WO2015033624A1 - Composition de revêtement et article revêtu - Google Patents

Composition de revêtement et article revêtu Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
hydroxyl group
coating composition
mass
coating
resin
Prior art date
Application number
PCT/JP2014/063893
Other languages
English (en)
Japanese (ja)
Inventor
正人 中水
Original Assignee
関西ペイント株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 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/zh
Priority to JP2014550954A priority patent/JP5692481B1/ja
Publication of WO2015033624A1 publication Critical patent/WO2015033624A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention vise à procurer : une composition de revêtement qui peut former, sur des bases plastiques, un film de revêtement excellent en termes de résistance aux rayures, dureté, aspect, adhérence et résistance chimique ; et un article revêtu. Cette composition de revêtement comprend : un ingrédient principal comportant une résine acrylique hydroxylée (A) spécifique et une résine de polyester hydroxylée (B) spécifique ; et un durcisseur comprenant un composé polyisocyanate (C) spécifique. La composition de revêtement procure un film de revêtement présentant une température de transition vitreuse de 20 à 60 °C.
PCT/JP2014/063893 2013-09-09 2014-05-26 Composition de revêtement et article revêtu WO2015033624A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201480049628.9A CN105658747B (zh) 2013-09-09 2014-05-26 涂料组合物及涂装物品
JP2014550954A JP5692481B1 (ja) 2013-09-09 2014-05-26 塗料組成物及び塗装物品

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013186025 2013-09-09
JP2013-186025 2013-09-09

Publications (1)

Publication Number Publication Date
WO2015033624A1 true WO2015033624A1 (fr) 2015-03-12

Family

ID=52628114

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/063893 WO2015033624A1 (fr) 2013-09-09 2014-05-26 Composition de revêtement et article revêtu

Country Status (3)

Country Link
JP (1) JP5692481B1 (fr)
CN (1) CN105658747B (fr)
WO (1) WO2015033624A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018070847A (ja) * 2016-11-04 2018-05-10 サカタインクス株式会社 マットコート剤、マットコート層、および積層フィルム
JP2019172811A (ja) * 2018-03-28 2019-10-10 東洋紡株式会社 共重合ポリエステル樹脂およびこれを含む粘着剤組成物
JP2020007540A (ja) * 2018-06-27 2020-01-16 荒川化学工業株式会社 熱硬化性コーティング剤、硬化物及びフィルム
CN112500808A (zh) * 2020-12-02 2021-03-16 合肥乐凯科技产业有限公司 一种抗菌型漆面保护膜
CN115151589A (zh) * 2020-02-20 2022-10-04 株式会社大赛璐 多异氰酸酯化合物、以及使用该多异氰酸酯化合物的聚氨酯树脂形成用组合物及其固化物

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108727955B (zh) * 2017-04-20 2021-08-31 关西涂料株式会社 多成分型的水性底漆涂料组合物以及涂装方法
CN107177289B (zh) * 2017-06-13 2020-05-29 Ppg涂料(天津)有限公司 单组分涂料组合物及用其涂覆的基底
JP7074984B2 (ja) * 2017-11-29 2022-05-25 関西ペイント株式会社 水性２液型１コート塗料組成物
PT3818117T (pt) * 2018-07-02 2022-09-06 Akzo Nobel Coatings Int Bv Composição de revestimento com base em solvente com dois componentes, método de revestimento de um substrato, substrato revestido e uso dessa composição de revestimento para aumentar a resistência à erosão
JP2020037637A (ja) * 2018-09-03 2020-03-12 富士ゼロックス株式会社 表面保護樹脂部材、積層樹脂部材、及び液セット
WO2020196845A1 (fr) 2019-03-28 2020-10-01 大日精化工業株式会社 Composition de revêtement et film de revêtement
CN109971292A (zh) * 2019-04-11 2019-07-05 益帆涂料(无锡)有限公司 一种耐刮擦可镭雕汽车内饰涂料及其喷涂方法
JP7420513B2 (ja) * 2019-09-17 2024-01-23 株式会社ダイセル 組成物及びその硬化物

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0885908A1 (fr) * 1997-06-19 1998-12-23 Basf Corporation Composition de revêtement à base d'un résin acrylique contenant des groupes hydroxyles et son utilisation dans la préparation des revêtements
JP2002275415A (ja) * 2001-03-21 2002-09-25 Kansai Paint Co Ltd ２液型塗料組成物
JP2003514966A (ja) * 1999-11-23 2003-04-22 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 改善された初期硬度と耐水性を有する透明な塗料組成物
JP2006348172A (ja) * 2005-06-16 2006-12-28 Basf Coatings Japan Ltd 熱硬化性塗料組成物
JP2008163204A (ja) * 2006-12-28 2008-07-17 Kansai Paint Co Ltd ベース塗料組成物およびこれを含む塗料組成物

