 to 150 mgKOH / g and a glass transition temperature. Containing a vinyl polymer (A) having a temperature of 70 to 140 ° C. and a polyisocyanate compound (B), wherein the polyisocyanate compound (B) has a solid content hydroxyl value of 2 to 2 in the vinyl polymer (A). A curable resin composition for a thermoforming film characterized by a content that reacts with 80 mg KOH / g is disclosed. However, the curable resin composition for thermoforming film is not sufficient in adhesion to the ABS plate and scratch resistance in the 1-coat 1-bake coating process.
日本国特開２００６－１７６６３４号公報Japanese Unexamined Patent Publication No. 2006-176634 日本国特開２００９－４６６４２号公報Japanese Unexamined Patent Publication No. 2009-46642 日本国特開２０１２－９７１２７号公報Japanese Unexamined Patent Publication No. 2012-97127 日本国特開２０１２－９７１７３号公報Japanese Unexamined Patent Publication No. 2012-97173 日本国特開２０１２－８７１８３号公報Japanese Unexamined Patent Publication No. 2012-87183 日本国特開２０１２－１４０６１４号公報Japanese Unexamined Patent Publication No. 2012-140614 日本国特開２０１２－９７２４８号公報Japanese Unexamined Patent Publication No. 2012-97248
　本発明はこれらの点を考慮してなされたものであり、１コート１ベーク塗装工程において、プラスチック基材に対して優れた耐擦り傷性、硬度、外観、付着性及び紫外線吸収剤等を含有する組成物に対する耐性を有する塗膜を形成することができる塗料組成物及び塗装物品を提供することを目的とする。 The present invention has been made in consideration of these points, and contains excellent scratch resistance, hardness, appearance, adhesion, ultraviolet absorbers and the like for a plastic substrate in a 1-coat 1-bake coating process. It is an object of the present invention to provide a coating composition and a coated article capable of forming a coating film having resistance to the composition.
　本発明者は、上記の目的を達成すべく鋭意検討を重ねた結果、特定の水酸基含有アクリル樹脂及び水酸基含有ポリエステル樹脂を含有する主剤、及び特定のポリイソシアネート化合物を含有する硬化剤とを含み、得られる塗膜のガラス転移温度が２０～６０℃である塗料組成物を用いることにより、上記課題を解決することができることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventor includes a main agent containing a specific hydroxyl group-containing acrylic resin and a hydroxyl group-containing polyester resin, and a curing agent containing a specific polyisocyanate compound, It has been found that the above problems can be solved by using a coating composition having a glass transition temperature of 20 to 60 ° C. of the obtained coating film, and the present invention has been completed.
　すなわち、本発明は、以下の塗料組成物、ならびに、該塗料組成物を塗装して得られる物品を提供するものである。
　本発明は、以下の（１）～（５）に関する。
（１）水酸基含有アクリル樹脂（Ａ）及び水酸基含有ポリエステル樹脂（Ｂ）を含有する主剤と、ポリイソシアネート化合物（Ｃ）を含有する硬化剤とを含む塗料組成物であって、
　水酸基含有アクリル樹脂（Ａ）が、水酸基価１００～２００ｍｇＫＯＨ／ｇ、ガラス転移温度－２０℃未満であり、
　　重合性不飽和モノマー（ａ１）～（ａ３）の合計量を基準として、
　　メチルメタクリレート（ａ１）１５～３５質量％、
　　炭素数４～９のヒドロキシアルキル基を有する重合性不飽和モノマー（ａ２）５～３０質量％、及び
　　その他の重合性不飽和モノマー（ａ３）３５～８０質量％
　　を反応させて得られる水酸基含有アクリル樹脂であり、
　水酸基含有ポリエステル樹脂（Ｂ）が、水酸基価５０～２００ｍｇＫＯＨ／ｇ、数平均分子量２，０００～２０，０００であって、ヌレート構造を有する環状ポリオール化合物（ｂ１）を含む多価アルコールと多塩基酸との反応によって得られる水酸基含有ポリエステル樹脂であり、
　ポリイソシアネート化合物（Ｃ）がビウレット基含有ポリイソシアネート化合物及びアロファネート基含有ポリイソシアネート化合物からなる群から選択される少なくとも１つであり、
　得られる塗膜のガラス転移温度が２０～６０℃である
塗料組成物。
（２）主剤中の樹脂固形分質量を基準として、水酸基含有アクリル樹脂（Ａ）を１０～８０質量部、水酸基含有ポリエステル樹脂（Ｂ）を２０～９０質量部含有する前記（１）に記載の塗料組成物。
（３）得られる塗膜の架橋間分子量が３００～１０００である前記（１）又は（２）に記載の塗料組成物。
（４）プラスチック基材に、前記（１）～（３）のいずれか１つに記載の塗料組成物を塗装する方法。
（５）プラスチック基材に、前記（１）～（３）のいずれか１つに記載の塗料組成物を塗装して得られる塗装物品。 That is, the present invention provides the following coating composition and an article obtained by coating the coating composition.
The present invention relates to the following (1) to (5).
(1) A coating composition comprising a main ingredient containing a hydroxyl group-containing acrylic resin (A) and a hydroxyl group-containing polyester resin (B), and a curing agent containing a polyisocyanate compound (C),
The hydroxyl group-containing acrylic resin (A) has a hydroxyl value of 100 to 200 mgKOH / g and a glass transition temperature of less than −20 ° C.
Based on the total amount of polymerizable unsaturated monomers (a1) to (a3),
Methyl methacrylate (a1) 15 to 35% by mass,
5-30% by mass of polymerizable unsaturated monomer (a2) having a hydroxyalkyl group having 4 to 9 carbon atoms, and 35-80% by mass of other polymerizable unsaturated monomer (a3)
Is a hydroxyl group-containing acrylic resin obtained by reacting
Polyhydric alcohol and polybasic acid having a hydroxyl value of 50 to 200 mg KOH / g and a number average molecular weight of 2,000 to 20,000 and containing a cyclic polyol compound (b1) having a nurate structure A hydroxyl group-containing polyester resin obtained by reaction with
The polyisocyanate compound (C) is at least one selected from the group consisting of a biuret group-containing polyisocyanate compound and an allophanate group-containing polyisocyanate compound;
A coating composition having a glass transition temperature of 20 to 60 ° C. of the obtained coating film.
(2) The composition according to (1), wherein 10 to 80 parts by mass of the hydroxyl group-containing acrylic resin (A) and 20 to 90 parts by mass of the hydroxyl group-containing polyester resin (B) are contained on the basis of the resin solid mass in the main agent. Paint composition.
(3) The coating composition according to (1) or (2), wherein the obtained coating film has a molecular weight between crosslinks of 300 to 1,000.
(4) A method of applying the coating composition according to any one of (1) to (3) on a plastic substrate.
(5) A coated article obtained by coating the plastic substrate with the coating composition according to any one of (1) to (3).
　本発明の塗料組成物によれば、１コート１ベーク塗装工程において、プラスチック基材に対して優れた耐擦り傷性、硬度、外観、付着性及び紫外線吸収剤等を含有する組成物に対する耐性を有する塗膜を形成することが可能となる。 The coating composition of the present invention has excellent scratch resistance, hardness, appearance, adhesion, and resistance to a composition containing an ultraviolet absorber, etc., for a plastic substrate in a 1-coat 1-bake coating process. A coating film can be formed.
　以下、本発明の塗料組成物についてさらに詳細に説明する。
　なお、本明細書において、「質量」は「重量」のことを意味するものとする。 Hereinafter, the coating composition of the present invention will be described in more detail.
In the present specification, “mass” means “weight”.
　本発明の塗料組成物は、水酸基含有アクリル樹脂（Ａ）及び水酸基含有ポリエステル樹脂（Ｂ）を含有する主剤と、ポリイソシアネート化合物（Ｃ）を含有する硬化剤とを含む。 The coating composition of the present invention contains a main agent containing a hydroxyl group-containing acrylic resin (A) and a hydroxyl group-containing polyester resin (B) and a curing agent containing a polyisocyanate compound (C).
（主剤）
＜水酸基含有アクリル樹脂（Ａ）＞
　本発明において水酸基含有アクリル樹脂（Ａ）は、分子中に水酸基を含有するアクリル樹脂を指す。水酸基含有アクリル樹脂（Ａ）は、重合性不飽和モノマーである、メチルメタクリレート（ａ１）、炭素数４～９のヒドロキシアルキル基を有する重合性不飽和モノマー（ａ２）及びその他の重合性不飽和モノマー（ａ３）を常法により共重合せしめることによって合成することができる。 (Main agent)
<Hydroxyl-containing acrylic resin (A)>
In the present invention, the hydroxyl group-containing acrylic resin (A) refers to an acrylic resin containing a hydroxyl group in the molecule. The hydroxyl group-containing acrylic resin (A) is a polymerizable unsaturated monomer such as methyl methacrylate (a1), a polymerizable unsaturated monomer (a2) having a hydroxyalkyl group having 4 to 9 carbon atoms, and other polymerizable unsaturated monomers. It can be synthesized by copolymerizing (a3) by a conventional method.
　炭素数４～９のヒドロキシアルキル基を有する重合性不飽和モノマー（ａ２）としては、４－ヒドロキシブチル（メタ）アクリレート、５－ヒドロキシペンチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、７－ヒドロキシヘプチル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレート、７－メチル－８－ヒドロキシオクチル（メタ）アクリレート、２－メチル－８－ヒドロキシオクチル（メタ）アクリレート、９－ヒドロキシノニル（メタ）アクリレートなどが挙げられ、これらはそれぞれ単独で又は２種以上組み合わせて使用することができる。炭素数４～９のヒドロキシアルキル基を有する重合性不飽和モノマー（ａ２）としては、耐擦り傷性、外観、付着性及び紫外線吸収剤等を含有する組成物に対する耐性に優れるという観点から、なかでも４－ヒドロキシブチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレートが特に好ましい。 Examples of the polymerizable unsaturated monomer (a2) having a hydroxyalkyl group having 4 to 9 carbon atoms include 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 7 -Hydroxyheptyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 7-methyl-8-hydroxyoctyl (meth) acrylate, 2-methyl-8-hydroxyoctyl (meth) acrylate, 9-hydroxynonyl (meth) An acrylate etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively. As the polymerizable unsaturated monomer (a2) having a hydroxyalkyl group having 4 to 9 carbon atoms, from the viewpoint of excellent scratch resistance, appearance, adhesion and resistance to a composition containing an ultraviolet absorber, among others, 4-hydroxybutyl (meth) acrylate and 6-hydroxyhexyl (meth) acrylate are particularly preferred.
