TWI636102B - Coatings and laminates - Google Patents

Coatings and laminates Download PDF

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Publication number
TWI636102B
TWI636102B TW103143410A TW103143410A TWI636102B TW I636102 B TWI636102 B TW I636102B TW 103143410 A TW103143410 A TW 103143410A TW 103143410 A TW103143410 A TW 103143410A TW I636102 B TWI636102 B TW I636102B
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TW
Taiwan
Prior art keywords
resin
meth
acrylate
coating agent
group
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TW103143410A
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Chinese (zh)
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TW201529764A (en
Inventor
小柳達史
北田滿
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迪愛生股份有限公司
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Publication of TWI636102B publication Critical patent/TWI636102B/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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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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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    • 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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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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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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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • 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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
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    • C08G59/4042—Imines; Imides
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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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    • C08J7/12—Chemical modification
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
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    • 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
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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    • 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
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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Epoxy Resins (AREA)

Abstract

本發明提供一種被覆劑，其係含有乙烯酯樹脂(A)、具有芳香環之胺基甲酸酯樹脂(B)於水性介質(C)中分散而得之水性樹脂組成物(D)，以及碳二亞胺系交聯劑(E)之被覆劑，其中，上述乙烯酯樹脂(A)係使選自酚醛清漆型環氧樹脂及雙酚型環氧樹脂所成群組中之1種以上的環氧樹脂(a1)、與具有酸基及聚合性不飽和基之化合物(a2)反應而得者，上述胺基甲酸酯樹脂(B)係使含有具芳香環之多元醇(b1-1)及具親水性基之多元醇(b1-2)的(b1)、與聚異氰酸酯(b2)反應而得者。本發明之被覆劑可使基材與活性能量線硬化組成物之硬化塗膜的密著性提高，且可形成耐藥性及耐濕熱性優異之底塗層。 The present invention provides a coating agent comprising an aqueous resin composition (D) containing a vinyl ester resin (A) and an urethane resin (B) having an aromatic ring dispersed in an aqueous medium (C), and A coating agent for a carbodiimide-based crosslinking agent (E), wherein the vinyl ester resin (A) is one or more selected from the group consisting of a novolac epoxy resin and a bisphenol epoxy resin. It is obtained by reacting an epoxy resin (a1) with a compound (a2) having an acid group and a polymerizable unsaturated group, and the urethane resin (B) is made of an aromatic ring-containing polyol (b1- 1) It is obtained by reacting (b1) of the polyhydric alcohol (b1-2) having a hydrophilic group with a polyisocyanate (b2). The coating agent of the present invention can improve the adhesion between the substrate and the hardened coating film of the active energy ray hardening composition, and can form an undercoat layer having excellent chemical resistance and moisture and heat resistance.

Description

被覆劑及積層體 Coatings and laminates

本發明係有關在基材表面形成活性能量線硬化性組成物之硬化塗膜時可作為提高基材與上述硬化塗膜之密著性的底漆使用之被覆劑，以及積層體。 The present invention relates to a coating agent and a laminate that can be used as a primer for improving the adhesion between a substrate and the cured coating film when a cured coating film of an active energy ray-curable composition is formed on the surface of the substrate.

水性胺基甲酸酯樹脂組成物，近年來研究對光學用途之膜或薄片的應用。上述光學用途，具體上可列舉如：液晶顯示器、觸摸面板等。上述液晶顯示器等之顯示裝置，一般為了顯示清晰的影像而層積具有各種機能的多數光學膜所構成，而該光學膜可列舉如：抗反射膜、相位差膜及稜鏡片等。 The water-based urethane resin composition has been studied in recent years for use in films or sheets for optical applications. Specific examples of the optical application include a liquid crystal display and a touch panel. A display device such as the above-mentioned liquid crystal display is generally constituted by laminating a plurality of optical films having various functions in order to display a clear image. Examples of the optical film include an anti-reflection film, a retardation film, and a diaphragm.

作為該等光學膜之基材，係因聚酯膜，特別是聚對酞酸乙二酯(PET)膜之光學特性、機械強度及耐久性優異而使用。而且，在光學用途方面，藉由在聚酯膜之表面塗布活性能量線硬化性組成物使之硬化而形成硬塗層、或裝設鑄塑活性能量線硬化性組成物之層而將聚酯膜作成稜鏡片，惟因聚酯膜之結晶性高而有與活性能量線硬化性組成物之硬化塗膜之密著性低之問題。 As a substrate of such optical films, polyester films, especially polyethylene terephthalate (PET) films are used because they are excellent in optical characteristics, mechanical strength, and durability. For optical applications, polyester is coated with an active energy ray-curable composition on the surface of the polyester film to harden it to form a hard coat layer, or a layer of cast active energy ray-curable composition is applied to the polyester film. The film is made into a cymbal sheet, but because of the high crystallinity of the polyester film, there is a problem that the adhesion to the hardened coating film of the active energy ray-curable composition is low.

作為提高聚酯膜與活性能量線硬化性組成物之硬化塗膜的密著性之方法，係提案在基材之聚酯膜與活性能量線硬化性組成物的硬化塗膜之間設置包含丙烯酸 樹脂之底塗層(例如：參照專利文獻1)。然而，即使裝設包含丙烯酸樹脂之底塗層，聚酯膜與活性能量線硬化性組成物的硬化塗膜之密著性亦不充分。 As a method for improving the adhesion between the polyester film and the hardened coating film of the active energy ray-curable composition, it is proposed to include acrylic acid between the polyester film of the substrate and the hardened coating film of the active energy ray-curable composition. Resin undercoat (see, for example, Patent Document 1). However, even if an undercoat layer containing an acrylic resin is installed, the adhesion between the polyester film and the cured coating film of the active energy ray-curable composition is insufficient.

而且，使用胺基甲酸酯樹脂作為底塗層者，與活性能量線硬化性組成物的硬化塗膜之密著性雖為充分，然而對於耐濕熱試驗後之密著性及耐藥性卻有無法發揮充分的性能之問題。 In addition, although the urethane resin is used as the undercoat layer, although the adhesiveness with the cured coating film of the active energy ray-curable composition is sufficient, the adhesiveness and chemical resistance after the moist heat resistance test are not sufficient. There is a problem that the full performance cannot be exerted.

因此，要求一種使聚酯膜與活性能量線硬化性組成物的硬化塗膜之密著性充分，且可在具有優異耐藥性及耐濕熱性之底塗層中使用之被覆劑。 Therefore, there is a need for a coating agent that allows the polyester film and the cured coating film of the active energy ray-curable composition to have sufficient adhesiveness and can be used in an undercoat layer having excellent chemical resistance and moisture and heat resistance.

[先前技術文獻] [Prior technical literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開2010-215843號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2010-215843

本發明所欲解決之課題係提供一種被覆劑，其係對與基材或活性能量線硬化性組成物的硬化塗膜之任一者均具有優異之密著性，且可形成耐藥性及耐濕熱性優異之底塗層。 The problem to be solved by the present invention is to provide a coating agent which has excellent adhesion to any of a substrate or a cured coating film of an active energy ray-curable composition, and is capable of forming chemical resistance and Undercoat with excellent moisture and heat resistance.

本發明者等為解決上述問題而專心致志進行研究，結果發現使特定之環氧樹脂與具有酸基及聚合性不飽和基之化合物反應而得之乙烯酯樹脂及具有芳香環之胺基甲酸酯樹脂，藉由使用分散於水性介質中之水性樹脂組成物及交聯劑之組合的底漆，即使為聚酯膜般之不 易接著之基材，亦提高該基材與活性能量線硬化性組成物的硬化塗膜之密著性，以及大幅提升底塗層之耐藥性及耐濕熱性，遂而完成本發明。 The present inventors made intensive research in order to solve the above problems. As a result, they discovered that vinyl ester resins obtained by reacting specific epoxy resins with compounds having acid groups and polymerizable unsaturated groups, and urethanes having aromatic rings. Resin, by using a primer based on a combination of an aqueous resin composition and a crosslinking agent dispersed in an aqueous medium, even if it is a polyester film The substrate that is easy to adhere also improves the adhesion between the substrate and the hardened coating film of the active energy ray-curable composition, and greatly improves the chemical resistance and humidity and heat resistance of the undercoat layer, thereby completing the present invention.

亦即，本發明係關於被覆劑及積層體者，該被 覆劑係含有乙烯酯樹脂(A)、具有芳香環之胺基甲酸酯樹脂(B)於水性介質(C)中分散而得之水性樹脂組成物(D)，以及碳二亞胺系交聯劑(E)者，上述乙烯酯樹脂(A)係使選自酚醛清漆型環氧樹脂及雙酚型環氧樹脂所成群組中之1種以上的環氧樹脂(a1)、與具有酸基及聚合性不飽和基之化合物(a2)反應而得者，上述胺基甲酸酯樹脂(B)係使含有具芳香環之多元醇(b1-1)及具親水性基之(b1-2)的多元醇(b1)、與聚異氰酸酯(b2)反應而得者。 That is, the present invention relates to a coating agent and a laminate. The coating agent is an aqueous resin composition (D) containing a vinyl ester resin (A), an urethane resin (B) having an aromatic ring dispersed in an aqueous medium (C), and a carbodiimide system. For the crosslinking agent (E), the vinyl ester resin (A) is one or more epoxy resins (a1) selected from the group consisting of novolac epoxy resins and bisphenol epoxy resins, and It is obtained by reacting an acidic group and a polymerizable unsaturated compound (a2). The urethane resin (B) contains a polyol (b1-1) having an aromatic ring and (b1) having a hydrophilic group. -2) A polyol (b1) obtained by reacting with a polyisocyanate (b2).

本發明之被覆劑，即使為聚酯膜般之不易接著之基材，由於可提高該基材與活性能量線硬化性組成物的硬化塗膜之密著性，以及作為耐藥性及耐濕熱性優異之底漆使用，故適合以聚酯膜為基材，於該表面形成活性能量線硬化性組成物之硬化塗膜的積層體。作為如此之積層體之例可列舉如：抗反射膜、相位差膜及稜鏡片等之光學膜。並且，該等光學膜可應用在包括液晶顯示器之影像顯示裝置。 The coating agent of the present invention can improve the adhesiveness of the cured coating film of the substrate and the active energy ray-curable composition, as well as chemical resistance and resistance to moist heat, even if the substrate is difficult to adhere like a polyester film. A primer with excellent properties is used, so it is suitable to use a polyester film as a substrate to form a laminate of a cured coating film of an active energy ray-curable composition on the surface. Examples of such a laminated body include optical films such as an antireflection film, a retardation film, and a reticle. In addition, these optical films can be applied to an image display device including a liquid crystal display.

[實施發明之形態] [Form of Implementing Invention]

本發明之被覆劑係含有乙烯酯樹脂(A)、具有 芳香環之胺基甲酸酯樹脂(B)於水性介質(C)中分散而得之水性樹脂組成物(D)，以及碳二亞胺系交聯劑(E)者。 The coating agent of the present invention contains a vinyl ester resin (A), and has An aqueous resin composition (D) obtained by dispersing an aromatic ring urethane resin (B) in an aqueous medium (C), and a carbodiimide-based crosslinking agent (E).

上述乙烯酯樹脂(A)係使選自酚醛清漆型環氧 樹脂及雙酚型環氧樹脂所成群組中之1種以上的環氧樹脂(a1)、與具有酸基及聚合性不飽和基之化合物(a2)反應而得者。 The vinyl ester resin (A) is selected from a novolac epoxy Resin and bisphenol-type epoxy resin are obtained by reacting one or more types of epoxy resin (a1) with a compound (a2) having an acid group and a polymerizable unsaturated group.

上述化合物(a2)所具有之聚合性不飽和基，係 在與上述環氧樹脂之反應中，因不參與該反應，故以結果而言使上述乙烯酯樹脂(A)具有源自上述化合物(a2)之聚合性不飽和基。該乙烯酯樹脂(A)所具有之聚合性不飽和基，藉由與後述活性能量線硬化性組成物中所含之樹脂或單體所具有的聚合性不飽和基進行聚合反應，形成共價鍵，成為與包含本發明之被覆劑之底塗層之間的密著強固者。 The polymerizable unsaturated group of the compound (a2) is Since it does not participate in the reaction with the said epoxy resin, the said vinyl ester resin (A) has a polymerizable unsaturated group derived from the said compound (a2) as a result. The polymerizable unsaturated group of the vinyl ester resin (A) is polymerized with the polymerizable unsaturated group of the resin or monomer contained in the active energy ray-curable composition described later to form a covalent polymer. The bond becomes a strong adhesion with the undercoat layer containing the coating agent of the present invention.

上述乙烯酯樹脂(A)所具有之聚合性不飽和基 的當量係以250至2,000g/eq.之範圍為佳。 Polymerizable unsaturated group of the vinyl ester resin (A) The equivalent weight is preferably in the range of 250 to 2,000 g / eq.

