WO2012160891A1 - Composition de revêtement et procédé de formation d'un film de revêtement - Google Patents

Composition de revêtement et procédé de formation d'un film de revêtement Download PDF

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Publication number
WO2012160891A1
WO2012160891A1 PCT/JP2012/059780 JP2012059780W WO2012160891A1 WO 2012160891 A1 WO2012160891 A1 WO 2012160891A1 JP 2012059780 W JP2012059780 W JP 2012059780W WO 2012160891 A1 WO2012160891 A1 WO 2012160891A1
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Prior art keywords
acrylate
meth
mass
coating film
coating composition
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English (en)
Japanese (ja)
Inventor
祐一 稲田
近藤　充
正春 石黒
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Kansai Paint Co Ltd
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Kansai Paint Co Ltd
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Priority to JP2013516247A priority Critical patent/JP5889291B2/ja
Publication of WO2012160891A1 publication Critical patent/WO2012160891A1/fr
Anticipated expiration legal-status Critical
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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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
    • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
    • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
    • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a coating composition and a coating film forming method.
  • an electrodeposition coating, an intermediate coating, and a base coating are formed on the body and parts of vehicles such as motorcycles, automobiles, and containers, and then a clear coating is formed.
  • the clear coating film is, for example, a thermosetting coating composition containing a thermosetting functional group-containing resin such as a hydroxyl group-containing acrylic resin and a crosslinking agent such as a melamine resin, a heat containing an acid group-containing resin and an epoxy group-containing resin. It is formed by a coating film forming method in which a curable coating composition or the like is applied and then heated and cured. According to this coating film forming method, a coating film excellent in coating film performance such as adhesion and coating film hardness can be formed.
  • thermosetting coating composition usually requires a heating temperature of about 140 ° C. and a heating time of about 20 to 40 minutes in a general coating process, and satisfies the demands for energy saving and productivity improvement. Not what you want.
  • Patent Document 1 discloses an acrylic resin, a colorant, and an organic solvent obtained by copolymerizing a monomer mixture containing 30% by weight or more of n-butyl (meth) acrylate and methyl (meth) acrylate as essential components.
  • a coating material containing the above is applied onto a thermoplastic resin substrate and dried on a colored layer, and a compound having three or more (meth) acryloyl groups and methyl (meth) acrylate as essential components
  • There is disclosed a method for forming a laminated coating film in which an energy ray-curable top coating containing an acrylic resin obtained by copolymerizing a monomer mixture containing 20% by weight or more is applied and cured by irradiation with energy rays.
  • the present invention it is possible to obtain a coating film excellent in abrasion resistance, interlayer adhesion between the colored layer and the top coating material, and adhesion between the thermoplastic resin substrate.
  • the two-coat method is not satisfied, and does not satisfy the demands for energy saving and productivity improvement, and does not satisfy the sufficient scratch resistance, weather resistance, and finished appearance.
  • the present invention has been made in view of the above circumstances, and the object of the present invention is to reduce the heating temperature and shorten the heating time in the coating process, as well as the adhesion to the material and the appearance of the coating film in one coat, Furthermore, it is providing the coating composition and coating-film formation method which can obtain the colored coating film which is excellent in abrasion resistance and a weather resistance.
  • the present inventors have found that a specific urethane acrylate compound, a hydroxyl group-containing acrylic resin having 65 to 90% by weight of methyl methacrylate as a copolymerization component, a polyisocyanate compound, and light It has been found that the problem can be solved by using a coating composition containing a polymerization initiator.
  • the present inventors have found that a coating film having excellent adhesion and finished appearance can be obtained with a single coating at a low temperature and in a short time, and the present invention has been completed. .
  • A having an unsaturated group equivalent of 100 to 900 and a weight average molecular weight of 500 to 2500, 65 to 90% by mass of methyl methacrylate
  • a hydroxyl group-containing polymerizable unsaturated monomer
  • B Hydroxyl-containing acrylic resin
  • C polyisocyanate compound
  • E photopolymerization initiator
  • Item 2 The coating composition according to Item 1, comprising 10 to 70 parts by mass of the urethane acrylate (A) in 100 parts by mass of the total resin solid content in the coating composition.
  • Item 3. The coating composition according to Item 1 or 2, further comprising a coloring component (D).
  • Item 4. The coating composition according to any one of Items 1 to 3, wherein the light transmittance at 375 nm of the coating film formed with a dry film thickness of 30 ⁇ m is 3.0% or more.
  • a coating composition according to any one of claims 1 to 4 is applied onto an object to be coated and subjected to setting and / or preheating, so that the solid content of the coating film obtained is 90% by mass or more. And then irradiating with active energy rays.
  • Item 6 The method for forming a coating film according to Item 4, wherein heating is performed after the active energy ray irradiation.
  • Item 7. The method for forming a coating film according to Item 5 or 6, wherein the object to be coated is acrylonitrile-butadiene-styrene resin, acrylonitrile-styrene-acrylate resin, polycarbonate resin, polybutylene terephthalate resin, or a hybrid of at least two of these resins.
  • Item 8 The method for forming a coating film according to any one of Items 5 to 7, wherein the maximum temperature reached to the surface of the object to be coated is less than 90 ° C. during irradiation with the active energy ray.
  • Item 9. An article coated with the coating composition according to any one of items 1 to 4.
  • Item 10 An article coated by the method for forming a coating film according to any one of items 5 to 8.
  • the present invention it is possible to obtain a coating composition capable of lowering the heating temperature and shortening the heating time in the coating process and capable of forming a coating film having excellent scratch resistance and weather resistance. Moreover, the coating film excellent also in the adhesiveness to a to-be-coated object, and a finishing external appearance can be obtained only by coating the said coating composition on the to-be-coated object. In addition, even when the object to be coated is a plastic material, a coating film excellent in scratch resistance and weather resistance, adhesion to the object to be coated, and finished appearance can be obtained without deforming the object to be coated.
  • A having an unsaturated group equivalent of 100 to 900 and a weight average molecular weight of 500 to 2500, and 65 to 90% by mass of methyl methacrylate (a) based on the total amount of copolymerization components and containing hydroxyl groups Hydroxyl group-containing acrylic resin (B), polyisocyanate compound (C) having 10 to 35% by weight of polymerizable unsatur
  • the urethane acrylate (A) having an unsaturated group equivalent of 100 to 900 and a weight average molecular weight of 500 to 2500 used in the coating composition of the present invention is a component that contributes to improving the curability by irradiation with active energy rays, and is usually in one molecule.
  • a polyurethane compound having two or more acryloyl groups is a component that contributes to improving the curability by irradiation with active energy rays, and is usually in one molecule.
  • a polyurethane compound having two or more acryloyl groups are examples of the urethane compound having two or more acryloyl groups.
  • the urethane acrylate (A) may be urethane acrylate having 100 to 900 and a weight average molecular weight of 500 to 2500, and may be one kind or a combination of two or more kinds.
  • Examples of the urethane acrylate (A) include: It is obtained by reacting a polyisocyanate compound (a1) with a hydroxyl group-containing acrylate (a2) having at least one hydroxyl group and one or more acryloyl groups in one molecule and, if necessary, a polyol compound (a3).