　その他の重合性不飽和モノマー（ａ３）としては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート等の多価アルコールと（メタ）アクリル酸とのモノエステル化物、該多価アルコールと（メタ）アクリル酸とのモノエステル化物にε－カプロラクトンを開環重合した化合物、等の炭素数４～９のヒドロキシアルキル基を有する重合性不飽和モノマー以外の水酸基含有重合性不飽和モノマー；
メチルアクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２－エチルヘキシルアクリレート、シクロヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ステアリル（メタ）アクリレート等の（メタ）アクリル酸のアルキルエステル；
（メタ）アクリル酸、マレイン酸、無水マレイン酸等のカルボキシル基含有重合性不飽和モノマー；
Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリレート等のアミノアルキル（メタ）アクリレート；
アクリルアミド、メタクリルアミド、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－メチロールアクリルアミドメチルエーテル、Ｎ－メチロールアクリルアミドブチルエーテル等の（メタ）アクリルアミド又はその誘導体；
２－（メタクリロイルオキシ）エチルトリメチルアンモニウムクロライド、２－（メタクリロイルオキシ）エチルトリメチルアンモニウムブロマイド等の第４級アンモニウム塩基含有モノマー；
２－アクリルアミド－２－メチルプロパンスルホン酸等の（メタ）アクリルアミド－アルカンスルホン酸、２－スルホエチル（メタ）アクリレート等のスルホアルキル（メタ）アクリレート；
アクリロニトリル、メタクリロニトリル、酢酸ビニル、スチレン、ビニルトルエン、α－メチルスチレン等の芳香環含有重合性不飽和モノマー；
アリルメタクリレート等の多ビニル化合物；
γ－（メタ）アクリロイルオキシプロピルトリメトキシシラン、γ－（メタ）アクリロイルオキシプロピルトリエトキシシラン、γ－（メタ）アクリロイルオキシプロピルメチルジメトキシシラン等の加水分解性シリル基含有重合性不飽和モノマー等が挙げられ、これらはそれぞれ単独で又は２種以上組み合わせて使用することができる。 Examples of other polymerizable unsaturated monomers (a3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, Monoesterified product of polyhydric alcohol such as polypropylene glycol (meth) acrylate and (meth) acrylic acid, compound obtained by ring-opening polymerization of ε-caprolactone to monoesterified product of polyhydric alcohol and (meth) acrylic acid, etc. A hydroxyl group-containing polymerizable unsaturated monomer other than the polymerizable unsaturated monomer having a hydroxyalkyl group having 4 to 9 carbon atoms;
Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate Hexyl (meth) acrylate, 2-ethylhexyl acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, stearyl (meth) acrylate, etc. An alkyl ester of (meth) acrylic acid;
Carboxyl group-containing polymerizable unsaturated monomers such as (meth) acrylic acid, maleic acid, maleic anhydride;
Aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate;
Acrylamide, methacrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-methylolacrylamide, N-methylolacrylamide methyl (Meth) acrylamide or derivatives thereof such as ether and N-methylolacrylamide butyl ether;
Quaternary ammonium base-containing monomers such as 2- (methacryloyloxy) ethyltrimethylammonium chloride and 2- (methacryloyloxy) ethyltrimethylammonium bromide;
(Meth) acrylamide-alkanesulfonic acids such as 2-acrylamido-2-methylpropanesulfonic acid, sulfoalkyl (meth) acrylates such as 2-sulfoethyl (meth) acrylate;
Aromatic ring-containing polymerizable unsaturated monomers such as acrylonitrile, methacrylonitrile, vinyl acetate, styrene, vinyltoluene, α-methylstyrene;
Polyvinyl compounds such as allyl methacrylate;
Hydrolyzable silyl group-containing polymerizable unsaturated monomers such as γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, etc. These may be used alone or in combination of two or more.
　なかでも、その他の重合性不飽和モノマー（ａ３）として、耐擦り傷性、硬度、外観、付着性及び紫外線吸収剤等を含有する組成物に対する耐性に優れる塗膜を得る観点から、炭素数４～９のヒドロキシアルキル基を有する重合性不飽和モノマー以外の水酸基含有重合性不飽和モノマー、（メタ）アクリル酸のアルキルエステルを含有することが好ましい。 Among these, as the other polymerizable unsaturated monomer (a3), from the viewpoint of obtaining a coating film excellent in resistance to a composition containing scratch resistance, hardness, appearance, adhesion, and an ultraviolet absorber, the carbon number of 4 to It is preferable to contain a hydroxyl group-containing polymerizable unsaturated monomer other than the polymerizable unsaturated monomer having 9 hydroxyalkyl groups, and an alkyl ester of (meth) acrylic acid.
　炭素数４～９のヒドロキシアルキル基を有する重合性不飽和モノマー以外の水酸基含有重合性不飽和モノマーとしては、特に２－ヒドロキシエチル（メタ）アクリレートが好ましい。 2-hydroxyethyl (meth) acrylate is particularly preferable as the hydroxyl group-containing polymerizable unsaturated monomer other than the polymerizable unsaturated monomer having a hydroxyalkyl group having 4 to 9 carbon atoms.
　（メタ）アクリル酸のアルキルエステルとしては、特に、アルキル部分の炭素数が４～８である重合性不飽和モノマーが好ましく、なかでも、得られる塗膜の耐擦り傷性、硬度、外観、付着性及び紫外線吸収剤等を含有する組成物に対する耐性等の観点から、ｎ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレートが特に好ましい。 As the alkyl ester of (meth) acrylic acid, a polymerizable unsaturated monomer having 4 to 8 carbon atoms in the alkyl portion is particularly preferable. In particular, the scratch resistance, hardness, appearance, and adhesion of the resulting coating film are preferred. And n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are particularly preferred from the viewpoint of resistance to a composition containing an ultraviolet absorber and the like.
　尚、本明細書において、「（メタ）アクリレート」は、アクリレート又はメタクリレートを意味し、「（メタ）アクリル酸」は、アクリル酸又はメタクリル酸を意味する。また、「（メタ）アクリロイル」は、アクリロイル又はメタクリロイルを意味し、「（メタ）アクリルアミド」は、アクリルアミド又はメタクリルアミドを意味する。 In the present specification, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acrylic acid” means acrylic acid or methacrylic acid. “(Meth) acryloyl” means acryloyl or methacryloyl, and “(meth) acrylamide” means acrylamide or methacrylamide.
　前記モノマー成分における、メチルメタクリレート（ａ１）、炭素数４～９のヒドロキシアルキル基を有する重合性不飽和モノマー（ａ２）、及びその他の重合性不飽和モノマー（ａ３）の使用割合は、得られる塗膜の耐擦り傷性、硬度、外観、付着性及び紫外線吸収剤等を含有する組成物に対する耐性等の観点から、モノマー成分（重合性不飽和モノマー（ａ１）～（ａ３））の合計質量を基準として、下記の範囲内である。 The proportions of methyl methacrylate (a1), polymerizable unsaturated monomer (a2) having a hydroxyalkyl group having 4 to 9 carbon atoms, and other polymerizable unsaturated monomer (a3) used in the monomer component are determined as follows. From the viewpoint of scratch resistance, hardness, appearance, adhesion, and resistance to a composition containing an ultraviolet absorber, etc., the total mass of monomer components (polymerizable unsaturated monomers (a1) to (a3)) is used as a basis. Is within the following range.
　メチルメタクリレート（ａ１）：１５～３５質量％、好ましくは２０～３０質量％、さらに好ましくは２２～２７質量％、
　炭素数４～９のヒドロキシアルキル基を有する重合性不飽和モノマー（ａ２）：５～３０質量％、好ましくは１０～２５質量％、さらに好ましくは１２～２０質量％、
　その他の重合性不飽和モノマー（ａ３）：３５～８０質量％、好ましくは４５～７０質量％、さらに好ましくは４３～６６質量％。 Methyl methacrylate (a1): 15 to 35% by mass, preferably 20 to 30% by mass, more preferably 22 to 27% by mass,
Polymerizable unsaturated monomer (a2) having a hydroxyalkyl group having 4 to 9 carbon atoms: 5 to 30% by mass, preferably 10 to 25% by mass, more preferably 12 to 20% by mass,
Other polymerizable unsaturated monomer (a3): 35 to 80% by mass, preferably 45 to 70% by mass, more preferably 43 to 66% by mass.
　前記の重合性不飽和モノマー（ａ１）～（ａ３）の共重合は、溶液重合法による共重合が好適であり、例えば、重合性不飽和モノマーとラジカル重合開始剤の混合物を、有機溶剤に溶解もしくは分散せしめ、通常、約８０℃～約２００℃の温度で、１～１０時間程度撹拌しながら加熱して重合させる方法を挙げることができる。 The copolymerization of the polymerizable unsaturated monomers (a1) to (a3) is preferably a solution polymerization method. For example, a mixture of a polymerizable unsaturated monomer and a radical polymerization initiator is dissolved in an organic solvent. Alternatively, a method may be mentioned in which the polymerization is carried out by dispersing and heating at about 80 ° C. to about 200 ° C. with stirring for about 1 to 10 hours.
　本発明において水酸基含有アクリル樹脂（Ａ）は、水酸基価１００～２００ｍｇＫＯＨ／ｇ、好ましくは１０５～１７０ｍｇＫＯＨ／ｇ、さらに好ましくは１１０～１５０ｍｇＫＯＨ／ｇ、かつ、ガラス転移温度－２０℃未満、好ましくは－２３℃未満、さらに好ましくは－２５℃未満の水酸基含有アクリル樹脂である。水酸基含有アクリル樹脂（Ａ）の水酸基価が１００ｍｇＫＯＨ／ｇ以上であると紫外線吸収剤等を含有する組成物に対する耐性が良好となり、２００ｍｇＫＯＨ／ｇ以下であると得られる塗膜の耐擦り傷性が良好となるため好ましい。また、ガラス転移温度が－２０℃を超えると塗膜の耐擦り傷性や硬度が劣る場合がある。 In the present invention, the hydroxyl group-containing acrylic resin (A) has a hydroxyl value of 100 to 200 mgKOH / g, preferably 105 to 170 mgKOH / g, more preferably 110 to 150 mgKOH / g, and a glass transition temperature of less than −20 ° C., preferably − A hydroxyl group-containing acrylic resin having a temperature of less than 23 ° C., more preferably less than −25 ° C. When the hydroxyl value of the hydroxyl group-containing acrylic resin (A) is 100 mgKOH / g or more, the resistance to a composition containing an ultraviolet absorber is good, and when it is 200 mgKOH / g or less, the resulting coating film has good scratch resistance. This is preferable. On the other hand, if the glass transition temperature exceeds −20 ° C., the scratch resistance and hardness of the coating film may be inferior.