上述環氧樹脂(a1)係選自酚醛清漆型環氧樹脂 及雙酚型環氧樹脂所成群組中之1種以上者，具體而言，可使用以下者。 The epoxy resin (a1) is selected from a novolac epoxy resin And one or more of the groups formed by bisphenol-type epoxy resin, specifically, the following can be used.

上述酚醛清漆型環氧樹脂可列舉例如：甲酚酚 醛清漆型環氧樹脂、酚酚醛清漆型環氧樹脂等。並且，上述雙酚型環氧樹脂可列舉如：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、四溴雙酚A型環氧樹脂等。該等環氧樹脂(a1)可單獨使用，亦可將2種以上併 用。 Examples of the novolac-type epoxy resin include cresol Novolac epoxy resin, phenol novolac epoxy resin, etc. Examples of the bisphenol epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and tetrabromobisphenol A epoxy resin. These epoxy resins (a1) can be used alone or in combination of two or more kinds. use.

上述環氧樹脂(a1)中，係以使用具有大量可與 上述化合物(a2)所具有之酸基反應的環氧基之酚醛清漆型環氧樹脂者為佳。 In the above epoxy resin (a1), a large amount of It is preferred that the compound (a2) has an acid group-reacting epoxy-based novolac epoxy resin.

並且，上述環氧樹脂(a1)之環氧當量係以150 至2,000g/eq.之範圍為佳，以160至1,000g/eq.之範圍更佳。 The epoxy equivalent of the epoxy resin (a1) is 150. The range is preferably from 2,000 g / eq., And more preferably from 160 to 1,000 g / eq.

更且，以使上述環氧樹脂(a1)所具有之環氧基 之總量中的80至100莫耳%與上述化合物(a2)之酸基反應者為佳，使上述環氧基全部與上述化合物(a2)之酸基反應者為更佳。 In addition, the epoxy group of the epoxy resin (a1) is provided. It is preferable that 80 to 100 mole% of the total amount react with the acid group of the compound (a2), and it is more preferable that all the epoxy groups react with the acid group of the compound (a2).

上述化合物(a2)係具有酸基與聚合性不飽和基 者。藉由使上述化合物(a2)具有之酸基與上述環氧樹脂(a1)具有之環氧基反應，即可在上述乙烯酯樹脂(A)中導入聚合性不飽和基。 The compound (a2) has an acid group and a polymerizable unsaturated group By. By reacting the acid group of the compound (a2) with the epoxy group of the epoxy resin (a1), a polymerizable unsaturated group can be introduced into the vinyl ester resin (A).

上述化合物(a2)可列舉例如：丙烯酸、甲基丙 烯酸、伊康酸、2-丙烯醯氧基乙基琥珀酸酯、2-甲基丙烯醯氧基乙基琥珀酸酯、2,2,2-參丙烯醯氧基甲基乙基酞酸酯等。該等化合物之中，亦以可將容易與後述活性能量線硬化性組成物中之樹脂或單體所具有之聚合性不飽和基進行聚合反應之丙烯醯基導入上述乙烯酯樹脂(A)之丙烯酸為佳。並且，該等化合物(a2)可單獨使用，亦可將2種以上併用，惟在上述化合物(a2)之總量中，所使用之丙烯酸以50質量%以上為佳。 Examples of the compound (a2) include acrylic acid and methacrylic acid. Enoic acid, itaconic acid, 2-acrylic acid ethoxyethyl succinate, 2-methacrylic acid ethoxyethyl succinate, 2,2,2-propene ethoxymethyl ethyl phthalic acid Esters, etc. Among these compounds, acryl fluorenyl group which can easily polymerize with the polymerizable unsaturated group of the resin or monomer in the active energy ray-curable composition described later is introduced into the vinyl ester resin (A). Acrylic is preferred. In addition, these compounds (a2) may be used alone, or two or more of them may be used in combination, but the acrylic acid used is preferably 50% by mass or more of the total amount of the compound (a2).

上述環氧樹脂(a1)與上述化合物(a2)之反應溫 度係以60至150℃之範圍為佳，以80至120℃之範圍更佳。 Reaction temperature of the epoxy resin (a1) and the compound (a2) The degree is preferably in the range of 60 to 150 ° C, and more preferably in the range of 80 to 120 ° C.

並且，當上述環氧樹脂(a1)與上述化合物(a2) 反應時，為了防止上述化合物(a2)所具有之聚合性不飽和基的熱聚合，以使用聚合抑制劑為佳。聚合抑制劑之添加量，相對於上述環氧樹脂(a1)與上述化合物(a2)之合計質量，以500至5,000ppm之範圍為佳。 When the epoxy resin (a1) and the compound (a2) During the reaction, it is preferable to use a polymerization inhibitor in order to prevent the thermal polymerization of the polymerizable unsaturated group of the compound (a2). The addition amount of the polymerization inhibitor is preferably in the range of 500 to 5,000 ppm based on the total mass of the epoxy resin (a1) and the compound (a2).

上述聚合抑制劑可列舉例如：2,6-雙(三級丁基 )-4-甲基酚、氫醌、甲基氫醌、氫醌單甲醚(對苯二酚單甲醚)、對-三級丁基兒茶酚、硝基苯、硝基苯甲酸、鄰-二硝基苯、間-二硝基苯、對-二硝基苯、2,4-二硝基酚、三硝基苯等。該等聚合抑制劑可單獨使用，亦可將2種以上併用。 Examples of the polymerization inhibitor include: 2,6-bis (tertiary butyl) ) -4-methylphenol, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether (hydroquinone monomethyl ether), p-tertiary butyl catechol, nitrobenzene, nitrobenzoic acid, O-dinitrobenzene, m-dinitrobenzene, p-dinitrobenzene, 2,4-dinitrophenol, trinitrobenzene, etc. These polymerization inhibitors may be used alone or in combination of two or more kinds.

更且，當上述環氧樹脂(a1)與上述化合物(a2) 反應時，可使用反應觸媒。上述反應觸媒之使用量，相對於上述環氧樹脂(a1)100質量份，以0.1至5質量份之範圍為佳。 Furthermore, when the above-mentioned epoxy resin (a1) and the above-mentioned compound (a2) During the reaction, a reaction catalyst can be used. The amount of the reaction catalyst used is preferably in the range of 0.1 to 5 parts by mass based on 100 parts by mass of the epoxy resin (a1).

上述反應觸媒可列舉例如：胺觸媒、咪唑觸媒 、磷觸媒、硼觸媒、磷-硼觸媒等。具體上可列舉如：乙基胍、三甲基胍、苯基胍、二苯基胍等之烷基取代胍；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)-1,1-二甲基脲等之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之咪唑啉；2-胺基吡啶等之單胺基吡啶；N,N-二甲基-N-(2-羥基-3-烯丙氧基丙基)胺-N'-乳 醯亞胺等之胺醯亞胺；乙膦、丙膦、丁膦、苯膦、三甲膦、三乙膦、三丁膦、三辛膦、三苯膦、三環己膦、三苯膦-三苯硼烷錯合物、四苯鏻四苯硼酸鹽等之有機磷觸媒；1,8-二氮雜雙環[5.4.0]十一烯-7、1,4-二氮雜雙環[2.2.2]辛烷等之二氮雜雙環十一烯等。該等反應觸媒可單獨使用，亦可將2種以上併用。 Examples of the above reaction catalyst include: amine catalyst, imidazole catalyst , Phosphorus catalyst, boron catalyst, phosphorus-boron catalyst, etc. Specific examples include alkyl-substituted guanidines such as ethylguanidine, trimethylguanidine, phenylguanidine, and diphenylguanidine; 3- (3,4-dichlorophenyl) -1,1-dimethyl 3-substituted phenyl-1,1-dimethylurea, 3-phenyl-1,1-dimethylurea, 3- (4-chlorophenyl) -1,1-dimethylurea, etc. ; 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline and other imidazolines; 2-aminopyridine and other monoaminopyridines; N , N-dimethyl-N- (2-hydroxy-3-allyloxypropyl) amine-N'-milk Ammonium imines such as iminoimide; ethylphosphine, triphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine- Organophosphorus catalysts such as triphenylborane complex, tetraphenylphosphonium tetraphenylborate, etc .; 1,8-diazabicyclo [5.4.0] undecene-7, 1,4-diazabicyclo [ 2.2.2] Diazabicycloundecene and the like. These reaction catalysts may be used alone or in combination of two or more kinds.

以上述方法所得之乙烯酯樹脂(A)之重量平均 分子量，從樹脂粒子之分散安定性的改善來看，以500至10,000之範圍為佳，以1,000至6,000之範圍更佳。 Weight average of vinyl ester resin (A) obtained by the above method From the viewpoint of improving the dispersion stability of the resin particles, the molecular weight is preferably in the range of 500 to 10,000, and more preferably in the range of 1,000 to 6,000.

具有芳香環之胺基甲酸酯樹脂(B)係使含有具 芳香環之多元醇(b1-1)及具親水性基之(b1-2)的多元醇(b1)、與聚異氰酸酯(b2)反應而得者。 The urethane resin (B) having an aromatic ring contains An aromatic ring polyol (b1-1) and a polyhydric alcohol (b1) having a hydrophilic group (b1-2) are obtained by reacting with a polyisocyanate (b2).

在使用上述多元醇(b1-1)作為上述胺基甲酸酯 樹脂(B)之原料使用時，上述胺基甲酸酯樹脂(B)成為具有芳香環者。並且，上述多元醇(b1-1)中之芳香環濃度係以1.5至8mol/kg之範圍為佳，以1.6至5mol/kg之範圍更佳。 When using the above polyol (b1-1) as the above urethane When the raw material of resin (B) is used, the said urethane resin (B) becomes a thing which has an aromatic ring. In addition, the aromatic ring concentration in the polyol (b1-1) is preferably in a range of 1.5 to 8 mol / kg, and more preferably in a range of 1.6 to 5 mol / kg.

上述多元醇(b1-1)可列舉例如：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、雙酚之環氧烷加成物等。該等可單獨使用，亦可將2種以上併用。 Examples of the polyol (b1-1) include: aromatic polyester Alcohols, aromatic polycarbonate polyols, aromatic polyether polyols, alkylene oxide adducts of bisphenols, and the like. These may be used alone or in combination of two or more.

並且，即使在上述多元醇(b1-1)之中，芳香族 聚酯多元醇、雙酚之環氧烷加成物之1種的雙酚A之環氧烷加成物因基材密著性與抗黏結性(Blocking resistance)優異，因而為佳。因此，上述多元醇(b1-1)係以使用包含 芳香族聚酯多元醇及雙酚A之環氧烷加成物之中的至少1種者為佳。 Moreover, even among the above-mentioned polyols (b1-1), aromatic Polyester polyol and bisphenol A alkylene oxide adduct, which is one of the bisphenol A alkylene oxide adducts, are excellent in substrate adhesion and blocking resistance. Therefore, the above-mentioned polyol (b1-1) contains Preferably, at least one of the aromatic polyester polyol and the alkylene oxide adduct of bisphenol A is used.

上述芳香族聚酯多元醇係使多元羧酸與多元醇 進行酯化反應而得者，惟使用上述多元羧酸與多元醇中之至少1個具有芳香環者。 The aromatic polyester polyol is a polycarboxylic acid and a polyhydric alcohol. It is obtained by performing an esterification reaction, but at least one of the above-mentioned polycarboxylic acid and polyol has an aromatic ring.

上述多元羧酸脂之中具有芳香環者可列舉例如 ：酞酸、間酞酸、對酞酸、萘二羧酸等之芳香族二羧酸或其酯化物。不具芳香環者可列舉例如：琥珀酸、戊二酸、己二酸、馬來酸、庚二酸、辛二酸、壬二酸、伊康酸、癸二酸、氯橋酸、1,2,4-丁烷三羧酸、癸烷二羧酸、環己二羧酸、二聚物酸、延胡索酸等之脂肪族二羧酸或其酯化物，該等多元羧酸或其酯化物可單獨使用，亦可將2種以上併用。 Examples of those having an aromatic ring among the polyvalent carboxylic acid esters include : Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, or their esterified products. Examples of those without an aromatic ring include: succinic acid, glutaric acid, adipic acid, maleic acid, pimelic acid, suberic acid, azelaic acid, itaconic acid, sebacic acid, chlorobridged acid, 1,2 , 4-butanetricarboxylic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, fumaric acid, etc. aliphatic dicarboxylic acids or their esterifications, these polycarboxylic acids or their esterifications may be separately You can use 2 or more types together.

上述多元醇之中，具有芳香環者可列舉例如： 苯二甲醇、甲苯二甲醇、二甲苯甲醇等之芳香族二醇。 並且，不具芳香環者可列舉例如：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、環己烷-1,4-二醇、環己烷-1,4-二甲醇、新戊二醇乙二醇等之脂肪族多元醇。該等多元醇可單獨使用，亦可將2種以上併用。 Among the above-mentioned polyols, those having an aromatic ring include, for example: Aromatic diols such as xylylene, toluene, and xylene. Examples of those without an aromatic ring include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, and diethylene glycol. , Triethylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, neopentyl glycol ethylene glycol and the like. These polyols may be used alone or in combination of two or more kinds.

