KR20120105557A - Actinic-radiation curable composition and uses thereof - Google Patents

Actinic-radiation curable composition and uses thereof Download PDF

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KR20120105557A
KR20120105557A KR1020127020646A KR20127020646A KR20120105557A KR 20120105557 A KR20120105557 A KR 20120105557A KR 1020127020646 A KR1020127020646 A KR 1020127020646A KR 20127020646 A KR20127020646 A KR 20127020646A KR 20120105557 A KR20120105557 A KR 20120105557A
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세이치로 하야카와
세이지 마에다
유미코 야마모토
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닛폰고세이가가쿠고교 가부시키가이샤
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
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    • C08F222/245—Esters containing sulfur the ester chains containing seven or more carbon atoms

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Abstract

본 발명은, 속경화성이면서 한편 고굴절률의 경화물을 얻을 수 있는, 유황 원자 및 방향족환을 갖는 특정 구조의 우레탄 (메타)아크릴레이트계 화합물과 방향족환을 갖는 특정 구조의 단관능 (메타)아크릴레이트를 함유하는 활성 에너지선 경화성 조성물을 제공한다. 상기 특정의 단관능 (메타)아크릴레이트를 희석 모노머로서 사용함으로써, 상기 우레탄 (메타)아크릴레이트계 화합물이 본래 갖는 뛰어난 광학적 특성을 해치는 일 없이, 조성물의 점도를 내릴 수 있다.This invention is a monofunctional (meth) acryl of the specific structure which has a urethane (meth) acrylate type compound of the specific structure which has a sulfur atom and an aromatic ring, and an aromatic ring which can obtain hardened | cured material of a fast refractive index and high refractive index. An active energy ray curable composition containing a rate is provided. By using the said specific monofunctional (meth) acrylate as a dilution monomer, the viscosity of a composition can be lowered without spoiling the outstanding optical characteristic which the said urethane (meth) acrylate type compound originally had.

Description

활성 에너지선 경화성 조성물 및 이의 용도{Actinic-radiation curable composition and uses thereof}Active energy ray curable composition and use thereof

본 발명은, 활성 에너지선 경화성 조성물에 관한 것으로, 더욱 상세하게는, 저점도이며, 또한 고굴절률로 기재와의 밀착성이 뛰어난 경화물을 형성하는데 유용한 활성 에너지선 경화성 조성물 및 이의 경화물, 또한, 이러한 에너지선 경화성 조성물로 이루어지는 렌즈 형성제, 코팅제, 접착제 및 봉지제 등의 용도에 관한 것이다.The present invention relates to an active energy ray-curable composition, and more particularly, an active energy ray-curable composition and a cured product thereof, which are useful for forming a cured product having low viscosity and excellent adhesion to a substrate at high refractive index, It relates to the use of such a lens forming agent, coating agent, adhesive agent and encapsulating agent made of such an energy ray curable composition.

최근, 디스플레이나 광통신, 태양전지, 조명 등의 광 관련 산업의 진전과 함께, 굴절률 등의 광학 성능이 뛰어난 투명성 수지가 필요해지고 있다. 이들 중에서도 렌즈 형성 재료, 코팅제, 광학 접착제, 봉지제로의 요구가 강한데, 예를 들면, 액정 디스플레이에 사용되는 광학 필름에서는, 고휘도화를 목적으로 하여 기재상에 미세한 렌즈를 형성하기 위한 렌즈 형성 재료, 반사 방지나 간섭 무늬 방지를 위한 코트층을 형성하는 코팅제 등이 요망되고 있다.In recent years, with advances in light-related industries such as displays, optical communications, solar cells, and lighting, there is a need for transparent resins having excellent optical performance such as refractive index. Among these, there is a strong demand for a lens forming material, a coating agent, an optical adhesive, and an encapsulant. For example, in an optical film used for a liquid crystal display, a lens forming material for forming a fine lens on a substrate for the purpose of high brightness, There is a demand for a coating agent for forming a coat layer for reflection prevention or interference fringe prevention.

렌즈 형성 재료에 관해서는, 최근 발전이 현저한 2P성형이나 나노임프린트(Nanoimprint)라는 미세 성형 프로세스에 적용할 수 있는 재료가 바람직하다. 또, 발광 다이오드를 이용한 고체 조명에서는, 고휘도화를 위한 고굴절률 봉지제가 바람직하다.As for the lens forming material, a material which can be applied to a fine molding process such as 2P molding or nanoimprint, which has recently developed remarkably, is preferable. Moreover, in the solid state illumination using a light emitting diode, the high refractive index sealing agent for high brightness is preferable.

이러한 상황하에서, 렌즈 형성 재료 등의 광학 분야에서 이용되는 투명성 수지에 대해서는, 광기능의 다양화나 생산성의 향상에 대응하기 위해, 고굴절률 및 속경화성의 쌍방을 충족하는 것이 요구되고 있다. 특허 문헌 1에는, 활성 에너지선 조사로의 경화성이 뛰어나고 딱딱해서 손상입기 어려운 투명한 경화물이 얻어지는 (메타)아크릴계 재료로서, 예를 들면, 분자 구조중에 방향족환, 유황 원자를 도입한 (메타)아크릴레이트계 화합물이 제안되고 있다.Under such circumstances, in order to cope with the diversification of optical functions and the improvement of productivity, it is required to satisfy both the high refractive index and the fast curing property for the transparent resin used in the optical field such as the lens forming material. Patent document 1 is a (meth) acrylic material which is excellent in the curability by active energy ray irradiation, and is hard and hard to be damaged. For example, (meth) acrylate in which an aromatic ring and a sulfur atom are introduced into a molecular structure. System compounds have been proposed.

또한, 코팅제, 접착제, 봉지제의 용도에서는, 각종 플라스틱 필름, 유리, 금속 등으로의 밀착성이 뛰어날 필요가 있다. 특허 문헌 2, 특허 문헌 3에는, 분자 중에 방향족환, 유황 원자에 더하여 우레탄 결합을 갖는 우레탄 (메타)아크릴레이트계 화합물이 더욱 제안되고 있다.Moreover, in the use of a coating agent, an adhesive agent, and a sealing agent, it is necessary to be excellent in adhesiveness to various plastic films, glass, a metal, etc. In patent document 2 and patent document 3, the urethane (meth) acrylate type compound which has a urethane bond in addition to an aromatic ring and a sulfur atom in a molecule | numerator is further proposed.

