KR102405075B1 - Active energy ray-curable composition, cured product, and film - Google Patents

Active energy ray-curable composition, cured product, and film Download PDF

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KR102405075B1
KR102405075B1 KR1020197024169A KR20197024169A KR102405075B1 KR 102405075 B1 KR102405075 B1 KR 102405075B1 KR 1020197024169 A KR1020197024169 A KR 1020197024169A KR 20197024169 A KR20197024169 A KR 20197024169A KR 102405075 B1 KR102405075 B1 KR 102405075B1
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시게토시 니시자와
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디아이씨 가부시끼가이샤
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    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Abstract

본 발명은, 활성 에너지선 경화성 화합물(A)과, 지환 구조 및 4급 암모늄염을 갖는 수지(B)와, 디메틸아세트아미드를 포함하는 유기 용제(C)를 함유하는 것을 특징으로 하는 활성 에너지선 경화성 조성물을 제공하는 것이다. 또한, 본 발명의 상기 활성 에너지선 경화성 조성물의 경화물, 및, 경화 도막을 갖는 필름을 제공하는 것이다. 상기 디메틸아세트아미드의 함유량은, 상기 활성 에너지선 경화성 화합물(A) 100질량부에 대해서, 5∼200질량부의 범위가 바람직하다. 본 발명이 해결하려고 하는 과제는, 백탁, 겔화, 침전을 발생하기 어렵기 때문에, 공기 중의 수분이나 결로에 대한 도공액의 양호한 내수성으로부터 연속생산성이 우수하며, 또한, 우수한 대전방지성을 갖는 하드코트층을 형성할 수 있는 활성 에너지선 경화성 조성물을 제공하는 것이다.The present invention contains an active energy ray-curable compound (A), a resin (B) having an alicyclic structure and a quaternary ammonium salt, and an organic solvent (C) containing dimethylacetamide. to provide a composition. Moreover, it is providing the hardened|cured material of the said active energy ray-curable composition of this invention, and the film which has a cured coating film. As for content of the said dimethylacetamide, the range of 5-200 mass parts is preferable with respect to 100 mass parts of said active energy ray-curable compounds (A). The problem to be solved by the present invention is that it is difficult to cause cloudiness, gelation, and precipitation, so it is excellent in continuous productivity from good water resistance of the coating solution to moisture and dew in the air, and a hard coat having excellent antistatic properties To provide an active energy ray-curable composition capable of forming a layer.

Description

활성 에너지선 경화성 조성물, 경화물, 및, 필름Active energy ray-curable composition, cured product, and film

본 발명은, 활성 에너지선 경화성 조성물, 그 경화물, 및 필름에 관한 것이다.The present invention relates to an active energy ray-curable composition, a cured product thereof, and a film.

액정 디스플레이(LCD), 유기 EL 디스플레이(OLED), 플라스마 디스플레이(PDP) 등의 플랫패널 디스플레이(FPD) 표면에 사용되고 있는 반사 방지(LR) 필름은, 필름 기재 상에 굴절률차가 큰 두 층을 형성한 다층 구성(기재/고굴률층/저굴률층)에 의해 실현하고 있다. 이들 각층은, 반사 방지 필름의 제조 과정에서의 흠집 발생 방지를 위하여, 높은 내찰상성(耐擦傷性)이 요구됨과 함께, 필름의 오염 방지나 블로킹 방지를 위하여, 높은 대전방지성도 요구된다. 또한, 반사 방지 필름은 광학 필름이기 때문에, 각층에는 높은 투명성도 요구된다.An anti-reflection (LR) film used on the surface of a flat panel display (FPD) such as a liquid crystal display (LCD), an organic EL display (OLED), and a plasma display (PDP) is formed by forming two layers with a large refractive index difference on the film substrate. It is realized by a multilayer structure (base material / high refractive index layer / low refractive index layer). Each of these layers is required to have high abrasion resistance in order to prevent scratches in the manufacturing process of the antireflection film, and high antistatic properties are also required to prevent contamination and blocking of the film. Moreover, since the antireflection film is an optical film, high transparency is also calculated|required by each layer.

상기한 요구되는 특성 중, 대전방지성을 부여하는 방법으로서, 4급 암모늄염을 갖는 수지를 배합한 재료를 사용하는 것이 제안되어 있다(예를 들면, 특허문헌 1∼3을 참조). 그러나, 4급 암모늄염은, 친수성이 높고, 소수성인 활성 에너지선 경화성 조성물과는 상용성이 나쁘고, 도막이 백화하여 외관 불량으로 되는 문제가 있었다.As a method of imparting antistatic properties among the required properties, it is proposed to use a material containing a resin having a quaternary ammonium salt (for example, refer to Patent Documents 1 to 3). However, the quaternary ammonium salt had high hydrophilicity, poor compatibility with the hydrophobic active energy ray-curable composition, and had a problem of whitening of a coating film, and becoming an appearance defect.

일본 특개2012-102166호 공보Japanese Patent Laid-Open No. 2012-102166 일본 특개2008-013636호 공보Japanese Patent Laid-Open No. 2008-013636 일본 특개2008-255184호 공보Japanese Patent Laid-Open No. 2008-255184

본 발명이 해결하려고 하는 과제는, 우수한 대전방지성을 가지며, 또한, 물이 혼입해도 백탁하지 않아 외관 불량을 일으키지 않는 우수한 내수성을 갖는 하드코트층을 형성할 수 있는 활성 에너지선 경화성 조성물을 제공하는 것이다.The problem to be solved by the present invention is to provide an active energy ray-curable composition capable of forming a hard coat layer having excellent antistatic properties, and excellent water resistance that does not cause a poor appearance even when mixed with water is not cloudy will be.

본 발명은, 활성 에너지선 경화성 화합물(A)과, 지환 구조 및 4급 암모늄염을 갖는 수지(B)와, 디메틸아세트아미드를 함유하는 유기 용제(C)를 함유하는 것을 특징으로 하는 활성 에너지선 경화성 조성물을 제공하는 것이다. 또한, 본 발명은 상기 활성 에너지선 경화성 조성물의 경화물, 및, 경화 도막을 갖는 필름을 제공하는 것이다.The present invention contains an active energy ray-curable compound (A), a resin (B) having an alicyclic structure and a quaternary ammonium salt, and an organic solvent (C) containing dimethylacetamide. to provide a composition. Moreover, this invention provides the hardened|cured material of the said active energy ray-curable composition, and the film which has a cured coating film.

본 발명의 활성 에너지선 경화성 조성물은, 도공 시에 물이 혼입해도 백탁하기 어려운 내수성을 갖는 조성을 제공함으로써 연속생산성이 우수하며, 또한, 경화 후, 필름 표면에 우수한 대전방지성을 갖는 하드코트층을 형성할 수 있다.The active energy ray-curable composition of the present invention is excellent in continuous productivity by providing a composition having water resistance that is difficult to become cloudy even when water is mixed during coating, and furthermore, after curing, a hard coat layer having excellent antistatic properties on the film surface can be formed

또한, 본 발명의 활성 에너지선 경화성 조성물의 경화 도막으로 이루어지는 하드코트층을 갖는 필름은, 액정 디스플레이(LCD), 유기 EL 디스플레이(OLED), 플라스마 디스플레이(PDP) 등의 플랫패널 디스플레이(FPD)에 사용하는 광학 필름으로서 호적하게 사용할 수 있다. 또한, 이들 용도에 사용할 때에도 우수한 대전방지성이 있으므로, 먼지 등의 부착을 억제할 수 있다. 또한, 이 필름을 액정 디스플레이 등에 사용했을 경우, 발생한 정전기에 의한 디스플레이의 오동작도 방지할 수 있다.Moreover, the film which has a hard-coat layer which consists of a cured coating film of the active energy ray-curable composition of this invention is flat panel displays (FPD), such as a liquid crystal display (LCD), an organic electroluminescent display (OLED), and a plasma display (PDP). It can be used suitably as an optical film to be used. Moreover, since there is an excellent antistatic property even when used for these uses, adhesion of dust etc. can be suppressed. In addition, when this film is used for a liquid crystal display or the like, malfunction of the display due to generated static electricity can be prevented.

본 발명의 활성 에너지선 경화성 조성물은, 활성 에너지선 경화성 화합물(A)과, 지환 구조 및 4급 암모늄염을 갖는 수지(B)와, 디메틸아세트아미드를 함유하는 유기 용제(C)를 함유하는 것이다.The active energy ray-curable composition of this invention contains an active energy ray-curable compound (A), resin (B) which has an alicyclic structure and a quaternary ammonium salt, and the organic solvent (C) containing dimethylacetamide.

상기 활성 에너지선 경화성 화합물(A)로서는, 예를 들면, 다관능 (메타)아크릴레이트(A1), 우레탄(메타)아크릴레이트(A2), 굴절률이 1.55 이상인 고굴절률 중합성 단량체(A3), 에폭시(메타)아크릴레이트, 폴리에스테르(메타)아크릴레이트, 폴리에테르(메타)아크릴레이트 등을 들 수 있다. 이들은, 단독으로 사용해도 되고 2종 이상을 병용해도 된다. 상기 활성 에너지선 경화성 화합물(A)로서는, 한층 더 우수한 경화 도막의 내찰상성, 하드코트성, 내수성, 및 투명성이 얻어지는 점으로부터, 다관능 (메타)아크릴레이트(A1), 우레탄(메타)아크릴레이트(A2), 및, 굴절률이 1.55 이상인 고굴절률 중합성 단량체(A3)로 이루어지는 군에서 선택되는 1종 이상을 사용하는 것이 바람직하고, 다관능 (메타)아크릴레이트(A1)와 우레탄(메타)아크릴레이트(A2)와의 조합, 또는, 다관능 (메타)아크릴레이트(A1)와 고굴절률 중합성 단량체(A3)와의 조합이 보다 바람직하다.Examples of the active energy ray-curable compound (A) include polyfunctional (meth)acrylate (A1), urethane (meth)acrylate (A2), a high refractive index polymerizable monomer (A3) having a refractive index of 1.55 or more, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, etc. are mentioned. These may be used independently and may use 2 or more types together. As said active energy ray-curable compound (A), from the point from which the abrasion resistance of the further excellent cured coating film, hard-coat property, water resistance, and transparency are obtained, polyfunctional (meth)acrylate (A1), urethane (meth)acrylate It is preferable to use at least one selected from the group consisting of (A2) and a high refractive index polymerizable monomer (A3) having a refractive index of 1.55 or more, and polyfunctional (meth)acrylate (A1) and urethane (meth)acryl The combination with the rate (A2) or the combination of the polyfunctional (meth)acrylate (A1) and the high refractive index polymerizable monomer (A3) is more preferable.

