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CN105829464A - Coating agent and laminate - Google Patents

Coating agent and laminate Download PDF

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Publication number
CN105829464A
CN105829464A CN201480068831.0A CN201480068831A CN105829464A CN 105829464 A CN105829464 A CN 105829464A CN 201480068831 A CN201480068831 A CN 201480068831A CN 105829464 A CN105829464 A CN 105829464A
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CN
China
Prior art keywords
resin
polyol
meth
coating agent
acrylate
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
CN201480068831.0A
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Chinese (zh)
Other versions
CN105829464B (en
Inventor
小柳达史
北田满
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
Dainippon Ink and Chemicals Co Ltd
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Filing date
Publication date
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Publication of CN105829464A publication Critical patent/CN105829464A/en
Application granted granted Critical
Publication of CN105829464B publication Critical patent/CN105829464B/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
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    • 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
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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    • C08G18/72—Polyisocyanates or polyisothiocyanates
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    • 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
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    • 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
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    • 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
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    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
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    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L63/10—Epoxy resins modified by unsaturated compounds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (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

本发明提供一种含有水性树脂组合物(D)和碳化二亚胺类交联剂(E)的涂布剂，其中，所述水性树脂组合物(D)是将乙烯基酯树脂(A)和具有芳香环的氨基甲酸酯树脂(B)分散于水性介质(C)中而得到的；所述乙烯基酯树脂(A)是使环氧树脂(a1)与化合物(a2)反应而得到的，其中，所述环氧树脂(a1)为选自由线性酚醛型环氧树脂和双酚型环氧树脂组成的组中的一种以上，所述化合物(a2)具有酸基和聚合性不饱和基；所述氨基甲酸酯树脂(B)是使含有多元醇(b1?1)和多元醇(b1?2)的多元醇(b1)与多异氰酸酯(b2)反应而得到的，其中，所述多元醇(b1?1)具有芳香环，所述多元醇(b1?2)具有亲水性基。本发明的涂布剂可使基材与活性能量射线固化组合物的固化涂膜的密合性提高、且形成耐化学品性和耐湿热性优异的底涂层。The present invention provides a coating agent containing a water-based resin composition (D) and a carbodiimide crosslinking agent (E), wherein the water-based resin composition (D) is made of vinyl ester resin (A) obtained by dispersing a urethane resin (B) having an aromatic ring in an aqueous medium (C); the vinyl ester resin (A) is obtained by reacting an epoxy resin (a1) with a compound (a2) wherein, the epoxy resin (a1) is at least one selected from the group consisting of novolac epoxy resins and bisphenol epoxy resins, and the compound (a2) has acid groups and polymerizability a saturated group; the urethane resin (B) is obtained by reacting a polyol (b1) containing a polyol (b1-1) and a polyol (b1-2) with a polyisocyanate (b2), wherein, The polyol (b1-1) has an aromatic ring, and the polyol (b1-2) has a hydrophilic group. The coating agent of the present invention can improve the adhesion between the base material and the cured coating film of the active energy ray-curable composition, and can form an undercoat layer excellent in chemical resistance and heat-and-moisture resistance.

Description

涂布剂及层叠体Coating agent and laminate

技术领域technical field

本发明涉及一种在基材表面形成活性能量射线固化性组合物的固化涂膜时，可以用作提高基材与所述固化涂膜密合性的底涂剂(primer)的涂布剂及层叠体。The present invention relates to a coating agent that can be used as a primer for improving the adhesion between a base material and the cured coating film when forming a cured coating film of an active energy ray-curable composition on the surface of a base material, and laminated body.

背景技术Background technique

近年来，对于水性氨基甲酸酯树脂组合物研究了在面向光学用途的膜或片中的应用。作为所述光学用途，具体地可列举：液晶显示器、触摸面板等。所述液晶显示器等显示装置通常为了显示清晰的影像，而将具有各种功能的多个光学膜层叠而构成，作为该光学膜，可列举：防反射膜、相位差膜、棱镜透镜片等。In recent years, the application of the aqueous urethane resin composition to a film or sheet for optical use has been studied. As said optical use, a liquid crystal display, a touch panel, etc. are mentioned specifically. Display devices such as liquid crystal displays are generally constructed by laminating a plurality of optical films having various functions in order to display clear images. Examples of the optical film include antireflection films, retardation films, and prism lens sheets.

因为光学特性、机械强度、耐久性优异，作为这些光学膜的基材使用聚酯膜，尤其是聚对苯二甲酸乙二醇酯(PET)膜。此外，在光学用途中，在聚酯膜的表面或通过涂布并固化活性能量射线固化性组合物而形成硬涂层，或设置将活性能量射线固化性组合物注模而得的层，将聚酯膜作为棱镜片，但存在着由于聚酯膜的结晶性高而导致与活性能量射线固化性组合物的固化涂膜的密合性低的问题。A polyester film, especially a polyethylene terephthalate (PET) film is used as a base material of these optical films because of excellent optical characteristics, mechanical strength, and durability. In addition, in optical applications, a hard coat layer is formed on the surface of a polyester film or by applying and curing an active energy ray-curable composition, or a layer obtained by injection molding an active energy ray-curable composition is provided, and the The polyester film is used as a prism sheet, but there is a problem that the adhesion with the cured coating film of the active energy ray-curable composition is low due to the high crystallinity of the polyester film.

作为提高聚酯膜与活性能量射线固化性组合物的固化涂膜的密合性的方法，提出了在作为基材的聚酯膜与活性能量射线固化性组合物的固化涂膜之间设置包含丙烯酸类树脂的底涂层(例如参照专利文献1)。但是，即使设置包含丙烯酸类树脂的底涂层，聚酯膜与活性能量射线固化性组合物的固化涂膜的密合性也不足够。As a method of improving the adhesion between the polyester film and the cured coating film of the active energy ray-curable composition, it is proposed to provide An undercoat layer of an acrylic resin (for example, refer to Patent Document 1). However, even if an undercoat layer containing an acrylic resin is provided, the adhesion between the polyester film and the cured coating film of the active energy ray-curable composition is insufficient.

此外，作为底涂层使用了氨基甲酸酯树脂的层存在如下问题：虽然与活性能量射线固化性组合物的固化涂膜的密合性足够，但对于耐湿热试验后的密合性和耐化学品性不能表现出足够的性能。In addition, a layer using a urethane resin as a primer layer has a problem that although the adhesiveness with the cured coating film of the active energy ray-curable composition is sufficient, the adhesiveness and resistance after the heat-and-moisture resistance test are insufficient. Chemical properties do not exhibit sufficient performance.

因而，希望有使聚酯膜与活性能量射线固化性组合物的固化涂膜的密合性达到足够，而且可在具有优异的耐化学品性和耐湿热性的底涂层中使用的涂布剂。Therefore, it is desirable to have a coating that can achieve sufficient adhesion between the polyester film and the cured coating film of the active energy ray-curable composition, and can be used as an undercoat layer having excellent chemical resistance and heat and humidity resistance. agent.

现有技术文献prior art literature

专利文献patent documents

专利文献1：日本特开2010-215843号公报Patent Document 1: Japanese Patent Laid-Open No. 2010-215843

发明内容Contents of the invention

发明要解决的课题The problem to be solved by the invention

本发明所要解决的问题是提供一种对于基材或活性能量射线固化组合物的固化涂膜均具有优异的密合性、且可形成耐化学品性和耐湿热性优异的底涂层的涂布剂。The problem to be solved by the present invention is to provide a coating that has excellent adhesion to both the base material and the cured coating film of the active energy ray-curable composition, and can form an undercoat layer excellent in chemical resistance and heat and humidity resistance. Cloth agent.

解决课题的手段means of solving problems

本发明人等为了解决上述问题而进行了反复深入的研究，结果发现：使特定的环氧树脂、与具有酸基和聚合性不饱和基的化合物反应而得到的乙烯基酯树脂和具有芳香环的氨基甲酸酯树脂分散于水性介质中而得到水性树脂组合物，通过使用在该水性树脂组合物中组合交联剂而成的底涂剂，即使是聚酯膜这样的难以粘接的基材，也可以提高该基材与活性能量射线固化性组合物的固化涂膜的密合性，以及大幅提高底涂层的耐化学品性和耐湿热性，从而完成了本发明。The inventors of the present invention have conducted intensive studies in order to solve the above problems. As a result, they have found that a specific epoxy resin, a vinyl ester resin obtained by reacting a compound having an acid group and a polymerizable unsaturated group, and a compound having an aromatic ring A water-based resin composition obtained by dispersing a urethane resin in an aqueous medium, and using a primer obtained by combining a cross-linking agent with the water-based resin composition, even a difficult-to-adhesive substrate such as a polyester film material, the adhesion between the substrate and the cured coating film of the active energy ray-curable composition can be improved, and the chemical resistance and heat and humidity resistance of the undercoat layer can be greatly improved, thereby completing the present invention.

即本发明涉及一种涂布剂及层叠体，其特征在于，该涂布剂含有水性树脂组合物(D)和碳化二亚胺类交联剂(E)，其中，所述水性树脂组合物(D)是将乙烯基酯树脂(A)和具有芳香环的氨基甲酸酯树脂(B)分散于水性介质(C)中而得到的；That is, the present invention relates to a coating agent and a laminate, characterized in that the coating agent contains an aqueous resin composition (D) and a carbodiimide crosslinking agent (E), wherein the aqueous resin composition (D) is obtained by dispersing a vinyl ester resin (A) and a urethane resin (B) having an aromatic ring in an aqueous medium (C);

所述乙烯基酯树脂(A)是使环氧树脂(a1)与化合物(a2)反应而得到的，其中，所述环氧树脂(a1)为选自由线性酚醛型环氧树脂和双酚型环氧树脂组成的组中的一种以上，所述化合物(a2)具有酸基和聚合性不饱和基；The vinyl ester resin (A) is obtained by reacting an epoxy resin (a1) with a compound (a2), wherein the epoxy resin (a1) is selected from novolak type epoxy resins and bisphenol type epoxy resins. One or more of the group consisting of epoxy resins, the compound (a2) has an acid group and a polymerizable unsaturated group;

所述氨基甲酸酯树脂(B)是使含有多元醇(b1-1)和多元醇(b1-2)的多元醇(b1)与多异氰酸酯(b2)反应而得到的，其中，所述多元醇(b1-1)具有芳香环，所述多元醇(b1-2)具有亲水性基。The urethane resin (B) is obtained by reacting polyol (b1) containing polyol (b1-1) and polyol (b1-2) with polyisocyanate (b2), wherein the polyhydric The alcohol (b1-1) has an aromatic ring, and the polyol (b1-2) has a hydrophilic group.

发明效果Invention effect

即使是聚酯膜这样的难以粘接的基材，本发明的涂布剂也可以用作可以提高该基材与活性能量射线固化性组合物的固化涂膜的密合性、以及耐化学品性和耐湿热性优异的底涂剂，由此适合于以聚酯膜作为基材，并在其表面形成有活性能量射线固化性组合物的固化涂膜的层叠体。作为这样的层叠体，例如可列举：防反射膜、相位差膜、棱镜透镜片等光学膜。此外，这些光学膜可应用于以液晶显示器为代表的图像显示装置。The coating agent of the present invention can also be used to improve the adhesiveness between the base material and the cured coating film of the active energy ray-curable composition, and chemical resistance even for substrates that are difficult to bond, such as polyester films. It is a primer agent excellent in moisture and heat resistance, and thus is suitable for a laminate in which a polyester film is used as a substrate and a cured coating film of an active energy ray-curable composition is formed on the surface. As such a laminated body, optical films, such as an antireflection film, a retardation film, and a prism lens sheet, are mentioned, for example. In addition, these optical films can be applied to image display devices typified by liquid crystal displays.

具体实施方式detailed description

本发明的涂布剂含有水性树脂组合物(D)和碳化二亚胺类交联剂(E)，其中，所述水性树脂组合物(D)是将乙烯基酯树脂(A)和具有芳香环的氨基甲酸酯树脂(B)分散于水性介质(C)中而得到。The coating agent of the present invention contains a water-based resin composition (D) and a carbodiimide crosslinking agent (E), wherein the water-based resin composition (D) is a combination of vinyl ester resin (A) and aromatic Cyclic urethane resin (B) is obtained by dispersing in aqueous medium (C).

所述乙烯基酯树脂(A)是使环氧树脂(a1)与化合物(a2)反应而得到的，其中，环氧树脂(a1)是选自由线性酚醛型环氧树脂和双酚型环氧树脂组成的组中的一种以上，化合物(a2)具有酸基和聚合性不饱和基。The vinyl ester resin (A) is obtained by reacting the epoxy resin (a1) with the compound (a2), wherein the epoxy resin (a1) is selected from the group consisting of novolac type epoxy resin and bisphenol type epoxy resin One or more compounds in the group consisting of resins, the compound (a2) has an acid group and a polymerizable unsaturated group.

