KR20190042451A - Active energy ray-curable composition and film using the same - Google Patents

Active energy ray-curable composition and film using the same Download PDF

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KR20190042451A
KR20190042451A KR1020180120170A KR20180120170A KR20190042451A KR 20190042451 A KR20190042451 A KR 20190042451A KR 1020180120170 A KR1020180120170 A KR 1020180120170A KR 20180120170 A KR20180120170 A KR 20180120170A KR 20190042451 A KR20190042451 A KR 20190042451A
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meth
active energy
energy ray
acrylate
compound
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KR102625535B1 (en
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시게토시 니시자와
가즈아키 오니와
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디아이씨 가부시끼가이샤
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    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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Abstract

The present invention provides an active energy ray-curable composition and a film using the same. The active energy ray-curable composition comprises an active energy ray-curable compound (A), a resin (B) having an alicyclic structure and a quaternary ammonium salt, a compound (C) which has the quaternary ammonium salt and does not have the alicyclic structure, and an organic solvent (D). A mass ratio [(B)/(C)] of the resin (B) to the compound (C) is preferably in a range of 5/95-40/60. A total mixing amount of the resin (B) and the compound (C) is preferably in a range of 1-10 parts by mass with respect to 100 parts by mass of the active energy ray-curable compound (A). The purpose of the present invention is to provide an active energy ray-curable composition which is capable of forming a hard coat layer having compatible both excellent antistatic properties and bleed resistance, and a film using the active energy ray-curable composition.

Description

활성 에너지선 경화성 조성물 및 그것을 사용한 필름{ACTIVE ENERGY RAY-CURABLE COMPOSITION AND FILM USING THE SAME}ACTIVE ENERGY RAY-CURABLE COMPOSITION AND FILM USING THE SAME [0002]

본 발명은, 활성 에너지선 경화성 조성물 및 그것을 사용한 필름에 관한 것이다.The present invention relates to an active energy ray curable composition and a film using the same.

각종 수지 필름은, 액정 디스플레이(LCD), 유기 EL 디스플레이(OLED), 플라스마 디스플레이(PDP) 등의 플랫패널 디스플레이(FPD) 표면의 흠집 방지용 필름, 자동차의 내외장용 가식 필름(시트), 창문용의 저반사 필름이나 열선컷 필름 등 각종 용도에 사용되고 있다. 그러나, 수지 필름 표면은 유연하며 내찰상성(耐擦傷性)이 낮기 때문에, 이것을 보충하는 목적으로, UV경화성 조성물 등으로 이루어지는 하드코트제를 필름 표면에 도공, 경화시켜 하드코트층을 필름 표면에 마련하는 것이 일반적으로 행해지고 있다. 하드코트층을 마련하는 공정을 개략하면, 롤상으로 감겨 있는 필름 원반으로부터 도공기에 송출되고, 하드코트제가 도공되고, 자외선 조사에 의해 경화해서 하드코트층을 형성한 후, 다시 롤상으로 권취(卷取)된다.Various types of resin films are widely used in various fields such as a film for preventing scratches 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), a decorative film And is used in various applications such as a low reflective film and a heat ray cut film. However, since the surface of the resin film is flexible and has low scratch resistance, a hard coat agent comprising a UV-curable composition or the like is coated and cured on the surface of the film to provide a hard coat layer on the film surface Is generally performed. If the process of providing the hard coat layer is outlined, the film is fed from the original film wound in a roll form to the coater, coated with a hard coat agent, cured by ultraviolet irradiation to form a hard coat layer, )do.

이 권취 공정에서 필름끼리의 마찰에 의해 필름 표면에 정전기가 발생하기 때문에, 재가공 시에 필름을 롤로부터 조출(繰出)했을 때에 필름끼리가 달라붙어 버리는 문제나 정전기에 의해 필름 표면에 먼지 등이 부착하기 쉬워지는 문제가 있었다. 또한, 이 필름을 액정 디스플레이 등에 사용했을 경우, 발생한 정전기에 의해 디스플레이가 오동작하는 문제도 있었다.Since static electricity is generated on the surface of the film by the friction between the films in the winding step, there is a problem that the films adhere to each other when the film is fed out from the roll at the time of reprocessing, There was a problem that became easier. Further, when the film is used for a liquid crystal display or the like, there is a problem that the display malfunctions due to the generated static electricity.

이 필름 표면에서의 정전기의 발생을 억제하기 위하여, 하드코트제에 대전방지제를 배합하는 방법이 일반적으로 행해지고 있다. 예를 들면, 폴리옥시에틸렌쇄와 4급 암모늄염을 갖는 화합물을 대전방지제로서 하드코트제에 배합하는 방법이 제안되어 있다(예를 들면, 특허문헌 1 참조).In order to suppress the generation of static electricity on the surface of the film, a method of mixing an antistatic agent with a hard coat agent is generally used. For example, a method of compounding a compound having a polyoxyethylene chain and a quaternary ammonium salt as an antistatic agent in a hard coat agent has been proposed (see, for example, Patent Document 1).

또한, 4급 암모늄염을 갖는 중합성 단량체를 원료로 한 2종의 공중합체를 대전방지제로서 하드코트제에 배합하는 방법이 제안되어 있다(예를 들면, 특허문헌 2 참조).Further, there has been proposed a method of compounding two kinds of copolymers having a quaternary ammonium salt-containing polymerizable monomer as raw materials in a hard coat agent as an antistatic agent (see, for example, Patent Document 2).

그러나, 이들 대전방지제를 배합한 하드코트제는, 대전 방지 성능이 충분하지는 않았다. 또한, 대전방지제를 다량으로 배합한 경우에는, 대전 방지 성능이 향상하지만, 습열 조건 하에서의 사용 후에 대전방지제의 블리드가 발생해 버리는 문제가 있었다.However, the hard coat agent containing these antistatic agents did not have sufficient antistatic performance. In addition, when a large amount of an antistatic agent is blended, the antistatic performance is improved, but bleeding of the antistatic agent occurs after use under a humid condition.

일본 특개2004-143303호 공보Japanese Patent Application Laid-Open No. 2004-143303 일본 특개2004-123924호 공보Japanese Patent Application Laid-Open No. 2004-123924

본 발명이 해결하려고 하는 과제는, 우수한 대전방지성, 및, 내블리드성을 양립한 하드코트층을 형성할 수 있는 활성 에너지선 경화성 조성물 및 그것을 사용한 필름을 제공하는 것이다.An object to be solved by the present invention is to provide an active energy ray curable composition capable of forming a hard coat layer having both excellent antistatic properties and anti-bleeding properties and a film using the same.

본 발명은, 활성 에너지선 경화성 화합물(A)과, 지환 구조 및 4급 암모늄염을 갖는 수지(B)와, 4급 암모늄염을 가지며, 또한 지환 구조를 갖지 않는 화합물(C)과, 유기 용제(D)를 함유하는 것을 특징으로 하는 활성 에너지선 경화성 조성물, 및, 그것을 사용한 필름을 제공하는 것이다.(B) a quaternary ammonium salt, a compound (C) having no alicyclic structure, and an organic solvent (D) having an aliphatic structure and a quaternary ammonium salt. ), And a film using the active energy ray curable composition.