또, 본 발명에 있어서, 「(메타)아크릴레이트」란, 아크릴레이트와 메타크릴레이트의 한쪽 또는 양쪽을 말하며, 「(메타)아크릴로일」이란, 아크릴로일과 메타크릴로일의 한쪽 또는 양쪽을 말한다.In addition, in this invention, "(meth)acrylate" means one or both of acrylate and methacrylate, and "(meth)acryloyl" means one or both of acryloyl and methacryloyl. say

상기 다관능 (메타)아크릴레이트(A1)는, 1분자 중에 둘 이상의 (메타)아크릴로일기를 갖는 화합물이다. 이 다관능 (메타)아크릴레이트(a1)의 구체예로서는, 1,4-부탄디올디(메타)아크릴레이트, 3-메틸-1,5-펜탄디올디(메타)아크릴레이트, 1,6-헥산디올디(메타)아크릴레이트, 네오펜틸글리콜디(메타)아크릴레이트, 2-메틸-1,8-옥탄디올디(메타)아크릴레이트, 2-부틸-2-에틸-1,3-프로판디올디(메타)아크릴레이트, 트리시클로데칸디메탄올디(메타)아크릴레이트, 에틸렌글리콜디(메타)아크릴레이트, 디에틸렌글리콜디(메타)아크릴레이트, 트리에틸렌글리콜디(메타)아크릴레이트, 디프로필렌글리콜디(메타)아크릴레이트, 트리프로필렌글리콜디(메타)아크릴레이트 등의 2가 알코올의 디(메타)아크릴레이트, 폴리에틸렌글리콜디(메타)아크릴레이트, 폴리프로필렌글리콜디(메타)아크릴레이트, 트리스(2-히드록시에틸)이소시아누레이트의 디(메타)아크릴레이트, 네오펜틸글리콜 1몰에 4몰 이상의 에틸렌옥사이드 혹은 프로필렌옥사이드를 부가해서 얻은 디올의 디(메타)아크릴레이트, 비스페놀A 1몰에 2몰의 에틸렌옥사이드 혹은 프로필렌옥사이드를 부가해서 얻은 디올의 디(메타)아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, 에틸렌옥사이드 변성 트리메틸올프로판트리(메타)아크릴레이트, 프로필렌옥사이드 변성 트리메틸올프로판트리(메타)아크릴레이트, 디트리메틸올프로판트리(메타)아크릴레이트, 디트리메틸올프로판테트라(메타)아크릴레이트, 트리스(2-(메타)아크릴로일옥시에틸)이소시아누레이트, 펜타에리트리톨트리(메타)아크릴레이트, 펜타에리트리톨테트라(메타)아크릴레이트, 디펜타에리트리톨트리(메타)아크릴레이트, 디펜타에리트리톨테트라(메타)아크릴레이트, 디펜타에리트리톨펜타(메타)아크릴레이트, 디펜타에리트리톨헥사(메타)아크릴레이트 등을 들 수 있다. 이들 다관능 (메타)아크릴레이트(A1)는, 1종으로 사용할 수도 있고 2종 이상 병용할 수도 있다. 또한, 이들 다관능 (메타)아크릴레이트(A1) 중에서도, 본 발명의 활성 에너지선 경화성 조성물의 경화 도막의 내찰상성이 향상하므로, 디펜타에리트리톨헥사(메타)아크릴레이트, 디펜타에리트리톨펜타(메타)아크릴레이트, 펜타에리트리톨테트라(메타)아크릴레이트, 및, 펜타에리트리톨트리(메타)아크릴레이트로 이루어지는 군에서 선택되는 1종 이상의 화합물을 사용하는 것이 바람직하고, 디펜타에리트리톨헥사(메타)아크릴레이트가 보다 바람직하다.The said polyfunctional (meth)acrylate (A1) is a compound which has two or more (meth)acryloyl groups in 1 molecule. Specific examples of the polyfunctional (meth)acrylate (a1) include 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, and 1,6-hexanediol. Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di ( Meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth)acrylate, di(meth)acrylate of dihydric alcohols such as tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tris(2) -Di(meth)acrylate of hydroxyethyl)isocyanurate, di(meth)acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol, 2 to 1 mol of bisphenol A Di(meth)acrylate of diol obtained by adding moles of ethylene oxide or propylene oxide, trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri (meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, pentaerythritol tri (meth)acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa(meth)acrylate etc. are mentioned. These polyfunctional (meth)acrylates (A1) may be used by 1 type, and may be used together 2 or more types. Moreover, among these polyfunctional (meth)acrylates (A1), since the abrasion resistance of the cured coating film of the active energy ray-curable composition of this invention improves, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta ( It is preferable to use at least one compound selected from the group consisting of meth) acrylate, pentaerythritol tetra (meth) acrylate, and pentaerythritol tri (meth) acrylate, and dipentaerythritol hexa (meth) ) acrylate is more preferable.

상기 우레탄(메타)아크릴레이트(A2)는, 폴리이소시아네이트(a2-1)와 수산기를 갖는 (메타)아크릴레이트(a2-2)와의 반응물 등을 사용할 수 있다.As said urethane (meth)acrylate (A2), the reaction product of polyisocyanate (a2-1) and (meth)acrylate (a2-2) which has a hydroxyl group, etc. can be used.

상기 폴리이소시아네이트(a2-1)로서는, 지방족 폴리이소시아네이트와 방향족 폴리이소시아네이트를 들 수 있지만, 본 발명의 활성 에너지선 경화성 조성물의 경화 도막의 착색을 저감할 수 있으므로, 지방족 폴리이소시아네이트가 바람직하다.Although aliphatic polyisocyanate and aromatic polyisocyanate are mentioned as said polyisocyanate (a2-1), Since coloring of the cured coating film of the active energy ray-curable composition of this invention can be reduced, aliphatic polyisocyanate is preferable.

상기 지방족 폴리이소시아네이트는, 이소시아네이트기를 제외한 부위가 지방족 탄화수소로 구성되는 화합물이다. 이 지방족 폴리이소시아네이트의 구체예로서는, 헥사메틸렌디이소시아네이트, 리신디이소시아네이트, 리신트리이소시아네이트 등의 지방족 폴리이소시아네이트; 노르보르난디이소시아네이트, 이소포론디이소시아네이트, 메틸렌비스(4-시클로헥실이소시아네이트), 1,3-비스(이소시아나토메틸)시클로헥산, 2-메틸-1,3-디이소시아나토시클로헥산, 2-메틸-1,5-디이소시아나토시클로헥산 등의 지환식 폴리이소시아네이트 등을 들 수 있다. 또한, 상기 지방족 폴리이소시아네이트 또는 지환식 폴리이소시아네이트를 3량화한 3량화물도 상기 지방족 폴리이소시아네이트로서 사용할 수 있다. 또한, 이들 지방족 폴리이소시아네이트는, 1종으로 사용할 수도 있고 2종 이상 병용할 수도 있다.The said aliphatic polyisocyanate is a compound in which the site|part except an isocyanate group is comprised from an aliphatic hydrocarbon. As a specific example of this aliphatic polyisocyanate, Aliphatic polyisocyanate, such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; Norbornane diisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2- Alicyclic polyisocyanate, such as methyl-1, 5- diisocyanatocyclohexane, etc. are mentioned. Moreover, the trimerized product obtained by trimerizing the said aliphatic polyisocyanate or alicyclic polyisocyanate can also be used as said aliphatic polyisocyanate. In addition, these aliphatic polyisocyanates may be used individually by 1 type, and may be used together 2 or more types.

상기 지방족 폴리이소시아네이트 중에서도 도막의 내찰상성을 향상시키기 위해서는, 헥사메틸렌디이소시아네이트, 노르보르난디이소시아네이트, 및 이소포론디이소시아네이트로 이루어지는 군에서 선택되는 1종 이상을 사용하는 것이 바람직하고, 이소포론디이소시아네이트가 보다 바람직하다.Among the aliphatic polyisocyanates, in order to improve the scratch resistance of the coating film, it is preferable to use at least one selected from the group consisting of hexamethylene diisocyanate, norbornane diisocyanate, and isophorone diisocyanate, and isophorone diisocyanate is more preferably.

상기 (메타)아크릴레이트(a2-2)는, 수산기와 (메타)아크릴로일기를 갖는 화합물이다. 이 (메타)아크릴레이트(a2-2)의 구체예로서는, 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 2-히드록시부틸(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 1,5-펜탄디올모노(메타)아크릴레이트, 1,6-헥산디올모노(메타)아크릴레이트, 네오펜틸글리콜모노(메타)아크릴레이트, 히드록시피발산네오펜틸글리콜모노(메타)아크릴레이트 등의 2가 알코올의 모노(메타)아크릴레이트; 트리메틸올프로판디(메타)아크릴레이트, 에틸렌옥사이드(EO) 변성 트리메틸올프로판(메타)아크릴레이트, 프로필렌옥사이드(PO) 변성 트리메틸올프로판디(메타)아크릴레이트, 글리세린디(메타)아크릴레이트, 비스(2-(메타)아크릴로일옥시에틸)히드록시에틸이소시아누레이트 등의 3가의 알코올의 모노 또는 디(메타)아크릴레이트, 혹은, 이들 알코올성 수산기의 일부를 ε-카프로락톤으로 변성한 수산기를 갖는 모노 및 디(메타)아크릴레이트; 펜타에리트리톨트리(메타)아크릴레이트, 디트리메틸올프로판트리(메타)아크릴레이트, 디펜타에리트리톨펜타(메타)아크릴레이트 등의 1관능의 수산기와 3관능 이상의 (메타)아크릴로일기를 갖는 화합물, 혹은, 당해 화합물을 추가로 ε-카프로락톤으로 변성한 수산기를 갖는 다관능 (메타)아크릴레이트; 디프로필렌글리콜모노(메타)아크릴레이트, 디에틸렌글리콜모노(메타)아크릴레이트, 폴리프로필렌글리콜모노(메타)아크릴레이트, 폴리에틸렌글리콜모노(메타)아크릴레이트 등의 옥시알킬렌쇄를 갖는 (메타)아크릴레이트; 폴리에틸렌글리콜-폴리프로필렌글리콜모노(메타)아크릴레이트, 폴리옥시부틸렌-폴리옥시프로필렌모노(메타)아크릴레이트 등의 블록 구조의 옥시알킬렌쇄를 갖는 (메타)아크릴레이트; 폴리(에틸렌글리콜-테트라메틸렌글리콜)모노(메타)아크릴레이트, 폴리(프로필렌글리콜-테트라메틸렌글리콜)모노(메타)아크릴레이트 등의 랜덤 구조의 옥시알킬렌쇄를 갖는 (메타)아크릴레이트 등을 들 수 있다. 이들 (메타)아크릴레이트(a2-2)는, 1종으로 사용할 수도 있고 2종 이상 병용할 수도 있다.The said (meth)acrylate (a2-2) is a compound which has a hydroxyl group and a (meth)acryloyl group. As a specific example of this (meth)acrylate (a2-2), 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4- Hydroxybutyl (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, hydroxypivalic acid neo mono(meth)acrylates of dihydric alcohols such as pentyl glycol mono(meth)acrylate; Trimethylolpropane di(meth)acrylate, ethylene oxide (EO) modified trimethylolpropane (meth)acrylate, propylene oxide (PO) modified trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, bis Mono- or di(meth)acrylates of trihydric alcohols such as (2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate, or hydroxyl groups obtained by modifying some of these alcoholic hydroxyl groups with ε-caprolactone having mono and di (meth) acrylates; Compounds having monofunctional hydroxyl groups, such as pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate, and trifunctional or more (meth) acryloyl groups Or, polyfunctional (meth)acrylate having a hydroxyl group further modified with ε-caprolactone of the compound; (meth)acrylates having an oxyalkylene chain, such as dipropylene glycol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and polyethylene glycol mono(meth)acrylate ; (meth)acrylates having an oxyalkylene chain having a block structure, such as polyethylene glycol-polypropylene glycol mono(meth)acrylate and polyoxybutylene-polyoxypropylene mono(meth)acrylate; (meth)acrylates having an oxyalkylene chain having a random structure, such as poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate and poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate; have. These (meth)acrylates (a2-2) may be used by 1 type, and may be used together 2 or more types.