　なお、本明細書において、水酸基含有アクリル樹脂（Ａ）のガラス転移温度Ｔｇは、下記式により算出される値である。
　　１／Ｔｇ（Ｋ）＝Ｗ１／Ｔ１＋Ｗ２／Ｔ２＋・・・Ｗｎ／Ｔｎ
　　Ｔｇ（℃）＝Ｔｇ（Ｋ）－２７３
　式中、Ｗ１、Ｗ２、・・・Ｗｎは各モノマーの質量分率であり、Ｔ１、Ｔ２・・・Ｔｎは各モノマーのホモポリマーのガラス転移温度Ｔｇ（Ｋ）である。
　なお、各モノマーのホモポリマーのガラス転移温度は、ＰＯＬＹＭＥＲＨＡＮＤＢＯＯＫＦｏｕｒｔｈＥｄｉｔｉｏｎ，Ｊ．Ｂｒａｎｄｒｕｐ，Ｅ．ｈ．Ｉｍｍｅｒｇｕｔ，Ｅ．Ａ．Ｇｒｕｌｋｅ編（１９９９年）による値であり、該文献に記載されていないモノマーのガラス転移温度は、該モノマーのホモポリマーを重量平均分子量が５０，０００程度になるようにして合成し、そのガラス転移温度を示差走査型熱分析により測定したときの値を使用する。 In addition, in this specification, the glass transition temperature Tg of a hydroxyl-containing acrylic resin (A) is a value calculated by a following formula.
1 / Tg (K) = W1 / T1 + W2 / T2 +... Wn / Tn
Tg (° C.) = Tg (K) -273
In the formula, W1, W2,... Wn are mass fractions of the respective monomers, and T1, T2... Tn are glass transition temperatures Tg (K) of the homopolymers of the respective monomers.
The glass transition temperature of the homopolymer of each monomer is described in POLYMERHANDBOOKFourth Edition, J. MoI. Brandrup, E .; h. Immergut, E .; A. The glass transition temperature of a monomer not described in this document, which is a value according to Grulk ed. (1999), was synthesized such that the monomer homopolymer had a weight average molecular weight of about 50,000, and its glass transition. The value when the temperature is measured by differential scanning thermal analysis is used.
　本発明において水酸基含有アクリル樹脂（Ａ）の重量平均分子量は、耐擦り傷性、硬度、外観、付着性及び紫外線吸収剤等を含有する組成物に対する耐性の点から、５，０００～３３，０００、好ましくは８，０００～３０，０００の範囲である。 In the present invention, the hydroxyl group-containing acrylic resin (A) has a weight average molecular weight of 5,000 to 33,000 in view of scratch resistance, hardness, appearance, adhesion, and resistance to a composition containing an ultraviolet absorber, The range is preferably 8,000 to 30,000.
　また本明細書において、重量平均分子量及び数平均分子量は、ゲルパーミエーションクロマトグラフ（ＧＰＣ）を用いて測定した保持時間（保持容量）を、同一条件で測定した分子量既知の標準ポリスチレンの保持時間（保持容量）によりポリスチレンの分子量に換算して求めた値である。カラムは、「ＴＳＫｇｅｌ　Ｇ－４０００Ｈ×Ｌ」、「ＴＳＫｇｅｌ　Ｇ－３０００Ｈ×Ｌ」、「ＴＳＫｇｅｌ　Ｇ－２５００Ｈ×Ｌ」、「ＴＳＫｇｅｌ　Ｇ－２０００Ｈ×Ｌ」（いずれも東ソー（株）社製、商品名）の４本を用い、移動相；テトラヒドロフラン、測定温度；４０℃、流速；１ｍｌ／分、検出器；ＲＩの条件で行ったものである。 Further, in this specification, the weight average molecular weight and the number average molecular weight are the retention time (retention capacity) measured using a gel permeation chromatograph (GPC), and the retention time of standard polystyrene with a known molecular weight measured under the same conditions ( It is a value obtained by converting to the molecular weight of polystyrene by (retention capacity). Columns are “TSKgel G-4000H × L”, “TSKgel G-3000H × L”, “TSKgel G-2500H × L”, “TSKgel G-2000H × L” (all manufactured by Tosoh Corporation, trade names) ), Mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 ml / min, detector: RI.
　本発明において水酸基含有アクリル樹脂（Ａ）の含有量は、主剤中の合計樹脂固形分質量を基準として１０～８０質量部であることが好ましく、より好ましくは５５～７５質量部である。前記範囲であると、得られる塗膜の耐擦り傷性、硬度、外観、付着性及び紫外線吸収剤等を含有する組成物に対する耐性等の観点から、好適である。 In the present invention, the content of the hydroxyl group-containing acrylic resin (A) is preferably 10 to 80 parts by mass, more preferably 55 to 75 parts by mass, based on the total resin solid content in the main agent. It is suitable from the viewpoint of scratch resistance, hardness, appearance, adhesion, resistance to a composition containing an ultraviolet absorber and the like of the resulting coating film within the above range.
＜水酸基含有ポリエステル樹脂（Ｂ）＞
　水酸基含有ポリエステル樹脂（Ｂ）は、一般に多価アルコール及び多塩基酸をそれ自体既知の方法で、水酸基過剰でエステル化反応せしめることによって得ることができる。多価アルコールは１分子中に２個以上の水酸基を有する化合物であり、多塩基酸は１分子中に２個以上のカルボキシル基を有する化合物である。 <Hydroxyl-containing polyester resin (B)>
The hydroxyl group-containing polyester resin (B) can be generally obtained by esterifying a polyhydric alcohol and a polybasic acid with an excess of hydroxyl groups by a method known per se. The polyhydric alcohol is a compound having two or more hydroxyl groups in one molecule, and the polybasic acid is a compound having two or more carboxyl groups in one molecule.
　本発明の塗料組成物において水酸基含有ポリエステル樹脂（Ｂ）は、多価アルコールとしてヌレート構造を有する環状ポリオール化合物（ｂ１）を含む。 In the coating composition of the present invention, the hydroxyl group-containing polyester resin (B) contains a cyclic polyol compound (b1) having a nurate structure as a polyhydric alcohol.
　ヌレート構造を有する環状ポリオール化合物（ｂ１）としては、例えば、トリス（ヒドロキシエチル）イソシアヌレート、トリス（ヒドロキシプロピル）イソシアヌレートおよびトリス（ヒドロキシブチル）イソシアヌレート等のトリス（ヒドロキシアルキル）イソシアヌレート、該トリス（ヒドロキシアルキル）イソシアヌレートのε－カプロラクトン変性体、トリス（ヒドロキシエチル）イソシアヌレート、ジオール化合物およびジカルボン酸を、トリス（ヒドロキシエチル）イソシアヌレートおよびジオール化合物の中の水酸基がジカルボン酸中のカルボキシル基に対し過剰な状態で反応させて得られるトリス（ヒドロキシエチル）イソシアヌレートのエステル化物並びにヌレート構造を有するポリイソシアネート化合物とジオール化合物とを、ジオール化合物中の水酸基がヌレート構造を有するポリイソシアネート化合物中のイソシアネート基に対し過剰な状態で反応させて得られる反応生成物等が挙げられる。これらは単独でもしくは２種以上組み合わせて使用することができる。 Examples of the cyclic polyol compound (b1) having a nurate structure include tris (hydroxyalkyl) isocyanurate such as tris (hydroxyethyl) isocyanurate, tris (hydroxypropyl) isocyanurate and tris (hydroxybutyl) isocyanurate, the tris Ε-caprolactone modified form of (hydroxyalkyl) isocyanurate, tris (hydroxyethyl) isocyanurate, diol compound and dicarboxylic acid, and the hydroxyl group in tris (hydroxyethyl) isocyanurate and diol compound is converted to a carboxyl group in dicarboxylic acid. Tris (hydroxyethyl) isocyanurate esterified product obtained by reacting in excess, and polyisocyanate compound having nurate structure and diol A compound, a hydroxyl group in the diol compound reaction product obtained by reacting with excess state to isocyanate groups in the polyisocyanate compounds and the like having a isocyanurate structure. These can be used alone or in combination of two or more.
　これらのなかでも、得られる塗膜の紫外線吸収剤等を含有する組成物に対する耐性の観点から、トリス（２－ヒドロキシエチル）イソシアヌレートおよびトリス（２－ヒドロキシエチル）イソシアヌレートのε－カプロラクトン変性体が好ましく、トリス（２－ヒドロキシエチル）イソシアヌレートがさらに好ましい。 Of these, tris (2-hydroxyethyl) isocyanurate and ε-caprolactone-modified products of tris (2-hydroxyethyl) isocyanurate from the viewpoint of resistance of the resulting coating film to a composition containing an ultraviolet absorber or the like. Is preferred, and tris (2-hydroxyethyl) isocyanurate is more preferred.
　成分（ｂ１）以外の多価アルコールとしては、例えば、エチレングリコール、プロピレングリコール、ジエチレングリコール、トリメチレングリコール、テトラエチレングリコール、トリエチレングリコール、ジプロピレングリコール、１，４－ブタンジオール、１，３－ブタンジオール、２，３－ブタンジオール、１，２－ブタンジオール、３－メチル－１，２－ブタンジオール、１，２－ペンタンジオール、１，５－ペンタンジオール、１，４－ペンタンジオール、２，４－ペンタンジオール、２，３－ジメチルトリメチレングリコール、テトラメチレングリコール、３－メチル－４，３－ペンタンジオール、３－メチル－４，５－ペンタンジオール、２，２，４－トリメチル－１，３－ペンタンジオール、１，６－ヘキサンジオール、１，５－ヘキサンジオール、１，４－ヘキサンジオール、２，５－ヘキサンジオール、ネオペンチルグリコール、ヒドロキシピヴァリン酸ネオペンチルグリコールエステルなどの２価アルコール；これらの２価アルコールにε－カプロラクトンなどのラクトン類を付加したポリラクトンジオール；ビス（ヒドロキシエチル）テレフタレートなどのエステルジオール類；ビスフェノールＡのアルキレンオキサイド付加物、ポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコールなどのポリエーテルジオール類；プロピレンオキサイド及びブチレンオキサイドなどのα－オレフィンエポキシド、カージュラＥ１０［シェル化学社製、商品名、合成高分岐飽和脂肪酸のグリシジルエステル］などのモノエポキシ化合物；グリセリン、トリメチロールプロパン、トリメチロールエタン、ジグリセリン、トリグリセリン、１，２，６－ヘキサントリオール、ペンタエリスリトール、ジペンタエリスリトール、ソルビトール、マンニットなどの３価以上のアルコール；これらの３価以上のアルコールにε－カプロラクトンなどのラクトン類を付加させたポリラクトンポリオール類；１，４－シクロヘキサンジメタノール、トリシクロデカンジメタノール、水添ビスフェノールＡ、水添ビスフェノールＦ、水添ビスフェノールＡ及び水添ビスフェノールＦなど脂環族多価アルコールなどが挙げられる。 Examples of the polyhydric alcohol other than the component (b1) include ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, and 1,3-butane. Diol, 2,3-butanediol, 1,2-butanediol, 3-methyl-1,2-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,4-pentanediol, 2, 4-pentanediol, 2,3-dimethyltrimethylene glycol, tetramethylene glycol, 3-methyl-4,3-pentanediol, 3-methyl-4,5-pentanediol, 2,2,4-trimethyl-1, 3-pentanediol, 1,6-hexanediol Dihydric alcohols such as 1,5-hexanediol, 1,4-hexanediol, 2,5-hexanediol, neopentyl glycol, and hydroxypivalic acid neopentyl glycol ester; ε-caprolactone and the like to these dihydric alcohols Polylactone diols with addition of lactones; Ester diols such as bis (hydroxyethyl) terephthalate; Alkylene oxide adducts of bisphenol A, polyether diols such as polyethylene glycol, polypropylene glycol, polybutylene glycol; Propylene oxide and butylene Mono-epoxy compounds such as α-olefin epoxides such as oxide, Cardura E10 [manufactured by Shell Chemical Co., Ltd., trade name, glycidyl ester of synthetic hyperbranched saturated fatty acid]; Trihydric or higher alcohols such as phosphorus, trimethylolpropane, trimethylolethane, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, sorbitol, mannitol; Polylactone polyols obtained by adding lactones such as ε-caprolactone to alcohol; 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol Examples thereof include alicyclic polyhydric alcohols such as F.