  • Urethane acrylate (Ai) that is, urethane acrylate obtained by reacting polyisocyanate compound (a1) with hydroxyl group-containing acrylate (a2) having at least one hydroxyl group and one or more acryloyl groups in one molecule ( Ai) or a polyisocyanate compound (a1), a urethane acrylate obtained by reacting a polyol compound (a3) with a hydroxyl group-containing acrylate (a2) having at least one hydroxyl group and one or more acryloyl groups in one molecule (Ai)),
  • urethane acrylate (Aii) or polyol compound (a3) obtained by the above isocyanate group-containing acrylate (a4) having one isocyanate group and one or more acryloyl groups in one molecule, and polyisocyanate compound (a1)
  • the urethane acrylate obtained by making it react so that an unsaturated group equivalent may be set to 100-900, such as urethane acrylate (Aii)) obtained by making it react.
  • Polyisocyanate compound (a1) is a compound having two or more isocyanate groups in one molecule.
  • aliphatic polyisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, lysine diisocyanate and uretdione type adducts, adduct type adducts, burette type adducts, isocyanurate cycloadditions of these polyisocyanates.
  • Isophorone diisocyanate 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,3-di (isocyanatomethyl) cyclohexane, 1,4- Di (isocyanatomethyl) cyclohexane, 1,4-cyclohexane diisocyanate, 1,3-cyclopentane diisocyanate, 1,2-cyclo Alicyclic polyisocyanate compounds such as hexane diisocyanate and uretdione type adducts, adduct type adducts, burette type adducts, isocyanurate cycloadducts of these polyisocyanates; xylylene diisocyanate, metaxylylene diisocyanate, tetramethylxylylene Diisocyanate, to
  • aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds and the like can be suitably used from the viewpoint of the weather resistance of the coating film.
  • the hydroxyl group-containing acrylate (a2) is a compound having at least one hydroxyl group and one or more acryloyl groups in one molecule, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl.
  • polyacrylates and ⁇ -caprolactone These polyacrylates and ⁇ -caprolactone These adducts, adducts of these hydroxyl group-containing polyacrylates and alkylene oxides, hydroxyl group-containing epoxy acrylates, and the like. These can be used alone or in combination of two or more.
  • a hydroxyl group-containing acrylate having one hydroxyl group and 3 to 5 acryloyl groups in one molecule is preferable.
  • acrylates examples include pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and the like, and these can be preferably used from the viewpoint of obtaining a cured film with high hardness.
  • the polyol compound (a3) is a compound having two or more hydroxyl groups in one molecule.
  • polylactone diols obtained by adding lactone compounds such as ⁇ -caprolactone to these dihydric alcohols
  • ester diol compounds such as bis (hydroxyethyl) terephthalate
  • alkylene oxide adducts of bisphenol A polyethylene glycol
  • Polyether diol compounds such as propylene glycol and polybutylene glycol
  • glycerin trimethylolethane, trimethylolpropane, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, tris (2-hydroxy Ethyl) Trivalent or higher alcohols such as isocyanuric acid, sorbitol and mannitol
  • Isocyanate group-containing acrylate (a4) is a compound having at least one isocyanate group and one or more acryloyl groups in one molecule, such as 2-acryloyloxyethyl isocyanate, m-isopropenyl- ⁇ . , ⁇ -dimethylbenzyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, and the like. These can be used alone or in combination of two or more.
  • urethane acrylate (A) is a part of its components
  • the coating film contains urethane acrylate (Ai-I) having an isocyanate group and an acryloyl group in one molecule obtained by reacting caprolactone-modified hydroxyalkyl acrylate (a5) with polyisocyanate compound (a1). From the viewpoint of improving weather resistance, particularly crack resistance.
  • polyisocyanate compound (a1) used in the above (Ai-I) hexamethylene which is an isocyanurate cycloaddition product of an aliphatic polyisocyanate compound is used from the viewpoint of curability at low temperature and the weather resistance of the coating film.
  • a polyisocyanate compound which is an isocyanurate cycloadduct of diisocyanate and a uretdione type adduct can be preferably used.
  • Caprolactone-modified hydroxyalkyl acrylate (a5) As the caprolactone-modified hydroxyalkyl acrylate (a5), a compound represented by the following general formula (I) can be preferably used.
  • R 1 is an alkylene group having 2 to 6 carbon atoms, and n is an integer of 1 to 5].
  • the caprolactone-modified hydroxyalkyl (meth) acrylate includes “Placcel FA-1”, “Placcel FA-2”, “Placcel FA-2D”, “Placcel FA-3”, “Placcel FA-4”, “Placcel FA-5” (all manufactured by Daicel Chemical Industries, trade name, Plaxel ⁇ PLACCEL is a registered trademark) and the like can be mentioned.
  • caprolactone-modified hydroxyethyl acrylate in which R 1 is an ethylene group in general formula (I) is preferred from the viewpoint of active energy ray curability.
  • caprolactone-modified hydroxyethyl acrylate in which n is in the range of 1 to 3 in the general formula (I) is preferable.
  • the urethane acrylate (A) can be synthesized by subjecting a hydroxyl group-containing component and an isocyanate group-containing component to a known urethanization reaction.
  • the above reaction can be usually performed in an organic solution.
  • the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and ester solvents such as ethyl acetate, propyl acetate, isobutyl acetate, and butyl acetate. These can be used as one or a mixture of two or more.
  • the reaction temperature is preferably from room temperature to 100 ° C., and the reaction time is preferably from 1 to 10 hours.
  • an organic tin catalyst such as dibutyltin dilaurate, dibutyltin diethylhexoate or dibutyltin sulfite may be used as necessary.
  • the amount of the catalyst is preferably 0.01 to 1.0 part by mass, more preferably 0.1 to 0.5 part by mass, with respect to 100 parts by mass of the total amount of reaction raw materials.
  • a polymerization inhibitor such as hydroquinone monomethyl ether may be used.
  • the addition amount of the polymerization inhibitor is preferably 0.01 to 1.0 part by mass with respect to 100 parts by mass of the total amount of reaction raw materials.
  • Urethane acrylate (A) has an unsaturated group equivalent of 100 to 900, preferably 120 to 900, and a weight average molecular weight of 500 to 2500, preferably 700 to 2500. When the unsaturated group equivalent and the weight average molecular weight are within these ranges, it is possible to obtain a coating film having more excellent scratch resistance and weather resistance.
  • the weight average molecular weight is in the above range from the viewpoint that the viscosity of the coating composition can be easily handled.
  • the polymerizable unsaturated group means an unsaturated group capable of radical polymerization, and may be simply referred to as an unsaturated group in the present specification.
  • the polymerizable unsaturated group include a vinyl group, a (meth) acryloyl group, a (meth) acrylamide group, a vinyl ether group, and an allyl group.
  • an unsaturated group equivalent is calculated
  • the isocyanate equivalent of the urethane acrylate (A) is preferably in the range of 500 to 2,500 from the viewpoint of scratch resistance of the coating film.
  • the isocyanate equivalent is an isocyanate equivalent determined by back titration using dibutylamine.
  • the reverse titration is carried out by adding excess dibutylamine to the sample for reaction, and titrating the remaining dibutylamine with an aqueous hydrochloric acid solution using bromophenol blue as a titration indicator.
  • the weight average molecular weight is the retention time (retention capacity) measured with a gel permeation chromatograph (“HLC (registered trademark) 8120GPC” manufactured by Tosoh Corporation) using tetrahydrofuran as a solvent. The value is calculated based on the weight average molecular weight of polystyrene.
  • the columns are “TSK-gel G4000H XL ”, “TSK-gel G3000H XL ”, “TSK-gel G2500H XL ”, “TSK-gel G2000 XL ” (both manufactured by Tosoh Corporation, trade name, TSK-gel).