상기 우레탄(메타)아크릴레이트(A2) 중에서도, 본 발명의 활성 에너지선 경화성 조성물의 경화 도막의 내찰상성을 향상할 수 있기 때문에, 1분자 중에 4개 이상의 (메타)아크릴로일기를 갖는 것이 바람직하다. 상기 우레탄(메타)아크릴레이트(A2)를 1분자 중에 4개 이상의 (메타)아크릴로일기를 갖는 것으로 하기 위하여, 상기 (메타)아크릴레이트(a2-2)로서는, (메타)아크릴로일기는 둘 이상 갖는 것이 바람직하다. 이와 같은 (메타)아크릴레이트(a2-2)로서는, 예를 들면, 트리메틸올프로판디(메타)아크릴레이트, 에틸렌옥사이드 변성 트리메틸올프로판디(메타)아크릴레이트, 프로필렌옥사이드 변성 트리메틸올프로판디(메타)아크릴레이트, 글리세린디(메타)아크릴레이트, 비스(2-(메타)아크릴로일옥시에틸)히드록시에틸이소시아누레이트, 펜타에리트리톨트리(메타)아크릴레이트, 펜타에리트리톨테트라(메타)아크릴레이트, 디트리메틸올프로판트리(메타)아크릴레이트, 디펜타에리트리톨펜타(메타)아크릴레이트 등을 들 수 있다. 이들 (메타)아크릴레이트(a2-2)는, 상기 지방족 폴리이소시아네이트의 1종에 대해서, 1종을 사용할 수도 있고 2종 이상 병용할 수도 있다. 또한, 이들 (메타)아크릴레이트(a2-2) 중에서도, 내찰상성을 한층 더 향상할 수 있기 때문에, 펜타에리트리톨트리(메타)아크릴레이트, 펜타에리트리톨테트라(메타)아크릴레이트, 및 디펜타에리트리톨펜타(메타)아크릴레이트가 바람직하고, 펜타에리트리톨테트라(메타)아크릴레이트가 보다 바람직하다.Among the said urethane (meth)acrylates (A2), since the abrasion resistance of the cured coating film of the active energy ray-curable composition of this invention can be improved, it is preferable to have 4 or more (meth)acryloyl groups in 1 molecule. . In order for the urethane (meth)acrylate (A2) to have four or more (meth)acryloyl groups in one molecule, as the (meth)acrylate (a2-2), two (meth)acryloyl groups It is preferable to have more than one. As such (meth)acrylate (a2-2), for example, trimethylolpropane di(meth)acrylate, ethylene oxide modified trimethylolpropane di(meth)acrylate, propylene oxide modified trimethylolpropane di(meth) ) acrylate, glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, ditrimethylol propane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc. are mentioned. These (meth)acrylates (a2-2) may use 1 type with respect to 1 type of the said aliphatic polyisocyanate, and may use 2 or more types together. Moreover, among these (meth)acrylates (a2-2), since scratch resistance can be improved further, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaeryth Ritol penta (meth) acrylate is preferable, and pentaerythritol tetra (meth) acrylate is more preferable.

상기 폴리이소시아네이트(a2-1)와 상기 (메타)아크릴레이트(a2-2)와의 반응은, 통상의 방법의 우레탄화 반응에 의해 행할 수 있다. 또한, 우레탄화 반응의 진행을 촉진하기 위하여, 우레탄화 촉매의 존재 하에서 우레탄화 반응을 행하는 것이 바람직하다. 상기 우레탄화 촉매로서는, 예를 들면, 피리딘, 피롤, 트리에틸아민, 디에틸아민, 디부틸아민 등의 아민 화합물; 트리페닐포스핀, 트리에틸포스핀 등의 인 화합물; 디부틸주석디라우레이트, 옥틸주석트리라우레이트, 옥틸주석디아세테이트, 디부틸주석디아세테이트, 옥틸산주석 등의 유기 주석 화합물, 옥틸산아연 등의 유기 아연 화합물 등을 들 수 있다.Reaction of the said polyisocyanate (a2-1) and the said (meth)acrylate (a2-2) can be performed by the urethanation reaction of a normal method. Moreover, in order to accelerate progress of a urethanation reaction, it is preferable to perform a urethanation reaction in presence of a urethanization catalyst. Examples of the urethanization catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; phosphorus compounds such as triphenylphosphine and triethylphosphine; Organotin compounds, such as organic tin compounds, such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate, and tin octylate, and organic zinc compounds, such as zinc octylate, etc. are mentioned.

상기 굴절률이 1.55 이상인 고굴절률 중합성 단량체(A3)는, 경화 전의 굴절률이 1.55 이상의 고굴절률의 것이면 되고, 예를 들면, 방향환을 2∼6개 갖는 방향족계 중합성 단량체, 플루오렌계 중합성 단량체 등을 바람직하게 들 수 있다. 또한, 상기 중합성 단량체(A)의 구체예로서는, 하기 일반식(1)으로 표시되는 화합물; o-페닐벤질(메타)아크릴레이트, p-페닐벤질(메타)아크릴레이트 등의 페닐벤질기를 갖는 (메타)아크릴레이트 화합물; 페닐페놀 EO 아크릴레이트 등의 페닐페놀기를 갖는 (메타)아크릴레이트 화합물; 프로폭시화비스페놀A디(메타)아크릴레이트, 에톡시화비스페놀A디(메타)아크릴레이트, 옥시에틸렌기를 갖는 비스페놀A디(메타)아크릴레이트, 옥시에틸렌기를 갖는 비스페놀A트리(메타)아크릴레이트 등의 (메타)아크릴로일기를 2∼4개의 범위에서 갖는 비스페놀 화합물 등을 들 수 있다. 이들 중합성 단량체(A)는, 1종으로 사용할 수도 있고 2종 이상 병용할 수도 있다. 이들 중에서도, 후술하는 특정의 유기 용제를 사용해도 굴절률을 제어하기 쉽고 높은 굴절률을 얻을 수 있는 점으로부터, 하기 일반식(1)으로 표시되는 화합물, 페닐벤질기를 갖는 (메타)아크릴레이트 화합물, 및, (메타)아크릴로일기를 2∼4개의 범위에서 갖는 비스페놀 화합물로 이루어지는 군에서 선택되는 1종 이상의 단량체를 사용하는 것이 바람직하다. 상기 중합성 단량체(A3)로서 사용할 수 있는 시판품으로서는, 오사카가스케미컬가부시키가이샤제의 「OGSOL EA-0200」, 「OGSOL EA-0300」, 「OGSOL GA-5060P」; DIC가부시키가이샤제의 「UNIDIC EKZ-948」, 「UNIDIC EQS-1179」; 신나카무라가가쿠고교가부시키가이샤제의 「A-BPEF」, MIWON사제 「MIRAMER HR6042」 등을 들 수 있다. 이들 중합성 단량체(A)는, 1종으로 사용할 수도 있고 2종 이상 병용할 수도 있다.The high refractive index polymerizable monomer (A3) having a refractive index of 1.55 or more may have a high refractive index of 1.55 or more before curing, for example, an aromatic polymerizable monomer having 2 to 6 aromatic rings, a fluorene polymerizable monomer. A monomer etc. are mentioned preferably. Moreover, as a specific example of the said polymerizable monomer (A), it is a compound represented by the following general formula (1); (meth)acrylate compounds having a phenylbenzyl group such as o-phenylbenzyl (meth)acrylate and p-phenylbenzyl (meth)acrylate; (meth)acrylate compounds having a phenylphenol group such as phenylphenol EO acrylate; Propoxylated bisphenol A di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, bisphenol A di(meth)acrylate having an oxyethylene group, bisphenol A tri(meth)acrylate having an oxyethylene group, etc. The bisphenol compound etc. which have a (meth)acryloyl group in 2-4 ranges are mentioned. These polymerizable monomers (A) may be used alone or in combination of two or more. Among these, the (meth)acrylate compound having a compound represented by the following general formula (1), a phenylbenzyl group, and It is preferable to use the 1 or more types of monomers chosen from the group which consists of a bisphenol compound which has a (meth)acryloyl group in 2-4 ranges. As a commercial item which can be used as the said polymerizable monomer (A3), "OGSOL EA-0200", "OGSOL EA-0300", "OGSOL GA-5060P" manufactured by Osaka Chemical Co., Ltd.; "UNIDIC EKZ-948", "UNIDIC EQS-1179" manufactured by DIC Corporation; "A-BPEF" by Shin-Nakamura Chemical Co., Ltd., "MIRAMER HR6042" by MIWON, etc. are mentioned. These polymerizable monomers (A) may be used alone or in combination of two or more.

Figure 112019084538608-pct00001
Figure 112019084538608-pct00001

(식(1) 중, R1, R2은 각각 수소기 또는 메틸기를 나타내고, m, n은 각각 0∼5의 정수를 나타낸다)(In formula (1), R 1 and R 2 each represent a hydrogen group or a methyl group, and m and n each represent an integer of 0 to 5)

상기 수지(B)는, 지환 구조 및 4급 암모늄염을 갖는 것이다.The said resin (B) has an alicyclic structure and a quaternary ammonium salt.

상기 수지(B)의 제조 방법으로서는, 예를 들면, 지환 구조를 갖는 중합성 단량체(b1) 및 4급 암모늄염을 갖는 중합성 단량체(b2)를 필수 성분으로서, 상기 중합성 단량체(b1) 및 상기 중합성 단량체(b2)와, 공중합 가능한 중합성 단량체(b3)를 공중합하는 방법을 들 수 있다.As the manufacturing method of the said resin (B), for example, the polymerizable monomer (b1) which has an alicyclic structure and the polymerizable monomer (b2) which has a quaternary ammonium salt are essential components, The said polymerizable monomer (b1) and the said The method of copolymerizing a polymerizable monomer (b2) and a copolymerizable polymerizable monomer (b3) is mentioned.

상기 중합성 단량체(b1)는, 지환 구조를 갖는 중합성 단량체이다. 상기 지환 구조로서는, 예를 들면, 시클로프로판환, 시클로부탄환, 시클로펜탄환, 시클로헥산환, 시클로헵탄환, 시클로옥탄환, 시클로노난환, 시클로데칸환 등의 단환 지환 구조; 비시클로운데칸환, 데카히드로나프탈렌(데칼린)환, 트리시클로[5.2.1.02,6]데칸환, 비시클로[4.3.0]노난환, 트리시클로[5.3.1.1]도데칸환, 트리시클로[5.3.1.1]도데칸환, 스피로[3.4]옥탄환 등의 다환 지환 구조 등을 들 수 있다. 또한, 상기 중합성 단량체(c1)의 구체예로서는, 시클로헥실(메타)아크릴레이트, 1,4-시클로헥산디메탄올모노(메타)아크릴레이트, 이소보르닐(메타)아크릴레이트, 디시클로펜테닐(메타)아크릴레이트, 디시클로펜테닐옥시에틸(메타)아크릴레이트, 디시클로펜타닐(메타)아크릴레이트 등을 들 수 있다. 이들 중합성 단량체(b1)는, 1종으로 사용할 수도 있고 2종 이상 병용할 수도 있다.The said polymerizable monomer (b1) is a polymerizable monomer which has an alicyclic structure. Examples of the alicyclic structure include monocyclic alicyclic structures such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, and a cyclodecane ring; Bicycloundecane ring, decahydronaphthalene (decalin) ring, tricyclo[5.2.1.0 2,6 ]decane ring, bicyclo[4.3.0]nonane ring, tricyclo[5.3.1.1]dodecane ring, tricyclo[5.3. 1.1] polycyclic alicyclic structures, such as a dodecane ring and a spiro [3.4] octane ring, etc. are mentioned. In addition, as specific examples of the polymerizable monomer (c1), cyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl ( Meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, etc. are mentioned. These polymerizable monomers (b1) may be used alone or in combination of two or more.

