[go: up one dir, main page]

WO2015093299A1 - Coating agent and laminate - Google Patents

Coating agent and laminate Download PDF

Info

Publication number
WO2015093299A1
WO2015093299A1 PCT/JP2014/082103 JP2014082103W WO2015093299A1 WO 2015093299 A1 WO2015093299 A1 WO 2015093299A1 JP 2014082103 W JP2014082103 W JP 2014082103W WO 2015093299 A1 WO2015093299 A1 WO 2015093299A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
polyol
coating agent
meth
acrylate
Prior art date
Application number
PCT/JP2014/082103
Other languages
French (fr)
Japanese (ja)
Inventor
達史 小柳
北田　満
Original Assignee
Dic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 Dic株式会社 filed Critical Dic株式会社
Priority to JP2015553472A priority Critical patent/JP5963033B2/en
Priority to CN201480068831.0A priority patent/CN105829464B/en
Priority to KR1020167016518A priority patent/KR102254872B1/en
Publication of WO2015093299A1 publication Critical patent/WO2015093299A1/en

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
    • 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
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • 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
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4042—Imines; Imides
    • 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
    • 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
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/006—Anti-reflective 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/022—Emulsions, e.g. oil in water
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/10—Epoxy resins modified by unsaturated compounds
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds

Definitions

  • the present invention provides a coating agent and a laminate that can be used as a primer for improving the adhesion between a substrate and the cured coating film when a cured coating film of an active energy ray-curable composition is formed on the surface of the substrate. About.
  • the optical application include a liquid crystal display and a touch panel.
  • the display device such as the liquid crystal display is usually configured by laminating a large number of optical films having various functions in order to display clear images.
  • the optical film include an antireflection film, a retardation film, and a prism. A lens sheet etc. are mentioned.
  • polyester films especially polyethylene terephthalate (PET) films are used because of their excellent optical properties, mechanical strength, and durability.
  • PET polyethylene terephthalate
  • the active energy ray-curable composition is applied to the surface of the polyester film and cured to form a hard coat layer or a layer in which the active energy ray-curable composition is cast.
  • the polyester film may be a prism sheet, but the polyester film has a problem of low adhesion to the cured coating film of the active energy ray-curable composition due to its high crystallinity.
  • an acrylic resin is used between the polyester film as the base material and the cured coating film of the active energy ray-curable composition. It has been proposed to provide a primer layer (see, for example, Patent Document 1). However, even when a primer layer made of an acrylic resin is provided, the adhesion between the polyester film and the cured coating film of the active energy ray-curable composition is not sufficient.
  • those using a urethane resin as the primer layer have sufficient adhesion to the cured coating film of the active energy ray-curable composition, but are sufficient for adhesion and chemical resistance after the wet heat resistance test. There was a problem that performance could not be expressed.
  • the problem to be solved by the present invention is a primer having excellent adhesion to both the base material and the cured coating film of the active energy ray curable composition, and excellent in chemical resistance and heat and moisture resistance. It is to provide a coating agent capable of forming a layer.
  • the present inventors have obtained a vinyl ester resin obtained by reacting a specific epoxy resin with a compound having an acid group and a polymerizable unsaturated group, and an aromatic ring. Even if it is a hard-to-adhere substrate such as a polyester film by using a primer in which the urethane resin has a combination of an aqueous resin composition dispersed in an aqueous medium and a crosslinking agent, the substrate and the active energy ray The inventors have found that the adhesion of the curable composition to the cured coating film and the chemical resistance and heat-and-moisture resistance of the primer layer are greatly improved, and the present invention has been completed.
  • the present invention relates to an aqueous resin composition (F) obtained by dispersing a vinyl ester resin (A) and a urethane resin (B) having an aromatic ring in an aqueous medium (C), and a carbodiimide type.
  • the vinyl ester resin (A) is one or more epoxy resins (a1) selected from the group consisting of novolak type epoxy resins and bisphenol type epoxy resins, a compound (a2) having an acid group and a polymerizable unsaturated group, It was obtained by reacting
  • the urethane resin (B) is obtained by reacting a polyol (b1) containing a polyol (b1-1) having an aromatic ring and a polyol (b1-2) having a hydrophilic group with a polyisocyanate (b2).
  • the present invention relates to a coating agent and a laminate.
  • the coating agent of the present invention improves the adhesion between the base material and the cured coating film of the active energy ray-curable composition, and is resistant to chemicals, even if it is a difficult-to-adhere base material such as a polyester film. And since it can be used as a primer excellent in heat-and-moisture resistance, it is suitable for a laminate in which a cured film of an active energy ray-curable composition is formed on the surface of a polyester film. Examples of such a laminate include optical films such as an antireflection film, a retardation film, and a prism lens sheet. Further, these optical films can be applied to image display devices such as liquid crystal displays.
  • the coating agent of the present invention includes an aqueous resin composition (D) in which a vinyl ester resin (A) and a urethane resin (B) having an aromatic ring are dispersed in an aqueous medium (C), and a carbodiimide-based crosslinking agent. It is a coating agent containing (E).
  • the vinyl ester resin (A) includes at least one epoxy resin (a1) selected from the group consisting of a novolac type epoxy resin and a bisphenol type epoxy resin, a compound (a2) having an acid group and a polymerizable unsaturated group, It was obtained by reacting.
  • the vinyl ester resin (A) is polymerizable from the compound (a2). Has an unsaturated group.
  • the polymerizable unsaturated group of the vinyl ester resin (A) is covalently bonded by a polymerization reaction with the polymerizable unsaturated group of the resin or monomer contained in the active energy ray-curable composition described later.
  • the adhesion with the primer layer formed and formed of the coating agent of the present invention becomes strong.
  • the equivalent of the polymerizable unsaturated group contained in the vinyl ester resin (A) is 250 to 2,000 g / eq.
  • the range of is preferable.
  • the epoxy resin (a1) is at least one selected from the group consisting of a novolac type epoxy resin and a bisphenol type epoxy resin, and specifically, the following can be used.
  • Examples of the novolac type epoxy resin include a cresol novolac type epoxy resin and a phenol novolac type epoxy resin.
  • Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and tetrabromobisphenol A type epoxy resin. These epoxy resins (a1) can be used alone or in combination of two or more.
  • epoxy resins (a1) it is preferable to use a novolac type epoxy resin having a large number of epoxy groups capable of reacting with the acid group of the compound (a2).
  • the epoxy equivalent of the epoxy resin (a1) is 150 to 2,000 g / eq. In the range of 160 to 1,000 g / eq. The range of is more preferable.
  • the compound (a2) has an acid group and a polymerizable unsaturated group.
  • a polymerizable unsaturated group can be introduced into the vinyl ester resin (A) by reacting the acid group of the compound (a2) with the epoxy group of the epoxy resin (a1).
  • Examples of the compound (a2) include acrylic acid, methacrylic acid, itaconic acid, 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl succinate, 2,2,2, -trisacryloyloxymethylethylphthalic acid, and the like. Is mentioned. Among these compounds, an acryloyl group that easily undergoes a polymerization reaction with a polymerizable unsaturated group of a resin or monomer in the active energy ray-curable composition described later can be introduced into the vinyl ester resin (A). Acrylic acid is preferred. These compounds (a2) can be used alone or in combination of two or more, but it is preferable to use 50% by mass or more of acrylic acid in the total amount of the compound (a2).
  • the reaction temperature between the epoxy resin (a1) and the compound (a2) is preferably in the range of 60 to 150 ° C., more preferably in the range of 80 to 120 ° C.
  • the polymerization inhibitor is preferably in the range of 500 to 5,000 ppm with respect to the total mass of the epoxy resin (a1) and the compound (a2).
  • polymerization inhibitor examples include 2,6-bis (tert-butyl) -4-methylphenol, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether (methoquinone), p-tert-butylcatechol, nitrobenzene, nitrobenzoic acid, o-Dinitrobenzene, m-dinitrobenzene, p-dinitrobenzene, 2,4-dinitrophenol, trinitrobenzene and the like. These polymerization inhibitors can be used alone or in combination of two or more.
  • reaction catalyst can be used when the epoxy resin (a1) and the compound (a2) are reacted.
  • the amount of the reaction catalyst used is preferably in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the epoxy resin (a1).
  • reaction catalyst examples include an amine catalyst, an imidazole catalyst, a phosphorus catalyst, a boron catalyst, and a phosphorus-boron catalyst.
  • alkyl-substituted guanidines such as ethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine; 3- (3,4-dichlorophenyl) -1,1-dimethylurea, 3-phenyl-1,1-dimethylurea 3-substituted 4-phenyl-1,1-dimethylureas such as 3- (4-chlorophenyl) -1,1-dimethylurea; 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline Imidazolines such as 2-aminopyridine; amine imides such as N, N-dimethyl-N- (2-hydroxy-3-allyloxypropyl) amine
  • the weight average molecular weight of the vinyl ester resin (A) obtained by the above method is preferably in the range of 500 to 10,000, more preferably in the range of 1,000 to 6,000, since the dispersion stability of the resin particles is improved. More preferred.
  • the urethane resin (B) having an aromatic ring reacts a polyol (b1) containing a polyol (b1-1) having an aromatic ring and a polyol (b1-2) having a hydrophilic group with a polyisocyanate (b2). It was obtained.
  • the urethane resin (B) has an aromatic ring.
  • the aromatic ring concentration in the polyol (b1-1) is preferably in the range of 1.5 to 8 mol / kg, more preferably in the range of 1.6 to 5 mol / kg.
  • polyol (b1-1) examples include aromatic polyester polyols, aromatic polycarbonate polyols, aromatic polyether polyols, and alkylene oxide adducts of bisphenol. These can be used alone or in combination of two or more.
  • an aromatic polyester polyol and an alkylene oxide adduct of bisphenol A which is a kind of alkylene oxide adduct of bisphenol, are preferable because of excellent substrate adhesion and blocking resistance. . Therefore, as the polyol (b1-1), it is preferable to use one containing at least one of an aromatic polyester polyol and an alkylene oxide adduct of bisphenol A.
  • the aromatic polyester polyol is obtained by an esterification reaction of a polyvalent carboxylic acid and a polyhydric alcohol, and at least one of the polyvalent carboxylic acid and the polyol has an aromatic ring. Use.
  • those having an aromatic ring include, for example, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, or esterified products thereof.
  • Examples of those having no aromatic ring include succinic acid, glutaric acid, adipic acid, maleic acid, pimelic acid, suberic acid, azelaic acid, itaconic acid, sebacic acid, chlorendic acid, 1,2,4- Examples thereof include aliphatic dicarboxylic acids such as butane-tricarboxylic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, and fumaric acid, or esterified products thereof. These polyvalent carboxylic acids or esterified products thereof can be used alone or in combination of two or more.
  • those having an aromatic ring include aromatic diols such as benzene dimethanol, toluene dimethanol, and xylene dimethanol.
  • aromatic diols such as benzene dimethanol, toluene dimethanol, and xylene dimethanol.
  • those having no aromatic ring include ethylene glycol, propylene glycol, 1,3-propylene diol, 1,4-butane diol, 1,6-hexane diol, 1,8-octane diol, diethylene glycol
  • examples thereof include aliphatic polyols such as triethylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, and neopentyl glycol ethylene glycol.
  • These polyhydric alcohols can be used alone or in combination of two or more.
  • the polyol (b1-2) is a polyol having a hydrophilic group.
  • the hydrophilic group include an anionic group, a cationic group, and a nonionic group.
  • An anionic group is preferable, and among the anionic groups, a carboxyl group and a sulfonic acid group are preferable.
  • polyol having a carboxyl group as a hydrophilic group examples include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid and the like. Among these, 2,2-dimethylolpropionic acid is preferable.
  • polyester polyol which has a carboxyl group obtained by making the polyol and carboxylate which have the said carboxyl group react can also be used.
  • polyol having a sulfonic acid group as a hydrophilic group examples include dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5- (4-sulfophenoxy) isophthalic acid, or salts thereof.
  • dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5- (4-sulfophenoxy) isophthalic acid, or salts thereof.
  • polyester polyols obtained by reacting low molecular polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and neopentyl glycol.
  • a part of or all of the anionic group can be neutralized with a basic compound to impart good water dispersibility to the urethane resin (B).
  • the basic compound examples include ammonia; organic amines such as triethylamine, morpholine, monoethanolamine, and diethylethanolamine; and metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide. Since the water dispersion stability of the aqueous resin composition of the present invention can be further improved, the amount of the basic compound used is 0 in terms of the molar ratio of the basic compound to the anionic group [basic compound / anionic group]. The range of 0.5 to 3 is preferable, and the range of 0.7 to 1.5 is more preferable.
  • esterification catalyst for the purpose of promoting the esterification reaction.
  • esterification catalyst include metals such as titanium, tin, zinc, aluminum, zirconium, magnesium, hafnium, and germanium; titanium tetraisopropoxide, titanium tetrabutoxide, titanium oxyacetylacetonate, dibutyltin oxide, and dibutyltin.
  • a metal compound etc. are mentioned.
  • the alkylene oxide adduct of bisphenol A is obtained by adding alkylene oxide to the phenolic hydroxyl group of bisphenol A.
  • alkylene oxide include ethylene oxide and propylene oxide.
  • the average number of moles of alkylene oxide added per mole of bisphenol A is preferably in the range of 1 to 8, and more preferably in the range of 1 to 4.
  • the polyol (b1) contains the polyol (b1-1) and the polyol (b1-2) as essential components, but may contain other polyols (b1-3).
  • the polyol (b1-3) include aliphatic polyester polyols, aliphatic polycarbonate polyols, aliphatic polyether polyols, and alkylene oxide adducts of hydrogenated bisphenol.
  • the polyol (b1-3) the polyhydric alcohol mentioned as the raw material for the aromatic polyester polyol may be used. These polyols (b1-3) can be used alone or in combination of two or more.
  • the ratio of the polyol (b1-1) having an aromatic ring contained in the polyol (b1) is preferably in the range of 40 to 98% by mass and more preferably in the range of 60 to 98% by mass because the adhesion to the substrate is further improved. % Range is more preferred.
  • Examples of the polyisocyanate (b2) used as a raw material for the urethane resin (B) include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, and tolylene diene.
  • Examples include aromatic polyisocyanates such as isocyanate and naphthalene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate; cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate.
  • aromatic polyisocyanates such as isocyanate and naphthalene diisocyanate
  • aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate
  • cyclohexane diisocyanate dicyclohexylmethane diisocyanate
  • isophorone diisocyanate can be
  • the polyisocyanates (b2) those containing an aromatic polyisocyanate are preferable because adhesion to a substrate is further improved.
  • the content of the aromatic polyisocyanate in the polyisocyanate (b2) is preferably in the range of 15 to 35% by mass.
  • the urethane resin (B) is prepared by mixing the polyol (b1) and the polyisocyanate (b2) in the absence of a solvent or in the presence of an organic solvent, and at a temperature of 40 to 120 ° C. for 3 to 20 hours. It can be produced by reacting. Moreover, when manufacturing the said urethane resin (B), you may use a chain extender as needed.
  • the reaction between the polyol (b1) and the polyisocyanate (b2) is such that the equivalent ratio [isocyanate group / hydroxyl group] of the hydroxyl group of the polyol (b1) and the isocyanate group of the polyisocyanate (b2) is 0. It is preferably carried out in the range of 5 to 3.5, more preferably in the range of 0.9 to 2.5.
  • Examples of the organic solvent that can be used in producing the urethane resin (B) include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; acetate solvents such as ethyl acetate and butyl acetate; acetonitrile Nitrile solvents such as amide solvents such as dimethylformamide and N-methylpyrrolidone. These organic solvents can be used alone or in combination of two or more.
  • the adhesion between the substrate and the cured coating film of the active energy ray-curable composition is further improved.
  • 000 is preferable, and a range of 3,000 to 100,000 is more preferable.
  • Examples of the aqueous medium (C) include water, organic solvents miscible with water, and mixtures thereof.
  • organic solvents miscible with water include alcohol solvents such as methanol, ethanol, n-propanol, and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol, and propylene glycol; Alkyl ether solvents; lactam solvents such as N-methyl-2-pyrrolidone and the like.
  • These water-miscible organic solvents can be used alone or in combination of two or more.
  • the aqueous medium (C) is preferably water alone or a mixture of water and an organic solvent miscible with water, more preferably water alone, in consideration of safety and environmental load reduction.
  • the ratio of the aqueous medium (C) is preferably in the range of 10 to 90% by mass, more preferably in the range of 30 to 70% by mass.
  • the aqueous resin composition (D) is obtained by dispersing the vinyl ester resin (A) and the urethane resin (B) in the aqueous medium (C).
  • the vinyl ester resin (A) and the urethane resin (B) may exist as separate resin particles in the aqueous medium (C), but the vinyl ester resin (A) It is preferable to use a part or all of which formed resin particles (F) inherent in the urethane resin (B) particles. More specifically, it is preferable that the vinyl ester resin (A) is a core-shell type resin particle (F) in which a core part is formed and the urethane resin (B) is a shell part.
  • the vinyl ester resin (A) and the urethane resin (B) are manufactured in advance, and then the vinyl resin (A) and the urethane resin are added to the urethane resin (B). It can manufacture by mixing the basic compound which neutralizes the anionic group which (B) has, and the said aqueous medium (C).
  • the organic solvent may be removed by a distillation method or the like in order to reduce safety and environmental burden. Thereby, the aqueous resin composition (D) in which the resin particles (F) are dispersed in the aqueous medium (C) can be obtained.
  • the mass ratio [(A) / (B)] of the vinyl ester resin (A) and the urethane resin (B) improves the adhesion with the cured coating film of the active energy ray-curable composition.
  • the range of 60/40 to 10/90 is preferable, and the range of 55/45 to 20/80 is more preferable. This range is the same when the vinyl ester resin (A) and the urethane resin (B) are used as the resin particles (F).
  • the ratio of the total amount of the vinyl ester resin (A) and the urethane resin (B) in the total amount of the aqueous resin composition (D) is preferably in the range of 10 to 90% by mass, and preferably 30 to 70% by mass. A range is more preferred.
  • a film-forming aid if necessary, a film-forming aid, a curing agent, a plasticizer, an antistatic agent, a wax, a light stabilizer, a flow regulator, a dye, a leveling agent, a rheology control agent, Additives such as ultraviolet absorbers, antioxidants, photocatalytic compounds, inorganic pigments, organic pigments and extender pigments; other resins such as polyester resins, urethane resins and acrylic resins can be blended.
  • the coating agent of the present invention contains a carbodiimide-based crosslinking agent (E) as an essential component.
  • the carbodiimide group possessed by the crosslinking agent (E) reacts with a hydrophilic group such as a carboxyl group possessed by the urethane resin (B) to form a three-dimensional crosslinked structure.
  • the adhesion of the composition to the cured coating film is improved, and when the coating agent of the present invention is used as a primer, the primer layer to be formed has high adhesion after a heat and humidity test and excellent chemical resistance. Can be granted.
  • the crosslinking agent (E) preferably has two or more carbodiimide groups.
  • examples of such a crosslinking agent (E) include poly (4,4′-diphenylmethanecarbodiimide), poly (p-phenylenecarbodiimide), poly ( m-phenylenecarbodiimide), poly (diisopropylphenylcarbodiimide), poly (triisopropylphenylcarbodiimide) and other aromatic polycarbodiimides; poly (dicyclohexylmethanecarbodiimide) and other alicyclic polycarbodiimides, poly (diisopropylcarbodiimide) and other aliphatics Examples thereof include polycarbodiimide.
  • the coating agent of this invention disperse
  • crosslinking agent (E) Commercially available products that can be used as the crosslinking agent (E) include “Carbodilite SV-02”, “Carbodilite V-02”, “Carbodilite V-02-L2”, and “Carbodilite V-04” manufactured by Nisshinbo Chemical Co., Ltd. ”,“ Carbodilite E-01 ”,“ Carbodilite E-02 ”and the like.
  • the amount of the crosslinking agent (E) used is an amount that reacts with 80 to 100 mol% of the hydrophilic group of the urethane resin (B) that can react with the carbodiimide group, since sufficient crosslinking performance is exhibited.
  • the amount reacting with 100 mol% is more preferable.
  • the crosslinking agent (E) improves adhesion and storage stability with the aqueous resin composition (D). Therefore, the crosslinking agent (E) is in the range of 3 to 5% by mass with respect to the aqueous resin composition (D). It is preferable to add at.
  • the laminate of the present invention has a primer layer formed using the coating agent of the present invention described above, and has a cured coating film formed using an active energy ray-curable composition on the surface of the primer layer. Is.
  • the active energy ray-curable composition preferably contains a resin having a polymerizable unsaturated group and a monomer having a polymerizable unsaturated group.
  • the type of the monomer having a polymerizable unsaturated group is preferably appropriately selected according to the properties required for the cured coating film of the active energy ray-curable composition.
  • Examples of the resin having a polymerizable unsaturated group include urethane (meth) acrylate resin, unsaturated polyester resin, epoxy (meth) acrylate resin, polyester (meth) acrylate resin, acrylic (meth) acrylate resin, and resin having maleimide group. Etc. These resins having a polymerizable unsaturated group can be used alone or in combination of two or more.
  • (meth) acrylate refers to one or both of acrylate and methacrylate
  • (meth) acryloyl group refers to one or both of acryloyl group and methacryloyl group.
  • urethane (meth) acrylate resin examples include a urethane bond and a (meth) acryloyl group obtained by urethanization reaction of an aliphatic polyisocyanate or an aromatic polyisocyanate with a (meth) acrylate having a hydroxyl group.
  • resins examples include resins.
  • aliphatic polyisocyanate examples include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1 , 5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, Hydrogenated tolylene diisocyanate, hydrogenated xylylene diene Isocyanate, hydrogenated tetramethylxylylene diisocyanate, cyclohexyl diisocyan
  • aromatic polyisocyanate examples include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, and the like.
  • Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1 Monohydric alcohols such as 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, and hydroxypivalate neopentyl glycol mono (meth) acrylate (Meth) acrylate; trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerin di (meth) Mono- or di (meth) acrylates of trivalent alcohols such as acryl
  • a compound having a group, or a polyfunctional (meth) acrylate having a hydroxyl group obtained by modifying the compound with ⁇ -caprolactone; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, (Meth) acrylate compounds having an oxyalkylene chain such as propylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate; polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-polyoxypropylene mono (meth) (Meth) acrylate compounds having block structure oxyalkylene chains such as acrylate; random structures such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate And (meth) acrylate compounds having an oxyalkylene chain.
  • the unsaturated polyester resin is a curable resin obtained by polycondensation of ⁇ , ⁇ -unsaturated dibasic acid or its acid anhydride, aromatic saturated dibasic acid or its acid anhydride, and glycol.
  • ⁇ , ⁇ -unsaturated dibasic acid or acid anhydrides thereof include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof.
  • Examples of the aromatic saturated dibasic acid or acid anhydride thereof include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride, and the like. And the like.
  • Examples of the aliphatic or alicyclic saturated dibasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof.
  • glycol examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, Examples include tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl) propane, etc.
  • oxides such as ethylene oxide and propylene oxide can be used in the same manner.
  • epoxy (meth) acrylate resin (meth) acrylic acid is reacted with an epoxy group of an epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, or the like. What is obtained is mentioned.
  • an epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, or the like. What is obtained is mentioned.
  • polyester (meth) acrylate resin examples include those obtained by reacting a hydroxyl group of a polyester polyol with (meth) acrylic acid.
  • acrylic (meth) acrylate resin after polymerizing (meth) acrylate monomers, such as glycidyl methacrylate and alkyl (meth) acrylate as needed, for example, after obtaining the acrylic resin which has an epoxy group And those obtained by reacting the epoxy group with (meth) acrylic acid.
  • (meth) acrylate monomers such as glycidyl methacrylate and alkyl (meth) acrylate
  • Examples of the resin having a maleimide group include a bifunctional maleimide urethane compound obtained by urethanizing N-hydroxyethylmaleimide and isophorone diisocyanate, a bifunctional maleimide ester compound obtained by esterifying maleimide acetic acid and polytetramethylene glycol, Examples thereof include a tetrafunctional maleimide ester compound obtained by esterification of maleimidocaproic acid and a tetraethylene oxide adduct of pentaerythritol, a polyfunctional maleimide ester compound obtained by esterification of maleimide acetic acid and a polyhydric alcohol compound, and the like.
  • Examples of the monomer having a polymerizable unsaturated group include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and a number average molecular weight in the range of 150 to 1,000.
  • the active energy ray-curable composition can be formed into a cured coating film by irradiating active energy rays after being applied to a substrate or the like.
  • the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
  • a photopolymerization initiator is added to the active energy ray-curable composition to improve curability. It is preferable to do. Further, if necessary, a photosensitizer can be further added to improve curability.
  • a photopolymerization initiator or a photosensitizer is used. Since it cures quickly even if it is not used, it is not necessary to add a photopolymerization initiator or a photosensitizer.
  • photopolymerization initiator examples include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) -phenyl] -2.
  • the photosensitizer examples include amine compounds such as aliphatic amines and aromatic amines, urea compounds such as o-tolylthiourea, sulfur such as sodium diethyldithiophosphate, s-benzylisothiuronium-p-toluenesulfonate, and the like. Compound etc. are mentioned.
  • Examples of the substrate used in the laminate of the present invention include a metal substrate, a plastic substrate, a glass substrate, a paper substrate, a wood substrate, and a fibrous substrate.
  • a plastic base material is preferable when the aqueous resin composition of the present invention is used as a primer in order to improve the adhesion between the cured coating film of the active energy ray-curable composition and the base material. It is.
  • Materials for the plastic substrate include polyester, acrylic resin (polymethyl methacrylate, etc.), polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS resin), composite resin of ABS resin and polycarbonate, polystyrene, polyurethane, epoxy resin , Polyvinyl chloride, polyamide, polyolefin (polyethylene, polypropylene, polycycloolefin (COP), etc.), triacetyl cellulose (TAC), and the like.
  • polyester acrylic resin (polymethyl methacrylate, etc.), polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS resin), composite resin of ABS resin and polycarbonate, polystyrene, polyurethane, epoxy resin , Polyvinyl chloride, polyamide, polyolefin (polyethylene, polypropylene, polycycloolefin (COP), etc.), triacetyl cellulose (TAC), and the like
  • the coating agent of the present invention is very useful as a primer for a polyester base material among the above plastic base materials.
  • Specific examples of the polyester include polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).
  • the plastic substrate examples include plastic molded products such as mobile phones, home appliances, automobile interior and exterior materials, and OA equipment. Moreover, the film base material which used the plastic as a raw material is also mentioned.
  • the film substrate when used as the substrate of the laminate of the present invention, it can be used for optical films such as antireflection films, retardation films, and prism lens sheets; and high-performance films such as food packaging such as aluminum vapor deposition films. it can.
  • the laminate of the present invention when used as an optical film such as an antireflection film, a retardation film, or a prism lens sheet, various kinds of liquid crystal display (LCD), organic EL display (OLED), plasma display (PDP), etc. It can be used as a member of a screen display device.
  • LCD liquid crystal display
  • OLED organic EL display
  • PDP plasma display
  • the coating agent of the present invention can form a coating film on the surface of the substrate by, for example, directly applying to the surface of the substrate and then drying and curing.
  • the method of drying the coating agent of the present invention and allowing the curing to proceed may be a method of curing at room temperature for about 1 to 10 days. However, since the curing can proceed rapidly, 100 ° C. to 150 ° C. A method of heating at a temperature of about 1 to 600 seconds is preferable.
  • Examples of the method for applying the coating agent of the present invention to the surface of the substrate include a gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, flow coater, spin coater, Examples of the application method include dipping, screen printing, spraying, brush coating, applicator, and bar coater.
  • the film thickness of the coating film formed using the coating agent of the present invention can be appropriately adjusted according to the intended use, but is usually preferably in the range of 0.01 to 20 ⁇ m.
  • the laminate of the present invention is further coated with the active energy ray-curable composition on the surface of the primer layer, which is the coating film of the coating agent of the present invention obtained as described above, and irradiated with active energy rays. By doing, it can obtain by forming the cured coating film of the said active energy ray curable composition.
  • the coating method of the said active energy ray curable composition can use the same method as the coating method of the coating agent of said this invention.
  • Table 1 shows the raw materials for the vinyl ester resin (1) synthesized in Production Example 1.
  • Table 2 shows the compositions of the aqueous resin compositions (1) obtained in Examples 1 to 9.
  • the composition in the table represents the nonvolatile content (amount of resin alone).
  • UV curable composition (UV-1) 50 parts by mass of urethane acrylate resin (“Unidic V-4260” manufactured by DIC Corporation), 50 parts by mass of tripropylene glycol diacrylate, and photopolymerization initiator (“Irgacure 184” manufactured by BASF Japan Ltd., 1-hydroxycyclohexyl phenyl ketone )
  • UV curable composition (UV-1) was obtained by mixing 3 parts by mass.
  • UV curable composition (UV-2) 50 parts by mass of an epoxy acrylate resin (“Unidic V-5500” manufactured by DIC Corporation), 50 parts by mass of tripropylene glycol diacrylate, and 3 parts by mass of a photopolymerization initiator (“Irgacure 184” manufactured by BASF Japan Ltd.) are mixed. As a result, an ultraviolet curable composition (UV-2) was obtained.
  • an epoxy acrylate resin (“Unidic V-5500” manufactured by DIC Corporation)
  • tripropylene glycol diacrylate 50 parts by mass of tripropylene glycol diacrylate
  • a photopolymerization initiator (“Irgacure 184” manufactured by BASF Japan Ltd.)
  • Example 1 Preparation of primer (1) 100 parts by mass of the aqueous resin composition (1) obtained in Preparation Example 1, 2.8 parts by mass of a carbodiimide crosslinking agent (“Carbodilite E-02” manufactured by Nisshinbo Chemical Co., Ltd.), and 593 parts by mass of ion-exchanged water
  • the primer (P-1) was obtained by mixing.
  • Example 2 Preparation of primer (2) 100 parts by mass of the aqueous resin composition (1) obtained in Preparation Example 1, 2.8 parts by mass of a carbodiimide crosslinking agent (“Carbodilite V-02” manufactured by Nisshinbo Chemical Co., Ltd.), and 589 parts by mass of ion-exchanged water
  • the primer (P-2) was obtained by mixing.
  • Example 3 Preparation of primer (3) 100 parts by mass of the aqueous resin composition (1) obtained in Preparation Example 1, 2.8 parts by mass of a carbodiimide crosslinking agent (“Carbodilite SV-02” manufactured by Nisshinbo Chemical Co., Ltd.), and 593 parts by mass of ion-exchanged water A primer (P-3) was obtained by mixing.
  • a carbodiimide crosslinking agent (“Carbodilite SV-02” manufactured by Nisshinbo Chemical Co., Ltd.)
  • P-3 ion-exchanged water
  • Example 4 Production of laminate (1)
  • the primer (P--) obtained in Example 1 was formed so that the film thickness after drying was about 1 ⁇ m on the surface of a film substrate (thickness 125 ⁇ m) made of polyethylene terephthalate (hereinafter abbreviated as “PET”).
  • PET polyethylene terephthalate
  • the primer layer was formed on the surface of the substrate by applying 1) and heating at 150 ° C. for 5 minutes.
  • the ultraviolet curable composition (UV-1) obtained in Preparation Example 2 was applied to the surface of the primer layer with a coating thickness of 15 ⁇ m, and the irradiation intensity was 0 on the coated surface using a high-pressure mercury lamp as a light source.
  • the surface of the substrate has a primer layer, and the surface of the primer layer is a cured coating film of an ultraviolet curable composition (hereinafter abbreviated as “UV coating film”).
  • UV coating film an ultraviolet curable composition
  • Example 5 Production of laminate (2)
  • UV-2 ultraviolet curable composition obtained in Preparation Example 3
  • UV-1 ultraviolet curable composition used in Example 4.
  • a laminate (2) was obtained.
  • Example 6 Production of laminate (3)
  • the primer (P-2) obtained in Example 2 was applied to the surface of the PET film substrate so that the film thickness after drying was about 1 ⁇ m, and the substrate was heated at 150 ° C. for 5 minutes. A primer layer was formed on the surface of the material.
  • the ultraviolet curable composition (UV-2) obtained in Preparation Example 3 was applied to the surface of the primer layer with an application thickness of 15 ⁇ m, and the application surface was irradiated with an irradiation intensity of 0.
  • UV-2 ultraviolet curable composition obtained in Preparation Example 3
  • Example 7 Production of laminate (4)
  • a laminate (4) was obtained in the same manner as in Example 6 except that the primer (P-3) obtained in Example 3 was used instead of the primer (P-2) used in Example 6. It was.
  • a primer layer is applied to the surface of the base material by applying a primer on the surface of a base material made of polyethylene terephthalate having a thickness of 125 ⁇ m so that the film thickness when dried is about 1 ⁇ m and heating at 150 ° C. for 5 minutes.
  • a test plate made of laminated members was prepared.
  • a 24 mm wide adhesive tape made by Nichiban Co., Ltd. was affixed to the surface of the primer layer of the test plate produced by the above method.
  • the surface of the primer layer when the pressure-sensitive adhesive tape was pulled in a direction perpendicular to the primer layer and the pressure-sensitive adhesive tape was peeled off from the surface of the primer layer was visually evaluated according to the following evaluation criteria.
  • Double-circle The primer layer did not peel at all from the base-material surface which comprises a test board.
  • ⁇ A part of the primer layer was peeled off from the surface of the base material constituting the test plate, but the peeled range was less than 10% with respect to the total area of the film constituting the test plate.
  • X The primer layer of the range of 50% or more with respect to the whole area of the primer layer which comprises a test board peeled from the base-material surface which comprises a test board.
  • the surface of the UV coating film is visually evaluated according to the following evaluation criteria when the pressure-sensitive adhesive tape is pulled in a direction perpendicular to the UV coating film and the pressure-sensitive adhesive tape is peeled off from the surface of the UV coating film.
  • did. (Double-circle): UV coating film did not peel from the base-material surface which comprises a laminated body at all.
  • ⁇ A part of the UV coating film was peeled off from the surface of the substrate constituting the laminate, but the peeled range was less than 10% with respect to the total area of the UV coating constituting the laminate. .
  • the primer layer is applied to the surface of the base material by applying the primer to the surface of the base material made of polyethylene terephthalate having a thickness of 125 ⁇ m so that the film thickness when dried is about 1 ⁇ m and heating at 150 ° C. for 5 minutes. Formed.
  • ⁇ When the surface of the primer layer was visually observed, it was transparent.
  • delta When the surface of the primer layer was observed visually, although it was transparent, the crack was able to be confirmed.
  • X When the surface of the primer layer was visually observed, cracks to the extent that whitening occurred appeared, and a part of the primer layer was easily peeled from the polyethylene terephthalate substrate.
  • Table 3 shows the base materials, primers and ultraviolet curable compositions used in the laminates (1) to (4) obtained in Examples 10 to 20, and the evaluation results.
  • a primer (P′-1) was obtained by mixing 100 parts by mass of the aqueous resin composition (1) and 577 parts by mass of ion-exchanged water.
  • Comparative Examples 6 to 8 Production of laminates (R2) to (R4)) Comparative Example 5 except that the primers (P'-2) to (P'-4) obtained in Comparative Examples 2 to 4 were used in place of the primer (P'-1) used in Comparative Example 5, respectively. In the same manner as above, laminates (R2) to (R4) were obtained.
  • Table 4 shows the substrates, primers, and ultraviolet curable compositions used in the laminates (R1) and (R2) obtained in Comparative Examples 4 to 7, and the evaluation results.
  • the primer layer formed using the coating agent of the present invention is excellent in adhesion to the substrate and also in adhesion to the cured coating film of the active energy ray-curable composition. It was confirmed that it was excellent.
  • the primer layer formed using the coating agent of the present invention has high adhesion after the heat and humidity resistance test and excellent chemical resistance.
  • Comparative Example 5 is an example using a coating agent that does not contain a crosslinking agent. Compared to the primer layer formed using the coating agent of the present invention, it was confirmed that the adhesion after the wet heat resistance test was insufficient and the chemical resistance was insufficient.
  • Comparative Example 6 is an example using a melamine crosslinking agent. It was confirmed that the chemical resistance was insufficient as compared with the primer layer formed using the coating agent containing the carbodiimide crosslinking agent of the present invention.
  • Comparative Example 7 is an example using an oxazoline crosslinking agent. Compared with the primer layer formed using the coating agent containing the carbodiimide cross-linking agent of the present invention, it was confirmed that the adhesion after the wet heat resistance test was insufficient and the chemical resistance was also insufficient. .
  • Comparative Example 8 is an example using an epoxy crosslinking agent. It was confirmed that the chemical resistance was insufficient as compared with the primer layer formed using the coating agent containing the carbodiimide crosslinking agent of the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Epoxy Resins (AREA)