JPS61-072748 AJPS61-072748 A JPJP 2006-2911482006-291148 AA JPJP 2008-2972932008-297293 AA

그러나, 특허 문헌 1에 개시되어 있는 (메타)아크릴레이트계 화합물에서는, 고굴절률이지만, 분자 구조중에 우레탄기 등의 밀착성을 향상시키는 구조 단위가 없기 때문에, 렌즈 형성 재료, 코팅제, 접착제, 또는 봉지제로서 사용했을 때에 기재와의 밀착성이 뒤떨어지는 것이다.However, in the (meth) acrylate type compound disclosed in patent document 1, since it has a high refractive index but there is no structural unit which improves adhesiveness, such as a urethane group, in molecular structure, it is a lens forming material, a coating agent, an adhesive agent, or an encapsulant. When used as a substrate, the adhesion to the substrate is inferior.

또, 특허 문헌 2에 개시되어 있는 우레탄 (메타)아크릴레이트 화합물의 경우, 단일 화합물을 제조하는 것이 매우 곤란하다. 이 때문에, 합성된 우레탄 (메타)아크릴레이트 화합물을 분별 증류 등을 하지 않고 이용한 경우, 우레탄 (메타)아크릴레이트 화합물의 분자량의 불균형에 기인하여, 화합물(조성물)의 굴절률에 불균형이 생겨, 얻어지는 경화물의 굴절률에도 불균형이 생기기 쉽고, 최종적으로 얻어지는 제품의 품질 격차의 원인이 될 우려가 있다.Moreover, in the case of the urethane (meth) acrylate compound disclosed by patent document 2, it is very difficult to manufacture a single compound. Therefore, when the synthesized urethane (meth) acrylate compound is used without fractional distillation or the like, due to an imbalance in the molecular weight of the urethane (meth) acrylate compound, an imbalance occurs in the refractive index of the compound (composition), resulting in curing Unevenness tends to occur in the refractive index of water, and there is a risk of causing a quality gap in the finally obtained product.

특허 문헌 3의 명시된 우레탄 (메타) 아크릴레이트는 고점도의 액체이기 때문에, 접착제나 코팅제로서 이용할 경우, 취급성이 좋지 않다. 특허 문헌 3의 실시 예에서는, 용제로서 초산에틸(단락 번호 0074)을 이용하여 희석한 코팅제가 개시되어 있다. 그러나 상술한 2P성형이나 나노임프린트라는 미세 성형 프로세스에 있어서는 용제를 사용할 수 없는 경우가 많기 때문에, 용제로 희석한 조성물은, 렌즈 형성 재료 용도에 사용하는 것은 곤란하다.Since the urethane (meth) acrylate specified in patent document 3 is a high viscosity liquid, when it is used as an adhesive agent or a coating agent, handleability is not good. In the Example of patent document 3, the coating agent diluted using ethyl acetate (paragraph number 0074) as a solvent is disclosed. However, in the above-mentioned fine molding process of 2P molding or nanoimprint, a solvent cannot be used in many cases, and therefore, it is difficult to use the composition diluted with a solvent for the lens forming material use.

용제 이외에, 다른 에틸렌성 불포화 모노머를, 희석용 모노머로서 배합함으로써, 조성물 점도를 내리는 것을 생각할 수 있다. 특허 문헌 3에 있어서도, 실시 예는 존재하지 않지만, 단락 번호 0050-0053에, 다른 공중합 모노머가 열거되고 있다. 그러나 이들 공중합 모노머를 희석용 모노머로서 사용함으로써 점도를 내려 핸들링성을 높일 수 있다고 하더라도, 고굴절률도 유지하는 것은 매우 곤란하다.In addition to the solvent, it is conceivable to lower the composition viscosity by blending another ethylenically unsaturated monomer as the diluent monomer. Also in patent document 3, although an Example does not exist, another copolymerization monomer is enumerated in Paragraph No. 0050-0053. However, even if it is possible to lower the viscosity by using these copolymerized monomers as the diluent monomer and improve the handling property, it is very difficult to maintain the high refractive index.

본 발명에서는 이러한 배경하에서, 용제로 희석하지 않아도, 핸들링성에 매우 적합한 저점도의 조성물이며, 또한 고굴절률로 밀착성이 뛰어난 경화물을 형성할 수 있는 활성 에너지선 경화성 조성물을 제공하는 것을 목적으로 한다.Under this background, an object of the present invention is to provide an active energy ray curable composition which is capable of forming a cured product having a low viscosity, which is very suitable for handling properties, and having excellent adhesion at high refractive index even without dilution with a solvent.

본 발명자 등은, 이상과 같은 사정을 감안하여, 여러 가지의 우레탄 (메타)아크릴레이트계 화합물과 에틸렌성 불포화 모노머로서의 단관능 (메타)아크릴레이트계 화합물에 대해 검토한 결과, 조성물로서의 저점도화를 달성할 수 있고, 또한, 고굴절률로 기재와의 밀착성에도 뛰어난 경화물을 형성할 수 있는, 우레탄 (메타) 아크릴레이트계 화합물과 단관능 (메타)아크릴레이트계 화합물과의 조합을 발견하여, 본 발명을 완성하였다.In view of the above circumstances, the present inventors have studied various urethane (meth) acrylate-based compounds and monofunctional (meth) acrylate-based compounds as ethylenically unsaturated monomers. The combination of the urethane (meth) acrylate type compound and the monofunctional (meth) acrylate type compound which can achieve and hardened | cured material which is excellent also in adhesiveness with a base material at high refractive index is discovered, The invention has been completed.

즉, 본 발명의 요지는, 하기와 같은 성분(A) 및 성분(B)을 함유하여 이루어지는 것을 특징으로 하는 활성 에너지 경화성 조성물에 관한 것이다.That is, the gist of the present invention relates to an active energy curable composition comprising the following component (A) and component (B).