所述化合物(a2)所具有的聚合性不饱和基在与所述环氧树脂的反应中不参与其反应，由此其结果是，所述乙烯基酯树脂(A)具有来自于所述化合物(a2)的聚合性不饱和基。该乙烯基酯树脂(A)所具有的聚合性不饱和基与后述的活性能量射线固化性组合物中所含的树脂、单体所具有的聚合性不饱和基发生聚合反应，由此形成共价键，使与包含本发明涂布剂的底涂层的密合变得牢固。The polymerizable unsaturated group possessed by the compound (a2) does not participate in the reaction with the epoxy resin, and as a result, the vinyl ester resin (A) has (a2) polymerizable unsaturated group. The polymerizable unsaturated group contained in the vinyl ester resin (A) polymerizes with the polymerizable unsaturated group contained in the active energy ray curable composition described later and the polymerizable unsaturated group contained in the monomer, thereby forming The covalent bond strengthens the adhesion with the undercoat layer containing the coating agent of the present invention.

所述乙烯基酯树脂(A)所具有的聚合性不饱和基的当量优选为250～2,000g/eq.的范围。It is preferable that the equivalent weight of the polymerizable unsaturated group which the said vinyl ester resin (A) has is the range of 250-2,000 g/eq.

所述环氧树脂(a1)是选自由线性酚醛型环氧树脂和双酚型环氧树脂组成的组中的一种以上的环氧树脂，具体而言可使用以下的环氧树脂。The epoxy resin (a1) is one or more epoxy resins selected from the group consisting of novolak-type epoxy resins and bisphenol-type epoxy resins. Specifically, the following epoxy resins can be used.

作为所述线性酚醛型环氧树脂，例如可列举：甲酚线性酚醛型环氧树脂、苯酚线性酚醛型环氧树脂等。此外，作为所述双酚型环氧树脂，可列举：双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、四溴双酚A型环氧树脂等。这些环氧树脂(a1)可以单独使用，也可以同时使用两种以上。As said novolak type epoxy resin, a cresol novolak type epoxy resin, a phenol novolac type epoxy resin, etc. are mentioned, for example. Moreover, as said bisphenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetrabromobisphenol A type epoxy resin, etc. are mentioned. These epoxy resins (a1) may be used alone or in combination of two or more.

所述环氧树脂(a1)中，优选使用具有多个可与所述化合物(a2)所具有的酸基反应的环氧基的线性酚醛型环氧树脂。Among the epoxy resins (a1), it is preferable to use a novolac type epoxy resin having a plurality of epoxy groups that can react with the acid groups contained in the compound (a2).

此外，所述环氧树脂(a1)的环氧当量优选为150～2,000g/eq.的范围，更优选为160～1,000g/eq.的范围。In addition, the epoxy equivalent of the epoxy resin (a1) is preferably in the range of 150 to 2,000 g/eq., more preferably in the range of 160 to 1,000 g/eq.

并且，优选使所述环氧树脂(a1)所具有的环氧基的总量中的80～100摩尔％与所述化合物(a2)的酸基反应，更优选使所述环氧基的全部与所述化合物(a2)的酸基反应。In addition, it is preferable to react 80 to 100 mol % of the total amount of epoxy groups in the epoxy resin (a1) with the acid groups of the compound (a2), and it is more preferable to react all of the epoxy groups. Reaction with the acid group of the compound (a2).

所述化合物(a2)是具有酸基和聚合性不饱和基的化合物。通过使所述化合物(a2)所具有的酸基、与所述环氧树脂(a1)所具有的环氧基反应，从而可以将聚合性不饱和基导入所述乙烯基酯树脂(A)中。The compound (a2) is a compound having 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) .

作为所述化合物(a2)，例如可列举：丙烯酸、甲基丙烯酸、衣康酸、2-丙烯酰氧基乙基琥珀酸酯、2-甲基丙烯酰氧基乙基琥珀酸酯、2，2，2，-三丙烯酰氧基甲基乙基邻苯二甲酸酯等。这些化合物中，优选可以将容易与后述的活性能量射线固化性组合物中的树脂、单体所具有的聚合性不饱和基发生聚合反应的丙烯酰基导入所述乙烯基酯树脂(A)中的丙烯酸。此外，这些化合物(a2)可以单独使用，也可以同时使用两种以上，在所述化合物(a2)的总量中优选使用50质量％以上的丙烯酸。Examples of the compound (a2) include: acrylic acid, methacrylic acid, itaconic acid, 2-acryloyloxyethylsuccinate, 2-methacryloyloxyethylsuccinate, 2, 2,2,-triacryloyloxymethylethyl phthalate, etc. Among these compounds, it is preferable that an acryloyl group capable of polymerizing with a polymerizable unsaturated group contained in a resin or a monomer in the active energy ray-curable composition described later can be introduced into the vinyl ester resin (A). of acrylic. In addition, these compounds (a2) may be used alone or in combination of two or more, and it is preferable to use 50% by mass or more of acrylic acid in the total amount of the compounds (a2).

所述环氧树脂(a1)与所述化合物(a2)的反应温度优选为60～150℃的范围，更优选为80～120℃的范围。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.

此外，在使所述环氧树脂(a1)与所述化合物(a2)反应时，为了防止所述化合物(a2)所具有的聚合性不饱和基发生热聚合，优选使用阻聚剂。相对于所述环氧树脂(a1)和所述化合物(a2)的总质量，阻聚剂的添加量优选为500～5,000ppm的范围。In addition, when the epoxy resin (a1) is reacted with the compound (a2), it is preferable to use a polymerization inhibitor in order to prevent thermal polymerization of the polymerizable unsaturated group contained in the compound (a2). It is preferable that the addition amount of a polymerization inhibitor is the range of 500-5,000 ppm with respect to the total mass of the said epoxy resin (a1) and the said compound (a2).

作为所述阻聚剂，例如可列举：2，6-双(叔丁基)-4-甲基苯酚、对苯二酚、甲基对苯二酚、对苯二酚单甲醚(对甲氧基苯酚)、对叔丁基儿茶酚、硝基苯、硝基苯甲酸、邻二硝基苯、间二硝基苯、对二硝基苯、2，4-二硝基苯酚、三硝基苯等。这些阻聚剂可以单独使用，也可以同时使用两种以上。As the polymerization inhibitor, for example, 2,6-bis(tert-butyl)-4-methylphenol, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether (p-methylhydroquinone) oxyphenol), p-tert-butylcatechol, nitrobenzene, nitrobenzoic acid, o-dinitrobenzene, m-dinitrobenzene, p-dinitrobenzene, 2,4-dinitrophenol, three Nitrobenzene etc. These polymerization inhibitors may be used alone or in combination of two or more.

并且，在使所述环氧树脂(a1)与所述化合物(a2)反应时，可使用反应催化剂。相对于所述环氧树脂(a1)100质量份，所述反应催化剂的用量优选为0.1～5质量份的范围。Moreover, when making the said epoxy resin (a1) and the said compound (a2) react, a reaction catalyst can be used. It is preferable that the usage-amount of the said reaction catalyst is the range of 0.1-5 mass parts with respect to 100 mass parts of said epoxy resins (a1).

作为所述反应催化剂，例如可列举：胺催化剂、咪唑催化剂、磷催化剂、硼催化剂、磷-硼催化剂等。具体地可列举：乙基胍、三甲基胍、苯基胍、二苯基胍等烷基取代胍；3-(3，4-二氯苯基)-1，1-二甲基脲、3-苯基-1，1-二甲基脲、3-(4-氯苯基)-1，1-二甲基脲等3-取代苯基-1，1-二甲基脲；2-甲基咪唑啉、2-苯基咪唑啉、2-十一烷基咪唑啉、2-十七烷基咪唑啉等咪唑啉；2-氨基吡啶等单氨基吡啶；N，N-二甲基-N-(2-羟基-3-烯丙氧基丙基)胺-N’-乳酰胺等胺酰亚胺；乙基膦、丙基膦、丁基膦、苯基膦、三甲基膦、三乙基膦、三丁基膦、三辛基膦、三苯基膦、三环己基膦、三苯基膦-三苯基硼烷络合物、四苯基鏻四苯基硼酸盐等有机磷催化剂、1，8-二氮杂双环[5.4.0]十一碳-7-烯、1，4-二氮杂双环[2.2.2]辛烷等二氮杂双环十一烯催化剂等。这些反应催化剂可以单独使用，也可以同时使用两种以上。As said reaction catalyst, an amine catalyst, an imidazole catalyst, a phosphorus catalyst, a boron catalyst, a phosphorus-boron catalyst etc. are mentioned, for example. Specific examples include: ethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine and other alkyl-substituted guanidines; 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, etc. 3-substituted phenyl-1,1-dimethylurea; 2- Methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline and other imidazolines; 2-aminopyridine and other monoaminopyridines; N, N-dimethyl- Amine imides such as N-(2-hydroxy-3-allyloxypropyl)amine-N'-lactamide; ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, Triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine-triphenylborane complex, tetraphenylphosphonium tetraphenylborate, etc. Organophosphorus catalysts, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,4-diazabicyclo[2.2.2]octane and other diazabicycloundecene catalysts, etc. . These reaction catalysts may be used alone or in combination of two or more.

由于树脂粒子的分散稳定性提高，因此作为用所述方法得到的乙烯基酯树脂(A)的重均分子量优选为500～10,000的范围，更优选为1,000～6,000的范围。Since the dispersion stability of the resin particles improves, 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.

具有芳香环的氨基甲酸酯树脂(B)是使含有多元醇(b1-1)和多元醇(b1-2)的多元醇(b1)与多异氰酸酯(b2)反应而得到的，其中，所述多元醇(b1-1)具有芳香环，所述多元醇(b1-2)具有亲水性基。The urethane resin (B) having an aromatic ring is obtained by reacting a polyol (b1) containing a polyol (b1-1) and a polyol (b1-2) with a polyisocyanate (b2), wherein the The polyol (b1-1) has an aromatic ring, and the polyol (b1-2) has a hydrophilic group.

将所述多元醇(b1-1)用作所述氨基甲酸酯树脂(B)的原料，由此所述氨基甲酸酯树脂(B)成为具有芳香环的树脂。此外，所述多元醇(b1-1)中的芳香环浓度优选为1.5～8mol/kg的范围，更优选为1.6～5mol/kg的范围。By using the polyol (b1-1) as a raw material of the urethane resin (B), the urethane resin (B) becomes a resin having an aromatic ring. In addition, 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.

作为所述多元醇(b1-1)，例如可列举：芳香族聚酯多元醇、芳香族聚碳酸酯多元醇、芳香族聚醚多元醇、双酚的环氧烷加成物等。这些可以单独使用，也可以同时使用两种以上。Examples of the polyol (b1-1) include aromatic polyester polyols, aromatic polycarbonate polyols, aromatic polyether polyols, and alkylene oxide adducts of bisphenols. These may be used alone or in combination of two or more.

此外，因为基材密合性和抗粘连性优异，所述多元醇(b1-1)中优选为芳香族聚酯多元醇、作为双酚的环氧烷加成物的一种的双酚A的环氧烷加成物。由此，作为所述多元醇(b1-1)，优选使用包含芳香族聚酯多元醇和双酚A的环氧烷加成物中的至少一种的多元醇。In addition, among the polyols (b1-1), aromatic polyester polyols and bisphenol A, which is a kind of alkylene oxide adducts of bisphenols, are preferable because of excellent substrate adhesion and blocking resistance. of alkylene oxide adducts. Therefore, as the polyol (b1-1), it is preferable to use a polyol containing at least one of an aromatic polyester polyol and an alkylene oxide adduct of bisphenol A.

所述芳香族聚酯多元醇是使多元羧酸与多元醇进行酯化反应而得到的，使用所述多元羧酸和多元醇中的至少一种中具有芳香环的芳香族聚酯多元醇。The aromatic polyester polyol is obtained by esterifying a polycarboxylic acid and a polyol, and an aromatic polyester polyol having an aromatic ring in at least one of the polycarboxylic acid and polyol is used.

所述多元羧酸中，作为具有芳香环的多元羧酸，例如可列举：邻苯二甲酸、间苯二甲酸、对苯二甲酸、萘二甲酸等芳香族二元羧酸或其酯化物。此外，作为不具有芳香环的多元羧酸，例如可列举：丁二酸、戊二酸、己二酸、马来酸、庚二酸、辛二酸、壬二酸、衣康酸、癸二酸、氯菌酸、1，2，4-丁烷三甲酸、癸烷二甲酸、环己烷二甲酸、二聚酸、富马酸等脂肪族二羧酸或其酯化物。这些多元羧酸或其酯化物可以单独使用，也可以同时使用两种以上。Among the polyvalent carboxylic acids, examples of the polyvalent carboxylic acid having an aromatic ring include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalene dicarboxylic acid, or esterified products thereof. In addition, examples of polyvalent carboxylic acids not having an aromatic ring include succinic acid, glutaric acid, adipic acid, maleic acid, pimelic acid, suberic acid, azelaic acid, itaconic acid, sebacic acid, Aliphatic dicarboxylic acids such as chlorobenic acid, chlorobenic acid, 1,2,4-butanetricarboxylic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, fumaric acid, or their esters. These polyvalent carboxylic acids or their ester compounds may be used alone, or two or more of them may be used in combination.