본 발명의 활성 에너지선 경화성 조성물은, 필름 표면에 도공, 경화함으로써, 우수한 대전방지성, 및, 연필 경도를 갖는 하드코트층을 형성할 수 있다. 따라서, 본 발명의 활성 에너지선 경화성 조성물의 경화 도막은, 필름 표면에 정전기를 발생하는 것을 억제할 수 있다. 따라서, 각종 필름에, 달라붙음 방지, 정전기에 의한 먼지 등의 부착 방지 등의 기능을 부여할 수 있다. 따라서, 본 발명의 활성 에너지선 경화성 조성물의 경화 도막을 갖는 필름은, 롤상으로 권취할 때, 롤로부터 조출할 때에도, 달라붙음, 먼지 등의 부착 등의 트러블도 회피할 수 있기 때문에, 그 후의 핸들링이 우수한 필름을 제공할 수 있다. 또한, 본 발명의 활성 에너지선 경화성 조성물의 경화 도막은, 우수한 내블리드성을 갖는 것이고, 습열 조건 하에서의 사용 후에 있어서도, 대전방지제의 블리드가 발생하지 않고, 대전방지성의 변화도 적은 것이다.The active energy ray curable composition of the present invention can be coated on the surface of the film and cured to form a hard coat layer having excellent antistatic properties and pencil hardness. Therefore, the cured coating film of the active energy ray curable composition of the present invention can suppress generation of static electricity on the film surface. Therefore, various films can be provided with functions such as prevention of sticking and prevention of adhesion of dust or the like due to static electricity. Therefore, even when the film having the cured coating film of the active energy ray-curable composition of the present invention is rolled up in a rolled state and fed out from a roll, troubles such as sticking and adhesion of dust or the like can be avoided, And this excellent film can be provided. In addition, the cured coating film of the active energy ray curable composition of the present invention has excellent bleed resistance and does not cause bleeding of an antistatic agent even after use under a moist heat condition, and also shows little change in antistatic property.

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.The film having the hard coat layer formed of the cured coating film of the active energy ray curable composition of the present invention can be applied to a flat panel display (FPD) such as a liquid crystal display (LCD), an organic EL display (OLED), a plasma display It can be suitably used as an optical film to be used. Further, since they have excellent antistatic property even when used in these applications, adhesion of dust or the like can be suppressed. In addition, when this film is used for a liquid crystal display or the like, a malfunction of the display due to the 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, 4급 암모늄염을 가지며, 또한 지환 구조를 갖지 않는 화합물(C)과, 유기 용제(D)를 함유하는 것이다.The active energy ray curable composition of the present invention comprises an active energy ray curable compound (A), a resin (B) having an alicyclic structure and a quaternary ammonium salt, a compound (C) having a quaternary ammonium salt, , And an organic solvent (D).

상기 활성 에너지선 경화성 화합물(A)로서는, 예를 들면, 다관능 (메타)아크릴레이트, 우레탄(메타)아크릴레이트 등을 사용할 수 있다.As the active energy ray-curable compound (A), for example, polyfunctional (meth) acrylate, urethane (meth) acrylate and the like can be used.

상기 다관능 (메타)아크릴레이트로서는, 예를 들면, 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, 글리세린트리(메타)아크릴레이트, 펜타에리트리톨트리(메타)아크릴레이트, 펜타에리트리톨테트라(메타)아크릴레이트, 디펜타에리트리톨트리(메타)아크릴레이트, 디펜타에리트리톨테트라(메타)아크릴레이트, 디펜타에리트리톨펜타(메타)아크릴레이트, 디펜타에리트리톨헥사(메타)아크릴레이트, 트리펜타에리트리톨헵타(메타)아크릴레이트, 트리펜타에리트리톨옥타(메타)아크릴레이트, 폴리펜타에리트리톨폴리(메타)아크릴레이트 등을 들 수 있다. 이들 화합물은 단독으로 사용해도 되고 2종 이상을 병용해도 된다.Examples of the polyfunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, (Meth) acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di Acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethylene glycol di (Meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and dipropylene glycol di Hydroxyethyl) isocyanurate, di (meth) acrylate of neopentyl A di (meth) acrylate of a diol obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of recall, a di (meth) acrylate of a 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 trimethylol propane tri (meth) acrylate, propylene oxide modified trimethylol propane tri (meth) acrylate, ditrimethylol propane tri (meth) (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, tris (2- (Meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (metha) acrylate, dipentaerythritol hexa Poly (meth) acrylate, and the like. These compounds may be used alone or in combination of two or more.

상기 우레탄(메타)아크릴레이트는, 폴리이소시아네이트와 수산기를 갖는 (메타)아크릴레이트와의 반응물을 사용할 수 있다.As the urethane (meth) acrylate, a reaction product of a polyisocyanate and (meth) acrylate having a hydroxyl group can be used.

상기 폴리이소시아네이트로서는, 지방족 폴리이소시아네이트와 방향족 폴리이소시아네이트를 들 수 있지만, 본 발명의 활성 에너지선 경화성 조성물의 경화 도막의 착색을 저감할 수 있으므로, 지방족 폴리이소시아네이트가 바람직하다.Examples of the polyisocyanate include an aliphatic polyisocyanate and an aromatic polyisocyanate, but aliphatic polyisocyanate is preferable because coloring of the cured coating film of the active energy ray-curable composition of the present 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 aliphatic polyisocyanate is a compound in which a moiety other than an isocyanate group is composed of an aliphatic hydrocarbon. Specific examples of the aliphatic polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate and lysine triisocyanate; (Isocyanatomethyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2- Methyl-1,5-diisocyanatocyclohexane, and other alicyclic polyisocyanates. Further, a trihydrate obtained by trimerizing the aliphatic polyisocyanate or alicyclic polyisocyanate can also be used as the aliphatic polyisocyanate. These aliphatic polyisocyanates may be used alone or in combination of two or more.

상기 지방족 폴리이소시아네이트 중에서도 도막의 내찰상성을 향상시키기 위해서는, 지방족 폴리이소시아네이트 중에서도, 직쇄 지방족 탄화수소의 디이소시아네이트인 헥사메틸렌디이소시아네이트, 지환식 디이소시아네이트인 노르보르난디이소시아네이트, 이소포론디이소시아네이트가 바람직하다.Among aliphatic polyisocyanates, hexamethylene diisocyanate, which is a diisocyanate of straight chain aliphatic hydrocarbons, norbornadiisocyanate which is an alicyclic diisocyanate, and isophorone diisocyanate are preferable among the aliphatic polyisocyanates in order to improve scratch resistance of the coating film.

상기 (메타)아크릴레이트는, 수산기와 (메타)아크릴로일기를 갖는 화합물이다. 이 (메타)아크릴레이트의 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, 이들의 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)아크릴레이트는, 1종으로 사용할 수도 있고 2종 이상 병용할 수도 있다.The (meth) acrylate is a compound having a hydroxyl group and a (meth) acryloyl group. Specific examples of the (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, hydroxypivalic acid neopentyl glycol mono ) Mono (meth) acrylates of divalent alcohols such as acrylate; (Meth) acrylate, trimethyleneol propane di (meth) acrylate, ethylene oxide (EO) modified trimethylol propane (meth) acrylate, propylene oxide (PO) modified trimethylol propane di Mono or di (meth) acrylate of a trihydric alcohol such as (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or a part of the alcoholic hydroxyl group thereof modified with? -Caprolactone Mono and di (meth) acrylates having a hydroxyl group; (Meth) acryloyl group having three or more functional groups such as pentaerythritol tri (meth) acrylate, ditrimethylol propane tri (meth) acrylate, dipentaerythritol penta , Or a polyfunctional (meth) acrylate having a hydroxyl group modified with ε-caprolactone in addition to the compound; (Meth) acrylate 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 having an oxyalkylene chain having a block structure such as polyethylene glycol-polypropylene glycol mono (meth) acrylate and polyoxybutylene-polyoxypropylene mono (meth) acrylate; (Meth) acrylate having a random oxyalkylene chain such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate. have. These (meth) acrylates may be used singly or in combination of two or more.