Abstract

The present invention provides a coating agent comprising: (D) an aqueous resin composition produced by dispersing both (A) a vinyl ester resin and (B) a urethane resin having an aromatic ring in (C) an aqueous medium; and (E) a carbodiimide-type cross-linking agent. In the coating agent, the vinyl ester resin (A) is produced by reacting (a1) at least one epoxy resin selected from the group consisting of a novolac-type epoxy resin and a bisphenol-type epoxy resin with (a2) a compound having an acid group and a polymerizable unsaturated group, and the urethane resin (B) is produced by reacting (b1) a polyol comprising (b1-1) a polyol having an aromatic ring and (b1-2) a polyol having a hydrophilic group with (b2) a polyisocyanate. The coating agent according to the present invention enables the formation of a primer layer which can improve the adhesion between a base material and a cured coating film made from an active energy ray-curable composition and which has excellent chemical resistance and wet heat resistance.

Description

コーティング剤及び積層体Coating agent and laminate
　本発明は、基材表面に活性エネルギー線硬化性組成物の硬化塗膜を形成する際に、基材と前記硬化塗膜との密着性を向上するプライマーとして用いることができるコーティング剤及び積層体に関する。 The present invention provides a coating agent and a laminate that can be used as a primer for improving the adhesion between a substrate and the cured coating film when a cured coating film of an active energy ray-curable composition is formed on the surface of the substrate. About.
　水性ウレタン樹脂組成物は、近年、光学用途向けのフィルムやシートへの適用が検討されている。前記光学用途としては、具体的には、液晶ディスプレイ、タッチパネル等が挙げられる。前記液晶ディスプレイ等の表示装置は、通常、鮮明な映像を表示するために各種機能を有する多数の光学フィルムが積層され構成されており、かかる光学フィルムとしては、反射防止フィルム、位相差フィルム、プリズムレンズシート等が挙げられる。 In recent years, application of water-based urethane resin compositions to films and sheets for optical applications has been studied. Specific examples of the optical application include a liquid crystal display and a touch panel. The display device such as the liquid crystal display is usually configured by laminating a large number of optical films having various functions in order to display clear images. Examples of the optical film include an antireflection film, a retardation film, and a prism. A lens sheet etc. are mentioned.
　これらの光学フィルムの基材としては、ポリエステルフィルム、とりわけ、ポリエチレンテレフタレート（ＰＥＴ）フィルムが光学特性、機械強度、耐久性に優れることから使用されている。また、光学用途においては、ポリエステルフィルムの表面に活性エネルギー線硬化性組成物を塗工、硬化することによって、ハードコート層を形成したり、活性エネルギー線硬化性組成物を注型した層を設け、ポリエステルフィルムをプリズムシートとしたりするが、ポリエステルフィルムは結晶性が高いことに起因して、活性エネルギー線硬化性組成物の硬化塗膜との密着性が低いという問題があった。 As the base material of these optical films, polyester films, especially polyethylene terephthalate (PET) films are used because of their excellent optical properties, mechanical strength, and durability. For optical applications, the active energy ray-curable composition is applied to the surface of the polyester film and cured to form a hard coat layer or a layer in which the active energy ray-curable composition is cast. The polyester film may be a prism sheet, but the polyester film has a problem of low adhesion to the cured coating film of the active energy ray-curable composition due to its high crystallinity.
　ポリエステルフィルムと活性エネルギー線硬化性組成物の硬化塗膜との密着性を向上する方法として、基材であるポリエステルフィルムと活性エネルギー線硬化性組成物の硬化塗膜との間に、アクリル樹脂からなるプライマー層を設けることが提案されている（例えば、特許文献１参照。）。しかしながら、アクリル樹脂からなるプライマー層を設けても、ポリエステルフィルムと活性エネルギー線硬化性組成物の硬化塗膜との密着性は十分なものではなかった。 As a method for improving the adhesion between the polyester film and the cured coating film of the active energy ray-curable composition, an acrylic resin is used between the polyester film as the base material and the cured coating film of the active energy ray-curable composition. It has been proposed to provide a primer layer (see, for example, Patent Document 1). However, even when a primer layer made of an acrylic resin is provided, the adhesion between the polyester film and the cured coating film of the active energy ray-curable composition is not sufficient.
　また、プライマー層としてウレタン樹脂を用いたものは、活性エネルギー線硬化性組成物の硬化塗膜との密着性は十分なものの、耐湿熱試験後の密着性及び耐薬品性に対しては十分な性能を発現できない問題があった。 In addition, those using a urethane resin as the primer layer have sufficient adhesion to the cured coating film of the active energy ray-curable composition, but are sufficient for adhesion and chemical resistance after the wet heat resistance test. There was a problem that performance could not be expressed.
　そこで、ポリエステルフィルムと活性エネルギー線硬化性組成物の硬化塗膜との密着性を十分なものとし、また、優れた耐薬品性及び耐湿熱性を有するプライマー層に用いることのできるコーティング剤が求められていた。 Accordingly, there is a need for a coating agent that has sufficient adhesion between the polyester film and the cured coating film of the active energy ray-curable composition, and that can be used for a primer layer having excellent chemical resistance and moist heat resistance. It was.
特開２０１０－２１５８４３号公報JP 2010-215843 A
　本発明が解決しようとする課題は、基材や活性エネルギー線硬化組成物の硬化塗膜とのいずれに対しても優れた密着性を有し、かつ、耐薬品性及び耐湿熱性に優れたプライマー層を形成可能なコーティング剤を提供することである。 The problem to be solved by the present invention is a primer having excellent adhesion to both the base material and the cured coating film of the active energy ray curable composition, and excellent in chemical resistance and heat and moisture resistance. It is to provide a coating agent capable of forming a layer.
　本発明者らは、上記の課題を解決すべく鋭意研究した結果、特定のエポキシ樹脂と酸基及び重合性不飽和基を有する化合物とを反応させて得られたビニルエステル樹脂、及び芳香環を有するウレタン樹脂が、水性媒体中に分散された水性樹脂組成物に架橋剤を組み合わせたプライマーを用いることで、ポリエステルフィルムのような難接着の基材であっても、その基材と活性エネルギー線硬化性組成物の硬化塗膜との密着性の向上、ならびに、プライマー層の耐薬品性及び耐湿熱性が大幅に向上することを見出し、本発明を完成させた。 As a result of diligent research to solve the above problems, the present inventors have obtained a vinyl ester resin obtained by reacting a specific epoxy resin with a compound having an acid group and a polymerizable unsaturated group, and an aromatic ring. Even if it is a hard-to-adhere substrate such as a polyester film by using a primer in which the urethane resin has a combination of an aqueous resin composition dispersed in an aqueous medium and a crosslinking agent, the substrate and the active energy ray The inventors have found that the adhesion of the curable composition to the cured coating film and the chemical resistance and heat-and-moisture resistance of the primer layer are greatly improved, and the present invention has been completed.
　すなわち、本発明は、ビニルエステル樹脂（Ａ）、及び芳香環を有するウレタン樹脂（Ｂ）が、水性媒体（Ｃ）中に分散して得られた水性樹脂組成物（Ｆ）、ならびに、カルボジイミド系架橋剤（Ｅ）を含有するコーティング剤であって、
前記ビニルエステル樹脂（Ａ）が、ノボラック型エポキシ樹脂及びビスフェノール型エポキシ樹脂からなる群より選ばれる１種以上のエポキシ樹脂（ａ１）と、酸基及び重合性不飽和基を有する化合物（ａ２）とを反応させて得られたものであり、
前記ウレタン樹脂（Ｂ）が、芳香環を有するポリオール（ｂ１－１）及び親水性基を有するポリオール（ｂ１－２）を含有するポリオール（ｂ１）と、ポリイソシアネート（ｂ２）とを反応させて得られたものであることを特徴とするコーティング剤及び積層体に関するものである。 That is, the present invention relates to an aqueous resin composition (F) obtained by dispersing a vinyl ester resin (A) and a urethane resin (B) having an aromatic ring in an aqueous medium (C), and a carbodiimide type. A coating agent containing a crosslinking agent (E),
The vinyl ester resin (A) is one or more epoxy resins (a1) selected from the group consisting of novolak type epoxy resins and bisphenol type epoxy resins, a compound (a2) having an acid group and a polymerizable unsaturated group, It was obtained by reacting
The urethane resin (B) is obtained by reacting a polyol (b1) containing a polyol (b1-1) having an aromatic ring and a polyol (b1-2) having a hydrophilic group with a polyisocyanate (b2). In particular, the present invention relates to a coating agent and a laminate.
　本発明のコーティング剤は、ポリエステルフィルムのような難接着の基材であっても、その基材と活性エネルギー線硬化性組成物の硬化塗膜との密着性を向上させ、ならびに、耐薬品性及び耐湿熱性に優れたプライマーとして用いることができることからポリエステルフィルムを基材として、その表面に活性エネルギー線硬化性組成物の硬化塗膜を形成した積層体に好適である。このような積層体としては、例えば、反射防止フィルム、位相差フィルム、プリズムレンズシート等の光学フィルムが挙げられる。また、これらの光学フィルムは、液晶ディスプレイをはじめとする画像表示装置に応用可能である。 The coating agent of the present invention improves the adhesion between the base material and the cured coating film of the active energy ray-curable composition, and is resistant to chemicals, even if it is a difficult-to-adhere base material such as a polyester film. And since it can be used as a primer excellent in heat-and-moisture resistance, it is suitable for a laminate in which a cured film of an active energy ray-curable composition is formed on the surface of a polyester film. Examples of such a laminate include optical films such as an antireflection film, a retardation film, and a prism lens sheet. Further, these optical films can be applied to image display devices such as liquid crystal displays.
　本発明のコーティング剤は、ビニルエステル樹脂（Ａ）、及び芳香環を有するウレタン樹脂（Ｂ）が、水性媒体（Ｃ）中に分散された水性樹脂組成物（Ｄ）、ならびに、カルボジイミド系架橋剤（Ｅ）を含有するコーティング剤である。 The coating agent of the present invention includes an aqueous resin composition (D) in which a vinyl ester resin (A) and a urethane resin (B) having an aromatic ring are dispersed in an aqueous medium (C), and a carbodiimide-based crosslinking agent. It is a coating agent containing (E).
　前記ビニルエステル樹脂（Ａ）は、ノボラック型エポキシ樹脂及びビスフェノール型エポキシ樹脂からなる群より選ばれる１種以上のエポキシ樹脂（ａ１）と、酸基及び重合性不飽和基を有する化合物（ａ２）とを反応させて得られたものである。 The vinyl ester resin (A) includes at least one epoxy resin (a1) selected from the group consisting of a novolac type epoxy resin and a bisphenol type epoxy resin, a compound (a2) having an acid group and a polymerizable unsaturated group, It was obtained by reacting.
　前記化合物（ａ２）が有する重合性不飽和基は、前記エポキシ樹脂との反応において、その反応に関与しないため、結果として、前記ビニルエステル樹脂（Ａ）は、前記化合物（ａ２）由来の重合性不飽和基を有する。このビニルエステル樹脂（Ａ）が有する重合性不飽和基は、後述する活性エネルギー線硬化性組成物中に含まれる樹脂や単量体が有する重合性不飽和基と重合反応することにより共有結合が形成され、本発明のコーティング剤からなるプライマー層との密着が強固なものとなる。 Since the polymerizable unsaturated group of the compound (a2) does not participate in the reaction with the epoxy resin, as a result, the vinyl ester resin (A) is polymerizable from the compound (a2). Has an unsaturated group. The polymerizable unsaturated group of the vinyl ester resin (A) is covalently bonded by a polymerization reaction with the polymerizable unsaturated group of the resin or monomer contained in the active energy ray-curable composition described later. The adhesion with the primer layer formed and formed of the coating agent of the present invention becomes strong.
　前記ビニルエステル樹脂（Ａ）が有する重合性不飽和基の当量は、２５０～２，０００ｇ／ｅｑ．の範囲が好ましい。 The equivalent of the polymerizable unsaturated group contained in the vinyl ester resin (A) is 250 to 2,000 g / eq. The range of is preferable.
　前記エポキシ樹脂（ａ１）は、ノボラック型エポキシ樹脂及びビスフェノール型エポキシ樹脂からなる群より選ばれる１種以上のものであるが、具体的には、以下のものを用いることができる。 The epoxy resin (a1) is at least one selected from the group consisting of a novolac type epoxy resin and a bisphenol type epoxy resin, and specifically, the following can be used.
　前記ノボラック型エポキシ樹脂としては、例えば、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂等が挙げられる。また、前記ビスフェノール型エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、テトラブロモビスフェノールＡ型エポキシ樹脂等が挙げられる。これらのエポキシ樹脂（ａ１）は、単独で用いることも２種以上併用することもできる。 Examples of the novolac type epoxy resin include a cresol novolac type epoxy resin and a phenol novolac type epoxy resin. Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and tetrabromobisphenol A type epoxy resin. These epoxy resins (a1) can be used alone or in combination of two or more.
　前記エポキシ樹脂（ａ１）の中でも、前記化合物（ａ２）が有する酸基と反応しうるエポキシ基を多数有するノボラック型エポキシ樹脂を使用することが好ましい。 Among the epoxy resins (a1), it is preferable to use a novolac type epoxy resin having a large number of epoxy groups capable of reacting with the acid group of the compound (a2).
　また、前記エポキシ樹脂（ａ１）のエポキシ当量は、１５０～２，０００ｇ／ｅｑ．の範囲が好ましく、１６０～１，０００ｇ／ｅｑ．の範囲がより好ましい。 The epoxy equivalent of the epoxy resin (a1) is 150 to 2,000 g / eq. In the range of 160 to 1,000 g / eq. The range of is more preferable.
　さらに、前記エポキシ樹脂（ａ１）が有するエポキシ基の全量中の８０～１００モル％を、前記化合物（ａ２）の酸基と反応させることが好ましく、前記エポキシ基のすべてが前記化合物（ａ２）の酸基と反応させることがより好ましい。 Furthermore, it is preferable to react 80 to 100 mol% of the total amount of epoxy groups of the epoxy resin (a1) with the acid group of the compound (a2), and all of the epoxy groups of the compound (a2) It is more preferable to react with an acid group.
　前記化合物（ａ２）は、酸基及び重合性不飽和基を有するものである。前記化合物（ａ２）が有する酸基と、前記エポキシ樹脂（ａ１）が有するエポキシ基とを反応させることにより、前記ビニルエステル樹脂（Ａ）に重合性不飽和基を導入することができる。 The compound (a2) has an acid group and a polymerizable unsaturated group. A polymerizable unsaturated group can be introduced into the vinyl ester resin (A) by reacting the acid group of the compound (a2) with the epoxy group of the epoxy resin (a1).
　前記化合物（ａ２）としては、例えば、アクリル酸、メタクリル酸、イタコン酸、２－アクリロイルオキシエチルサクシネート、２－メタクリロイルオキシエチルサクシネート、２，２，２，－トリスアクリロイルオキシメチルエチルフタル酸等が挙げられる。これらの化合物の中でも、後述する活性エネルギー線硬化性組成物中の樹脂や単量体が有する重合性不飽和基と重合反応しやすいアクリロイル基を前記ビニルエステル樹脂（Ａ）に導入することができるアクリル酸が好ましい。また、これらの化合物（ａ２）は、単独で用いることも２種以上併用することもできるが、前記化合物（ａ２）の全量中にアクリル酸を５０質量％以上用いることが好ましい。 Examples of the compound (a2) include acrylic acid, methacrylic acid, itaconic acid, 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl succinate, 2,2,2, -trisacryloyloxymethylethylphthalic acid, and the like. Is mentioned. Among these compounds, an acryloyl group that easily undergoes a polymerization reaction with a polymerizable unsaturated group of a resin or monomer in the active energy ray-curable composition described later can be introduced into the vinyl ester resin (A). Acrylic acid is preferred. These compounds (a2) can be used alone or in combination of two or more, but it is preferable to use 50% by mass or more of acrylic acid in the total amount of the compound (a2).
　前記エポキシ樹脂（ａ１）と前記化合物（ａ２）との反応温度は、６０～１５０℃の範囲が好ましく、８０～１２０℃の範囲がより好ましい。 The reaction temperature between the epoxy resin (a1) and the compound (a2) is preferably in the range of 60 to 150 ° C., more preferably in the range of 80 to 120 ° C.
　また、前記エポキシ樹脂（ａ１）と前記化合物（ａ２）とを反応させる際には、前記化合物（ａ２）が有する重合性不飽和基の熱重合を防止するため、重合禁止剤を用いることが好ましい。重合禁止剤の添加量は、前記エポキシ樹脂（ａ１）及び前記化合物（ａ２）の合計質量に対して、５００～５，０００ｐｐｍの範囲が好ましい。 Moreover, when making the said epoxy resin (a1) and the said compound (a2) react, in order to prevent the thermal polymerization of the polymerizable unsaturated group which the said compound (a2) has, it is preferable to use a polymerization inhibitor. . The addition amount of the polymerization inhibitor is preferably in the range of 500 to 5,000 ppm with respect to the total mass of the epoxy resin (a1) and the compound (a2).
　前記重合禁止剤としては、例えば、２，６－ビス（ｔｅｒｔ－ブチル）－４－メチルフェノール、ハイドロキノン、メチルハイドロキノン、ハイドロキノンモノメチルエーテル（メトキノン）、ｐ－ｔｅｒｔ－ブチルカテコール、ニトロベンゼン、ニトロ安息香酸、ｏ－ジニトロベンゼン、ｍ－ジニトロベンゼン、ｐ－ジニトロベンゼン、２，４－ジニトロフェノール、トリニトロベンゼン等が挙げられる。これらの重合禁止剤は、単独で用いることも２種以上併用することもできる。 Examples of the polymerization inhibitor include 2,6-bis (tert-butyl) -4-methylphenol, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether (methoquinone), p-tert-butylcatechol, nitrobenzene, nitrobenzoic acid, o-Dinitrobenzene, m-dinitrobenzene, p-dinitrobenzene, 2,4-dinitrophenol, trinitrobenzene and the like. These polymerization inhibitors can be used alone or in combination of two or more.
　さらに、前記エポキシ樹脂（ａ１）と前記化合物（ａ２）とを反応させる際には、反応触媒を用いることができる。前記反応触媒の使用量は、前記エポキシ樹脂（ａ１）１００質量部に対して、０．１～５質量部の範囲が好ましい。 Furthermore, a reaction catalyst can be used when the epoxy resin (a1) and the compound (a2) are reacted. The amount of the reaction catalyst used is preferably in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the epoxy resin (a1).
　前記反応触媒としては、例えば、アミン触媒、イミダゾール触媒、リン触媒、ホウ素触媒、リン－ホウ素触媒等が挙げられる。具体的には、エチルグアニジン、トリメチルグアニジン、フェニルグアジニン、ジフェニルグアニジン等のアルキル置換グアニジン；３－（３，４－ジクロロフェニル）－１，１－ジメチル尿素、３－フェニル－１，１－ジメチル尿素、３－（４－クロロフェニル）－１，１－ジメチル尿素等の３－置換フェニル－１，１－ジメチル尿素；２－メチルイミダゾリン、２－フェニルイミダゾリン、２－ウンデシルイミダゾリン、２－ヘプタデシルイミダゾリン等のイミダゾリン；２－アミノピリジン等のモノアミノピリジン；Ｎ，Ｎ－ジメチル－Ｎ－（２－ヒドロキシ－３－アリロキシプロピル）アミン－Ｎ’－ラクトイミド等のアミンイミド；エチルホスフィン、プロピルホスフィン、ブチルホスフィン、フェニルホスフィン、トリメチルホスフィン、トリエチルホスフィン、トリブチルホスフィン、トリオクチルホスフィン、トリフェニルホスフィン、トリシクロヘキシルホスフィン、トリフェニルホスフィン－トリフェニルボラン錯体、テトラフェニルホスホニウムテトラフェニルボレート等の有機リン触媒、１，８－ジアザビシクロ［５．４．０］ウンデセン－７、１，４－ジアザビシクロ［２．２．２］オクタン等のジアザビシクロウンデセン触媒などが挙げられる。これらの反応触媒は、単独で用いることも２種以上併用することもできる。 Examples of the reaction catalyst include an amine catalyst, an imidazole catalyst, a phosphorus catalyst, a boron catalyst, and a phosphorus-boron catalyst. Specifically, alkyl-substituted guanidines such as ethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine; 3- (3,4-dichlorophenyl) -1,1-dimethylurea, 3-phenyl-1,1-dimethylurea 3-substituted 4-phenyl-1,1-dimethylureas such as 3- (4-chlorophenyl) -1,1-dimethylurea; 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline Imidazolines such as 2-aminopyridine; amine imides such as N, N-dimethyl-N- (2-hydroxy-3-allyloxypropyl) amine-N′-lactoimide; ethylphosphine, propylphosphine, butyl Phosphine, phenylphosphine, trimethylphos Organophosphorus catalysts such as fin, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine-triphenylborane complex, tetraphenylphosphonium tetraphenylborate, 1,8-diazabicyclo [5.4 .0] undecene-7,1,4-diazabicyclo [2.2.2] octane and other diazabicycloundecene catalysts. These reaction catalysts can be used alone or in combination of two or more.