  • TSK_GEL is a registered trademark), and used under conditions of mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 ml / min, detector: RI.
  • the hydroxyl group-containing acrylic resin (B) used in the coating composition of the present invention comprises, based on the total amount of copolymerization components, methyl methacrylate (a) 65 to 90% by mass, hydroxyl group-containing polymerizable unsaturated monomer (b) 10 to 35% by mass and 0 to 25% by mass of other polymerizable unsaturated monomer (c) can be produced by copolymerization by a method known per se, for example, a solution polymerization method in an organic solvent.
  • Hydroxyl-containing polymerizable unsaturated monomer (b) Specific examples of the hydroxyl group-containing polymerizable unsaturated monomer (b) used in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate.
  • Monoesterified product of (meth) acrylic acid such as 4-hydroxybutyl (meth) acrylate and a dihydric alcohol having 2 to 8 carbon atoms; and (meth) acrylic acid and a dihydric alcohol having 2 to 8 carbon atoms ⁇ -caprolactone modified monoester product; N-hydroxymethyl (meth) acrylamide; allyl alcohol, and (meth) acrylate having a polyoxyethylene chain having a hydroxyl group at the molecular end.
  • the monomer corresponding to the polymerizable unsaturated monomer having an ultraviolet-absorbing functional group should be defined as the other polymerizable unsaturated monomer (c), and the hydroxyl group-containing polymerizable property. Excluded from unsaturated monomer (b).
  • (meth) acrylate means acrylate and methacrylate
  • (meth) acrylic acid means acrylic acid and methacrylic acid
  • (meth) acryloyl means acryloyl and methacryloyl.
  • the other polymerizable unsaturated monomer (c) copolymerizable with the methyl methacrylate (a) and the hydroxyl group-containing polymerizable unsaturated monomer (b) is appropriately selected according to the properties desired for the hydroxyl group-containing acrylic resin (B). You can select and use.
  • Polymerizable unsaturated monomer having an isobornyl group; isobornyl (meth) acrylate and the like Polymerizable unsaturated monomer having an adamantyl group; adamantyl (meth) acrylate and the like Polymerizable unsaturated monomer having a photopolymerizable functional group such as a maleimide group Vinyl Aromatic compounds; styrene, ⁇ -methylstyrene, vinyltoluene and the like.
  • Polymerizable unsaturated monomer having alkoxysilyl group vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, ⁇ - (meth) acryloyloxypropyltrimethoxysilane, ⁇ - (meth) acryloyloxypropyl Triethoxysilane and the like.
  • Polymerizable unsaturated monomer having a fluorinated alkyl group such as perfluorobutylethyl (meth) acrylate and perfluorooctylethyl (meth) acrylate; fluoroolefin and the like.
  • Polymerizable unsaturated monomer having a phosphoric acid group 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxypropyl acid phosphate, 2-methacryloyloxypropyl acid phosphate and the like.
  • Carboxyl group-containing polymerizable unsaturated monomer (meth) acrylic acid, maleic acid, crotonic acid, ⁇ -carboxyethyl acrylate and the like.
  • Nitrogen-containing polymerizable unsaturated monomers vinyl compounds such as N-vinylpyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate and vinyl acetate; carboxyls such as (meth) acrylic acid, maleic acid, crotonic acid and ⁇ -carboxyethyl acrylate Group-containing polymerizable unsaturated monomer: (meth) acrylonitrile, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, glycidyl (meth) acrylate and amine compound Addenda etc. with.
  • vinyl compounds such as N-vinylpyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate and vinyl acetate
  • carboxyls such as (meth) acrylic acid, maleic acid, crotonic acid and ⁇ -
  • Polymerizable unsaturated monomer having at least two polymerizable unsaturated groups in one molecule allyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate and the like.
  • Epoxy group-containing polymerizable unsaturated monomer polymerizable unsaturated monomer having two or more polymerizable unsaturated groups in one molecule such as allyl (meth) acrylate and 1,6-hexanediol di (meth) acrylate; glycidyl ( (Meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, allyl Glycidyl ether and the like.
  • Polymerizable unsaturated monomer having a sulfonic acid group 2-acrylamido-2-methylpropane sulfonic acid, allyl sulfonic acid, sodium styrene sulfonate, sulfoethyl methacrylate and its sodium salt, ammonium salt and the like.
  • Polymerizable unsaturated monomer having a UV-absorbing functional group 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2-hydroxy-4- (3-acryloyloxy-2-hydroxypropoxy) benzophenone 2,2′-dihydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2,2′-dihydroxy-4- (3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2- (2 ′ -Hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole and the like.
  • UV-stable polymerizable unsaturated monomer 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethyl Piperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-teto Methylpiperidine, and the like.
  • Polymerizable unsaturated monomer having a carbonyl group acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formyl styrene, vinyl alkyl ketone having 4 to 7 carbon atoms (eg, vinyl methyl ketone, vinyl ethyl) Ketone, vinyl butyl ketone) and the like.
  • Polymerizable unsaturated monomer having an acid anhydride group examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.
  • the hydroxyl group-containing acrylic resin (B) is 65 to 90% by mass, more preferably 65 to 80% by mass of methyl methacrylate (a) based on the total amount of copolymerization components based on the adhesion to the object and the coating film hardness.
  • Hydroxyl group-containing polymerizable unsaturated monomer (b) 10 to 35% by mass, more preferably 20 to 35% by mass, other polymerizable unsaturated monomer (c) 0 to 25% by mass, more preferably 0 to 15% by mass. It is preferable that
  • a tough film By containing 65 to 90% by mass of methyl methacrylate based on the total amount of copolymerization components, adhesion to a plastic material is particularly good, and at the same time, 10 to 35 of the hydroxyl group-containing polymerizable unsaturated monomer (b). By containing the mass%, a tough film can be formed by reacting with the polyisocyanate compound (C).
  • the hydroxyl group-containing acrylic resin (B) preferably has an acid group such as a carboxyl group from the viewpoint of reactivity with other components having an isocyanate group.
  • the hydroxyl group-containing acrylic resin (B) preferably has an acid value in the range of 1 to 25 mgKOH / g, particularly 1 to 20 mgKOH / g.
  • the hydroxyl group-containing acrylic resin (B) generally has a weight within the range of 3,000 to 100,000, particularly 4,000 to 50,000, more particularly 5,000 to 30,000, from the viewpoint of the weather resistance of the coating film. It preferably has an average molecular weight.
  • the polyisocyanate compound (C) is a compound having two or more isocyanate groups in one molecule, and examples thereof include those exemplified in the section of the polyisocyanate compound (a1) of the urethane acrylate (A).
  • coloring component (D) As the coloring component, coloring components of various tones exemplified below such as coloring pigments and coloring dyes can be used singly or in combination of two or more in order to obtain a desired coating color tone. . However, it is not limited to the following examples.
  • color pigment examples include titanium oxide, zinc white, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, selenium pigment, perylene pigment, dioxazine pigment, diketopyrrolopyrrole. And pigments.
  • White pigment Titanium white, zinc white, lithopone, zinc sulfide, antimony white, etc .
  • Black pigment carbon black, acetylene black, lamp black, graphite, iron black, aniline black, etc .