상기 폴리이소시아네이트와 상기 (메타)아크릴레이트와의 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.The reaction between the polyisocyanate and the (meth) acrylate can be carried out by a conventional urethane-forming reaction. Further, in order to promote the progress of the urethanation reaction, it is preferable to conduct the urethanation reaction in the presence of the urethanation catalyst. Examples of the urethanization catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; Phosphorus compounds such as triphenylphosphine and triethylphosphine; Organic tin compounds such as dibutyltin dilaurate, octyltin tris laurate, octyltin diacetate, dibutyltin diacetate and tin octylate, and organic zinc compounds such as zinc octylate.

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

상기 활성 에너지선 경화성 화합물(A)로서는, 상기한 중에서도, 한층 더 우수한 대전방지성, 및, 고경도성이 얻어지므로, 수산기가가 40mgKOH/g 이하인 것을 사용하는 것이 바람직하고, 디펜타에리트리톨헥사아크릴레이트, 및/또는, 펜타에리트리톨테트라아크릴레이트를 사용하는 것이 보다 바람직하다.As the active energy ray-curable compound (A), it is preferable to use a compound having a hydroxyl value of not more than 40 mgKOH / g, and more preferably a dipentaerythritol hexaacrylate Rate, and / or pentaerythritol tetraacrylate is more preferably used.

상기 수지(B)는, 우수한 대전방지성을 얻는데, 4급 암모늄염을 갖는 것임이 필수이다.The resin (B) is required to have quaternary ammonium salt to obtain excellent antistatic property.

상기 수지(B)는, 우수한 대전방지성을 얻는데, 지환 구조 및 4급 암모늄염을 갖는 것이 필수이다.The resin (B) is required to have an alicyclic structure and a quaternary ammonium salt to obtain an excellent antistatic property.

상기 수지(B)로서는, 구체적으로는, 예를 들면, 지환 구조를 갖는 중합성 단량체(b1)와, 4급 암모늄염을 갖는 중합성 단량체(b2)와, 및, 상기 (b1) 및 (b2)와 공중합 가능한 그 밖의 중합성 단량체(b3)와의 공중합체를 들 수 있다.Specific examples of the resin (B) include a polymerizable monomer (b1) having an alicyclic structure, a polymerizable monomer (b2) having a quaternary ammonium salt, and the polymerizable monomer (b1) And another polymerizable monomer (b3) copolymerizable therewith.

상기 중합성 단량체(b1)는, 지환 구조를 갖는 것이다. 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(b1)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) 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] dodecane ring, and spiro [3.4] octane ring. Specific examples of the polymerizable monomer (b1) include cyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like. These polymerizable monomers (b1) may be used singly or in combination of two or more.

상기 4급 암모늄염을 갖는 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; 디메틸아미노에틸(메타)아크릴아미드염화메틸4급염, 디메틸아미노프로필(메타)아크릴아미드염화메틸4급염 등을 들 수 있다. 이들 중합성 단량체(b2)는, 1종으로 사용할 수도 있고 2종 이상 병용할 수도 있다.Examples of the polymerizable monomer (b2) having a quaternary ammonium salt include 2- [(meth) acryloyloxy] ethyltrimethylammonium chloride, 3- [(meth) acryloyloxy] propyltrimethylammonium chloride and the like The counter anion is chloride; A counter anion such as 2 - [(meth) acryloyloxy] ethyltrimethylammonium bromide and 3 - [(meth) acryloyloxy] propyltrimethylammonium bromide is a bromide; (Meth) acryloyloxypropyltrimethylammonium chloride, 2 - [(meth) acryloyloxy] ethyltrimethylammonium methylphenylsulfonate, 2- [(meth) acryloyloxy] ethyltrimethylammonium methylsulfonate, 3- 3 - [(meth) acryloyloxy] propyltrimethylammonium methylsulfonate, 2 - [(meth) acryloyloxy] ethyltrimethylammonium methylsulfate, 3- [ The counter anion such as propyltrimethylammonium methylsulfate is non-halogen-based; Dimethylaminoethyl (meth) acrylamide methyl chloride quaternary salt, dimethylaminopropyl (meth) acrylamide methyl chloride quaternary salt, and the like. These polymerizable monomers (b2) may be used singly or in combination of two or more.

상기 그 밖의 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 other polymerizable monomer (b3) include 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 , Alkyl (meth) acrylates such as nonyl (meth) acrylate, decyl (meth) acrylate and dodecyl (meth) acrylate; Acrylate, methoxypolyethylene glycol mono (meth) acrylate, octoxypolyethylene glycol polypropylene glycol mono (meth) acrylate, lauroxypolyethylene glycol mono (meth) acrylate, stearoxypolyethylene glycol mono (Meth) acrylates such as polyethylene glycol mono (meth) acrylate, phenoxypolyethylene glycol · polypropylene glycol mono (meth) acrylate, nonylphenoxypolypropylene glycol mono (meth) acrylate, nonylphenoxypoly (ethylene glycol · propylene glycol) Mono (meth) acrylates of polyalkylene glycols such as methyl (meth) acrylate; (Meth) acrylate having a fluorinated alkyl group such as 2-perfluorohexylethyl (meth) acrylate. These polymerizable monomers (b3) may be used singly or in combination of two or more.

상기 중합성 단량체(b3)로서는, 한층 더 우수한 대전방지성이 얻어지는 점으로부터, 불소화알킬기를 갖는 (메타)아크릴레이트, 및/또는, 폴리알킬렌글리콜의 모노(메타)아크릴레이트를 사용하는 것이 바람직하고, 또한 상기 폴리알킬렌글리콜의 모노(메타)아크릴레이트로서는 메톡시폴리에틸렌글리콜모노(메타)아크릴레이트가 보다 바람직하다.(Meth) acrylate having a fluorinated alkyl group and / or a mono (meth) acrylate of a polyalkylene glycol is preferably used as the polymerizable monomer (b3) from the viewpoint of obtaining more excellent antistatic property , And the mono (meth) acrylate of the polyalkylene glycol is more preferably methoxypolyethylene glycol mono (meth) acrylate.

상기 폴리알킬렌글리콜의 모노(메타)아크릴레이트 중에서도, 한층 더 우수한 대전방지성이 얻어지는 점으로부터, 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 above mono (meth) acrylates of polyalkylene glycols, the polyalkylene glycols which are raw materials of the mono (meth) acrylate of the polyalkylene glycols have a number average molecular weight More preferably in the range of 300 to 6,000, more preferably in the range of 400 to 4,000, and particularly preferably in the range of 400 to 2,000.