所述多元醇中，作为具有芳香环的多元醇，例如可列举：苯二甲醇、甲苯二甲醇、二甲苯二甲醇等芳香族二醇。此外，作为不具有芳香环的多元醇，例如可列举：乙二醇、丙二醇、1，3-丙二醇、1，4-丁二醇、1，6-己二醇、1，8-辛二醇、二乙二醇、三乙二醇、1，4-环己二醇、1，4-环己烷二甲醇、新戊二醇乙二醇等脂肪族多元醇。这些多元醇可以单独使用，也可以同时使用两种以上。Among the above-mentioned polyols, examples of polyols having an aromatic ring include aromatic diols such as benzenedimethanol, toluenedimethanol, and xylenedimethanol. In addition, examples of polyhydric alcohols not having an aromatic ring include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,8-octanediol , diethylene glycol, triethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol ethylene glycol and other aliphatic polyols. These polyols may be used alone or in combination of two or more.

所述多元醇(b1-2)是具有亲水性基的多元醇。作为所述亲水性基，可列举：阴离子性基、阳离子性基、非离子性基，优选为阴离子性基，阴离子性基中优选为羧基、磺酸基。The polyol (b1-2) is a polyol having a hydrophilic group. Examples of the hydrophilic group include anionic groups, cationic groups, and nonionic groups, preferably anionic groups, and among anionic groups, carboxyl groups and sulfonic acid groups are preferable.

作为具有以羧基为亲水性基的多元醇，例如可列举：2，2-二羟甲基丙酸、2，2-二羟甲基丁酸、2，2-二羟甲基戊酸等。它们之中，优选2，2-二羟甲基丙酸。此外，也可以使用使所述具有羧基的多元醇与多元羧酸反应而得的具有羧基的聚酯多元醇。Examples of the polyhydric alcohol having a carboxyl group as a hydrophilic group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, etc. . Among them, 2,2-dimethylolpropionic acid is preferable. Moreover, you may use the polyester polyol which has a carboxyl group obtained by reacting the said polyol which has a carboxyl group, and polyhydric carboxylic acid.

作为具有以磺酸基为亲水性基的多元醇、例如可列举：使5-磺基间苯二甲酸、磺基对苯二甲酸、4-磺基邻苯二甲酸、5-(4-磺基苯氧基)间苯二甲酸等二羧酸或它们的盐与乙二醇、丙二醇、1，4-丁二醇、1，6-己二醇、二乙二醇、新戊二醇等低分子多元醇反应而得的聚酯多元醇等。As a polyhydric alcohol having a sulfonic acid group as a hydrophilic group, for example, 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5-(4- Dicarboxylic acids such as sulfophenoxy) isophthalic acid or their salts with ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol Polyester polyols obtained by reacting low-molecular-weight polyols, etc.

因为可对所述氨基甲酸酯树脂(B)赋予良好的水分散性，因此优选将所述阴离子性基的一部分或全部用碱性化合物进行中和。Since good water dispersibility can be imparted to the urethane resin (B), it is preferable to neutralize a part or all of the anionic groups with a basic compound.

作为所述碱性化合物，例如可列举：氨；三乙胺、吗啉、单乙醇胺、二乙基乙醇胺等有机胺；氢氧化钠、氢氧化钾、氢氧化锂等金属氢氧化物等。因为可以更提高本发明的水性树脂组合物的水分散稳定性，所述碱性化合物的用量以碱性化合物与阴离子性基的摩尔比[碱性化合物/阴离子性基]计，优选为0.5～3的范围，更优选为0.7～1.5的范围。Examples of the basic compound include ammonia; organic amines such as triethylamine, morpholine, monoethanolamine, and diethylethanolamine; metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; and the like. Because the water dispersion stability of the water-based resin composition of the present invention can be further improved, the amount of the basic compound is based on the molar ratio [basic compound/anionic group] of the basic compound to the anionic group, preferably 0.5- 3, more preferably 0.7 to 1.5.

在制造所述芳香族聚酯多元醇时的酯化反应中，为了促进酯化反应，优选使用酯化催化剂。作为所述酯化催化剂，例如可列举：钛、锡、锌、铝、锆、镁、铪、锗等金属；四异丙醇钛、四丁醇钛、乙酰丙酮氧钛、二丁基氧化锡、二乙酸二丁基锡、二月桂酸二丁基锡、辛酸锡、2-乙基己酸锡、乙酰丙酮锌、四氯化锆、四氯化锆四氢呋喃络合物、四氯化铪、四氯化铪四氢呋喃络合物、氧化锗、四乙氧基锗等金属化合物等。In the esterification reaction at the time of producing the said aromatic polyester polyol, it is preferable to use an esterification catalyst in order to accelerate an 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 acetylacetonate, and dibutyltin oxide. , dibutyltin diacetate, dibutyltin dilaurate, tin octoate, tin 2-ethylhexanoate, zinc acetylacetonate, zirconium tetrachloride, zirconium tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride Metal compounds such as tetrahydrofuran complexes, germanium oxide, tetraethoxygermanium, etc.

所述双酚A的环氧烷加成物是在双酚A所具有的酚性羟基上加成环氧烷而成的。作为所述环氧烷，可列举：环氧乙烷、环氧丙烷等。此外，相对于1摩尔的双酚A，环氧烷的平均加成摩尔数优选为1～8的范围，更优选为1～4的范围。The alkylene oxide adduct of bisphenol A is obtained by adding alkylene oxide to the phenolic hydroxyl group of bisphenol A. As said alkylene oxide, ethylene oxide, propylene oxide, etc. are mentioned. Moreover, it is preferable that the average added mole number of an alkylene oxide is the range of 1-8 with respect to 1 mol of bisphenol A, and it is more preferable that it is the range of 1-4.

本发明中，多元醇(b1)作为必需成分而含有所述多元醇(b1-1)和所述多元醇(b1-2)，也可以含有除它们以外的多元醇(b1-3)。作为所述多元醇(b1-3)，例如可列举：脂肪族聚酯多元醇、脂肪族聚碳酸酯多元醇、脂肪族聚醚多元醇、氢化双酚的环氧烷加成物等。此外，作为所述多元醇(b1-3)，也可以使用作为所述芳香族聚酯多元醇的原料而列举的所述多元醇。这些多元醇(b1-3)可以单独使用，也可以同时使用两种以上。In the present invention, the polyol (b1) contains the above-mentioned polyol (b1-1) and the above-mentioned polyol (b1-2) as essential components, and may contain polyols (b1-3) other than these. Examples of the polyol (b1-3) include aliphatic polyester polyols, aliphatic polycarbonate polyols, aliphatic polyether polyols, alkylene oxide adducts of hydrogenated bisphenols, and the like. In addition, as the polyol (b1-3), the polyols listed as the raw material of the aromatic polyester polyol can also be used. These polyols (b1-3) may be used alone or in combination of two or more.

此外，因为更提高对基材的密合性，多元醇(b1)中所含的具有芳香环的多元醇(b1-1)的比例优选为40～98质量％的范围，更优选为60～98质量％的范围。In addition, 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, more preferably 60 to 98% by mass.

作为成为所述氨基甲酸酯树脂(B)的原料的多异氰酸酯(b2)，例如可列举：4，4’-二苯基甲烷二异氰酸酯、2，4’-二苯基甲烷二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、粗制二苯基甲烷二异氰酸酯、苯二异氰酸酯、甲苯二异氰酸酯、萘二异氰酸酯等芳香族多异氰酸酯；六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯等脂肪族多异氰酸酯；环己烷二异氰酸酯、双环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯等。这些多异氰酸酯(b2)可以单独使用，也可以同时使用两种以上。Examples of the polyisocyanate (b2) used as a raw material for the urethane resin (B) include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbonized Diimine modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, toluene diisocyanate, naphthalene diisocyanate and other aromatic polyisocyanates; hexamethylene diisocyanate, lysine diisocyanate , xylylene diisocyanate, tetramethylxylylene diisocyanate and other aliphatic polyisocyanates; cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, etc. These polyisocyanates (b2) may be used alone or in combination of two or more.

因为更提高对基材的密合性，所述多异氰酸酯(b2)中优选含有芳香族多异氰酸酯。此时的所述多异氰酸酯(b2)中的芳香族多异氰酸酯的含量优选为15～35质量％的范围。It is preferable to contain an aromatic polyisocyanate in the said polyisocyanate (b2) in order to improve the adhesiveness to a base material more. In this case, it is preferable that content of the aromatic polyisocyanate in the said polyisocyanate (b2) is the range of 15-35 mass %.

所述氨基甲酸酯树脂(B)可以例如在无溶剂下或有机溶剂的存在下，混合所述多元醇(b1)和所述多异氰酸酯(b2)，使之在40～120℃的温度下反应3～20小时进行制造。此外，制造所述氨基甲酸酯树脂(B)时，根据需要，也可以使用扩链剂。The urethane resin (B) can be, for example, mixed with the polyol (b1) and the polyisocyanate (b2) in the absence of a solvent or in the presence of an organic solvent so that it can be mixed at a temperature of 40 to 120°C. Production is carried out by reacting for 3 to 20 hours. Moreover, when producing the said urethane resin (B), you may use a chain extender as needed.

所述多元醇(b1)与所述多异氰酸酯(b2)的反应优选所述多元醇(b1)所具有的羟基与所述多异氰酸酯(b2)所具有的异氰酸酯基的当量比[异氰酸酯基/羟基]在0.5～3.5的范围内进行，更优选在0.9～2.5的范围内进行。The reaction between the polyol (b1) and the polyisocyanate (b2) is preferably an equivalent ratio of the hydroxyl groups of the polyol (b1) to the isocyanate groups of the polyisocyanate (b2) [isocyanate group/hydroxyl group ] in the range of 0.5 to 3.5, more preferably in the range of 0.9 to 2.5.

作为可在制造所述氨基甲酸酯树脂(B)时使用的有机溶剂，例如可列举：丙酮、甲乙酮等酮溶剂；四氢呋喃、二噁烷等醚溶剂；乙酸乙酯、乙酸丁酯等乙酸酯溶剂；乙腈等腈溶剂；二甲基甲酰胺、N-甲基吡咯烷酮等酰胺溶剂等。这些有机溶剂可以单独使用，也可以同时使用两种以上。Examples of organic solvents that can be used for the production of the urethane resin (B) include: ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; acetic acid solvents such as ethyl acetate and butyl acetate; Ester solvents; nitrile solvents such as acetonitrile; amide solvents such as dimethylformamide and N-methylpyrrolidone, etc. These organic solvents may be used alone or in combination of two or more.

因为更提高基材与活性能量射线固化性组合物的固化涂膜的密合性，作为用上述的方法得到的所述氨基甲酸酯树脂(B)的重均分子量优选为3,000～200,000的范围，更优选为3,000～100,000的范围。The weight-average molecular weight of the urethane resin (B) obtained by the above-mentioned method is preferably in the range of 3,000 to 200,000 in order to further improve the adhesion between the base material and the cured coating film of the active energy ray-curable composition. , more preferably in the range of 3,000 to 100,000.

作为水性介质(C)，可列举：水、与水混和的有机溶剂、以及它们的混合物。作为与水混和的有机溶剂，例如可列举：甲醇、乙醇、正丙醇、异丙醇等醇溶剂；丙酮、甲乙酮等酮溶剂；乙二醇、二乙二醇、丙二醇等聚亚烷基二醇；聚亚烷基二醇的烷基醚溶剂；N-甲基-2-吡咯烷酮等内酰胺溶剂等。这些与水混和的有机溶剂可以单独使用，也可以同时使用两种以上。Examples of the aqueous medium (C) include water, an organic solvent mixed with water, and mixtures thereof. Examples of organic solvents to be mixed 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; alcohol; alkyl ether solvent of polyalkylene glycol; lactam solvent such as N-methyl-2-pyrrolidone, etc. These water-mixable organic solvents may be used alone or in combination of two or more.

此外，如果考虑到安全性和减轻环境负担，则作为所述水性介质(C)优选为仅为水、或者水和与水混和的有机溶剂的混合物，更优选为仅为水。In addition, in consideration of safety and reduction of environmental load, the aqueous medium (C) is preferably water alone or a mixture of water and an organic solvent mixed with water, more preferably only water.

所述水性介质(C)的比例优选为10～90质量％的范围，更优选为30～70质量％的范围。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.

水性树脂组合物(D)是将所述乙烯基酯树脂(A)和所述氨基甲酸酯树脂(B)分散于所述水性介质(C)中而得的。此时，所述乙烯基酯树脂(A)与所述氨基甲酸酯树脂(B)也可以作为各自的树脂粒子存在于所述水性介质(C)中，优选使用形成了所述乙烯基酯树脂(A)的一部分或全部内置于所述氨基甲酸酯树脂(B)粒子中的树脂粒子(F)的物品。更具体地，优选为所述乙烯基酯树脂(A)形成芯部、所述氨基甲酸酯树脂(B)形成壳部的芯/壳型的树脂粒子(F)。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 also exist in the aqueous medium (C) as separate resin particles. An article in which part or all of the resin (A) is embedded in the resin particles (F) in the urethane resin (B) particles. More specifically, core/shell type resin particles (F) in which the vinyl ester resin (A) forms the core and the urethane resin (B) forms the shell are preferred.