성분(A)는, 하기 화학식 1 및/또는 2로 표시되는 우레탄 (메타)아크릴레이트계 화합물이다.Component (A) is a urethane (meth) acrylate type compound represented by following General formula (1) and / or 2.

Figure pct00001
Figure pct00001

Figure pct00002
Figure pct00002

식 1에서, R1, R2는 수소 또는 메틸기, R3, R4는 탄소수 1?3의 탄화수소기, X는 염소, 브롬 또는 요오드, a와 b는 같거나 다르게 0?4의 정수, Y는 산소 또는 유황이다.In formula 1, R 1 , R 2 is hydrogen or methyl group, R 3 , R 4 is a hydrocarbon group of 1 to 3 carbon atoms, X is chlorine, bromine or iodine, a and b are integers equal to or different from 0 to 4, Y Is oxygen or sulfur.

식 2에서, R5, R6는 수소 또는 메틸기, R7, R8는 탄소수 1?3의 탄화수소기, Z는 염소, 브롬, 또는 요오드, c는 0?4의 정수, W는 산소 또는 유황이다.In formula 2, R 5 , R 6 is hydrogen or methyl group, R 7 , R 8 is a hydrocarbon group of 1 to 3 carbon atoms, Z is chlorine, bromine, or iodine, c is an integer of 0-4, W is oxygen or sulfur to be.

성분(B)는 하기 화학식 3 및/또는 4로 표시되는 단관능 (메타)아크릴레이트계 화합물이다.Component (B) is a monofunctional (meth) acrylate type compound represented by the following general formula (3) and / or 4.

Figure pct00003
Figure pct00003

Figure pct00004
Figure pct00004

식 3에서, R9는 수소 또는 메틸기, R10는 탄소수 1?3의 탄화수소기이다.In formula 3, R <9> is hydrogen or a methyl group, R <10> is a C1-C3 hydrocarbon group.

식 4에서, R11는 수소 또는 메틸기, R12는 탄소수 1?3의 탄화수소기이다.In Equation 4, R 11 is Hydrogen or a methyl group, R <12> is a C1-C3 hydrocarbon group.

또한, 본 발명은, 이와 같은 활성 에너지선 경화성 조성물로 이루어지는 렌즈 형성제, 코팅제, 접착제, 발광 다이오드의 봉지제도 제공한다.Moreover, this invention provides the lens forming agent, coating agent, adhesive agent, and sealing agent of a light emitting diode which consist of such an active energy ray curable composition.

본 발명의 활성 에너지선 경화성 조성물은, 용제를 포함하지 않아도 저점도로 취급성이 매우 뛰어난 것이며, 또한 활성 에너지선의 조사에 의해 얻어지는 경화물은, 고굴절률로 또한 기재와의 밀착성에도 우수하다.The active energy ray curable composition of the present invention is very excellent in handleability at low viscosity even without containing a solvent, and the cured product obtained by irradiation of active energy ray has a high refractive index and is also excellent in adhesion to the substrate.

이하, 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.

본 발명에서, 성분(A)로서 사용되는 우레탄 (메타)아크릴레이트계 화합물은, 상기 특허 문헌 3에 예시되는 제조 방법으로 제조할 수 있다. 즉, 이하와 같다.In this invention, the urethane (meth) acrylate type compound used as a component (A) can be manufactured by the manufacturing method illustrated by the said patent document 3. That is, it is as follows.

본 발명에서 이용되는 성분(A)의 우레탄 (메타)아크릴레이트계 화합물은, 상기 화학식 1 및/또는 2로 나타낸 것이며, 분자 구조 중에 방향환, 유황 원자, 필요에 따라서 염소, 브롬, 요오드 등의 할로겐 원자를 갖는다. 이들 원자나 원자단은, 화합물, 및 중합 후의 경화물의 굴절률을 향상시킨다.The urethane (meth) acrylate type compound of the component (A) used by this invention is shown by the said General formula (1) and / or 2, In an molecular structure, such as an aromatic ring, a sulfur atom, if necessary, chlorine, bromine, iodine, etc. Has a halogen atom. These atoms and atom groups improve the refractive index of a compound and the hardened | cured material after superposition | polymerization.

본 발명의 우레탄 (메타)아크릴레이트계 화합물은, 하기 화학식 5 또는 6으로 표시되는 화합물과, 이소시아나토알킬 (메타)아크릴레이트를 반응시킴으로써 얻어진다.The urethane (meth) acrylate type compound of this invention is obtained by making the compound represented by following formula (5) or 6 and isocyanatoalkyl (meth) acrylate react.

Figure pct00005
Figure pct00005

식 5 중, R3는 탄소수 1?3의 탄화수소기, X는 염소, 브롬, 또는 요오드, a와 b는 같거나 다르게 0?4의 정수, Y는 산소 또는 유황이다.In formula 5, R <3> is a C1-C3 hydrocarbon group, X is chlorine, bromine, or iodine, a and b are the same or differently, an integer of 0-4, Y is oxygen or sulfur.

Figure pct00006
Figure pct00006

식 6 중, R7는 탄소수 1?3의 탄화수소기, Z는 염소, 브롬, 또는 요오드, c는 0?4의 정수, W는 산소 또는 유황이다.In formula 6, R <7> is a C1-C3 hydrocarbon group, Z is chlorine, bromine, or iodine, c is an integer of 0-4, W is oxygen or sulfur.