　前記方法で得られるビニルエステル樹脂（Ａ）の重量平均分子量としては、樹脂粒子の分散安定性が向上することから、５００～１０，０００の範囲が好ましく、１，０００～６，０００の範囲がより好ましい。 The weight average molecular weight of the vinyl ester resin (A) obtained by the above method is preferably in the range of 500 to 10,000, more preferably in the range of 1,000 to 6,000, since the dispersion stability of the resin particles is improved. More preferred.
　芳香環を有するウレタン樹脂（Ｂ）は、芳香環を有するポリオール（ｂ１－１）及び親水性基を有するポリオール（ｂ１－２）を含有するポリオール（ｂ１）と、ポリイソシアネート（ｂ２）とを反応させて得られたものである。 The urethane resin (B) having an aromatic ring reacts a polyol (b1) containing a polyol (b1-1) having an aromatic ring and a polyol (b1-2) having a hydrophilic group with a polyisocyanate (b2). It was obtained.
　前記ポリオール（ｂ１－１）を前記ウレタン樹脂（Ｂ）の原料として用いることで、前記ウレタン樹脂（Ｂ）が芳香環を有するものとなる。また、前記ポリオール（ｂ１－１）中の芳香環濃度は、１．５～８ｍｏｌ／ｋｇの範囲が好ましく、１．６～５ｍｏｌ／ｋｇの範囲がより好ましい。 By using the polyol (b1-1) as a raw material for the urethane resin (B), the urethane resin (B) has an aromatic ring. The aromatic ring concentration in the polyol (b1-1) is preferably in the range of 1.5 to 8 mol / kg, more preferably in the range of 1.6 to 5 mol / kg.
　前記ポリオール（ｂ１－１）としては、例えば、芳香族ポリエステルポリオール、芳香族ポリカーボネートポリオール、芳香族ポリエーテルポリオール、ビスフェノールのアルキレンオキサイド付加物等が挙げられる。これらは、単独で用いることも２種以上併用することもできる。 Examples of the polyol (b1-1) include aromatic polyester polyols, aromatic polycarbonate polyols, aromatic polyether polyols, and alkylene oxide adducts of bisphenol. These can be used alone or in combination of two or more.
　また、前記ポリオール（ｂ１－１）の中でも、芳香族ポリエステルポリオール、ビスフェノールのアルキレンオキサイド付加物の１種であるビスフェノールＡのアルキレンオキサイド付加物が、基材密着性と耐ブロッキング性に優れることから好ましい。したがって、前記ポリオール（ｂ１－１）としては、芳香族ポリエステルポリオール及びビスフェノールＡのアルキレンオキサイド付加物のうち、少なくとも１つを含むものを用いることが好ましい。 Among the polyols (b1-1), an aromatic polyester polyol and an alkylene oxide adduct of bisphenol A, which is a kind of alkylene oxide adduct of bisphenol, are preferable because of excellent substrate adhesion and blocking resistance. . Therefore, as the polyol (b1-1), it is preferable to use one containing at least one of an aromatic polyester polyol and an alkylene oxide adduct of bisphenol A.
　前記芳香族ポリエステルポリオールは、多価カルボン酸と多価アルコールとをエステル化反応させて得られたものであるが、前記多価カルボン酸及びポリオールのうち、少なくとも１つに芳香環を有するものを用いる。 The aromatic polyester polyol is obtained by an esterification reaction of a polyvalent carboxylic acid and a polyhydric alcohol, and at least one of the polyvalent carboxylic acid and the polyol has an aromatic ring. Use.
　前記多価カルボン酸のうち、芳香環を有するものとしては、例えば、フタル酸、イソフタル酸、テレフタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸又はそのエステル化物が挙げられる。また、芳香環を有さないものとしては、例えば、コハク酸、グルタル酸、アジピン酸、マレイン酸、ピメリン酸、スベリン酸、アゼライン酸、イタコン酸、セバシン酸、クロレンド酸、１，２，４－ブタン－トリカルボン酸、デカンジカルボン酸、シクロヘキサンジカルボン酸、ダイマー酸、フマル酸等の脂肪族ジカルボン酸又はそのエステル化物が挙げられる。これらの多価カルボン酸又はそのエステル化物は、単独で用いることも２種以上併用することもできる。 Among the polyvalent carboxylic acids, those having an aromatic ring include, for example, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, or esterified products thereof. Examples of those having no aromatic ring include succinic acid, glutaric acid, adipic acid, maleic acid, pimelic acid, suberic acid, azelaic acid, itaconic acid, sebacic acid, chlorendic acid, 1,2,4- Examples thereof include aliphatic dicarboxylic acids such as butane-tricarboxylic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, and fumaric acid, or esterified products thereof. These polyvalent carboxylic acids or esterified products thereof can be used alone or in combination of two or more.
　前記多価アルコールのうち、芳香環を有するものとしては、例えば、ベンゼンジメタノール、トルエンジメタノール、キシレンジメタノール等の芳香族ジオールが挙げられる。また、芳香環を有さないものとしては、例えば、エチレングリコール、プロピレングリコール、１，３－プロピレンジオール、１，４－ブタンジオール、１，６－ヘキサンジオール、１，８－オクタンジオール、ジエチレングリコール、トリエチレングリコール、シクロヘキサン－１，４－ジオール、シクロヘキサン－１，４－ジメタノール、ネオペンチルグリコールエチレングリコール等の脂肪族ポリオールが挙げられる。これらの多価アルコールは、単独で用いることも２種以上併用することもできる。 Among the polyhydric alcohols, those having an aromatic ring include aromatic diols such as benzene dimethanol, toluene dimethanol, and xylene dimethanol. Examples of those having no aromatic ring include ethylene glycol, propylene glycol, 1,3-propylene diol, 1,4-butane diol, 1,6-hexane diol, 1,8-octane diol, diethylene glycol, Examples thereof include aliphatic polyols such as triethylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, and neopentyl glycol ethylene glycol. These polyhydric alcohols can be used alone or in combination of two or more.
　前記ポリオール（ｂ１－２）は、親水性基を有するポリオールである。前記親水性基としては、アニオン性基、カチオン性基、ノニオン性基が挙げられるが、アニオン性基が好ましく、アニオン性基の中でもカルボキシル基、スルホン酸基が好ましい。 The polyol (b1-2) is a polyol having a hydrophilic group. Examples of the hydrophilic group include an anionic group, a cationic group, and a nonionic group. An anionic group is preferable, and among the anionic groups, a carboxyl group and a sulfonic acid group are preferable.
　親水性基としてカルボキシル基を有するポリオールとしては、例えば、２，２－ジメチロールプロピオン酸、２，２－ジメチロールブタン酸、２，２－ジメチロール吉草酸等が挙げられる。これらの中でも、２，２－ジメチロールプロピオン酸が好ましい。また、前記カルボキシル基を有するポリオールと多価カルボン酸とを反応させて得られるカルボキシル基を有するポリエステルポリオールも用いることができる。 Examples of the polyol having a carboxyl group as a hydrophilic group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid and the like. Among these, 2,2-dimethylolpropionic acid is preferable. Moreover, the polyester polyol which has a carboxyl group obtained by making the polyol and carboxylate which have the said carboxyl group react can also be used.
　親水性基としてスルホン酸基を有するポリオールとしては、例えば、５－スルホイソフタル酸、スルホテレフタル酸、４－スルホフタル酸、５－（４－スルホフェノキシ）イソフタル酸等のジカルボン酸又はそれらの塩と、エチレングリコール、プロピレングリコール、１，４－ブタンジオール、１，６－ヘキサンジオール、ジエチレングリコール、ネオペンチルグリコール等の低分子ポリオールとを反応させて得られるポリエステルポリオールなどが挙げられる。 Examples of the polyol having a sulfonic acid group as a hydrophilic group include dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5- (4-sulfophenoxy) isophthalic acid, or salts thereof. Examples thereof include polyester polyols obtained by reacting low molecular polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and neopentyl glycol.
　前記アニオン性基の一部又は全部を、塩基性化合物によって中和することで、前記ウレタン樹脂（Ｂ）に良好な水分散性を付与できることから好ましい。 It is preferable because a part of or all of the anionic group can be neutralized with a basic compound to impart good water dispersibility to the urethane resin (B).
　前記塩基性化合物としては、例えば、アンモニア；トリエチルアミン、モルホリン、モノエタノールアミン、ジエチルエタノールアミン等の有機アミン；水酸化ナトリウム、水酸化カリウム、水酸化リチウム等の金属水酸化物などが挙げられる。本発明の水性樹脂組成物の水分散安定性をより向上できることから、前記塩基性化合物の使用量は、塩基性化合物とアニオン性基とのモル比［塩基性化合物／アニオン性基］で、０．５～３の範囲が好ましく、０．７～１．５の範囲がより好ましい。 Examples of the basic compound include ammonia; organic amines such as triethylamine, morpholine, monoethanolamine, and diethylethanolamine; and metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide. Since the water dispersion stability of the aqueous resin composition of the present invention can be further improved, the amount of the basic compound used is 0 in terms of the molar ratio of the basic compound to the anionic group [basic compound / anionic group]. The range of 0.5 to 3 is preferable, and the range of 0.7 to 1.5 is more preferable.
　前記芳香族ポリエステルポリオールを製造する際のエステル化反応においては、エステル化反応を促進する目的で、エステル化触媒を用いることが好ましい。前記エステル化触媒としては、例えば、チタン、スズ、亜鉛、アルミニウム、ジルコニウム、マグネシウム、ハフニウム、ゲルマニウム等の金属；チタンテトライソプロポキシド、チタンテトラブトキシド、チタンオキシアセチルアセトナート、ジブチル錫オキサイド、ジブチル錫ジアセテート、ジブチル錫ジラウレート、オクタン酸錫、２－エチルヘキサンスズ、アセチルアセトナート亜鉛、４塩化ジルコニウム、４塩化ジルコニウムテトラヒドロフラン錯体、４塩化ハフニウム、４塩化ハフニウムテトラヒドロフラン錯体、酸化ゲルマニウム、テトラエトキシゲルマニウム等の金属化合物などが挙げられる。 In the esterification reaction when producing the aromatic polyester polyol, it is preferable to use an esterification catalyst for the purpose of promoting the esterification reaction. Examples of the esterification catalyst include metals such as titanium, tin, zinc, aluminum, zirconium, magnesium, hafnium, and germanium; titanium tetraisopropoxide, titanium tetrabutoxide, titanium oxyacetylacetonate, dibutyltin oxide, and dibutyltin. Such as diacetate, dibutyltin dilaurate, tin octoate, 2-ethylhexanetin, zinc acetylacetonate, zirconium tetrachloride, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride tetrahydrofuran complex, germanium oxide, tetraethoxy germanium, etc. A metal compound etc. are mentioned.
　前記ビスフェノールＡのアルキレンオキサイド付加物は、ビスフェノールＡが有するフェノール性水酸基にアルキレンオキサイドを付加したものである。前記アルキレンオキサイドとしては、エチレンオキサイド、プロピレンオキサイド等が挙げられる。また、１モルのビスフェノールＡに対するアルキレンオキサイドの平均付加モル数は、１～８の範囲が好ましく、１～４の範囲がより好ましい。 The alkylene oxide adduct of bisphenol A is obtained by adding alkylene oxide to the phenolic hydroxyl group of bisphenol A. Examples of the alkylene oxide include ethylene oxide and propylene oxide. The average number of moles of alkylene oxide added per mole of bisphenol A is preferably in the range of 1 to 8, and more preferably in the range of 1 to 4.
　本発明において、ポリオール（ｂ１）は、前記ポリオール（ｂ１－１）及び前記ポリオール（ｂ１－２）を必須成分として含有するが、それ以外のポリオール（ｂ１－３）を含有しても構わない。前記ポリオール（ｂ１－３）としては、例えば、脂肪族ポリエステルポリオール、脂肪族ポリカーボネートポリオール、脂肪族ポリエーテルポリオール、水添ビスフェノールのアルキレンオキサイド付加物等が挙げられる。また、前記ポリオール（ｂ１－３）として、前記芳香族ポリエステルポリオールの原料として挙げた前記多価アルコールを用いてもよい。これらのポリオール（ｂ１－３）は、単独で用いることも２種以上併用することもできる。 In the present invention, the polyol (b1) contains the polyol (b1-1) and the polyol (b1-2) as essential components, but may contain other polyols (b1-3). Examples of the polyol (b1-3) include aliphatic polyester polyols, aliphatic polycarbonate polyols, aliphatic polyether polyols, and alkylene oxide adducts of hydrogenated bisphenol. Further, as the polyol (b1-3), the polyhydric alcohol mentioned as the raw material for the aromatic polyester polyol may be used. These polyols (b1-3) can be used alone or in combination of two or more.
　また、ポリオール（ｂ１）中に含まれる芳香環を有するポリオール（ｂ１－１）の割合は、基材に対する密着性がより向上することから、４０～９８質量％の範囲が好ましく、６０～９８質量％の範囲がより好ましい。 Further, the ratio of the polyol (b1-1) having an aromatic ring contained in the polyol (b1) is preferably in the range of 40 to 98% by mass and more preferably in the range of 60 to 98% by mass because the adhesion to the substrate is further improved. % Range is more preferred.
　前記ウレタン樹脂（Ｂ）の原料となるポリイソシアネート（ｂ２）としては、例えば、４，４’－ジフェニルメタンジイソシアネート、２，４’－ジフェニルメタンジイソシアネート、カルボジイミド変性ジフェニルメタンジイソシアネート、クルードジフェニルメタンジイソシアネート、フェニレンジイソシアネート、トリレンジイソシアネート、ナフタレンジイソシアネート等の芳香族ポリイソシアネート；ヘキサメチレンジイソシアネート、リジンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート等の脂肪族ポリイソシアネート；シクロヘキサンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネート等が挙げられる。これらのポリイソシアネート（ｂ２）は、単独で用いることも２種以上併用することもできる。 Examples of the polyisocyanate (b2) used as a raw material for the urethane resin (B) include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, and tolylene diene. Examples include aromatic polyisocyanates such as isocyanate and naphthalene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate; cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate. These polyisocyanates (b2) can be used alone or in combination of two or more.
　前記ポリイソシアネート（ｂ２）の中でも、基材に対する密着性がより向上することから、芳香族ポリイソシアネートを含むものが好ましい。この際の前記ポリイソシアネート（ｂ２）中の芳香族ポリイソシアネートの含有量は、１５～３５質量％の範囲が好ましい。 Among the polyisocyanates (b2), those containing an aromatic polyisocyanate are preferable because adhesion to a substrate is further improved. In this case, the content of the aromatic polyisocyanate in the polyisocyanate (b2) is preferably in the range of 15 to 35% by mass.
　前記ウレタン樹脂（Ｂ）は、例えば、無溶剤下又は有機溶剤の存在下で、前記ポリオール（ｂ１）と前記ポリイソシアネート（ｂ２）とを混合し、４０～１２０℃の温度で、３～２０時間反応させることによって製造することができる。また、前記ウレタン樹脂（Ｂ）の製造の際に、必要に応じて鎖伸長剤を用いてもよい。 For example, the urethane resin (B) is prepared by mixing the polyol (b1) and the polyisocyanate (b2) in the absence of a solvent or in the presence of an organic solvent, and at a temperature of 40 to 120 ° C. for 3 to 20 hours. It can be produced by reacting. Moreover, when manufacturing the said urethane resin (B), you may use a chain extender as needed.
　前記ポリオール（ｂ１）と前記ポリイソシアネート（ｂ２）との反応は、前記ポリオール（ｂ１）が有する水酸基と、前記ポリイソシアネート（ｂ２）が有するイソシアネート基との当量比［イソシアネート基／水酸基］が、０．５～３．５の範囲で行うことが好ましく、０．９～２．５の範囲で行うことがより好ましい。 The reaction between the polyol (b1) and the polyisocyanate (b2) is such that the equivalent ratio [isocyanate group / hydroxyl group] of the hydroxyl group of the polyol (b1) and the isocyanate group of the polyisocyanate (b2) is 0. It is preferably carried out in the range of 5 to 3.5, more preferably in the range of 0.9 to 2.5.
　前記ウレタン樹脂（Ｂ）を製造する際に用いることのできる有機溶剤としては、例えば、アセトン、メチルエチルケトン等のケトン溶剤；テトラヒドロフラン、ジオキサン等のエーテル溶剤；酢酸エチル、酢酸ブチル等の酢酸エステル溶剤；アセトニトリル等のニトリル溶剤；ジメチルホルムアミド、Ｎ－メチルピロリドン等のアミド溶剤などが挙げられる。これらの有機溶剤は、単独で用いることも２種以上併用することもできる。 Examples of the organic solvent that can be used in producing the urethane resin (B) include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; acetate solvents such as ethyl acetate and butyl acetate; acetonitrile Nitrile solvents such as amide solvents such as dimethylformamide and N-methylpyrrolidone. These organic solvents can be used alone or in combination of two or more.
　上記の方法で得られる前記ウレタン樹脂（Ｂ）の重量平均分子量としては、基材と活性エネルギー線硬化性組成物の硬化塗膜との密着性がより向上することから、３，０００～２００，０００の範囲が好ましく、３，０００～１００，０００の範囲がより好ましい。 As the weight average molecular weight of the urethane resin (B) obtained by the above method, the adhesion between the substrate and the cured coating film of the active energy ray-curable composition is further improved. 000 is preferable, and a range of 3,000 to 100,000 is more preferable.
　水性媒体（Ｃ）としては、水、水と混和する有機溶剤、及び、これらの混合物が挙げられる。水と混和する有機溶剤としては、例えば、メタノール、エタノール、ｎ－プロパノール、イソプロパノール等のアルコール溶剤；アセトン、メチルエチルケトン等のケトン溶剤；エチレングリコール、ジエチレングリコール、プロピレングリコール等のポリアルキレングリコール；ポリアルキレングリコールのアルキルエーテル溶剤；Ｎ－メチル－２－ピロリドン等のラクタム溶剤などが挙げられる。これらの水と混和する有機溶剤は、単独で用いることも２種以上併用することもできる。 Examples of the aqueous medium (C) include water, organic solvents miscible with water, and mixtures thereof. Examples of organic solvents miscible with water include alcohol solvents such as methanol, ethanol, n-propanol, and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol, and propylene glycol; Alkyl ether solvents; lactam solvents such as N-methyl-2-pyrrolidone and the like. These water-miscible organic solvents can be used alone or in combination of two or more.
　また、前記水性媒体（Ｃ）としては、安全性や環境に対する負荷低減を考慮すると、水のみ、又は、水及び水と混和する有機溶剤との混合物が好ましく、水のみがより好ましい。 In addition, the aqueous medium (C) is preferably water alone or a mixture of water and an organic solvent miscible with water, more preferably water alone, in consideration of safety and environmental load reduction.
　前記水性媒体（Ｃ）の割合は、１０～９０質量％の範囲が好ましく、３０～７０質量％の範囲がより好ましい。 The ratio of the aqueous medium (C) is preferably in the range of 10 to 90% by mass, more preferably in the range of 30 to 70% by mass.
　水性樹脂組成物（Ｄ）は、前記水性媒体（Ｃ）中に、前記ビニルエステル樹脂（Ａ）及び前記ウレタン樹脂（Ｂ）を分散したものである。この際、前記ビニルエステル樹脂（Ａ）と前記ウレタン樹脂（Ｂ）とが、前記水性媒体（Ｃ）中で、別個の樹脂粒子として存在していてもよいが、前記ビニルエステル樹脂（Ａ）の一部又は全部が、前記ウレタン樹脂（Ｂ）粒子中に内在した樹脂粒子（Ｆ）を形成したものを用いることが好ましい。より具体的には、前記ビニルエステル樹脂（Ａ）がコア部を形成し、前記ウレタン樹脂（Ｂ）がシェル部を形成したコア・シェル型の樹脂粒子（Ｆ）であることが好ましい。 The aqueous resin composition (D) is obtained by dispersing the vinyl ester resin (A) and the urethane resin (B) in the aqueous medium (C). At this time, the vinyl ester resin (A) and the urethane resin (B) may exist as separate resin particles in the aqueous medium (C), but the vinyl ester resin (A) It is preferable to use a part or all of which formed resin particles (F) inherent in the urethane resin (B) particles. More specifically, it is preferable that the vinyl ester resin (A) is a core-shell type resin particle (F) in which a core part is formed and the urethane resin (B) is a shell part.