所述树脂粒子(F)可通过如下方法来制造：预先制造所述乙烯基酯树脂(A)和所述氨基甲酸酯树脂(B)，然后向所述氨基甲酸酯树脂(B)混合所述乙烯基酯树脂(A)、中和所述氨基甲酸酯树脂(B)所具有的阴离子性基的碱性化合物和所述水性介质(C)。The resin particles (F) can be produced by preparing the vinyl ester resin (A) and the urethane resin (B) in advance, and then mixing them with the urethane resin (B). The said vinyl ester resin (A), the basic compound which neutralizes the anionic group which the said urethane resin (B) has, and the said aqueous medium (C).

在用所述方法得到的水性树脂组合物(D)中含有有机溶剂的情况下，为了实现安全性和减轻环境负荷，也可以利用蒸馏法等除去所述有机溶剂。由此，可以得到将所述树脂粒子(F)分散于水性介质(C)中而成的水性树脂组合物(D)。When an organic solvent is contained in the aqueous resin composition (D) obtained by the said method, you may remove the said organic solvent by the distillation method etc. in order to realize safety and environmental load reduction. Thereby, the aqueous resin composition (D) which disperse|distributed the said resin particle (F) in an aqueous medium (C) can be obtained.

因为更提高与活性能量射线固化性组合物的固化涂膜的密合性，所述乙烯基酯树脂(A)与所述氨基甲酸酯树脂(B)的质量比例[(A)/(B)]优选为60/40～10/90的范围，更优选为55/45～20/80的范围。予以说明，该范围在将所述乙烯基酯树脂(A)和所述氨基甲酸酯树脂(B)用作所述树脂粒子(F)的情况下也相同。The mass ratio of the vinyl ester resin (A) to the urethane resin (B) [(A)/(B )] is preferably in the range of 60/40 to 10/90, more preferably in the range of 55/45 to 20/80. In addition, this range is the same also when using the said vinyl ester resin (A) and the said urethane resin (B) as the said resin particle (F).

此外，所述水性树脂组合物(D)总量中的所述乙烯基酯树脂(A)和所述氨基甲酸酯树脂(B)的总量的比例优选为10～90质量％的范围，更优选为30～70质量％的范围。In addition, the proportion 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, More preferably, it is the range of 30-70 mass %.

根据需要，所述水性树脂组合物(D)中可配合：成膜助剂、固化剂、增塑剂、抗静电剂、蜡、光稳定剂、流动调节剂、染料、流平剂、流变调节剂、紫外线吸收剂、抗氧化剂、光催化性化合物、无机颜料、有机颜料、体质颜料等添加剂；聚酯树脂、氨基甲酸酯树脂、丙烯酸类树脂等其他的树脂等。According to needs, the water-based resin composition (D) can be mixed with: film-forming aids, curing agents, plasticizers, antistatic agents, waxes, light stabilizers, flow regulators, dyes, leveling agents, rheological Additives such as modifiers, ultraviolet absorbers, antioxidants, photocatalytic compounds, inorganic pigments, organic pigments, and extender pigments; other resins such as polyester resins, urethane resins, and acrylic resins, etc.

本发明的涂布剂以碳化二亚胺类交联剂(E)为必需成分。所述交联剂(E)所具有的碳化二亚胺基与所述氨基甲酸酯树脂(B)所具有的羧基等亲水性基反应形成三维的交联构造，由此提高基材与活性能量射线固化性组合物的固化涂膜的密合性，此外，在将本发明的涂布剂用作底涂剂的情况下，可以对形成的底涂层赋予耐湿热试验后的高密合性和优异的耐化学品性。The coating agent of the present invention contains a carbodiimide crosslinking agent (E) as an essential component. The carbodiimide group possessed by the crosslinking agent (E) reacts with the carboxyl group and other hydrophilic groups possessed by the urethane resin (B) to form a three-dimensional crosslinked structure. The adhesiveness of the cured coating film of the active energy ray-curable composition, and when the coating agent of the present invention is used as an undercoating agent, it is possible to impart high adhesion after the heat-and-moisture resistance test to the formed undercoat layer. and excellent chemical resistance.

作为所述交联剂(E)，优选为具有两个以上碳化二亚胺基的交联剂，作为这样的交联剂，例如可列举：聚(4，4’-二苯基甲烷碳化二亚胺)、聚(对亚苯基碳化二亚胺)、聚(间亚苯基碳化二亚胺)、聚(二异丙基苯基碳化二亚胺)、聚(三异丙基苯基碳化二亚胺)等芳香族聚碳化二亚胺；聚(双环己基甲烷碳化二亚胺)等脂环族聚碳化二亚胺、聚(二异丙基碳化二亚胺)等脂肪族聚碳化二亚胺等。The crosslinking agent (E) is preferably a crosslinking agent having two or more carbodiimide groups, and examples of such a crosslinking agent include poly(4,4'-diphenylmethanecarbodiimide imine), poly(p-phenylenecarbodiimide), poly(m-phenylenecarbodiimide), poly(diisopropylphenylcarbodiimide), poly(triisopropylphenylene Aromatic polycarbodiimides such as carbodiimide); aliphatic polycarbodiimides such as poly(dicyclohexylmethanecarbodiimide) and aliphatic polycarbodiimides such as poly(diisopropylcarbodiimide) Diimine etc.

此外，作为所述交联剂(E)，因为本发明的涂布剂是将所述乙烯基酯树脂(A)和所述氨基甲酸酯树脂(B)分散于水性介质(C)中而得的，因此优选为具有水溶性或水分散性(乳液型)的交联剂。In addition, as the crosslinking agent (E), the coating agent of the present invention is obtained by dispersing the vinyl ester resin (A) and the urethane resin (B) in the aqueous medium (C). Therefore, it is preferably a water-soluble or water-dispersible (emulsion type) crosslinking agent.

作为可用作所述交联剂(E)的市售品，可列举：日清纺化学株式会社制造的“CARBODILITE SV-02”、“CARBODILITE V-02”、“CARBODILITE V-02-L2”、“CARBODILITE V-04”、“CARBODILITEE-01”、“CARBODILITE E-02”等。Examples of commercially available products that can be used as the crosslinking agent (E) include "Carbodilite SV-02", "Carbodilite V-02", and "Carbodilite V-02-L2" manufactured by Nisshinbo Chemical Co., Ltd. , "CARBODILITE V-04", "CARBODILITEE-01", "CARBODILITE E-02", etc.

因为表现足够的交联性能，所述交联剂(E)的用量优选为能与亲水性基的80～100摩尔％反应的量，更优选为与100摩尔％反应的量，其中，所述亲水性基为可与碳化二亚胺基反应的所述氨基甲酸酯树脂(B)所具有的亲水性基。Because of sufficient cross-linking performance, the amount of the cross-linking agent (E) is preferably an amount capable of reacting with 80-100 mol% of the hydrophilic group, more preferably an amount reacting with 100 mol%, wherein, The said hydrophilic group is the hydrophilic group which the said urethane resin (B) has which can react with a carbodiimide group.

此外，因为提高密合性、与所述水性树脂组合物(D)的保存稳定性，相对于所述水性树脂组合物(D)，所述交联剂(E)优选在3～5质量％的范围内添加。In addition, the crosslinking agent (E) is preferably contained in an amount of 3 to 5% by mass relative to the aqueous resin composition (D) in order to improve adhesion and storage stability with the aqueous resin composition (D). added within the range.

本发明的层叠体是具有使用上述说明的本发明的涂布剂形成的底涂层、且在所述底涂层的表面具有使用活性能量射线固化性组合物形成的固化涂膜的层叠体。The laminate of the present invention has an undercoat 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 undercoat layer.

作为所述活性能量射线固化性组合物，优选含有具有聚合性不饱和基的树脂和具有聚合性不饱和基的单体，这些具有聚合性不饱和基的树脂和具有聚合性不饱和基的单体的种类优选根据所述活性能量射线固化性组合物的固化涂膜所要求的特性来适当地选择。The active energy ray-curable composition preferably contains a resin having a polymerizable unsaturated group and a monomer having a polymerizable unsaturated group, and these resins having a polymerizable unsaturated group and monomers having a polymerizable unsaturated group The type of body is preferably appropriately selected according to the properties required for the cured coating film of the active energy ray-curable composition.

作为所述具有聚合性不饱和基的树脂，可列举：氨基甲酸酯(甲基)丙烯酸酯树脂、不饱和聚酯树脂、环氧(甲基)丙烯酸酯树脂、聚酯(甲基)丙烯酸酯树脂、丙烯酰基(甲基)丙烯酸酯树脂、具有马来酰亚胺基的树脂等。这些具有聚合性不饱和基的树脂可以单独使用，也可以同时使用两种以上。Examples of the resin having a polymerizable unsaturated group include: urethane (meth)acrylate resins, unsaturated polyester resins, epoxy (meth)acrylate resins, polyester (meth)acrylate resins, Ester resins, acryloyl (meth)acrylate resins, resins having maleimide groups, and the like. These polymerizable unsaturated group-containing resins may be used alone or in combination of two or more.

本发明中，“(甲基)丙烯酸酯”是指丙烯酸酯和甲基丙烯酸酯的一者或两者，“(甲基)丙烯酰基”是指丙烯酰基和甲基丙烯酰基的一者或两者。In the present invention, "(meth)acrylate" refers to one or both of acrylate and methacrylate, and "(meth)acryloyl" refers to one or both of acryloyl and methacryloyl. By.

作为所述氨基甲酸酯(甲基)丙烯酸酯树脂，例如可列举：使脂肪族多异氰酸酯或芳香族多异氰酸酯与具有羟基的(甲基)丙烯酸酯发生氨基甲酸酯化反应而得到的具有氨基甲酸酯键和(甲基)丙烯酰基的树脂等。Examples of the above-mentioned urethane (meth)acrylate resins include those obtained by urethane-forming an aliphatic polyisocyanate or an aromatic polyisocyanate and a (meth)acrylate having a hydroxyl group. Urethane bond and (meth)acryloyl resin, etc.

作为所述脂肪族多异氰酸酯，例如可列举：四亚甲基二异氰酸酯、五亚甲基二异氰酸酯、六亚甲基二异氰酸酯、七亚甲基二异氰酸酯、八亚甲基二异氰酸酯、十亚甲基二异氰酸酯、2-甲基-1，5-戊烷二异氰酸酯、3-甲基-1，5-戊烷二异氰酸酯、十二亚甲基二异氰酸酯、2-甲基五亚甲基二异氰酸酯、2，2，4-三甲基六亚甲基二异氰酸酯、2，4，4-三甲基六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、降冰片烷二异氰酸酯、氢化二苯基甲烷二异氰酸酯、氢化甲苯二异氰酸酯、氢化苯二亚甲基二异氰酸酯、氢化四甲基苯二亚甲基二异氰酸酯、环己基二异氰酸酯等。此外，作为所述芳香族多异氰酸酯，可列举：甲苯二异氰酸酯、4，4’-二苯基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、1，5-萘二异氰酸酯、联甲苯胺二异氰酸酯、对苯二异氰酸酯等。Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 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 diphenyl Methane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, cyclohexyl diisocyanate, and the like. In addition, examples of the aromatic polyisocyanate include toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, and benzidine diisocyanate. , p-phenylene diisocyanate, etc.

作为所述具有羟基的(甲基)丙烯酸酯，例如可列举：(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、(甲基)丙烯酸2-羟基丁酯、(甲基)丙烯酸4-羟基丁酯、1，5-戊二醇单(甲基)丙烯酸酯、1，6-己二醇单(甲基)丙烯酸酯、新戊二醇单(甲基)丙烯酸酯、羟基特戊酸新戊二醇单(甲基)丙烯酸酯等二元醇的单(甲基)丙烯酸酯；三羟甲基丙烷二(甲基)丙烯酸酯、乙氧基化三羟甲基丙烷(甲基)丙烯酸酯、丙氧基化三羟甲基丙烷二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、双(2-(甲基)丙烯酰氧基乙基)羟基乙基异氰脲酸酯等三元醇的单或二(甲基)丙烯酸酯、或者具有将这些醇性羟基的一部分用ε-己内酯改性的羟基的单和二(甲基)丙烯酸酯；季戊四醇三(甲基)丙烯酸酯、双三羟甲基丙烷三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯等具有单官能的羟基与三官能以上的(甲基)丙烯酰基的化合物，或者具有将该化合物进一步用ε-己内酯改性的羟基的多官能(甲基)丙烯酸酯；二丙二醇单(甲基)丙烯酸酯、二乙二醇单(甲基)丙烯酸酯、聚丙二醇单(甲基)丙烯酸酯、聚乙二醇单(甲基)丙烯酸酯等具有氧化烯链的(甲基)丙烯酸酯化合物；聚乙二醇-聚丙二醇单(甲基)丙烯酸酯、聚氧丁烯-聚氧丙烯单(甲基)丙烯酸酯等具有嵌段结构的氧化烯链的(甲基)丙烯酸酯化合物；聚(乙二醇-1，4-丁二醇)单(甲基)丙烯酸酯、聚(丙二醇-1，4-丁二醇)单(甲基)丙烯酸酯等具有无规结构的氧化烯链的(甲基)丙烯酸酯化合物等。Examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-Hydroxybutyl (meth)acrylate, 1,5-pentanediol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate Mono(meth)acrylates of glycols such as acrylates, hydroxypivalate neopentyl glycol mono(meth)acrylate; trimethylolpropane di(meth)acrylate, ethoxylated trihydroxy Methylpropane (meth)acrylate, propoxylated trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, bis(2-(meth)acryloyloxyethyl ) Mono- or di-(meth)acrylates of trihydric alcohols such as hydroxyethyl isocyanurate, or mono- and di-(methyl) ) acrylates; pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc. have monofunctional hydroxyl groups and trifunctional or more (methyl) ) acryloyl compound, or a multifunctional (meth)acrylate with a hydroxyl group that further modifies the compound with ε-caprolactone; dipropylene glycol mono(meth)acrylate, diethylene glycol mono(methyl) ) acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate and other (meth)acrylate compounds with oxyalkylene chains; polyethylene glycol-polypropylene glycol mono(meth)acrylate ) acrylate, polyoxybutylene-polyoxypropylene mono(meth)acrylate and other (meth)acrylate compounds with block-structured oxyalkylene chains; poly(ethylene glycol-1,4-butanediol ) mono(meth)acrylate, poly(propylene glycol-1,4-butylene glycol) mono(meth)acrylate and other (meth)acrylate compounds having an oxyalkylene chain having a random structure, and the like.