上述多元醇(b1-2)係具有親水性基之多元醇。 上述親水性基可列舉如：陰離子性基、陽離子性基及非離子性基，惟以陰離子性基為佳，在陰離子性基之中亦以羧基、磺酸基為佳。 The polyol (b1-2) is a polyol having a hydrophilic group. Examples of the hydrophilic group include an anionic group, a cationic group, and a nonionic group, but an anionic group is preferred, and a carboxyl group and a sulfonic acid group are also preferred among the anionic groups.

具有作為親水性基之羧基的多元醇之例可列舉 如：2,2-二羥甲基丙酸、2,2-二羥甲基丁酸及2,2-二羥甲基戊酸等。該等之中，以2,2-二羥甲基丙酸為佳。並且，亦可使用使具有上述羧基之多元醇與多元羧酸反應而得之具有羧基的聚酯多元醇。 Examples of the polyol having a carboxyl group as a hydrophilic group include Such as: 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid and 2,2-dimethylolvaleric acid. Among these, 2,2-dimethylolpropionic acid is preferable. Further, a polyester polyol having a carboxyl group obtained by reacting a polyol having a carboxyl group with a polycarboxylic acid may be used.

具有作為親水性基之磺酸基的多元醇之例可列 舉如：5-磺基間酞酸、磺基對酞酸、4-磺基酞酸、5-(4-磺基苯氧基)間酞酸等之二羧酸或該等之鹽，與乙二醇、丙二醇、1,4-丁二醇、1,6-己二醇、二乙二醇及新戊二醇等之低分子多元醇反應而得之聚酯多元醇等。 Examples of the polyol having a sulfonic acid group as a hydrophilic group are listed. Examples include dicarboxylic acids such as 5-sulfoisophthalic acid, sulfophthalic acid, 4-sulfophthalic acid, 5- (4-sulfophenoxy) isophthalic acid, or the like, and Polyester polyols obtained by reacting low molecular polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol and neopentyl glycol.

將上述陰離子性基的一部分或全部，藉由鹼性 化合物中和，即可對上述胺基甲酸酯樹脂(B)賦予良好的水分散性，因而為佳。 A part or all of the anionic group is made basic It is preferable that the compound is neutralized to impart good water dispersibility to the urethane resin (B).

上述鹼性化合物之例可列舉如：氨；三乙胺、 嗎福林、單乙醇胺、二乙基乙醇胺等之有機胺；氫氧化鈉、氫氧化鉀、氫氧化鋰等之金屬氫氧化物等。從可進一步提升本發明之水性樹脂組成物的水分散安定性來看，上述鹼性化合物之使用量，以鹼性化合物與陰離子性基之莫耳比[鹼性化合物/陰離子性基]，係以0.5至3之範圍為佳，以0.7至1.5之範圍更佳。 Examples of the basic compound include ammonia; triethylamine, Organic amines such as morpholin, monoethanolamine, and diethylethanolamine; metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide. From the viewpoint of further improving the water-dispersing stability of the aqueous resin composition of the present invention, the amount of the basic compound used is based on the molar ratio of the basic compound to the anionic group [basic compound / anionic group]. A range of 0.5 to 3 is preferable, and a range of 0.7 to 1.5 is more preferable.

在製造上述芳香族聚酯多元醇時之酯化反應中 ，以促進酯化反應之目的，以使用酯化觸媒為佳。上述酯化觸媒之例可列舉如：鈦、錫、鋅、鋁、鋯，鎂、鉿、鍺等之金屬；四異丙氧基鈦、四丁氧基鈦、乙醯丙酮氧鈦、二丁基錫氧化物、二乙酸二丁基錫、二月桂酸二丁基錫、辛酸錫、2-乙基己烷錫、乙醯丙酮鋅、四氯化 鋯、四氯化鋯四氫呋喃錯合物、四氯化鉿、四氯化鉿四氫呋喃錯合物、氧化鍺、四乙氧基鍺等之金屬化合物等。 In the esterification reaction in the production of the above aromatic polyester polyol For the purpose of promoting the esterification reaction, it is better to use an esterification catalyst. Examples of the above-mentioned esterification catalysts include metals such as titanium, tin, zinc, aluminum, zirconium, magnesium, hafnium, germanium, etc .; titanium tetraisopropoxide, titanium tetrabutoxide, titanium acetoacetate, titanium Butyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, tin octoate, 2-ethylhexanetin, zinc acetoacetone, tetrachloride Metal compounds such as zirconium, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride tetrahydrofuran complex, germanium oxide, tetraethoxy germanium, and the like.

上述雙酚A之環氧烷加成物係在雙酚A所具有 之酚性羥基加成有環氧烷者。上述環氧烷係可列舉如：環氧乙烷、環氧丙烷等。並且，相對於1莫耳之雙酚A，環氧烷之平均加成莫耳數係以1至8之範圍為佳，以1至4之範圍更佳。 The alkylene oxide adduct of the above bisphenol A is possessed by the bisphenol A The phenolic hydroxyl group is added with alkylene oxide. Examples of the alkylene oxide system include ethylene oxide and propylene oxide. In addition, the average addition mole number of the alkylene oxide is preferably in the range of 1 to 8 and more preferably in the range of 1 to 4 with respect to 1 mol of bisphenol A.

本發明中，多元醇(b1)含有上述多元醇(b1-1) 及上述多元醇(b1-2)作為必要成分，惟亦可含有此外之多元醇(b1-3)。上述多元醇(b1-3)之例可列舉如：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、氫化雙酚之環氧烷加成物等。並且，上述多元醇(b1-3)亦可使用作為上述芳香族聚酯多元醇之原料所列舉之上述多元醇。該等多元醇(b1-3)可單獨使用，亦可將2種以上併用。 In the present invention, the polyol (b1) contains the above-mentioned polyol (b1-1) The above-mentioned polyol (b1-2) is an essential component, but it may contain other polyol (b1-3). Examples of the polyol (b1-3) include aliphatic polyester polyols, aliphatic polycarbonate polyols, aliphatic polyether polyols, and alkylene oxide adducts of hydrogenated bisphenols. Moreover, the said polyol (b1-3) can also use the said polyol mentioned as a raw material of the said aromatic polyester polyol. These polyols (b1-3) may be used alone or in combination of two or more kinds.

並且，多元醇(b1)中所含之具有芳香環之多元 醇(b1-1)的比例，從進一步提高對基材之密著性來看，係以40至98質量%之範圍為佳，以60至98質量%之範圍更佳。 In addition, the polyhydric alcohol (b1) contains a polyvalent aromatic ring The ratio of the alcohol (b1-1) is more preferably in the range of 40 to 98% by mass, and more preferably in the range of 60 to 98% by mass from the viewpoint of further improving the adhesion to the substrate.

上述胺基甲酸酯樹脂(B)之原料的聚異氰酸酯 (b2)之例可列舉如：4,4'-二苯基甲烷二異氰酸酯、2,4'-二苯基甲烷二異氰酸酯、碳二亞胺改質二苯基甲烷二異氰酸酯、粗二苯基甲烷二異氰酸酯(crude diphenyl methane diisocyanate)、伸苯二異氰酸酯、甲苯二異氰酸 酯、萘二異氰酸酯等之芳香族聚異氰酸酯；六亞甲基二異氰酸酯、離胺酸二異氰酸酯、苯二甲基二異氰酸酯、四甲基苯二甲基二異氰酸酯等之脂肪族聚異氰酸酯；環己烷二異氰酸酯、二環己基甲烷二異氰酸酯、異佛爾酮二異氰酸酯等。該等聚異氰酸酯(b2)可單獨使用，亦可將2種以上併用。 Polyisocyanate as a raw material for the urethane resin (B) Examples of (b2) include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, and crude diphenyl. Crude diphenyl methane diisocyanate, benzene diisocyanate, toluene diisocyanate Esters, naphthalene diisocyanates and other aromatic polyisocyanates; hexamethylene diisocyanates, lysine diisocyanates, xylylene diisocyanates, tetramethylxylylene diisocyanates and other aliphatic polyisocyanates; cyclohexyl Alkane diisocyanate, dicyclohexyl methane diisocyanate, isophorone diisocyanate, etc. These polyisocyanates (b2) may be used alone or in combination of two or more kinds.

上述聚異氰酸酯(b2)之中，從對基材之密著性進一步提升來看，又以包含芳香族聚異氰酸酯者為佳。此時，上述聚異氰酸酯(b2)中之芳香族聚異氰酸酯之含量係以15至35質量%之範圍為佳。 Among the above-mentioned polyisocyanates (b2), from the viewpoint of further improving the adhesion to the substrate, it is more preferable to include an aromatic polyisocyanate. At this time, the content of the aromatic polyisocyanate in the polyisocyanate (b2) is preferably in a range of 15 to 35% by mass.

上述胺基甲酸酯樹脂(B)係例如可藉由在無溶劑下或有機溶劑之存在下，將上述多元醇(b1)與上述聚異氰酸酯(b2)混合，在40至120℃之溫度下，使其反應3至20小時而製造。並且，上述胺基甲酸酯樹脂(B)之製造時，可依需要而使用鏈伸長劑。 The urethane resin (B) is, for example, a mixture of the above-mentioned polyol (b1) and the above-mentioned polyisocyanate (b2) in a solvent-free or organic solvent at a temperature of 40 to 120 ° C. It is produced by reacting for 3 to 20 hours. In the production of the urethane resin (B), a chain elongating agent may be used if necessary.

上述多元醇(b1)與上述聚異氰酸酯(b2)之反應，係以上述多元醇(b1)所具有之羥基與上述聚異氰酸酯(b2)所具有之異氰酸酯基之當量比[異氰酸酯基/羥基]在0.5至3.5之範圍下進行者為佳，以在0.9至2.5之範圍下進行者更佳。 The reaction between the polyol (b1) and the polyisocyanate (b2) is based on the equivalent ratio [isocyanate group / hydroxyl] of the hydroxyl group of the polyol (b1) to the isocyanate group of the polyisocyanate (b2). It is preferably performed in a range of 0.5 to 3.5, and more preferably performed in a range of 0.9 to 2.5.

可在上述胺基甲酸酯樹脂(B)之製造時使用之有機溶劑，其例可列舉如：丙酮、甲基乙基酮等之酮溶劑；四氫呋喃、二烷等之醚溶劑；乙酸乙酯、乙酸丁酯等之乙酸酯溶劑；乙腈等之腈溶劑；二甲基甲醯胺、N-甲基吡咯啶酮等之醯胺溶劑等。該等有機溶劑可單獨 使用，亦可將2種以上併用。 Examples of the organic solvent that can be used in the production of the aforementioned urethane resin (B) include ketone solvents such as acetone, methyl ethyl ketone, and the like; Ether solvents such as alkane; acetate solvents such as ethyl acetate and butyl acetate; nitrile solvents such as acetonitrile; amine solvents such as dimethylformamide and N-methylpyrrolidone. These organic solvents may be used alone or in combination of two or more.

以上述方法而得之上述胺基甲酸酯樹脂(B)的 重量平均分子量，從更提高基材與活性能量線硬化性組成物之硬化塗膜的密著性來看，以3,000至200,000之範圍為佳，以3,000至100,000之範圍更佳。 The urethane resin (B) obtained by the above method The weight average molecular weight is more preferably in the range of 3,000 to 200,000, and more preferably in the range of 3,000 to 100,000, from the viewpoint of further improving the adhesion of the cured coating film of the substrate and the active energy ray-curable composition.

水性介質(C)係可列舉如：水、與水混合之有 機溶劑及該等之混合物。與水混合之有機溶劑，其例可列舉如：甲醇、乙醇、正丙醇、異丙醇等之純溶劑；丙酮、甲基乙基酮等之酮溶劑；乙二醇、二乙二醇、丙二醇等之聚烷二醇；聚烷二醇之烷基醚溶劑；N-甲基-2-吡咯啶酮等之內醯胺溶劑等。該等之與水混合之有機溶劑可單獨使用，亦可將2種以上併用。 Examples of the aqueous medium (C) include: water, mixed with water Organic solvents and mixtures of these. Examples of organic solvents mixed with water include pure solvents such as methanol, ethanol, n-propanol, and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; ethylene glycol, diethylene glycol, Polyalkylene glycols such as propylene glycol; Alkyl ether solvents of polyalkylene glycols; Limonamine solvents such as N-methyl-2-pyrrolidone and the like. These organic solvents mixed with water can be used alone or in combination of two or more kinds.

並且，上述水性介質(C)，如考量對安全性及 環境負荷之降低，則以單獨之水、或水及與水混合之有機溶劑的混合物為佳，以單獨之水更佳。 In addition, the above-mentioned aqueous medium (C), in consideration of safety and The reduction of environmental load is preferably water alone, or a mixture of water and an organic solvent mixed with water, and more preferably water alone.

