KR20190124219A - 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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KR20190124219A
KR20190124219A KR1020197024169A KR20197024169A KR20190124219A KR 20190124219 A KR20190124219 A KR 20190124219A KR 1020197024169 A KR1020197024169 A KR 1020197024169A KR 20197024169 A KR20197024169 A KR 20197024169A KR 20190124219 A KR20190124219 A KR 20190124219A
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시게토시 니시자와
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디아이씨 가부시끼가이샤
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    • C08F222/106—Esters of polycondensation macromers
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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
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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.This invention contains an active energy ray curable compound (A), resin (B) which has alicyclic structure and a quaternary ammonium salt, and the organic solvent (C) containing dimethyl acetamide, The active energy ray curable characterized by the above-mentioned. It is to provide a composition. Moreover, it is providing the film which has the hardened | cured material of the said active energy ray curable composition of this invention, and a cured coating film. As for content of the said dimethyl acetamide, 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 generate turbidity, gelation, and precipitation, and therefore, a hard coat having excellent continuous productivity from excellent water resistance of the coating liquid against moisture and condensation in the air, and excellent antistatic property. It is 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.The anti-reflective (LR) film used for flat panel display (FPD) surfaces, such as a liquid crystal display (LCD), an organic electroluminescent display (OLED), and a plasma display (PDP), forms two layers with a large refractive index difference on a film base material. This is achieved by a multilayer structure (base material / high refractive index layer / low refractive index layer). These layers are required to have high scratch resistance in order to prevent scratches in the manufacturing process of the antireflection film, and also to have high antistatic properties in order to prevent contamination and blocking of the film. Moreover, since an 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.It is proposed to use the material which mix | blended the resin which has quaternary ammonium salt as a method of providing antistatic property among the said requested | required characteristics (for example, refer patent documents 1-3). However, quaternary ammonium salts have high hydrophilicity, poor compatibility with hydrophobic active energy ray-curable compositions, and have a problem of whitening of the coating film and poor appearance.

일본 특개2012-102166호 공보Japanese Patent Application Laid-Open No. 2012-102166 일본 특개2008-013636호 공보Japanese Patent Application 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 which has an excellent antistatic property and can form a hard coat layer having excellent water resistance that does not become cloudy and does not cause poor appearance even when water is mixed. 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.This invention contains an active energy ray curable compound (A), resin (B) which has alicyclic structure and a quaternary ammonium salt, and the organic solvent (C) containing dimethylacetamide, The active energy ray curable It is 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 a water resistance that is hard to be cloudy even when water is mixed during coating, and furthermore, after curing, a hard coat layer having excellent antistatic property is provided on the surface of the film. 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 used for 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 it is excellent antistatic property also when using for these uses, adhesion of dust etc. can be suppressed. Moreover, when this film is used for a liquid crystal display etc., malfunction of the display by the generated static electricity can also 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 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), and a high refractive index polymerizable monomer (A3) having an index of refraction of 1.55 or higher, and epoxy. (Meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, etc. are mentioned. These may be used independently or may use 2 or more types together. As said active energy ray curable compound (A), polyfunctional (meth) acrylate (A1) and urethane (meth) acrylate are obtained from the point which the scratch resistance, hard coat property, water resistance, and transparency of the cured coating film which is further excellent are obtained. It is preferable to use 1 or more types chosen from the group which consists of (A2) and the high refractive index polymerizable monomer (A3) whose refractive index is 1.55 or more, and polyfunctional (meth) acrylate (A1) and urethane (meth) acryl A combination with a rate (A2) or a combination of a polyfunctional (meth) acrylate (A1) and a 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 an acrylate and a 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. As a specific example of this polyfunctional (meth) acrylate (a1), 1, 4- butanediol di (meth) acrylate, 3-methyl- 1, 5- pentanediol di (meth) acrylate, 1, 6- hexanediol Di (meth) acrylate, neopentyl glycoldi (meth) acrylate, 2-methyl-1,8-octanedioldi (meth) acrylate, 2-butyl-2-ethyl-1,3-propanedioldi ( Meta) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di Di (meth) acrylate of dihydric alcohols, such as (meth) acrylate and tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and tris (2) Di (meth) acrylate, neopentylglycol of hydroxyethyl) isocyanurate Di (meth) acrylate of diol obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of recall, di (meth) acrylate of diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A , Trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethyl All propane tetra (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerytate Lithitol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol 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 scratch resistance of the cured coating film of the active-energy-ray-curable composition of this invention improves, dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta ( It is preferable to use 1 or more types of compounds chosen from the group which consists of a meta) acrylate, a pentaerythritol tetra (meth) acrylate, and a pentaerythritol tri (meth) acrylate, and it is dipentaerythritol hexa (meth). ) Acrylate is more preferred.