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∼55질량%의 범위가 바람직하고, 10∼50질량%의 범위가 보다 바람직하고, 12∼45질량%의 범위가 더 바람직하다.The proportion of the polymerizable monomer (b1) in the total amount of the raw materials 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, , More preferably from 10 to 50 mass%, and even more preferably from 12 to 45 mass%.

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.The proportion of the polymerizable monomer (b2) in the entire 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, , More preferably in a range of 40 to 80 mass%, and still more preferably in a range of 45 to 70 mass%.

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.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, (Meth) acrylate of the polyalkylene glycol in the total amount of the raw material (B) is preferably in the range of 5 to 60 mass%, more preferably in the range of 10 to 50 mass%, more preferably in the range of 20 to 40 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.When the (meth) acrylate having the fluorinated alkyl group 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, (Meth) acrylate having a fluorinated alkyl group in the whole 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%, more preferably 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.The weight average molecular weight of the resin (B) is preferably in the range of 1,000 to 100,000, more preferably in the range of 2,000 to 50,000, since the antistatic property of the cured coating film of the active energy ray- , And a range of 3,000 to 30,000 is more preferable. The weight average molecular weight in the present invention is a value in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

상기 수지(B)의 배합량은, 본 발명의 활성 에너지선 경화성 조성물의 경화 도막의 대전방지성 및 내블리드성을 보다 향상할 수 있으므로, 상기 활성 에너지선 경화성 조성물(A) 100질량부에 대해서, 0.1∼10질량부의 범위가 바람직하고, 1.3∼5질량부의 범위가 보다 바람직하고, 1.5∼2질량부의 범위가 더 바람직하다.The blending amount of the resin (B) can further improve the antistatic property and anti-bleeding property of the cured coating film of the active energy ray curable composition of the present invention. Therefore, the amount of the resin (B) More preferably from 0.1 to 10 parts by mass, still more preferably from 1.3 to 5 parts by mass, and still more preferably from 1.5 to 2 parts by mass.

상기 화합물(C)은, 4급 암모늄염을 가지며, 또한 지환 구조를 갖지 않는 것이다. 상기 화합물(C)과 상기 수지(B)를 병용함에 의해, 대전방지제(상기 수지(B) 및 화합물(C))의 사용량을 저감한 경우여도, 경화 도막의 우수한 대전방지성을 발현할 수 있고, 블리드도 억제할 수 있다.The compound (C) has a quaternary ammonium salt and does not have an alicyclic structure. By using the compound (C) and the resin (B) in combination, excellent antistatic properties of the cured coating film can be exhibited even when the amount of the antistatic agent (the resin (B) and the compound (C) , Bleeding can also be suppressed.

상기 화합물(C)로서는, 예를 들면, 상기 수지(B)의 원료로서 사용할 수 있는 상기 4급 암모늄염을 갖는 중합성 단량체(b2), 상기 4급 암모늄염을 갖는 중합성 단량체(b2)와 상기 그 밖의 중합성 단량체(b3)와의 공중합체를 사용할 수 있다.Examples of the compound (C) include a polymerizable monomer (b2) having the quaternary ammonium salt that can be used as a raw material of the resin (B), a polymerizable monomer (b2) having the quaternary ammonium salt, And a polymerizable monomer (b3) other than the polymerizable monomer (b3).

상기 화합물(C)의 중량 평균 분자량으로서는, 한층 더 우수한 대전방지성 및 내블리드성이 얻어지는 점으로부터, 100∼1,000의 범위인 것이 바람직하고, 130∼500의 범위가 보다 바람직하고, 150∼300의 범위가 더 바람직하다.The weight average molecular weight of the compound (C) is preferably in the range of 100 to 1,000, more preferably in the range of 130 to 500, and still more preferably in the range of 150 to 300, in view of obtaining further excellent antistatic property and anti- Range is more preferable.

상기 화합물(C)에는, 내블리드성을 높이는 점으로부터, 활성 에너지선 경화성 관능기를 갖는 것이 더 바람직하다.The compound (C) preferably has an active energy ray-curable functional group from the viewpoint of enhancing bleeding resistance.

상기 화합물(C)로서는, 상기한 중에서도, 한층 더 우수한 대전방지성 및 내블리드성이 얻어지는 점으로부터, 2-[(메타)아크릴로일옥시]에틸트리메틸암모늄클로라이드, 3-[(메타)아크릴로일옥시]프로필트리메틸암모늄클로라이드, 디메틸아미노에틸(메타)아크릴아미드염화메틸4급염, 및, 디메틸아미노프로필(메타)아크릴아미드염화메틸4급염으로 이루어지는 군에서 선택되는 1종 이상의 화합물을 사용하는 것이 바람직하다.(Meth) acryloyloxy] ethyltrimethylammonium chloride, 3 - [(meth) acryloyloxyethyl] trimethylammonium chloride, and the like are preferable from the viewpoint of further superior antistatic property and anti- It is preferable to use at least one compound selected from the group consisting of methyl iodide, methyl iodide, ethyl iodide, diethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylamide methyl chloride quaternary salt and dimethylaminopropyl (meth) acrylamide methyl chloride quaternary salt Do.

상기 화합물(C)의 배합량은, 본 발명의 활성 에너지선 경화성 조성물의 경화 도막의 대전방지성 및 내블리드성을 보다 향상할 수 있으므로, 상기 활성 에너지선 경화성 조성물(A) 100질량부에 대해서, 0.1∼15질량부의 범위가 바람직하고, 1∼10질량부의 범위가 보다 바람직하고, 3∼8질량부의 범위가 더 바람직하다.The compounding amount of the compound (C) can further improve the antistatic property and anti-bleeding property of the cured coating film of the active energy ray curable composition of the present invention. Therefore, More preferably from 0.1 to 15 parts by mass, still more preferably from 1 to 10 parts by mass, and still more preferably from 3 to 8 parts by mass.

상기 수지(B)와 상기 화합물(C)과의 합계 배합량으로서는, 대전방지성과 내블리드성의 밸런스를 한층 더 향상할 수 있고, 습열 조건 하에서의 사용 후에 있어서도 대전방지성의 변화도 적은 점으로부터, 상기 활성 에너지선 경화성 화합물(A) 100질량부에 대해서, 1∼10질량부의 범위인 것이 바람직하고, 3∼8질량부의 범위가 보다 바람직하다.As the total amount of the resin (B) and the compound (C), the balance between the antistatic property and the anti-bleeding property can be further improved, and also the antistatic property can be changed even after use under the moist heat condition. Is preferably in the range of 1 to 10 parts by mass, and more preferably in the range of 3 to 8 parts by mass with respect to 100 parts by mass of the ray curable compound (A).

상기 수지(B)와 상기 화합물(C)과의 질량비[(B)/(C)]로서는, 대전방지성과 내블리드성의 밸런스를 한층 더 향상할 수 있으며, 또한 습열 조건 하에서의 사용 후에 있어서도 대전방지성의 변화도 적은 점으로부터, 5/95∼40/60의 범위인 것이 바람직하고, 10/90∼30/70의 범위가 보다 바람직하고, 13/87∼20/80의 범위가 더 바람직하다.(B) / (C)] between the resin (B) and the compound (C), the balance between the antistatic property and the bleeding resistance can be further improved, and also the antistatic But it is preferably in the range of 5/95 to 40/60, more preferably in the range of 10/90 to 30/70, and still more preferably in the range of 13/87 to 20/80, from the viewpoint of small change.