所述不饱和聚酯树脂是通过α，β-不饱和二元酸或其酸酐、芳香族饱和二元酸或其酸酐、以及二醇的缩聚而得到的固化性树脂。作为所述α，β-不饱和二元酸或其酸酐，例如可列举：马来酸、马来酸酐、富马酸、衣康酸、柠康酸、氯马来酸、以及它们的酯等。作为所述芳香族饱和二元酸或其酸酐，可列举：邻苯二甲酸、邻苯二甲酸酐、间苯二甲酸、对苯二甲酸、硝基邻苯二甲酸、四氢邻苯二甲酸酐、内亚甲基四氢邻苯二甲酸酐、卤代邻苯二甲酸酐及它们的酯等。作为脂肪族或者脂环族饱和二元酸，可列举：乙二酸、丙二酸、丁二酸、己二酸、癸二酸、壬二酸、戊二酸、六氢邻苯二甲酸酐及它们的酯等。作为所述二醇，可列举：乙二醇、丙二醇、二乙二醇、二丙二醇、1，3-丁二醇、1，4-丁二醇、2-甲基丙烷-1，3-二醇、新戊二醇、三乙二醇、四乙二醇、1，5-戊二醇、1，6-己二醇、双酚A、氢化双酚A、乙二醇碳酸酯、2，2-二(4-羟基丙氧基二苯基)丙烷等，除此以外，也可同样地使用环氧乙烷、环氧丙烷等氧化物。The unsaturated polyester resin is a curable resin obtained by polycondensation of an α,β-unsaturated dibasic acid or an anhydride thereof, an aromatic saturated dibasic acid or an anhydride thereof, and a diol. Examples of the α,β-unsaturated dibasic acid or anhydride 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 its anhydride include: phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic acid Acid anhydride, endomethylene tetrahydrophthalic anhydride, halogenated phthalic anhydride and their esters, etc. Examples of aliphatic or alicyclic saturated dibasic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, and hexahydrophthalic anhydride and their esters. Examples of the diol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol Alcohol, neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2, In addition to 2-bis(4-hydroxypropoxydiphenyl)propane and the like, oxides such as ethylene oxide and propylene oxide can also be used in the same manner.

作为所述环氧(甲基)丙烯酸酯树脂，可列举：使(甲基)丙烯酸与双酚A型环氧树脂、双酚F型环氧树脂、苯酚线性酚醛型环氧树脂、甲酚线性酚醛型环氧树脂等环氧树脂的环氧基反应而得到的树脂。As said epoxy (meth)acrylate resin, can enumerate: make (meth)acrylic acid and bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol linear Resin obtained by reacting epoxy groups of epoxy resins such as novolac epoxy resins.

作为所述聚酯(甲基)丙烯酸酯树脂，例如可列举：使(甲基)丙烯酸与聚酯多元醇的羟基反应而得到的树脂。As said polyester (meth)acrylate resin, the resin obtained by making (meth)acrylic acid and the hydroxyl group of a polyester polyol react is mentioned, for example.

作为所述丙烯酰基(甲基)丙烯酸酯树脂，例如可列举通过如下反应得到的树脂：使甲基丙烯酸缩水甘油酯、以及根据需要(甲基)丙烯酸烷基酯等(甲基)丙烯酸酯单体聚合，得到具有环氧基的丙烯酸类树脂后，使(甲基)丙烯酸与该环氧基反应。Examples of the acryloyl (meth)acrylate resin include resins obtained by reacting glycidyl methacrylate and (meth)acrylate monomers such as alkyl (meth)acrylate if necessary. After bulk polymerization to obtain an acrylic resin having an epoxy group, (meth)acrylic acid is reacted with the epoxy group.

作为所述具有马来酰亚胺基的树脂，可列举：将N-羟基乙基马来酰亚胺与异佛尔酮二异氰酸酯进行氨基甲酸酯化而得到的双官能马来酰亚胺氨基甲酸酯化合物、将马来酰亚胺乙酸与1，4-丁二醇进行酯化而得到的双官能马来酰亚胺酯化合物、将马来酰亚胺己酸与季戊四醇的四环氧乙烷加成物进行酯化而得到的四官能马来酰亚胺酯化合物、将马来酰亚胺乙酸与多元醇化合物进行酯化而得到的多官能马来酰亚胺酯化合物等。Examples of the above-mentioned resin having a maleimide group include bifunctional maleimide obtained by carbamate-forming N-hydroxyethylmaleimide and isophorone diisocyanate. Urethane compounds, bifunctional maleimide ester compounds obtained by esterifying maleimide acetic acid and 1,4-butanediol, tetracyclic A tetrafunctional maleimide ester compound obtained by esterifying an oxyethane adduct, a polyfunctional maleimide ester compound obtained by esterifying maleimide acetic acid and a polyol compound, and the like.

作为所述具有聚合性不饱和基的单体，例如可列举：乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、数均分子量在150～1000的范围内的聚乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、数均分子量在150～1000的范围内的聚丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1，3-丁二醇二(甲基)丙烯酸酯、1，4-丁二醇二(甲基)丙烯酸酯、1，6-己二醇二(甲基)丙烯酸酯、羟基特戊酸酯新戊二醇二(甲基)丙烯酸酯、双酚A二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、三羟甲基丙烷二(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、(甲基)丙烯酸双环戊烯酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸异硬脂酯等脂肪族烷基(甲基)丙烯酸酯、(甲基)丙烯酸甘油酯、(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸3-氯-2-羟基丙酯、(甲基)丙烯酸缩水甘油酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸2-丁氧基乙酯、(甲基)丙烯酸2-(二乙基氨基)乙酯、(甲基)丙烯酸2-(二甲基氨基)乙酯、γ-(甲基)丙烯酰氧基丙基三甲氧基硅烷、(甲基)丙烯酸2-甲氧基乙酯、甲氧基二乙二醇(甲基)丙烯酸酯、甲氧基二丙二醇(甲基)丙烯酸酯、壬基苯氧基聚乙二醇(甲基)丙烯酸酯、壬基苯氧基聚丙二醇(甲基)丙烯酸酯、(甲基)丙烯酸苯氧基乙酯、苯氧基二丙二醇(甲基)丙烯酸酯、苯氧基聚丙二醇(甲基)丙烯酸酯、聚丁二烯(甲基)丙烯酸酯、聚乙二醇-聚丙二醇(甲基)丙烯酸酯、聚乙二醇-聚丁二醇(甲基)丙烯酸酯、聚苯乙烯基乙基(甲基)丙烯酸酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸双环戊酯、(甲基)丙烯酸双环戊烯酯、(甲基)丙烯酸异冰片酯、甲氧基化环癸三烯(甲基)丙烯酸酯、(甲基)丙烯酸苯酯；马来酰亚胺、N-甲基马来酰亚胺、N-乙基马来酰亚胺、N-丙基马来酰亚胺、N-丁基马来酰亚胺、N-己基马来酰亚胺、N-辛基马来酰亚胺、N-十二烷基马来酰亚胺、N-硬脂基马来酰亚胺、N-苯基马来酰亚胺、N-环己基马来酰亚胺、2-马来酰亚胺乙基-乙基碳酸酯、2-马来酰亚胺乙基-丙基碳酸酯、N-乙基-(2-马来酰亚胺乙基)氨基甲酸酯、N，N-六亚甲基双马来酰亚胺、聚丙二醇-双(3-马来酰亚胺丙基)醚、双(2-马来酰亚胺乙基)碳酸酯、1，4-双马来酰亚胺环己烷等马来酰亚胺化合物等。这些具有聚合性不饱和基的单体可以单独使用也可以同时使用两种以上。Examples of the monomer having a polymerizable unsaturated group include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate. ester, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate with number average molecular weight in the range of 150-1000 ) acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylic acid with number average molecular weight in the range of 150-1000 ester, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, bis Phenol A di(meth)acrylate, Trimethylolpropane tri(meth)acrylate, Trimethylolpropane di(meth)acrylate, Pentaerythritol tetra(meth)acrylate, Pentaerythritol tri(meth)acrylate ) acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dicyclopentenyl (meth)acrylate, methyl (meth)acrylate, propyl (meth)acrylate, Butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, (meth)acrylic acid Aliphatic alkyl (meth)acrylates such as isodecyl, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, glyceryl (meth)acrylate, 2-Hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, allyl (meth)acrylate, 2-(meth)acrylate -Butoxyethyl ester, 2-(diethylamino)ethyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, γ-(meth)acryloyloxypropyl Trimethoxysilane, 2-methoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, nonylphenoxy Polyethylene glycol (meth)acrylate, nonylphenoxypolypropylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydipropylene glycol (meth)acrylate, phenoxy Polypropylene glycol (meth)acrylate, polybutadiene (meth)acrylate, polyethylene glycol-polypropylene glycol (meth)acrylate, polyethylene glycol-polybutylene glycol (meth)acrylate , polystyrene ethyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, Isobornyl (meth)acrylate, methoxycyclodecatriene (meth)acrylate, phenyl (meth)acrylate; maleimide, N-methylmaleimide, N- Ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-deca dialkylmaleimide Amine, N-stearylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimide ethyl-ethyl carbonate, 2- Maleimide ethyl-propyl carbonate, N-ethyl-(2-maleimide ethyl) carbamate, N,N-hexamethylenebismaleimide, poly Propylene glycol-bis(3-maleimide propyl) ether, bis(2-maleimide ethyl) carbonate, 1,4-bismaleimide cyclohexane and other maleimides compounds etc. These monomers having a polymerizable unsaturated group may be used alone or in combination of two or more.

所述活性能量射线固化性组合物可以涂布于基材等后，通过照射活性能量射线而作为固化涂膜。作为该活性能量射线，可列举：紫外线、电子束、α射线、β射线、γ射线等电离放射线。作为活性能量射线而照射紫外线，将所述活性能量射线固化性组合物作为固化涂膜的情况下，优选向所述活性能量射线固化性组合物中添加光聚合引发剂而提高固化性。此外，如果需要，也可以进一步添加光敏剂而提高固化性。另一方面，作为活性能量射线而照射电子束、α射线、β射线或γ射线，将所述活性能量射线固化性组合物作为固化涂膜的情况下，即使不使用光聚合引发剂或光敏剂也会快速地固化，因此不需要添加光聚合引发剂或光敏剂。The active energy ray-curable composition can be applied as a cured coating film by irradiating an active energy ray after coating on 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 ultraviolet rays are irradiated as active energy rays and the active energy ray-curable composition is used as a cured coating film, it is preferable to add a photopolymerization initiator to the active energy ray-curable composition to improve curability. In addition, if necessary, a photosensitizer may be further added to improve curability. On the other hand, when the active energy ray-curable composition is irradiated with electron beams, α-rays, β-rays, or γ-rays as active energy rays to form a cured coating film, even if no photopolymerization initiator or photosensitizer is used, It also cures quickly, so no photopolymerization initiators or photosensitizers need to be added.

作为所述光聚合引发剂，例如可列举：1-羟基环己基苯基酮、2-羟基-2-甲基-1-苯基丙烷-1-酮、1-[4-(2-羟基乙氧基)-苯基]-2-羟基-甲基-1-丙烷-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-吗啉代丙烷-1-酮、2-苄基-2-二甲基氨基-1-(4-吗啉代苯基)-丁酮、双(2，6-二甲氧基苯甲酰基)-2，4，4-三甲基戊基氧化膦、双(2，4，6-三甲基苯甲酰基)-苯基氧化膦等。Examples of the photopolymerization initiator include: 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethyl Oxygen)-phenyl]-2-hydroxy-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1 -ketone, 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.