  • Yellow pigments ocher, yellow iron oxide, naphthol yellow S, Hansa Yellow 10G, Hansa Yellow 5G, Hansa Yellow 3G, Hansa Yellow G, Hansa Yellow GR, Hansa Yellow A, Hansa Yellow RN, Hansa Yellow R, Pigment Yellow L, Benzidine Yellow, Benzidine Yellow G, Benzidine Yellow G GR, Permanent Yellow NCG, Vulcan Fast Yellow 5G, Vulcan Fast Yellow R, Tartrage Lake, Quinoline Yellow Lake, Anslagen Yellow 6GL, etc .; Orange pigments: chrome orange, chrome vermilion, Sudan I, permanent orange, Resol Fast Orange 3GL, permanent orange GTR, Hansa Yellow 3R, Vulcan Fast Orange GG, Benzidine Orange G, Persian Orange, Indant
  • examples of metallic pigments include aluminum flakes and alumina flakes.
  • extender pigments may be blended as necessary, and examples of extender pigments include calcium carbonate, barium sulfate, talc, and quartz.
  • These coloring components are preferably mixed and dispersed with a dispersant and a dispersion resin, and are preferably pasted into a paint.
  • a dispersant e.g., sodium bicarbonate
  • a dispersion resin e.g., sodium bicarbonate
  • dispersion methods can be used.
  • the coating composition of the present invention further contains a photopolymerization initiator (E).
  • Examples of the photopolymerization initiator (E) include ⁇ -diketone compounds such as benzyl and diacetyl; acyloin compounds such as benzoin; acyloin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; thioxanthone, 2, 4 Thioxanthone compounds such as diethylthioxanthone, 2-isopropylthioxanthone, thioxanthone-4-sulfonic acid; benzophenone compounds such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone; Michler's ketone Compound: acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, ⁇ , ⁇ '
  • photopolymerization initiators include, for example, IRGACURE-184, IRGACURE-261, IRGACURE-500, IRGACURE-651, IRGACURE-819, IRGACURE-907, IRGACURE-CGI-1700 (product of BASF Corp., product) Name, IRGACURE ⁇ Irgacure is a registered trademark), Darocur-1173, Darocur-1116, Darocur-2959, Darocur-1664, Darocur-4043, Darocur-TPO (Merck Japan, trade name, Darocur ⁇ Darocur is registered) Trademarks), Kayacure-MBP, Kayacure-DETX-S, Kayacure-DMBI, Kayacure-EPA, Kayacure-OA (manufactured by Nippon Kayaku Co., Ltd., trade name, Kayacure ⁇ Kayacure is a registered trademark), Bicure (VI CURE) -10, Vicure-55 (trade name, manufactured by S
  • the photopolymerization initiator (E) in particular, those having an absorbance at a wavelength of 375 nm of 1.0 or more measured in a cell having an optical path length of 10 mm in a 0.1% acetonitrile solution are those having a deep film curable point. Can be preferably used.
  • acyl phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (acyl) phosphine oxide. It is not limited to.
  • Examples of commercially available products include IRGACURE-819, DAROCUR TPO, and the like.
  • the absorbance can be measured by a known measuring method, and an ultraviolet / visible spectrophotometer can be used for the spectrum measurement.
  • an ultraviolet / visible spectrophotometer can be used for the spectrum measurement.
  • the measurement cell a cell made of quartz and having an optical path length of 10 mm can be used.
  • the coating composition of the present invention may further contain a polymerizable unsaturated group-containing compound (F) other than the urethane acrylate (A) as necessary. Accordingly, the coating composition of the present invention includes those containing a polymerizable unsaturated group-containing compound (F) other than the urethane acrylate (A) in addition to the above components.
  • Examples of the polymerizable unsaturated group-containing compound (F) include a monofunctional polymerizable unsaturated group-containing compound (f1) and a polyfunctional polymerizable unsaturated group-containing compound (f2).
  • Examples of the monofunctional polymerizable unsaturated group-containing compound (f1) include an esterified product of a monohydric alcohol and (meth) acrylic acid. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (Meth) acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, N-acryloyloxyethylhexahydro Examples include phthalimide.
  • hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate; acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid
  • Carboxyl group-containing (meth) acrylates such as 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate and 5-carboxypentyl (meth) acrylate; glycidyl groups such as glycidyl (meth) acrylate and allyl glycidyl ether Containing radically polymerizable unsaturated group-containing compounds; vinyl aromatic compounds such as styrene, ⁇ -methylstyrene, vinyltoluene, ⁇ -chlorostyrene; N, N-dimethylaminoethy
  • Examples of the polyfunctional polymerizable unsaturated group-containing compound (f2) include an esterified product of a polyhydric alcohol and (meth) acrylic acid.
  • Meth) acrylate compounds glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, ⁇ -caprolactone-modified tris (acryloxyethyl) isocyanurate and other tri (meth) acrylate compounds; pentaerythritol tetra (meth) acrylate and other tetra (meth) acrylate compounds; other dipentaerythritol penta (meth) acrylates And dipentaerythritol hexa (meth) acrylate.
  • the epoxy resin which has a (meth) acryloyl group the polyester resin which has a (meth) acryloyl group, etc. are mentioned
  • the coating composition of this invention can contain hydroxyl-containing resin (G) other than a hydroxyl-containing acrylic resin (B) as needed further. Accordingly, the coating composition of the present invention includes those containing a hydroxyl group-containing resin (G) other than the hydroxyl group-containing acrylic resin (B) in addition to the above components.
  • hydroxyl group-containing resin (G) examples include resins having a hydroxyl group, such as polyester resin, acrylic resin, polyether resin, polycarbonate resin, polyurethane resin, epoxy resin, and alkyd resin. These can be used alone or in combination of two or more.
  • the hydroxyl group-containing resin (G) is preferably a hydroxyl group-containing acrylic resin other than the hydroxyl group-containing acrylic resin (B) from the viewpoint of the weather resistance of the resulting coating film.
  • the hydroxyl group-containing acrylic resin (G) other than the hydroxyl group-containing acrylic resin (B) can impart flexibility to the coating film, and the glass transition temperature is improved in terms of weather resistance, particularly crack resistance. It is preferable to use one having an angle of 30 ° or less, particularly preferably 0 ° or more and 30 ° or less.
  • the coating composition of the present invention further comprises a curing catalyst, an ultraviolet absorber, a light stabilizer, a thickener, an antifoaming agent, a rust preventive agent, a plasticizer, an organic solvent, a surface conditioner, and an antisettling agent as necessary.
  • the usual paint additives such as can be contained singly or in combination of two or more.
  • curing catalyst examples include tin octylate, dibutyltin diacetate, dibutyltin di (2-ethylhexanoate), dibutyltin dilaurate, dioctyltin diacetate, dioctyltin di (2-ethylhexanoate), Dibutyltin oxide, dioctyltin oxide, dibutyltin fatty acid salt, lead 2-ethylhexanoate, zinc octylate, zinc naphthenate, fatty acid zinc compound, cobalt naphthenate, calcium octylate, copper naphthenate, tetra (2-ethylhexyl)
  • Organometallic compounds such as titanate; tertiary amines and the like can be mentioned, and these can be used alone or in combination of two or more.
  • the ultraviolet absorber has an action of suppressing the arrival of the deterioration of the film by absorbing incident light and converting light energy into a harmless form such as heat.
  • ultraviolet absorber conventionally known ones can be used, and for example, benzotriazole absorber, triazine absorber, salicylic acid derivative absorber, benzophenone absorber and the like can be used.
  • benzotriazole absorbent examples include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2 '-Hydroxy-3', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- ⁇ 2′-hydroxy-3 ′-(3 ′′, 4 ′′, 5 ′′, 6 ′′ -tetrahydrophthalimi Methyl) -5'-methyl
  • triazine absorbent examples include 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-isooctyloxyphenyl) -1,3,5-triazine, 2- [ 4 ((2-hydroxy-3-dodecyloxypropyl) -oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4 -((2-hydroxy-3-tridecyloxypropyl) -oxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- ( 2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like.