상기 유기 용제(D)는, 본 발명의 활성 에너지선 경화성 조성물 중의 다른 성분을 용해할 수 있는 것이면 특히 제한 없이 사용할 수 있다. 상기 유기 용제(D)로서는, 예를 들면, 톨루엔, 자일렌 등의 방향족 탄화수소; 메탄올, 에탄올, 이소프로판올, t-부탄올 등의 알코올류; 아세트산에틸, 아세트산부틸, 프로필렌글리콜모노메틸에테르아세테이트 등의 에스테르류; 아세톤, 메틸에틸케톤, 메틸이소부틸케톤, 시클로헥산온 등의 케톤류 등을 들 수 있다. 이들 유기 용제는 단독으로 사용해도 되고 2종 이상을 병용해도 된다.The organic solvent (D) is not particularly limited as long as it can dissolve other components in the active energy ray-curable composition of the present invention. Examples of the organic solvent (D) include aromatic hydrocarbons such as toluene and xylene; Alcohols such as methanol, ethanol, isopropanol and t-butanol; Esters such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; And ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. These organic solvents may be used alone or in combination of two or more.

본 발명의 활성 에너지선 경화성 조성물 중의 상기 유기 용제(D)의 배합량은, 후술하는 도공 방법에 적합한 점도로 되는 양으로 하는 것이 바람직하다.The blending amount of the organic solvent (D) in the active energy ray curable composition of the present invention is preferably such that the viscosity becomes suitable for the coating method described 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 전리방사선을 말한다. 활성 에너지선으로서 자외선을 조사해서 경화 도막으로 하는 경우에는, 본 발명의 활성 에너지선 경화성 조성물 중에 광중합개시제(E)를 첨가하여, 경화성을 향상하는 것이 바람직하다. 또한, 필요하면 추가로 광증감제를 첨가해서, 경화성을 향상할 수도 있다. 한편, 전자선, α선, β선, γ선 등의 전리방사선을 사용하는 경우에는, 광중합개시제(E)나 광증감제를 사용하지 않아도 신속히 경화하므로, 특히 광중합개시제(E)나 광증감제를 첨가할 필요는 없다.Further, the active energy ray curable composition of the present invention can be formed into a cured coating film by applying an active energy ray after coating the substrate. This active energy ray refers to ionizing radiation such as ultraviolet rays, electron rays, alpha rays, beta rays, and gamma rays. When ultraviolet rays are irradiated as an active energy ray to form a cured coating film, it is preferable to add a photopolymerization initiator (E) to the active energy ray curable composition of the present invention to improve the curability. In addition, if necessary, a photosensitizer may be further added to improve the curability. On the other hand, in the case of using ionizing radiation such as electron beams, alpha rays, beta rays and gamma rays, it is possible to rapidly cure even without using a photopolymerization initiator (E) or a photosensitizer, It does not need to be added.

상기 광중합개시제(E)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(E)는, 1종으로 사용할 수도 있고, 2종 이상 병용할 수도 있다.Examples of the photopolymerization initiator (E) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo {2-hydroxy- - (1-methylvinyl) phenyl] propanone}, benzyldimethylketal, 1- (4-isopropylphenyl) -2-hydroxypropyl- 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2 -Acetophenone-based 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-trimethylbenzoindienylphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; Benzyl (methoxy) ethers such as benzyl (dibenzoyl), methylphenylglyoxyester, oxyphenylacetic acid 2- (2-hydroxyethoxy) ethyl ester and oxyphenylacetic acid 2- Based compound; Benzoylbenzoic acid methyl-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ' , 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, Benzophenone compounds; Thioxanthone 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; 2-chloroanilide, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1- [4- (4- benzoylphenylsulfanyl) phenyl] - (4-methylphenylsulfonyl) propan-1-one. These photopolymerization initiators (E) may be used singly or in combination of two or more.

또한, 상기 광증감제로서는, 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.Examples of the photosensitizer include tertiary amine compounds such as diethanolamine, N-methyldiethanolamine and tributylamine, urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, and sulfur compounds such as s-benzylisothiuronium-p-toluenesulfonate.

상기한 광중합개시제(E) 및 광증감제의 사용량은, 본 발명의 활성 에너지선 경화성 조성물 중의 상기 활성 에너지선 경화성(A) 100질량부에 대하여, 각각 0.05∼20질량부가 바람직하고, 0.5∼10질량%가 보다 바람직하다.The amount of the photopolymerization initiator (E) and the photosensitizer is preferably 0.05 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the active energy ray curable resin (A) in the active energy ray- % By mass is more preferable.

본 발명의 활성 에너지선 경화성 조성물에는, 상기한 성분(A)∼(E) 이외의 그 밖의 배합물로서, 용도, 요구 특성에 따라서, 중합금지제, 표면조정제, 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.The active energy ray curable composition of the present invention may contain other additives other than the above-mentioned components (A) to (E) as polymerization inhibitors, surface conditioners, defoamers, viscosity modifiers, Additives such as stabilizers, heat stabilizers, ultraviolet absorbers, antioxidants, leveling agents, organic pigments, inorganic pigments, pigment dispersants, silica beads and organic beads; Inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, antimony pentoxide, and the like. These other compounds 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 the present invention is obtained by applying the active energy ray-curable composition of the present invention to at least one surface of a film substrate and then irradiating an active energy ray to form 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.The material of the film base used in the film of the present invention is preferably a resin having high transparency, and examples thereof include polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; Polyolefin-based resins such as polypropylene, polyethylene, and polymethylpentene-1; Cellulose-based resins such as cellulose acetate (diacetylcellulose, triacetylcellulose, 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 resins such as polyvinyl chloride and polyvinylidene chloride; Polyvinyl alcohol; Ethylene-vinyl acetate copolymer; polystyrene; Polyamide; Polycarbonate; Polysulfone; Polyethersulfone; Polyether ether ketone; Polyimide resins such as polyimide and polyetherimide; (For example, "Aton" manufactured by JSR Corporation), a cyclic olefin copolymer (for example, a norbornene-based resin such as a norbornene-based resin And " APEL " manufactured by Mitsui Chemicals, Inc.). Further, two or more types of base materials made of these resins may be used in combination.

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.The film substrate may be a film or a sheet, and the thickness is preferably in the range of 20 to 500 mu m. When a film base film is used, the thickness is preferably in the range of 20 to 200 mu m, more preferably in the range of 30 to 150 mu m, and further preferably in the range of 40 to 130 mu m. By setting the thickness of the film base material to the above range, curl can be easily suppressed even when a hard coat layer is provided on one side of the film by the active energy ray curable composition of the present 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, 실크스크린에 의한 솔리드 코트, 와이어바 코트, 플로 코트 등을 들 수 있다.Examples of the method for applying the active energy ray-curable composition of the present invention to the film substrate include die coating, micro gravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, , A spinner coat, a brush coating, a solid coat by a silk screen, a wire bar coat, a float coat, and the like.