상기 우레탄(메타)아크릴레이트(A2)는, 폴리이소시아네이트(a2-1)와 수산기를 갖는 (메타)아크릴레이트(a2-2)와의 반응물 등을 사용할 수 있다.As the urethane (meth) acrylate (A2), a reactant of a polyisocyanate (a2-1) and a (meth) acrylate (a2-2) having a hydroxyl group 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), Aliphatic polyisocyanate is preferable because coloring of the cured coating film of the active-energy-ray-curable composition of this invention can be reduced.

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 consists of aliphatic hydrocarbons. Specific examples of the aliphatic polyisocyanate include aliphatic polyisocyanates 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- diisocyanato cyclohexane, etc. are mentioned. Moreover, the trimer which trimerized the said aliphatic polyisocyanate or alicyclic polyisocyanate can also be used as said aliphatic polyisocyanate. In addition, these aliphatic polyisocyanate may be used 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.In order to improve the scratch resistance of a coating film among the said aliphatic polyisocyanate, it is preferable to use 1 or more types chosen from the group which consists of hexamethylene diisocyanate, norbornane diisocyanate, and isophorone diisocyanate, More preferred.

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.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, hydroxy pivalane neo Mono (meth) acrylates of dihydric alcohols such as pentyl glycol mono (meth) acrylate; Trimethylolpropanedi (meth) acrylate, ethylene oxide (EO) modified trimethylolpropane (meth) acrylate, propylene oxide (PO) modified trimethylolpropanedi (meth) acrylate, glycerin di (meth) acrylate, bis Hydroxyl group which modified | denatured mono or di (meth) acrylate of trihydric alcohols, such as (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or these alcoholic hydroxyl groups by (epsilon) -caprolactone Mono and di (meth) acrylates having; Compound which has monofunctional hydroxyl group and trifunctional or more (meth) acryloyl group, such as pentaerythritol tri (meth) acrylate, ditrimethylol propane tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate Or polyfunctional (meth) acrylate which has a hydroxyl group which modified this compound further with (epsilon) -caprolactone; (Meth) acrylates having oxyalkylene chains such as dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate ; (Meth) acrylate which has an oxyalkylene chain of block structure, such as polyethyleneglycol polypropylene glycol mono (meth) acrylate and polyoxybutylene-polyoxypropylene mono (meth) acrylate; (Meth) acrylate which has the oxyalkylene chain of random structures, such as a poly (ethylene glycol- tetramethylene glycol) mono (meth) acrylate and a poly (propylene glycol- tetramethylene glycol) mono (meth) acrylate, etc. are mentioned. have. These (meth) acrylates (a2-2) may be used by 1 type, or 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.Since the scratch resistance of the cured coating film of the active energy ray curable composition of this invention can be improved among the said urethane (meth) acrylate (A2), it is preferable to have four or more (meth) acryloyl groups in 1 molecule. . In order to make the urethane (meth) acrylate (A2) 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 it above. As such (meth) acrylate (a2-2), for example, trimethylolpropanedi (meth) acrylate, ethylene oxide modified trimethylolpropanedi (meth) acrylate, and propylene oxide modified trimethylolpropanedi (meth) ) Acrylate, glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) An acrylate, ditrimethylol propane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. are mentioned. 1 type may be used for these (meth) acrylates (a2-2) with respect to 1 type of the said aliphatic polyisocyanate, and may be used together 2 or more types. Moreover, among these (meth) acrylates (a2-2), since abrasion resistance can be improved further, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythrate 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 conventional method. Moreover, in order to promote the progress of a urethanation reaction, it is preferable to perform a urethanation reaction in presence of a urethanation catalyst. As said urethanization catalyst, For example, Amine compounds, such as a pyridine, a pyrrole, a triethylamine, a diethylamine, a dibutylamine; Phosphorus compounds such as triphenylphosphine and triethylphosphine; Organic tin compounds such as dibutyltin dilaurate, octyl tin trilaurate, octyl tin diacetate, dibutyl tin diacetate, and octylic acid tin, and organic zinc compounds such as zinc octylate.