상기 중합성 단량체(b2)로서는, 예를 들면, 2-[(메타)아크릴로일옥시]에틸트리메틸암모늄클로라이드, 3-[(메타)아크릴로일옥시]프로필트리메틸암모늄클로라이드 등의 카운터 음이온이 클로라이드인 것; 2-[(메타)아크릴로일옥시]에틸트리메틸암모늄브로마이드, 3-[(메타)아크릴로일옥시]프로필트리메틸암모늄브로마이드 등의 카운터 음이온이 브로마이드인 것; 2-[(메타)아크릴로일옥시]에틸트리메틸암모늄메틸페닐설포네이트, 2-[(메타)아크릴로일옥시]에틸트리메틸암모늄메틸설포네이트, 3-[(메타)아크릴로일옥시]프로필트리메틸암모늄메틸페닐설포네이트, 3-[(메타)아크릴로일옥시]프로필트리메틸암모늄메틸설포네이트, 2-[(메타)아크릴로일옥시]에틸트리메틸암모늄메틸설페이트, 3-[(메타)아크릴로일옥시]프로필트리메틸암모늄메틸설페이트 등의 카운터 음이온이 비할로겐계인 것 등을 들 수 있다. 이들 중합성 단량체(b2)는, 1종으로 사용할 수도 있고 2종 이상 병용할 수도 있다.As the polymerizable monomer (b2), for example, a counter anion such as 2-[(meth)acryloyloxy]ethyltrimethylammonium chloride and 3-[(meth)acryloyloxy]propyltrimethylammonium chloride is chloride being; counter anions such as 2-[(meth)acryloyloxy]ethyltrimethylammonium bromide and 3-[(meth)acryloyloxy]propyltrimethylammonium bromide are bromide; 2-[(meth)acryloyloxy]ethyltrimethylammoniummethylphenylsulfonate, 2-[(meth)acryloyloxy]ethyltrimethylammoniummethylsulfonate, 3-[(meth)acryloyloxy]propyltrimethylammonium Methylphenylsulfonate, 3-[(meth)acryloyloxy]propyltrimethylammonium methylsulfonate, 2-[(meth)acryloyloxy]ethyltrimethylammoniummethylsulfate, 3-[(meth)acryloyloxy] A non-halogen type counter anion, such as a propyl trimethylammonium methyl sulfate, etc. are mentioned. These polymerizable monomers (b2) may be used alone or in combination of two or more.

상기 중합성 단량체(b3)로서는, 예를 들면, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, n-프로필(메타)아크릴레이트, n-부틸(메타)아크릴레이트, 이소부틸(메타)아크릴레이트, n-펜틸(메타)아크릴레이트, n-헥실(메타)아크릴레이트, n-헵틸(메타)아크릴레이트, n-옥틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 노닐(메타)아크릴레이트, 데실(메타)아크릴레이트, 도데실(메타)아크릴레이트 등의 알킬(메타)아크릴레이트; 메톡시폴리에틸렌글리콜모노(메타)아크릴레이트, 옥톡시폴리에틸렌글리콜·폴리프로필렌글리콜모노(메타)아크릴레이트, 라우록시폴리에틸렌글리콜모노(메타)아크릴레이트, 스테아록시폴리에틸렌글리콜모노(메타)아크릴레이트, 페녹시폴리에틸렌글리콜모노(메타)아크릴레이트, 페녹시폴리에틸렌글리콜·폴리프로필렌글리콜모노(메타)아크릴레이트, 노닐페녹시폴리프로필렌글리콜모노(메타)아크릴레이트, 노닐페녹시폴리(에틸렌글리콜·프로필렌글리콜)모노(메타)아크릴레이트 등의 폴리알킬렌글리콜의 모노(메타)아크릴레이트; 2-퍼플루오로헥실에틸(메타)아크릴레이트 등의 불소화알킬기를 갖는 (메타)아크릴레이트 등을 들 수 있다. 이들 중합성 단량체(b3)는, 1종으로 사용할 수도 있고 2종 이상 병용할 수도 있다.Examples of the polymerizable monomer (b3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate. Acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl Alkyl (meth)acrylates, such as (meth)acrylate, decyl (meth)acrylate, and dodecyl (meth)acrylate; Methoxy polyethylene glycol mono (meth) acrylate, octoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate, stearoxy polyethylene glycol mono (meth) acrylate, phenoxy Polyethylene glycol mono (meth) acrylate, phenoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, nonylphenoxy polypropylene glycol mono (meth) acrylate, nonyl phenoxy poly (ethylene glycol propylene glycol) mono ( mono(meth)acrylates of polyalkylene glycol such as meth)acrylate; (meth)acrylate which has fluorinated alkyl groups, such as 2-perfluorohexylethyl (meth)acrylate, etc. are mentioned. These polymerizable monomers (b3) may be used alone or in combination of two or more.

상기 중합성 단량체(b3) 중에서도, 본 발명의 활성 에너지선 경화성 조성물의 경화 도막의 대전방지성을 보다 향상할 수 있으므로, 폴리알킬렌글리콜의 모노(메타)아크릴레이트가 바람직하고, 메톡시폴리에틸렌글리콜모노(메타)아크릴레이트가 보다 바람직하다. 또한, 불소화알킬기를 갖는 (메타)아크릴레이트도 본 발명의 활성 에너지선 경화성 조성물의 경화 도막의 대전방지성을 보다 향상할 수 있는 효과가 있으므로 바람직하다.Among the said polymerizable monomers (b3), since the antistatic property of the cured coating film of the active energy ray-curable composition of this invention can be improved more, mono(meth)acrylate of polyalkylene glycol is preferable, and methoxypolyethylene glycol Mono(meth)acrylate is more preferable. Moreover, (meth)acrylate which has a fluorinated alkyl group is also preferable since it has the effect which can improve the antistatic property of the cured coating film of the active-energy-ray-curable composition of this invention more.

상기 폴리알킬렌글리콜의 모노(메타)아크릴레이트 중에서도, 본 발명의 활성 에너지선 경화성 조성물의 경화 도막의 대전방지성을 더 향상할 수 있으므로, 상기 폴리알킬렌글리콜의 모노(메타)아크릴레이트의 원료로 되는 폴리알킬렌글리콜의 수 평균 분자량이 200∼8,000의 범위인 것이 바람직하고, 300∼6,000의 범위인 것이 보다 바람직하고, 400∼4,000의 범위인 것이 더 바람직하고, 400∼2,000의 범위인 것이 특히 바람직하다.Among the mono(meth)acrylates of the polyalkylene glycol, since the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved, the raw material of the mono(meth)acrylate of the polyalkylene glycol It is preferable that the number average molecular weight of the polyalkylene glycol used as Especially preferred.

상기 수지(B)의 원료 전량 중의 상기 중합성 단량체(b1)의 비율은, 본 발명의 활성 에너지선 경화성 조성물의 경화 도막의 대전방지성을 보다 향상할 수 있으므로, 5∼40질량%의 범위가 바람직하고, 10∼50질량%의 범위가 보다 바람직하고, 12∼45질량%의 범위가 더 바람직하다.Since the ratio of the polymerizable monomer (b1) in the total amount of the raw material of the resin (B) can further improve the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention, the range of 5 to 40 mass% is It is preferable, the range of 10-50 mass % is more preferable, The range of 12-45 mass % is still more preferable.

또한, 상기 수지(B)의 원료 전량 중의 상기 중합성 단량체(b2)의 비율은, 본 발명의 활성 에너지선 경화성 조성물의 경화 도막의 대전방지성을 보다 향상할 수 있으므로, 30∼90질량%의 범위가 바람직하고, 40∼80질량%의 범위가 보다 바람직하고, 45∼70질량%의 범위가 보다 바람직하다.In addition, since the ratio of the said polymerizable monomer (b2) in the raw material whole amount of the said resin (B) can further improve the antistatic property of the cured coating film of the active energy ray-curable composition of this invention, 30-90 mass % The range is preferable, the range of 40-80 mass % is more preferable, The range of 45-70 mass % is more preferable.

또한, 상기 중합성 단량체(b3)로서 상기 폴리알킬렌글리콜의 모노(메타)아크릴레이트를 사용하는 경우는, 본 발명의 활성 에너지선 경화성 조성물의 경화 도막의 대전방지성을 보다 향상할 수 있으므로, 상기 수지(B)의 원료 전량 중의 폴리알킬렌글리콜의 모노(메타)아크릴레이트의 비율은, 5∼60질량%의 범위가 바람직하고, 10∼50질량%의 범위가 보다 바람직하고, 20∼40질량%의 범위가 더 바람직하다.In addition, when the mono (meth) acrylate of the polyalkylene glycol is used as the polymerizable monomer (b3), the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved, The range of 5-60 mass % is preferable, as for the ratio of the mono(meth)acrylate of polyalkylene glycol in the raw material whole quantity of the said resin (B), the range of 10-50 mass % is more preferable, 20-40 The range of mass % is more preferable.

또한, 상기 중합성 단량체(b3)로서 상기 불소화알킬기를 갖는 (메타)아크릴레이트를 사용하는 경우는, 본 발명의 활성 에너지선 경화성 조성물의 경화 도막의 대전방지성을 보다 향상할 수 있으므로, 상기 수지(B)의 원료 전량 중의 불소화알킬기를 갖는 (메타)아크릴레이트의 비율은, 0.1∼20질량%의 범위가 바람직하고, 0.5∼10질량%의 범위가 보다 바람직하고, 1∼5질량%의 범위가 더 바람직하다.Moreover, when using the (meth)acrylate which has the said fluorinated alkyl group as said polymerizable monomer (b3), since the antistatic property of the cured coating film of the active energy ray-curable composition of this invention can be improved more, the said resin The ratio of the (meth)acrylate having a fluorinated alkyl group in the total amount of the raw material (B) is preferably in the range of 0.1 to 20 mass%, more preferably in the range of 0.5 to 10 mass%, and in the range of 1 to 5 mass%. is more preferable

상기 수지(B)의 중량 평균 분자량은, 본 발명의 활성 에너지선 경화성 조성물의 경화 도막의 대전방지성을 보다 향상할 수 있으므로, 1,000∼100,000의 범위가 바람직하고, 2,000∼50,000의 범위가 보다 바람직하고, 3,000∼30,000의 범위가 더 바람직하다. 또, 본 발명에 있어서의 중량 평균 분자량은, 겔·퍼미에이션·크로마토그래피(GPC)법에 의해 측정한 폴리스티렌 환산에서의 값이다.Since the weight average molecular weight of the said resin (B) can improve the antistatic property of the cured coating film of the active energy ray-curable composition of this invention more, the range of 1,000-100,000 is preferable, and the range of 2,000-50,000 is more preferable. and more preferably in the range of 3,000 to 30,000. In addition, the weight average molecular weight in this invention is a value in polystyrene conversion measured by the gel permeation chromatography (GPC) method.