본 발명의 활성 에너지선 경화성 조성물 중에 포함하는 유기 용매는, 활성 에너지선 경화성 조성물을 기재 필름에 도공한 후, 활성 에너지선을 조사하기 전에 휘발시키고, 또한, 상기 수지(B) 및 화합물(C)을 도막 표면에 편석시키기 위해서, 가열 또는 실온 건조하는 것이 바람직하다. 가열 건조의 조건으로서는, 유기 용제가 휘발하는 조건이면, 특히 한정하지 않지만, 통상은, 온도 50∼100℃의 범위에서, 시간은 0.5∼10분의 범위에서 가열 건조하는 것이 바람직하다.The organic solvent contained in the active energy ray-curable composition of the present invention can be obtained by coating the base film with an active energy ray curable composition and volatilizing it before irradiating the active energy ray, It is preferable to heat or dry at room temperature. The conditions for heating and drying are not particularly limited as long as the organic solvent is volatile, but it is usually preferable to heat and dry at a temperature in the range of 50 to 100 占 폚 and for a time in the range of 0.5 to 10 minutes.

본 발명의 활성 에너지선 경화성 조성물을 경화시키는 활성 에너지선으로서는, 상기한 바와 같이, 자외선, 전자선, α선, β선, γ선 등의 전리방사선이다. 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, 쇼트아크등, 헬륨·가돌리늄 레이저, 아르곤 레이저, 태양광, LED 램프 등을 들 수 있다.As described above, the active energy ray for curing the active energy ray-curable composition of the present invention is ionizing radiation such as ultraviolet ray, electron ray,? Ray,? Ray and? Ray. Here, when ultraviolet rays are used as active energy rays, examples of the apparatus for irradiating the ultraviolet rays include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, electrodeless lamps (fusion lamps) , A black light lamp, a mercury-xenon lamp, a short arc lamp, a helium-gadolinium laser, an argon laser, a solar lamp, and an LED lamp.

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 when forming the cured coating film of the active energy ray-curable composition of the present invention on the film substrate is sufficient to make the hardness of the cured coating film satisfactory and to suppress curling of the film due to curing shrinkage of the coating film It is preferably in the range of 1 to 30 mu m, more preferably in the range of 3 to 15 mu m, and further preferably in the range of 4 to 10 mu m.

이상, 본 발명의 활성 에너지선 경화성 조성물은, 우수한 대전방지성, 및, 내블리드성을 갖는 하드코트층을 형성할 수 있는 것이다. 상기 활성 에너지선 경화성 조성물의 경화 도막의 표면 저항값으로서는, 1×107∼9.99×109Ω/□의 범위인 것이 바람직하고, 1×108∼9.99×108Ω/□의 범위가 보다 바람직하다. 또, 상기 경화 도막의 표면 저항값의 측정 방법은, 실시예에서 기재한다.As described above, the active energy ray curable composition of the present invention is capable of forming a hard coat layer having excellent antistatic property and anti-bleeding property. As the surface resistance of the active energy beam curable composition of the cured film, is 1 × 10 7 ~9.99 × 10 9 Ω / □ preferably in the range of to, 1 × 10 8 ~9.99 × 10 8 Ω / □ range than desirable. A method of measuring the surface resistance value of the cured coating film is described in the examples.

(실시예)(Example)

이하, 실시예에 의해 본 발명을 보다 구체적으로 설명한다.Hereinafter, the present invention will be described more specifically with reference to Examples.

(제조예 1 : 지환 구조 및 4급 암모늄염을 갖는 수지(B-1)의 제조)(Production Example 1: Production of resin (B-1) having 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 PGME 2.4질량부로 용해한 용액을 30분 걸쳐서 적하한 후, 65℃에서 3시간 반응시켰다. 다음으로, 메탄올을 더해서 희석하여, 지환 구조 및 4급 암모늄염을 갖는 수지(B-2)의 45질량% 용액을 얻었다. 얻어진 수지(B-1)의 중량 평균 분자량은 1만이었다.A nitrogen gas was introduced into a flask equipped with a stirrer, a reflux condenser and a nitrogen-introducing tube, and 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, 50 parts by mass of methoxypolyethylene glycol methacrylate (Blender PME- 1000 ", number of repeating units n 23, molecular weight 1,000), 0.5 parts by mass of methacrylic acid, 50 parts by mass of methanol and 10 parts by mass of PGME. Next, a solution prepared by dissolving 0.1 part by mass of a polymerization initiator (azobisisobutyronitrile) in 2.4 parts by mass of PGME was added dropwise over 30 minutes, followed by reaction at 65 ° C for 3 hours. Next, methanol was added and diluted to obtain a 45 mass% solution of the resin (B-2) having an alicyclic structure and quaternary ammonium salt. The weight average molecular weight of the obtained resin (B-1) was 10,000.

(제조예 2 : 지환 구조 및 4급 암모늄염을 갖는 수지(B-2)의 제조)(Production Example 2: Production of resin (B-2) having 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 53.7질량부, 시클로헥실메타크릴레이트 29.3질량부, 메톡시폴리에틸렌글리콜메타크릴레이트(니찌유가부시키가이샤제 「브렌마 PME-1000」; 반복 단위수 n≒23, 분자량 1,000) 14.6질량부, 2-퍼플루오로헥실에틸아크릴레이트 1.9질량부, 메타크릴산 0.5질량부, 메탄올 50질량부 및 프로필렌글리콜모노메틸에테르 10질량부를 더했다. 다음으로, 중합개시제(아조비스이소부티로니트릴) 0.1질량부를 프로필렌글리콜모노메틸에테르 2.4질량부로 용해한 용액을 30분 걸쳐서 적하한 후, 65℃에서 3시간 반응시켰다. 다음으로, 메탄올을 더해서 희석하여, 지환 구조 및 4급 암모늄염을 갖는 수지(B-2)의 45질량% 용액을 얻었다. 얻어진 수지(B-1)의 중량 평균 분자량은 1만이었다.A nitrogen gas was introduced into a flask equipped with a stirrer, a reflux condenser and a nitrogen-introducing tube, and air in the flask was replaced with nitrogen gas. Thereafter, 53.7 parts by mass of 2- (methacryloyloxy) ethyltrimethylammonium chloride, 29.3 parts by mass of cyclohexyl methacrylate, methoxypolyethylene glycol methacrylate ("Bremma PME- 14.6 parts by mass of repeating units n 23, molecular weight 1,000), 1.9 parts by mass of 2-perfluorohexylethyl acrylate, 0.5 parts by mass of methacrylic acid, 50 parts by mass of methanol and 10 parts by mass of propylene glycol monomethyl ether I added. Next, a solution prepared by dissolving 0.1 part by mass of a polymerization initiator (azobisisobutyronitrile) in 2.4 parts by mass of propylene glycol monomethyl ether was added dropwise over 30 minutes, followed by reaction at 65 ° C for 3 hours. Next, methanol was added and diluted to obtain a 45 mass% solution of the resin (B-2) having an alicyclic structure and quaternary ammonium salt. The weight average molecular weight of the obtained resin (B-1) was 10,000.

상기에서 얻어진 수지(B-1), 및, (B-2)의 중량 평균 분자량은, 겔·퍼미에이션·크로마토그래피(GPC)법에 의해, 하기의 조건에서 측정했다.The weight average molecular weights of the resins (B-1) and (B-2) obtained above were measured by gel permeation chromatography (GPC) under the following conditions.