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 be a high refractive index having a refractive index of 1.55 or more before curing. For example, an aromatic polymerizable monomer having 2 to 6 aromatic rings and a fluorene polymerizable polymer. A monomer etc. are mentioned preferably. Moreover, as a specific example of the said polymerizable monomer (A), the compound represented by following General formula (1); (meth) acrylate compounds having phenylbenzyl groups such as o-phenylbenzyl (meth) acrylate and p-phenylbenzyl (meth) acrylate; (Meth) acrylate compounds which have phenylphenol groups, such as phenylphenol EO acrylate; Such as propoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, bisphenol A di (meth) acrylate having an oxyethylene group, and bisphenol A tri (meth) acrylate having an oxyethylene group The bisphenol compound etc. which have a (meth) acryloyl group in the range of 2-4 are mentioned. These polymerizable monomers (A) may be used by 1 type and may be used together 2 or more types. Among these, the compound represented by following General formula (1), the (meth) acrylate compound which has a phenylbenzyl group from the point which can easily control a refractive index and can obtain a high refractive index even using the specific organic solvent mentioned later, and It is preferable to use 1 or more types of monomers chosen from the group which consists of a bisphenol compound which has a (meth) acryloyl group in the 2-4 range. As a commercial item which can be used as said polymerizable monomer (A3), "OGSOL EA-0200", "OGSOL EA-0300", "OGSOL GA-5060P" by the Osaka Chemical Co., Ltd .; "UNIDIC EKZ-948" and "UNIDIC EQS-1179" by DIC Corporation; "A-BPEF" by Shin-Nakamura Chemical Industries Co., Ltd., "MIRAMER HR6042" by MIWON Corporation, etc. are mentioned. These polymerizable monomers (A) may be used by 1 type and may be used together 2 or more types.

Figure pct00001
Figure pct00001

(식(1) 중, R1, R2은 각각 수소기 또는 메틸기를 나타내고, m, n은 각각 0∼5의 정수를 나타낸다)(In formula (1), R <1> , R <2> represents a hydrogen group or a methyl group, respectively, and m and n represent the integer of 0-5, respectively.)

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 a manufacturing method of the said resin (B), the polymerizable monomer (b1) and the said polymerizable monomer (b1) which have an alicyclic structure, and the polymerizable monomer (b2) which have a quaternary ammonium salt are essential components, for example. The method of copolymerizing a polymerizable monomer (b2) and a polymerizable monomer (b3) copolymerizable 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 polymerizable monomer (b1) is a polymerizable monomer having an alicyclic structure. As said alicyclic structure, For example, 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, a cyclodecane ring; Bicyclo undecane 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. Moreover, as a specific example of the said polymerizable monomer (c1), cyclohexyl (meth) acrylate, 1, 4- cyclohexane dimethanol mono (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl ( Meta) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like. These polymerizable monomers (b1) may be used by 1 type and may be used together 2 or more types.

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.Examples of the polymerizable monomer (b2) include a counter anion such as 2-[(meth) acryloyloxy] ethyltrimethylammonium chloride and 3-[(meth) acryloyloxy] propyltrimethylammonium chloride. To be; 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] propyltrimethylammoniummethylsulfonate, 2-[(meth) acryloyloxy] ethyltrimethylammoniummethylsulfate, 3-[(meth) acryloyloxy] Counter anions, such as propyl trimethylammonium methyl sulfate, are non-halogen type, etc. are mentioned. These polymerizable monomers (b2) may be used by 1 type and may be used together 2 or more types.

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.As said polymerizable monomer (b3), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) 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, lauoxy 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, nonyl phenoxy polypropylene glycol mono (meth) acrylate, nonyl phenoxy poly (ethylene glycol propylene glycol) mono ( Mono (meth) acrylates of polyalkylene glycols such as meth) acrylate; (Meth) acrylate etc. which have fluorinated alkyl groups, such as 2-perfluorohexylethyl (meth) acrylate, are mentioned. These polymerizable monomers (b3) may be used by 1 type and may be used together 2 or more types.