상기 수지(B)의 배합량은, 본 발명의 활성 에너지선 경화성 조성물의 경화 도막의 대전방지성을 보다 향상할 수 있으므로, 상기 활성 에너지선 경화성 화합물(A) 100질량부에 대해서, 0.1∼30질량부의 범위가 바람직하고, 0.3∼20질량부의 범위가 보다 바람직하고, 0.5∼10질량부의 범위가 더 바람직하고, 0.7∼7질량부의 범위가 특히 바람직하다.Since the compounding quantity of the said resin (B) can improve more the antistatic property of the cured coating film of the active energy ray-curable composition of this invention, 0.1-30 mass with respect to 100 mass parts of said active energy ray-curable compounds (A). The range of negative is preferable, the range of 0.3-20 mass parts is more preferable, the range of 0.5-10 mass parts is still more preferable, The range of 0.7-7 mass parts is especially preferable.

상기 유기 용제(C)로서는, 우수한 내수성을 얻는데, 디메틸아세트아미드를 함유하는 것이 필수이다. 디메틸아세트아미드는, 상기 수지(B)와의 상성이 좋고, 비점도 비교적 높으므로 물이 혼입해도 완전 혼합하며, 고분자용해성도 높기 때문에, 친수성·소수성 양성분이 혼재하여 있는 경우에도 건조 공정에서 증발하기 때문에, 백화 등의 문제를 억제할 수 있고, 우수한 내수성을 얻을 수 있다.As said organic solvent (C), in order to acquire the outstanding water resistance, it is essential to contain dimethylacetamide. Since dimethylacetamide has good compatibility with the resin (B) and has a relatively high boiling point, it is completely mixed even when water is mixed, and has high polymer solubility. , problems such as whitening can be suppressed, and excellent water resistance can be obtained.

상기 디메틸아세트아미드의 함유량으로서는, 한층 더 우수한 내수성이 얻어지는 점으로부터, 상기 활성 에너지선 경화성 화합물(A) 100질량부에 대해서, 5∼200질량부의 범위인 것이 바람직하고, 7∼150질량부의 범위가 보다 바람직하다.As content of the said dimethylacetamide, it is preferable that it is the range of 5-200 mass parts with respect to 100 mass parts of said active energy ray-curable compound (A) from the point from which further excellent water resistance is obtained, and the range of 7-150 mass parts is more preferably.

또한, 상기 디메틸아세트아미드의 함유량으로서는, 한층 더 우수한 내수성이 얻어지는 점으로부터, 유기 용제(C) 중 3질량% 이상인 것이 바람직하고, 5질량% 이상이 보다 바람직하고, 7질량% 이상 99질량% 이하가 더 바람직하다.Moreover, as content of the said dimethylacetamide, it is preferable that it is 3 mass % or more in organic solvent (C) from the point from which further outstanding water resistance is acquired, 5 mass % or more is more preferable, 7 mass % or more and 99 mass % or less is more preferable

상기 유기 용제(C)로서는, 상기 디메틸아세트아미드 이외에도, 예를 들면, 소수성 용제, 상기 디메틸아세트아미드 이외의 친수성 용제를 사용할 수 있다.As said organic solvent (C), other than the said dimethylacetamide, hydrophobic solvent and hydrophilic solvents other than the said dimethylacetamide can be used, for example.

상기 소수성 용제로서는, 예를 들면, 디에틸에테르, 벤젠, 톨루엔, 아세트산에틸, 아세트산부틸, 메틸에틸케톤, 메틸이소부틸케톤, 아세틸아세톤, 자일렌, n-부탄올, 디메틸카보네이트, 디에틸카보네이트, 메틸에틸카보네이트, 클로로포름, 프로필렌글리콜모노메틸에테르아세테이트 등을 들 수 있다. 이들 용제는 단독으로 사용해도 되고 2종 이상을 병용해도 된다. 상기 소수성 용제로서는, 활성 에너지선 경화성 조성물의 도공안정성이 한층 더 향상하고, 경화 도막에 금이 가는 것을 방지할 수 있고, 한층 더 우수한 도막 외관을 얻을 수 있는 점으로부터, 디메틸카보네이트, 메틸에틸케톤, 및, 메틸이소부틸케톤으로 이루어지는 군에서 선택되는 1종 이상을 사용하는 것이 바람직하고, 디메틸카보네이트, 및/또는, 메틸에틸케톤이 보다 바람직하다.Examples of the hydrophobic solvent include diethyl ether, benzene, toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, xylene, n-butanol, dimethyl carbonate, diethyl carbonate, methyl Ethyl carbonate, chloroform, propylene glycol monomethyl ether acetate, etc. are mentioned. These solvents may be used independently and may use 2 or more types together. As the hydrophobic solvent, the coating stability of the active energy ray-curable composition is further improved, the cured coating film can be prevented from being cracked, and a more excellent coating film appearance can be obtained, so dimethyl carbonate, methyl ethyl ketone, And it is preferable to use 1 or more types chosen from the group which consists of methyl isobutyl ketone, and dimethyl carbonate and/or methyl ethyl ketone are more preferable.

상기 친수성 용제(d-3)로서는, 예를 들면, 아세톤, 메탄올, 에탄올, n-프로판올, 이소프로필알코올, 다이아세톤알코올, 에틸렌글리콜모노에틸에테르, 프로필렌글리콜모노메틸에테르, 디옥솔란, 테트라히드로퓨란, 테트라히드로피란, 디메틸포름아미드 등을 들 수 있다. 이들 용제는 단독으로 사용해도 되고 2종 이상을 병용해도 된다. 상기 친수성 용제로서는, 활성 에너지선 경화성 조성물의 도공안정성이 한층 더 향상하고, 경화 도막에 금이 가는 것을 방지할 수 있고, 한층 더 우수한 도막 외관을 얻을 수 있는 점으로부터, 메탄올, 에탄올, n-프로판올, 및, 프로필렌글리콜모노메틸에테르로 이루어지는 군에서 선택되는 1종 이상을 사용하는 것이 바람직하고, 메탄올과 프로필렌글리콜모노메틸에테르와의 병용, 또는, 메탄올, 에탄올, n-프로판올, 및, 프로필렌글리콜모노메틸에테르를 조합 사용하는 것이 보다 바람직하다.Examples of the hydrophilic solvent (d-3) include acetone, methanol, ethanol, n-propanol, isopropyl alcohol, diacetone alcohol, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dioxolane, tetrahydrofuran. , tetrahydropyran, dimethylformamide, and the like. These solvents may be used independently and may use 2 or more types together. As the hydrophilic solvent, the coating stability of the active energy ray-curable composition is further improved, cracking of the cured coating film can be prevented, and a further excellent coating film appearance can be obtained, so methanol, ethanol, n-propanol It is preferable to use at least one selected from the group consisting of , and propylene glycol monomethyl ether, in combination with methanol and propylene glycol monomethyl ether, or methanol, ethanol, n-propanol, and propylene glycol monomethyl ether. It is more preferable to use methyl ether in combination.

또, 본 발명에 있어서, 상기 친수성 용제란, 물에의 용해도가 10g/100ml 이상인 용제를 나타내고, 이것과 상기 디메틸아세트아미드 이외의 것이 소수성 용제로 된다. 또, 유기 용제의 물에의 용해도는, 100ml의 물(25℃)에의 용해도를 나타낸다.Moreover, in this invention, the said hydrophilic solvent shows the solvent whose solubility in water is 10 g/100 ml or more, and this and things other than the said dimethylacetamide become a hydrophobic solvent. In addition, the solubility to the water of an organic solvent shows the solubility to 100 ml of water (25 degreeC).

상기 유기 용제(C)로서는, 활성 에너지선 경화성 조성물의 도공안정성이 한층 더 향상하고, 경화 도막에 금이 가는 것을 방지할 수 있고, 한층 더 우수한 도막 외관을 얻을 수 있는 점으로부터, 디메틸아세트아미드와 그 이외의 친수성 용제와의 병용, 또는, 디메틸아세트아미드와 그 이외의 친수성 용제와 소수성 용제를 조합 사용하는 것이 바람직하다.As the organic solvent (C), the coating stability of the active energy ray-curable composition is further improved, the cured coating film can be prevented from being cracked, and a more excellent coating film appearance can be obtained. It is preferable to use in combination with other hydrophilic solvents, or to use dimethylacetamide in combination with other hydrophilic solvents and hydrophobic solvents.

상기 유기 용제(C)로서, 디메틸아세트아미드와 그 이외의 친수성 용제를 병용하는 경우의 상기 친수성 용제의 사용량으로서는, 상기 활성 에너지선 경화성 화합물(A) 100질량부에 대해서, 0.1∼50질량부의 범위인 것이 바람직하고, 1∼30질량부의 범위가 보다 바람직하다.As said organic solvent (C), the usage-amount of the said hydrophilic solvent in the case of using dimethylacetamide and other hydrophilic solvents together is the range of 0.1-50 mass parts with respect to 100 mass parts of said active energy ray-curable compounds (A). It is preferable that it is, and the range of 1-30 mass parts is more preferable.

상기 유기 용제(C)로서, 디메틸아세트아미드와 그 이외의 친수성 용제와 소수성 용제의 조합을 사용하는 경우에는, 상기 친수성 용제의 사용량으로서는, 상기 활성 에너지선 경화성 화합물(A) 100질량부에 대해서, 0.1∼40질량부의 범위가 바람직하고, 3∼25질량부의 범위가 보다 바람직하고, 상기 소수성 용제의 사용량으로서는, 상기 활성 에너지선 경화성 화합물(A) 100질량부에 대해서, 10∼95질량부의 범위가 바람직하고, 30∼93질량부의 범위가 보다 바람직하다.When using a combination of dimethylacetamide and other hydrophilic solvents and hydrophobic solvents as the organic solvent (C), the amount of the hydrophilic solvent used is relative to 100 parts by mass of the active energy ray-curable compound (A), The range of 0.1-40 mass parts is preferable, the range of 3-25 mass parts is more preferable, As the usage-amount of the said hydrophobic solvent, the range of 10-95 mass parts with respect to 100 mass parts of said active energy ray-curable compound (A) is It is preferable, and the range of 30-93 mass parts is more preferable.

본 발명의 활성 에너지선 경화성 조성물 중의 상기 유기 용제(C)의 배합량은, 후술하는 도공 방법에 적합한 점도로 되는 양으로 하는 것이 바람직하다.It is preferable to make the compounding quantity of the said organic solvent (C) in the active-energy-ray-curable composition of this invention into the quantity used as the viscosity suitable for the coating method mentioned later.

또한, 본 발명의 활성 에너지선 경화성 조성물은, 기재에 도공 후, 활성 에너지선을 조사함으로써 경화 도막으로 할 수 있다. 이 활성 에너지선이란, 자외선, 전자선, α선, β선, γ선 등의 전리 방사선을 말한다. 활성 에너지선으로서 자외선을 조사해서 경화 도막으로 하는 경우에는, 본 발명의 활성 에너지선 경화성 조성물 중에 광중합개시제(D)를 첨가하여, 경화성을 향상하는 것이 바람직하다. 또한, 필요하면 광증감제(E)를 더 첨가해서, 경화성을 향상할 수도 있다. 한편, 전자선, α선, β선, γ선 등의 전리 방사선을 사용하는 경우에는, 광중합개시제(D)나 광증감제(E)를 사용하지 않아도 신속히 경화하므로, 특히 광중합개시제(D)나 광증감제(E)를 첨가할 필요는 없다.Moreover, the active energy ray-curable composition of this invention can be set as a cured coating film by irradiating an active energy ray after coating to a base material. This active energy ray means ionizing radiation, such as an ultraviolet-ray, an electron beam, an alpha ray, a beta ray, and a gamma ray. When irradiating an ultraviolet-ray as an active energy ray and setting it as a cured coating film, it is preferable to add a photoinitiator (D) in the active energy ray-curable composition of this invention, and to improve sclerosis|hardenability. Moreover, if necessary, a photosensitizer (E) can be further added and sclerosis|hardenability can also be improved. On the other hand, when ionizing radiation such as electron beam, α-ray, β-ray, or γ-ray is used, it cures quickly without using a photoinitiator (D) or a photosensitizer (E). It is not necessary to add a sensitizer (E).