　前記樹脂粒子（Ｆ）は、前記ビニルエステル樹脂（Ａ）及び前記ウレタン樹脂（Ｂ）を予め製造しておき、次いで、前記ウレタン樹脂（Ｂ）に、前記ビニルエステル樹脂（Ａ）、前記ウレタン樹脂（Ｂ）が有するアニオン性基を中和する塩基性化合物及び前記水性媒体（Ｃ）を混合することによって製造することができる。 For the resin particles (F), the vinyl ester resin (A) and the urethane resin (B) are manufactured in advance, and then the vinyl resin (A) and the urethane resin are added to the urethane resin (B). It can manufacture by mixing the basic compound which neutralizes the anionic group which (B) has, and the said aqueous medium (C).
　前記方法で得られた水性樹脂組成物（Ｄ）中に有機溶剤が含まれる場合には、安全性や環境に対する負荷低減を図るため、蒸留法等によって前記有機溶剤を除去してもよい。これにより、水性媒体（Ｃ）中に前記樹脂粒子（Ｆ）が分散した水性樹脂組成物（Ｄ）を得ることができる。 When the aqueous resin composition (D) obtained by the above method contains an organic solvent, the organic solvent may be removed by a distillation method or the like in order to reduce safety and environmental burden. Thereby, the aqueous resin composition (D) in which the resin particles (F) are dispersed in the aqueous medium (C) can be obtained.
　前記ビニルエステル樹脂（Ａ）と前記ウレタン樹脂（Ｂ）との質量割合［（Ａ）／（Ｂ）］は、活性エネルギー線硬化性組成物の硬化塗膜との密着性がより向上することから、６０／４０～１０／９０の範囲が好ましく、５５／４５～２０／８０の範囲がより好ましい。なお、この範囲は、前記ビニルエステル樹脂（Ａ）及び前記ウレタン樹脂（Ｂ）を前記樹脂粒子（Ｆ）として用いる場合も同様である。 Since the mass ratio [(A) / (B)] of the vinyl ester resin (A) and the urethane resin (B) improves the adhesion with the cured coating film of the active energy ray-curable composition. The range of 60/40 to 10/90 is preferable, and the range of 55/45 to 20/80 is more preferable. This range is the same when the vinyl ester resin (A) and the urethane resin (B) are used as the resin particles (F).
　また、前記水性樹脂組成物（Ｄ）全量中の前記ビニルエステル樹脂（Ａ）及び前記ウレタン樹脂（Ｂ）の合計量の割合は、１０～９０質量％の範囲が好ましく、３０～７０質量％の範囲がより好ましい。 The ratio of the total amount of the vinyl ester resin (A) and the urethane resin (B) in the total amount of the aqueous resin composition (D) is preferably in the range of 10 to 90% by mass, and preferably 30 to 70% by mass. A range is more preferred.
　前記水性樹脂組成物（Ｄ）には、必要に応じて、造膜助剤、硬化剤、可塑剤、帯電防止剤、ワックス、光安定剤、流動調整剤、染料、レベリング剤、レオロジーコントロール剤、紫外線吸収剤、酸化防止剤、光触媒性化合物、無機顔料、有機顔料、体質顔料等の添加剤；ポリエステル樹脂、ウレタン樹脂、アクリル樹脂等のその他の樹脂などを配合することができる。 In the aqueous resin composition (D), if necessary, a film-forming aid, a curing agent, a plasticizer, an antistatic agent, a wax, a light stabilizer, a flow regulator, a dye, a leveling agent, a rheology control agent, Additives such as ultraviolet absorbers, antioxidants, photocatalytic compounds, inorganic pigments, organic pigments and extender pigments; other resins such as polyester resins, urethane resins and acrylic resins can be blended.
　本発明のコーティング剤は、カルボジイミド系架橋剤（Ｅ）を必須成分とする。前記架橋剤（Ｅ）が有するカルボジイミド基は、前記ウレタン樹脂（Ｂ）が有するカルボキシル基等の親水性基と反応して３次元の架橋構造を形成することで、基材と活性エネルギー線硬化性組成物の硬化塗膜との密着性を向上させ、また、本発明のコーティング剤をプライマーとして用いた場合に、形成されるプライマー層に耐湿熱試験後の高い密着性及び優れた耐薬品性を付与することができる。 The coating agent of the present invention contains a carbodiimide-based crosslinking agent (E) as an essential component. The carbodiimide group possessed by the crosslinking agent (E) reacts with a hydrophilic group such as a carboxyl group possessed by the urethane resin (B) to form a three-dimensional crosslinked structure. The adhesion of the composition to the cured coating film is improved, and when the coating agent of the present invention is used as a primer, the primer layer to be formed has high adhesion after a heat and humidity test and excellent chemical resistance. Can be granted.
　前記架橋剤（Ｅ）としては、カルボジイミド基を２つ以上有するものが好ましく、このようなものとしては、例えば、ポリ（４，４’－ジフェニルメタンカルボジイミド）、ポリ（ｐ－フェニレンカルボジイミド）、ポリ（ｍ－フェニレンカルボジイミド）、ポリ（ジイソプロピルフェニルカルボジイミド）、ポリ（トリイソプロピルフェニルカルボジイミド）等の芳香族ポリカルボジイミド；ポリ（ジシクロヘキシルメタンカルボジイミド）等の脂環族ポリカルボジイミド、ポリ（ジイソプロピルカルボジイミド）等の脂肪族ポリカルボジイミドなどが挙げられる。 The crosslinking agent (E) preferably has two or more carbodiimide groups. Examples of such a crosslinking agent (E) include poly (4,4′-diphenylmethanecarbodiimide), poly (p-phenylenecarbodiimide), poly ( m-phenylenecarbodiimide), poly (diisopropylphenylcarbodiimide), poly (triisopropylphenylcarbodiimide) and other aromatic polycarbodiimides; poly (dicyclohexylmethanecarbodiimide) and other alicyclic polycarbodiimides, poly (diisopropylcarbodiimide) and other aliphatics Examples thereof include polycarbodiimide.
　また、前記架橋剤（Ｅ）としては、本発明のコーティング剤が、前記ビニルエステル樹脂（Ａ）及び前記ウレタン樹脂（Ｂ）を水性媒体（Ｃ）中に分散したものであることから、水溶性または水分散性（エマルジョン型）があるものが好ましい。 Moreover, as said crosslinking agent (E), since the coating agent of this invention disperse | distributes the said vinyl ester resin (A) and the said urethane resin (B) in the aqueous medium (C), it is water-soluble. Or what has water dispersibility (emulsion type) is preferable.
　前記架橋剤（Ｅ）として用いることのできる市販品としては、日清紡ケミカル株式会社製の「カルボジライトＳＶ－０２」、「カルボジライトＶ－０２」、「カルボジライトＶ－０２－Ｌ２」、「カルボジライトＶ－０４」、「カルボジライトＥ－０１」、「カルボジライトＥ－０２」等が挙げられる。 Commercially available products that can be used as the crosslinking agent (E) include “Carbodilite SV-02”, “Carbodilite V-02”, “Carbodilite V-02-L2”, and “Carbodilite V-04” manufactured by Nisshinbo Chemical Co., Ltd. ”,“ Carbodilite E-01 ”,“ Carbodilite E-02 ”and the like.
　前記架橋剤（Ｅ）の使用量は、十分な架橋性能を発現することから、カルボジイミド基と反応可能な前記ウレタン樹脂（Ｂ）が有する親水性基の８０～１００モル％と反応する量であることが好ましく、１００モル％と反応する量であることがより好ましい。 The amount of the crosslinking agent (E) used is an amount that reacts with 80 to 100 mol% of the hydrophilic group of the urethane resin (B) that can react with the carbodiimide group, since sufficient crosslinking performance is exhibited. The amount reacting with 100 mol% is more preferable.
　また、前記架橋剤（Ｅ）は、密着性や前記水性樹脂組成物（Ｄ）との保存安定性が向上することから、前記水性樹脂組成物（Ｄ）に対して３～５質量％の範囲で添加することが好ましい。 Further, the crosslinking agent (E) improves adhesion and storage stability with the aqueous resin composition (D). Therefore, the crosslinking agent (E) is in the range of 3 to 5% by mass with respect to the aqueous resin composition (D). It is preferable to add at.
　本発明の積層体は、上記で説明した本発明のコーティング剤を用いて形成したプライマー層を有し、前記プライマー層の表面に活性エネルギー線硬化性組成物を用いて形成した硬化塗膜を有するものである。 The laminate of the present invention has a primer layer formed using the coating agent of the present invention described above, and has a cured coating film formed using an active energy ray-curable composition on the surface of the primer layer. Is.
　前記活性エネルギー線硬化性組成物としては、重合性不飽和基を有する樹脂と、重合性不飽和基を有する単量体とを含有するものが好ましく、これら重合性不飽和基を有する樹脂及び重合性不飽和基を有する単量体の種類は、前記活性エネルギー線硬化性組成物の硬化塗膜に要求される特性に応じて、適宜選択することが好ましい。 The active energy ray-curable composition preferably contains a resin having a polymerizable unsaturated group and a monomer having a polymerizable unsaturated group. The type of the monomer having a polymerizable unsaturated group is preferably appropriately selected according to the properties required for the cured coating film of the active energy ray-curable composition.
　前記重合性不飽和基を有する樹脂としては、ウレタン（メタ）アクリレート樹脂、不飽和ポリエステル樹脂、エポキシ（メタ）アクリレート樹脂、ポリエステル（メタ）アクリレート樹脂、アクリル（メタ）アクリレート樹脂、マレイミド基を有する樹脂等が挙げられる。これらの重合性不飽和基を有する樹脂は、単独で用いることも２種以上併用することもできる。 Examples of the resin having a polymerizable unsaturated group include urethane (meth) acrylate resin, unsaturated polyester resin, epoxy (meth) acrylate resin, polyester (meth) acrylate resin, acrylic (meth) acrylate resin, and resin having maleimide group. Etc. These resins having a polymerizable unsaturated group can be used alone or in combination of two or more.
　本発明において、「（メタ）アクリレート」とは、アクリレート及びメタクリレートの一方又は両方をいい、「（メタ）アクリロイル基」とは、アクリロイル基及びメタクリロイル基の一方又は両方をいう。 In the present invention, “(meth) acrylate” refers to one or both of acrylate and methacrylate, and “(meth) acryloyl group” refers to one or both of acryloyl group and methacryloyl group.
　前記ウレタン（メタ）アクリレート樹脂としては、例えば、脂肪族ポリイソシアネート又は芳香族ポリイソシアネートと、水酸基を有する（メタ）アクリレートとをウレタン化反応させて得られるウレタン結合と（メタ）アクリロイル基とを有する樹脂等が挙げられる。 Examples of the urethane (meth) acrylate resin include a urethane bond and a (meth) acryloyl group obtained by urethanization reaction of an aliphatic polyisocyanate or an aromatic polyisocyanate with a (meth) acrylate having a hydroxyl group. Examples thereof include resins.
　前記脂肪族ポリイソシアネートとしては、例えば、テトラメチレンジイソシアネート、ペンタメチレンジイソシアネート、ヘキサメチレンジイソシアネート、ヘプタメチレンジイソシアネート、オクタメチレンジイソシアネート、デカメチレンジイソシアネート、２－メチル－１，５－ペンタンジイソシアネート、３－メチル－１，５－ペンタンジイソシアネート、ドデカメチレンジイソシアネート、２－メチルペンタメチレンジイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート、イソホロンジイソシアネート、ノルボルナンジイソシアネート、水素添加ジフェニルメタンジイソシアネート、水素添加トリレンジイソシアネート、水素添加キシリレンジイソシアネート、水素添加テトラメチルキシリレンジイソシアネート、シクロヘキシルジイソシアネート等が挙げられる。また、前記芳香族ポリイソシアネートとしては、トリレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、１，５－ナフタレンジイソシアネート、トリジンジイソシアネート、ｐ－フェニレンジイソシアネート等が挙げられる。 Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1 , 5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, Hydrogenated tolylene diisocyanate, hydrogenated xylylene diene Isocyanate, hydrogenated tetramethylxylylene diisocyanate, cyclohexyl diisocyanate, and the like. Examples of the aromatic polyisocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, and the like.
　前記水酸基を有する（メタ）アクリレートとしては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、１，５－ペンタンジオールモノ（メタ）アクリレート、１，６－ヘキサンジオールモノ（メタ）アクリレート、ネオペンチルグリコールモノ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールモノ（メタ）アクリレート等の２価アルコールのモノ（メタ）アクリレート；トリメチロールプロパンジ（メタ）アクリレート、エトキシ化トリメチロールプロパン（メタ）アクリレート、プロポキシ化トリメチロールプロパンジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ビス（２－（メタ）アクリロイルオキシエチル）ヒドロキシエチルイソシアヌレート等の３価のアルコールのモノ又はジ（メタ）アクリレート、あるいは、これらのアルコール性水酸基の一部をε－カプロラクトンで変性した水酸基を有するモノ及びジ（メタ）アクリレート；ペンタエリスリトールトリ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート等の１官能の水酸基と３官能以上の（メタ）アクリロイル基を有する化合物、あるいは、該化合物をさらにε－カプロラクトンで変性した水酸基を有する多官能（メタ）アクリレート；ジプロピレングリコールモノ（メタ）アクリレート、ジエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート等のオキシアルキレン鎖を有する（メタ）アクリレート化合物；ポリエチレングリコール－ポリプロピレングリコールモノ（メタ）アクリレート、ポリオキシブチレン－ポリオキシプロピレンモノ（メタ）アクリレート等のブロック構造のオキシアルキレン鎖を有する（メタ）アクリレート化合物；ポリ（エチレングリコール－テトラメチレングリコール）モノ（メタ）アクリレート、ポリ（プロピレングリコール－テトラメチレングリコール）モノ（メタ）アクリレート等のランダム構造のオキシアルキレン鎖を有する（メタ）アクリレート化合物などが挙げられる。 Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1 Monohydric alcohols such as 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, and hydroxypivalate neopentyl glycol mono (meth) acrylate (Meth) acrylate; trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerin di (meth) Mono- or di (meth) acrylates of trivalent alcohols such as acrylate and bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or hydroxyl groups obtained by modifying some of these alcoholic hydroxyl groups with ε-caprolactone Mono- and di (meth) acrylates having a monofunctional hydroxyl group and tri- or more functional (meth) acryloyl such as pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. A compound having a group, or a polyfunctional (meth) acrylate having a hydroxyl group obtained by modifying the compound with ε-caprolactone; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, (Meth) acrylate compounds having an oxyalkylene chain such as propylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate; polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-polyoxypropylene mono (meth) (Meth) acrylate compounds having block structure oxyalkylene chains such as acrylate; random structures such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate And (meth) acrylate compounds having an oxyalkylene chain.
　前記不飽和ポリエステル樹脂は、α，β－不飽和二塩基酸又はその酸無水物、芳香族飽和二塩基酸又はその酸無水物、及び、グリコールの重縮合によって得られる硬化性樹脂である。前記α，β－不飽和二塩基酸又はその酸無水物としては、例えば、マレイン酸、無水マレイン酸、フマル酸、イタコン酸、シトラコン酸、クロロマレイン酸、及びこれらのエステル等が挙げられる。前記芳香族飽和二塩基酸又はその酸無水物としては、フタル酸、無水フタル酸、イソフタル酸、テレフタル酸、ニトロフタル酸、テトラヒドロ無水フタル酸、エンドメチレンテトラヒドロ無水フタル酸、ハロゲン化無水フタル酸及びこれらのエステル等が挙げられる。脂肪族あるいは脂環族飽和二塩基酸としては、シュウ酸、マロン酸、コハク酸、アジピン酸、セバシン酸、アゼライン酸、グルタル酸、ヘキサヒドロ無水フタル酸及びこれらのエステル等が挙げられる。前記グリコールとしては、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、１，３－ブタンジオール、１，４－ブタンジオール、２－メチルプロパン－１，３－ジオール、ネオペンチルグリコール、トリエチレングリコール、テトラエチレングリコール、１，５－ペンタンジオール、１，６－ヘキサンジオール、ビスフェノールＡ、水素化ビスフェノールＡ、エチレングリコールカーボネート、２，２－ジ－（４－ヒドロキシプロポキシジフェニル）プロパン等が挙げられ、その他にエチレンオキサイド、プロピレンオキサイド等の酸化物も同様に用いることができる。 The unsaturated polyester resin is a curable resin obtained by polycondensation of α, β-unsaturated dibasic acid or its acid anhydride, aromatic saturated dibasic acid or its acid anhydride, and glycol. Examples of the α, β-unsaturated dibasic acid or acid anhydrides thereof include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof. Examples of the aromatic saturated dibasic acid or acid anhydride thereof include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride, and the like. And the like. Examples of the aliphatic or alicyclic saturated dibasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof. Examples of the glycol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, Examples include tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl) propane, etc. In addition, oxides such as ethylene oxide and propylene oxide can be used in the same manner.
　前記エポキシ（メタ）アクリレート樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂等のエポキシ樹脂のエポキシ基に（メタ）アクリル酸を反応させて得られるものが挙げられる。 As the epoxy (meth) acrylate resin, (meth) acrylic acid is reacted with an epoxy group of an epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, or the like. What is obtained is mentioned.
　前記ポリエステル（メタ）アクリレート樹脂としては、例えば、ポリエステルポリオールの水酸基に（メタ）アクリル酸を反応させて得られるものが挙げられる。 Examples of the polyester (meth) acrylate resin include those obtained by reacting a hydroxyl group of a polyester polyol with (meth) acrylic acid.
　前記アクリル（メタ）アクリレート樹脂としては、例えば、グリシジルメタクリレート、及び必要に応じてアルキル（メタ）アクリレート等の（メタ）アクリレート単量体とを重合させて、エポキシ基を有するアクリル樹脂を得た後、そのエポキシ基に（メタ）アクリル酸を反応させて得られるものが挙げられる。 As said acrylic (meth) acrylate resin, after polymerizing (meth) acrylate monomers, such as glycidyl methacrylate and alkyl (meth) acrylate as needed, for example, after obtaining the acrylic resin which has an epoxy group And those obtained by reacting the epoxy group with (meth) acrylic acid.
　前記マレイミド基を有する樹脂としては、Ｎ－ヒドロキシエチルマレイミドとイソホロンジイソシアネートとをウレタン化して得られる２官能マレイミドウレタン化合物、マレイミド酢酸とポリテトラメチレングリコールとをエステル化して得られる２官能マレイミドエステル化合物、マレイミドカプロン酸とペンタエリスリトールのテトラエチレンオキサイド付加物とをエステル化して得られる４官能マレイミドエステル化合物、マレイミド酢酸と多価アルコール化合物とをエステル化して得られる多官能マレイミドエステル化合物等が挙げられる。 Examples of the resin having a maleimide group include a bifunctional maleimide urethane compound obtained by urethanizing N-hydroxyethylmaleimide and isophorone diisocyanate, a bifunctional maleimide ester compound obtained by esterifying maleimide acetic acid and polytetramethylene glycol, Examples thereof include a tetrafunctional maleimide ester compound obtained by esterification of maleimidocaproic acid and a tetraethylene oxide adduct of pentaerythritol, a polyfunctional maleimide ester compound obtained by esterification of maleimide acetic acid and a polyhydric alcohol compound, and the like.