　上記水酸基含有ポリエステル樹脂（Ｂ）におけるヌレート構造を有する環状ポリオール化合物（ｂ１）の含有割合は、得られる塗膜の紫外線吸収剤等を含有する組成物に対する耐性の点から、アルコール成分の総量を基準として、１～７５ｍｏｌ％の範囲内であることが好ましく、１０～６０ｍｏｌ％の範囲内であることがより好ましい。ヌレート構造を有する環状ポリオール化合物（ｂ１）の含有割合が前記範囲であると紫外線吸収剤等を含有する組成物に対する耐性が良好となる。 The content ratio of the cyclic polyol compound (b1) having a nurate structure in the hydroxyl group-containing polyester resin (B) is based on the total amount of alcohol components from the viewpoint of resistance to a composition containing an ultraviolet absorber or the like of the obtained coating film. As a result, it is preferably in the range of 1 to 75 mol%, more preferably in the range of 10 to 60 mol%. When the content ratio of the cyclic polyol compound (b1) having a nurate structure is within the above range, resistance to a composition containing an ultraviolet absorber or the like is improved.
　多塩基酸は、例えば、テレフタル酸、イソフタル酸、フタル酸、ナフタレンジカルボン酸、４，４’－ビフェニルジカルボン酸、ジフェニルメタン－４，４’－ジカルボン酸などの芳香族多塩基酸及びその無水物；ヘキサヒドロイソフタル酸、ヘキサヒドロテレフタル酸、ヘキサヒドロフタル酸、テトラヒドロフタル酸などの脂環族ジカルボン酸及びその無水物；アジピン酸、セバシン酸、スベリン酸、コハク酸、グルタル酸、マレイン酸、クロロマレイン酸、フマル酸、ドデカン二酸、ピメリン酸、アゼライン酸、イタコン酸、シトラコン酸、ダイマー酸などの脂肪族多塩基酸及びその無水物；これらのジカルボン酸のメチルエステル、エチルエステルなどの低級アルキルエステル；トリメリット酸、無水トリメリット酸、ピロメリット酸、無水ピロメット酸、トリメシン酸、メチルシクロヘキセントリカルボン酸、テトラクロロヘキセン多塩基酸及びその無水物などの３価以上の多塩基酸などが挙げられる。 Examples of the polybasic acid include aromatic polybasic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, diphenylmethane-4,4′-dicarboxylic acid, and anhydrides thereof; Hexahydroisophthalic acid, hexahydroterephthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid and other alicyclic dicarboxylic acids and their anhydrides; adipic acid, sebacic acid, suberic acid, succinic acid, glutaric acid, maleic acid, chloroformate Aliphatic polybasic acids such as acids, fumaric acid, dodecanedioic acid, pimelic acid, azelaic acid, itaconic acid, citraconic acid and dimer acid and their anhydrides; lower alkyl esters such as methyl esters and ethyl esters of these dicarboxylic acids ; Trimellitic acid, trimellitic anhydride, pyromellitic , Anhydrous pyromellitic acid, trimesic acid, methylcyclohexene tricarboxylic acid, such as tri- or more polybasic acids such as tetrachloro hexene polybasic acids and anhydrides thereof.
　水酸基の導入は、例えば、１分子中に３個以上の水酸基を有する多価アルコールを併用することによって行なうことができる。 The introduction of a hydroxyl group can be performed, for example, by using a polyhydric alcohol having 3 or more hydroxyl groups in one molecule.
　また上記多塩基酸と多価アルコールの反応時に、さらに必要に応じて一塩基酸、油成分（この脂肪酸も含む）などを用いてもよい。一塩基酸としては、例えば安息香酸やｔ－ブチル安息香酸などが挙げられ、油成分としては、例えばヒマシ油、脱水ヒマシ油、サフラワー油、大豆油、あまに油、トール油、ヤシ油及びこれらの脂肪酸などが挙げられ、これらは１種又は２種以上使用できる。さらにポリエステル樹脂は、必要に応じて、ブチルグリシジルエーテル、アルキルフェニルグリシジルエーテル、ネオデカン酸グリシジルエステルなどのエポキシ化合物で変性されていてもよい。 Further, at the time of the reaction of the polybasic acid and the polyhydric alcohol, a monobasic acid, an oil component (including this fatty acid) and the like may be used as necessary. Examples of the monobasic acid include benzoic acid and t-butylbenzoic acid. Examples of the oil component include castor oil, dehydrated castor oil, safflower oil, soybean oil, linseed oil, tall oil, coconut oil, and the like. These fatty acids etc. are mentioned, These can be used 1 type or 2 or more types. Furthermore, the polyester resin may be modified with an epoxy compound such as butyl glycidyl ether, alkylphenyl glycidyl ether, or neodecanoic acid glycidyl ester, if necessary.
　本発明では、水酸基含有ポリエステル樹脂（Ｂ）は、得られる塗膜の耐擦り傷性、硬度、外観、付着性及び紫外線吸収剤等を含有する組成物に対する耐性等の観点から、水酸基価５０～２００ｍｇＫＯＨ／ｇ、好ましくは５０～１５０ｇＫＯＨ／ｇ、数平均分子量２，０００～２０，０００、好ましくは２，０００～１５，０００である。 In the present invention, the hydroxyl group-containing polyester resin (B) has a hydroxyl value of 50 to 200 mgKOH from the viewpoint of scratch resistance, hardness, appearance, adhesion, resistance to a composition containing an ultraviolet absorber, etc. / G, preferably 50 to 150 g KOH / g, number average molecular weight 2,000 to 20,000, preferably 2,000 to 15,000.
　水酸基含有ポリエステル樹脂（Ｂ）の含有量は、得られる塗膜の耐擦り傷性、硬度、外観、付着性及び紫外線吸収剤等を含有する組成物に対する耐性等の観点から、主剤中の合計固形分を基準として、２０～９０質量部であることが好ましく、より好ましくは２５～４５質量部の範囲である。 The content of the hydroxyl group-containing polyester resin (B) is determined from the viewpoint of the scratch resistance, hardness, appearance, adhesion, resistance to the composition containing an ultraviolet absorber, etc. Is preferably 20 to 90 parts by mass, more preferably 25 to 45 parts by mass.
　本発明の主剤は、水酸基含有アクリル樹脂（Ａ）及び水酸基含有ポリエステル樹脂（Ｂ）を必須成分とするものであり、さらに必要に応じて水酸基含有ウレタン樹脂、フェノール樹脂、ポリカーボネート樹脂及びエポキシ樹脂等の樹脂成分を含有することができる。 The main agent of the present invention comprises a hydroxyl group-containing acrylic resin (A) and a hydroxyl group-containing polyester resin (B) as essential components, and further includes a hydroxyl group-containing urethane resin, a phenol resin, a polycarbonate resin, and an epoxy resin as necessary. A resin component can be contained.
（硬化剤）
　本発明で用いられる硬化剤は、ポリイソシアネート化合物（Ｃ）を含有するものである。 (Curing agent)
The curing agent used in the present invention contains a polyisocyanate compound (C).
＜ポリイソシアネート化合物（Ｃ）＞
　ポリイソシアネート化合物（Ｃ）は、アロファネート基含有ポリイソシアネート化合物及びビウレット基含有ポリイソシアネート化合物からなる群から選択される少なくとも１つを必須成分として含むものである。 <Polyisocyanate compound (C)>
The polyisocyanate compound (C) contains at least one selected from the group consisting of an allophanate group-containing polyisocyanate compound and a biuret group-containing polyisocyanate compound as an essential component.
　上記アロファネート基含有ポリイソシアネート化合物は、脂肪族ポリイソシアネート、脂環族ポリイソシアネート及び芳香族ポリイソシアネート等から選ばれるポリイソシアネートを既知の方法でアロファネート化反応させて得られる化合物である。 The allophanate group-containing polyisocyanate compound is a compound obtained by subjecting a polyisocyanate selected from an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate and the like to an allophanate reaction by a known method.
　前記ビウレット基含有ポリイソシアネート化合物は、脂肪族ポリイソシアネート、脂環族ポリイソシアネート及び芳香族ポリイソシアネート等から選ばれるポリイソシアネートを既知の方法でビウレット化反応させて得られる化合物である。 The biuret group-containing polyisocyanate compound is a compound obtained by subjecting a polyisocyanate selected from an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate and the like to a biuret reaction by a known method.
　前記脂肪族ポリイソシアネートとしては、ジイソシアネート（例えば、トリメチレンジイソシアネート、１，２－プロピレンジイソシアネート、テトラメチレンジイソシアネート、１，２－ブチレンジイソシアネート、２，３－ブチレンジイソシアネート、１，３－ブチレンジイソシアネート、ヘキサメチレンジイソシアネート、ペンタメチレンジイソシアネート、２，４，４－又は２，２，４－トリメチルヘキサメチレンジイソシアネートなどのＣ２－１６アルカンジイソシアネート、２，６－ジイソシアナトメチルカプロエートなど）、ポリイソシアネート（例えば、リジンエステルトリイソシアネート、１，４，８－トリイソシアナトオクタン、１，６，１１－トリイソシアナトウンデカン、１，８－ジイソシアナト－４－イソシアナトメチルオクタン、１，３，６－トリイソシアナトヘキサン、２，５，７－トリメチル－１，８－ジイソシアナト－５－イソシアナトメチルオクタンなどのＣ６－２０アルカントリイソシアネートなど）などが挙げられる。 Examples of the aliphatic polyisocyanate include diisocyanates (for example, trimethylene diisocyanate, 1,2-propylene diisocyanate, tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, hexamethylene. Diisocyanates, pentamethylene diisocyanates, C2-16 alkane diisocyanates such as 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate), polyisocyanates (eg lysine) Ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanate DOO methyl octane, 1,3,6-triisocyanato hexane, C6-20 alkanes triisocyanates such as 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyl octane) and the like.