  • salicylic acid derivative absorbent examples include phenyl salicylate, p-octylphenyl salicylate, 4-tert-butylphenyl salicylate, and the like.
  • benzophenone absorbent examples include 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2 -Hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone Sodium 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 5-chloro-2- Hydroxybenzo Examples include phenone, resorcinol monobenzoate, 2,4-dibenzoyl resorcinol, 4,6-di
  • ultraviolet absorbers include, for example, 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole, 2,2′-dihydroxy-4 (3-methacryloxy-2-hydroxy Propoxy) benzophenone and the like can also be used.
  • UV absorbers include, for example, TINUVIN 900, TINUVIN 928, TINUVIN 348-2, TINUVIN 479, TINUVIN 405 (trade name, TINUVIN ⁇ Tinuvin is a registered trademark), RUVA 93 (Otsuka Chemical Co., Ltd.) Product name).
  • light stabilizers While light stabilizers, light stabilizers, one used as a radical chain inhibitor to capture active radical species produced in the degradation process of the coating, for example, light stabilizers such as hindered amine compounds.
  • a hindered piperidine compound may be mentioned as a light stabilizer exhibiting an excellent light stabilizing action.
  • the hindered piperidine compound include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis ( N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 4-benzoyloxy-2,2 ′, 6,6′-tetramethylpiperidine, bis (1,2,2,6, Monomer type such as 6-pentamethyl-4-piperidyl) ⁇ [3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl ⁇ butyl malonate; poly ⁇ [6- (1,1 , 3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-te
  • TINUVIN 123 TINUVIN 152
  • TINUVIN 292 trade name, TINUVIN ⁇ Tinuvin is a registered trademark
  • HOSTAVIN 3058 trade name, Hostavin is a registered trademark, manufactured by Clariant
  • ADK STAB LA-82 manufactured by ADEKA Corporation, trade name, ADK STAB ⁇ ADKSTAB and ADK STAB are registered trademarks
  • ADK STAB LA-82 manufactured by ADEKA Corporation, trade name, ADK STAB ⁇ ADKSTAB and ADK STAB are registered trademarks
  • composition of the present invention is not particularly limited, but the following ranges are preferable from the viewpoint of the following coating film performance.
  • the solid content of the urethane acrylate (A) is preferably 10 to 70 parts by mass with respect to 100 parts by mass of the total resin solids in the coating composition of the present invention, from the viewpoint of scratch resistance and weather resistance. More preferably, it is 15 to 60 parts by mass.
  • the total resin solid content means urethane acrylate (A), hydroxyl group-containing acrylic resin (B), and polyisocyanate (C), hydroxyl group-containing resin (G), and polymerizable unsaturated group-containing compound (F). When it contains, it is the total resin solid content which put them all together.
  • the proportion of the urethane acrylate (Ai-I) is 10 mass% or more, preferably 10 to 70 mass% in the total solid content of the urethane acrylate (A). Preferably there is. These ranges are significant in terms of improving the weather resistance of the coating film, particularly in terms of crack resistance.
  • the solid content of the hydroxyl group-containing acrylic resin (B) is preferably from 100 parts by weight of the total resin solid content in the coating composition of the present invention, from the viewpoint of low-temperature curability and adhesion to an object to be coated. 1 to 70 parts by mass, more preferably 5 to 60 parts by mass.
  • the solid content of the polyisocyanate compound (C) is preferably 5 to 30 parts by mass with respect to 100 parts by mass of the total resin solids in the coating composition of the present invention in terms of low temperature curability. More preferably, it is 10 to 25 parts by mass.
  • the coating composition of the present invention contains the coloring component (D), the content is not particularly limited, but the total resin solid content in the coating composition is 100 in terms of material concealment and design. A range of 0.1 to 5.0 parts by mass is preferable with respect to parts by mass, and a range of 0.2 to 3.0 parts by mass is more preferable.
  • the coating composition of the present invention is preferably a coating composition having a light transmittance of 2.0 or more at 375 nm of a coating film formed with a dry film thickness of 30 ⁇ m, and is 3.0% or more.
  • a coating composition is more preferred.
  • a spectrophotometer such as UV-3100 manufactured by Shimadzu Corporation is used. It is desirable to adjust the content of the coloring component (D) so that the light transmittance is 3.0% or more.
  • the content of the photopolymerization initiator (E) is preferably 0.5 to 6.0 parts by mass, more preferably 1 to 100 parts by mass of the total resin solid content in the coating composition of the present invention. 0.0 to 5.0 parts by mass. These ranges are significant in terms of reactivity to active energy rays.
  • the solid content thereof is 1 to 50 masses with respect to 100 mass parts of the total resin solid content in the coating composition of the present invention in terms of weather resistance. Part, preferably in the range of 3 to 40 parts by weight.
  • the solid content is based on 100 mass parts of the total resin solid content in the coating composition of the present invention, and the hydroxyl group-containing acrylic resin (B) and other hydroxyl group content.
  • the content of the hydroxyl group-containing resin (G) is preferably selected so that the total resin solid content of the resin (G) is in the range of 1 to 70 parts by mass, more preferably 5 to 60 parts by mass.
  • the content thereof is 0.005 to 5 parts by mass, preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total resin solid content in the coating composition of the present invention, from the viewpoint of scratch resistance. It is suitable that the content is in the range of 0.5 parts by mass, more preferably 0.03 to 0.3 parts by mass.
  • the content is not particularly limited, but from the viewpoint of adhesion to the article to be coated and weather resistance, the total resin solid content in the coating composition of the present invention is 100 parts by mass. On the other hand, the range of 0.1 to 15 parts by mass, preferably 0.3 to 10 parts by mass is appropriate.
  • the light stabilizer When the light stabilizer is used, its content is not particularly limited, but from the viewpoint of weather resistance, it is 0.1 to 10 with respect to 100 parts by mass of the total resin solid content in the coating composition of the present invention. Part by mass, preferably in the range of 0.2 to 5, is suitable.
  • urethane acrylate (A) has an isocyanate group in this invention
  • hydroxyl groups other than a hydroxyl-containing acrylic resin (B), a polyisocyanate compound (C), and a hydroxyl-containing acrylic resin (B) mix
  • the blending ratio of the containing resin (G) is the total amount of isocyanate groups of the polyisocyanate compound (C) and the urethane acrylate (A) and the total amount of hydroxyl groups of the hydroxyl group-containing acrylic resin (B) and the hydroxyl group-containing resin (G).
  • are preferably in a range where the equivalent ratio is NCO / OH 0.30 to 2.0, and more preferably in a range of 0.50 to 1.8. These ranges are significant in terms of scratch resistance and weather resistance of the coating film.
  • the coating composition of the present invention may be either an organic solvent-type coating composition or a water-based coating composition, but is preferably an organic solvent-type coating composition from the viewpoint of storage stability and the like.
  • the water-based coating composition is a coating in which the main component of the solvent is water
  • the organic solvent-type coating composition is a coating that does not substantially contain water as a solvent.
  • the coating composition is applied onto an object to be coated, set and / or preheated, and the resulting coating has a solid content of 90% by mass or more.
  • the coating film forming method is characterized by irradiating active energy rays.