측정 장치 : 고속 GPC 장치(도소가부시키가이샤제 「HLC-8220GPC」)Measurement apparatus: High-speed GPC apparatus ("HLC-8220GPC" manufactured by Tosoh Corporation)

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

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

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

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

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

검출기 : RI(시차굴절계)Detector: RI (differential refractometer)

칼럼 온도 : 40℃Column temperature: 40 DEG C

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

유속 : 1.0mL/분Flow rate: 1.0 mL / min

주입량 : 100μL(시료 농도 0.4질량%의 테트라히드로퓨란 용액)Injection amount: 100 mu L (tetrahydrofuran solution with 0.4 mass% of sample concentration)

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」 Quot; TSKgel Standard Polystyrene A-500 " manufactured by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 A-1000」 Quot; TSKgel standard polystyrene A-1000 " manufactured by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 A-2500」 Quot; TSKgel Standard Polystyrene A-2500 " manufactured by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 A-5000」 Quot; TSKgel Standard Polystyrene A-5000 " manufactured by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 F-1」 Quot; TSKgel standard polystyrene F-1 " manufactured by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 F-2」 Quot; TSKgel standard polystyrene F-2 " manufactured by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 F-4」 Quot; TSKgel standard polystyrene F-4 " manufactured by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 F-10」 Quot; TSKgel standard polystyrene F-10 " manufactured by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 F-20」 Quot; TSKgel standard polystyrene F-20 " manufactured by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 F-40」 Quot; TSKgel standard polystyrene F-40 " manufactured by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 F-80」 Quot; TSKgel standard polystyrene F-80 " manufactured by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 F-128」 Quot; TSKgel standard polystyrene F-128 " manufactured by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 F-288」 Quot; TSKgel standard polystyrene F-288 " manufactured by Tosoh Corporation

도소가부시키가이샤제 「TSKgel 표준 폴리스티렌 F-550」 Quot; TSKgel standard polystyrene F-550 " manufactured by Tosoh Corporation

[수산기가의 측정 방법][Method for measuring hydroxyl value]

활성 에너지선 경화성 화합물의 수산기가는 JIS-K0070에 기재된 수산기가 측정 방법을 사용해서, 이하와 같이 측정했다.The hydroxyl group value of the active energy ray-curable compound was measured as follows using the hydroxyl value measurement method described in JIS-K0070.

무수아세트산 25g을 전량 플라스크 100ml에 취하고, 피리딘을 더해서 전량을 100ml로 하고 혼합 균일하게 한 혼합액을 5ml 칭량하고, 이것에 활성 에너지선 경화성 화합물을 용해시킨 후, 100℃에서 1시간, 무수아세트산과 활성 에너지선 경화성 화합물 중의 수산기를 반응시킨다. 방냉(放冷) 후, 물 1ml를 더하여 교반 혼합하고, 추가로 100℃에서 10분간 교반해서, 과잉의 무수아세트산을 분해하고, 방냉 후 에탄올 5ml로 플라스크 등의 벽을 씻었다. 페놀프탈레인 용액 몇 방울을 지시약으로서 더하고, 0.5mol/L 수산화칼륨에탄올 용액으로 적정했다(적정량 βml). 활성 에너지선 경화성 화합물을 사용하지 않은 블랭크 측정을 마찬가지로 행하여 적정했다(적정량 β0ml). 수산기가는 하기 식(1)으로부터 구해진다.25 g of acetic anhydride was added to 100 ml of a flask and pyridine was added thereto to make 100 ml. The mixture was homogenized to give 5 ml. The active energy ray-curable compound was dissolved in the mixture and the mixture was stirred at 100 캜 for 1 hour, The hydroxyl group in the energy ray-curable compound is reacted. After cooling, 1 ml of water was added, and the mixture was stirred and further stirred at 100 ° C for 10 minutes to decompose excess acetic anhydride. After cooling, the wall of the flask and the like was washed with 5 ml of ethanol. A few drops of a phenolphthalein solution were added as an indicator and titrated with a 0.5 mol / L potassium hydroxide ethanol solution (a proper amount of beta ml). Blank measurement without using an active energy ray-curable compound was similarly performed (titration? 0 ml). The hydroxyl value is obtained from the following formula (1).

수산기가(mgKOH/g)=(β0-β)×f×28.05/S+D (1)(MgKOH / g) = (? 0- ?) X f? 28.05 / S + D (1)

단 f : 0.5mol/L 수산화칼륨에탄올 용액의 팩터F: Factor of 0.5 mol / L potassium hydroxide ethanol solution

S : 활성 에너지선 경화성 화합물의 실채취 중량(단위 : g)S: actual harvest weight of active energy ray-curable compound (unit: g)

D : 산가(mgKOH/g)D: acid value (mgKOH / g)

(실시예 1)(Example 1)

디펜타에리트리톨헥사아크릴레이트(이하, 「DPHA」로 약기한다) 100질량부, 제조예 1에서 얻어진 수지(B-1) 용액 2.22질량부(수지(B-1)로서 1질량부), 디메틸아미노프로필아크릴아미드염화메틸4급염(이하, (C-1)로 약기한다) 5질량부, 광중합개시제(1-히드록시시클로헥실페닐케톤) 5질량부, 용제(에탄올/n-프로필알코올/메탄올=85.5/9.6/4.9(질량비)) 100질량부를 균일하게 혼합해서 활성 에너지선 경화성 조성물(1)을 얻었다.100 parts by mass of dipentaerythritol hexaacrylate (hereinafter abbreviated as DPHA), 2.22 parts by mass of the resin (B-1) solution obtained in Production Example 1 (1 part by mass as the resin (B-1) 5 parts by weight of a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone), 5 parts by weight of a solvent (ethanol / n-propyl alcohol / methanol = 85.5 / 9.6 / 4.9 (mass ratio)) were uniformly mixed to obtain an active energy ray curable composition (1).

(실시예 2, 비교예 1∼3)(Example 2, Comparative Examples 1 to 3)

표 1에 나타낸 조성으로 변경한 이외는 실시예 1과 마찬가지로 행하여, 활성 에너지선 경화성 조성물(2), (R1)∼(R3)을 얻었다.(2) and (R1) to (R3) were obtained in the same manner as in Example 1, except that the composition shown in Table 1 was changed.

[평가용 샘플의 제작][Production of sample 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 조사광량 3kJ/㎡로 조사하여, 경화 도막을 갖는 TAC 필름을 평가용 샘플로서 얻었다.The active energy ray curable composition was coated on a triacetylcellulose (TAC) film (manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 60 占 퐉 in a thickness of 5 占 퐉 with a bar coater and dried at 60 占 폚 for 1.5 minutes. Under irradiation with an irradiation light quantity of 3 kJ / m < 2 > using an ultraviolet ray irradiation apparatus (manufactured by IGraphics, Inc., high pressure mercury lamp) to obtain a TAC film having a cured coating film as an evaluation sample.

또한, 이 평가용 샘플을, 온도 : 65℃, 습도 : 95%의 조건 하에서 300시간 방치하여, 이것을 내습열 시험 후의 평가용 샘플로 했다.The sample for evaluation was allowed to stand under the conditions of a temperature of 65 ° C and a humidity of 95% for 300 hours, and this sample was used as an evaluation sample after the moisture resistance heat test.