상기 식 5로 표시되는 화합물로서는, 예를 들면, 4,4＇-비스〔β-히드록시메틸티오〕디페닐술폰, 4,4＇-비스〔β-히드록시에틸티오〕디페닐술폰, 4,4＇-비스〔β-히드록시프로필티오〕디페닐술폰, 4,4＇-비스〔β-히드록시에틸티오〕-3,3＇, 5,5＇-테트라클로로디페닐술폰, 4,4＇-비스〔β-히드록시에틸티오〕-3,3＇, 5,5＇-테트라브로모디페닐술폰 등의 디올 화합물；4,4＇-비스〔β-메르캅토메틸티오〕디페닐술폰, 4,4＇-비스〔β-메르캅토에틸티오〕디페닐술폰, 4,4＇-비스〔β-메르캅토프로필티오〕디페닐술폰, 4,4＇-비스〔β-메르캅토에틸티오〕-3,3＇, 5,5＇-테트라클로로디페닐술폰, 4,4＇-비스〔β-메르캅토에틸티오〕-3,3＇, 5,5＇-테트라브로모디페닐술폰 등의 디티올 화합물 등을 들 수 있다.As a compound represented by the said Formula 5, 4,4'-bis [(beta) -hydroxymethylthio] diphenyl sulfone, 4,4'-bis [(beta) -hydroxyethylthio] diphenyl sulfone, 4, for example. , 4′-bis [β-hydroxypropylthio] diphenylsulfone, 4,4′-bis [β-hydroxyethylthio] -3,3 ′, 5,5′-tetrachlorodiphenylsulphone, 4, Diol compounds such as 4′-bis [β-hydroxyethylthio] -3,3 ′, 5,5′-tetrabromodiphenyl sulfone; 4,4′-bis [β-mercaptomethylthio] diphenyl sulfone , 4,4′-bis [β-mercaptoethylthio] diphenylsulfone, 4,4′-bis [β-mercaptopropylthio] diphenylsulfone, 4,4′-bis [β-mercaptoethylthio ], 3,3 ', 5,5'- tetrachlorodiphenyl sulfone, 4,4'-bis [(beta) -mercaptoethylthio] -3,3', 5,5'- tetrabromodiphenyl sulfone, etc. And dithiol compounds.

이들 중에서도, 악취의 관점으로부터 디올 화합물이 바람직하고, 환경적인 관점으로부터 비할로겐 화합물이 보다 바람직하고, 얻어지는 우레탄 (메타)아크릴레이트계 화합물의 점도의 관점에서, 특히 바람직하게는, 하기 식 7의 화학 구조를 갖는 4,4＇-비스〔β-히드록시에틸티오〕디페닐술폰이다.Among these, a diol compound is preferable from a viewpoint of a bad smell, a non-halogen compound is more preferable from an environmental standpoint, Especially from a viewpoint of the viscosity of the urethane (meth) acrylate type compound obtained, Especially preferably, the chemistry of following formula 7 4,4'-bis [β-hydroxyethylthio] diphenyl sulfone having a structure.

Figure pct00007
Figure pct00007

상기 식 6으로 표시되는 화합물로서는, 디올 화합물, 디티올 화합물을 들 수 있고, 디올 화합물에 속하는 화합물로서는, 예를 들면, 히드록시메틸티오-p-자일렌, 히드록시메틸티오-m-자일렌, 히드록시메틸티오-o-자일렌, β-히드록시 에틸 티오-p-자일렌, β-히드록시 에틸 티오-m-자일렌, β-히드록시에틸티오-o-자일렌, 3-히드록시프로필티오-p-자일렌, 3-히드록시프로필티오-m-자일렌, 3-히드록시프로필티오-o-자일렌, 1,4-비스〔히드록시메틸티오메틸〕-모노클로로벤젠, 1,4-비스〔히드록시메틸티오메틸〕-디클로로벤젠, 1,4-비스〔히드록시메틸 티오메틸〕-트리클로로벤젠, 1,4-비스〔히드록시메틸티오메틸〕-2,3,5,6-테트라클로로벤젠, 1,3-비스〔히드록시메틸티오메틸〕-2,4,5,6-테트라클로로벤젠, 1,2-비스〔히드록시메틸티오메틸〕-3,4,5,6-테트라클로로벤젠, 1,4-비스〔β-히드록시에틸티오메틸〕-2,3,5,6-테트라클로로벤젠, 1,3-비스〔β-히드록시에틸티오메틸〕-2,4,5,6-테트라클로로벤젠, 1,2-비스〔β-히드록시에틸티오메틸〕-3,4,5,6-테트라클로로벤젠, 1,4-비스〔3-히드록시프로필티오메틸〕-2,3, 5,6-테트라클로로벤젠, 1,3-비스〔3-히드록시프로필티오메틸〕-2,4,5,6-테트라클로로벤젠, 1,2-비스〔3-히드록시프로필티오메틸〕-3,4,5,6-테트라클로로벤젠, 1,4-비스〔히드록시메틸티오메틸〕-2,3,5,6-테트라브로모벤젠, 1,3-비스〔히드록시메틸티오메틸〕-2,4,5,6-테트라브로모벤젠, 1,2-비스〔히드록시메틸 티오메틸〕-3,4,5,6-테트라브로모벤젠, 1,4-비스〔β-히드록시에틸티오메틸〕-2,3,5,6-테트라브로모벤젠, 1,3-비스〔β-히드록시에틸티오메틸〕-2,4,5,6-테트라브로모벤젠, 1,2-비스〔β-히드록시에틸티오메틸〕-3,4,5,6-테트라브로모벤젠, 1,4-비스〔3-히드록시프로필티오메틸〕-2,3,5,6-테트라브로모벤젠, 1,3-비스〔3-히드록시프로필티오메틸〕-2,4,5,6-테트라브로모벤젠, 1,2-비스〔3-히드록시프로필티오메틸〕-3,4,5,6-테트라브로모벤젠 등을 들 수 있다.Examples of the compound represented by the formula (6) include a diol compound and a dithiol compound. Examples of the compound belonging to the diol compound include hydroxymethylthio-p-xylene and hydroxymethylthio-m-xylene. , Hydroxymethylthio-o-xylene, β-hydroxy ethyl thio-p-xylene, β-hydroxy ethyl thio-m-xylene, β-hydroxyethylthio-o-xylene, 3-hydroxy Hydroxypropylthio-p-xylene, 3-hydroxypropylthio-m-xylene, 3-hydroxypropylthio-o-xylene, 1,4-bis [hydroxymethylthiomethyl] -monochlorobenzene, 1,4-bis [hydroxymethylthiomethyl] -dichlorobenzene, 1,4-bis [hydroxymethyl thiomethyl] -trichlorobenzene, 1,4-bis [hydroxymethylthiomethyl] -2,3, 5,6-tetrachlorobenzene, 1,3-bis [hydroxymethylthiomethyl] -2,4,5,6-tetrachlorobenzene, 1,2-bis [hydroxymethylthiomethyl] -3,4, 5,6-tetrachlorobenzene, 1,4- S [β-hydroxyethylthiomethyl] -2,3,5,6-tetrachlorobenzene, 1,3-bis [β-hydroxyethylthiomethyl] -2,4,5,6-tetrachlorobenzene, 1,2-bis [β-hydroxyethylthiomethyl] -3,4,5,6-tetrachlorobenzene, 1,4-bis [3-hydroxypropylthiomethyl] -2,3, 5,6- Tetrachlorobenzene, 1,3-bis [3-hydroxypropylthiomethyl] -2,4,5,6-tetrachlorobenzene, 1,2-bis [3-hydroxypropylthiomethyl] -3,4, 5,6-tetrachlorobenzene, 1,4-bis [hydroxymethylthiomethyl] -2,3,5,6-tetrabromobenzene, 1,3-bis [hydroxymethylthiomethyl] -2,4 , 5,6-tetrabromobenzene, 1,2-bis [hydroxymethyl thiomethyl] -3,4,5,6-tetrabromobenzene, 1,4-bis [β-hydroxyethylthiomethyl] -2,3,5,6-tetrabromobenzene, 1,3-bis [β-hydroxyethylthiomethyl] -2,4,5,6-tetrabromobenzene, 1,2-bis [β- Hydroxyethylthiomethyl] -3,4,5,6-tetrabromobenzene , 1,4-bis [3-hydroxypropylthiomethyl] -2,3,5,6-tetrabromobenzene, 1,3-bis [3-hydroxypropylthiomethyl] -2,4,5, 6-tetrabromobenzene, 1,2-bis [3-hydroxypropylthiomethyl] -3,4,5,6- tetrabromobenzene, etc. are mentioned.