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, the mono (meth) acrylate of polyalkylene glycol is preferable, and methoxy polyethylene glycol Mono (meth) acrylate is more preferable. Moreover, the (meth) acrylate which has a fluorinated alkyl group is also preferable since there exists an effect which can improve antistatic property of the cured coating film of the active energy ray curable composition of this invention further.

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.Since the antistatic property of the cured coating film of the active-energy-ray-curable composition of this invention can further be improved among the mono (meth) acrylate of the said polyalkylene glycol, the raw material of the mono (meth) acrylate of the said polyalkylene glycol It is preferable that the number average molecular weight of the polyalkylene glycol used becomes the range of 200-8,000, It is more preferable that it is the range of 300-6,000, It is more preferable that it is the range of 400-4,000, It is the range of 400-2,000 Particularly 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 said polymerizable monomer (b1) in the raw material whole quantity of the said resin (B) can improve antistatic property of the cured coating film of the active energy ray curable composition of this invention more, the range of 5-40 mass% is Preferably, the range of 10-50 mass% is more preferable, and the range of 12-45 mass% is 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.Moreover, since the ratio of the said polymerizable monomer (b2) in the raw material whole quantity of the said resin (B) can improve antistatic property of the cured coating film of the active energy ray curable composition of this invention more, it is 30-90 mass% A 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.Moreover, when using the mono (meth) acrylate of the said polyalkylene glycol 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, As for the ratio of the mono (meth) acrylate of the polyalkylene glycol in the raw material whole quantity of the said resin (B), the range of 5-60 mass% is preferable, 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 range of 0.1-20 mass% is preferable, as for the ratio of the (meth) acrylate which has a fluorinated alkyl group in the raw material whole quantity of (B), the range of 0.5-10 mass% is more preferable, The range of 1-5 mass% More preferred.

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 antistatic property of the cured coating film of the active energy ray curable composition of this invention can further improve the weight average molecular weight of the said resin (B), the range of 1,000-100,000 is preferable, and the range of 2,000-50,000 is more preferable. And, the range of 3,000-30,000 is more preferable. 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 antistatic property of the cured coating film of the active energy ray curable composition of this invention more, 0.1-30 mass with respect to 100 mass parts of said active energy ray curable compounds (A). The range of a part is preferable, The range of 0.3-20 mass parts is more preferable, The range of 0.5-10 mass parts is 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 dimethyl acetamide. Since dimethylacetamide has good compatibility with the resin (B) and has a relatively high boiling point, even if water is mixed, the dimethylacetamide is completely mixed, and the polymer solubility is also high. Therefore, even when a hydrophilic and hydrophobic positive component is mixed, the dimethylacetamide evaporates in a drying step. Problems such as whitening and 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 dimethyl acetamide, since further excellent water resistance is obtained, 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 compounds (A), and the range of 7-150 mass parts is More preferred.

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, since it is further excellent water resistance, it is preferable that it is 3 mass% or more in an organic solvent (C), 5 mass% or more is more preferable, 7 mass% or more and 99 mass% or less More preferred.

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), hydrophobic solvents other than the said dimethylacetamide, 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.As the hydrophobic solvent, for example, diethyl ether, benzene, toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, xylene, n-butanol, dimethyl carbonate, diethyl carbonate, methyl Ethyl carbonate, chloroform, propylene glycol monomethyl ether acetate, and the like. These solvents may be used independently or may use 2 or more types together. As said hydrophobic solvent, the coating stability of an active-energy-ray-curable composition further improves, it can prevent that a cured coating film cracks, and can obtain the more excellent coating film external appearance, and it is 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 and tetrahydrofuran. , Tetrahydropyran, dimethylformamide, and the like. These solvents may be used independently or may use 2 or more types together. As the hydrophilic solvent, the coating stability of the active energy ray-curable composition can be further improved, and the cracking of the cured coating film can be prevented, and a superior coating film appearance can be obtained, and thus methanol, ethanol and n-propanol can be obtained. It is preferable to use 1 or more types chosen from the group which consists of propylene glycol monomethyl ether, and it uses together with methanol and propylene glycol monomethyl ether, or methanol, ethanol, n-propanol, and propylene glycol mono 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.In addition, in this invention, the said hydrophilic solvent shows the solvent whose solubility in water is 10 g / 100 ml or more, and what is other than this and the said dimethylacetamide becomes a hydrophobic solvent. Moreover, the solubility in water of the organic solvent shows the solubility in 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 said organic solvent (C), since the coating stability of an active-energy-ray-curable composition further improves, it can prevent that a hardening coating film cracks, and can obtain the more excellent coating film external appearance, It is preferable to use together with other hydrophilic solvents, or to use a combination of dimethylacetamide, another hydrophilic solvent, and a hydrophobic solvent.