　前記脂環族ポリイソシアネートとしては、ジイソシアネート（例えば、１，３－シクロペンタンジイソシアネート、１，４－シクロヘキサンジイソシアネート、１，３－シクロヘキサンジイソシアネート、３－イソシアナトメチル－３，５，５－トリメチルシクロヘキシルイソシアネート（慣用名：イソホロンジイソシアネート）、４，４’－メチレンビス（シクロヘキシルイソシアネート）、メチル－２，４－シクロヘキサンジイソシアネート、メチル－２，６－シクロヘキサンジイソシアネート、１，３－又は１，４－ビス（イソシアナトメチル）シクロヘキサン（慣用名：水添キシリレンジイソシアネート）もしくはその混合物、ノルボルナンジイソシアネートなど）、ポリイソシアネート（例えば、１，３，５－トリイソシアナトシクロヘキサン、１，３，５－トリメチルイソシアナトシクロヘキサン、２－（３－イソシアナトプロピル）－２，５－ジ（イソシアナトメチル）－ビシクロ［２．２．１］ヘプタン、２－（３－イソシアナトプロピル）－２，６－ジ（イソシアナトメチル）－ビシクロ（２．２．１）ヘプタン、３－（３－イソシアナトプロピル）－２，５－ジ（イソシアナトメチル）－ビシクロ［２．２．１］ヘプタン、５－（２－イソシアナトエチル）－２－イソシアナトメチル－３－（３－イソシアナトプロピル）－ビシクロ［２．２．１］ヘプタン、６－（２－イソシアナトエチル）－２－イソシアナトメチル－３－（３－イソシアナトプロピル）－ビシクロ［２．２．１］ヘプタン、５－（２－イソシアナトエチル）－２－イソシアナトメチル－２－（３－イソシアナトプロピル）－ビシクロ［２．２．１］－ヘプタン、６－（２－イソシアナトエチル）－２－イソシアナトメチル－２－（３－イソシアナトプロピル）－ビシクロ［２．２．１］ヘプタンなどのトリイソシアネートなど）が挙げられる。 Examples of the alicyclic polyisocyanate include diisocyanates (for example, 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate. (Common name: isophorone diisocyanate), 4,4′-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 1,3- or 1,4-bis (isocyanato) Methyl) cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof, norbornane diisocyanate, etc., polyisocyanate (for example, 1,3,5-triisocyanato) Chlorohexane, 1,3,5-trimethylisocyanatocyclohexane, 2- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo [2.2.1] heptane, 2- (3- Isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 3- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo [2 2.1] heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2.2.1] heptane, 6- (2-isocyanato Ethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2.2.1] heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl- -(3-isocyanatopropyl) -bicyclo [2.2.1] -heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo [2. 2.1] triisocyanate such as heptane).
　前記芳香族ポリイソシアネートとしては、ジイソシアネート（例えば、１，３－または１，４－キシリレンジイソシアネートもしくはその混合物、ω，ω’－ジイソシアナト－１，４－ジエチルベンゼン、１，３－または１，４－ビス（１－イソシアナト－１－メチルエチル）ベンゼン（慣用名：テトラメチルキシリレンジイソシアネート）もしくはその混合物、ｍ－フェニレンジイソシアネート、ｐ－フェニレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、１，５－ナフタレンジイソシアネート、２，４’－または４，４’－ジフェニルメタンジイソシアネートもしくはその混合物、２，４－または２，６－トリレンジイソシアネートもしくはその混合物、４，４’－トルイジンジイソシアネート、４，４’－ジフェニルエーテルジイソシアネートなど）、ポリイソシアネート（例えば、１，３，５－トリイソシアナトメチルベンゼンなどのトリイソシアネート、トリフェニルメタン－４，４’，４’’－トリイソシアネート、１，３，５－トリイソシアネートベンゼン、２，４，６－トリイソシアネートトルエンなどのトリイソシアネート、例えば、４，４’－ジフェニルメタン－２，２’，５，５’－テトライソシアネートなどのテトライソシアネートなど）が挙げられる。 Examples of the aromatic polyisocyanate include diisocyanates (for example, 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω, ω′-diisocyanato-1,4-diethylbenzene, 1,3- or 1,4- Bis (1-isocyanato-1-methylethyl) benzene (common name: tetramethylxylylene diisocyanate) or a mixture thereof, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate 2,4'- or 4,4'-diphenylmethane diisocyanate or mixtures thereof, 2,4- or 2,6-tolylene diisocyanate or mixtures thereof, 4,4'-toluidine diisocyanate, 4,4'-diph Phenyl ether diisocyanate), polyisocyanate (eg, triisocyanate such as 1,3,5-triisocyanatomethylbenzene, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanate) And triisocyanates such as isocyanate benzene and 2,4,6-triisocyanate toluene, for example, tetraisocyanates such as 4,4′-diphenylmethane-2,2 ′, 5,5′-tetraisocyanate, etc.).
　これらのうち、特に脂肪族ポリイソシアネートのビウレット基含有ポリイソシアネート化合物やアロファネート基含有ポリイソシアネート化合物が、得られる塗膜の耐擦り傷性、硬度、外観、付着性及び紫外線吸収剤等を含有する組成物に対する耐性等の点から好適に使用できる。 Among these, in particular, a biuret group-containing polyisocyanate compound or an allophanate group-containing polyisocyanate compound of an aliphatic polyisocyanate contains the scratch resistance, hardness, appearance, adhesion, ultraviolet absorber and the like of the resulting coating film. Can be preferably used from the standpoint of resistance to the like.
　前記脂肪族ポリイソシアネートのなかでも特にヘキサメチレンジイソシアネートが得られる塗膜の耐擦り傷性、硬度、外観、付着性及び紫外線吸収剤等を含有する組成物に対する耐性等の点から好適に使用できる。 Among the above-mentioned aliphatic polyisocyanates, the coating film from which hexamethylene diisocyanate can be used can be preferably used in terms of scratch resistance, hardness, appearance, adhesion, resistance to a composition containing an ultraviolet absorber, and the like.
　ポリイソシアネート化合物（Ｃ）は、前記アロファネート基含有ポリイソシアネート化合物及び／又はビウレット基含有ポリイソシアネート化合物以外のポリイソシアネート化合物を必要に応じて含むことができる。 The polyisocyanate compound (C) can contain a polyisocyanate compound other than the allophanate group-containing polyisocyanate compound and / or the biuret group-containing polyisocyanate compound as necessary.
　例えば、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ダイマー酸ジイソシアネート、リジンジイソシアネートなどの脂肪族ポリイソシアネート類；これらの脂肪族ポリイソシアネートのイソシアヌレート環付加物、ウレトジオンタイプ付加物；イソホロンジイソシアネート、４，４’－メチレンビス（シクロヘキシルイソシアネート）、メチルシクロヘキサン－２，４－もしくは－２，６－ジイソシアネートなどの脂環族ジイソシアネート類；これらの脂環族ジイソシアネートのイソシアヌレート環付加物；キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート、トリレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート（ＭＤＩ）、１，５－ナフタレンジイソシアネート、１，４－ナフタレンジイソシアネートなどの芳香族ジイソシアネート化合物；これらの芳香族ジイソシアネートのイソシアヌレート環付加物；水添ＭＤＩ及び水添ＭＤＩの誘導体；エチレングリコール、プロピレングリコール、１，４－ブチレングリコール、ジメチロールプロピオン酸、ポリアルキレングリコール、トリメチロールプロパン、ヘキサントリオールなどのポリオールの水酸基にイソシアネート基が過剰量となる比率でポリイソシアネート化合物を反応させてなるウレタン化付加物；これらのウレタン化付加物のイソシアヌレート環付加物等を挙げることができる。 For example, aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, lysine diisocyanate; isocyanurate cycloadducts, uretdione type adducts of these aliphatic polyisocyanates; isophorone diisocyanate, 4,4 ′ -Alicyclic diisocyanates such as methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4- or -2,6-diisocyanate; isocyanurate cycloadducts of these alicyclic diisocyanates; xylylene diisocyanate, tetramethylxylylene diisocyanate Isocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate , Aromatic diisocyanate compounds such as 1,4-naphthalene diisocyanate; isocyanurate cycloadducts of these aromatic diisocyanates; hydrogenated MDI and hydrogenated MDI derivatives; ethylene glycol, propylene glycol, 1,4-butylene glycol, Urethane adducts obtained by reacting a polyisocyanate compound with an excess ratio of isocyanate groups to hydroxyl groups of polyols such as dimethylolpropionic acid, polyalkylene glycol, trimethylolpropane and hexanetriol; Examples include isocyanurate cycloadducts.
　上記ポリイソシアネート化合物（Ｃ）の使用量は、この中に含まれるイソシアネート基（ＮＣＯ）が、上記主剤中の水酸基（ＯＨ）に対して、ＮＣＯ／ＯＨの当量比で、通常、０．５～２．０、好ましくは０．８～１．５となる範囲内となるように選択されることが適当である。 The amount of the polyisocyanate compound (C) used is generally such that the isocyanate group (NCO) contained in the polyisocyanate compound (C) is an equivalent ratio of NCO / OH with respect to the hydroxyl group (OH) in the main agent. It is appropriate to select it within a range of 2.0, preferably 0.8 to 1.5.
　本発明の塗料組成物では、さらに必要に応じて、有機溶剤、硬化触媒、顔料、顔料分散剤、レベリング剤、紫外線吸収剤、光安定剤、可塑剤等の、通常塗料の分野で用いられる塗料用添加剤を適宜組み合わせて主剤及び／又は硬化剤に配合することができる。 In the coating composition of the present invention, if necessary, a coating used in the field of ordinary coatings such as an organic solvent, a curing catalyst, a pigment, a pigment dispersant, a leveling agent, an ultraviolet absorber, a light stabilizer, and a plasticizer. Additives can be combined in the main agent and / or curing agent in an appropriate combination.
　前記有機溶剤としては特に限定されるものではなく、例えば炭化水素系、エステル系、エーテル系、アルコール系、ケトン系などの通常の塗料用溶剤が使用できる。 The organic solvent is not particularly limited, and for example, usual paint solvents such as hydrocarbon, ester, ether, alcohol, and ketone can be used.
　前記硬化触媒としては、例えば、オクチル酸錫、ジブチル錫ジ（２－エチルヘキサノエート）、ジオクチル錫ジ（２－エチルヘキサノエート）、ジオクチル錫ジアセテート、ジブチル錫ジラウレート、ジブチル錫オキサイド、ジオクチル錫オキサイド、ジブチル錫脂肪酸塩、２－エチルヘキサン酸鉛、オクチル酸亜鉛、ナフテン酸亜鉛、脂肪酸亜鉛類、ナフテン酸コバルト、オクチル酸カルシウム、ナフテン酸銅、テトラ（２－エチルヘキシル）チタネートなどの有機金属化合物が挙げられ、これらは１種又は２種以上混合して用いることができる。これらには、さらに必要に応じて第三級アミン、りん酸化合物など公知のウレタン硬化触媒を併用することもできる。本発明の塗料組成物が硬化触媒を含有する場合、硬化触媒の使用量は、通常、塗料組成物中の樹脂固形分１００質量部に対して０．００１～２質量部、好ましくは０．０１～１質量部の範囲内が適当である。 Examples of the curing catalyst include tin octylate, dibutyltin di (2-ethylhexanoate), dioctyltin di (2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, and dioctyl. Organic metals such as tin oxide, dibutyltin fatty acid salt, lead 2-ethylhexanoate, zinc octylate, zinc naphthenate, fatty acid zinc, cobalt naphthenate, calcium octylate, copper naphthenate, tetra (2-ethylhexyl) titanate A compound is mentioned, These can be used 1 type or in mixture of 2 or more types. These may be used in combination with known urethane curing catalysts such as tertiary amines and phosphoric acid compounds, if necessary. When the coating composition of the present invention contains a curing catalyst, the amount of the curing catalyst used is usually 0.001 to 2 parts by mass, preferably 0.01 to 100 parts by mass of the resin solid content in the coating composition. The range of ~ 1 part by mass is appropriate.