상기 식 6으로 표시되는 화합물 중, 디티올 화합물에 속하는 화합물로서는, 예를 들면, 메르캅토메틸티오-p-자일렌, 메르캅토메틸티오-m-자일렌, 메르캅토메틸티오-o-자일렌, β-메르캅토에틸티오-p-자일렌, β-메르캅토에틸티오-m-자일렌, β-메르캅토에틸티오-o-자일렌, 3-메르캅토프로필티오-p-자일렌, 3-메르캅토프로필티오-m-자일렌, 3-메르캅토프로필티오-o-자일렌, 1,4-비스〔메르캅토메틸티오메틸〕-모노클로로벤젠, 1,4-비스〔메르캅토메틸티오메틸〕-디클로로벤젠, 1,4-비스〔메르캅토메틸티오메틸〕-트리클로로벤젠, 1,4-비스〔메르캅토메틸티오메틸〕-2,3,5,6-테트라클로로벤젠, 1,3-비스〔메르캅토메틸티오메틸〕-2,4,5,6-테트라클로로벤젠, 1,2-비스〔메르캅토메틸티오메틸〕-3,4,5,6-테트라클로로벤젠, 1,4-비스〔β-메르캅토에틸티오메틸〕-2,3,5,6-테트라클로로벤젠, 1,3-비스〔β-메르캅토 에틸 티오메틸〕-2,4,5,6-테트라클로로벤젠, 1,2-비스〔β-메르캅토에틸티오메틸〕-3,4,5,6-테트라클로로벤젠, 1,4-비스〔3-메르캅토프로필티오메틸〕-2,3,5,6-테트라클로로벤젠, 1,3-비스〔3-메르캅토프로필티오메틸〕-2,4,5,6-테트라클로로벤젠, 1,2-비스〔3-메르캅토프로필티오메틸〕-3,4,5,6-테트라클로로벤젠, 1, 4-비스〔메르캅토메틸 티오메틸〕-2,3,5,6-테트라브로모벤젠, 1,3-비스〔메르캅토메틸티오메틸〕-2,4,5,6-테트라브로모벤젠, 1,2-비스〔메르캅토메틸 티오메틸〕-3,4,5,6-테트라 브로모 벤젠, 1,4-비스〔β-메르캅토에틸티오메틸〕-2,3,5,6-테트라브로모 벤젠, 1,3-비스〔β-메르캅토에틸티오메틸〕-2,4,5,6-테트라브로모벤젠, 1,2-비스〔β-메르캅토에틸티오메틸〕-3,4,5,6-테트라브로모벤젠, 1,4-비스〔3-메르캅토프로필티오메틸〕-2,3,5,6-테트라브로모벤젠, 1,3-비스〔3-메르캅토프로필티오메틸〕-2,4,5,6-테트라브로모벤젠, 1,2-비스〔3-메르캅토프로필티오메틸〕-3,4,5,6-테트라브로모벤젠 등을 들 수 있다.As a compound which belongs to a dithiol compound among the compounds represented by the said Formula 6, mercaptomethylthio-p-xylene, mercaptomethylthio-m-xylene, mercaptomethylthio-o-xylene, for example , β-mercaptoethylthio-p-xylene, β-mercaptoethylthio-m-xylene, β-mercaptoethylthio-o-xylene, 3-mercaptopropylthio-p-xylene, 3 -Mercaptopropylthio-m-xylene, 3-mercaptopropylthio-o-xylene, 1,4-bis [mercaptomethylthiomethyl] -monochlorobenzene, 1,4-bis [mercaptomethylthio Methyl] -dichlorobenzene, 1,4-bis [mercaptomethylthiomethyl] -trichlorobenzene, 1,4-bis [mercaptomethylthiomethyl] -2,3,5,6-tetrachlorobenzene, 1, 3-bis [mercaptomethylthiomethyl] -2,4,5,6-tetrachlorobenzene, 1,2-bis [mercaptomethylthiomethyl] -3,4,5,6-tetrachlorobenzene, 1, 4-bis [β-mercaptoethylthiomethyl] -2,3,5,6-tetra Lorobenzene, 1,3-bis [β-mercapto ethyl thiomethyl] -2,4,5,6-tetrachlorobenzene, 1,2-bis [β-mercaptoethylthiomethyl] -3,4,5 , 6-tetrachlorobenzene, 1,4-bis [3-mercaptopropylthiomethyl] -2,3,5,6-tetrachlorobenzene, 1,3-bis [3-mercaptopropylthiomethyl] -2 , 4,5,6-tetrachlorobenzene, 1,2-bis [3-mercaptopropylthiomethyl] -3,4,5,6-tetrachlorobenzene, 1,4-bis [mercaptomethyl thiomethyl] -2,3,5,6-tetrabromobenzene, 1,3-bis [mercaptomethylthiomethyl] -2,4,5,6-tetrabromobenzene, 1,2-bis [mercaptomethyl thio Methyl] -3,4,5,6-tetrabromo benzene, 1,4-bis [β-mercaptoethylthiomethyl] -2,3,5,6-tetrabromo benzene, 1,3-bis [ β-mercaptoethylthiomethyl] -2,4,5,6-tetrabromobenzene, 1,2-bis [β-mercaptoethylthiomethyl] -3,4,5,6-tetrabromobenzene, 1,4-bis [3-mercaptopropylthiomethyl] -2,3, 5,6-tetrabromobenzene, 1,3-bis [3-mercaptopropylthiomethyl] -2,4,5,6-tetrabromobenzene, 1,2-bis [3-mercaptopropylthiomethyl ], 3,4,5,6- tetrabromobenzene, etc. are mentioned.