상기 광중합개시제(D)로서는, 예를 들면, 디에톡시아세토페논, 2-히드록시-2-메틸-1-페닐프로판-1-온, 올리고{2-히드록시-2-메틸-1-[4-(1-메틸비닐)페닐]프로판온}, 벤질디메틸케탈, 1-(4-이소프로필페닐)-2-히드록시-2-메틸프로판-1-온, 4-(2-히드록시에톡시)페닐-(2-히드록시-2-프로필)케톤, 1-히드록시시클로헥실페닐케톤, 2-메틸-2-모르폴리노(4-티오메틸페닐)프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)-부탄온 등의 아세토페논계 화합물; 벤조인, 벤조인메틸에테르, 벤조인이소프로필에테르 등의 벤조인계 화합물; 2,4,6-트리메틸벤조인디페닐포스핀옥사이드, 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드 등의 아실포스핀옥사이드계 화합물; 벤질(디벤조일), 메틸페닐글리옥시에스테르, 옥시페닐아세트산2-(2-히드록시에톡시)에틸에스테르, 옥시페닐아세트산2-(2-옥소-2-페닐아세톡시에톡시)에틸에스테르 등의 벤질계 화합물; 벤조페논, o-벤조일벤조산메틸-4-페닐벤조페논, 4,4'-디클로로벤조페논, 히드록시벤조페논, 4-벤조일-4'-메틸-디페닐설파이드, 아크릴화벤조페논, 3,3',4,4'-테트라(t-부틸퍼옥시카르보닐)벤조페논, 3,3'-디메틸-4-메톡시벤조페논, 2,4,6-트리메틸벤조페논, 4-메틸벤조페논 등의 벤조페논계 화합물; 2-이소프로필티오잔톤, 2,4-디메틸티오잔톤, 2,4-디에틸티오잔톤, 2,4-디클로로티오잔톤 등의 티오잔톤계 화합물; 미힐러케톤, 4,4'-디에틸아미노벤조페논 등의 아미노벤조페논계 화합물; 10-부틸-2-클로로아크리돈, 2-에틸안트라퀴논, 9,10-페난트렌퀴논, 캄포르퀴논, 1-[4-(4-벤조일페닐설파닐)페닐]-2-메틸-2-(4-메틸페닐설포닐)프로판-1-온 등을 들 수 있다. 이들 광중합개시제(D)는, 1종으로 사용할 수도 있고, 2종 이상 병용할 수도 있다.Examples of the photopolymerization initiator (D) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and oligo{2-hydroxy-2-methyl-1-[4]. -(1-methylvinyl)phenyl]propanone}, benzyldimethylketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy) ) Phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2 -Acetophenone compounds, such as dimethylamino-1-(4-morpholinophenyl)-butanone; benzoin compounds such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; acylphosphine oxide-based compounds such as 2,4,6-trimethylbenzoindiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; Benzyl such as benzyl (dibenzoyl), methylphenylglyoxyester, oxyphenylacetic acid 2-(2-hydroxyethoxy)ethyl ester, and oxyphenylacetic acid 2-(2-oxo-2-phenylacetoxyethoxy)ethyl ester compound; Benzophenone, o-benzoylbenzoic acid methyl-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylated benzophenone, 3,3' ,4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, etc. benzophenone compounds; thioxanthone-based compounds such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; aminobenzophenone compounds such as Michler's ketone and 4,4'-diethylaminobenzophenone; 10-Butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2 -(4-methylphenylsulfonyl)propan-1-one etc. are mentioned. These photoinitiators (D) may be used by 1 type, and may be used together 2 or more types.

또한, 상기 광증감제(E)로서는, 예를 들면, 디에탄올아민, N-메틸디에탄올아민, 트리부틸아민 등의 3급 아민 화합물, o-톨릴티오요소 등의 요소 화합물, 나트륨디에틸디티오포스페이트, s-벤질이소티우로늄-p-톨루엔설포네이트 등의 황 화합물 등을 들 수 있다.Moreover, as said photosensitizer (E), For example, tertiary amine compounds, such as diethanolamine, N-methyldiethanolamine, tributylamine, urea compounds, such as o-tolylthiourea, sodium diethyl dithi Sulfur compounds, such as ophosphate and s-benzylisothiuronium-p-toluenesulfonate, etc. are mentioned.

상기한 광중합개시제(D) 및 광증감제(E)의 사용량은, 본 발명의 활성 에너지선 경화성 조성물 중의 상기 활성 에너지선 경화성 화합물(A) 100질량부에 대하여, 각각 0.05∼20질량부가 바람직하고, 0.5∼10질량%가 보다 바람직하다.The amount of the photoinitiator (D) and the photosensitizer (E) used is preferably 0.05 to 20 parts by mass, respectively, with respect to 100 parts by mass of the active energy ray-curable compound (A) in the active energy ray-curable composition of the present invention. , 0.5-10 mass % is more preferable.

본 발명의 활성 에너지선 경화성 조성물에는, 상기한 성분(A)∼(E) 이외의 그 밖의 배합물로서, 용도, 요구 특성에 따라서, 중합금지제, 표면조정제, 대전방지제, 소포제, 점도조정제, 내광안정제, 내후안정제, 내열안정제, 자외선 흡수제, 산화방지제, 레벨링제, 유기 안료, 무기 안료, 안료분산제, 실리카 비드, 유기 비드 등의 첨가제; 산화규소, 산화알루미늄, 산화티타늄, 지르코니아, 오산화안티몬 등의 무기 충전제 등을 배합할 수 있다. 이들 그 밖의 배합물은, 1종으로 사용할 수도 있고 2종 이상 병용할 수도 있다.In the active energy ray-curable composition of the present invention, as other formulations other than the above-described components (A) to (E), depending on the use and required properties, a polymerization inhibitor, a surface control agent, an antistatic agent, an antifoaming agent, a viscosity modifier, a light resistance additives such as stabilizers, weathering stabilizers, heat stabilizers, ultraviolet absorbers, antioxidants, leveling agents, organic pigments, inorganic pigments, pigment dispersants, silica beads and organic beads; Inorganic fillers, such as a silicon oxide, aluminum oxide, a titanium oxide, zirconia, and antimony pentoxide, etc. can be mix|blended. These other combinations may be used alone or in combination of two or more.

본 발명의 필름은, 필름 기재의 적어도 1면에, 본 발명의 활성 에너지선 경화성 조성물을 도공하고, 그 후 활성 에너지선을 조사해서 경화 도막으로 함으로써 얻어진 것이다.The film of this invention is obtained by coating the active energy ray-curable composition of this invention on at least 1 surface of a film base material, irradiating an active energy ray after that, and setting it as a cured coating film.

본 발명의 필름에서 사용하는 상기 필름 기재의 재질로서는, 투명성이 높은 수지가 바람직하며, 예를 들면, 폴리에틸렌테레프탈레이트, 폴리부틸렌테레프탈레이트, 폴리에틸렌나프탈레이트 등의 폴리에스테르계 수지; 폴리프로필렌, 폴리에틸렌, 폴리메틸펜텐-1 등의 폴리올레핀계 수지; 셀룰로오스아세테이트(디아세틸셀룰로오스, 트리아세틸셀룰로오스 등), 셀룰로오스아세테이트프로피오네이트, 셀룰로오스아세테이트부티레이트, 셀룰로오스아세테이트프로피오네이트부티레이트, 셀룰로오스아세테이트프탈레이트, 질산셀룰로오스 등의 셀룰로오스계 수지; 폴리메틸메타크릴레이트 등의 아크릴계 수지; 폴리염화비닐, 폴리염화비닐리덴 등의 염화비닐계 수지; 폴리비닐알코올; 에틸렌-아세트산비닐 공중합체; 폴리스티렌; 폴리아미드; 폴리카보네이트; 폴리설폰; 폴리에테르설폰; 폴리에테르에테르케톤; 폴리이미드, 폴리에테르이미드 등의 폴리이미드계 수지; 노르보르넨계 수지(예를 들면, 니혼제온가부시키가이샤제 「제오노아」), 변성 노르보르넨계 수지(예를 들면, JSR가부시키가이샤제 「아톤」), 환상 올레핀 공중합체(예를 들면, 미쓰이가가쿠가부시키가이샤제 「아펠」) 등을 들 수 있다. 또한, 이들 수지로 이루어지는 기재를 2종 이상 첩합한 것을 사용해도 상관없다.As a material of the said film base material used in the film of this invention, resin with high transparency is preferable, For example, Polyester-type resin, such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin resins such as polypropylene, polyethylene, and polymethylpentene-1; Cellulose resins, such as cellulose acetate (diacetyl cellulose, triacetyl cellulose, etc.), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, and cellulose nitrate; acrylic resins such as polymethyl methacrylate; vinyl chloride-based resins such as polyvinyl chloride and polyvinylidene chloride; polyvinyl alcohol; ethylene-vinyl acetate copolymer; polystyrene; polyamide; polycarbonate; polysulfone; polyethersulfone; polyether ether ketone; polyimide-based resins such as polyimide and polyetherimide; Norbornene-based resin (for example, “Zeonoa” manufactured by Nippon Zeon Corporation), modified norbornene-based resin (eg, “Aton” manufactured by JSR Corporation), cyclic olefin copolymer (eg, Mitsui Chemicals Co., Ltd. "Apel") etc. are mentioned. Moreover, you may use what bonded 2 or more types of base materials which consist of these resins together.

또한, 상기 필름 기재는, 필름상이어도 되며 시트상이어도 되고, 그 두께는, 20∼500㎛의 범위가 바람직하다. 또한, 필름상의 기재 필름을 사용하는 경우에는, 그 두께는, 20∼200㎛의 범위가 바람직하고, 30∼150㎛의 범위가 보다 바람직하고, 40∼130㎛의 범위가 더 바람직하다. 필름 기재의 두께를 당해 범위로 함으로써, 필름의 편면에, 본 발명의 활성 에너지선 경화성 조성물에 의해 하드코트층을 마련한 경우에도 컬을 억제하기 쉬워진다.Moreover, a film form or a sheet form may be sufficient as the said film base material, and the range of the thickness of 20-500 micrometers is preferable. Moreover, when using a film-form base film, the range of 20-200 micrometers is preferable, as for the thickness, the range of 30-150 micrometers is more preferable, and the range of 40-130 micrometers is still more preferable. By making the thickness of a film base material into the said range, even when a hard-coat layer is provided in the single side|surface of a film with the active energy ray-curable composition of this invention, it becomes easy to suppress curl.

상기 필름 기재에 본 발명의 활성 에너지선 경화성 조성물을 도공하는 방법으로서는, 예를 들면, 다이 코트, 마이크로 그라비어 코트, 그라비어 코트, 롤 코트, 콤마 코트, 에어나이프 코트, 키스 코트, 스프레이 코트, 딥 코트, 스피너 코트, 브러쉬 도포, 실크 스크린에 의한 솔리드 코트, 와이어바 코트, 플로 코트 등을 들 수 있다.As a method of coating the active energy ray-curable composition of the present invention on the film substrate, for example, die coat, micro gravure coat, gravure coat, roll coat, comma coat, air knife coat, kiss coat, spray coat, dip coat , spinner coat, brush application, solid coat by silk screen, wire bar coat, flow coat, and the like.