　前記重合性不飽和基を有する単量体としては、例えば、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、数平均分子量が１５０～１０００の範囲にあるポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、数平均分子量が１５０～１０００の範囲にあるポリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，３－ブタンジオールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ヒドロキシピバリン酸エステルネオペンチルグリコールジ（メタ）アクリレート、ビスフェノールＡジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、メチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート等の脂肪族アルキル（メタ）アクリレート、グリセロール（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、３－クロロ－２－ヒドロキシプロピル（メタ）アクリレート、グリシジル（メタ）アクリレート、アリル（メタ）アクリレート、２－ブトキシエチル（メタ）アクリレート、２－（ジエチルアミノ）エチル（メタ）アクリレート、２－（ジメチルアミノ）エチル（メタ）アクリレート、γ－（メタ）アクリロキシプロピルトリメトキシシラン、２－メトキシエチル（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート、メトキシジプロピレングリコール（メタ）アクリレート、ノニルフェノキシポリエチレングリコール（メタ）アクリレート、ノニルフェノキシポリプロピレングリコール（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシジプロピレングルリコール（メタ）アクリレート、フェノキシポリプロピレングリコール（メタ）アクリレート、ポリブタジエン（メタ）アクリレート、ポリエチレングリコール－ポリプロピレングリコール（メタ）アクリレート、ポリエチレングリコール－ポリブチレングリコール（メタ）アクリレート、ポリスチリルエチル（メタ）アクリレート、ベンジル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、メトキシ化シクロデカトリエン（メタ）アクリレート、フェニル（メタ）アクリレート；マレイミド、Ｎ－メチルマレイミド、Ｎ－エチルマレイミド、Ｎ－プロピルマレイミド、Ｎ－ブチルマレイミド、Ｎ－ヘキシルマレイミド、Ｎ－オクチルマレイミド、Ｎ－ドデシルマレイミド、Ｎ－ステアリルマレイミド、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド、２－マレイミドエチル－エチルカーボネート、２－マレイミドエチル－プロピルカーボネート、Ｎ－エチル－（２－マレイミドエチル）カーバメート、Ｎ，Ｎ－ヘキサメチレンビスマレイミド、ポリプロピレングリコール－ビス（３－マレイミドプロピル）エーテル、ビス（２－マレイミドエチル）カーボネート、１，４－ジマレイミドシクロヘキサン等のマレイミド化合物などが挙げられる。これらの重合性不飽和基を有する単量体は、単独で用いることも２種以上併用することもできる。 Examples of the monomer having a polymerizable unsaturated group include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and a number average molecular weight in the range of 150 to 1,000. Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (number average molecular weight in the range of 150 to 1000) (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di ( Acrylate), hydroxypivalate ester neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tetra (meth) acrylate , Pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dicyclopentenyl (meth) acrylate, methyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) ) Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate Lilate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, aliphatic alkyl (meth) acrylate such as isostearyl (meth) acrylate, glycerol (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 3-chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, 2- (dimethyl Amino) ethyl (meth) acrylate, γ- (meth) acryloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxydipro Lenglycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydipropylene glycolicol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, Polybutadiene (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polystyrylethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopenta Nyl (meth) acrylate, dicyclopentenyl (meth) acrelane , Isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, phenyl (meth) acrylate; maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-stearylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimidoethyl-ethylcarbonate, 2-maleimidoethyl-propylcarbonate, N-ethyl- (2-maleimidoethyl ) Carbamate, N, N-hexamethylene bismaleimide, polypropylene glycol-bis (3-maleimidopropyl) ether, bis (2-maleimidoethyl) carbonate, 1,4-dimale And maleimide compounds such as imidocyclohexane. These monomers having a polymerizable unsaturated group can be used alone or in combination of two or more.
　前記活性エネルギー線硬化性組成物は、基材等に塗布後、活性エネルギー線を照射することで硬化塗膜とすることができる。この活性エネルギー線としては、紫外線、電子線、α線、β線、γ線等の電離放射線が挙げられる。活性エネルギー線として紫外線を照射して、前記活性エネルギー線硬化性組成物を硬化塗膜とする場合には、前記活性エネルギー線硬化性組成物中に光重合開始剤を添加し、硬化性を向上することが好ましい。また、必要であればさらに光増感剤を添加して、硬化性を向上することもできる。一方、活性エネルギー線として電子線、α線、β線又はγ線を照射して、前記活性エネルギー線硬化性組成物を硬化塗膜とする場合には、光重合開始剤や光増感剤を用いなくても速やかに硬化するため、光重合開始剤や光増感剤を添加する必要はない。 The active energy ray-curable composition can be formed into a cured coating film by irradiating active energy rays after being applied to a substrate or the like. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When the active energy ray-curable composition is used as a cured coating by irradiating ultraviolet rays as active energy rays, a photopolymerization initiator is added to the active energy ray-curable composition to improve curability. It is preferable to do. Further, if necessary, a photosensitizer can be further added to improve curability. On the other hand, when irradiating an active energy ray with electron beam, α ray, β ray or γ ray to make the active energy ray curable composition as a cured coating film, a photopolymerization initiator or a photosensitizer is used. Since it cures quickly even if it is not used, it is not necessary to add a photopolymerization initiator or a photosensitizer.
　前記光重合開始剤としては、例えば、１－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－メチル－１－プロパン－１－オン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド等が挙げられる。 Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) -phenyl] -2. -Hydroxy-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.
　前記光増感剤としては、例えば、脂肪族アミン、芳香族アミン等のアミン化合物、ｏ－トリルチオ尿素等の尿素化合物、ナトリウムジエチルジチオホスフェート、ｓ－ベンジルイソチウロニウム－ｐ－トルエンスルホネート等の硫黄化合物などが挙げられる。 Examples of the photosensitizer include amine compounds such as aliphatic amines and aromatic amines, urea compounds such as o-tolylthiourea, sulfur such as sodium diethyldithiophosphate, s-benzylisothiuronium-p-toluenesulfonate, and the like. Compound etc. are mentioned.
　本発明の積層体に用いる基材としては、例えば、金属基材、プラスチック基材、ガラス基材、紙基材、木材基材、繊維質基材等が挙げられる。これらの基材の中でも、前記活性エネルギー線硬化性組成物の硬化塗膜と基材との密着性を向上するため、本発明の水性樹脂組成物をプライマーとして用いる場合は、プラスチック基材が好適である。 Examples of the substrate used in the laminate of the present invention include a metal substrate, a plastic substrate, a glass substrate, a paper substrate, a wood substrate, and a fibrous substrate. Among these base materials, a plastic base material is preferable when the aqueous resin composition of the present invention is used as a primer in order to improve the adhesion between the cured coating film of the active energy ray-curable composition and the base material. It is.
　前記プラスチック基材の材質としては、ポリエステル、アクリル樹脂（ポリメチルメタクリレート等）、ポリカーボネート、アクリロニトリル－ブタジエン－スチレン共重合体（ＡＢＳ樹脂）、ＡＢＳ樹脂とポリカーボネートとの複合樹脂、ポリスチレン、ポリウレタン、エポキシ樹脂、ポリ塩化ビニル、ポリアミド、ポリオレフィン（ポリエチレン、ポリプロピレン、ポリシクロオレフィン（ＣＯＰ）等）、トリアセチルセルロース（ＴＡＣ）等が挙げられる。 Materials for the plastic substrate include polyester, acrylic resin (polymethyl methacrylate, etc.), polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS resin), composite resin of ABS resin and polycarbonate, polystyrene, polyurethane, epoxy resin , Polyvinyl chloride, polyamide, polyolefin (polyethylene, polypropylene, polycycloolefin (COP), etc.), triacetyl cellulose (TAC), and the like.
　本発明のコーティング剤は、上記のプラスチック基材の中でも、ポリエステル基材のプライマーとして、非常に有用である。前記ポリエステルの具体例としては、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）等が挙げられる。 The coating agent of the present invention is very useful as a primer for a polyester base material among the above plastic base materials. Specific examples of the polyester include polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).
　前記プラスチック基材としては、例えば、携帯電話、家電製品、自動車内外装材、ＯＡ機器等のプラスチック成形品が挙げられる。また、プラスチックを素材としたフィルム基材も挙げられる。フィルム基材を本発明の積層体の基材とする場合には、反射防止フィルム、位相差フィルム、プリズムレンズシート等の光学フィルム；アルミ蒸着フィルム等の食品包装などの高機能フィルムに用いることができる。 Examples of the plastic substrate include plastic molded products such as mobile phones, home appliances, automobile interior and exterior materials, and OA equipment. Moreover, the film base material which used the plastic as a raw material is also mentioned. When the film substrate is used as the substrate of the laminate of the present invention, it can be used for optical films such as antireflection films, retardation films, and prism lens sheets; and high-performance films such as food packaging such as aluminum vapor deposition films. it can.
　また、本発明の積層体を反射防止フィルム、位相差フィルム、プリズムレンズシート等の光学フィルムとする場合には、液晶ディスプレイ（ＬＣＤ）、有機ＥＬディスプレイ（ＯＬＥＤ）、プラズマディスプレイ（ＰＤＰ）等の各種画面表示装置の部材として用いることができる。 Further, when the laminate of the present invention is used as an optical film such as an antireflection film, a retardation film, or a prism lens sheet, various kinds of liquid crystal display (LCD), organic EL display (OLED), plasma display (PDP), etc. It can be used as a member of a screen display device.
　本発明のコーティング剤は、例えば、前記基材の表面に直接、塗布し、次いで、乾燥、硬化させることによって、基材の表面に塗膜を形成することができる。本発明のコーティング剤を乾燥し硬化を進行させる方法としては、常温下で１～１０日程度養生する方法であってもよいが、硬化を迅速に進行させることができるから、１００℃～１５０℃の温度で、１～６００秒程度加熱する方法が好ましい。また、比較的高温で変形や変色をしやすいプラスチック基材を用いる場合には、７０℃～１００℃程度の比較的低温で加熱することが好ましい。 The coating agent of the present invention can form a coating film on the surface of the substrate by, for example, directly applying to the surface of the substrate and then drying and curing. The method of drying the coating agent of the present invention and allowing the curing to proceed may be a method of curing at room temperature for about 1 to 10 days. However, since the curing can proceed rapidly, 100 ° C. to 150 ° C. A method of heating at a temperature of about 1 to 600 seconds is preferable. In addition, when using a plastic substrate that is easily deformed or discolored at a relatively high temperature, it is preferable to heat at a relatively low temperature of about 70 ° C. to 100 ° C.
　前記基材の表面に、本発明のコーティング剤を塗布する方法としては、例えば、グラビアコーター、ロールコーター、コンマコーター、ナイフコーター、エアナイフコーター、カーテンコーター、キスコーター、シャワーコーター、フローコーター、スピンコーター、ディッピング、スクリーン印刷、スプレー、刷毛塗り、アプリケーター、バーコーター等を用いた塗布方法が挙げられる。 Examples of the method for applying the coating agent of the present invention to the surface of the substrate include a gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, flow coater, spin coater, Examples of the application method include dipping, screen printing, spraying, brush coating, applicator, and bar coater.
　本発明のコーティング剤を用いて形成する塗膜の膜厚は、使用される用途に応じて適宜調整可能であるが、通常は、０．０１～２０μｍの範囲であることが好ましい。 The film thickness of the coating film formed using the coating agent of the present invention can be appropriately adjusted according to the intended use, but is usually preferably in the range of 0.01 to 20 μm.
　本発明の積層体は、上記のようにして得られた本発明のコーティング剤の塗膜であるプライマー層の表面に、さらに、前記活性エネルギー線硬化性組成物を塗布し、活性エネルギー線を照射することにより、前記活性エネルギー線硬化性組成物の硬化塗膜を形成することにより得ることができる。なお、前記活性エネルギー線硬化性組成物の塗布方法は、上記の本発明のコーティング剤の塗布方法と同じ方法を用いることができる。 The laminate of the present invention is further coated with the active energy ray-curable composition on the surface of the primer layer, which is the coating film of the coating agent of the present invention obtained as described above, and irradiated with active energy rays. By doing, it can obtain by forming the cured coating film of the said active energy ray curable composition. In addition, the coating method of the said active energy ray curable composition can use the same method as the coating method of the coating agent of said this invention.
　以下、本発明を実施例及び比較例により、具体的に説明する。 Hereinafter, the present invention will be specifically described by way of examples and comparative examples.
（合成例１：芳香族ポリエステルポリオール（１）の合成）
　温度計、窒素ガス導入管、攪拌機を備えた反応容器中で窒素ガスを導入しながら、イソフタル酸２７．６質量部、テレフタル酸２７．６質量部、ジエチレングリコール１９．９質量部及びジブチル錫オキサイド０．０３質量部を仕込み１８０～２３０℃で酸価が１以下になるまで２３０℃で２４時間重縮合反応を行い、芳香族ポリエステルポリオール（１）〔酸価０．６、水酸基価５０．０、芳香環濃度４．７７ｍｏｌ／Ｋｇ〕を得た。 (Synthesis Example 1: Synthesis of aromatic polyester polyol (1))
While introducing nitrogen gas in a reaction vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 27.6 parts by mass of isophthalic acid, 27.6 parts by mass of terephthalic acid, 19.9 parts by mass of diethylene glycol, and dibutyltin oxide 0 .03 parts by mass and carrying out a polycondensation reaction at 230 ° C. for 24 hours until the acid value becomes 1 or less at 180 to 230 ° C., the aromatic polyester polyol (1) [acid value 0.6, hydroxyl value 50.0, Aromatic ring concentration 4.77 mol / Kg] was obtained.
（製造例１：ビニルエステル樹脂（１）の合成）
　反応容器にクレゾールノボラック型エポキシ樹脂（ＤＩＣ株式会社製「ＥＰＩＣＬＯＮ　Ｎ－６７３－８０Ｍ」、固形分エポキシ当量：２０９ｇ／ｅｑ．、不揮発分：８０質量％、溶媒：メチルエチルケトン）を４６．７質量部、アクリル酸１３．３質量部、メトキノン０．０８質量部、メチルエチルケトン１３．３質量部を仕込み、攪拌させて均一に混合した。次いでトリフェニルホスフィン０．３７質量部を加え、反応温度８０℃下で酸価が１．５以下になるまで反応させて、ビニルエステル樹脂（１）の不揮発分７５質量％溶液を得た。 (Production Example 1: Synthesis of vinyl ester resin (1))
46.7 parts by mass of a cresol novolak type epoxy resin (“EPICLON N-673-80M” manufactured by DIC Corporation, solid content epoxy equivalent: 209 g / eq., Nonvolatile content: 80% by mass, solvent: methyl ethyl ketone) in a reaction vessel, Acrylic acid (13.3 parts by mass), methoquinone (0.08 parts by mass), and methyl ethyl ketone (13.3 parts by mass) were charged and mixed uniformly. Next, 0.37 parts by mass of triphenylphosphine was added and reacted at a reaction temperature of 80 ° C. until the acid value became 1.5 or less to obtain a 75% by mass solution of a vinyl ester resin (1) with a nonvolatile content.
　製造例１で合成したビニルエステル樹脂（１）の原料を表１に示す。 Table 1 shows the raw materials for the vinyl ester resin (1) synthesized in Production Example 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
（製造例２：芳香環を有するウレタン樹脂（１）の合成）
　反応容器に合成例１で得られた芳香族ポリエステルポリオール（１）１００．０質量部を減圧下１００℃で脱水し、その後８０℃まで冷却後、メチルエチルケトン６６．６質量部を加え、攪拌し均一に混合した。次に、２，２’－ジメチロールプロピオン酸６．１質量部を加え、次いでイソホロンジイソシアネート２３．１質量部を加えて、８０℃で１２時間反応させ、ウレタン化工程を実施した。イソシアネート値が０．１％以下になったのを確認し、ｎ－ブタノール３質量部を加え、さらに２時間反応させた後、５０℃まで冷却し、芳香環を有するウレタン樹脂（１）の不揮発分６５質量％溶液を得た。 (Production Example 2: Synthesis of urethane resin (1) having an aromatic ring)
In a reaction vessel, 100.0 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1 was dehydrated at 100 ° C. under reduced pressure, and after cooling to 80 ° C., 66.6 parts by mass of methyl ethyl ketone was added and stirred to be uniform. Mixed. Next, 6.1 parts by mass of 2,2′-dimethylolpropionic acid was added, and then 23.1 parts by mass of isophorone diisocyanate was added and reacted at 80 ° C. for 12 hours to carry out a urethanization step. After confirming that the isocyanate value was 0.1% or less, 3 parts by mass of n-butanol was added, and the mixture was further reacted for 2 hours, then cooled to 50 ° C., and the non-volatile urethane resin (1) having an aromatic ring A 65% by weight solution was obtained.
（調整例１：水性樹脂組成物（１）の調製）
　製造例２で得られた芳香環を有するウレタン樹脂（１）の不揮発分６５質量％溶液１４７．７質量部（前記ウレタン樹脂（１）として９６質量部）に、製造例１で得られたビニルエステル樹脂（１）の不揮発分７５質量％溶液１２８．０質量部（前記ビニルエステル樹脂（１）として９６質量部）、トリエチルアミン５．５質量部を加え、イオン交換水９３８．５質量部をゆっくりと添加し水溶化を実施した。次いで減圧下、３０～５０℃にてメチルエチルケトンを除去し、不揮発分４０質量％の水性樹脂組成物（１）を得た。 (Preparation Example 1: Preparation of aqueous resin composition (1))
Vinyl obtained in Production Example 1 into 147.7 parts by mass of a 65% by mass nonvolatile solution of urethane resin (1) having an aromatic ring obtained in Production Example 2 (96 parts by mass as urethane resin (1)). Add 128.0 parts by mass of a non-volatile content 75% by mass solution of ester resin (1) (96 parts by mass as vinyl ester resin (1)), 5.5 parts by mass of triethylamine, and slowly add 938.5 parts by mass of ion-exchanged water. And water solubilization was carried out. Next, methyl ethyl ketone was removed under reduced pressure at 30 to 50 ° C. to obtain an aqueous resin composition (1) having a nonvolatile content of 40% by mass.
　実施例１～９で得られた水性樹脂組成物（１）の組成を表２に示す。なお、表中の組成は不揮発分量（樹脂のみの量）を表す。 Table 2 shows the compositions of the aqueous resin compositions (1) obtained in Examples 1 to 9. The composition in the table represents the nonvolatile content (amount of resin alone).
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
（調製例２：紫外線硬化性組成物（ＵＶ－１）の調製）
　ウレタンアクリレート樹脂（ＤＩＣ株式会社製「ユニディックＶ－４２６０」）５０質量部、トリプロピレングリコールジアクリレート５０質量部及び光重合開始剤（ＢＡＳＦジャパン株式会社製「イルガキュア１８４」、１－ヒドロキシシクロヘキシルフェニルケトン）３質量部を混合することによって、紫外線硬化性組成物（ＵＶ－１）を得た。 (Preparation Example 2: Preparation of UV curable composition (UV-1))
50 parts by mass of urethane acrylate resin (“Unidic V-4260” manufactured by DIC Corporation), 50 parts by mass of tripropylene glycol diacrylate, and photopolymerization initiator (“Irgacure 184” manufactured by BASF Japan Ltd., 1-hydroxycyclohexyl phenyl ketone ) An ultraviolet curable composition (UV-1) was obtained by mixing 3 parts by mass.
（調製例３：紫外線硬化性組成物（ＵＶ－２）の調製）
　エポキシアクリレート樹脂（ＤＩＣ株式会社製「ユニディックＶ－５５００」）５０質量部、トリプロピレングリコールジアクリレート５０質量部及び光重合開始剤（ＢＡＳＦジャパン株式会社製「イルガキュア１８４」）３質量部を混合することによって、紫外線硬化性組成物（ＵＶ－２）を得た。 (Preparation Example 3: Preparation of UV curable composition (UV-2))
50 parts by mass of an epoxy acrylate resin (“Unidic V-5500” manufactured by DIC Corporation), 50 parts by mass of tripropylene glycol diacrylate, and 3 parts by mass of a photopolymerization initiator (“Irgacure 184” manufactured by BASF Japan Ltd.) are mixed. As a result, an ultraviolet curable composition (UV-2) was obtained.
（実施例１：プライマー（１）の作製）
　調製例１で得られた水性樹脂組成物（１）１００質量部と、カルボジイミド架橋剤（日清紡ケミカル株式会社製「カルボジライトＥ－０２」）２．８質量部と、イオン交換水５９３質量部とを混合することによってプライマー（Ｐ－１）を得た。 (Example 1: Preparation of primer (1))
100 parts by mass of the aqueous resin composition (1) obtained in Preparation Example 1, 2.8 parts by mass of a carbodiimide crosslinking agent (“Carbodilite E-02” manufactured by Nisshinbo Chemical Co., Ltd.), and 593 parts by mass of ion-exchanged water The primer (P-1) was obtained by mixing.
（実施例２：プライマー（２）の作製）
　調製例１で得られた水性樹脂組成物（１）１００質量部と、カルボジイミド架橋剤（日清紡ケミカル株式会社製「カルボジライトＶ－０２」）２．８質量部と、イオン交換水５８９質量部とを混合することによってプライマー（Ｐ－２）を得た。 (Example 2: Preparation of primer (2))
100 parts by mass of the aqueous resin composition (1) obtained in Preparation Example 1, 2.8 parts by mass of a carbodiimide crosslinking agent (“Carbodilite V-02” manufactured by Nisshinbo Chemical Co., Ltd.), and 589 parts by mass of ion-exchanged water The primer (P-2) was obtained by mixing.