作为所述光敏剂，例如可列举：脂肪族胺、芳香族胺等胺化合物、邻甲苯基硫脲等脲化合物、二乙基二硫代磷酸钠、s-苄基异硫脲-对甲苯磺酸盐等硫化合物等。Examples of the photosensitizer include amine compounds such as aliphatic amines and aromatic amines, urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiourea-p-toluenesulfonate Sulfur compounds such as acid salts, etc.

作为用于本发明的层叠体的基材，例如可列举：金属基材、塑料基材、玻璃基材、纸基材、木材基材、纤维基材等。这些基材中，为了提高所述活性能量射线固化性组合物的固化涂膜与基材的密合性，在将本发明的水性树脂组合物用作底涂剂的情况下，适宜为塑料基材As a base material used for the laminated body of this invention, a metal base material, a plastic base material, a glass base material, a paper base material, a wood base material, a fiber base material etc. are mentioned, for example. Among these substrates, in order to improve the adhesion between the cured coating film of the active energy ray-curable composition and the substrate, when the aqueous resin composition of the present invention is used as a primer, a plastic-based material

作为所述塑料基材的材质，可列举：聚酯、丙烯酸类树脂(聚甲基丙烯酸甲酯等)、聚碳酸酯、丙烯腈-丁二烯-苯乙烯共聚物(ABS树脂)、ABS树脂与聚碳酸酯的复合树脂、聚苯乙烯、聚氨酯、环氧树脂、聚氯乙烯、聚酰胺、聚烯烃(聚乙烯、聚丙烯、聚环烯烃(COP)等)、三乙酰纤维素(TAC)等。Examples of the material of the plastic base material include: polyester, acrylic resin (polymethyl methacrylate, etc.), polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS resin), ABS resin Composite resin with polycarbonate, polystyrene, polyurethane, epoxy resin, polyvinyl chloride, polyamide, polyolefin (polyethylene, polypropylene, polycycloolefin (COP), etc.), triacetyl cellulose (TAC) Wait.

上述的塑料基材中，本发明的涂布剂作为聚酯基材的底涂剂非常有用。作为所述聚酯的具体例，可列举：聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)等。Among the above plastic substrates, the coating agent of the present invention is very useful as a primer for polyester substrates. Specific examples of the polyester include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and the like.

作为所述塑料基材，例如可列举：移动电话、家电产品、汽车内外装材料、OA设备等塑料成形品。此外，也可举出将塑料作为原材料的膜基材。在将膜基材作为本发明的层叠体的基材的情况下，可使用在防反射膜、相位差膜、棱镜透镜片等光学膜；铝蒸镀膜等食品包装等的高功能膜中。Examples of the plastic substrate include plastic molded articles such as mobile phones, home electric appliances, automotive interior and exterior materials, and OA equipment. Moreover, the film base material which uses 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 in optical films such as antireflection films, retardation films, and prism lens sheets; high-functional films such as food packaging such as aluminum vapor-deposited films.

此外，在将本发明的层叠体作为防反射膜、相位差膜、棱镜透镜片等光学膜的情况下，可用作液晶显示器(LCD)、有机EL显示器(OLED)、等离子体显示器(PDP)等各种画面显示装置的部件。In addition, 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, it can be used as a liquid crystal display (LCD), an organic EL display (OLED), or a plasma display (PDP). Components of various screen display devices.

本发明的涂布剂例如可通过直接在所述基材的表面涂布，然后使之干燥并固化，从而在基材的表面形成涂膜。作为使本发明的涂布剂干燥并进行固化的方法，可以是在常温下养护1～10日左右的方法，为了可迅速地进行固化，优选在100℃～150℃的温度下加热1～600秒左右的方法。此外，在使用容易在较高温度下变形或变色的塑料基材的情况下，优选在70℃～100℃左右的较低温度下加热。The coating agent of the present invention can form a coating film on the surface of the substrate by, for example, directly coating the surface of the substrate, followed by drying and curing. As the method of drying and curing the coating agent of the present invention, it may be a method of curing at room temperature for about 1 to 10 days. In order to quickly cure, it is preferable to heat at a temperature of 100°C to 150°C for 1 to 600 method in seconds or so. 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.

作为将本发明的涂布剂涂布于所述基材的表面的方法，例如可列举使用如下的涂布方法：凹版涂布机、辊涂机、逗点型涂布机、刮刀涂布机、气刀涂布机、幕涂机、舔涂机、淋涂机、流涂机、旋涂机、浸渍、丝网印刷、喷雾、毛刷涂布、敷贴器、棒涂机等。As a method of applying the coating agent of the present invention to the surface of the base material, for example, the following coating methods can be mentioned: gravure coater, roll coater, comma coater, knife coater , Air knife coater, curtain coater, lick coater, flow coater, flow coater, spin coater, dipping, screen printing, spray, brush coating, applicator, rod coater, etc.

使用本发明的涂布剂形成的涂膜的膜厚可根据使用用途进行适当调整，通常优选为0.01～20μm的范围。The film thickness of the coating film formed using the coating agent of this invention can be adjusted suitably according to a use, Usually, it is preferable that it is the range of 0.01-20 micrometers.

本发明的层叠体可通过如下方式得到：在作为如上述得到的本发明的涂布剂的涂膜即底涂层的表面，进一步涂布所述活性能量射线固化性组合物并照射活性能量射线，由此形成所述活性能量射线固化性组合物的固化涂膜。予以说明，所述活性能量射线固化性组合物的涂布方法可使用与上述的本发明的涂布剂的涂布方法相同的方法。The laminate of the present invention can be obtained by further coating the active energy ray-curable composition on the surface of the undercoat layer that is the coating film of the coating agent of the present invention obtained as described above and irradiating active energy rays. , thereby forming a cured coating film of the active energy ray-curable composition. In addition, the coating method of the said active energy ray curable composition can use the method similar to the coating method of the coating agent of this invention mentioned above.

实施例Example

下面，通过实施例和比较例对本发明作具体地说明。Next, the present invention will be specifically described by way of examples and comparative examples.

(合成例1：芳香族聚酯多元醇(1)的合成)(Synthesis Example 1: Synthesis of Aromatic Polyester Polyol (1))

一边在具备温度计、氮气导入管、搅拌机的反应容器中导入氮气，一边加入间苯二甲酸27.6质量份、对苯二甲酸27.6质量份、二乙二醇19.9质量份和二丁基氧化锡0.03质量份，在230℃下进行24小时缩聚反应直至在180～230℃下酸值为1以下，得到芳香族聚酯多元醇(1)〔酸值0.6、羟值50.0、芳香环浓度4.77mol/Kg〕。While introducing nitrogen gas into a reaction container equipped with a thermometer, a nitrogen introduction pipe, 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 0.03 parts by mass of dibutyltin oxide were added Parts, carry out polycondensation reaction at 230°C for 24 hours until the acid value is 1 or less at 180-230°C to obtain aromatic polyester polyol (1) [acid value 0.6, hydroxyl value 50.0, aromatic ring concentration 4.77mol/Kg ].

(制造例1：乙烯基酯树脂(1)的合成)(Production example 1: Synthesis of vinyl ester resin (1))

向反应容器中加入甲酚线性酚醛型环氧树脂(DIC株式会社制“EPICLON N-673-80M”、固体成分环氧当量：209g/eq.、非挥发性成分：80质量％、溶剂：甲乙酮)46.7质量份、丙烯酸13.3质量份、对甲氧基苯酚0.08质量份、甲乙酮13.3质量份，搅拌使之均匀地混合。然后加入三苯基膦0.37质量份，在反应温度80℃下进行反应至酸值为1.5以下，得到乙烯基酯树脂(1)的非挥发性成分为75质量％的溶液。A cresol novolak type epoxy resin ("EPICLON N-673-80M" manufactured by DIC Corporation, solid content epoxy equivalent: 209 g/eq., non-volatile content: 80% by mass, solvent: methyl ethyl ketone was added to the reaction vessel. ) 46.7 parts by mass, 13.3 parts by mass of acrylic acid, 0.08 parts by mass of p-methoxyphenol, and 13.3 parts by mass of methyl ethyl ketone were stirred and mixed uniformly. Then, 0.37 parts by mass of triphenylphosphine was added, and the reaction was carried out at a reaction temperature of 80° C. until the acid value was 1.5 or less to obtain a solution having a nonvolatile content of vinyl ester resin (1) of 75% by mass.

制造例1中合成的乙烯基酯树脂(1)的原料如表1所示。Table 1 shows the raw materials of the vinyl ester resin (1) synthesized in Production Example 1.

[表1][Table 1]

(制造例2：具有芳香环的氨基甲酸酯树脂(1)的合成)(Production example 2: Synthesis of urethane resin (1) having an aromatic ring)

在反应容器中将在合成例1得到的芳香族聚酯多元醇(1)100.0质量份在减压下100℃下进行脱水，随后冷却至80℃后，加入甲乙酮66.6质量份，搅拌并均匀地混合。然后，加入2，2’-二羟甲基丙酸6.1质量份，接着加入异佛尔酮二异氰酸酯23.1质量份，在80℃下反应12小时，实施氨基甲酸酯化工序。确认到异氰酸酯值为0.1％以下，加入正丁醇3质量份，进一步反应2小时后，冷却至50℃，得到具有芳香环的氨基甲酸酯树脂(1)的非挥发性成分为65质量％的溶液。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, stirred and uniformly mix. Then, 6.1 parts by mass of 2,2'-dimethylolpropionic acid was added, followed by 23.1 parts by mass of isophorone diisocyanate, and reacted at 80°C for 12 hours to implement a urethanization step. After confirming that the isocyanate value was 0.1% or less, 3 parts by mass of n-butanol was added, and after further reaction for 2 hours, it was cooled to 50° C. to obtain a urethane resin (1) having an aromatic ring with a non-volatile component of 65 mass % The solution.

(制备例1：水性树脂组合物(1)的制备)(Preparation Example 1: Preparation of Waterborne Resin Composition (1))

向制造例2中得到的具有芳香环的氨基甲酸酯树脂(1)的非挥发性成分为65质量％的溶液147.7质量份(作为所述氨基甲酸酯树脂(1)为96质量份)中加入制造例1中得到的乙烯基酯树脂(1)的非挥发性成分75质量％的溶液128.0质量份(作为所述乙烯基酯树脂(1)为96质量份)、三乙基胺5.5质量份，缓慢添加离子交换水938.5质量份实施水溶化。然后在减压下、在30～50℃下除去甲乙酮，得到非挥发性成分为40质量％的水性树脂组合物(1)。147.7 parts by mass of a non-volatile component of the urethane resin (1) having an aromatic ring obtained in Production Example 2 of 65% by mass (96 parts by mass as the urethane resin (1)) 128.0 parts by mass of a solution of 75% by mass of the non-volatile components of the vinyl ester resin (1) obtained in Production Example 1 (96 parts by mass as the vinyl ester resin (1)), 5.5 parts by mass of triethylamine 938.5 parts by mass of ion-exchanged water were slowly added to dissolve in water. Then, methyl ethyl ketone was removed under reduced pressure at 30 to 50° C. to obtain an aqueous resin composition (1) having a nonvolatile component of 40% by mass.

实施例1～9中得到的水性树脂组合物(1)的组成如表2所示。予以说明，表中的组成表示非挥发性成分量(仅为树脂的量)。Table 2 shows the composition of the aqueous resin composition (1) obtained in Examples 1-9. In addition, the composition in a table shows the non-volatile component amount (only the amount of resin).

[表2][Table 2]

(制备例2：紫外线固化性组合物(UV-1)的制备)(Preparation Example 2: Preparation of Ultraviolet Curable Composition (UV-1))

混合氨基甲酸酯丙烯酸酯树脂(DIC株式会社制“UNIDIC V-4260”)50质量份、三丙二醇二丙烯酸酯50质量份和光聚合引发剂(巴斯夫日本株式会社制“IRGACURE 184”、1-羟基环己基苯基酮)3质量份，由此得到紫外线固化性组合物(UV-1)。Mix 50 parts by mass of urethane acrylate resin ("UNIDIC V-4260" manufactured by DIC Corporation), 50 parts by mass of tripropylene glycol diacrylate, and a photopolymerization initiator ("IRGACURE 184" manufactured by BASF Japan Co., Ltd., 1-hydroxyl Cyclohexyl phenyl ketone) 3 parts by mass to obtain an ultraviolet curable composition (UV-1).

(制备例3：紫外线固化性组合物(UV-2)的制备)(Preparation Example 3: Preparation of Ultraviolet Curable Composition (UV-2))

混合环氧丙烯酸酯树脂(DIC株式会社制“UNIDIC V-5500”)50质量份、三丙二醇二丙烯酸酯50质量份和光聚合引发剂(巴斯夫日本株式会社制“IRGACURE 184”)3质量份，由此得到紫外线固化性组合物(UV-2)。Mix 50 parts by mass of epoxy acrylate resin ("UNIDIC V-5500" manufactured by DIC Corporation), 50 parts by mass of tripropylene glycol diacrylate, and 3 parts by mass of photopolymerization initiator ("IRGACURE 184" manufactured by BASF Japan Co., Ltd.), by This gave an ultraviolet curable composition (UV-2).