이들 중에서도, 악취의 관점으로부터 디올 화합물이 바람직하고, 환경적인 관점에서 비할로겐 화합물이 보다 바람직하고, 특히 바람직하게는 얻어지는 우레탄 (메타)아크릴레이트계 화합물의 점도의 관점에서, 하기 식 8의 화학 구조를 갖는 β-히드록시에틸티오-p-자일렌이다.Among these, a diol compound is preferable from a odor viewpoint, and a non-halogen compound is more preferable from an environmental viewpoint, Especially preferably, from a viewpoint of the viscosity of the urethane (meth) acrylate type compound obtained, the chemical structure of following formula (8) Β-hydroxyethylthio-p-xylene having

Figure pct00008
Figure pct00008

이소시아나토알킬 (메타)아크릴레이트의 구체적인 예로서는, 예를 들면, 이소시아나토메틸 (메타)아크릴레이트, 2-이소시아나토에틸 (메타)아크릴레이트, 2-이소시아나토프로필 (메타)아크릴레이트, 3-이소시아나토프로필 (메타)아크릴레이트 등의 지방족계 이소시아나토알킬 (메타)아크릴레이트를 들 수 있다.As a specific example of isocyanatoalkyl (meth) acrylate, for example, isocyanatomethyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 2-isocyanatopropyl (meth) acrylate And aliphatic isocyanatoalkyl (meth) acrylates such as 3-isocyanatopropyl (meth) acrylate.

이들 중에서도 입수의 용이함 때문에 2-이소시아나토에틸(메타)아크릴레이트가 바람직하고, 특히 바람직하게는, 얻어지는 우레탄 (메타)아크릴레이트계 화합물의 속경화성의 관점에서 2-이소시아나토에틸아크릴레이트이다.Among these, 2-isocyanatoethyl (meth) acrylate is preferable because of its availability, and particularly preferably 2-isocyanatoethyl acrylate from the viewpoint of fast curing properties of the urethane (meth) acrylate compound obtained. .

상기 식 5 또는 6으로 표시되는 화합물과 이소시아나토알킬 (메타)아크릴레이트의 반응에 있어서의 혼합 비율은, 상기 식 5 또는 6으로 표시되는 화합물 1 몰에 대해서, 이소시아나토알킬 (메타)아크릴레이트를 2?2.1 몰인 것이 바람직하다. 너무 적으면 반응 후에 수산기 말단이나 메르캅토기 말단의 화합물이 반응계내에 남기 때문에, 목적으로 하는 우레탄 (메타)아크릴레이트계 화합물이 수율 좋게 얻어지지 않는 경향이 있고, 반대로, 너무 많으면, 반응 후에 원료의 이소시아나토알킬 (메타)아크릴레이트가 반응계내에 남기 때문에, 목적으로 하는 우레탄 (메타)아크릴레이트계 화합물이 수율 좋게 얻어지지 않는 경향이 있다.The mixing ratio in reaction of the compound represented by said Formula 5 or 6 and isocyanate alkyl (meth) acrylate is isocyanatoalkyl (meth) acryl with respect to 1 mol of compounds represented by said Formula 5 or 6. The rate is preferably 2 to 2.1 moles. If the amount is too small, the compound at the hydroxyl end or the mercapto group is left in the reaction system after the reaction, so that the desired urethane (meth) acrylate compound tends not to be obtained in a good yield. Since isocyanatoalkyl (meth) acrylate remains in the reaction system, there is a tendency that the desired urethane (meth) acrylate compound is not obtained in good yield.

본 발명에서는, 상기 식 5 또는 6으로 표시되는 화합물을 유기용제에 용해하고, 이 용액을 이소시아나토알킬 (메타)아크릴레이트에 적하하는 반응 방식이 바람직하다. 사용되는 유기용제로서는, 예를 들면, 톨루엔, 자일렌 등의 방향족 탄화수소류, 초산에틸, 초산부틸 등의 에스테르류, n-프로필 알코올, 이소-프로필알코올등의 지방족알코올류, 아세톤, 메틸에틸케톤, 시클로헥사논 등의 케톤류, 테트라 하이드로퓨란, 디에틸에테르 등의 에테르류 등을 들 수 있다. 그 중에서도 용해성의 관점에서 테트라하이드로퓨란이 특히 바람직하다.In this invention, the reaction system which melt | dissolves the compound represented by said Formula 5 or 6 in the organic solvent, and this solution is dripped at the isocyanatoalkyl (meth) acrylate is preferable. As an organic solvent used, For example, aromatic hydrocarbons, such as toluene and xylene, esters, such as ethyl acetate and butyl acetate, aliphatic alcohols, such as n-propyl alcohol and iso-propyl alcohol, acetone, methyl ethyl ketone And ketones such as cyclohexanone, ethers such as tetrahydrofuran and diethyl ether, and the like. Among them, tetrahydrofuran is particularly preferable in view of solubility.