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), as a usage-amount of the said hydrophilic solvent when using dimethyl acetamide and other hydrophilic solvents together, it 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, another hydrophilic solvent, and a hydrophobic solvent as said organic solvent (C), as a usage-amount of the said hydrophilic solvent, with respect to 100 mass parts of said active energy ray curable compounds (A), The range of 0.1-40 mass parts is preferable, The range of 3-25 mass parts is more preferable, The usage-amount of the said hydrophobic solvent has a range of 10-95 mass parts with respect to 100 mass parts of said active energy ray curable compounds (A). Preferably, 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 a 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.In addition, the active energy ray curable composition of this invention can be made into 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, (alpha) ray, (beta) ray, and (gamma) ray. When irradiating an ultraviolet-ray as an active energy ray and making it a cured coating film, it is preferable to add a photoinitiator (D) to the active energy ray curable composition of this invention, and to improve curability. Moreover, if necessary, a photosensitizer (E) can be further added and curability can be improved. On the other hand, in the case of using ionizing radiation such as electron beams, α rays, β rays, and γ rays, the curing is performed quickly without using a photopolymerization initiator (D) or a photosensitizer (E). Therefore, in particular, the photopolymerization initiator (D) or light It is not necessary to add the 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.As said photoinitiator (D), for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo {2-hydroxy-2-methyl-1- [4 -(1-methylvinyl) phenyl] propanone}, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy ) Phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 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 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, oxyphenylacetic acid 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester System compounds; Benzophenone, o-benzoylbenzoate methyl-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylated benzophenone, 3,3 ' Such as, 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, and 4-methylbenzophenone Benzophenone compounds; Thioxanthone compounds such as 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone and 2,4-dichloro thioxanthone; 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-methyl diethanolamine, and tributylamine, urea compounds, such as o-tolyl thiourea, sodium diethyl dithi Sulfur compounds such as phosphate and s-benzylisothiuronium-p-toluenesulfonate.

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.As for the usage-amount of said photoinitiator (D) and a photosensitizer (E), 0.05-20 mass parts respectively is preferable with respect to 100 mass parts of said active energy ray curable compounds (A) in the active energy ray curable composition of this 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 a compounding agent other than the above-mentioned components (A) to (E), depending on the use and required characteristics, a polymerization inhibitor, a surface conditioner, an antistatic agent, an antifoaming agent, a viscosity regulator, and a light resistance Additives such as stabilizers, weather stabilizers, heat stabilizers, ultraviolet absorbers, antioxidants, leveling agents, organic pigments, inorganic pigments, pigment dispersants, silica beads, organic beads; Inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, antimony pentoxide and the like can be blended. These other compound may be used by 1 type and may be used together 2 or more types.

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 one surface of a film base material, and irradiating an active energy ray after that to make 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 by the film of this invention, resin with high transparency is preferable, For example, Polyester-based resin, such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; Polyolefin resins such as polypropylene, polyethylene, and polymethylpentene-1; Cellulose resins such as cellulose acetate (diacetyl cellulose, triacetyl cellulose and the like), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate and cellulose nitrate; Acrylic resins such as polymethyl methacrylate; Vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; Polyvinyl alcohol; Ethylene-vinyl acetate copolymers; polystyrene; Polyamides; Polycarbonate; Polysulfones; Polyethersulfones; Polyether ether ketone; Polyimide resins such as polyimide and polyetherimide; Norbornene-based resin (e.g., "Zenooa" manufactured by Nippon Zeon Co., Ltd.), modified norbornene-based resin (e.g., "Aton" made by JSR Corporation), cyclic olefin copolymer (e.g., Mitsui Chemical Co., Ltd. "Apel") etc. are mentioned. Moreover, you may use what bonded two or more types of base materials which consist of these resin.

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 may be sufficient as the said film base material, and a sheet form may be sufficient, and the thickness has the preferable range of 20-500 micrometers. Moreover, when using a film-form base film, the thickness has the preferable range of 20-200 micrometers, The range of 30-150 micrometers is more preferable, The range of 40-130 micrometers is more preferable. By making the thickness of a film base material into the said range, curling becomes easy to be suppressed also when the hard coat layer is provided in the single side | surface of a film by the active energy ray curable composition of this invention.