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

상기에서 얻어진 평가용 샘플, 및, 내구성 시험 후의 평가용 샘플의 경화 도막의 표면에 대하여, JIS 시험 방법 K6911-1995에 준거해서, 고저항률계(가부시키가이샤미쓰비시가가쿠애널리텍제 「하이레스타-UP MCP-HT450」)를 사용해서, 인가 전압 500V, 측정 시간 10초로 표면 저항값을 측정했다.The surface of the cured coating film of the evaluation sample obtained above and the evaluation sample after the durability test was measured in accordance with JIS Test Method K6911-1995 using a high resistivity meter (manufactured by Mitsubishi Kagaku Analytec, UP MCP-HT450 ") was used to measure the surface resistance value at an applied voltage of 500 V and a measurement time of 10 seconds.

[내블리드성의 평가 방법][Evaluation method of bleeding resistance]

상기에서 얻어진 평가용 샘플, 및, 내구성 시험 후의 평가용 샘플의 경화 도막의 표면에 대하여, 목시 관찰에 의해 이하와 같이 평가했다.The surface of the cured coating film of the evaluation sample obtained as described above and the sample for evaluation after the durability test was evaluated by visual observation as follows.

「○」 : 블리드물이 확인되지 않음 "○": Bleed water not confirmed

「×」 : 블리드물이 확인됨 "×": bleed water confirmed

[연필 경도의 평가 방법][Evaluation method of pencil hardness]

상기에서 얻어진 평가용 샘플, 및, 내구성 시험 후의 평가용 샘플의 경화 도막의 표면에 대하여, JIS 시험 방법 K5600-5-4:1999에 준거해서, 연필 경도를 측정했다.Pencil hardness was measured on the surface of the cured coating film of the sample for evaluation obtained above and the sample for evaluation after the durability test according to JIS Test Method K5600-5-4: 1999.

[표 1][Table 1]

Figure pat00001
Figure pat00001

표 1에 나타내는 약어는 하기의 화합물을 나타낸다.Abbreviations shown in Table 1 represent the following compounds.

「PETA」 : 펜타에리트리톨테트라아크릴레이트&Quot; PETA ": pentaerythritol tetraacrylate

「(C-2)」 : 2-[메타아크릴로일옥시]에틸트리메틸암모늄클로라이드&Quot; (C-2) ": 2- [methacryloyloxy] ethyltrimethylammonium chloride

본 발명의 활성 에너지선 경화성 조성물의 경화 도막은, 우수한 연필 경도를 갖고, 표면 저항값이 10의 8승∼9승 오더이며 대전방지성도 높은 것을 확인할 수 있었다. 또한, 내습열 시험 후에 있어서도, 표면 저항값의 변화가 적고, 블리드물도 확인되지 않았다.It was confirmed that the cured coating film of the active energy ray curable composition of the present invention had an excellent pencil hardness, a surface resistance value of 10 to 8 and an antistatic property. Further, even after the resistance heating test, the change of the surface resistance value was small, and the bleeding was not confirmed.

한편, 비교예 1은, 수지(B)를 배합하지 않는 태양이지만, 표면 저항값이 10의 13승 오더이고, 대전방지성이 불량이었다.On the other hand, in Comparative Example 1, the resin (B) was not blended, but the surface resistance value was 13 orders of magnitude and the antistatic property was poor.

비교예 2는, 화합물(C)을 배합하지 않는 태양이지만, 표면 저항값이 10의 11승 오더이고, 대전방지성이 불량이었다.Comparative Example 2 is a mode in which the compound (C) is not compounded, but the surface resistance value is 11 orders of magnitude and the antistatic property is poor.

비교예 3도 화합물(C)을 배합하지 않는 태양이고, 표면 저항값은 양호하지만, 내습열 시험 후의 블리드물이 현저하게 확인되었다.Comparative Example 3 was also an embodiment in which the compound (C) was not compounded, and the surface resistance value was good, but the bleed water after the wet heat resistance test was remarkably confirmed.

Claims (10)

활성 에너지선 경화성 화합물(A)과, 지환 구조 및 4급 암모늄염을 갖는 수지(B)와, 4급 암모늄염을 가지며, 또한 지환 구조를 갖지 않는 화합물(C)과, 유기 용제(D)를 함유하는 것을 특징으로 하는 활성 에너지선 경화성 조성물.(A), a resin (B) having an alicyclic structure and a quaternary ammonium salt, a compound (C) having a quaternary ammonium salt and no alicyclic structure, and an organic solvent (D) ≪ / RTI > 제1항에 있어서,
상기 수지(B)가, 원료로서 지환 구조를 갖는 중합성 단량체(b1)를 5∼55질량% 사용한 중합체인 활성 에너지선 경화성 조성물.The method according to claim 1,
Wherein the resin (B) is a polymer using 5 to 55 mass% of a polymerizable monomer (b1) having an alicyclic structure as a raw material. 제1항 또는 제2항에 있어서,
상기 수지(B)의 중량 평균 분자량이, 1,000∼100,000의 범위인 활성 에너지선 경화성 조성물.3. The method according to claim 1 or 2,
Wherein the weight average molecular weight of the resin (B) ranges from 1,000 to 100,000. 제1항 내지 제3항 중 어느 한 항에 있어서,
상기 화합물(C)의 중량 평균 분자량이, 100∼1,000의 범위인 활성 에너지선 경화성 조성물.4. The method according to any one of claims 1 to 3,
Wherein the weight average molecular weight of the compound (C) ranges from 100 to 1,000. 제1항 내지 제4항 중 어느 한 항에 있어서,
상기 화합물(C)이 활성 에너지선 경화성 관능기를 갖는 것을 특징으로 하는 활성 에너지선 경화성 조성물.5. The method according to any one of claims 1 to 4,
Wherein the compound (C) has an active energy ray-curable functional group. 제1항 내지 제5항 중 어느 한 항에 있어서,
상기 수지(B)와 화합물(C)과의 질량비[(B)/(C)]가, 5/95∼40/60의 범위인 활성 에너지선 경화성 조성물.6. The method according to any one of claims 1 to 5,
Wherein the mass ratio [(B) / (C)] of the resin (B) to the compound (C) is in the range of 5/95 to 40/60. 제1항 내지 제6항 중 어느 한 항에 있어서,
상기 수지(B)와 화합물(C)과의 합계 배합량이, 상기 활성 에너지선 경화성 화합물(A) 100질량부에 대해서, 1∼10질량부의 범위인 활성 에너지선 경화성 조성물.7. The method according to any one of claims 1 to 6,
Wherein the total amount of the resin (B) and the compound (C) is in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the active energy ray curable compound (A). 제1항 내지 제7항 중 어느 한 항에 있어서,
상기 활성 에너지선 경화성 화합물(A)의 수산기가가 40mgKOH/g 이하인 활성 에너지선 경화성 조성물.8. The method according to any one of claims 1 to 7,
Wherein the active energy ray-curable compound (A) has a hydroxyl value of not more than 40 mgKOH / g. 제1항 내지 제8항 중 어느 한 항에 기재된 활성 에너지선 경화성 조성물의 경화물.A cured product of the active energy ray-curable composition according to any one of claims 1 to 8. 제1항 내지 제8항 중 어느 한 항에 기재된 활성 에너지선 경화성 조성물의 경화 도막을 갖는 것을 특징으로 하는 필름.A film characterized by having a cured coating film of the active energy ray-curable composition according to any one of claims 1 to 8.
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