　前記顔料としては、例えば、酸化チタン、亜鉛華、カーボンブラック、カドミウムレッド、モリブデンレッド、クロムエロー、酸化クロム、プルシアンブルー、コバルトブルー、アゾ顔料、フタロシアニン顔料、キナクリドン顔料、イソインドリン顔料、スレン系顔料、ペリレン顔料等の着色顔料；タルク、クレー、カオリン、バリタ、硫酸バリウム、炭酸バリウム、炭酸カルシウム、アルミナホワイト等の体質顔料；アルミニウム粉末、雲母粉末、酸化チタンで被覆した雲母粉末等のメタリック顔料等を挙げることができる。これらは単独で又は２種以上組み合わせて使用することができる。 Examples of the pigment include titanium oxide, zinc white, carbon black, cadmium red, molybdenum red, chromium yellow, chromium oxide, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, selenium pigment, Color pigments such as perylene pigments; body pigments such as talc, clay, kaolin, barita, barium sulfate, barium carbonate, calcium carbonate, alumina white; metallic pigments such as aluminum powder, mica powder, mica powder coated with titanium oxide, etc. Can be mentioned. These can be used alone or in combination of two or more.
　本発明の塗料組成物がクリヤ塗料として使用される場合であって、顔料を含有する場合、顔料の配合量は、得られる塗膜の透明性を阻害しない程度の量であることが好ましく、例えば塗料組成物中の固形分１００質量部を基準として、通常０．１～２０質量部の範囲内であることが好ましく、０．３～１０質量部の範囲内であることがより好ましく、０．５～５質量部の範囲内であることがさらに好ましい。 When the coating composition of the present invention is used as a clear coating and contains a pigment, the amount of the pigment is preferably an amount that does not hinder the transparency of the resulting coating film. Usually, it is preferably in the range of 0.1 to 20 parts by weight, more preferably in the range of 0.3 to 10 parts by weight, based on 100 parts by weight of the solid content in the coating composition. More preferably, it is in the range of 5 to 5 parts by mass.
　また、本発明の塗料組成物が着色塗料として使用される場合であって、顔料を含有する場合、顔料の配合量は、塗料組成物中の固形分１００質量部を基準として、通常１～２００質量部の範囲内であることが好ましく、２～１００質量部の範囲内であることがより好ましく、５～５０質量部の範囲内であることがさらに好ましい。 In the case where the coating composition of the present invention is used as a colored coating and contains a pigment, the blending amount of the pigment is usually 1 to 200 based on 100 parts by mass of the solid content in the coating composition. It is preferably in the range of parts by mass, more preferably in the range of 2 to 100 parts by mass, and still more preferably in the range of 5 to 50 parts by mass.
　前記紫外線吸収剤としては、従来から公知のものが使用でき、例えば、ベンゾトリアゾール系吸収剤、トリアジン系吸収剤、サリチル酸誘導体系吸収剤、ベンゾフェノン系吸収剤等の紫外線吸収剤を挙げることができる。これらは単独で又は２種以上組み合わせて使用することができる。 As the ultraviolet absorber, conventionally known ones can be used, and examples thereof include ultraviolet absorbers such as benzotriazole absorbers, triazine absorbers, salicylic acid derivative absorbers, and benzophenone absorbers. These can be used alone or in combination of two or more.
　本発明の塗料組成物が、紫外線吸収剤を含有する場合、紫外線吸収剤の配合量は、塗料組成物中の固形分１００質量部を基準として、０．１～１０質量部の範囲内であることが好ましく、０．２～５質量部の範囲内であることがより好ましく、０．３～２質量部の範囲内であることがさらに好ましい。 When the coating composition of the present invention contains an ultraviolet absorber, the blending amount of the ultraviolet absorber is in the range of 0.1 to 10 parts by mass based on 100 parts by mass of the solid content in the coating composition. It is preferably within the range of 0.2 to 5 parts by mass, and more preferably within the range of 0.3 to 2 parts by mass.
　光安定剤としては、従来から公知のものが使用でき、例えば、ヒンダードアミン系光安定剤を挙げることができる。 As the light stabilizer, conventionally known light stabilizers can be used, and examples thereof include hindered amine light stabilizers.
　本発明の塗料組成物が、光安定剤を含有する場合、光安定剤の配合量は、艶消し塗料組成物中の固形分１００質量部を基準として、０．１～１０質量部の範囲内であることが好ましく、０．２～５質量部の範囲内であることがより好ましく、０．３～２質量部の範囲内であることがさらに好ましい。 When the coating composition of the present invention contains a light stabilizer, the blending amount of the light stabilizer is in the range of 0.1 to 10 parts by mass based on 100 parts by mass of the solid content in the matte coating composition. Preferably, it is within the range of 0.2 to 5 parts by mass, and more preferably within the range of 0.3 to 2 parts by mass.
　本発明では、上記塗料組成物をプラスチック基材面に塗装して、塗装物品を得ることができる。プラスチック基材としては、特に限定されるものではなく、例えばポリエチレン、ポリプロピレンなどに代表されるポリオレフィン系樹脂；ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート（ＰＢＴ）樹脂、ポリカーボネート（ＰＣ）樹脂、ポリカーボネート－ポリブチレンテレフタレート（ＰＣ／ＰＢＴ）樹脂などの熱可塑性ポリエステル樹脂；アクリロニトリル－スチレン樹脂、アクリロニトリル－ブタジエン－スチレン（ＡＢＳ）樹脂、アクリロニトリル－スチレン－アクリレート（ＡＳＡ）樹脂などのスチレン系樹脂；その他ポリメチルメタクリレート樹脂、アクリル樹脂、塩化ビニリデン、ポリアミド樹脂、ポリフェニレンエーテル樹脂、ポリオキシメチレン樹脂、ポリウレタン樹脂、エポキシ樹脂などまたはこれらのハイブリッド樹脂や繊維強化プラスチック（Fiber-Reinforced Plastics）などの素材面を挙げることができる。これらの素材面は必要に応じて適宜、脱脂処理や表面処理がなされてもよい。さらに、プラスチック基材面に下塗り塗膜を形成させた後、本発明の塗料組成物を塗装してもよい。 In the present invention, a coated article can be obtained by painting the coating composition on the surface of a plastic substrate. The plastic substrate is not particularly limited. For example, a polyolefin-based resin represented by polyethylene, polypropylene, etc .; polyethylene terephthalate resin, polybutylene terephthalate (PBT) resin, polycarbonate (PC) resin, polycarbonate-polybutylene terephthalate Thermoplastic polyester resins such as (PC / PBT) resin; Styrenic resins such as acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene-acrylate (ASA) resin; Other polymethyl methacrylate resin, acrylic Resin, vinylidene chloride, polyamide resin, polyphenylene ether resin, polyoxymethylene resin, polyurethane resin, epoxy resin, etc. It can be mentioned materials surface, such as a hybrid resin and fiber reinforced plastic (Fiber-Reinforced Plastics). These material surfaces may be subjected to a degreasing treatment or a surface treatment as needed. Furthermore, after forming an undercoat film on the plastic substrate surface, the coating composition of the present invention may be applied.
　本発明の塗料組成物を塗装する方法は、特に限定されない。例えば、エアスプレー、エアレススプレー、回転霧化塗装機、浸漬塗装、刷毛などにより塗装することができる。 The method for applying the coating composition of the present invention is not particularly limited. For example, it can be applied by air spray, airless spray, rotary atomizing coater, dip coating, brush or the like.
　本発明の塗料組成物による塗膜は、通常、硬化膜厚で通常３～１００μｍ、好ましくは３～５０μｍの範囲内とすることができる。 The coating film of the coating composition of the present invention can usually have a cured film thickness of usually 3 to 100 μm, preferably 3 to 50 μm.
　本発明の塗料組成物の塗膜形成方法における、加熱条件は特に限定されないが、５０～１００℃、好ましくは５０～９０℃で１０～９０分保持することにより行なうことができる。熱によりプラスチック材料に変形が伴う場合の加熱条件は、例えばＡＢＳ樹脂などを用いる場合には、５０℃～８０℃で１０～９０分保持することが好ましい。 In the method for forming a coating film of the coating composition of the present invention, the heating conditions are not particularly limited, but it can be carried out by holding at 50 to 100 ° C., preferably 50 to 90 ° C. for 10 to 90 minutes. When the plastic material is deformed by heat, the heating condition is preferably maintained at 50 to 80 ° C. for 10 to 90 minutes, for example, when an ABS resin is used.
　本発明の塗料組成物によって得られた塗膜は、耐擦り傷性、硬度、外観、付着性及び紫外線吸収剤等を含有する組成物に対する耐性等の点から、硬化塗膜のガラス転移温度が２０～６０℃であり、好ましくは３０～５５℃、さらに好ましくは３５～５０℃である。上記ガラス転移温度は、動的粘弾性測定装置を用いて、測定試料として、８０℃で３０分間加熱硬化を行なった膜厚２５μｍの塗膜を短冊状の遊離膜（０．５ｃｍ×２ｃｍ）に調製したものを使用し、昇温速度３℃／分で、温度範囲－２５～１００℃で、周波数１１Ｈｚの条件下でｔａｎδ値を測定した時に、ｔａｎδの値が極大値を示す時の温度である。動的粘弾性測定装置としては、ＦＴレオスペクトラＤＶＥ－Ｖ４（商品名、レオロジ社製）を用いることができる。 The coating film obtained by the coating composition of the present invention has a glass transition temperature of 20 in terms of scratch resistance, hardness, appearance, adhesion and resistance to a composition containing an ultraviolet absorber and the like. -60 ° C, preferably 30-55 ° C, more preferably 35-50 ° C. The glass transition temperature is obtained by using a dynamic viscoelasticity measuring apparatus as a measurement sample, and forming a 25 μm-thick coating film that has been heat-cured at 80 ° C. for 30 minutes into a strip-shaped free film (0.5 cm × 2 cm). When the tan δ value was measured under the conditions of a temperature rise rate of 3 ° C./minute, a temperature range of −25 to 100 ° C., and a frequency of 11 Hz using the prepared one, the temperature at which the tan δ value showed a maximum value is there. As a dynamic viscoelasticity measuring apparatus, FT Rheospectra DVE-V4 (trade name, manufactured by Rheology) can be used.