上述水性介質(C)之比例係以10至90質量%之 範圍為佳，以30至70質量%之範圍更佳。 The proportion of the above-mentioned aqueous medium (C) is 10 to 90% by mass The range is preferably, and a range of 30 to 70% by mass is more preferable.

水性樹脂組成物(D)係上述乙烯酯樹脂(A)及上 述胺基甲酸酯樹脂(B)分散在上述水性介質(C)中者。此時，上述乙烯酯樹脂(A)與上述胺基甲酸酯樹脂(B)在上述水性介質(C)中可存在作為個別的樹脂粒子，惟以使用形成有上述乙烯酯樹脂(A)之一部分或全部存在於上述胺基甲酸酯樹脂(B)粒子中之樹脂粒子(F)者為佳。更具體而言，係以上述乙烯酯樹脂(A)形成芯部且上述胺基甲酸酯樹脂(B)形成殼部之芯-殼型樹脂粒子(F)者為佳。 The water-based resin composition (D) is the vinyl ester resin (A) and above The urethane resin (B) is dispersed in the aqueous medium (C). At this time, the vinyl ester resin (A) and the urethane resin (B) may exist as individual resin particles in the aqueous medium (C). The resin particles (F) which are partially or entirely present in the urethane resin (B) particles are preferred. More specifically, the core-shell type resin particles (F) in which the core portion is formed by the vinyl ester resin (A) and the shell portion is formed by the urethane resin (B) are more preferable.

上述樹脂粒子(F)係預先製造上述乙烯酯樹脂 (A)及上述胺基甲酸酯樹脂(B)，接著，可藉由在上述胺基甲酸酯樹脂(B)，將中和上述乙烯酯樹脂(A)、上述胺基甲酸酯樹脂(B)所具有之陰離子性基的鹼性化合物及上述水性介質(C)進行混合而製造。 The resin particles (F) are produced in advance of the vinyl ester resin (A) and the urethane resin (B), and then the urethane resin (B) can be used to neutralize the vinyl resin (A) and the urethane resin. (B) An anionic group-containing basic compound and the above-mentioned aqueous medium (C) are produced by mixing.

以上述方法所得之水性樹脂組成物(D)中包含 有機溶劑時，為了降低對安全性及環境之負擔，可藉由蒸餾法等而去除上述有機溶劑。藉此，可得到上述水性介質(C)中分散有上述樹脂粒子(F)之水性樹脂組成物(D)。 The aqueous resin composition (D) obtained by the above method contains In the case of an organic solvent, in order to reduce the burden on safety and the environment, the organic solvent may be removed by a distillation method or the like. Thereby, the aqueous resin composition (D) in which the said resin particle (F) was disperse | distributed in the said aqueous medium (C) can be obtained.

上述乙烯酯樹脂(A)與上述胺基甲酸酯樹脂(B) 之質量比例[(A)/(B)]，從更提升與活性能量線硬化性組成物之硬化塗膜的密著性來看，以60/40至10/90之範圍為佳，以55/45至20/80之範圍更佳。另外，該範圍係將上述乙烯酯樹脂(A)與上述胺基甲酸酯樹脂(B)作為上述樹脂粒子(F)使用時亦為相同。 The vinyl ester resin (A) and the urethane resin (B) In terms of mass ratio [(A) / (B)], from the viewpoint of further improving the adhesion of the hardened coating film with the active energy ray-curable composition, a range of 60/40 to 10/90 is preferable, and 55 The range of / 45 to 20/80 is more preferable. This range is also the same when the vinyl ester resin (A) and the urethane resin (B) are used as the resin particles (F).

而且，上述水性樹脂組成物(D)總量中之上述 乙烯酯樹脂(A)與上述胺基甲酸酯樹脂(B)之合計量的比例，係以10至90質量%之範圍為佳，以30至70質量%之範圍更佳。 In addition, in the above-mentioned total amount of the aqueous resin composition (D), The ratio of the total amount of the vinyl ester resin (A) to the aforementioned urethane resin (B) is preferably in the range of 10 to 90% by mass, and more preferably in the range of 30 to 70% by mass.

上述水性樹脂組成物(D)可依需要而調配成膜 助劑、硬化劑、塑化劑、抗靜電劑、蠟、光穩定劑、流動調節劑、染料、調平劑、流變調節劑、紫外線吸收劑、抗氧化劑、光觸媒性化合物、無機顏料、有機顏料、體質顏料等之添加劑；聚酯樹脂、胺基甲酸酯樹脂、丙 烯酸樹脂等之其它樹脂等。 The above-mentioned water-based resin composition (D) can be formulated into a film as required Additives, hardeners, plasticizers, antistatic agents, waxes, light stabilizers, flow regulators, dyes, leveling agents, rheology modifiers, UV absorbers, antioxidants, photocatalyst compounds, inorganic pigments, organic Additives for pigments and extender pigments; polyester resins, urethane resins, acrylics Other resins such as enoic resins.

本發明之被覆劑係將碳二亞胺系交聯劑(E)作 為必要成分。上述交聯劑(E)具有之碳二亞胺基，係與上述胺基甲酸酯樹脂(B)所具有之羧基等的親水性基反應而形成3維交聯構造時，使基材與活性能量線硬化性組成物之硬化塗膜的密著性提高，且在使用本發明之被覆劑作為底漆時，可對所形成之底塗層在耐濕熱試驗後賦予高的密著性及優異之耐藥性。 The coating agent of the present invention is a carbodiimide-based crosslinking agent (E). Is an essential ingredient. When the carbodiimide group of the crosslinking agent (E) reacts with a hydrophilic group such as a carboxyl group of the urethane resin (B) to form a three-dimensional crosslinked structure, the base material and the The adhesiveness of the hardened coating film of the active energy ray-curable composition is improved, and when the coating agent of the present invention is used as a primer, the formed primer layer can be provided with high adhesiveness and moisture resistance after a heat and humidity test. Excellent resistance.

上述交聯劑(E)係以具有2個以上之碳二亞胺基 者為佳，作為如此者，其例可列舉如：聚(4,4'-二苯基甲烷碳二亞胺)、聚(對-伸苯碳二亞胺)、聚(間-伸苯碳二亞胺)、聚(二異丙基苯基碳二亞胺)、聚(三異丙基苯基碳二亞胺)等之芳香族聚碳二亞胺；聚(二環己基甲烷碳二亞胺)等之脂環族聚碳二亞胺、聚(二異丙基碳二亞胺)等之脂肪族聚碳二亞胺等。 The cross-linking agent (E) has two or more carbodiimide groups. It is preferably, and as such, examples thereof include poly (4,4'-diphenylmethanecarbodiimide), poly (p-phenylene carbodiimide), and poly (m-phenylene carbon) Diimide), poly (diisopropylphenylcarbodiimide), poly (triisopropylphenylcarbodiimide), and other aromatic polycarbodiimides; poly (dicyclohexylmethane carbodiimide) Alicyclic polycarbodiimides, poly (diisopropylcarbodiimide), etc., and aliphatic polycarbodiimides, etc.

並且，上述交聯劑(E)，由於本發明之被覆劑 係上述乙烯酯樹脂(A)及上述胺基甲酸酯樹脂(B)分散在上述水性介質(C)中者，故以水溶性或水分散性(乳液型)者為佳。 The above-mentioned crosslinking agent (E) is the coating agent of the present invention. Since the vinyl ester resin (A) and the urethane resin (B) are dispersed in the aqueous medium (C), a water-soluble or water-dispersible (emulsion type) is preferred.

作為可作為上述交聯劑(E)使用之市售品，可 列舉如：日清紡化工股份有限公司製造之「CARBODILITE SV-02」、「CARBODILITE V-02」、「CARBODILITE V-02-L2」、「CARBODILITE V-04」、「CARBODILITE E-01」、「CARBODILITE E-02」等。 As a commercially available product that can be used as the above-mentioned crosslinking agent (E), Examples include: "CARBODILITE SV-02", "CARBODILITE V-02", "CARBODILITE V-02-L2", "CARBODILITE V-04", "CARBODILITE E-01", "CARBODILITE E", "CARBODILITE E" manufactured by Nisshinbo Chemical Co., Ltd. -02 "and so on.

上述交聯劑(E)之使用量，從呈現充分的交聯 性能來看，以與可和碳二亞胺基反應之上述胺基甲酸酯樹脂(B)所具有之親水性基的80至100莫耳%反應之量者為佳，以與100莫耳%反應之量者更佳。 The amount of the cross-linking agent (E) used is from a sufficient degree of cross-linking. In terms of performance, it is preferable to react with 80 to 100 mole% of the hydrophilic group of the above-mentioned urethane resin (B) which can react with the carbodiimide group. % Response amount is better.

並且上述交聯劑(E)，從提高密著性、與上述 水性樹脂組成物(D)之保存安定性來看，相對於上述水性樹脂組成物(D)，以在3至5質量%之範圍添加為佳。 In addition, the cross-linking agent (E) improves adhesion to From the standpoint of storage stability of the aqueous resin composition (D), it is preferable to add the aqueous resin composition (D) in a range of 3 to 5% by mass.

本發明之積層體，係具有使用上述說明之本發 明的被覆劑所形成之底塗層，在上述底塗層之表面具有使用活性能量線硬化性組成物所形成之硬化塗膜者。 The laminated body of the present invention has the present invention using the above description. The undercoat layer formed by a clear coating agent has a hardened coating film formed using an active energy ray-curable composition on the surface of the undercoat layer.

上述活性能量線硬化性組成物，係以含有具有 聚合性不飽和基之樹脂及具有聚合性不飽和基之單體者為佳，該等具有聚合性不飽和基之樹脂及具有聚合性不飽和基之單體的種類，係以因應上述活性能量線硬化性組成物之硬化塗膜所要求之特性而適當地選擇者為佳。 The active energy ray-curable composition contains The polymerizable unsaturated group resin and the monomer having a polymerizable unsaturated group are preferred. The types of the resin having a polymerizable unsaturated group and the monomer having a polymerizable unsaturated group are based on the above-mentioned active energy. The characteristics required for the cured coating film of the wire-curable composition are appropriately selected.

上述具有聚合性不飽和基之樹脂可列舉如：胺 基甲酸酯(甲基)丙烯酸酯樹脂、不飽和聚酯樹脂、環氧(甲基)丙烯酸酯樹脂、聚酯(甲基)丙烯酸酯樹脂、丙烯(甲基)丙烯酸酯樹脂、具有馬來醯亞胺基之樹脂等。該等具有聚合性不飽和基之樹脂可單獨使用，亦可將2種以上併用。 Examples of the resin having a polymerizable unsaturated group include: amines Urethane (meth) acrylate resin, unsaturated polyester resin, epoxy (meth) acrylate resin, polyester (meth) acrylate resin, acrylic (meth) acrylate resin,树脂 imino resin. These resins having a polymerizable unsaturated group may be used alone or in combination of two or more kinds.

本發明中，「(甲基)丙烯酸酯」係指丙烯酸酯 及(甲基)丙烯酸酯之一者或兩者，「(甲基)丙烯醯基」係指丙烯醯基及(甲基)丙烯醯基之一者或兩者。 In the present invention, "(meth) acrylate" means acrylate And one or both of (meth) acrylic esters, and "(meth) acrylfluorenyl" refers to one or both of acrylfluorenyl and (meth) acrylfluorenyl.

上述胺基甲酸酯(甲基)丙烯酸酯樹脂之例可列 舉如：使脂肪族聚異氰酸酯或芳香族聚異氰酸酯與具有 羥基之(甲基)丙烯酸酯進行胺基甲酸酯化反應而得之具有胺基甲酸酯鍵與(甲基)丙烯醯基之樹脂等。 Examples of the aforementioned urethane (meth) acrylate resins are listed. For example: make aliphatic polyisocyanate or aromatic polyisocyanate and have A resin having a urethane bond and a (meth) acrylfluorenyl group, which is obtained by subjecting a hydroxy (meth) acrylate to a urethane reaction.

上述脂肪族聚異氰酸酯之例可列舉如：四亞甲 基二異氰酸酯、五亞甲基二異氰酸酯、六亞甲基二異氰酸酯、七亞甲基二異氰酸酯、八亞甲基二異氰酸酯、十亞甲基二異氰酸酯、2-甲基-1,5-戊烷二異氰酸酯、3-甲基-1,5-戊烷二異氰酸酯、十二亞甲基二異氰酸酯、2-甲基五亞甲基二異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、降莰烷二異氰酸酯、氫化二苯基甲烷二異氰酸酯、氫化甲苯二異氰酸酯、氫化二甲苯二異氰酸酯、氫化四甲基苯二甲基二異氰酸酯、環己基二異氰酸酯等。並且，上述芳香族聚異氰酸酯可列舉如：甲苯二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、苯二亞甲基二異氰酸酯、1,5-萘二異氰酸酯、聯甲苯胺二異氰酸酯、對苯二異氰酸酯等。 Examples of the above-mentioned aliphatic polyisocyanate include tetramethylene Diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1,5-pentane Diisocyanate, 3-methyl-1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene di Isocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, Tetramethylxylylene diisocyanate, cyclohexyl diisocyanate, etc. Examples of the aromatic polyisocyanate include toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, p-toluidine diisocyanate, and Benzene diisocyanate, etc.