  • coated materials include polyethylene resin, polypropylene resin, polymethyl methacrylate resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene-acrylate (ASA) resin, polyamide resin, acrylic resin, vinylidene chloride resin,
  • the resin include polycarbonate resin, polybutylene terephthalate (PBT) resin, polyurethane resin, and epoxy resin, and various plastic materials such as FRP, and these hybrid resins may also be used.
  • the object to be coated with the coating composition of the present invention is at least one selected from the group consisting of acrylonitrile-butadiene-styrene resin, acrylonitrile-styrene-acrylate resin, polycarbonate resin, polybutylene terephthalate resin, and hybrids thereof (ie, Acrylonitrile-butadiene-styrene resin, acrylonitrile-styrene-acrylate resin, polycarbonate resin, polybutylene terephthalate resin or a hybrid of at least two of these resins), among them, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile -Styrene-acrylate (ASA) resins are preferred.
  • ABS acrylonitrile-butadiene-styrene
  • ASA acrylonitrile -Styrene-acrylate
  • metal materials such as iron, aluminum, brass, copper, stainless steel, tinplate, galvanized steel, alloyed zinc (Zn-Al, Zn-Ni, Zn-Fe, etc.) plated steel, glass, cement, concrete, etc.
  • inorganic materials; wood; fiber materials paper, cloth, etc.
  • the application of the object to be coated with the coating composition of the present invention is not particularly limited, and examples thereof include an outer plate part of an automobile body such as a passenger car, a truck, a motorcycle, and a bus; an automobile part; a mobile phone and an audio.
  • an outer plate part of an automobile body such as a passenger car, a truck, a motorcycle, and a bus
  • an automobile part such as a motorcycle, and a bus
  • an automobile part such as a motorcycle, and a bus
  • a mobile phone and an audio an example of the outer plate of a household electric product such as a device can be given.
  • the coating film obtained by the coating composition of the present invention exhibits excellent adhesion to various plastic materials at a low temperature and in a short time, and has a finished appearance, scratch resistance, water resistance without any deformation of the material. Excellent in resistance and impact resistance. Especially, it can be used suitably for the use to the outer-plate part of a motor vehicle body, a motor vehicle component, especially a center pillar.
  • the coating composition of the present invention has a solid content of usually 15% by mass or more, particularly 20 to 60% by mass, and a viscosity of 5 to 30 seconds / Ford Cup # 4/20 ° C. It is preferable to adjust within the range.
  • 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. Electrostatic application may be performed during coating.
  • the coating film thickness can be in the range of usually 10 to 100 ⁇ m, preferably 10 to 50 ⁇ m, and more preferably 15 to 35 ⁇ m as a cured film thickness.
  • the coating composition is applied on an object to be coated, setting and / or preheating is performed, and after the solid content of the obtained coating film is 90% by mass or more, Irradiates active energy rays.
  • the confirmation of the solid content of the obtained coating film was performed by weighing the change in mass after curing and calculating the solid content. Specifically, 100 mm ⁇ 150 mm ⁇ 3.0 mm ABS coated object (m 0 ) was weighed, and this coating composition was applied onto the coated object. Then, after preheating at 80 ° C. for 3 minutes, a semi-cured coated plate (m 1 ) was obtained. Then heated 60 minutes at 80 ° C., to obtain fully cured painted plate (m 2). These ABS coated objects and coated plates were weighed and confirmed to be 90% by mass or more according to the following formula.
  • Solid content (mass%) of coating film (m 2 -m 0 ) / (m 1 -m 0 ) ⁇ 100 m 0 : Mass of the object to be coated before painting (g) m 1 : Mass (g) after pre-coating and semi-curing after coating m 2 : Mass (g) after the coating film is completely cured
  • Making the solid content of the coating film 90% by mass or more is performed in order to reduce the volatile content of the coating film immediately after coating or to remove the volatile component, and can be performed by an air blow, an IR furnace or the like. Setting can usually be performed by leaving the coated object to stand for 30 to 600 seconds at room temperature in a dust-free atmosphere.
  • the preheating can be usually performed by directly or indirectly heating the coated article in a drying furnace at a temperature of 40 to 90 ° C., preferably 50 to 70 ° C. for 1 to 30 minutes. Further, when air blowing is performed, it can be usually performed by blowing air heated to a normal temperature or a temperature of 25 ° C. to 80 ° C. on the coated surface of the object to be coated.
  • heating may be performed after active energy ray irradiation, or heating and active energy ray irradiation may be performed simultaneously.
  • heat from an active energy ray irradiation source (for example, heat generated by a lamp) may be used as a heat source.
  • the active energy ray irradiation may be performed in a state where the object to be coated is heated (a state having a residual heat).
  • the heating conditions at the time of irradiation with active energy rays are not particularly limited, but when the plastic material is deformed by heat, it is preferable that the maximum surface temperature of the object to be coated is less than 90 ° C, and further 50 ° C.
  • the temperature is preferably 80 ° C. or lower.
  • a heat ray cut filter and / or a cold mirror in order to control the temperature rise during irradiation with active energy rays.
  • the heating condition during irradiation with active energy rays is higher than the above range, it is not preferable because deformation occurs depending on the material.
  • the coating composition of the present invention has curability at a low temperature, and it is possible to obtain desired performance such as scratch resistance and weather resistance without heating at a high temperature (eg, 90 ° C. or higher). .
  • the coating composition of the present invention can be cured even with active energy rays, desired performance such as scratch resistance and weather resistance can be obtained without heating for a long time. Heating is preferably performed for 1 to 30 minutes, more preferably 1 to 20 minutes.
  • the active energy ray examples include ultraviolet light, visible light, and laser light (near infrared light, visible light laser, ultraviolet laser, etc.).
  • the irradiation dose is usually in the range of 100 to 5,000 mJ / cm 2 , preferably 300 to 3,000 mJ / cm 2 .
  • the active energy ray irradiation source conventionally used ones such as ultra-high pressure, high pressure, medium pressure, low pressure mercury lamp, FusionUV electrodeless lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide Lamps, fluorescent lamps, tungsten lamps, light sources obtained from each light source such as sunlight, visible light rays cut by an ultraviolet cut filter, various lasers having oscillation lines in the visible region, etc., but metal halide lamps are particularly suitable Can be used for
  • Part and % indicate “part by mass” and “% by mass” unless otherwise specified.
  • Plaxel FA-2D (trade name, manufactured by Daicel Chemical Industries) was added dropwise over 8 hours while keeping the temperature of the mixture not exceeding 60 ° C., and the mixture was further stirred at 60 ° C. for 1 hour.
  • a urethane acrylate (A-3) solution having a solid content of 80% was obtained.
  • the obtained urethane acrylate had an isocyanate equivalent of 681, an unsaturated group equivalent of 681, and a weight average molecular weight of 1021.
  • the mixture was further aged for 2 hours at the same temperature. Thereafter, a mixture of 10 parts of xylene and 0.50 part of 2,2′-azobisisobutyronitrile was added dropwise to the reaction vessel over 1 hour, and after completion of the addition, the mixture was aged for 1 hour to obtain a hydroxyl group-containing acrylic having a solid content of 55%. A resin (B-1) solution was obtained.
  • the resulting hydroxyl group-containing acrylic resin (B-1) had an acid value of 15.6 mgKOH / g, a hydroxyl value of 96.6 mgKOH / g, a weight average molecular weight of 10,000, and a glass transition temperature of 34.9 ° C.
  • the obtained hydroxyl group-containing acrylic resin (B-2) had an acid value of 15.6 mgKOH / g, a hydroxyl value of 96.6 mgKOH / g, a weight average molecular weight of 10,000, and a glass transition temperature of 48.2 ° C.