　本発明の塗料組成物によって得られた塗膜は、耐擦り傷性、硬度、外観、付着性及び紫外線吸収剤等を含有する組成物に対する耐性等の点から、硬化後の架橋間分子量が３００～１０００であることが好ましく、より好ましくは３５０～９００、さらに好ましくは４００～８００である。上記架橋間分子量は、上記の方法で測定した塗膜のガラス転移温度の値をＦｌｏｒｙなどの下記のゴム粘弾性理論式にあてはめて求めた理論計算値である。
　　架橋間分子量（Ｍｃ）＝３ρＲＴ／Ｅｍｉｎ
［式中、Ｅｍｉｎはゴム領域での貯蔵弾性率（ｄｙｎｅ／ｃｍ）、ρは試料塗膜の比重（ｇ／ｃｍ３）を示し、Ｒは気体定数であって、Ｒ＝８．３１×１０７（ｅｒｇ／ｄｅｇ・ｍｏｌ）であり、Ｔは貯蔵弾性率がＥｍｉｎのときの絶対温度を示す。］ The coating film obtained by the coating composition of the present invention has a molecular weight between crosslinks of 300 to 300 after curing from the viewpoints of scratch resistance, hardness, appearance, adhesion and resistance to a composition containing an ultraviolet absorber and the like. It is preferably 1000, more preferably 350 to 900, and still more preferably 400 to 800. The molecular weight between crosslinks is a theoretical calculated value obtained by applying the glass transition temperature value of the coating film measured by the above method to the following rubber viscoelastic theoretical formula such as Flory.
Molecular weight between crosslinks (Mc) = 3ρRT / E min
[Where E min is the storage elastic modulus (dyne / cm) in the rubber region, ρ is the specific gravity (g / cm 3 ) of the sample coating film, R is the gas constant, and R = 8.31 × 10 7 (erg / deg · mol), and T represents an absolute temperature when the storage elastic modulus is E min . ]
　以下、実施例及び比較例を挙げて本発明をさらに具体的に説明する。ただし、本発明はこれらの実施例のみに限定されるものではない。なお、「部」及び「％」はそれぞれ「質量部」及び「質量％」を示す。また、塗膜の膜厚は硬化塗膜に基づく。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to only these examples. “Part” and “%” represent “part by mass” and “% by mass”, respectively. Moreover, the film thickness of a coating film is based on a cured coating film.
〔水酸基含有アクリル樹脂（Ａ）の製造〕
　製造例１
　撹拌装置、温度計、還流冷却器、サーモスタットおよび滴下用ポンプを備えた反応容器に、酢酸ブチル６０部を仕込み、窒素ガスを吹き込みながら１２５℃±３℃で攪拌し、この中に、メチルメタクリレート２６部、４－ヒドロキシブチルアクリレート１４部、ｎ－ブチルアクリレ－ト２４部、２－エチルヘキシルアクリレート２４部、２－ヒドロキシエチルアクリレート１２部および２，２’－アゾビスイソブチロニトリル２．０部の混合物を３時間かけて一定速度で滴下し、さらに同温度で１時間熟成させた。その後さらに２，２’－アゾビスイソブチロニトリル０．５部および酢酸ブチル２１部の混合物を１時間かけて反応容器に滴下し、滴下終了後１時間熟成させ反応を終了した。
　得られた水酸基含有アクリル樹脂（Ａ－１）溶液は、固形分５５％の均一な透明溶液であった。またアクリル樹脂の重量平均分子量は約２１，０００、水酸基価は１１３ｍｇＫＯＨ／ｇ、ガラス転移点温度は－２９℃であった。 [Production of hydroxyl group-containing acrylic resin (A)]
Production Example 1
A reaction vessel equipped with a stirrer, thermometer, reflux condenser, thermostat and dropping pump was charged with 60 parts of butyl acetate and stirred at 125 ° C. ± 3 ° C. while blowing nitrogen gas. A mixture of 14 parts 4-hydroxybutyl acrylate, 24 parts n-butyl acrylate, 24 parts 2-ethylhexyl acrylate, 12 parts 2-hydroxyethyl acrylate and 2.0 parts 2,2′-azobisisobutyronitrile. Was dripped at a constant rate over 3 hours, and further aged at the same temperature for 1 hour. Thereafter, a mixture of 0.5 part of 2,2′-azobisisobutyronitrile and 21 parts of butyl acetate was added dropwise to the reaction vessel over 1 hour, and after completion of the addition, the mixture was aged for 1 hour to complete the reaction.
The obtained hydroxyl group-containing acrylic resin (A-1) solution was a uniform transparent solution having a solid content of 55%. The weight average molecular weight of the acrylic resin was about 21,000, the hydroxyl value was 113 mgKOH / g, and the glass transition temperature was −29 ° C.
　製造例２～１９
　上記製造例１において、モノマーの混合物を表１に示す配合組成とする以外は製造例１と同様の操作を行なって、固形分５５％の水酸基含有アクリル樹脂（Ａ－２）～（Ａ－１９）溶液を得た。得られた各水酸基含有アクリル樹脂の重量平均分子量、水酸基価、ガラス転移温度を表１に併せて示す。 Production Examples 2 to 19
In the above Production Example 1, the same operations as in Production Example 1 were conducted except that the monomer mixture had the composition shown in Table 1, and the hydroxyl group-containing acrylic resins (A-2) to (A-19) having a solid content of 55% were obtained. ) A solution was obtained. Table 1 shows the weight average molecular weight, hydroxyl value, and glass transition temperature of each hydroxyl group-containing acrylic resin obtained.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
〔水酸基含有ポリエステル樹脂（Ｂ）の製造〕
　製造例２０
　撹拌機、温度計、精留塔および水分離器を装備した反応容器に、ヘキサヒドロ無水フタル酸１３６部、１，６－ヘキサンジオール８３部、およびトリス（２－ヒドロキシエチル）イソシアヌレート７８部を仕込み、窒素雰囲気下で１６０℃まで昇温した。 [Production of hydroxyl group-containing polyester resin (B)]
Production Example 20
A reaction vessel equipped with a stirrer, thermometer, rectification column and water separator is charged with 136 parts of hexahydrophthalic anhydride, 83 parts of 1,6-hexanediol and 78 parts of tris (2-hydroxyethyl) isocyanurate. The temperature was raised to 160 ° C. in a nitrogen atmosphere.
　その後、３時間かけて２２０℃まで昇温し、キシレンを加えて水を留去しながら還流下反応させた。所望の酸価になったところで冷却後、次いで酢酸ブチルで希釈して固形分５０％のポリエステル樹脂（Ｂ－１）溶液を得た。このポリエステル樹脂（Ｂ－１）の数平均分子量は２，２００であり、水酸基価１０６ｍｇＫＯＨ／ｇであった。 Thereafter, the temperature was raised to 220 ° C. over 3 hours, and xylene was added to carry out the reaction under reflux while distilling off water. After cooling when the desired acid value was reached, it was diluted with butyl acetate to obtain a polyester resin (B-1) solution having a solid content of 50%. This polyester resin (B-1) had a number average molecular weight of 2,200 and a hydroxyl value of 106 mgKOH / g.
　製造例２１～２８
　上記製造例２０において、モノマー及び重合開始剤の混合物を表２に示す配合組成とする以外は製造例２０と同様の操作を行なって、固形分５０％の水酸基含有ポリエステル樹脂（Ｂ－２）～（Ｂ－９）溶液を得た。得られた各水酸基含有ポリエステル樹脂の数平均分子量、水酸基価を表２に併せて示す。 Production Examples 21 to 28
In the above Production Example 20, the same operation as in Production Example 20 was performed except that the mixture of the monomer and the polymerization initiator was changed to the composition shown in Table 2, and the hydroxyl group-containing polyester resin (B-2) having a solid content of 50% was obtained. (B-9) A solution was obtained. Table 2 shows the number average molecular weight and hydroxyl value of each hydroxyl group-containing polyester resin obtained.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
〔塗料組成物の製造〕
　実施例及び比較例
　表３に示す配合組成となるように成分（Ａ）、成分（Ｂ）及び黒顔料を混合・攪拌して固形分約４０％の各主剤を作成した。この主剤に表３に示す配合組成となるように成分（Ｃ）の硬化剤を加え、均一に混合した。次いで、得られた混合物に希釈溶剤を添加し、２０℃におけるフォードカップＮｏ．４による粘度が２５秒である塗料組成物を得た。 [Manufacture of coating composition]
Examples and Comparative Examples Component (A), component (B), and black pigment were mixed and stirred so as to have the composition shown in Table 3 to prepare each main agent having a solid content of about 40%. The curing agent of the component (C) was added to this main agent so as to have the composition shown in Table 3, and mixed uniformly. Next, a diluting solvent was added to the resulting mixture, and a Ford Cup No. A coating composition having a viscosity according to 4 of 25 seconds was obtained.
　尚、表３は固形分表示であり、表３中における（Ｃ－１）～（Ｃ－３）は下記の通りである。
（Ｃ－１）：デュラネート２４Ａ－９０Ｅ、商品名、旭化成ケミカルズ社製、ヘキサメチレンジイソシアネートを原料とするビウレット基含有ポリイソシアネート化合物、固形分９０％、イソシアネート基含有率２１．２％
（Ｃ－２）ＸＰ２５８０：商品名、バイエル社製、ヘキサメチレンジイソシアネートを原料とするアロファネート基含有ポリイソシアネート化合物、固形分１００％、イソシアネート基含有率１９．５％
（Ｃ－３）スミジュールＮ３３００：商品名、住友バイエルウレタン社製、ヘキサメチレンジイソシアネートのヌレート体、固形分１００％、イソシアネート基含有率２１．８％
　また、表３に記載の黒顔料は分散剤（「ソルスパーズ３７５００」、商品名、ルーブリゾール社製）１部とあらかじめ混合させてから配合した。 Table 3 shows the solid content, and (C-1) to (C-3) in Table 3 are as follows.
(C-1): Duranate 24A-90E, trade name, manufactured by Asahi Kasei Chemicals Corporation, biuret group-containing polyisocyanate compound using hexamethylene diisocyanate as a raw material, solid content 90%, isocyanate group content 21.2%
(C-2) XP2580: trade name, manufactured by Bayer, allophanate group-containing polyisocyanate compound starting from hexamethylene diisocyanate, solid content 100%, isocyanate group content 19.5%
(C-3) Sumidur N3300: trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd., hexamethylene diisocyanate nurate, solid content 100%, isocyanate group content 21.8%
Further, the black pigments shown in Table 3 were blended in advance with 1 part of a dispersant (“Solspers 37500”, trade name, manufactured by Lubrizol).
〔試験塗板の作製〕
　ＡＢＳ板（黒色、脱脂処理済み）に、上記のように製造した各塗料組成物を硬化膜厚で約２５μｍになるようにエアスプレー塗装を行ない、８０℃で３０分間加熱し硬化させて各試験塗板を得た。 [Preparation of test coated plate]
Each of the coating compositions prepared as described above is applied to an ABS plate (black, degreased) by air spray coating so that the cured film thickness is about 25 μm, and cured by heating at 80 ° C. for 30 minutes for each test. A coated plate was obtained.