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 this invention on the said film base material, it is a die coat, a micro gravure coat, a gravure coat, a roll coat, a comma coat, an air knife coat, a kiss coat, a spray coat, a dip coat, for example. And a spinner coat, brush coating, a silk coat solid coat, a wire bar coat, a 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, it is preferable to volatilize an organic solvent (C) before irradiating an active energy ray. The conditions for the heat drying are not particularly limited as long as the conditions are such that the organic solvent (C) is volatilized. Usually, it is preferable to heat-dry the time in the range of 0.5 to 10 minutes in the temperature range of 50 to 100 ° C.

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, it is ionizing radiation, such as an ultraviolet-ray, an electron beam, (alpha) ray, (beta) ray, (gamma) ray. Here, when ultraviolet rays are used as the active energy ray, as the device for irradiating the ultraviolet rays, for example, low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, electrodeless lamp (fusion lamp), chemical lamp And black light lamps, mercury-xenon lamps, short arc lamps, helium cadmium lasers, argon lasers, sunlight, and LED lamps.

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 this invention on the said film base material shall make sufficient hardness of a cured coating film, and can suppress the curl of the film by the cure shrinkage of a coating film. Since 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 more preferable.

(실시예)(Example)

이하에 실시예에 의해 본 발명을 보다 구체적으로 설명한다.The present invention will be described in more detail with reference to the following Examples.

(제조예 1 : 지환 구조 및 4급 암모늄염을 갖는 수지(B-1)의 제조)(Manufacture example 1: manufacture of resin (B-1) which has alicyclic structure and 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 introduce | transduced in the flask provided with the stirring apparatus, the reflux cooling tube, and the nitrogen inlet tube, and the air in the flask was replaced with nitrogen gas. Thereafter, 54.7 parts by mass of 2- (methacryloyloxy) ethyltrimethylammonium chloride, 19.9 parts by mass of cyclohexyl methacrylate, and methoxy polyethylene glycol methacrylate (Brenma PME-manufactured by Nichi Oil Corp.) 1000 "; repeating unit number n'23, molecular weight 1,000) 24.9 mass parts, methacrylic acid 0.5 mass part, 50 mass parts of methanol, and 10 mass parts of PGME were added. Next, the solution which melt | dissolved in the mass of 2.4 mass parts of propylene glycol monomethyl ether (hereinafter abbreviated as "PGME") of the polymerization initiator (azobisisobutyronitrile) was dripped over 30 minutes, and it was made to react at 65 degreeC for 3 hours. . Next, methanol was added and diluted, and the 45 mass% solution of resin (B-1) which has alicyclic structure and quaternary ammonium salt was obtained. The weight average molecular weight of 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 on the following conditions by the gel permeation chromatography (GPC) method.

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

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

「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 amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)

표준 시료 : 하기의 표준 폴리스티렌을 사용해서 검량선을 작성했다.Standard sample: The analytical curve was created using the following standard polystyrene.

(표준 폴리스티렌)(Standard polystyrene)

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

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

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

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

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

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

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

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

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

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

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

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

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

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 F-550」 "TSKgel standard polystyrene F-550" made by Toso 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 (reactant of pentaerythritol tetraacrylate and isophorone diisocyanate, solid content 100 mass%, abbreviated as "UA1" below) 50 parts by mass, 2.2 parts by mass of a 45% by mass solution of resin (C-1) obtained in Production Example 1 (1 part by mass as the resin (C-1)), a photopolymerization initiator (BASF Japan Co., Ltd. 184 ”, 1-hydroxycyclohexylphenyl ketone, abbreviated as" Irg184 "below, 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% by mass solution of resin (C-1) obtained in Production Example 1 (3 parts by mass as the resin (C-1)), 5 parts by mass of Irg184, and DMAC 36 mass parts, 54 mass parts of dimethyl carbonates (it abbreviates as "DMC" hereafter), 8.5 mass parts of ethanol, 0.5 mass part of methanol, and 1 mass part of n-propanol were mixed uniformly, and the active energy ray curable composition (2) was obtained. .