용액 중에 있어서의 상기 식 5 또는 6으로 표시되는 화합물의 농도는, 바람직하게는 1?500 중량부/ℓ, 보다 바람직하게는 10?300 중량부/ℓ, 더욱 바람직하게는 50?200 중량부/ℓ이다. 적하 속도의 바람직한 범위는, 상기 식 5 또는 6으로 표시되는 화합물의 전량을 100 몰로 했을 때에, 바람직하게는 1?100 몰/시간, 보다 바람직하게는 5?100 몰/시간, 더욱 바람직하게는 10?100 몰/시간이다. 적하 속도가 너무 늦으면 생산성에 뒤떨어지는 경향이 있고, 너무 빠르면 반응이 폭주하여, 그 발열에 의해 원료인 이소시아나토알킬 (메타)아크릴레이트가 중합해 버리는 경향이 있다.The concentration of the compound represented by the formula 5 or 6 in the solution is preferably 1 to 500 parts by weight, more preferably 10 to 300 parts by weight, and even more preferably 50 to 200 parts by weight. l. The preferred range of the dropping rate is preferably 1 to 100 mol / hour, more preferably 5 to 100 mol / hour, still more preferably 10 when the total amount of the compound represented by the formula 5 or 6 is 100 mol. ? 100 mol / hour. If the dropping speed is too slow, the productivity tends to be inferior, and if too fast, the reaction is runaway, and the isocyanate alkyl (meth) acrylate as a raw material tends to polymerize due to the exotherm.

본 발명에 대해서는, 반응을 촉진하는 목적으로 디부틸틴디라우레이트와 같은 금속 촉매나, 1,8-디아자비시클로［5.4.0］운데센-7과 같은 아민계 촉매 등을 이용하는 것이 바람직하다. 촉매의 첨가량은, 상기 식 5 또는 6으로 표시되는 화합물 100 중량부에 대해서, 0.01 중량부 이상인 것이 바람직하고, 특히는 0.01?0.1 중량부, 더욱은 0.02?0.05 중량부인 것이 바람직하다. 첨가량이 너무 적으면 생산성에 뒤떨어지는 경향이 된다.In the present invention, a metal catalyst such as dibutyl tin dilaurate, an amine catalyst such as 1,8-diazabicyclo [5.4.0] undecene-7, or the like is preferably used for the purpose of promoting the reaction. It is preferable that it is 0.01 weight part or more with respect to 100 weight part of compounds represented by said Formula 5 or 6, and, as for the addition amount of a catalyst, it is especially preferable that it is 0.01-0.1 weight part, Furthermore, it is 0.02-0.05 weight part. Too small an amount tends to be inferior in productivity.

반응 온도는, 통상 40?80℃, 바람직하게는 50?70℃, 보다 바람직하게는 55?65℃의 범위이다. 반응 온도가 너무 낮으면 생산성이 뒤떨어지는 경향이 되고, 너무 높으면 원료의 이소시아나토알킬 (메타)아크릴레이트가 중합해 버리는 경향이 있다.Reaction temperature is 40-80 degreeC normally, Preferably it is 50-70 degreeC, More preferably, it is the range of 55-65 degreeC. When reaction temperature is too low, there exists a tendency for productivity to be inferior, and when too high, there is a tendency for the isocyanate alkyl (meth) acrylate of a raw material to superpose | polymerize.

또, 반응은, 생성물의 색상 향상 때문에, 불활성 가스하에서 실시되는 것이 바람직하다. 반응의 종점은, 반응액 중의 이소시아네이트량을 적정 등의 수법으로 확인함으로써 판단할 수 있다. 적정의 수법으로서는, 반응물의 일부를 채취하여, 디-n-부틸아민에 더하여 반응시키고, 잔존하는 디-n-부틸 아민을 염산으로 역적정 하는 것 등을 들 수 있다.In addition, the reaction is preferably carried out under an inert gas for improving the color of the product. The end point of reaction can be judged by confirming the amount of isocyanate in reaction liquid by methods, such as a titration. As a suitable technique, a part of reactant is extract | collected, it is made to react in addition to di-n-butylamine, and back titration of the remaining di-n-butylamine with hydrochloric acid etc. are mentioned.

얻어지는 우레탄 (메타)아크릴레이트계 화합물은, 미량 잔존하는 원료의 이소시아네이트알킬 (메타)아크릴레이트 등을 제외하기 위하여 세정할 수 있다. 세정의 수법으로서는, 반응계 내에 화학식 1 또는 2의 화합물의 빈용매를 투입하고, 빈용매층으로 이행한 이소시아네이트알킬 (메타)아크릴레이트를 제거한다. 빈용매로서는, 메탄올, 에탄올 등의 저급 알코올, 및 이들 혼합 용매가 바람직하다.The urethane (meth) acrylate type compound obtained can be wash | cleaned in order to remove the isocyanate alkyl (meth) acrylate etc. of the raw material which remain in trace amounts. As a method of washing | cleaning, the poor solvent of the compound of Formula (1) or (2) is thrown into a reaction system, and the isocyanate alkyl (meth) acrylate which transferred to the poor solvent layer is removed. As a poor solvent, lower alcohols, such as methanol and ethanol, and these mixed solvents are preferable.

이렇게 하여 본 발명에서 사용되는 우레탄 (메타)아크릴레이트계 화합물(A)를 얻을 수 있다.In this way, the urethane (meth) acrylate type compound (A) used by this invention can be obtained.

본 발명에서 이용되는 우레탄 (메타)아크릴레이트계 화합물(A)는, 분자 구조의 양말단에 (메타)아크릴로일기를 갖기 때문에, 자외선 등의 활성 에너지선에 의해 신속하게 경화하여, 고도의 가교 구조를 갖는 경화물을 형성한다. 이 속경화성은 코팅 용도에 있어서는 중요하고, 적은 광량으로 충분히 경화시킬 수 있다.Since the urethane (meth) acrylate type compound (A) used by this invention has a (meth) acryloyl group in the sock end of molecular structure, it is hardened | cured rapidly by active energy rays, such as an ultraviolet-ray, and highly crosslinked A cured product having a structure is formed. This fast curing property is important for coating applications and can be sufficiently cured with a small amount of light.