또한, 본 발명의 활성 에너지선 경화성 조성물을 상기 기재 필름에 도공한 후, 활성 에너지선을 조사하기 전에, 유기 용매(C)를 휘발시키는 것이 바람직하다. 가열 건조의 조건으로서는, 유기 용제(C)가 휘발하는 조건이면, 특히 한정하지 않지만, 통상은, 온도 50∼100℃의 범위에서, 시간은 0.5∼10분의 범위에서 가열 건조하는 것이 바람직하다.Moreover, after coating the active energy ray-curable composition of this invention to the said base film, before irradiating an active energy ray, it is preferable to volatilize an organic solvent (C). Although it will not specifically limit as conditions for heat-drying as long as it is the conditions which the organic solvent (C) volatilizes, Usually, it is the range of the temperature of 50-100 degreeC, and it is preferable to heat-dry in the range of 0.5 to 10 minutes for time.

본 발명의 활성 에너지선 경화성 조성물을 경화시키는 활성 에너지선으로서는, 상기한 바와 같이, 자외선, 전자선, α선, β선, γ선 등의 전리 방사선이다. 여기에서, 활성 에너지선으로서 자외선을 사용할 경우, 그 자외선을 조사하는 장치로서는, 예를 들면, 저압 수은 램프, 고압 수은 램프, 초고압 수은 램프, 메탈할라이드 램프, 무전극 램프(퓨전 램프), 케미컬 램프, 블랙라이트 램프, 수은-제논 램프, 쇼트 아크등, 헬륨·카드뮴 레이저, 아르곤 레이저, 태양광, LED 램프 등을 들 수 있다.As an active energy ray which hardens the active energy ray-curable composition of this invention, as mentioned above, they are ionizing radiation, such as an ultraviolet-ray, an electron beam, an alpha ray, a beta ray, and a gamma ray. Here, when using ultraviolet rays as an active energy ray, as an apparatus for irradiating the ultraviolet rays, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an electrodeless lamp (fusion lamp), a chemical lamp. , a black light lamp, a mercury-xenon lamp, a short arc lamp, a helium-cadmium laser, an argon laser, sunlight, an LED lamp, and the like.

상기 필름 기재 상에 본 발명의 활성 에너지선 경화성 조성물의 경화 도막을 형성할 때의 경화 도막의 막두께는, 경화 도막의 경도를 충분한 것으로 하며, 또한 도막의 경화 수축에 의한 필름의 컬을 억제할 수 있으므로, 1∼30㎛의 범위가 바람직하지만, 3∼15㎛의 범위가 보다 바람직하고, 4∼10㎛의 범위가 더 바람직하다.The film thickness of the cured coating film at the time of forming the cured coating film of the active energy ray-curable composition of the present invention on the film substrate is such that the hardness of the cured coating film is sufficient, and the curl of the film due to curing shrinkage of the coating film is suppressed. Therefore, although the range of 1-30 micrometers is preferable, the range of 3-15 micrometers is more preferable, and the range of 4-10 micrometers is still more preferable.

(실시예)(Example)

이하에 실시예에 의해 본 발명을 보다 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail by way of Examples.

(제조예 1 : 지환 구조 및 4급 암모늄염을 갖는 수지(B-1)의 제조)(Production Example 1: Preparation of resin (B-1) having an alicyclic structure and a quaternary ammonium salt)

교반 장치, 환류 냉각관 및 질소 도입관을 구비한 플라스크 중에, 질소 가스를 도입해서, 플라스크 내의 공기를 질소 가스로 치환했다. 그 후, 플라스크에 2-(메타크릴로일옥시)에틸트리메틸암모늄클로라이드 54.7질량부, 시클로헥실메타크릴레이트 19.9질량부, 메톡시폴리에틸렌글리콜메타크릴레이트(니찌유가부시키가이샤제 「브렌마 PME-1000」; 반복 단위수 n≒23, 분자량 1,000) 24.9질량부, 메타크릴산 0.5질량부, 메탄올 50질량부 및 PGME 10질량부를 더했다. 다음으로, 중합개시제(아조비스이소부티로니트릴) 0.1질량부를 프로필렌글리콜모노메틸에테르(이하 「PGME」로 약기한다) 2.4질량부로 용해한 용액을 30분 걸쳐서 적하한 후, 65℃에서 3시간 반응시켰다. 다음으로, 메탄올을 더해서 희석하고, 지환 구조 및 4급 암모늄염을 갖는 수지(B-1)의 45질량% 용액을 얻었다. 얻어진 수지(B-1)의 중량 평균 분자량은 1만이었다.Nitrogen gas was introduced into a flask equipped with a stirring device, a reflux cooling tube, and a nitrogen introduction tube, and the air in the flask was replaced with nitrogen gas. Then, 54.7 parts by mass of 2-(methacryloyloxy)ethyltrimethylammonium chloride, 19.9 parts by mass of cyclohexyl methacrylate, and methoxypolyethylene glycol methacrylate (“Brenma PME- 1000"; repeating unit number n≒23, molecular weight 1,000) 24.9 mass parts, methacrylic acid 0.5 mass parts, methanol 50 mass parts, and PGME 10 mass parts were added. Next, a solution in which 0.1 parts by mass of a polymerization initiator (azobisisobutyronitrile) was dissolved in 2.4 parts by mass of propylene glycol monomethyl ether (hereinafter abbreviated as “PGME”) was added dropwise over 30 minutes, followed by reaction at 65° C. for 3 hours. . Next, methanol was added and diluted, and the 45 mass % solution of resin (B-1) which has an alicyclic structure and a quaternary ammonium salt was obtained. The weight average molecular weight of the obtained resin (B-1) was 10,000.

상기에서 얻어진 수지(B-1)의 중량 평균 분자량은, 겔·퍼미에이션·크로마토그래피(GPC)법에 의해, 하기의 조건에서 측정했다.The weight average molecular weight of resin (B-1) obtained above was measured by the gel permeation chromatography (GPC) method on the following conditions.

측정 장치 : 고속 GPC 장치(도소가부시키가이샤제 「HLC-8220GPC」)Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)

칼럼 : 도소가부시키가이샤제의 하기의 칼럼을 직렬로 접속해서 사용했다.Column: The following columns manufactured by Tosoh Corporation were connected in series and used.

「TSKgel G5000」(7.8㎜I.D.×30㎝)×1개 「TSKgel G5000」(7.8mmI.D.×30cm)×1

「TSKgel G4000」(7.8㎜I.D.×30㎝)×1개 「TSKgel G4000」(7.8mmI.D.×30cm)×1

「TSKgel G3000」(7.8㎜I.D.×30㎝)×1개 「TSKgel G3000」(7.8mmI.D.×30cm)×1

「TSKgel G2000」(7.8㎜I.D.×30㎝)×1개 「TSKgel G2000」(7.8mmI.D.×30cm)×1

검출기 : RI(시차 굴절계)Detector: RI (Differential Refractometer)

칼럼 온도 : 40℃Column temperature: 40℃

용리액 : 테트라히드로퓨란(THF)Eluent: tetrahydrofuran (THF)

유속 : 1.0mL/분Flow rate: 1.0mL/min

주입량 : 100μL(시료 농도 0.4질량%의 테트라히드로퓨란 용액)Injection volume: 100 µL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)

표준 시료 : 하기의 표준 폴리스티렌을 사용해서 검량선을 작성했다.Standard sample: A calibration curve was prepared using the following standard polystyrene.

(표준 폴리스티렌)(standard polystyrene)

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 A-500」 "TSKgel standard polystyrene A-500" made by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 A-1000」 "TSKgel standard polystyrene A-1000" made by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 A-2500」 "TSKgel standard polystyrene A-2500" made by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 A-5000」 "TSKgel standard polystyrene A-5000" made by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 F-1」 "TSKgel standard polystyrene F-1" made by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 F-2」 "TSKgel standard polystyrene F-2" made by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 F-4」 "TSKgel standard polystyrene F-4" made by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 F-10」 "TSKgel standard polystyrene F-10" made by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 F-20」 "TSKgel standard polystyrene F-20" made by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 F-40」 "TSKgel standard polystyrene F-40" made by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 F-80」 "TSKgel standard polystyrene F-80" made by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 F-128」 "TSKgel standard polystyrene F-128" made by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 F-288」 "TSKgel standard polystyrene F-288" made by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 F-550」 "TSKgel standard polystyrene F-550" made by Tosoh Corporation

(실시예 1)(Example 1)

디펜타에리트리톨헥사아크릴레이트(이하 「DPHA」로 약기한다) 50질량부, 우레탄아크릴레이트(펜타에리트리톨테트라아크릴레이트와 이소포론디이소시아네이트와의 반응물, 고형분 100질량%, 이하 「UA1」로 약기한다) 50질량부, 제조예 1에서 얻어진 수지(C-1)의 45질량% 용액 2.2질량부(수지(C-1)로서 1질량부), 광중합개시제(BASF재팬가부시키가이샤 「이르가큐어 184」; 1-히드록시시클로헥실페닐케톤, 이하 「Irg184」로 약기한다) 5질량부, 디메틸아세트아미드(이하 「DMAC」로 약기한다) 85질량부, PGME 5질량부, 에탄올 8.5질량부, 메탄올 0.5질량부, n-프로판올 1질량부를 균일하게 혼합해서, 활성 에너지선 경화성 조성물(1)을 얻었다.50 parts by mass of dipentaerythritol hexaacrylate (hereinafter abbreviated as "DPHA"), urethane acrylate (a reaction product of pentaerythritol tetraacrylate and isophorone diisocyanate, solid content 100% by mass, hereinafter abbreviated as "UA1") ) 50 parts by mass, 2.2 parts by mass of a 45 mass % solution of the resin (C-1) obtained in Production Example 1 (1 part by mass as the resin (C-1)), a photopolymerization initiator (BASF Japan Co., Ltd. "Irgacure") 184"; 1-hydroxycyclohexylphenyl ketone, hereinafter abbreviated as "Irg184") 5 parts by mass, dimethylacetamide (hereinafter abbreviated as "DMAC") 85 parts by mass, PGME 5 parts by mass, ethanol 8.5 parts by mass; 0.5 mass part of methanol and 1 mass part of n-propanol were mixed uniformly, and the active energy ray-curable composition (1) was obtained.

(실시예 2)(Example 2)

DPHA 50질량부, UA1을 50질량부, 제조예 1에서 얻어진 수지(C-1)의 45질량% 용액 6.6질량부(수지(C-1)로서 3질량부), Irg184를 5질량부, DMAC 36질량부, 디메틸카보네이트(이하 「DMC」로 약기한다) 54질량부, 에탄올 8.5질량부, 메탄올 0.5질량부, n-프로판올 1질량부를 균일하게 혼합해서, 활성 에너지선 경화성 조성물(2)을 얻었다.50 parts by mass of DPHA, 50 parts by mass of UA1, 6.6 parts by mass of a 45 mass % solution of resin (C-1) obtained in Production Example 1 (3 parts by mass as resin (C-1)), 5 parts by mass of Irg184, DMAC 36 parts by mass, 54 parts by mass of dimethyl carbonate (hereinafter abbreviated as "DMC"), 8.5 parts by mass of ethanol, 0.5 parts by mass of methanol, and 1 part by mass of n-propanol were uniformly mixed to obtain an active energy ray-curable composition (2). .