(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% by mass solution of resin (C-1) obtained in Production Example 1 (5 parts by mass as the resin (C-1)), 5 parts by mass of Irg184, and DMAC 10 mass parts, methyl ethyl ketone (it abbreviates as "MEK" hereafter) 30 mass parts, and DMC 60 mass parts were mixed uniformly, and the active energy ray curable composition (3) was obtained.

(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" (refractive index: 1.618, hereinafter abbreviated as "HR6042") manufactured by MIWON, 6.6 parts by mass of a 45% by mass solution of resin (C-1) obtained in Production Example 1 (resin ( 5 mass parts and 100 mass parts of DMAC were mixed uniformly as 3 mass parts) and Irg184 as C-1), 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% by mass solution of resin (C-1) obtained in Production Example 1 (5 parts by mass as the resin (C-1)), 5 parts by mass of Irg184, MEK 100 mass parts was mixed uniformly and the active energy ray curable composition (R1) was obtained.

(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 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.It is active similarly to Comparative Example 1 except having changed 100 mass parts of MEK into 90 mass parts of methyl isobutyl ketones (it abbreviates as "MIBK"), 8.5 mass parts of ethanol, 0.5 mass part of methanol, and 1 mass part 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 tests and measurements were performed using the active energy ray curable compositions (1) to (4) and (R1) to (R3) obtained in Examples 1 to 4 and Comparative Examples 1 to 3 described 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 is coated on a 60-μm-thick triacetyl cellulose (TAC) film (manufactured by Fujifilm Co., Ltd.) so as to have a thickness of 5 μm with a bar coater, and dried at 60 ° C. for 1.5 minutes, followed by an air atmosphere. It irradiated with the integrated light quantity of 3 kJ / m <2> using the ultraviolet irradiation device (Iggraphics make, high pressure mercury lamp) below, and obtained the TAC film which has a cured coating film as a sample for evaluation.

[표면 저항값의 측정(대전방지성의 평가)][Measurement of Surface Resistance (Evaluation of Antistatic)]

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.On the surface of the cured coating film of the sample for evaluation obtained above, based on JIS test method K6911-1995, using a high resistivity meter ("High Lester UP MCP-HT450" made by Mitsubishi Chemical Co., Ltd.). The surface resistance was measured at an applied voltage of 500 V and a measurement time of 10 seconds.

[내수성의 평가 방법][Evaluation method of water resistance]

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 it uniformly, visual appearance evaluated visually and discriminated as follows.

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

「△」 : 약간 백탁 "△": Slightly cloudy

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

[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 total light transmittance was measured using the "Haze Meter (model number NDH2000)" by the Nippon Denshoku Corporation.

[표 1]TABLE 1

Figure pct00002
Figure pct00002

[표 2]TABLE 2

Figure pct00003
Figure 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 result shown in Table 1, the cured coating film of the active-energy-ray-curable composition of this invention of Examples 1-4 confirmed that antistatic property was high and had the outstanding 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 1-3 were an aspect using dimethyl acetamide as an organic solvent (C), but all were poor in water resistance. In addition, in Comparative Example 3, it was confirmed that the surface resistance value exceeded 13 power of 10, and 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.An active energy ray curable composition comprising 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. 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). 제1항 또는 제2항에 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 according to claim 1 or 2,
In the group which the said active energy ray curable compound (A) consists of a polyfunctional (meth) acrylate (A1), a urethane (meth) acrylate (A2), and the high refractive index polymeric monomer (A3) whose refractive index is 1.55 or more. At least one active energy ray curable composition selected. 제1항 내지 제3항 중 어느 한 항에 있어서,
상기 수지(B)가, 원료로서 지환 구조를 갖는 중합성 단량체(b1)를 5∼40질량% 사용한 중합체인 활성 에너지선 경화성 조성물.The method according to any one of claims 1 to 3,
The active energy ray curable composition whose said resin (B) is a polymer using 5-40 mass% of polymerizable monomers (b1) which have alicyclic structure as a raw material. 제1항 내지 제4항 중 어느 한 항에 있어서,
상기 수지(B)의 배합량이, 활성 에너지선 경화성 화합물(A) 100질량부에 대해서, 0.1∼30질량부의 범위인 활성 에너지선 경화성 조성물.The method according to any one of claims 1 to 4,
The active energy ray curable composition whose 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 by the active-energy-ray-curable composition in any one of Claims 1-5. 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 of any one of Claims 1-5, The film characterized by the above-mentioned.
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