(实施例1：底涂剂(1)的制作)(embodiment 1: the making of primer (1))

混合制备例1中得到的水性树脂组合物(1)100质量份、碳化二亚胺交联剂(日清纺化学株式会社制“CARBODILITE E-02”)2.8质量份和离子交换水593质量份，由此得到底涂剂(P-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 (manufactured by Nisshinbo Chemical Co., Ltd. "CARBODILITE E-02"), and 593 parts by mass of ion-exchanged water were mixed. , thus obtaining a primer (P-1).

(实施例2：底涂剂(2)的制作)(embodiment 2: the making of primer (2))

混合制备例1中得到的水性树脂组合物(1)100质量份、碳化二亚胺交联剂(日清纺化学株式会社制“CARBODILITE V-02”)2.8质量份和离子交换水589质量份，由此得到底涂剂(P-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 (manufactured by Nisshinbo Chemical Co., Ltd. "CARBODILITE V-02"), and 589 parts by mass of ion-exchanged water were mixed. , thus obtaining a primer (P-2).

(实施例3：底涂剂(3)的制作)(embodiment 3: the making of primer (3))

混合制备例1中得到的水性树脂组合物(1)100质量份、碳化二亚胺交联剂(日清纺化学株式会社制“CARBODILITE SV-02”)2.8质量份和离子交换水593质量份，由此得到底涂剂(P-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 (manufactured by Nisshinbo Chemical Co., Ltd. "CARBODILITE SV-02"), and 593 parts by mass of ion-exchanged water were mixed. , thus obtaining a primer (P-3).

(实施例4：层叠体(1)的制作)(Example 4: Production of Laminate (1))

在聚对苯二甲酸乙二醇酯(以下简写为“PET”)制膜基材(厚度125μm)的表面上以干燥后的膜厚约为1μm的方式涂布实施例1中得到的底涂剂(P-1)，在150℃下加热5分钟，由此在所述基材的表面形成底涂层。然后，以15μm的涂布厚度，在所述底涂层的表面涂布制备例2中得到的紫外线固化性组合物(UV-1)，以高压汞灯作为光源，以照射强度0.5J/cm2对该涂布面照射紫外线，由此得到在所述基材的表面具有底涂层、且在该底涂层的表面具有紫外线固化性组合物的固化涂膜(以下简写为“UV涂膜”)的层叠体(1)。The primer obtained in Example 1 was applied to the surface of a polyethylene terephthalate (hereinafter abbreviated as "PET") film substrate (thickness 125 μm) so that the film thickness after drying was about 1 μm. Agent (P-1) was heated at 150° C. for 5 minutes, thereby forming an undercoat layer on the surface of the substrate. Then, with a coating thickness of 15 μm, the ultraviolet curable composition (UV-1) obtained in Preparation Example 2 was coated on the surface of the primer layer, and a high-pressure mercury lamp was used as a light source at an irradiation intensity of 0.5 J/cm 2. By irradiating the coated surface with ultraviolet rays, a cured coating film (hereinafter abbreviated as "UV coating film") having an undercoat layer on the surface of the substrate and an ultraviolet curable composition on the surface of the undercoat layer is obtained. ") stack (1).

(实施例5：层叠体(2)的制作)(Example 5: Production of Laminate (2))

使用制备例3中得到的紫外线固化性组合物(UV-2)代替实施例4中使用的紫外线固化性组合物(UV-1)，除此以外，与实施例4同样地进行制作，得到层叠体(2)。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, it was produced in the same manner as in Example 4 to obtain a laminated body (2).

(实施例6：层叠体(3)的制作)(Example 6: Production of laminate (3))

在PET膜基材的表面上以干燥后的膜厚约为1μm的方式涂布实施例2中得到的底涂剂(P-2)，在150℃下加热5分钟，由此在所述基材的表面形成底涂层。然后，以15μm的涂布厚度，在所述底涂层的表面涂布制备例3中得到的紫外线固化性组合物(UV-2)，以高压汞灯作为光源，以照射强度0.5J/cm2对该涂布面照射紫外线，由此得到在所述基材的表面具有底涂层、且在该底涂层的表面具有UV涂膜的层叠体(3)。The primer (P-2) obtained in Example 2 was coated on the surface of the PET film substrate so that the film thickness after drying was about 1 μm, and heated at 150° C. for 5 minutes, thereby Forms an undercoat on the surface of the material. Then, with a coating thickness of 15 μm, the ultraviolet curable composition (UV-2) obtained in Preparation Example 3 was coated on the surface of the primer layer, and a high-pressure mercury lamp was used as a light source at an irradiation intensity of 0.5 J/cm 2. By irradiating the coated surface with ultraviolet rays, a laminate (3) having an undercoat layer on the surface of the substrate and a UV coating film on the surface of the undercoat layer is obtained.

(实施例7：层叠体(4)的制作)(Example 7: Production of laminated body (4))

使用实施例3中得到的底涂剂(P-3)代替实施例6中使用的底涂剂(P-2)，除此以外，与实施例6同样地进行制作，得到层叠体(4)。Except that the primer (P-3) obtained in Example 3 was used instead of the primer (P-2) used in Example 6, it was produced in the same manner as in Example 6 to obtain a laminate (4) .

使用上述的实施例和比较例中得到的涂布剂和层叠体，对下述的密合性进行评价。The following adhesiveness was evaluated using the coating agent and laminated body obtained by the said Example and the comparative example.

[基材与底涂层的密合性(初期)的评价方法][Evaluation method of adhesion (initial stage) between base material and primer layer]

以使干燥时的膜厚达到约为1μm，在膜厚125μm的包含聚对苯二甲酸乙二醇酯的基材的表面涂布底涂剂，在150℃下加热5分钟，由此制作在所述基材的表面包含层叠有底涂层的部件的试验板。A primer was applied to the surface of a substrate made of polyethylene terephthalate with a film thickness of 125 μm so that the film thickness at the time of drying was about 1 μm, and heated at 150° C. for 5 minutes to produce a The surface of the substrate comprises a test panel of components laminated with an undercoat layer.

在用所述方法制作的试验板的底涂层的表面，粘贴NICHIBAN株式会社制造的24mm宽的粘合带。On the surface of the undercoat layer of the test plate produced by the said method, the 24-mm-wide adhesive tape by Nichiban Co., Ltd. was affixed.

然后，将所述粘合带沿着相对于所述底涂层的垂直方向拉伸，按照下述评价标准，目测评价将所述粘合带从底涂层的表面剥离时的所述底涂层的表面的状态：Then, the adhesive tape was stretched in a direction perpendicular to the primer layer, and the primer was visually evaluated when the adhesive tape was peeled off from the surface of the primer layer according to the following evaluation criteria. The state of the surface of the layer:

◎：底涂层完全没有从构成试验板的基材表面剥离。⊚: The undercoat layer was not peeled off from the surface of the base material constituting the test panel at all.

○：很少一部分的底涂层从构成试验板的基材表面剥离，相对于构成试验板的皮膜的总面积，该剥离的范围小于10％。◯: A small part of the undercoat layer peeled off from the surface of the base material constituting the test plate, and the extent of the peeling was less than 10% with respect to the total area of the film constituting the test plate.

△：相对于构成试验板的底涂层的面积为10％以上且小于50％的范围的底涂层从构成试验板的基材表面剥离。Δ: 10% to less than 50% of the undercoat layer area of the undercoat layer constituting the test panel was peeled off from the surface of the base material constituting the test panel.

×：相对于构成试验板的底涂层的总面积为50％以上的范围的底涂层从构成试验板的基材表面剥离。x: The undercoat layer in the range of 50% or more with respect to the total area of the undercoat layer constituting the test plate peeled off from the surface of the base material constituting the test plate.

[底涂层与UV涂膜的密合性(初期)的评价方法][Evaluation method of the adhesion (initial stage) between the primer layer and the UV coating film]

在构成实施例和比较例中得到的层叠体的UV涂膜的表面，粘贴NICHIBAN株式会社制造的24mm宽的粘合带。On the surface of the UV coating film which comprises the laminated body obtained by the Example and the comparative example, the 24 mm wide adhesive tape by Nichiban Corporation was stuck.

然后，将所述粘合带沿着相对于所述UV涂膜的垂直方向拉伸，按照下述评价标准，目测评价将所述粘合带从UV涂膜的表面剥离时的所述UV涂膜的表面的状态：Then, the adhesive tape was stretched in a direction perpendicular to the UV coating film, and the UV coating was visually evaluated when the adhesive tape was peeled off from the surface of the UV coating film according to the following evaluation criteria. State of the surface of the membrane:

◎：UV涂膜完全没有从构成层叠体的基材表面剥离。⊚: The UV coating film did not peel off from the surface of the substrate constituting the laminate at all.

○：很少一部分的UV涂膜从构成层叠体的基材表面剥离，相对于构成层叠体的UV涂膜的总面积，该剥离的范围小于10％。◯: A small part of the UV coating film is peeled off from the surface of the base material constituting the laminate, and the range of the peeling is less than 10% with respect to the total area of the UV coating film constituting the laminate.

△：相对于构成层叠体的UV涂膜的面积为10％以上且小于50％的范围的UV涂膜从构成层叠体的基材表面剥离。Δ: The UV coating film in the range of 10% to less than 50% of the area of the UV coating film constituting the laminate was peeled from the surface of the base material constituting the laminate.

×：相对于构成层叠体的UV涂膜的总面积为50％以上的范围的UV涂膜从构成层叠体的基材表面剥离。×: 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 from the surface of the base material constituting the laminate.

[底涂层与UV涂膜的密合性(耐湿热试验后)][Adhesion between primer and UV coating (after heat and humidity test)]

将所述得到的层叠体投入温度60℃、相对湿度90％的高温恒湿器中50小时。之后，取出所述层叠体，按照与所述[底涂层与UV涂膜的密合性(初期)]同样的方法评价底涂层与UV涂膜的密合性。The above-obtained laminate was placed in a high-temperature hygrostat at a temperature of 60° C. and a relative humidity of 90% for 50 hours. Then, the said laminated body was taken out, and the adhesiveness of a primer layer and a UV coating film was evaluated by the method similar to the said [adhesion (initial stage) of a primer layer and a UV coating film].

[底涂层与UV涂膜的密合性(耐化学品性试验后)][Adhesion between primer and UV coating (after chemical resistance test)]

将所述得到的层叠体投入温度25℃、5％氢氧化钠水溶液中30分钟。之后，取出所述层叠体，水洗/干燥后，按照与所述[底涂层与UV涂膜的密合性(初期)的评价方法]同样的方法评价底涂层与UV涂膜的密合性。The laminate thus obtained was thrown into a 5% sodium hydroxide aqueous solution at a temperature of 25° C. for 30 minutes. After that, the laminate was taken out, washed with water/dried, and the adhesion between the primer layer and the UV coating film was evaluated by the same method as the above-mentioned [Evaluation method of the adhesion between the primer layer and the UV coating film (initial stage)]. sex.

[成膜性的评价方法][Evaluation method of film-forming property]

以使干燥时的膜厚达到约为1μm，在膜厚125μm的包含聚对苯二甲酸乙二醇酯的基材的表面涂布所述底涂剂，在150℃で下加热5分钟，由此在所述基材的表面形成底涂层。The primer was coated on the surface of a substrate containing polyethylene terephthalate with a film thickness of 125 μm so that the film thickness at the time of drying was about 1 μm, and heated at 150° C. for 5 minutes. This forms an undercoat layer on the surface of the substrate.

○：目测观察底涂层的表面时为透明。◯: When visually observing the surface of the undercoat layer, it was transparent.

△：目测观察底涂层的表面时为透明，但可确认有裂纹。△: The surface of the undercoat layer was transparent when visually observed, but cracks were confirmed.

×：目测观察底涂层的表面时，发现有白化程度的裂纹，底涂层的一部分容易从聚对苯二甲酸乙二醇酯基材剥离。×: When the surface of the undercoat layer was visually observed, cracks of a degree of whitening were observed, and a part of the undercoat layer was easily peeled off from the polyethylene terephthalate substrate.

实施例10～20中得到的层叠体(1)～(4)中使用的基材、底涂剂和紫外线固化性组合物、评价结果如表3所示。Table 3 shows the substrates, primers, ultraviolet curable compositions and evaluation results used in the laminates (1) to (4) obtained in Examples 10 to 20.

[表3][table 3]

(比较例1：底涂剂(P’-1)的制作)(Comparative Example 1: Preparation of Primer (P'-1))

混合水性树脂组合物(1)100质量份和离子交换水577质量份，由此得到底涂剂(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.

(比较例2：底涂剂(P’-2)的制作)(Comparative example 2: Preparation of primer (P'-2))

混合水性树脂组合物(1)100质量份、三聚氰胺交联剂(DIC株式会社制“BECKAMINE M-3”)3质量份和离子交换水613质量份，由此得到底涂剂(P’-2)。A primer (P'-2 ).