上述具有羥基之(甲基)丙烯酸酯之例可列舉如 ：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、1,5-戊二醇單(甲基)丙烯酸酯、1,6-己二醇單(甲基)丙烯酸酯、新戊二醇單(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇單(甲基)丙烯酸酯等之二元醇的單(甲基)丙烯酸酯；三羥甲基丙烷二(甲基)丙烯酸酯、乙氧基化三羥甲基丙烷(甲基)丙烯酸酯、丙氧基化三羥甲基丙烷二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、雙(2-(甲基)丙烯醯氧基乙 基)羥基乙基三聚異氰酸酯等之3元醇之單或二(甲基)丙烯酸酯，或者該等之醇性羥基之一部分以ε-己內酯改質之具有羥基的單及二(甲基)丙烯酸酯；新戊四醇三(甲基)丙烯酸酯、二-三羥甲基丙烷三(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯等之具有1個官能基的羥基與3個官能基以上之(甲基)丙烯醯基之化合物，或者該化合物進一步以ε-己內酯改質之具有羥基的多官能(甲基)丙烯酸酯；二丙二醇單(甲基)丙烯酸酯、二乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯等之具有氧伸烷基鏈之(甲基)丙烯酸酯化合物；聚乙二醇-聚丙二醇單(甲基)丙烯酸酯、聚氧丁烯-聚氧丙烯單(甲基)丙烯酸酯等之嵌段構造之具有氧伸烷基鏈之(甲基)丙烯酸酯化合物；聚(乙二醇-丁二醇)單(甲基)丙烯酸酯、聚(丙二醇-丁二醇)單(甲基)丙烯酸酯等之無規構造之具有氧伸烷基鏈之(甲基)丙烯酸酯化合物等。 Examples of the above-mentioned (meth) acrylate having a hydroxyl group include : 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,5-pentyl Glycol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, hydroxytrimethyl acetate neopentyl glycol mono (methyl) ) Mono (meth) acrylates of glycols such as acrylates; trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane (meth) acrylate, propoxylated Trimethylolpropane di (meth) acrylate, glycerol di (meth) acrylate, bis (2- (meth) acryloxyethyl) Mono- or di (meth) acrylates of trihydric alcohols such as hydroxyethyltrimeric isocyanate, or mono- and di (methyl) hydroxy groups modified by ε-caprolactone as part of these alcoholic hydroxyl groups Base) acrylate; neopentaerythritol tri (meth) acrylate, di-trimethylolpropane tri (meth) acrylate, dinepentaerythritol penta (meth) acrylate, etc. have one function A compound of a hydroxy group of a group and a (meth) acrylfluorenyl group having 3 or more functional groups, or a polyfunctional (meth) acrylate having a hydroxy group modified by ε-caprolactone; (Meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, etc. ) Acrylate compounds; polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-polyoxypropylene mono (meth) acrylate, and the like Base) acrylate compounds; poly (ethylene glycol-butanediol) mono (meth) acrylate, poly (propylene glycol-butanediol) mono (meth) acrylate, etc. The gauge structure having alkylene oxide chains (meth) acrylate compound.

上述不飽和聚酯樹脂係藉由α,β-不飽和二元酸 或其酸酐、芳香族飽和二元酸或其酸酐、及二醇之縮聚得到的硬化性樹脂。上述α,β-不飽和二元酸或其酸酐之例可列舉如：馬來酸、馬來酸酐、丁烯二酸、伊康酸、檸康酸、氯馬來酸及該等之酯等。上述芳香族飽和二元酸或其酸酐可列舉如：酞酸、酞酸酐、間酞酸、對酞酸、硝基酞酸、四氫酞酸酐、橋亞甲基四氫酞酸酐、鹵化酞酸酐及該等之酯等。脂肪族或脂環族飽和二元酸可列舉如：草酸、丙二酸、琥珀酸、己二酸、癸二酸、壬二 酸、戊二酸、六氫酞酸酐及該等之酯等。上述二醇可列舉如：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、雙酚A、氫化雙酚A、碳酸乙二醇酯、2,2-二-(4-羥基丙氧基二苯基)丙烷等，此外，亦可同樣地使用環氧乙烷、環氧丙烷等之氧化物。 The unsaturated polyester resin is based on α, β-unsaturated dibasic acid. A curable resin obtained by polycondensation of an acid anhydride thereof, an aromatic saturated dibasic acid or an acid anhydride thereof, and a diol. Examples of the above-mentioned α, β-unsaturated dibasic acid or its anhydride include maleic acid, maleic anhydride, butenedioic 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 anhydride, bridge methylene tetrahydrophthalic anhydride, and halogenated phthalic anhydride And such esters. Examples of aliphatic or cycloaliphatic saturated dibasic acids include: oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, and azelaic acid Acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof. Examples of the diol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, Neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2- Di- (4-hydroxypropoxydiphenyl) propane and the like can also be used in the same manner as oxides such as ethylene oxide and propylene oxide.

上述環氧(甲基)丙烯酸酯樹脂係可列舉如：使 雙酚A型環氧樹脂、雙酚F型環氧樹脂、酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂等之環氧樹脂的環氧基與(甲基)丙烯酸反應而得者。 Examples of the epoxy (meth) acrylate resin system include: Epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, etc. are reacted with (meth) acrylic acid By.

上述聚酯(甲基)丙烯酸酯樹脂之例可列舉如： 使聚酯多元醇之羥基與(甲基)丙烯酸反應而得者。 Examples of the above polyester (meth) acrylate resin include: It is obtained by reacting the hydroxyl group of a polyester polyol with (meth) acrylic acid.

上述丙烯酸(甲基)丙烯酸酯樹脂之例可列舉如 ：使甲基丙烯酸縮水甘油酯及依所需之(甲基)丙烯酸烷酯等之(甲基)丙烯酸酯單體聚合，得到具有環氧基之丙烯酸樹脂後，使該環氧基與(甲基)丙烯酸反應而得者。 Examples of the aforementioned acrylic (meth) acrylate resins include : Polymerizing (meth) acrylic acid ester monomers such as glycidyl methacrylate and, if necessary, alkyl (meth) acrylic acid esters, to obtain an acrylic resin having an epoxy group, the epoxy group and (form Based) Acrylic reaction.

上述具有馬來醯亞胺基之樹脂可列舉如：將N- 羥乙基馬來醯亞胺與異佛爾酮二異氰酸酯進行胺基甲酸酯化而得之2官能馬來醯亞胺胺基甲酸酯化合物、馬來醯亞胺乙酸與聚丁二醇進行酯化而得之2官能馬來醯亞胺酯化合物、馬來醯亞胺己酸與新戊四醇的四環氧乙烷加成物進行酯化而得之4官能馬來醯亞胺酯化合物、馬來醯亞胺乙酸與多元醇化合物進行酯化而得之多官能馬來醯亞胺酯化合物等。 Examples of the aforementioned resin having a maleimidine group include: Bifunctional maleimide imine carbamate compound obtained by the urethanization of hydroxyethyl maleimide and isophorone diisocyanate, maleimide iminoacetic acid and polybutanediol Bifunctional maleimide imide compound obtained by esterification, tetrafunctional ethyleneimide adduct of maleimide iminohexanoic acid and neopentyl tetraol, esterified An ester compound, a polyfunctional maleimide imide compound obtained by esterification of a maleimide imineacetic acid and a polyol compound, and the like.

上述具有聚合性不飽和基之單體之例可列舉如 ：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、數量平均分子量在150至1000之範圍的聚乙二醇二(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、數量平均分子量在150至1000之範圍的聚丙二醇二(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、羥基三甲基乙酸酯新戊二醇二(甲基)丙烯酸酯、雙酚A二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二環戊烯基(甲基)丙烯酸酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸三級丁酯、(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)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯等之脂肪族(甲基)丙烯酸烷酯、(甲基)丙烯酸甘油酯、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸3-氯-2-羥丙酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸2-丁氧基乙酯、2-(二乙基胺基)乙基(甲基)丙烯酸酯、2-(二甲基胺基)乙基(甲基)丙烯酸酯、γ-(甲基)丙烯醯氧基丙基三甲氧基矽烷、(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、(甲基)丙烯酸聚苯乙烯基乙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸異莰酯、甲氧基化環癸三烯(甲基)丙烯酸酯、(甲基)丙烯酸苯酯；馬來醯亞胺、N-甲基馬來醯亞胺、N-乙基馬來醯亞胺、N-丙基馬來醯亞胺、N-丁基馬來醯亞胺、N-己基馬來醯亞胺、N-辛基馬來醯亞胺、N-十二烷基馬來醯亞胺、N-硬脂基馬來醯亞胺、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、2-馬來醯亞胺乙基-碳酸乙酯、2-馬來醯亞胺乙基-碳酸丙酯、N-乙基-(2-馬來醯亞胺乙基)胺基甲酸酯、N,N-六亞甲基雙馬來醯亞胺、聚丙二醇-雙(3-馬來醯亞胺基丙基)醚、雙(2-馬來醯亞胺基乙基)碳酸酯、1,4-二馬來醯亞胺環己烷等之馬來醯亞胺化合物等。該等具有聚合性不飽和基之單體可單獨使用，亦可將2種以上併用。 Examples of the monomer having a polymerizable unsaturated group include the following: : Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol having a number average molecular weight in the range of 150 to 1,000 Di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di with a number average molecular weight ranging from 150 to 1,000 (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, hydroxytrimethyl acetate neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, trimethylolpropane di (meth) acrylate, neopentaerythritol tetra (meth) acrylate, neopentaerythritol tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dicyclopentenyl (meth) acrylate, methyl (meth) acrylate, propyl (meth) acrylate, (formyl) Base) Butyl acrylate Tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, (formyl) Base) aliphatic (meth) acrylates such as lauryl acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, glyceryl (meth) acrylate, (meth) acrylic acid 2 -Hydroxyethyl ester, 3-chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, 2-butoxyethyl (meth) acrylate , 2- (diethylamino) ethyl (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, γ- (meth) acryloxypropyltrimethyl Oxysilane, 2-methoxyethyl (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy Dipropylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, Phenoxy dipropylene glycol (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, polybutadiene (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, poly Ethylene glycol-polybutylene glycol (meth) acrylate, polystyrene ethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dimethacrylate Cyclopentyl, dicyclopentenyl (meth) acrylate, isoamyl (meth) acrylate, methoxylated cyclodecadiene (meth) acrylate, phenyl (meth) acrylate; maleic acid Imine, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide Amine, N-octyl maleimide, N-dodecyl maleimide, N-stearyl maleimide, N-phenyl maleimide, N-cyclohexyl horse Lyme imine, 2-maleimide ethyl-ethyl carbonate, 2-maleimide Ethyl-propyl carbonate, N-ethyl- (2-maleimideethyl) carbamate, N, N-hexamethylenebismaleimide, polypropylene glycol-bis (3 -Maleimide imine propyl) ether, bis (2-maleimide iminoethyl) carbonate, maleimide compounds such as 1,4-dimaleimide imine cyclohexane, etc. . These monomers having a polymerizable unsaturated group may be used alone or in combination of two or more kinds.

上述活性能量線硬化性組成物可在塗布於基材 等之後照射活性能量線作成硬化塗膜。該活性能量線可列舉如：紫外線、電子束、α射線、β射線、γ射線等之電離輻射。在照射紫外線作為活性能量線，將上述活性能量線硬化性組成物作成硬化塗膜時，以在上述活性能量 線硬化性組成物中添加光聚合起始劑，使硬化性提高者為佳。並且，如有需要，亦可添加光敏劑使硬化性提高。另一方面，在照射電子束、α射線、β射線或γ射線作為活性能量線，將上述活性能量線硬化性組成物作成硬化塗膜時，由於不使用光聚合起始劑或光敏劑亦可迅速硬化，因此不需要添加光聚合起始劑或光敏劑。 The active energy ray-curable composition can be applied to a substrate After that, the active energy ray was irradiated to form a hardened coating film. Examples of the active energy ray include ionizing radiation such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays. When an ultraviolet ray is irradiated as an active energy ray, and the active energy ray-curable composition is used as a hardened coating film, It is preferable to add a photopolymerization initiator to the linear curable composition to improve the curability. If necessary, a photosensitizer may be added to improve the curability. On the other hand, when an electron beam, α-ray, β-ray, or γ-ray is irradiated as an active energy ray, and the active energy ray-curable composition is used as a hardened coating film, a photopolymerization initiator or a photosensitizer may not be used It hardens quickly, so there is no need to add a photopolymerization initiator or photosensitizer.

