WO2015093299A1 - Agent de revêtement et stratifié - Google Patents

Agent de revêtement et stratifié Download PDF

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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
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WO
WIPO (PCT)
Prior art keywords
resin
polyol
coating agent
meth
acrylate
Prior art date
Application number
PCT/JP2014/082103
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English (en)
Japanese (ja)
Inventor
達史 小柳
北田　満
Original Assignee
Dic株式会社
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Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2015553472A priority Critical patent/JP5963033B2/ja
Priority to CN201480068831.0A priority patent/CN105829464B/zh
Priority to KR1020167016518A priority patent/KR102254872B1/ko
Publication of WO2015093299A1 publication Critical patent/WO2015093299A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—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
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    • 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
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    • 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
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    • 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
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    • 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.

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

Abstract

La présente invention concerne un agent de revêtement comprenant : (D) une composition de résine aqueuse produite par dispersion à la fois de (A) une résine d'ester vinylique et de (B) une résine d'uréthane ayant un cycle aromatique dans (C) un milieu aqueux; et (E) un agent de réticulation de type carbodiimide. Dans ledit agent de revêtement, la résine d'ester vinylique (A) est produite par réaction de (a1) au moins une résine époxy choisie dans le groupe constitué d'une résine époxy de type novolaque et d'une résine époxy de type bisphénol, et de (a2) un composé ayant un groupe acide et un groupe insaturé polymérisable, et la résine d'uréthane (B) est produite par réaction de (b1) un polyol comprenant (b1-1) un polyol ayant un cycle aromatique et (b1-2) un polyol ayant un groupe hydrophile, et de (b2) un polyisocyanate. L'agent de revêtement selon la présente invention permet la formation d'une couche d'apprêt qui peut améliorer l'adhérence entre un matériau de base et un film de revêtement durci fabriqué à partir d'une composition durcissable par rayonnement d'énergie active et qui présente une excellente résistance aux agents chimiques et à la chaleur humide.
PCT/JP2014/082103 2013-12-20 2014-12-04 Agent de revêtement et stratifié WO2015093299A1 (fr)

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JP2016064517A (ja) * 2014-09-24 2016-04-28 三菱樹脂株式会社 積層フィルム
WO2017131102A1 (fr) * 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 Composition aqueuse de revêtement
WO2018100930A1 (fr) * 2016-12-01 2018-06-07 Dic株式会社 Composition de résine aqueuse et produit fibreux en couches
JP2018104535A (ja) * 2016-12-26 2018-07-05 Dic株式会社 水性樹脂組成物、コーティング剤及び物品
EP3348621A1 (fr) * 2017-01-16 2018-07-18 ALLNEX AUSTRIA GmbH Agent de revêtement anti-corrosion
WO2019131414A1 (fr) * 2017-12-26 2019-07-04 Dic株式会社 Composition de résine aqueuse, et corps stratifié et article l'utilisant
JP2019137072A (ja) * 2019-05-27 2019-08-22 三菱ケミカル株式会社 積層フィルムおよび製造方法
JP2021017014A (ja) * 2019-07-22 2021-02-15 コニカミノルタ株式会社 積層フィルムおよびその製造方法
WO2022229174A1 (fr) 2021-04-27 2022-11-03 Allnex Austria Gmbh Composition aqueuse de revêtement pour protection contre la corrosion
JP7496044B1 (ja) 2024-03-18 2024-06-05 第一工業製薬株式会社 ポリウレタン水系分散体、及び水性塗料

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JP7027813B2 (ja) * 2017-11-01 2022-03-02 Dic株式会社 合成皮革、及び、その製造方法
CN109608611A (zh) * 2018-10-23 2019-04-12 合肥科天水性科技有限责任公司 一种环氧丙烯酸树脂改性水性聚氨酯及其制备方法
TW202110995A (zh) * 2019-07-08 2021-03-16 日商Ｄｉｃ股份有限公司 樹脂組成物及其硬化物、含浸基材、預浸體、積層體、印刷配線板及半導體封裝
CN114746458A (zh) * 2019-12-02 2022-07-12 昭和电工株式会社 水性树脂组合物、皮膜及皮膜的形成方法

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JP2016055464A (ja) * 2014-09-06 2016-04-21 三菱樹脂株式会社 積層フィルム
JP2016064517A (ja) * 2014-09-24 2016-04-28 三菱樹脂株式会社 積層フィルム
WO2017131102A1 (fr) * 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 Composition aqueuse de revêtement
WO2018100930A1 (fr) * 2016-12-01 2018-06-07 Dic株式会社 Composition de résine aqueuse et produit fibreux en couches
JPWO2018100930A1 (ja) * 2016-12-01 2018-11-29 Dic株式会社 水性樹脂組成物、及び、繊維積層体
JP2018104535A (ja) * 2016-12-26 2018-07-05 Dic株式会社 水性樹脂組成物、コーティング剤及び物品
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EP3348621A1 (fr) * 2017-01-16 2018-07-18 ALLNEX AUSTRIA GmbH Agent de revêtement anti-corrosion
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JP2019137072A (ja) * 2019-05-27 2019-08-22 三菱ケミカル株式会社 積層フィルムおよび製造方法
JP2021017014A (ja) * 2019-07-22 2021-02-15 コニカミノルタ株式会社 積層フィルムおよびその製造方法
JP7326958B2 (ja) 2019-07-22 2023-08-16 コニカミノルタ株式会社 積層フィルムおよびその製造方法
WO2022229174A1 (fr) 2021-04-27 2022-11-03 Allnex Austria Gmbh Composition aqueuse de revêtement pour protection contre la corrosion
JP7496044B1 (ja) 2024-03-18 2024-06-05 第一工業製薬株式会社 ポリウレタン水系分散体、及び水性塗料

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CN105829464B (zh) 2017-10-24
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TWI636102B (zh) 2018-09-21

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