(比较例3：底涂剂(P’-3)的制作)(Comparative Example 3: Preparation of Primer (P'-3))

混合水性树脂组合物(1)100质量份、噁唑啉交联剂(株式会社日本触媒制“EPOCROS WS-700”)9.2质量份和离子交换水606质量份，由此得到底涂剂(P’-3)。Mix 100 parts by mass of aqueous resin composition (1), 9.2 parts by mass of oxazoline crosslinking agent ("EPOCROS WS-700" manufactured by Japan Shokubai Co., Ltd.) and 606 parts by mass of ion-exchanged water to obtain primer (P '-3).

(比较例4：底涂剂(P’-4)的制作)(Comparative Example 4: Preparation of Primer (P'-4))

混合水性树脂组合物(1)100质量份、环氧系交联剂(DIC株式会社制“CR-5L”)3质量份和离子交换水648质量份，由此得到底涂剂(P’-4)。Mix 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 to obtain a primer (P'- 4).

(比较例5：层叠体(R1)的制作)(Comparative Example 5: Production of Laminate (R1))

在PET膜基材的表面上以干燥后的膜厚约为1μm的方式涂布比较例2中得到的底涂剂(P’-1)，在150℃下加热5分钟加热，由此在所述基材的表面形成底涂层。然后，以15μm的涂布厚度，在所述底涂层的表面涂布制备例3中得到的紫外线固化性组合物(UV-2)，以高压汞灯作为光源，以照射强度0.5J/cm2对该涂布面照射紫外线，由此得到在所述基材的表面具有底涂层、且在该底涂层的表面具有UV涂膜的层叠体(R1)。The primer (P'-1) obtained in Comparative Example 2 was coated on the surface of the PET film base material so that the film thickness after drying was about 1 μm, and heated at 150° C. for 5 minutes, whereby the The base coat is formed on the surface of the substrate. Then, with a coating thickness of 15 μm, the ultraviolet curable composition (UV-2) obtained in Preparation Example 3 was coated on the surface of the primer layer, and a high-pressure mercury lamp was used as a light source at an irradiation intensity of 0.5 J/cm 2. By irradiating the coated surface with ultraviolet rays, a laminate (R1) having an undercoat layer on the surface of the substrate and a UV coating film on the surface of the undercoat layer is obtained.

(比较例6～8：层叠体(R2)～(R4)的制作)(Comparative Examples 6 to 8: Production of Laminates (R2) to (R4))

分别使用比较例2～4中得到的底涂剂(P’-2)～(P’-4)代替比较例5中使用的底涂剂(P’-1)，除此以外，与比较例5同样地进行制作，得到层叠体(R2)～(R4)。In place of the primer (P'-1) used in Comparative Example 5, the primers (P'-2) to (P'-4) obtained in Comparative Examples 2 to 4 were used respectively. 5 was produced in the same manner to obtain laminates (R2) to (R4).

比较例4～7中得到的层叠体(R1)和(R2)中使用的基材、底涂剂和紫外线固化性组合物、评价结果如表4所示。Table 4 shows the substrates, primers, ultraviolet curable compositions and evaluation results used in the laminates (R1) and (R2) obtained in Comparative Examples 4 to 7.

[表4][Table 4]

由表3中所示的评价结果，可确认到使用本发明的涂布剂形成的底涂层与基材的密合性优异，与活性能量射线固化性组合物的固化涂膜的密合性也优异。From the evaluation results shown in Table 3, it can be confirmed that the undercoat layer formed using the coating agent of the present invention has excellent adhesion to the substrate, and the adhesion to the cured coating film of the active energy ray-curable composition was confirmed to be excellent. Also excellent.

此外，使用本发明的涂布剂形成的底涂层，可确认到具有耐湿热试验后的高密合性和优异的耐化学品性。In addition, it was confirmed that the undercoat layer formed using the coating agent of the present invention has high adhesion and excellent chemical resistance after the heat and humidity resistance test.

另一方面，比较例5是使用不含有交联剂的涂布剂的例子。可确认到与使用本发明的涂布剂形成的底涂层相比，其耐湿热试验后的密合性不足够，此外，耐化学品性也不足够。On the other hand, Comparative Example 5 is an example using a coating agent that does not contain a crosslinking agent. Compared with the undercoat layer formed using the coating agent of this invention, it was confirmed that the adhesiveness after the heat-and-moisture resistance test was insufficient, and chemical resistance was also insufficient.

比较例6是使用三聚氰胺交联剂的例子。可确认到与使用本发明的含有碳化二亚胺交联剂的涂布剂形成的底涂层相比，其耐化学品性不足够。Comparative Example 6 is an example using a melamine crosslinking agent. It was confirmed that the chemical resistance was insufficient compared with the undercoat layer formed using the coating agent containing the carbodiimide crosslinking agent of the present invention.

比较例7是使用噁唑啉交联剂的例子。可确认到与使用本发明的含有碳化二亚胺交联剂的涂布剂形成的底涂层相比，其耐湿热试验后的密合性不足够，此外，耐化学品性也不足够。Comparative Example 7 is an example using an oxazoline crosslinking agent. Compared with the undercoat layer formed using the coating agent containing the carbodiimide crosslinking agent of the present invention, it was confirmed that the adhesiveness after the heat and humidity resistance test was insufficient, and the chemical resistance was also insufficient.

比较例8是使用环氧交联剂的例子。可确认到与使用本发明的含有碳化二亚胺交联剂的涂布剂形成的底涂层相比，其耐化学品性不足够。Comparative Example 8 is an example using an epoxy crosslinking agent. It was confirmed that the chemical resistance was insufficient compared with the undercoat layer formed using the coating agent containing the carbodiimide crosslinking agent of the present invention.

Claims (11)

1.一种涂布剂，其特征在于，该涂布剂含有水性树脂组合物(D)和碳化二亚胺类交联剂(E)，其中，所述水性树脂组合物(D)是将乙烯基酯树脂(A)和具有芳香环的氨基甲酸酯树脂(B)分散于水性介质(C)中而得到的；1. a coating agent, it is characterized in that, this coating agent contains aqueous resin composition (D) and carbodiimide crosslinking agent (E), wherein, described aqueous resin composition (D) is the A vinyl ester resin (A) and a urethane resin (B) having an aromatic ring are dispersed in an aqueous medium (C); 所述乙烯基酯树脂(A)是使环氧树脂(a1)与化合物(a2)反应而得到的，其中，所述环氧树脂(a1)为选自由线性酚醛型环氧树脂和双酚型环氧树脂组成的组中的一种以上，所述化合物(a2)具有酸基和聚合性不饱和基；The vinyl ester resin (A) is obtained by reacting an epoxy resin (a1) with a compound (a2), wherein the epoxy resin (a1) is selected from novolak type epoxy resins and bisphenol type epoxy resins. One or more of the group consisting of epoxy resins, the compound (a2) has an acid group and a polymerizable unsaturated group; 所述氨基甲酸酯树脂(B)是使含有多元醇(b1-1)和多元醇(b1-2)的多元醇(b1)与多异氰酸酯(b2)反应而得到的，其中，所述多元醇(b1-1)具有芳香环，所述多元醇(b1-2)具有亲水性基。The urethane resin (B) is obtained by reacting polyol (b1) containing polyol (b1-1) and polyol (b1-2) with polyisocyanate (b2), wherein the polyhydric The alcohol (b1-1) has an aromatic ring, and the polyol (b1-2) has a hydrophilic group. 2.根据权利要求1所述的涂布剂，其中，所述交联剂(E)的用量是与亲水性基的80～100摩尔％反应的量，所述亲水性基为能够与碳化二亚胺基反应的所述氨基甲酸酯树脂(B)所具有的亲水性基。2. The coating agent according to claim 1, wherein the amount of the crosslinking agent (E) is an amount that reacts with 80 to 100 mol% of the hydrophilic group, and the hydrophilic group is capable of reacting with The hydrophilic group which the said urethane resin (B) which reacted with a carbodiimide group has. 3.根据权利要求1所述的涂布剂，其中，所述多元醇(b1-1)中的芳香环浓度为1.5～8mol/kg的范围。3. The coating agent according to claim 1, wherein the aromatic ring concentration in the polyol (b1-1) is in the range of 1.5 to 8 mol/kg. 4.根据权利要求1所述的涂布剂，其中，所述具有芳香环的多元醇(b1-1)是含有芳香族聚酯多元醇(b1-a)和双酚A的环氧烷加成物(b1-b)中的至少一种的多元醇。4. The coating agent according to claim 1, wherein the polyol (b1-1) having an aromatic ring is an alkylene oxide compound containing an aromatic polyester polyol (b1-a) and bisphenol A. At least one polyol in the product (b1-b). 5.根据权利要求1所述的涂布剂，其中，所述多元醇(b1)中所含的具有芳香环的多元醇(b1-1)的比例为40～98质量％的范围。5. The coating agent according to claim 1, wherein the ratio 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.根据权利要求1所述的涂布剂，其中，所述多异氰酸酯(b2)含有芳香族多异氰酸酯。6. The coating agent according to claim 1, wherein the polyisocyanate (b2) contains an aromatic polyisocyanate. 7.根据权利要求1所述的涂布剂，其中，所述化合物(a2)为丙烯酸或甲基丙烯酸。7. The coating agent according to claim 1, wherein the compound (a2) is acrylic acid or methacrylic acid. 8.根据权利要求1所述的涂布剂，其中，所述乙烯基酯树脂(A)的一部分或全部内置于所述氨基甲酸酯树脂(B)粒子中而形成树脂粒子(F)。8 . The coating agent according to claim 1 , wherein a part or all of the vinyl ester resin (A) is embedded in the urethane resin (B) particles to form resin particles (F). 9.根据权利要求1所述的涂布剂，其中，所述乙烯基酯树脂(A)与所述氨基甲酸酯树脂(B)的质量比例(A)/(B)为60/40～10/90的范围。9. The coating agent according to claim 1, wherein the mass ratio (A)/(B) of the vinyl ester resin (A) to the urethane resin (B) is 60/40～ 10/90 range. 10.一种层叠体，其特征在于，在基材的表面具有涂布权利要求1～9中任意一项所述的涂布剂并通过干燥而形成的底涂层，并且在所述底涂层的表面具有使用活性能量射线固化性组合物而形成的固化涂膜。10. A laminated body, characterized in that an undercoat layer formed by applying the coating agent according to any one of claims 1 to 9 on the surface of a base material and drying it is formed, and the undercoat layer The surface of the layer has a cured coating film formed using an active energy ray-curable composition. 11.根据权利要求10所述的层叠体，其中，所述活性能量射线固化性树脂组合物含有具有聚合性不饱和基的树脂和具有聚合性不饱和基的单体。11. 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.
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WO2018123795A1 (en) * 2016-12-26 2018-07-05 Dic株式会社 Aqueous resin composition, laminate using same, optical film, and image display device
JP6988087B2 (en) * 2016-12-26 2022-01-05 Dic株式会社 Aqueous resin compositions, coatings and articles
JP6780738B2 (en) * 2019-05-27 2020-11-04 三菱ケミカル株式会社 Laminated film and manufacturing method
US20240084167A1 (en) 2021-04-27 2024-03-14 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

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3649244B1 (en) * 2003-05-28 2005-05-18 大日本インキ化学工業株式会社 Water-based coating agent
JP2007153958A (en) * 2005-12-01 2007-06-21 Unitika Ltd Aqueous primer composition and layered product
CN101796149A (en) * 2008-05-26 2010-08-04 Dic株式会社 Coating agent and its preparation method
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

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003218055A1 (en) * 2002-03-08 2003-09-22 Lord Corporation Flexible coatings for elastomer substrates
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
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
JP5360337B1 (en) * 2012-03-22 2013-12-04 Ｄｉｃ株式会社 Aqueous resin composition and cured product
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
JP3649244B1 (en) * 2003-05-28 2005-05-18 大日本インキ化学工業株式会社 Water-based coating agent
JP2007153958A (en) * 2005-12-01 2007-06-21 Unitika Ltd Aqueous primer composition and layered product
CN101796149A (en) * 2008-05-26 2010-08-04 Dic株式会社 Coating agent and its preparation method
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

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110139902B (en) * 2017-01-16 2021-12-07 湛新奥地利有限公司 Anticorrosive water-based coating composition
CN109750523A (en) * 2017-11-01 2019-05-14 Dic株式会社 Synthetic leather and method of making the same
CN109750523B (en) * 2017-11-01 2023-03-28 Dic株式会社 Synthetic leather and method for producing same
CN111511836A (en) * 2017-12-26 2020-08-07 Dic株式会社 Aqueous resin composition, laminate and article using the same
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
CN113950507A (en) * 2019-07-08 2022-01-18 Dic株式会社 Resin composition, prepreg, laminate, multilayer printed wiring board, and semiconductor package
CN112280078A (en) * 2019-07-22 2021-01-29 柯尼卡美能达株式会社 Laminated film and method for producing same
CN112280078B (en) * 2019-07-22 2022-12-30 柯尼卡美能达株式会社 Laminated film and method for producing same
CN114746458A (en) * 2019-12-02 2022-07-12 昭和电工株式会社 Aqueous resin composition, film, and method for forming film

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