上述光聚合起始劑之例可列舉如：1-羥基環己 基苯基酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-甲基-1-丙烷-1-酮、2-甲基-1-[4-(甲基硫基)苯基]-2-N-嗎福林基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎福林基苯基)-丁酮、雙(2,6-二甲氧基苄醯基)-2,4,4-三甲基戊基膦氧化物、雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物等。 Examples of the photopolymerization initiator include: 1-hydroxycyclohexyl Phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-methyl-1 -Propane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-N-morpholinylpropane-1-one, 2-benzyl-2-dimethyl Aminoamino-1- (4-morpholinylphenyl) -butanone, bis (2,6-dimethoxybenzylfluorenyl) -2,4,4-trimethylpentylphosphine oxide, Bis (2,4,6-trimethylbenzyl) phenylphosphine oxide and the like.

上述光敏劑之例可列舉如：脂肪族胺、芳香族 胺等之胺化合物、鄰-甲苯基硫脲(o-tolylthiourea)等之脲化合物、二乙基二硫代磷酸鈉、對甲苯磺酸S-苄基異硫脲陽離子鹽(S-benzyl-isothiouronium-p-toluene sulfonate)等之硫化合物等。 Examples of the above-mentioned photosensitizers include aliphatic amines and aromatics. Amine compounds such as amines, urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, S-benzyl-isothiouronium p-toluenesulfonic acid -p-toluene sulfonate).

本發明之積層體中使用之基材之例可列舉如： 金屬基材、塑膠基材、玻璃基材、紙基材、木材基材、纖維質基材等。該等基材之中，為提高上述活性能量線硬化性組成物之硬化塗膜與基材之密著性，在使用本發明之水性樹脂組成物作為底漆使用時，以塑膠基材為理想。 Examples of the base material used in the laminated body of the present invention include: Metal substrate, plastic substrate, glass substrate, paper substrate, wood substrate, fibrous substrate, etc. Among these substrates, in order to improve the adhesion between the cured coating film of the active energy ray-curable composition and the substrate, a plastic substrate is preferably used when the water-based resin composition of the present invention is used as a primer. .

上述塑膠基材之材質之例可列舉如：聚酯、丙 烯酸樹脂(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樹脂)、ABS樹脂與聚碳酸酯之複合樹脂、聚苯乙烯、聚胺基甲酸酯、環氧樹脂、聚氯乙烯、聚醯胺、聚烯烴(聚乙烯、聚丙烯)、聚環烯烴(COP)等)、三乙酸纖維素(TAC)等。 Examples of the material of the above plastic substrate include polyester, acrylic Acrylic resin (polymethyl methacrylate, etc.), polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS resin), composite resin of ABS resin and polycarbonate, polystyrene, polyamine Formates, epoxy resins, polyvinyl chloride, polyamides, polyolefins (polyethylene, polypropylene), polycyclic olefins (COP), etc.), cellulose triacetate (TAC), and the like.

本發明之被覆劑，即使在上述塑膠基材之中， 作為聚酯基材之底漆亦極為有用。上述聚酯之具體例可列舉如：聚對酞酸乙二酯(PET)、聚對酞酸丁二酯(PBT)等。 The coating agent of the present invention, even in the aforementioned plastic substrate, It is also extremely useful as a primer for polyester substrates. Specific examples of the polyester include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and the like.

上述塑膠基材之例可列舉如：行動電話、家電 製品、汽車內外裝材料、OA設備等之塑膠成形品。而且，亦可列舉以塑膠作為材料之膜基材。將膜基材作為本發明之積層體的基材時，可在抗反射膜、相位差膜、稜鏡片等之光學膜；鋁蒸鍍膜等食品包裝等的高機能膜中使用。 Examples of the above plastic substrates include mobile phones, home appliances Products, plastic materials for automotive interior and exterior materials, OA equipment, etc. Furthermore, a film substrate using plastic as a material can also be cited. When the film substrate is used as the substrate of the laminated body of the present invention, it can be used in high-performance films such as anti-reflection films, retardation films, reticle films, and food packaging such as aluminum vapor-deposited films.

並且，將本發明之積層體作為抗反射膜、相位 差膜、稜鏡片等之光學膜時，可作為液晶顯示器(LCD)、有機EL顯示器(OLED)、電漿顯示器(PDP)等之各種畫面顯示裝置的構件使用。 The multilayer body of the present invention is used as an anti-reflection film and a phase In the case of optical films such as differential films and cymbals, it can be used as a component of various screen display devices such as liquid crystal displays (LCD), organic EL displays (OLED), and plasma displays (PDP).

本發明之被覆劑例如可藉由在上述基材之表面 直接塗布，接著使其乾燥、硬化而可在基材之表面形成塗膜。將本發明之被覆劑進行乾燥而使其硬化之方法可為在常溫下熟化1至10日左右之方法，惟能夠迅速地進行固化，故以在100℃至150℃之溫度下加熱1至600秒鐘左右的方法為佳。並且，如使用在相對高的溫度下容易變 形或變色的塑膠基材時，以在70℃至100℃左右之相對低的溫度下加熱者為佳。 The coating agent of the present invention can be used, for example, by It can be directly applied, followed by drying and hardening to form a coating film on the surface of the substrate. The method for drying and curing the coating agent of the present invention may be a method of curing at room temperature for about 1 to 10 days, but it can be rapidly cured, so it is heated at a temperature of 100 to 150 ° C for 1 to 600 The method of about seconds is better. And, it is easy to change if used at relatively high temperature When deforming or discoloring a plastic substrate, it is better to heat it at a relatively low temperature of about 70 ° C to 100 ° C.

在上述基材的表面塗布本發明之被覆劑之方法 ，可列舉如使用例如：凹版塗布機、輥塗機、缺角輪塗布機、刮刀塗布機、氣刀塗布機、簾式塗布機、吻合式塗布機、淋浴塗布機、流塗機、旋塗機、浸塗機、網版印刷、噴塗、刷塗、點塗器、棒塗布機等之塗布方法。 Method for coating the coating agent of the present invention on the surface of the substrate For example, use can be made of, for example, gravure coater, roll coater, corner wheel coater, blade coater, air knife coater, curtain coater, anastomotic coater, shower coater, flow coater, spin coater, etc. Coating method for coating machine, dip coating machine, screen printing, spray coating, brush coating, spot coater, rod coating machine, etc.

使用本發明之被覆劑所形成之塗膜的膜厚可依 所使用之用途而適當地調整，一般係以0.01至20μm之範圍為佳。 The film thickness of the coating film formed by using the coating agent of the present invention can be determined according to The application to be used is appropriately adjusted, and it is generally preferably in the range of 0.01 to 20 μm.

本發明之積層體，係在如上述操作所得的本發 明之被覆劑的塗膜之底塗層表面，進一步塗布上述活性能量線硬化性組成物，藉由活性能量線的照射，即可藉由形成上述活性能量線硬化性組成物之硬化塗膜而得。 而且，上述活性能量線硬化性組成物之塗布方法係可使用與上述本發明之被覆劑的塗布方法相同之方法。 The laminated body of the present invention is based on the present invention obtained by the above operation. The surface of the undercoat layer of the coating film of Mingzhi coating agent is further coated with the above active energy ray-curable composition, and can be obtained by forming a hardened coating film of the above active energy ray-curable composition by irradiation of the active energy ray. . Moreover, the coating method of the said active-energy-ray-curable composition is the same method as the coating method of the coating agent of this invention mentioned above.

[實施例] [Example]

以下，藉由實施例及比較例以具體說明本發明。 Hereinafter, the present invention will be specifically described using examples and comparative examples.

(合成例1：芳香族聚酯多元醇(1)之合成) (Synthesis example 1: Synthesis of aromatic polyester polyol (1))

在具備溫度計、氮氣導入管及攪拌器之反應容器中導入氮氣之同時饋入間酞酸27.6質量份、對酞酸27.6質量份、二乙二醇19.9質量份以及氧化二丁錫0.03質量份，在180至230℃下，在230℃進行24小時之縮聚反應直到酸值成為1以下為止，得到芳香族聚酯多元醇(1)[酸值0.6、羥 值50.0、芳香環濃度4.77mol/kg]。 Introduce nitrogen into a reaction vessel equipped with a thermometer, a nitrogen introduction tube, and a stirrer while feeding in 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. A polycondensation reaction is carried out at 180 to 230 ° C for 24 hours at 230 ° C until the acid value becomes 1 or less to obtain an aromatic polyester polyol (1) [acid value 0.6, hydroxyl Value 50.0, aromatic ring concentration 4.77 mol / kg].

(製造例1：乙烯酯樹脂(1)之合成) (Production Example 1: Synthesis of vinyl ester resin (1))

在反應容器中饋入甲酚酚醛清漆型環氧樹脂(DIC股份有限公司製造之「EPICLON N-673-80M」、固體成分環氧當量：209g/eq、不揮發成分：80質量%、溶劑：甲基乙基酮)46.7質量份、丙烯酸13.3質量份、氫醌單甲醚0.08質量份、甲基乙基酮13.3質量份，進行攪拌使其均勻混合。接著，加入三苯膦0.37質量份，在反應溫度80℃下使其反應直到酸值成為1.5以下為止，得到乙烯酯樹脂(1)之不揮發成分75質量%溶液。 A cresol novolac-type epoxy resin ("EPICLON N-673-80M" manufactured by DIC Corporation), solid equivalent epoxy equivalent: 209 g / eq, non-volatile content: 80% by mass, and solvent: 46.7 parts by mass of methyl ethyl ketone), 13.3 parts by mass of acrylic acid, 0.08 parts by mass of hydroquinone monomethyl ether, and 13.3 parts by mass of methyl ethyl ketone, and stirred to uniformly mix them. Next, 0.37 parts by mass of triphenylphosphine was added and reacted at a reaction temperature of 80 ° C. until the acid value became 1.5 or less to obtain a 75% by mass solution of the non-volatile content of the vinyl ester resin (1).

將製造例1所合成之乙烯酯樹脂(1)之原料呈示於表1。 Table 1 shows the raw materials of the vinyl ester resin (1) synthesized in Production Example 1.

(製造例2：具有芳香環之胺基甲酸酯樹脂(1)之合成) (Production Example 2: Synthesis of Urethane Resin (1) with Aromatic Ring)

在反應容器中，將合成例1所得之芳香族聚酯多元醇(1)100.0質量份在減壓下100℃中進行脫水，然後冷卻 至80℃後，加入甲基乙基酮66.6質量份，進行攪拌使其均勻混合。接著，加入2,2'-二羥甲基丙酸6.1質量份，然後再加入異佛爾酮二異氰酸酯23.1質量份，使其在80℃反應12小時，進行胺基甲酸酯化步驟。經確認異氰酸酯值成為0.1%以下，加入正丁醇3質量份，進一步反應2小時後，冷卻至50℃，得到具有芳香環之胺基甲酸酯樹脂(1)之不揮發成分65質量%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 then cooled. After the temperature was reached to 80 ° C., 66.6 parts by mass of methyl ethyl ketone was added and stirred to uniformly mix. Next, 6.1 parts by mass of 2,2′-dimethylolpropionic acid was added, and then 23.1 parts by mass of isophorone diisocyanate was added, and they were reacted at 80 ° C. for 12 hours to perform a urethane step. After confirming that the isocyanate value was 0.1% or less, 3 parts by mass of n-butanol was added, and after further reacting for 2 hours, it was cooled to 50 ° C to obtain a 65% by mass solution of the nonvolatile component of the urethane resin (1) having an aromatic ring. .

(調製例1：水性樹脂組成物(1)之調製) (Preparation example 1: Preparation of aqueous resin composition (1))

在製造例2所得之具有芳香環的胺基甲酸酯樹脂(1)之不揮發成分65質量%溶液147.7質量份(以上述胺基甲酸酯樹脂(1)而言為96質量份)中，加入製造例1所得之乙烯酯樹脂(1)之不揮發成分75質量%溶液128.0質量份(以上述乙烯酯樹脂(1)而言為96質量份)及三乙胺5.5質量份，緩慢加入離子交換水938.5質量份以實施水溶化。然後於減壓下，在30至50℃中去除甲基乙基酮，得到不揮發成分40質量%之水性樹脂組成物(1)。 In 147.7 parts by mass of a 65% by mass solution of the nonvolatile matter of the urethane resin (1) having an aromatic ring obtained in Production Example 2 (96 parts by mass of the above-mentioned urethane resin (1)) Add 128.0 parts by mass of a 75% by mass solution of the non-volatile content of the vinyl ester resin (1) obtained in Production Example 1 (96 parts by mass of the above-mentioned vinyl ester resin (1)) and 5.5 parts by mass of triethylamine, and slowly add 938.5 parts by mass of ion-exchanged water was subjected to water melting. Then, methyl ethyl ketone was removed at 30 to 50 ° C. under reduced pressure to obtain an aqueous resin composition (1) having a non-volatile content of 40% by mass.

調製例1所得的水性樹脂組成物(1)之組成呈示於表2。而且，表中之組成表示不揮發成分量(僅為樹脂之量)。 The composition of the aqueous resin composition (1) obtained in Preparation Example 1 is shown in Table 2. The composition in the table indicates the amount of non-volatile components (only the amount of resin).