(실시예 3)(Example 3)

DPHA 50질량부, UA1을 50질량부, 제조예 1에서 얻어진 수지(C-1)의 45질량% 용액 11.1질량부(수지(C-1)로서 5질량부), Irg184를 5질량부, DMAC 10질량부, 메틸에틸케톤(이하 「MEK」로 약기한다) 30질량부, DMC 60질량부를 균일하게 혼합해서, 활성 에너지선 경화성 조성물(3)을 얻었다.50 parts by mass of DPHA, 50 parts by mass of UA1, 11.1 parts by mass of a 45 mass % solution of resin (C-1) obtained in Production Example 1 (5 parts by mass as resin (C-1)), 5 parts by mass of Irg184, DMAC 10 parts by mass, 30 parts by mass of methyl ethyl ketone (hereinafter abbreviated as "MEK"), and 60 parts by mass of DMC were uniformly mixed to obtain an active energy ray-curable composition (3).

(실시예 4)(Example 4)

DPHA 70질량부, MIWON사제 「MIRAMER HR6042」(굴절률 : 1.618, 이하 「HR6042」로 약기한다) 30질량부, 제조예 1에서 얻어진 수지(C-1)의 45질량% 용액 6.6질량부(수지(C-1)로서 3질량부), Irg184를 5질량부, DMAC 100질량부를 균일하게 혼합해서, 활성 에너지선 경화성 조성물(4)을 얻었다.70 parts by mass of DPHA, 30 parts by mass of "MIRAMER HR6042" manufactured by MIWON (refractive index: 1.618, hereinafter abbreviated as "HR6042"), 6.6 parts by mass of a 45 mass % solution of the resin (C-1) obtained in Production Example 1 (resin ( As C-1), 3 mass parts), 5 mass parts of Irg184, and DMAC 100 mass parts were mixed uniformly, and the active-energy-ray-curable composition (4) was obtained.

(비교예 1)(Comparative Example 1)

DPHA 50질량부, UA1을 50질량부, 제조예 1에서 얻어진 수지(C-1)의 45질량% 용액 11.1질량부(수지(C-1)로서 5질량부), Irg184를 5질량부, MEK 100질량부를 균일하게 혼합해서, 활성 에너지선 경화성 조성물(R1)을 얻었다.50 parts by mass of DPHA, 50 parts by mass of UA1, 11.1 parts by mass of a 45 mass % solution of resin (C-1) obtained in Production Example 1 (5 parts by mass as resin (C-1)), 5 parts by mass of Irg184, MEK 100 parts by mass was uniformly mixed to obtain an active energy ray-curable composition (R1).

(비교예 2)(Comparative Example 2)

MEK를 DMC로 변경한 이외는, 비교예 1과 마찬가지로 해서 활성 에너지선 경화성 조성물(R2)을 얻었다.Except having changed MEK into DMC, it carried out similarly to the comparative example 1, and obtained the active energy ray-curable composition (R2).

(비교예 3)(Comparative Example 3)

MEK 100질량부를, 메틸이소부틸케톤(이하 「MIBK」로 약기한다) 90질량부, 에탄올 8.5질량부, 메탄올 0.5질량부, n-프로판올 1질량부로 변경한 이외는, 비교예 1과 마찬가지로 해서 활성 에너지선 경화성 조성물(R3)을 얻었다.Active in the same manner as in Comparative Example 1, except that 100 parts by mass of MEK was changed to 90 parts by mass of methyl isobutyl ketone (hereinafter abbreviated as "MIBK"), 8.5 parts by mass of ethanol, 0.5 parts by mass of methanol, and 1 part by mass of n-propanol. An energy ray-curable composition (R3) was obtained.

상기한 실시예 1∼4 및 비교예 1∼3에서 얻어진 활성 에너지선 경화성 조성물(1)∼(4), (R1)∼(R3)을 사용해서, 하기의 시험, 측정을 행했다.The following test and measurement were performed using the active energy ray-curable compositions (1)-(4) and (R1)-(R3) obtained in Examples 1-4 and Comparative Examples 1-3 mentioned above.

[평가용 샘플의 제작][Production of samples for evaluation]

활성 에너지선 경화성 조성물을, 두께 60㎛의 트리아세틸셀룰로오스(TAC) 필름(후지필름가부시키가이샤제)에, 바 코터로 막두께 5㎛로 되도록 도공하고, 60℃에서 1.5분간 건조한 후, 공기 분위기 하에서 자외선 조사 장치(아이그래픽스가부시키가이샤제, 고압 수은 램프)를 사용해서 적산 광량 3kJ/㎡로 조사하여, 경화 도막을 갖는 TAC 필름을 평가용 샘플로서 얻었다.The active energy ray-curable composition was coated on a 60 µm-thick triacetyl cellulose (TAC) film (manufactured by FUJIFILM CO., LTD.) to a film thickness of 5 µm with a bar coater, dried at 60°C for 1.5 minutes, and then dried in an air atmosphere. It irradiated with the accumulated light amount 3kJ/m<2> using the ultraviolet irradiation apparatus (The Eye Graphics Co., Ltd. make, high pressure mercury lamp) under the conditions, and the TAC film which has a cured coating film was obtained as a sample for evaluation.

[표면 저항값의 측정(대전방지성의 평가)][Measurement of surface resistance value (evaluation of antistatic property)]

상기에서 얻어진 평가용 샘플의 경화 도막의 표면에 대하여, JIS 시험 방법K6911-1995에 준거해서, 고저항률계(가부시키가이샤미쓰비시가가쿠애널리텍제 「하이레스터UP MCP-HT450」)를 사용해서, 인가 전압 500V, 측정 시간 10초로 표면 저항값을 측정했다.With respect to the surface of the cured coating film of the evaluation sample obtained above, in accordance with JIS test method K6911-1995, using a high resistivity meter ("Hirester UP MCP-HT450" manufactured by Mitsubishi Chemical Analytech Co., Ltd.), The surface resistance value was measured with the applied voltage 500V and the measurement time of 10 second.

[내수성의 평가 방법][Water resistance evaluation method]

활성 에너지선 경화성 조성물에 각각 정제수 1질량% 및 2질량% 첨가해서 균일하게 혼합 후, 외관을 목시 평가하고 이하와 같이 판별했다.After adding 1 mass % and 2 mass % of purified water to an active energy ray-curable composition, respectively, and mixing uniformly, the external appearance was visually evaluated and it discriminated as follows.

「○」 : 투명 액상이며 침전 없음 「○」: Transparent liquid, no precipitation

「△」 : 약간 백탁 「△」 : Slightly cloudy

「×」 : 백탁 혹은, 겔화 또는, 침전 등 발생 "X": Occurrence of cloudiness, gelation, precipitation, etc.

[전광선 투과율의 측정][Measurement of total light transmittance]

상기에서 얻어진 평가용 샘플에 대하여, 니혼덴쇼쿠가부시키가이샤제 「Haze Meter(형식 번호 NDH2000)」를 사용해서 전광선 투과율을 측정했다.About the sample for evaluation obtained above, the Nippon Denshoku Co., Ltd. make "Haze Meter (model number NDH2000)" was used, and the total light transmittance was measured.

[표 1][Table 1]

Figure 112019084538608-pct00002
Figure 112019084538608-pct00002

[표 2][Table 2]

Figure 112019084538608-pct00003
Figure 112019084538608-pct00003

표 1에 나타낸 평가 결과로부터, 실시예 1∼4의 본 발명의 활성 에너지선 경화성 조성물의 경화 도막은, 대전방지성이 높으며, 또한, 우수한 내수성을 갖는 것을 확인할 수 있었다.From the evaluation results shown in Table 1, it was confirmed that the cured coating films of the active energy ray-curable compositions of the present invention of Examples 1 to 4 had high antistatic properties and excellent water resistance.

한편, 비교예 1∼3은, 유기 용제(C)로서, 디메틸아세트아미드를 사용한 태양이지만, 모두 내수성이 불량이었다. 또한, 비교예 3은, 표면 저항값이 10의 13승을 초과하여 있고, 대전방지성이 떨어지는 것도 확인되었다.On the other hand, Comparative Examples 1 to 3 were embodiments in which dimethylacetamide was used as the organic solvent (C), but all had poor water resistance. Moreover, in Comparative Example 3, the surface resistance value exceeded 10 to the 13th power, and it was also confirmed that the antistatic property was inferior.

Claims (7)

활성 에너지선 경화성 화합물(A)과, 지환 구조 및 4급 암모늄염을 갖는 수지(B)와, 디메틸아세트아미드를 포함하는 유기 용제(C)를 함유하는 것을 특징으로 하는 활성 에너지선 경화성 조성물.The active energy ray-curable compound (A), the resin (B) which has an alicyclic structure and a quaternary ammonium salt, and the organic solvent (C) containing dimethylacetamide are contained, The active-energy-ray-curable composition characterized by the above-mentioned. 제1항에 있어서,
상기 디메틸아세트아미드의 함유량이, 상기 활성 에너지선 경화성 화합물(A) 100질량부에 대해서, 5∼200질량부의 범위인 활성 에너지선 경화성 조성물.The method of claim 1,
The active energy ray-curable composition whose content of the said dimethylacetamide is the range of 5-200 mass parts with respect to 100 mass parts of said active-energy-ray-curable compounds (A). 제1항에 있어서,
상기 활성 에너지선 경화성 화합물(A)이, 다관능 (메타)아크릴레이트(A1), 우레탄(메타)아크릴레이트(A2), 및, 굴절률이 1.55 이상인 고굴절률 중합성 단량체(A3)로 이루어지는 군에서 선택되는 1종 이상인 활성 에너지선 경화성 조성물.The method of claim 1,
The active energy ray-curable compound (A) is a polyfunctional (meth)acrylate (A1), a urethane (meth)acrylate (A2), and a high refractive index polymerizable monomer (A3) having a refractive index of 1.55 or more. At least one selected active energy ray-curable composition. 제1항에 있어서,
상기 수지(B)가, 원료로서 지환 구조를 갖는 중합성 단량체(b1)를 5∼40질량% 사용한 중합체인 활성 에너지선 경화성 조성물.The method of claim 1,
The active energy ray-curable composition in which the said resin (B) is a polymer which used 5-40 mass % of polymerizable monomers (b1) which have an alicyclic structure as a raw material. 제1항에 있어서,
상기 수지(B)의 배합량이, 활성 에너지선 경화성 화합물(A) 100질량부에 대해서, 0.1∼30질량부의 범위인 활성 에너지선 경화성 조성물.The method of claim 1,
The active energy ray-curable composition in which the compounding quantity of the said resin (B) is the range of 0.1-30 mass parts with respect to 100 mass parts of active energy ray-curable compounds (A). 제1항 내지 제5항 중 어느 한 항에 기재된 활성 에너지선 경화성 조성물에 의해 형성된 것을 특징으로 하는 경화물.Hardened|cured material formed of the active energy ray-curable composition in any one of Claims 1-5, The hardened|cured material characterized by the above-mentioned. 제1항 내지 제5항 중 어느 한 항에 기재된 활성 에너지선 경화성 조성물의 경화 도막을 갖는 것을 특징으로 하는 필름.It has a cured coating film of the active energy ray-curable composition in any one of Claims 1-5, The film characterized by the above-mentioned.
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