  • the obtained hydroxyl group-containing acrylic resin (G-1) had an acid value of 15.6 mgKOH / g, a hydroxyl value of 96.6 mgKOH / g, a weight average molecular weight of 20000, and a glass transition temperature of 3.9 ° C.
  • the obtained hydroxyl group-containing acrylic resin (G-2) had an acid value of 15.6 mgKOH / g, a hydroxyl value of 96.66 mgKOH / g, a weight average molecular weight of 10,000, and a glass transition temperature of 21.0 ° C.
  • the obtained hydroxyl group-containing acrylic resin (G-3) had an acid value of 15.6 mgKOH / g, a hydroxyl value of 14.5 mgKOH / g, a weight average molecular weight of 10,000, and a glass transition temperature of 96.4 ° C.
  • Colored component paste (D-1) A mill base was prepared by mixing 52.4 parts of methoxypropyl acetate, 15 parts of carbon black and 32.6 parts of DISPERBYK-2001 (dispersant, 46% active ingredient manufactured by Big Chemie Japan). Dispersion was carried out for 60 minutes with a bead mill to obtain a black paste (D-1) having a pigment concentration of 15% by weight.
  • Colored component paste (D-2) A mill base was prepared by mixing 52.4 parts of methoxypropyl acetate, 15 parts of chlorinated copper phthalocyanine blue and 32.6 parts of DISPERBYK-2001 (dispersant, 46% active ingredient manufactured by Big Chemie Japan). Dispersion was carried out for 60 minutes with a bead mill to obtain a blue paste (D-2) having a pigment concentration of 15% by weight.
  • Colored component paste (D-3) A mill base was prepared by mixing 52.4 parts of methoxypropyl acetate, 15 parts of quinacridone magenta, and 32.6 parts of DISPERBYK-2001 (dispersant, 46% active ingredient, manufactured by BYK Japan). Dispersion was carried out for 60 minutes with a bead mill to obtain a blue paste (D-3) having a pigment concentration of 15% by weight.
  • urethane acrylate (A-7) solution having a weight molecular weight of 1056 [nonvolatile content: 80 996 parts of 3%, Gardner viscosity (25 ° C.): OP, Gardner color: 1 or less].
  • the unsaturated group equivalent of urethane acrylate (A-7) was 176. In this urethane acrylate (A-7), it was confirmed by IR measurement that the 2240 cm ⁇ 1 peak due to the isocyanate group had disappeared.
  • Acrylic resin (G-4) Synthesis Example 1 except that a premix containing 202.5 parts methyl methacrylate, 202.5 parts n-butyl methacrylate, 45 parts ⁇ -hydroxyethyl methacrylate, 2 parts perbutyl O and 2 parts perbutyl Z was used.
  • an acrylic resin (G-4) solution [nonvolatile content: 45.0%, Gardner viscosity (25 ° C.): V, Gardner color: 1 or less, number average molecular weight (Mn) of acrylic resin: 28,000 The weight average molecular weight (Mw) of acrylic resin (G-4): 60,000] 998 parts.
  • Examples 2 to 27, Comparative Examples 1 to 6) In the same manner as in Example 1 with the solid content shown in Tables 1 and 2, the coating composition No. 2-33 were obtained.
  • EBECRYL (registered trademark) 244 manufactured by Daicel Cytec Co., Ltd., trade name, bifunctional urethane acrylate, weight molecular weight 2000, unsaturated group equivalent 1000.
  • EBECRYL (registered trademark) 8405 manufactured by Daicel-Cytec, Inc., trade name, tetrafunctional urethane acrylate, weight molecular weight 2700, unsaturated group equivalent 675.
  • Duranate TM P301-75E Asahi Kasei Chemicals, product name, adduct type adduct of hexamethylene diisocyanate.
  • Light transmittance The average light transmittance at a wavelength of 375 nm of the cured coating film having a thickness of 30 ⁇ m was measured by the following method; First, each coating composition was applied on a polypropylene plate so that the thickness of the coating film when cured was 30 ⁇ m. Next, the coating film on the polypropylene plate was cured. Next, the cured coating film was peeled off and collected, and the light transmittance at a wavelength of 375 nm was measured using a spectrophotometer. As the spectrophotometer, “UV-3100” (trade name, manufactured by Shimadzu Corporation) was used.
  • ASA coating The surface of a 100 mm ⁇ 150 mm ⁇ 3.0 mm acrylonitrile-styrene-acrylate plate was degreased with isopropyl alcohol to obtain an ASA coating.
  • ABS substrate The surface of a 100 mm ⁇ 150 mm ⁇ 3.0 mm acrylonitrile-butadiene-styrene plate was degreased with isopropyl alcohol to obtain an ABS coating.
  • PC / PBT substrate The surface of a 100 mm ⁇ 150 mm ⁇ 3.0 mm polycarbonate-polybutylene terephthalate plate was degreased with isopropyl alcohol to obtain a PC / PBT coated object.
  • Al coated material 5182 material JIS
  • JIS Japanese Industrial Standard
  • Fe coating A steel sheet having a surface treated with zinc phosphate having a size of 100 mm ⁇ 150 mm ⁇ 1.0 mm was degreased with petroleum benzine to obtain an Fe coating.
  • Examples 28 to 63, Comparative Examples 9 to 14 Each of the coating compositions obtained in Examples 1 to 27 and Comparative Examples 1 to 6 was applied to the coating materials shown in Tables 3 and 4 by air spray so that the dry film thickness was 30 ⁇ m.
  • the curing process of preheating after coating, irradiation with active energy rays and heating was performed under the following conditions.
  • the solid content of the coating film is set to 90% by mass or more, and then 300 mW / d with a D-bulb (an ultraviolet irradiation device manufactured by Fusion UV Systems) with an aluminum mirror attached. UV irradiation of cm 2 and 1500 mJ / cm 2 was performed for 1 minute. The curing process time was 6 minutes.
  • D-bulb (ultraviolet irradiation device manufactured by Fusion UV Systems) equipped with a cold mirror after drying for 10 seconds using a parallel irradiation type line heater HYP-20N manufactured by Hibeck Co., Ltd. after setting at 20 ° C for 50 seconds And 300 mW / cm 2 and 1500 mJ / cm 2 of UV irradiation were performed for 1 minute.
  • the solid content of the coating film was 90 mass or more by drying with a parallel irradiation type line heater HYP-20N for 10 seconds.
  • the curing process time was 2 minutes.
  • Test plates were obtained from the coating compositions and processes described in Tables 3, 4 and 5 for the coating compositions obtained in Tables 1 and 2. The evaluation results of each test plate are also shown in Table 3, Table 4, and Table 5.
  • a colored coating composition no. No. 34 was spray-coated, and further, heat-dried at 70 ° C. for 10 minutes in a hot air drying furnace to obtain a colored coated plate having a colored layer having a thickness of 10 ⁇ m. Thereafter, the obtained colored coated plate was coated with a coating composition No. 35 (Comparative Example; energy beam curable top coat) was applied using a bar coater to a film thickness of 10 ⁇ m, dried in a hot air drying oven set at 70 ° C. for 10 minutes, and then 160 W / cm The sample was passed under a high-pressure mercury lamp No.