(調製例2：紫外線硬化性組成物(UV-1)之調製 ) (Preparation example 2: Preparation of ultraviolet curable composition (UV-1) )

藉由將胺基甲酸酯丙烯酸酯樹脂(DIC股份有限公司製造之「UNIDIC V-4260」)50質量份、三丙二醇二丙烯酸酯50質量份及光聚合起始劑(BASF JAPAN股份有限公司製造之「IRGACURE 184」；1-羥基環己基苯基酮)3質量份進行混合，得到紫外線硬化性組成物(UV-1)。 50 parts by mass of a urethane acrylate resin ("UNIDIC V-4260" manufactured by DIC Corporation), 50 parts by mass of tripropylene glycol diacrylate, and a photopolymerization initiator (manufactured by BASF Japan Co., Ltd.) "IRGACURE 184"; 3 parts by mass of 1-hydroxycyclohexylphenyl ketone) were mixed to obtain an ultraviolet curable composition (UV-1).

(調製例3：紫外線硬化性組成物(UV-2)之調製) (Preparation example 3: Preparation of ultraviolet curable composition (UV-2))

藉由將環氧丙烯酸酯樹脂(DIC股份有限公司製造之「UNIDIC V-5500」)50質量份、三丙二醇二丙烯酸酯50重量份及光聚合起始劑(BASF JAPAN股份有限公司製造之「IRGACURE 184」)3質量份進行混合，得到紫外線硬化性組成物(UV-2)。 50 parts by mass of epoxy acrylate resin ("UNIDIC V-5500" manufactured by DIC Corporation), 50 parts by weight of tripropylene glycol diacrylate, and a photopolymerization initiator ("IRGACURE" manufactured by BASF Japan Co., Ltd. 184 ″) 3 parts by mass were mixed to obtain an ultraviolet curable composition (UV-2).

(實施例1：底漆(1)之製作) (Example 1: Production of primer (1))

藉由將調製例1所得之水性樹脂組成物(1)100質量份、碳二亞胺交聯劑(日清紡化工股份有限公司製造之「CARBODILITE E-02」)2.8質量份及離子交換水593質量份混合，得到底漆(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 cross-linking agent ("CARBODILITE E-02" manufactured by Nisshinbo Chemical Co., Ltd.), and 593 parts by mass of ion-exchanged water Parts were mixed to obtain a primer (P-1).

(實施例2：底漆(2)之製作) (Example 2: Production of primer (2))

藉由將調製例1所得之水性樹脂組成物(1)100質量份、碳二亞胺交聯劑(日清紡化工股份有限公司製造之「CARBODILITE V-02」)2.8質量份及離子交換水589質量份混合，得到底漆(P-2)。 100 parts by mass of the aqueous resin composition (1) obtained in Preparation Example 1, 2.8 parts by mass of carbodiimide cross-linking agent ("CARBODILITE V-02" manufactured by Nisshinbo Chemical Co., Ltd.), and 589 parts by mass of ion-exchanged water Parts were mixed to obtain a primer (P-2).

(實施例3：底漆(3)之製作) (Example 3: Preparation of primer (3))

藉由將調製例1所得之水性樹脂組成物(1)100質量 份、碳二亞胺交聯劑(日清紡化工股份有限公司製造之「CARBODILITE SV-02」)2.8質量份及離子交換水593質量份混合，得到底漆(P-3)。 100 masses of the aqueous resin composition (1) obtained by preparing Example 1 2.8 parts by mass of carbodiimide cross-linking agent ("CARBODILITE SV-02" manufactured by Nisshinbo Chemical Co., Ltd.) and 593 parts by mass of ion-exchanged water were mixed to obtain a primer (P-3).

(實施例4：積層體(1)之製作) (Example 4: Production of laminated body (1))

在聚對酞酸乙二酯(以下簡稱為「PET」)製膜基材(厚度125μm)之表面，以乾燥後之膜厚成為約1μm之方式塗布實施例1所得的底漆(P-1)，在150℃中加熱5分鐘，藉此在上述基材之表面形成底塗層。然後，以15μm之塗布厚度，在上述底塗層表面塗布調製例2所得之紫外線硬化性組成物(UV-1)，在該塗布面上，藉由將高壓水銀燈作為光源，以照射強度0.5J/cm2照射紫外線，得到上述基材之表面具有底塗層，且在該底塗層表面具備紫外線硬化性組成物之硬化塗膜(以下簡稱為「UV塗膜」)的積層體(1)。 On the surface of a polyethylene terephthalate (hereinafter referred to as "PET") film-forming substrate (thickness: 125 μm), the primer (P-1) obtained in Example 1 was applied so that the film thickness after drying became about 1 μm. ), And heated at 150 ° C. for 5 minutes, thereby forming an undercoat layer on the surface of the substrate. Then, the ultraviolet curable composition (UV-1) obtained in Preparation Example 2 was coated on the surface of the undercoat layer with a coating thickness of 15 μm, and a high-pressure mercury lamp was used as the light source on the coated surface to irradiate the light at an intensity of 0.5 J. / cm 2 is irradiated with ultraviolet rays to obtain a laminated body (1) having a primer layer on the surface of the substrate and a cured coating film (hereinafter referred to as "UV coating film") on the surface of the primer layer with an ultraviolet curable composition. .

(實施例5：積層體(2)之製作) (Example 5: Production of laminated body (2))

除了使用調製例3所得之紫外線硬化性組成物(UV-2)以取代實施例4所使用之紫外線硬化性組成物(UV-1)以外，進行與實施例4相同之操作，得到積層體(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, the same operation as in Example 4 was performed to obtain a laminated body ( 2).

(實施例6：積層體(3)之製作) (Example 6: Production of laminated body (3))

在PET膜基材之表面，以乾燥後之膜厚成為約1μm之方式塗布實施例2所得的底漆(P-2)，在150℃加熱5分鐘，藉此在上述基材之表面形成底塗層。接著，在上述底塗層之表面以15μm之塗布厚度塗布調製例3所得之紫外線硬化性組成物(UV-2)，在該塗布面上，藉由將高壓水 銀燈作為光源，以照射強度0.5J/cm2照射紫外線，得到上述基材之表面具有底塗層，且在該底塗層表面具備UV塗膜的積層體(3)。 On the surface of the PET film substrate, the primer (P-2) obtained in Example 2 was applied so that the film thickness after drying became about 1 μm, and heated at 150 ° C. for 5 minutes to form a primer on the surface of the substrate. coating. Next, the UV curable composition (UV-2) obtained in Preparation Example 3 was coated on the surface of the undercoat layer with a coating thickness of 15 μm, and a high-pressure mercury lamp was used as a light source on the coated surface to irradiate the light at an intensity of 0.5 J. / cm 2 was irradiated with ultraviolet rays to obtain a layered product (3) having an undercoat layer on the surface of the substrate, and a UV coating film provided on the surface of the undercoat layer.

(實施例7：積層體(4)之製作) (Example 7: Production of laminated body (4))

除了使用實施例3所得之底漆(P-3)以取代實施例6所使用之底漆(P-2)以外，進行與實施例6相同之操作，得到積層體(4)。 Except that the primer (P-3) obtained in Example 3 was used instead of the primer (P-2) used in Example 6, the same operation as in Example 6 was performed to obtain a laminate (4).

使用上述實施例及比較例所得之被覆劑及積層體，進行下述密著性之評定。 The following adhesiveness evaluation was performed using the coating agent and laminated body obtained by the said Example and the comparative example.

[基材與底塗層之密著性(初期)之評定方法] [Evaluation method of adhesion (initial) of substrate and undercoat layer]

藉由在膜厚125μm之包含聚對酞酸乙二酯的基材之表面，以乾燥時之膜厚成為約1μm之方式塗布底漆，並在150℃下加熱5分鐘，藉此製作包含上述基材之表面積層有底塗層之構件的試驗板。 The surface of the base material containing polyethylene terephthalate having a film thickness of 125 μm was coated with a primer so that the film thickness at the time of drying became about 1 μm, and heated at 150 ° C. for 5 minutes, thereby producing a film including the above. A test panel for a component having a base layer on the surface area of the substrate.

在以上述方法製作之試驗板的底塗層表面黏貼有NICHIBAN股份有限公司製造之24mm寬度的黏著膠帶。 A 24 mm-wide adhesive tape manufactured by NICHIBAN Co., Ltd. was affixed to the surface of the undercoat layer of the test plate produced by the above method.

接著，將上述黏著膠帶朝相對於上述底塗層而言為垂直方向拉伸，依據下述評定基準以肉眼評定將上述黏著膠帶從底塗層之表面剝離時，上述底塗層之表面狀態。 Next, the adhesive tape was stretched in a direction perpendicular to the undercoat layer, and the surface state of the undercoat layer when the adhesive tape was peeled from the surface of the undercoat layer was visually evaluated based on the following evaluation criteria.

◎：底塗層完全不會從構成試驗板之基材表面剝離。 ：: The undercoat layer does not peel off from the surface of the base material constituting the test plate at all.

○：雖有極小部分的底塗層從構成試驗板之基材表面剝離，惟相對於構成試驗板之皮膜總面積，該剝離之範圍小於10%。 ○: Although a very small part of the undercoat layer is peeled off from the surface of the base material constituting the test plate, the range of the peeling is less than 10% with respect to the total area of the film constituting the test plate.

△：相對於構成試驗板之底塗層面積而言為10%以上且小於50%之範圍的底塗層，從構成試驗板之基材表面剝離。 Δ: The undercoat layer in the range of 10% or more and less than 50% with respect to the area of the undercoat layer constituting the test plate is peeled from the surface of the base material constituting the test plate.

×：相對於構成試驗板之底塗層總面積而言為50%以上之範圍的底塗層，從構成試驗板之基材表面剝離。 ×: The undercoat layer in a range of 50% or more relative to the total area of the undercoat layer constituting the test plate was peeled off from the surface of the base material constituting the test plate.

[底塗層與UV塗膜之密著性(初期)的評定方 法] [Evaluation method of adhesion (primary) of primer and UV coating law]

在構成實施例及比較例所得之積層體的UV塗膜之表面，黏貼NICHIBAN股份有限公司製造之24mm寬度的黏著膠帶。 On the surface of the UV coating film constituting the laminates obtained in the examples and comparative examples, a 24 mm wide adhesive tape manufactured by NICHIBAN Co., Ltd. was stuck.

接著，將上述黏著膠帶朝相對於上述UV塗膜 而言為垂直方向拉伸，依據下述評定基準以肉眼評定將上述黏著膠帶從UV塗膜之表面剝離時，上述UV塗膜之表面狀態。 Next, the adhesive tape is directed to the UV coating film. In the case of vertical stretching, the state of the surface of the UV coating film when the adhesive tape is peeled from the surface of the UV coating film is visually evaluated based on the following evaluation criteria.

◎：UV塗膜完全不會從構成積層體之基材表面剝離。 ：: The UV coating film does not peel off from the surface of the base material constituting the laminated body at all.

○：雖有極小部分的UV塗膜從構成積層體之基材表面剝離，惟相對於構成積層體之UV塗膜的總面積，該剝離之範圍小於10%。 ○: Although a very small part of the UV coating film is peeled off from the surface of the substrate constituting the laminate, the peeling range is less than 10% with respect to the total area of the UV coating film constituting the laminate.

△：相對於構成積層體之UV塗膜面積而言為10%以上且小於50%之範圍的UV塗膜，從構成積層體之基材表面剝離。 Δ: The UV coating film having a range of 10% or more and less than 50% with respect to the area of the UV coating film constituting the laminated body is peeled from the surface of the base material constituting the laminated body.

×：相對於構成積層體之UV塗膜總面積而言為50%以上之範圍的UV塗膜，從構成積層體之基材表面剝離。 ×: The UV coating film having a range of 50% or more relative to the total area of the UV coating film constituting the laminated body is peeled off from the surface of the base material constituting the laminated body.

[底塗層與UV塗膜之密著性(耐濕熱試驗後)] [Adhesion between undercoat and UV coating film (after moist heat resistance test)]

將上述所得之積層體投入溫度60℃、相對溼度90%之高溫恆濕器50小時。然後，取出上述積層體，以與上述[底塗層與UV塗膜之密著性(初期)]相同之方法評定底塗層與UV塗膜之密著性。 The obtained laminated body was put into a high-temperature humidistat at a temperature of 60 ° C. and a relative humidity of 90% for 50 hours. Then, the laminated body was taken out, and the adhesion between the undercoat layer and the UV coating film was evaluated in the same manner as the above [Adhesion between the undercoat layer and the UV coating film (initial stage)].

[底塗層與UV塗膜之密著性(耐藥性試驗後)] [Adhesion between primer and UV coating (after chemical resistance test)]

將上述所得之積層體投入溫度25℃、5%氫氧化鈉水溶液30分鐘。然後，取出上述積層體，經水洗、乾燥後，以與上述[底塗層與UV塗膜之密著性(初期)之評定方法]相同之方法評定底塗層與UV塗膜之密著性。 The obtained laminated body was put into a temperature of 25 ° C. and a 5% aqueous sodium hydroxide solution for 30 minutes. Then, the laminated body was taken out, washed with water, and dried, and then the adhesion between the undercoat layer and the UV coating film was evaluated in the same manner as in the above [Method for evaluating the adhesion (primary) of the undercoat layer and UV coating film]. .