　得られた各試験塗板を、下記の性能試験に供した。結果を表３に併せて示す。 Each obtained test coated plate was subjected to the following performance test. The results are also shown in Table 3.
〔塗膜性能試験〕
　耐擦り傷性：学振型摩擦堅牢試験機「ＲＴ－２００」（商品名、大栄化学精機製作所社製）に、上記のようにして得られた試験塗板をセットした。摩擦子にＮｏ．２０００のサンドペーパーを両面テープで貼り付け、摩擦子に２００ｇの重りを載せて、往復２回研磨することによって塗膜に傷を付けた。２５℃で２４時間静置した後に、塗膜のＬ１５°値を測定し、傷を付ける前の塗膜のＬ１５°値との差（ΔＬ１５°）から下記の基準で評価した。 [Coating performance test]
Scratch resistance: The test coated plate obtained as described above was set in a Gakushin type friction fastness tester “RT-200” (trade name, manufactured by Daiei Chemical Seiki Seisakusho Co., Ltd.). No. A 2000 sandpaper was affixed with double-sided tape, a 200 g weight was placed on the friction element, and the coating film was scratched by polishing twice back and forth. After standing at 25 ° C. for 24 hours, the L15 ° value of the coating film was measured and evaluated based on the following criteria from the difference (ΔL15 °) from the L15 ° value of the coating film before scratching.
　Ｌ１５°値の測定は、変角色差計「ＭＡ６８ＩＩ」（商品名、Ｘ－ｒｉｔｅ社製）を用いて、傷に対して垂直方向に光が入射する向きに対して受光角１５度方向のＬ値（これをＬ１５°値という）を読みとり、試験前後での差ΔＬ１５°を計算した。ΔＬ１５°が３０を超えるものは不合格である。 The L15 ° value is measured using a variable angle color difference meter “MA68II” (trade name, manufactured by X-rite), and the L in the direction of the light receiving angle of 15 degrees with respect to the direction in which light is incident in the direction perpendicular to the scratches. The value (this is referred to as L15 ° value) was read and the difference ΔL15 ° before and after the test was calculated. The case where ΔL15 ° exceeds 30 is rejected.
　鉛筆硬度：ＪＩＳ　Ｋ　５６００－５－４（１９９９）に準じて実施する。各試験塗板の塗膜面に対し約４５°の角度に鉛筆の芯を当て、芯が折れない程度に強く塗膜面に押し付けながら、鉛筆を前方に均一な速さで約１０ｍｍ動かした。当該操作を、場所を変えて５回繰り返し、塗膜に鉛筆芯の痕がつかない最も硬い鉛筆の硬度記号を鉛筆硬度とした。 Pencil hardness: Implemented according to JIS K 5600-5-4 (1999). The pencil lead was applied at an angle of about 45 ° with respect to the coating surface of each test coating plate, and the pencil was moved forward at a uniform speed by about 10 mm while pressing firmly against the coating surface so as not to break the core. This operation was repeated 5 times at different locations, and the hardness symbol of the hardest pencil that did not leave a pencil lead mark on the coating film was defined as pencil hardness.
　付着性：各試験塗板の塗膜面に素地に達するようにカッターで切り込み線を入れ、大きさ２ｍｍ×２ｍｍのマス目を１００個作った。続いて、該塗膜面にセロハン粘着テープ及び布粘着テープを貼着し、２０℃においてそれを急激に剥離した後に塗膜が残存しているマス目の数を調べ、下記の基準で評価した。 Adhesiveness: Cut lines were made with a cutter so as to reach the substrate on the coating film surface of each test coating plate, and 100 squares having a size of 2 mm × 2 mm were made. Subsequently, a cellophane pressure-sensitive adhesive tape and a cloth pressure-sensitive adhesive tape were adhered to the coating surface, and the number of cells remaining after the film was rapidly peeled off at 20 ° C. was evaluated according to the following criteria. .
　◎：セロハン粘着テープを剥離したときに塗膜が残存しているマス目の数が１００個であり、かつ、布粘着テープを剥離したときに塗膜が残存しているマス目の数が１００個である
　○：セロハン粘着テープを剥離したときに塗膜が残存しているマス目の数が１００個であり、かつ、布粘着テープを剥離したときに塗膜が残存しているマス目の数が９９個以下である
　×：セロハン粘着テープを剥離したときに塗膜が残存しているマス目の数が９９個以下であり、かつ、布粘着テープを剥離したときに塗膜が残存しているマス目の数が９９個以下である A: The number of cells remaining when the cellophane adhesive tape was peeled off was 100, and the number of cells remaining when the cloth adhesive tape was peeled off was 100. ○: The number of squares in which the coating film remains when the cellophane adhesive tape is peeled off, and the square in which the coating film remains when the cloth adhesive tape is peeled off The number is 99 or less. X: The number of cells remaining when the cellophane adhesive tape is peeled is 99 or less, and the film remains when the cloth adhesive tape is peeled off. The number of squares is 99 or less
　紫外線吸収剤等を含有する組成物に対する耐性：各試験塗板の塗膜面に単位塗装面積に対して０．５ｇ／１００ｃｍ２の化粧品（ジバンシイ　ＤＷ　ＵＶシールド、商品名、パルファム　ジバンシイ社製、ＳＰＦ５０　ＰＡ＋＋＋）を塗布し、５５℃で４時間放置した後に、室温に冷却し、表面の化粧品をふき取り、塗膜外観、鉛筆硬度及び付着性を評価した。
　鉛筆硬度の測定は上記方法と同様の方法で行ない、鉛筆硬度記号が上記「鉛筆硬度：」の項で得られた硬度記号から２ランクダウン以内だったものを合格とする。
　付着性の評価は上記方法と同様に行なった。塗膜外観については下記の基準で評価した。 Resistance to a composition containing an ultraviolet absorber, etc .: 0.5 g / 100 cm 2 of cosmetics per unit coating area on the coating surface of each test coating plate (Givenchy DW UV Shield, trade name, manufactured by Parfum Givenchy), SPF50 PA ++ ), Left at 55 ° C. for 4 hours, cooled to room temperature, wiped off the cosmetics on the surface, and evaluated the appearance of the coating film, pencil hardness and adhesion.
The pencil hardness is measured by the same method as described above, and the pencil hardness symbol that is within two ranks down from the hardness symbol obtained in the above-mentioned “pencil hardness:” section is regarded as acceptable.
The evaluation of adhesion was performed in the same manner as the above method. The appearance of the coating film was evaluated according to the following criteria.
　○：異常なし
　×：ちぢみ、変色、跡付き、剥離が発生 ○: No abnormality ×: Smudge, discoloration, marks, peeling occurred
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は、２０１３年９月９日出願の日本特許出願（特願２０１３－１８６０２５）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on September 9, 2013 (Japanese Patent Application No. 2013-186025), the contents of which are incorporated herein by reference.

Claims (5)

  1. 　水酸基含有アクリル樹脂（Ａ）及び水酸基含有ポリエステル樹脂（Ｂ）を含有する主剤と、ポリイソシアネート化合物（Ｃ）を含有する硬化剤とを含む塗料組成物であって、
    　水酸基含有アクリル樹脂（Ａ）が、水酸基価１００～２００ｍｇＫＯＨ／ｇ、ガラス転移温度－２０℃未満であり、
    　　重合性不飽和モノマー（ａ１）～（ａ３）の合計量を基準として、
    　　メチルメタクリレート（ａ１）１５～３５質量％、
    　　炭素数４～９のヒドロキシアルキル基を有する重合性不飽和モノマー（ａ２）５～３０質量％、及び
    　　その他の重合性不飽和モノマー（ａ３）３５～８０質量％
    　　を反応させて得られる水酸基含有アクリル樹脂であり、
    　水酸基含有ポリエステル樹脂（Ｂ）が、水酸基価５０～２００ｍｇＫＯＨ／ｇ、数平均分子量２，０００～２０，０００であって、ヌレート構造を有する環状ポリオール化合物（ｂ１）を含む多価アルコールと多塩基酸との反応によって得られる水酸基含有ポリエステル樹脂であり、
    　ポリイソシアネート化合物（Ｃ）がビウレット基含有ポリイソシアネート化合物及びアロファネート基含有ポリイソシアネート化合物からなる群から選択される少なくとも１つであり、
    　得られる塗膜のガラス転移温度が２０～６０℃である
    塗料組成物。     A coating composition comprising a main agent containing a hydroxyl group-containing acrylic resin (A) and a hydroxyl group-containing polyester resin (B), and a curing agent containing a polyisocyanate compound (C),
    The hydroxyl group-containing acrylic resin (A) has a hydroxyl value of 100 to 200 mgKOH / g and a glass transition temperature of less than −20 ° C.
    Based on the total amount of polymerizable unsaturated monomers (a1) to (a3),
    Methyl methacrylate (a1) 15 to 35% by mass,
    5-30% by mass of polymerizable unsaturated monomer (a2) having a hydroxyalkyl group having 4 to 9 carbon atoms, and 35-80% by mass of other polymerizable unsaturated monomer (a3)
    Is a hydroxyl group-containing acrylic resin obtained by reacting
    Polyhydric alcohol and polybasic acid having a hydroxyl value of 50 to 200 mg KOH / g and a number average molecular weight of 2,000 to 20,000 and containing a cyclic polyol compound (b1) having a nurate structure A hydroxyl group-containing polyester resin obtained by reaction with
    The polyisocyanate compound (C) is at least one selected from the group consisting of a biuret group-containing polyisocyanate compound and an allophanate group-containing polyisocyanate compound;
    A coating composition having a glass transition temperature of 20 to 60 ° C. of the obtained coating film.
  2. 　主剤中の樹脂固形分質量を基準として、水酸基含有アクリル樹脂（Ａ）を１０～８０質量部、水酸基含有ポリエステル樹脂（Ｂ）を２０～９０質量部含有する請求項１に記載の塗料組成物。 The coating composition according to claim 1, comprising 10 to 80 parts by mass of the hydroxyl group-containing acrylic resin (A) and 20 to 90 parts by mass of the hydroxyl group-containing polyester resin (B) based on the resin solid content in the main agent.
  3. 　得られる塗膜の架橋間分子量が３００～１０００である請求項１又は請求項２に記載の塗料組成物。 The coating composition according to claim 1 or 2, wherein the obtained coating film has a molecular weight between crosslinks of 300 to 1,000.
  4. 　プラスチック基材に、請求項１～請求項３のいずれか１項に記載の塗料組成物を塗装する方法。 4. A method of applying a coating composition according to any one of claims 1 to 3 to a plastic substrate.
  5. 　プラスチック基材に、請求項１～請求項３のいずれか１項に記載の塗料組成物を塗装して得られる塗装物品。 A coated article obtained by coating the plastic substrate with the coating composition according to any one of claims 1 to 3.
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