（実施例３：プライマー（３）の作製）
　調製例１で得られた水性樹脂組成物（１）１００質量部と、カルボジイミド架橋剤（日清紡ケミカル株式会社製「カルボジライトＳＶ－０２」）２．８質量部と、イオン交換水５９３質量部とを混合することによってプライマー（Ｐ－３）を得た。 (Example 3: Preparation of primer (3))
100 parts by mass of the aqueous resin composition (1) obtained in Preparation Example 1, 2.8 parts by mass of a carbodiimide crosslinking agent (“Carbodilite SV-02” manufactured by Nisshinbo Chemical Co., Ltd.), and 593 parts by mass of ion-exchanged water A primer (P-3) was obtained by mixing.
（実施例４：積層体（１）の作製）
　ポリエチレンテレフタレート（以下、「ＰＥＴ」と略記する。）製フィルム基材（厚さ１２５μｍ）の表面に、乾燥後の膜厚が約１μｍとなるように、実施例１で得られたプライマー（Ｐ－１）を塗布し、１５０℃で５分間加熱することによって、前記基材の表面にプライマー層を形成した。次いで、前記プライマー層の表面に、調整例２で得られた紫外線硬化性組成物（ＵＶ－１）を、１５μｍの塗布厚で塗布し、その塗布面に、高圧水銀灯を光源として、照射強度０．５Ｊ／ｃｍ２で紫外線を照射することによって、前記基材の表面にプライマー層を有し、そのプライマー層の表面に紫外線硬化性組成物の硬化塗膜（以下、「ＵＶ塗膜」と略記する。）を備えた積層体（１）を得た。 (Example 4: Production of laminate (1))
The primer (P--) obtained in Example 1 was formed so that the film thickness after drying was about 1 μm on the surface of a film substrate (thickness 125 μm) made of polyethylene terephthalate (hereinafter abbreviated as “PET”). The primer layer was formed on the surface of the substrate by applying 1) and heating at 150 ° C. for 5 minutes. Next, the ultraviolet curable composition (UV-1) obtained in Preparation Example 2 was applied to the surface of the primer layer with a coating thickness of 15 μm, and the irradiation intensity was 0 on the coated surface using a high-pressure mercury lamp as a light source. By irradiating ultraviolet rays at 5 J / cm 2 , the surface of the substrate has a primer layer, and the surface of the primer layer is a cured coating film of an ultraviolet curable composition (hereinafter abbreviated as “UV coating film”). To obtain a laminate (1).
（実施例５：積層体（２）の作製）
　実施例４で用いた紫外線硬化性組成物（ＵＶ－１）に代えて、調製例３で得られた紫外線硬化性組成物（ＵＶ－２）を用いた以外は、実施例４と同様に行い、積層体（２）を得た。 (Example 5: Production of laminate (2))
The same procedure as in Example 4 was performed except that the ultraviolet curable composition (UV-2) obtained in Preparation Example 3 was used instead of the ultraviolet curable composition (UV-1) used in Example 4. A laminate (2) was obtained.
（実施例６：積層体（３）の作製）
　ＰＥＴフィルム基材の表面に、乾燥後の膜厚が約１μｍとなるように、実施例２で得られたプライマー（Ｐ－２）を塗布し、１５０℃で５分間加熱することによって、前記基材の表面にプライマー層を形成した。次いで、前記プライマー層の表面に、調整例３で得られた紫外線硬化性組成物（ＵＶ－２）を１５μｍの塗布厚で塗布し、その塗布面に、高圧水銀灯を光源として、照射強度０．５Ｊ／ｃｍ２で紫外線を照射することによって、前記基材の表面にプライマー層を有し、そのプライマー層の表面にＵＶ塗膜を備えた積層体（３）を得た。 (Example 6: Production of laminate (3))
The primer (P-2) obtained in Example 2 was applied to the surface of the PET film substrate so that the film thickness after drying was about 1 μm, and the substrate was heated at 150 ° C. for 5 minutes. A primer layer was formed on the surface of the material. Next, the ultraviolet curable composition (UV-2) obtained in Preparation Example 3 was applied to the surface of the primer layer with an application thickness of 15 μm, and the application surface was irradiated with an irradiation intensity of 0. By irradiating ultraviolet rays at 5 J / cm 2 , a laminate (3) having a primer layer on the surface of the substrate and having a UV coating film on the surface of the primer layer was obtained.
（実施例７：積層体（４）の作製）
　実施例６で用いたプライマー（Ｐ－２）に代えて、実施例３で得られたプライマー（Ｐ－３）を用いた以外は、実施例６と同様に行い、積層体（４）を得た。 (Example 7: Production of laminate (4))
A laminate (4) was obtained in the same manner as in Example 6 except that the primer (P-3) obtained in Example 3 was used instead of the primer (P-2) used in Example 6. It was.
　上記の実施例及び比較例で得られたコーティング剤及び積層体を用いて、下記の密着性の評価を行った。 The following adhesion evaluation was performed using the coating agents and laminates obtained in the above Examples and Comparative Examples.
［基材とプライマー層との密着性（初期）の評価方法］
　膜厚１２５μｍのポリエチレンテレフタレートからなる基材の表面に、乾燥時の膜厚が約１μｍとなるようにプライマーを塗布し、１５０℃で５分間加熱することによって、前記基材の表面にプライマー層が積層した部材からなる試験板を作製した。
　前記方法で作製した試験板のプライマー層の表面に、ニチバン株式会社製の２４ｍｍ幅の粘着テープを貼付した。 [Evaluation method of adhesion (initial) between substrate and primer layer]
A primer layer is applied to the surface of the base material by applying a primer on the surface of a base material made of polyethylene terephthalate having a thickness of 125 μm so that the film thickness when dried is about 1 μm and heating at 150 ° C. for 5 minutes. A test plate made of laminated members was prepared.
A 24 mm wide adhesive tape made by Nichiban Co., Ltd. was affixed to the surface of the primer layer of the test plate produced by the above method.
　次いで、前記粘着テープを前記プライマー層に対して垂直方向に引張り、前記粘着テープをプライマー層の表面から剥がした際の、前記プライマー層の表面の状態を、下記評価基準に従って目視で評価した。
　◎：試験板を構成する基材表面からプライマー層が全く剥離しなかった。
　○：試験板を構成する基材表面から、ごく一部のプライマー層が剥離したが、その剥離した範囲は、試験板を構成する皮膜の全面積に対して１０％未満であった。
　△：試験板を構成するプライマー層の面積に対して１０％以上５０％未満の範囲のプライマー層が、試験板を構成する基材表面から剥離した。
　×：試験板を構成するプライマー層の全面積に対して５０％以上の範囲のプライマー層が、試験板を構成する基材表面から剥離した。 Next, the surface of the primer layer when the pressure-sensitive adhesive tape was pulled in a direction perpendicular to the primer layer and the pressure-sensitive adhesive tape was peeled off from the surface of the primer layer was visually evaluated according to the following evaluation criteria.
(Double-circle): The primer layer did not peel at all from the base-material surface which comprises a test board.
○: A part of the primer layer was peeled off from the surface of the base material constituting the test plate, but the peeled range was less than 10% with respect to the total area of the film constituting the test plate.
(Triangle | delta): The primer layer of the range of 10% or more and less than 50% with respect to the area of the primer layer which comprises a test board peeled from the base-material surface which comprises a test board.
X: The primer layer of the range of 50% or more with respect to the whole area of the primer layer which comprises a test board peeled from the base-material surface which comprises a test board.
［プライマー層とＵＶ塗膜との密着性（初期）の評価方法］
　実施例及び比較例で得た積層体を構成するＵＶ塗膜の表面に、ニチバン株式会社製の２４ｍｍ幅の粘着テープを貼付した。 [Evaluation method of adhesion (initial) between primer layer and UV coating]
A 24 mm wide adhesive tape made by Nichiban Co., Ltd. was affixed to the surface of the UV coating film constituting the laminates obtained in Examples and Comparative Examples.
　次いで、前記粘着テープを前記ＵＶ塗膜に対して垂直方向に引張り、前記粘着テープをＵＶ塗膜の表面から剥がした際の、前記ＵＶ塗膜の表面の状態を、下記評価基準に従って目視で評価した。
　◎：積層体を構成する基材表面からＵＶ塗膜が全く剥離しなかった。
　○：積層体を構成する基材表面から、ごく一部のＵＶ塗膜が剥離したが、その剥離した範囲は、積層体を構成するＵＶ塗膜の全面積に対して１０％未満であった。
　△：積層体を構成するＵＶ塗膜の面積に対して１０％以上５０％未満の範囲のＵＶ塗膜が、積層体を構成する基材表面から剥離した。
　×：積層体を構成するＵＶ塗膜の全面積に対して５０％以上の範囲のＵＶ塗膜が、積層体を構成する基材表面から剥離した。 Next, the surface of the UV coating film is visually evaluated according to the following evaluation criteria when the pressure-sensitive adhesive tape is pulled in a direction perpendicular to the UV coating film and the pressure-sensitive adhesive tape is peeled off from the surface of the UV coating film. did.
(Double-circle): UV coating film did not peel from the base-material surface which comprises a laminated body at all.
○: A part of the UV coating film was peeled off from the surface of the substrate constituting the laminate, but the peeled range was less than 10% with respect to the total area of the UV coating constituting the laminate. .
(Triangle | delta): The UV coating film of the range of 10% or more and less than 50% with respect to the area of the UV coating film which comprises a laminated body peeled from the base-material surface which comprises a laminated body.
X: The UV coating film in the range of 50% or more with respect to the total area of the UV coating film constituting the laminate was peeled off from the substrate surface constituting the laminate.
［プライマー層とＵＶ塗膜との密着性（耐湿熱試験後）］
　前記得られた積層体を温度６０℃、相対湿度９０％の高温恒湿器に５０時間投入した。その後、前記積層体を取り出し、プライマー層とＵＶ塗膜との密着性を、前記［プライマー層とＵＶ塗膜との密着性（初期）］と同様の方法で評価した。 [Adhesion between primer layer and UV coating (after wet heat resistance test)]
The obtained laminate was put into a high-temperature humidity chamber having a temperature of 60 ° C. and a relative humidity of 90% for 50 hours. Thereafter, the laminate was taken out, and the adhesion between the primer layer and the UV coating film was evaluated in the same manner as in [Adhesion between the primer layer and UV coating film (initial)].
［プライマー層とＵＶ塗膜との密着性（耐薬品性試験後）］
　前記得られた積層体を温度２５℃、５％水酸化ナトリウム水溶液に３０分間投入した。その後、前記積層体を取り出し、水洗・乾燥後、プライマー層とＵＶ塗膜との密着性を、前記［プライマー層とＵＶ塗膜との密着性（初期）の評価方法］と同様の方法で評価した。 [Adhesion between primer layer and UV coating (after chemical resistance test)]
The obtained laminate was put into a 5% aqueous sodium hydroxide solution at a temperature of 25 ° C. for 30 minutes. Thereafter, the laminate is taken out, washed with water and dried, and then the adhesion between the primer layer and the UV coating film is evaluated in the same manner as in the above [Method for evaluating the adhesion between the primer layer and the UV coating film (initial)]. did.
［造膜性の評価方法］
　膜厚１２５μｍのポリエチレンテレフタレートからなる基材の表面に、乾燥時の膜厚が約１μｍとなるように前記プライマーを塗布し、１５０℃で５分間加熱することによって、前記基材の表面にプライマー層を形成した。
　○：プライマー層の表面を目視観察すると、透明であった。
　△：プライマー層の表面を目視観察すると、透明であるがクラックを確認できた。
　×：プライマー層の表面を目視観察すると、白化する程のクラックが発現し、プライマー層の一部がポリエチレンテレフタレート基材から容易に剥離していた。 [Evaluation method of film-forming property]
The primer layer is applied to the surface of the base material by applying the primer to the surface of the base material made of polyethylene terephthalate having a thickness of 125 μm so that the film thickness when dried is about 1 μm and heating at 150 ° C. for 5 minutes. Formed.
○: When the surface of the primer layer was visually observed, it was transparent.
(Triangle | delta): When the surface of the primer layer was observed visually, although it was transparent, the crack was able to be confirmed.
X: When the surface of the primer layer was visually observed, cracks to the extent that whitening occurred appeared, and a part of the primer layer was easily peeled from the polyethylene terephthalate substrate.
　実施例１０～２０で得られた積層体（１）～（４）に用いた基材、プライマー及び紫外線硬化性組成物と、評価結果とを表３に示す。 Table 3 shows the base materials, primers and ultraviolet curable compositions used in the laminates (1) to (4) obtained in Examples 10 to 20, and the evaluation results.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
（比較例１：プライマー（Ｐ’－１）の作製）
　水性樹脂組成物（１）１００質量部とイオン交換水５７７質量部とを混合することによって、プライマー（Ｐ’－１）を得た。 (Comparative Example 1: Preparation of primer (P′-1))
A primer (P′-1) was obtained by mixing 100 parts by mass of the aqueous resin composition (1) and 577 parts by mass of ion-exchanged water.
（比較例２：プライマー（Ｐ’－２）の作製）
　水性樹脂組成物（１）１００質量部とメラミン架橋剤（ＤＩＣ株式会社製「ベッカミンＭ－３」）３質量部と、イオン交換水６１３質量部とを混合することによって、プライマー（Ｐ’－２）を得た。 (Comparative Example 2: Preparation of primer (P′-2))
By mixing 100 parts by weight of the aqueous resin composition (1), 3 parts by weight of a melamine crosslinking agent (“Beckamine M-3” manufactured by DIC Corporation), and 613 parts by weight of ion-exchanged water, a primer (P′-2 )
（比較例３：プライマー（Ｐ’－３）の作製）
　水性樹脂組成物（１）１００質量部とオキサゾリン架橋剤（株式会社日本触媒製「エポクロスＷＳ－７００」）９．２質量部と、イオン交換水６０６質量部とを混合することによって、プライマー（Ｐ’－３）を得た。 (Comparative Example 3: Preparation of primer (P′-3))
By mixing 100 parts by mass of the aqueous resin composition (1), 9.2 parts by mass of an oxazoline crosslinking agent (“Epocross WS-700” manufactured by Nippon Shokubai Co., Ltd.) and 606 parts by mass of ion-exchanged water, a primer (P '-3) was obtained.
（比較例４：プライマー（Ｐ’－４）の作製）
　水性樹脂組成物（１）１００質量部とエポキシ系架橋剤（ＤＩＣ株式会社製「ＣＲ－５Ｌ」）３質量部と、イオン交換水６４８質量部とを混合することによって、プライマー（Ｐ’－４）を得た。 (Comparative Example 4: Preparation of primer (P′-4))
By mixing 100 parts by mass of the aqueous resin composition (1), 3 parts by mass of an epoxy-based crosslinking agent (“CR-5L” manufactured by DIC Corporation), and 648 parts by mass of ion-exchanged water, a primer (P′-4 )
（比較例５：積層体（Ｒ１）の作製）
　ＰＥＴフィルム基材の表面に、乾燥後の膜厚が約１μｍとなるように、比較例２で得られたプライマー（Ｐ’－１）を塗布し、１５０℃で５分間加熱することによって、前記基材の表面にプライマー層を形成した。次いで、前記プライマー層の表面に、調整例３で得られた紫外線硬化性組成物（ＵＶ－２）を、１５μｍの塗布厚で塗布し、その塗布面に、高圧水銀灯を光源として、照射強度０．５Ｊ／ｃｍ２で紫外線を照射することによって、前記基材の表面にプライマー層を有し、そのプライマー層の表面にＵＶ塗膜を備えた積層体（Ｒ１）を得た。 (Comparative Example 5: Production of laminate (R1))
By applying the primer (P′-1) obtained in Comparative Example 2 on the surface of the PET film substrate so that the film thickness after drying is about 1 μm and heating at 150 ° C. for 5 minutes, A primer layer was formed on the surface of the substrate. Next, the ultraviolet curable composition (UV-2) obtained in Preparation Example 3 was applied to the surface of the primer layer with a coating thickness of 15 μm, and the irradiation intensity was 0 on the coated surface using a high pressure mercury lamp as a light source. The laminate (R1) having a primer layer on the surface of the base material and a UV coating film on the surface of the primer layer was obtained by irradiating with ultraviolet rays at 0.5 J / cm 2 .
（比較例６～８：積層体（Ｒ２）～（Ｒ４）の作製）
　比較例５で用いたプライマー（Ｐ’－１）に代えて、比較例２～４で得られたプライマー（Ｐ’－２）～（Ｐ’－４）をそれぞれ用いた以外は、比較例５と同様に行い、積層体（Ｒ２）～（Ｒ４）を得た。 (Comparative Examples 6 to 8: Production of laminates (R2) to (R4))
Comparative Example 5 except that the primers (P'-2) to (P'-4) obtained in Comparative Examples 2 to 4 were used in place of the primer (P'-1) used in Comparative Example 5, respectively. In the same manner as above, laminates (R2) to (R4) were obtained.
　比較例４～７で得られた積層体（Ｒ１）及び（Ｒ２）に用いた基材、プライマー及び紫外線硬化性組成物と、評価結果とを表４に示す。 Table 4 shows the substrates, primers, and ultraviolet curable compositions used in the laminates (R1) and (R2) obtained in Comparative Examples 4 to 7, and the evaluation results.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表３に示した評価結果から、本発明のコーティング剤を用いて形成されたプライマー層は、基材との密着性に優れ、活性エネルギー線硬化性組成物の硬化塗膜との密着性にも優れることが確認できた。 From the evaluation results shown in Table 3, the primer layer formed using the coating agent of the present invention is excellent in adhesion to the substrate and also in adhesion to the cured coating film of the active energy ray-curable composition. It was confirmed that it was excellent.
　また、本発明のコーティング剤を用いて形成されたプライマー層は、耐湿熱試験後の高い密着性及び優れた耐薬品性を有することが確認できた。 Further, it was confirmed that the primer layer formed using the coating agent of the present invention has high adhesion after the heat and humidity resistance test and excellent chemical resistance.
　一方、比較例５は、架橋剤を含有しないコーティング剤を用いた例のものである。本発明のコーティング剤を用いて形成されたプライマー層に比べ、耐湿熱試験後の密着性は不十分であり、また、耐薬品性においても不十分であることが確認できた。 On the other hand, Comparative Example 5 is an example using a coating agent that does not contain a crosslinking agent. Compared to the primer layer formed using the coating agent of the present invention, it was confirmed that the adhesion after the wet heat resistance test was insufficient and the chemical resistance was insufficient.
　比較例６は、メラミン架橋剤を用いた例のものである。本発明のカルボジイミド架橋剤含有のコーティング剤を用いて形成されたプライマー層に比べ、耐薬品性が不十分であることが確認できた。 Comparative Example 6 is an example using a melamine crosslinking agent. It was confirmed that the chemical resistance was insufficient as compared with the primer layer formed using the coating agent containing the carbodiimide crosslinking agent of the present invention.
　比較例７は、オキサゾリン架橋剤を用いた例のものである。本発明のカルボジイミド架橋剤含有のコーティング剤を用いて形成されたプライマー層に比べ、耐湿熱試験後の密着性は不十分であり、また、耐薬品性においても不十分であることが確認できた。 Comparative Example 7 is an example using an oxazoline crosslinking agent. Compared with the primer layer formed using the coating agent containing the carbodiimide cross-linking agent of the present invention, it was confirmed that the adhesion after the wet heat resistance test was insufficient and the chemical resistance was also insufficient. .
　比較例８は、エポキシ架橋剤を用いた例のものである。本発明のカルボジイミド架橋剤含有のコーティング剤を用いて形成されたプライマー層に比べ、耐薬品性が不十分であることが確認できた。 Comparative Example 8 is an example using an epoxy crosslinking agent. It was confirmed that the chemical resistance was insufficient as compared with the primer layer formed using the coating agent containing the carbodiimide crosslinking agent of the present invention.