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998768A (en) * 1974-12-24 1976-12-21 E. I. Du Pont De Nemours And Company Thermosetting powder coating composition of a blend of acrylic polymers having different glass transition temperatures and a blocked polyisocyanate cross-linking agent
DE3322037A1 (de) * 1983-06-18 1984-12-20 Basf Farben + Fasern Ag, 2000 Hamburg Ueberzugsmasse, insbesondere zur herstellung einer transparenten deckschicht
EP0653468A3 (fr) * 1993-11-12 1995-12-13 Herberts & Co Gmbh Revêtement pour les couches de couverture transparentes et utilisation dans des procédés de préparation des revêtements multicouches.
US6294607B1 (en) * 1999-09-08 2001-09-25 Arco Chemical Technology, L.P. Ultra-high-solids acrylic coatings
US20030026908A1 (en) * 2001-04-30 2003-02-06 Matthew Lane Sandable, self-healable coating compositions and a process of using the same
CA2487916A1 (fr) * 2003-12-04 2005-06-04 Rohm And Haas Company Revetement transparent flexible a un composant, resistant a l'attaque chimique
JP4368395B2 (ja) * 2007-08-22 2009-11-18 Ｂａｓｆコーティングスジャパン株式会社 塗料組成物、塗装仕上げ方法及び塗装物品
JP5885192B2 (ja) * 2011-12-29 2016-03-15 関西ペイント株式会社 メタリック塗料組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0885908A1 (fr) * 1997-06-19 1998-12-23 Basf Corporation Composition de revêtement à base d'un résin acrylique contenant des groupes hydroxyles et son utilisation dans la préparation des revêtements
JP2003514966A (ja) * 1999-11-23 2003-04-22 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 改善された初期硬度と耐水性を有する透明な塗料組成物
JP2002275415A (ja) * 2001-03-21 2002-09-25 Kansai Paint Co Ltd ２液型塗料組成物
JP2006348172A (ja) * 2005-06-16 2006-12-28 Basf Coatings Japan Ltd 熱硬化性塗料組成物
JP2008163204A (ja) * 2006-12-28 2008-07-17 Kansai Paint Co Ltd ベース塗料組成物およびこれを含む塗料組成物

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018070847A (ja) * 2016-11-04 2018-05-10 サカタインクス株式会社 マットコート剤、マットコート層、および積層フィルム
JP2019172811A (ja) * 2018-03-28 2019-10-10 東洋紡株式会社 共重合ポリエステル樹脂およびこれを含む粘着剤組成物
JP2020007540A (ja) * 2018-06-27 2020-01-16 荒川化学工業株式会社 熱硬化性コーティング剤、硬化物及びフィルム
JP7052774B2 (ja) 2018-06-27 2022-04-12 荒川化学工業株式会社 熱硬化性コーティング剤、硬化物及びフィルム
CN115151589A (zh) * 2020-02-20 2022-10-04 株式会社大赛璐 多异氰酸酯化合物、以及使用该多异氰酸酯化合物的聚氨酯树脂形成用组合物及其固化物
CN112500808A (zh) * 2020-12-02 2021-03-16 合肥乐凯科技产业有限公司 一种抗菌型漆面保护膜
CN112500808B (zh) * 2020-12-02 2022-04-15 合肥乐凯科技产业有限公司 一种抗菌型漆面保护膜

Also Published As

Publication number Publication date
CN105658747B (zh) 2017-09-29
CN105658747A (zh) 2016-06-08
JPWO2015033624A1 (ja) 2017-03-02
JP5692481B1 (ja) 2015-04-01

Similar Documents

Publication Publication Date Title
JP5692481B1 (ja) 塗料組成物及び塗装物品
JP5692482B1 (ja) 塗料組成物及び塗装物品
JP6869753B2 (ja) 高固形分塗料組成物
JP6656427B2 (ja) 水性塗料組成物及び複層塗膜形成方法
CA2576863C (fr) Compositions de revetement aqueux a base de copolymeres d'acrylate
EP1817386B1 (fr) Compositions de revetement et procede de production de revetements multicouches
JP7106558B2 (ja) 複層塗膜形成方法
JP5547398B2 (ja) 塗料組成物
JPWO2017115804A1 (ja) 水性塗料組成物および塗膜形成方法
WO2013047209A1 (fr) Procédé de formation de film de revêtement et objet revêtu
JP7187483B2 (ja) 塗料組成物
JP6188216B2 (ja) 塗料組成物及び塗装物品
JP6732913B2 (ja) 塗料組成物
WO2013047208A1 (fr) Composition de revêtement et article enduit
JP2018061939A (ja) 複層塗膜形成方法
JP2015105298A (ja) 塗料組成物及び塗装物品
KR100486798B1 (ko) 내스크래치성코팅조성물
JP2010058068A (ja) 複層塗膜形成方法
WO2021084804A1 (fr) Composition de revêtement à base d'eau
JPWO2020166197A1 (ja) 粘性調整剤及び塗料組成物
WO2013169871A1 (fr) Composition de revêtement aqueuse
JP2003082281A (ja) 自動車用クリア塗料組成物
JP7464618B2 (ja) 水性塗料組成物
WO2010143032A1 (fr) Compositions de revêtement, procédé de couche finale, et articles revêtus
US7022778B2 (en) High solid coating compositions

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2014550954

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14841938

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14841938

Country of ref document: EP

Kind code of ref document: A1