  • the measured gloss was evaluated according to the following criteria: S: No abnormality is observed on the coating film surface, and the specular gloss (60 degrees) is 85 or more A: The specular gloss (60 degrees) is 70 or more and less than 85 B: The specular gloss (60 degrees) is 60 or more and less than 70 C: Specular gloss (60 degrees) is less than 60 ⁇ Material concealment>
  • An ASA plate flat plate that was rubbed back and forth 10 times with # 2000 sandpaper and polished was used as the coated plate. Further, the coating composition was applied thereon so as to have a dry film thickness of 30 ⁇ m to prepare a cured coating film under predetermined curing conditions, and a test plate (with polishing) was obtained.
  • the ASA plate was coated under the same conditions as above without polishing, to produce a cured coating film, and a test plate (no polishing) was obtained.
  • the L * value of this test plate (without polishing) and the test plate (with polishing) was measured, and the difference ⁇ L * was determined to evaluate the material concealment property according to the following criteria: S: ⁇ L * is less than 0.3 A: ⁇ L * is 0.3 or more and less than 0.5 B: ⁇ L * is 0.5 or more and less than 1 C: ⁇ L * is 1.0 or more.
  • the gloss after the test relative to the gloss before the test was determined as a gloss retention (%) and evaluated according to the following criteria: S: Gloss retention 90% or more A: Gloss retention 80% or more and less than 90% B: Gloss retention 60% or more and less than 80% C: Gloss retention 60% or less ⁇ Adhesion (after weather resistance test)>
  • S: Gloss retention 90% or more A: Gloss retention 80% or more and less than 90%
  • B Gloss retention 60% or more and less than 80%
  • C Gloss retention 60% or less ⁇ Adhesion (after weather resistance test)>
  • Coating film hardness A pencil scratch test (hand scuffing method) was performed on the coating surface of each test plate in accordance with JIS K 5600-5-6 (1990). Evaluation was based on the following criteria: S: F or more A: HB or more and less than F B: B or more and less than HB C: Less than B.
  • Curing process time It refers to the total number of fractions required for setting, preheating using a hot air dryer or the like after application of the coating composition, irradiation with active energy rays, and post-baking using a hot air dryer after irradiation with active energy rays. In each step, the total time required for coating film curing was evaluated. The time required for the active energy ray irradiation step was uniformly 1 minute.
  • Warpage of workpiece Evaluation was made with each coated plate of 100 mm ⁇ 150 mm. For items with warpage, place them on a glass that is flat in a convex direction, and evaluate the warpage in millimeters based on the difference between the thickness of the plate before painting and the height from the glass surface to the highest part of the convex part according to the following criteria. did: S: No warpage at all A: Less than 0.5 mm B: 0.5 mm or more and less than 2.0 mm C: 2.0 mm or more
  • the heating temperature in the coating process can be reduced and the heating time can be shortened, the scratch resistance and weather resistance of the resulting coating film are high, and the finished appearance is good. It is desirable that there be good adhesion to the object.
  • S The above curing process time is 20 minutes or less, the maximum surface temperature is less than 90 ° C., and the finish ⁇ appearance (crude)>, finish ⁇ gloss measurement>, scratch resistance, adhesion (initial) , Water resistance ⁇ appearance (after water resistance test)>, water resistance ⁇ adhesion (after water resistance test)>, weather resistance ⁇ appearance (warming)>, weather resistance ⁇ gloss retention (after weather resistance test)>, weather resistance ⁇ Adhesiveness (after weather resistance test)>, coating film hardness, and warpage of the object are all S or A.
  • A The above curing process time is 20 minutes or less, and the maximum temperature reached on the surface is 90 ° C. And the above 11 items are all A.
  • B The curing process time is 20 minutes or less, the maximum surface temperature is less than 90 ° C., and all the 11 items are S, A or B. At least one is B.
  • C The above curing process time is longer than 20 minutes or Either the highest temperature is 90 ° C. or higher, or at least one of the 11 items is C.
  • urethane methacrylate (A) having an unsaturated group equivalent of 100 to 900 and a weight average molecular weight of 500 to 2500, methyl methacrylate (a) 65 to 90% by mass based on the total amount of copolymerization components , Hydroxyl group-containing acrylic resin (B) having a hydroxyl group-containing polymerizable unsaturated monomer (b) of 10 to 35% by mass and another polymerizable unsaturated monomer (c) of 0 to 25% by mass as a copolymerization component;
  • the coating composition containing C) and the photopolymerization initiator (E) can reduce the heating temperature and the heating time in the coating process, and the resulting coating film has high scratch resistance and weather resistance, and has a finished appearance. It can be seen that it is good and has good adhesion to the object. Moreover, material concealment property can further be improved by mix

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Abstract

La présente invention concerne une composition de revêtement caractérisée en ce qu'elle comprend : (A) un uréthane acrylate ayant un équivalent en groupes insaturés de 100-900 et une masse moléculaire moyenne en poids de 500-2 500 ; (B) une résine acrylique à teneur en groupe hydroxy comprenant, comme composants de copolymérisation, (a) un méthacrylate de méthyle dans une quantité de 65-90 % en masse, (b) un monomère insaturé polymérisable à teneur en groupe hydroxy dans une quantité de 10-35 % en masse et (c) un autre monomère insaturé polymérisable dans une quantité de 0-25 % en masse, tous ces pourcentages étant relatifs à la quantité totale des composants de copolymérisation ; (C) un composé polyisocyanate ; et (E) un initiateur de photo-polymérisation.
PCT/JP2012/059780 2011-05-20 2012-04-10 Composition de revêtement et procédé de formation d'un film de revêtement Ceased WO2012160891A1 (fr)

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JP2018193529A (ja) * 2017-05-16 2018-12-06 関西ペイント株式会社 塗料組成物
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WO2021006290A1 (fr) * 2019-07-11 2021-01-14 共栄社化学株式会社 Composition de résine durcissable, film durci, corps moulé en résine revêtue et film multicouche
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CN108291109A (zh) * 2015-07-28 2018-07-17 巴斯夫欧洲公司 涂料组合物
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JP7159051B2 (ja) 2016-03-02 2022-10-24 アルケマ フランス 二重硬化ソフトタッチコーティング
JP2019512034A (ja) * 2016-03-02 2019-05-09 アルケマ フランス 二重硬化ソフトタッチコーティング
JP2020114929A (ja) * 2017-05-16 2020-07-30 関西ペイント株式会社 塗料組成物
JP2018193529A (ja) * 2017-05-16 2018-12-06 関西ペイント株式会社 塗料組成物
JP2018192470A (ja) * 2017-05-16 2018-12-06 関西ペイント株式会社 塗膜形成方法
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JP7231424B2 (ja) 2019-01-30 2023-03-01 中国塗料株式会社 紫外線硬化性塗料組成物、その硬化方法、及び硬化塗膜
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CN114096622A (zh) * 2019-07-11 2022-02-25 共荣社化学株式会社 固化性树脂组合物、固化膜、被覆树脂成型体和多层膜
JP7377563B2 (ja) 2019-07-11 2023-11-10 共栄社化学株式会社 硬化性樹脂組成物、硬化膜、被覆樹脂成型体及び多層フィルム
JP2021102730A (ja) * 2019-12-25 2021-07-15 荒川化学工業株式会社 活性エネルギー線硬化型コーティング剤組成物、硬化物、積層体及び成型物
JP7392462B2 (ja) 2019-12-25 2023-12-06 荒川化学工業株式会社 活性エネルギー線硬化型コーティング剤組成物、硬化物、積層体及び成型物
CN117567935A (zh) * 2023-10-20 2024-02-20 深圳市华星光电半导体显示技术有限公司 硬化涂层组合物、制备方法、硬化膜及显示装置

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