Claims (11)

  1. 　ビニルエステル樹脂（Ａ）、及び芳香環を有するウレタン樹脂（Ｂ）が、水性媒体（Ｃ）中に分散して得られた水性樹脂組成物（Ｄ）、ならびに、カルボジイミド系架橋剤（Ｅ）を含有するコーティング剤であって、
    前記ビニルエステル樹脂（Ａ）が、ノボラック型エポキシ樹脂及びビスフェノール型エポキシ樹脂からなる群より選ばれる１種以上のエポキシ樹脂（ａ１）と、酸基及び重合性不飽和基を有する化合物（ａ２）とを反応させて得られたものであり、
    前記ウレタン樹脂（Ｂ）が、芳香環を有するポリオール（ｂ１－１）及び親水性基を有するポリオール（ｂ１－２）を含有するポリオール（ｂ１）と、ポリイソシアネート（ｂ２）とを反応させて得られたものであることを特徴とするコーティング剤。     An aqueous resin composition (D) obtained by dispersing a vinyl ester resin (A) and a urethane resin (B) having an aromatic ring in an aqueous medium (C), and a carbodiimide-based crosslinking agent (E) A coating agent containing,
    The vinyl ester resin (A) is one or more epoxy resins (a1) selected from the group consisting of novolak type epoxy resins and bisphenol type epoxy resins, a compound (a2) having an acid group and a polymerizable unsaturated group, It was obtained by reacting
    The urethane resin (B) is obtained by reacting a polyol (b1) containing a polyol (b1-1) having an aromatic ring and a polyol (b1-2) having a hydrophilic group with a polyisocyanate (b2). The coating agent characterized by being made.
  2. 　前記架橋剤（Ｅ）の使用量が、カルボジイミド基と反応可能な前記ウレタン樹脂（Ｂ）が有する親水性基の８０～１００モル％と反応する量である請求項１記載のコーティング剤。 The coating agent according to claim 1, wherein the amount of the crosslinking agent (E) used is an amount that reacts with 80 to 100 mol% of the hydrophilic group of the urethane resin (B) capable of reacting with a carbodiimide group.
  3. 　前記ポリオール（ｂ１－１）中の芳香環濃度が、１．５～８ｍｏｌ／ｋｇの範囲である請求項１記載のコーティング剤。 The coating agent according to claim 1, wherein the concentration of the aromatic ring in the polyol (b1-1) is in the range of 1.5 to 8 mol / kg.
  4. 　前記芳香環を有するポリオール（ｂ１－１）が、芳香族ポリエステルポリオール（ｂ１－ａ）及びビスフェノールＡのアルキレンオキサイド付加物（ｂ１－ｂ）のうち、少なくとも１つを含むポリオールである請求項１記載のコーティング剤。 2. The polyol (b1-1) having an aromatic ring is a polyol containing at least one of an aromatic polyester polyol (b1-a) and an alkylene oxide adduct (b1-b) of bisphenol A. Coating agent.
  5. 　前記ポリオール（ｂ１）中に含まれる芳香環を有するポリオール（ｂ１－１）の割合が４０～９８質量％の範囲である請求項１記載のコーティング剤。 The coating agent according to claim 1, wherein the proportion of the polyol (b1-1) having an aromatic ring contained in the polyol (b1) is in the range of 40 to 98% by mass.
  6. 　前記ポリイソシアネート（ｂ２）が芳香族ポリイソシアネートを含むものである請求項１記載のコーティング剤。 The coating agent according to claim 1, wherein the polyisocyanate (b2) contains an aromatic polyisocyanate.
  7. 　前記化合物（ａ２）がアクリル酸又はメタクリル酸である請求項１記載のコーティング剤。 The coating agent according to claim 1, wherein the compound (a2) is acrylic acid or methacrylic acid.
  8. 　前記ビニルエステル樹脂（Ａ）の一部又は全部が、前記ウレタン樹脂（Ｂ）粒子中に内在して樹脂粒子（Ｆ）を形成したものである請求項１記載のコーティング剤。 The coating agent according to claim 1, wherein a part or all of the vinyl ester resin (A) is present in the urethane resin (B) particles to form resin particles (F).
  9. 　前記ビニルエステル樹脂（Ａ）と前記ウレタン樹脂（Ｂ）との質量割合［（Ａ）／（Ｂ）］が６０／４０～１０／９０の範囲である請求項１記載のコーティング剤。 The coating agent according to claim 1, wherein the mass ratio [(A) / (B)] of the vinyl ester resin (A) and the urethane resin (B) is in the range of 60/40 to 10/90.
  10. 　基材の表面に、請求項１～９のいずれか１項記載のコーティング剤を塗布し、乾燥することによって形成されたプライマー層を有し、前記プライマー層の表面に、活性エネルギー線硬化性組成物を用いて形成された硬化塗膜を有することを特徴とする積層体。 A primer layer formed by applying the coating agent according to any one of claims 1 to 9 to a surface of a substrate and drying the coating, and an active energy ray-curable composition on the surface of the primer layer A laminate having a cured coating film formed using a product.
  11. 　前記活性エネルギー線硬化性樹脂組成物が、重合性不飽和基を有する樹脂と、重合性不飽和基を有する単量体とを含有するものである請求項１０記載の積層体。 The laminate according to claim 10, wherein the active energy ray-curable resin composition contains a resin having a polymerizable unsaturated group and a monomer having a polymerizable unsaturated group.
PCT/JP2014/082103 2013-12-20 2014-12-04 Coating agent and laminate WO2015093299A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2015553472A JP5963033B2 (en) 2013-12-20 2014-12-04 Coating agent and laminate
CN201480068831.0A CN105829464B (en) 2013-12-20 2014-12-04 Smears and layered product
KR1020167016518A KR102254872B1 (en) 2013-12-20 2014-12-04 Coating agent and laminate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013263816 2013-12-20
JP2013-263816 2013-12-20