[成膜性之評定方法] [Evaluation method of film-forming property]

藉由在膜厚125μm之包含聚對酞酸乙二酯的基材之表面，以乾燥時之膜厚成為約1μm之方式塗布上述底漆，並在150℃下加熱5分鐘，藉此於上述基材之表面形成底塗層。 The above-mentioned primer was applied on the surface of a substrate containing polyethylene terephthalate having a film thickness of 125 μm so that the film thickness during drying became approximately 1 μm, and heated at 150 ° C. for 5 minutes to thereby apply The surface of the substrate forms an undercoat layer.

○：以肉眼觀察底塗層之表面時，為透明。 ○: When the surface of the undercoat layer is observed with the naked eye, it is transparent.

△：以肉眼觀察底塗層之表面時，雖為透明但可確認有裂痕。 △: When the surface of the undercoat layer was observed with the naked eye, cracks were confirmed although the surface was transparent.

×：以肉眼觀察底塗層之表面時，發現白化程度的裂痕，部分底塗層容易從聚對酞酸乙二酯基材剝離。 ×: When the surface of the undercoat layer was observed with the naked eye, cracks in the degree of whitening were found, and part of the undercoat layer was easily peeled from the polyethylene terephthalate substrate.

將實施例4至7所得之積層體(1)至(4)中使用的基材、底漆及紫外線硬化性組成物，與評定結果呈示於表3。 Table 3 shows the substrates, primers, and UV-curable compositions used in the laminates (1) to (4) obtained in Examples 4 to 7, and the evaluation results.

(比較例1：底漆(P'-1)之製作) (Comparative Example 1: Production of primer (P'-1))

藉由將水性樹脂組成物(1)100質量份與離子交換水577質量份混合，得到底漆(P'-1)。 A primer (P′-1) was obtained by mixing 100 parts by mass of the aqueous resin composition (1) and 577 parts by mass of ion-exchanged water.

(比較例2：底漆(P'-2)之製作) (Comparative Example 2: Production of primer (P'-2))

藉由將水性樹脂組成物(1)100質量份與三聚氰胺交聯劑(DIC股份有限公司製造之「BECKAMINE M-3」)3質量份與離子交換水613質量份混合，得到底漆(P'-2)。 100 parts by mass of the aqueous resin composition (1) and 3 parts by mass of a melamine cross-linking agent ("BECKAMINE M-3" manufactured by DIC Corporation) were mixed with 613 parts by mass of ion-exchanged water to obtain a primer (P ' -2).

(比較例3：底漆(P'-3)之製作) (Comparative Example 3: Production of primer (P'-3))

藉由將水性樹脂組成物(1)100質量份與唑啉交聯劑(日本觸媒股份有限公司製造之「EPOCROS WS-700」)9.2質量份與離子交換水606質量份混合，得到底漆(P'-3)。 By mixing 100 parts by mass of the aqueous resin composition (1) with 9.2 parts by mass of an oxazoline cross-linking agent ("EPOCROS WS-700" manufactured by Japan Catalyst Co., Ltd.) was mixed with 606 parts by mass of ion-exchanged water to obtain a primer (P'-3).

(比較例4：底漆(P'-4)之製作) (Comparative Example 4: Production of primer (P'-4))

藉由將水性樹脂組成物(1)100質量份與環氧系交聯劑(DIC股份有限公司製造之「CR-5L」)3質量份與離子交換水648質量份混合，得到底漆(P'-4)。 100 parts by mass of the aqueous resin composition (1) and 3 parts by mass of an epoxy-based crosslinking agent ("CR-5L" manufactured by DIC Corporation) were mixed with 648 parts by mass of ion-exchanged water to obtain a primer (P '-4).

(比較例5：積層體(R1)之製作) (Comparative Example 5: Production of laminated body (R1))

在PET膜基材之表面，以乾燥後之膜厚成為約1μm之方式塗布比較例2所得之底漆(P'-1)，並在150℃下加熱5分鐘，藉此在上述基材之表面形成底塗層。然後，以15μm之塗布厚度，在上述底塗層之表面塗布調製例3所得之紫外線硬化性組成物(UV-2)，在該塗布面上，藉由將高壓水銀燈作為光源，以照射強度0.5J/cm2照射紫外線，得到上述基材之表面具有底塗層，且在該底塗層表面具備UV塗膜之積層體(R1)。 The surface of the PET film substrate was coated with the primer (P'-1) obtained in Comparative Example 2 so that the film thickness after drying became about 1 μm, and heated at 150 ° C. for 5 minutes to thereby apply the primer on the substrate. An undercoat is formed on the surface. Then, the ultraviolet curable composition (UV-2) obtained in Preparation Example 3 was coated on the surface of the above-mentioned undercoat layer with a coating thickness of 15 μm, and a high-pressure mercury lamp was used as the light source on the coated surface to irradiate the intensity of 0.5. J / cm 2 was irradiated with ultraviolet rays to obtain a laminated body (R1) having a primer layer on the surface of the substrate and a UV coating film on the surface of the primer layer.

(比較例6至8：積層體(R2)至(R4)之製作) (Comparative Examples 6 to 8: Production of laminated bodies (R2) to (R4))

除了分別使用比較例2至4所得之底漆(P'-2)至(P'-4)以取代比較例5所得之底漆(P'-1)之外，進行與比較例5相同之操作，得到積層體(R2)至(R4)。 The same procedure as in Comparative Example 5 was performed except that the primers (P'-2) to (P'-4) obtained in Comparative Examples 2 to 4 were used instead of the primer (P'-1) obtained in Comparative Example 5, respectively. This operation yielded laminated bodies (R2) to (R4).

將比較例5至8所得之積層體(R1)及(R2)中使用的基材、底漆及紫外線硬化性組成物，與評定結果呈示於表4。 Table 4 shows the substrates, primers, and UV-curable compositions used in the laminates (R1) and (R2) obtained in Comparative Examples 5 to 8 and the evaluation results.

由表3所示之評定結果，可確認使用本發明之 被覆劑所形成之底塗層係與基材之密著性優異，與活性能量線硬化性組成物之硬化塗膜之密著性亦優異。 From the evaluation results shown in Table 3, it can be confirmed that The undercoat layer formed by the coating agent has excellent adhesion to the substrate, and also has excellent adhesion to the cured coating film of the active energy ray-curable composition.

可確認使用本發明之被覆劑所形成之底塗層， 在耐濕熱試驗後具有高密著性及優異的耐藥性。 It can be confirmed that the undercoat layer formed by using the coating agent of the present invention, After the moist heat resistance test, it has high adhesion and excellent chemical resistance.

另一方面，比較例5係使用不含交聯劑之被覆 劑之例者。相較於使用本發明之被覆劑所形成之底塗層，可確認耐濕熱試驗後之密著性不足，並且，耐藥性亦為不足。 On the other hand, Comparative Example 5 uses a coating without a crosslinking agent. Examples of agents. Compared with the undercoat layer formed using the coating agent of the present invention, it was confirmed that the adhesion after the moist heat resistance test was insufficient, and the chemical resistance was also insufficient.

比較例6係使用三聚氰胺交聯劑之例者。相較 於使用本發明之含碳二亞胺交聯劑之被覆劑所形成之底塗層，可確認耐藥性不足。 Comparative Example 6 is an example using a melamine crosslinking agent. Compare The primer layer formed using the coating agent containing the carbodiimide cross-linking agent of the present invention was found to have insufficient resistance.

比較例7係使用唑啉交聯劑之例者。相較於 使用本發明之含碳二亞胺交聯劑之被覆劑所形成之底塗層，可確認耐濕熱試驗後之密著性不足，並且，耐藥性亦為不足。 Comparative Example 7 Examples of oxazoline cross-linking agents. Compared with the undercoat layer formed by using the coating agent containing the carbodiimide crosslinking agent of the present invention, it was confirmed that the adhesion after the moist heat resistance test was insufficient, and the chemical resistance was also insufficient.

比較例8係使用環氧交聯劑之例者。相較於使 用本發明之含碳二亞胺交聯劑之被覆劑所形成之底塗層，可確認耐藥性不足。 Comparative Example 8 is an example using an epoxy crosslinking agent. Compared to using The undercoating layer formed by the coating agent of the carbodiimide-containing crosslinking agent of the present invention can confirm insufficient resistance.

Claims (9)

一種被覆劑，其係含有乙烯酯樹脂(A)、具有芳香環之胺基甲酸酯樹脂(B)於水性介質(C)中分散而得之水性樹脂組成物(D)，以及碳二亞胺系交聯劑(E)之被覆劑，其特徵為：該乙烯酯樹脂(A)係使選自酚醛清漆型環氧樹脂及雙酚型環氧樹脂所成群組中之1種以上的環氧樹脂(a1)、與具有酸基及聚合性不飽和基之化合物(a2)反應而得者，該胺基甲酸酯樹脂(B)係使含有具芳香環之多元醇(b1-1)及具親水性基之(b1-2)的多元醇(b1)、與聚異氰酸酯(b2)反應而得者，該交聯劑(E)之使用量係和可與碳二亞胺基反應之該胺基甲酸酯樹脂(B)所具有之親水性基的80至100莫耳%反應之量，該乙烯酯樹脂(A)與該胺基甲酸酯樹脂(B)之質量比例[(A)/(B)]係在60/40至10/90之範圍。A coating agent comprising an aqueous resin composition (D) obtained by dispersing a vinyl ester resin (A), an urethane resin (B) having an aromatic ring in an aqueous medium (C), and carbodicarbonate A coating agent for an amine-based crosslinking agent (E), wherein the vinyl ester resin (A) is one or more selected from the group consisting of a novolac epoxy resin and a bisphenol epoxy resin. The urethane resin (B) is obtained by reacting an epoxy resin (a1) with a compound (a2) having an acid group and a polymerizable unsaturated group. The urethane resin (B) contains an aromatic ring-containing polyol (b1-1). ), And a polyol (b1) having a hydrophilic group (b1-2), which is obtained by reacting with a polyisocyanate (b2), the amount of the cross-linking agent (E) used and the reaction with the carbodiimide group The urethane resin (B) has an amount of 80 to 100 mol% of the hydrophilic group reacted, the mass ratio of the vinyl ester resin (A) to the urethane resin (B) [ (A) / (B)] is in the range of 60/40 to 10/90. 如請求項1之被覆劑，其中該多元醇(b1-1)中之芳香環濃度係在1.5至8mol/kg之範圍。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. 如請求項1之被覆劑，其中該具有芳香環之多元醇(b1-1)係包含芳香族聚酯多元醇(b1-a)及雙酚A之環氧烷加成物(b1-b)中之至少1個的多元醇。The coating agent according to claim 1, wherein the polyol (b1-1) having an aromatic ring is an alkylene oxide adduct (b1-b) containing an aromatic polyester polyol (b1-a) and bisphenol A At least one of the polyols. 如請求項1之被覆劑，其中該多元醇(b1)中所含之具有芳香環的多元醇(b1-1)之比例係在40至98質量%之範圍。The coating agent according to claim 1, wherein the proportion of the polyol (b1-1) having an aromatic ring contained in the polyol (b1) is in the range of 40 to 98% by mass. 如請求項1之被覆劑，其中該聚異氰酸酯(b2)係包含芳香族聚異氰酸酯者。The coating agent according to claim 1, wherein the polyisocyanate (b2) is an aromatic polyisocyanate. 如請求項1之被覆劑，其中該化合物(a2)係丙烯酸或甲基丙烯酸。The coating agent according to claim 1, wherein the compound (a2) is acrylic acid or methacrylic acid. 如請求項1之被覆劑，其中該乙烯酯樹脂(A)之部分或全部係留存在該胺基甲酸酯樹脂(B)粒子中而形成樹脂粒子(F)者。The coating agent according to claim 1, wherein a part or all of the vinyl ester resin (A) is retained in the urethane resin (B) particles to form resin particles (F). 一種積層體，其特徵為：在基材之表面具有藉由塗布如請求項1至7項中任一項之被覆劑並加以乾燥所形成之底塗層，並且在該底塗層表面具有使用活性能量線硬化性組成物所形成之硬化塗膜。A laminated body characterized in that an undercoat layer formed by coating and drying a coating agent according to any one of claims 1 to 7 is provided on a surface of a base material, and the surface of the base layer has a use A hardened coating film formed from an active energy ray-curable composition. 如請求項8之積層體，其中該活性能量線硬化性組成物係含有具有聚合性不飽和基之樹脂、與具有聚合性不飽和基之單體者。The laminated body according to claim 8, wherein the active energy ray-curable composition contains a resin having a polymerizable unsaturated group and a monomer having a polymerizable unsaturated group.
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KR20160099584A (en) 2016-08-22
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