Publications (1)

Publication Number Publication Date
WO2015093299A1 true WO2015093299A1 (en) 2015-06-25

Family

ID=53402648

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/082103 WO2015093299A1 (en) 2013-12-20 2014-12-04 Coating agent and laminate

Country Status (5)

Country Link
JP (1) JP5963033B2 (en)
KR (1) KR102254872B1 (en)
CN (1) CN105829464B (en)
TW (1) TWI636102B (en)
WO (1) WO2015093299A1 (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016055464A (en) * 2014-09-06 2016-04-21 三菱樹脂株式会社 Laminated film
JP2016064517A (en) * 2014-09-24 2016-04-28 三菱樹脂株式会社 Lamination film
WO2017131102A1 (en) * 2016-01-27 2017-08-03 日本ペイント・オートモーティブコーティングス株式会社 Aqueous coating composition
WO2018100930A1 (en) * 2016-12-01 2018-06-07 Dic株式会社 Aqueous resin composition and layered fibrous product
JP2018104535A (en) * 2016-12-26 2018-07-05 Dic株式会社 Aqueous resin composition, coating agent and article
EP3348621A1 (en) * 2017-01-16 2018-07-18 ALLNEX AUSTRIA GmbH Aqueous coating composition for corrosion protection
WO2019131414A1 (en) * 2017-12-26 2019-07-04 Dic株式会社 Aqueous resin composition and laminated body and article employing same
JP2019137072A (en) * 2019-05-27 2019-08-22 三菱ケミカル株式会社 Laminate film and manufacturing method
JP2021017014A (en) * 2019-07-22 2021-02-15 コニカミノルタ株式会社 Laminate film and method for producing the same
WO2022229174A1 (en) 2021-04-27 2022-11-03 Allnex Austria Gmbh Aqueous coating composition for corrosion protection
JP7496044B1 (en) * 2024-03-18 2024-06-05 第一工業製薬株式会社 Polyurethane water-based dispersion and water-based paint
JP7662885B1 (en) * 2024-09-24 2025-04-15 第一工業製薬株式会社 Active energy ray-curable resin composition, cured product thereof, and protective film

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6642737B2 (en) * 2016-12-26 2020-02-12 Dic株式会社 Aqueous resin composition, laminate using the same, optical film and image display device
JP7027813B2 (en) * 2017-11-01 2022-03-02 Dic株式会社 Synthetic leather and its manufacturing method
CN109608611A (en) * 2018-10-23 2019-04-12 合肥科天水性科技有限责任公司 A kind of epoxy acrylic resin modified aqueous polyurethane and preparation method thereof
CN119101328A (en) * 2019-07-08 2024-12-10 Dic株式会社 Resin composition and cured product thereof, impregnated substrate, prepreg, laminate, printed wiring board and semiconductor package
KR102825447B1 (en) * 2019-12-02 2025-06-30 가부시끼가이샤 레조낙 Mercury resin composition, film and method for forming film

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005154721A (en) * 2003-05-28 2005-06-16 Dainippon Ink & Chem Inc Water-based coating agent
JP2007153958A (en) * 2005-12-01 2007-06-21 Unitika Ltd Aqueous primer composition and layered product
JP2011256336A (en) * 2010-06-11 2011-12-22 Teijin Ltd Resin composition for water base coating liquid, water base coating liquid containing the composition dispersed therein, and composite film having coating layer coated with the liquid
JP2012102182A (en) * 2010-11-08 2012-05-31 Dic Corp Urethane resin composition for wet film formation, porous body and polishing pad obtained using the resin composition, and methods of manufacturing them
JP2012246465A (en) * 2011-05-31 2012-12-13 Dic Corp Active energy ray-curable resin composition, and coating agent for first coating containing the same

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003076537A1 (en) 2002-03-08 2003-09-18 Lord Corporation Flexible coatings for elastomer substrates
US8829080B2 (en) * 2008-05-26 2014-09-09 Dic Corporation Coating agent and method for production thereof
DE102009009791A1 (en) * 2009-02-20 2010-08-26 Mitsubishi Plastics, Inc. White, coated polyester film, process for its preparation and its use as back cover in solar modules
JP5396951B2 (en) 2009-03-18 2014-01-22 三菱化学株式会社 Active energy ray-curable composition and laminate
WO2013140893A1 (en) * 2012-03-22 2013-09-26 Dic株式会社 Aqueous resin composition and cured article
KR101389436B1 (en) * 2012-04-25 2014-04-28 도우성 Anti-Glare coating composition for water-blackboard and film sheet using the same material and method for thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005154721A (en) * 2003-05-28 2005-06-16 Dainippon Ink & Chem Inc Water-based coating agent
JP2007153958A (en) * 2005-12-01 2007-06-21 Unitika Ltd Aqueous primer composition and layered product
JP2011256336A (en) * 2010-06-11 2011-12-22 Teijin Ltd Resin composition for water base coating liquid, water base coating liquid containing the composition dispersed therein, and composite film having coating layer coated with the liquid
JP2012102182A (en) * 2010-11-08 2012-05-31 Dic Corp Urethane resin composition for wet film formation, porous body and polishing pad obtained using the resin composition, and methods of manufacturing them
JP2012246465A (en) * 2011-05-31 2012-12-13 Dic Corp Active energy ray-curable resin composition, and coating agent for first coating containing the same

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016055464A (en) * 2014-09-06 2016-04-21 三菱樹脂株式会社 Laminated film
JP2016064517A (en) * 2014-09-24 2016-04-28 三菱樹脂株式会社 Lamination film
WO2017131102A1 (en) * 2016-01-27 2017-08-03 日本ペイント・オートモーティブコーティングス株式会社 Aqueous coating composition
WO2018100930A1 (en) * 2016-12-01 2018-06-07 Dic株式会社 Aqueous resin composition and layered fibrous product
JPWO2018100930A1 (en) * 2016-12-01 2018-11-29 Dic株式会社 Aqueous resin composition and fiber laminate
JP2018104535A (en) * 2016-12-26 2018-07-05 Dic株式会社 Aqueous resin composition, coating agent and article
AU2018207180B2 (en) * 2017-01-16 2022-12-22 Allnex Austria Gmbh Aqueous coating composition for corrosion protection
EP3348621A1 (en) * 2017-01-16 2018-07-18 ALLNEX AUSTRIA GmbH Aqueous coating composition for corrosion protection
WO2018130700A1 (en) 2017-01-16 2018-07-19 Allnex Austria Gmbh Aqueous coating composition for corrosion protection
US11535770B2 (en) 2017-01-16 2022-12-27 Allnex Austria Gmbh Aqueous coating composition for corrosion protection
WO2019131414A1 (en) * 2017-12-26 2019-07-04 Dic株式会社 Aqueous resin composition and laminated body and article employing same
JPWO2019131414A1 (en) * 2017-12-26 2021-01-28 Dic株式会社 Aqueous resin composition, laminate and article using it
JP2019137072A (en) * 2019-05-27 2019-08-22 三菱ケミカル株式会社 Laminate film and manufacturing method
JP2021017014A (en) * 2019-07-22 2021-02-15 コニカミノルタ株式会社 Laminate film and method for producing the same
JP7326958B2 (en) 2019-07-22 2023-08-16 コニカミノルタ株式会社 LAMINATED FILM AND METHOD FOR MANUFACTURING THE SAME
WO2022229174A1 (en) 2021-04-27 2022-11-03 Allnex Austria Gmbh Aqueous coating composition for corrosion protection
JP7496044B1 (en) * 2024-03-18 2024-06-05 第一工業製薬株式会社 Polyurethane water-based dispersion and water-based paint
JP7662885B1 (en) * 2024-09-24 2025-04-15 第一工業製薬株式会社 Active energy ray-curable resin composition, cured product thereof, and protective film

Also Published As

Publication number Publication date
TWI636102B (en) 2018-09-21
KR102254872B1 (en) 2021-05-25
JPWO2015093299A1 (en) 2017-03-16
TW201529764A (en) 2015-08-01
KR20160099584A (en) 2016-08-22
CN105829464A (en) 2016-08-03
JP5963033B2 (en) 2016-08-03
CN105829464B (en) 2017-10-24

Similar Documents

Publication Publication Date Title
JP5963033B2 (en) Coating agent and laminate
JP5839251B2 (en) Aqueous resin composition, laminate using the same, and image display device
JP6642737B2 (en) Aqueous resin composition, laminate using the same, optical film and image display device
CN104379621B (en) Energy ray curable resin composition, solidfied material and layered product
JP2013173871A (en) Composition, antistatic coating agent, and antistatic laminate
JP6071028B2 (en) Laminate and optical film
JP2015218267A (en) Aqueous resin composition, and laminate and article using the same
JP2024032966A (en) Copolymers, curable polymer compositions, cured products, laminates
JP2013053249A (en) Film coating agent
JP2017014307A (en) Aqueous resin composition, laminate and article using the same
JP6874787B2 (en) Active energy ray-curable resin composition, cured product and laminate
JP6623744B2 (en) Aqueous resin composition, laminate and article using the same
JP7058144B2 (en) A curable composition, a film using the curable composition, and a molded product using the film.
JP6557966B2 (en) Laminate and optical film

Legal Events

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

Ref document number: 14871833

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015553472

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20167016518

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 14871833

Country of ref document: EP

Kind code of ref document: A1