또한, 이와 같은 우레탄 (메타)아크릴레이트계 화합물(A)는, 분자 구조중에 우레탄 결합이 있기 때문에, 형성되는 코트층은, 플라스틱 필름, 유리, 금속 등의 기재에 높은 밀착성을 갖는 것이 된다. 또, 상술한 제조 방법에 표시되는 바와 같이, 비교적 단순한 반응으로 제조되기 때문에, 올리고머체나 불순물이 지극히 적고, 굴절률의 정도에도 뛰어난 것이 된다.Moreover, since such a urethane (meth) acrylate type compound (A) has a urethane bond in a molecular structure, the coat layer formed becomes what has high adhesiveness to base materials, such as a plastic film, glass, and a metal. Moreover, since it is manufactured by comparatively simple reaction as shown in the manufacturing method mentioned above, there are very few oligomer bodies and impurities, and it is excellent also in the grade of refractive index.

본 발명에 있어서의 우레탄 (메타)아크릴레이트계 화합물의 굴절률 정도는, 바람직하게는 ±0.001 이내, 보다 바람직하게는 ±0.0005 이내, 특히 바람직하게는±0.0003 이내이다. 이와 같은 정도가 상기 범위를 넘으면 코트 층의 광학 설계가 곤란해지는 경향이 있다.The degree of refractive index of the urethane (meth) acrylate compound in the present invention is preferably within ± 0.001, more preferably within ± 0.0005, particularly preferably within ± 0.0003. When this degree exceeds the said range, there exists a tendency for the optical design of a coat layer to become difficult.

본 발명에서는, 우레탄 (메타)아크릴레이트계 화합물(A) 중에서도, 고굴절률의 점에서 화학식 1로 표시되는 화합물이 바람직하다.In this invention, among the urethane (meth) acrylate type compounds (A), the compound represented by General formula (1) from a point of high refractive index is preferable.

본 발명에서, 성분(B)로서 사용되는 단관능 (메타)아크릴레이트계 화합물은, 화학식 3 및/또는 4로 표시되는 것이며, 그 구체적인 예로서는, 예를 들면, 2-(o-페닐페녹시)메틸아크릴레이트, 2-(m-페닐페녹시)메틸아크릴레이트, 2-(p-페닐페녹시)메틸아크릴레이트, 2-(o-페닐페녹시)에틸아크릴레이트, 2-(m-페닐페녹시)에틸아크릴레이트, 2-(p-페닐페녹시)에틸아크릴레이트, 2-(o-페닐페녹시)프로필아크릴레이트, 2-(m-페닐페녹시)프로필아크릴레이트, 2-(p-페닐페녹시)프로필아크릴레이트 등의 화학식 3으로 표시되는 비페닐계 화합물；2-페닐-2′-(β-(메타)아크릴로일옥시메톡시페닐)프로판, 2-페닐-2′-(β-(메타)아크릴로일옥시에톡시 페닐)프로판, 2-페닐-2′-(β-(메타)아크릴로일옥시프로폭시페닐)프로판 등의 화학식 4로 표시되는 비스페놀 A계 화합물을 들 수 있다. 이들 중에서도, 고굴절률의 점에서, 화학식 3으로 표시되는 비페닐계 화합물이 바람직하고, 속경화성의 관점에서, 아크릴레이트가 보다 바람직하고, 저점도의 관점에서, 2-(o-페닐 페녹시)에틸아크릴레이트가 특히 바람직하다.In this invention, the monofunctional (meth) acrylate type compound used as a component (B) is represented by General formula (3) and / or 4, As a specific example, it is 2- (o-phenylphenoxy), for example. Methylacrylate, 2- (m-phenylphenoxy) methylacrylate, 2- (p-phenylphenoxy) methylacrylate, 2- (o-phenylphenoxy) ethylacrylate, 2- (m-phenylphenoxy Ethyl acrylate, 2- (p-phenylphenoxy) ethyl acrylate, 2- (o-phenylphenoxy) propyl acrylate, 2- (m-phenylphenoxy) propyl acrylate, 2- (p- Biphenyl type compounds represented by general formula (3), such as phenylphenoxy) propyl acrylate; 2-phenyl-2 '-((beta)-(meth) acryloyloxy methoxyphenyl) propane, 2-phenyl-2'-( Bisphenol A type compounds represented by general formula (4), such as (beta)-(meth) acryloyloxyethoxy phenyl) propane and 2-phenyl-2 '-((beta)-(meth) acryloyloxypropoxyphenyl) propane, are mentioned. Can be. Among these, from the point of high refractive index, the biphenyl type compound represented by General formula (3) is preferable, From a viewpoint of fast hardening property, an acrylate is more preferable, From a viewpoint of low viscosity, 2- (o-phenyl phenoxy) Ethyl acrylate is particularly preferred.

본 발명에 있어서의, 성분(B)의 배합량은, 성분(A)와 성분(B)의 합계 100 중량부에 대해서 10?90 중량부, 보다 바람직하게는 20?80 중량부, 더욱 바람직하게는 30?70 중량부, 특히 바람직하게는 40?60 중량부이다. 성분(B)의 배합량이 너무 적으면, 활성 에너지선 경화성 조성물의 저점도화가 곤란해지는 경향이 있고, 반대로 너무 많으면, 활성 에너지선에 의한 속경화성이 저하되며, 또한 기재와의 밀착성이 저하되는 경향이 있다.In this invention, the compounding quantity of a component (B) is 10-90 weight part with respect to a total of 100 weight part of a component (A) and a component (B), More preferably, it is 20-80 weight part, More preferably, It is 30-70 weight part, Especially preferably, it is 40-60 weight part. If the amount of the component (B) is too small, the viscosity of the active energy ray-curable composition tends to be difficult to be reduced. On the contrary, if the amount of component (B) is too high, the fast curing property of the active energy ray is lowered and the adhesion to the substrate is lowered. There is this.

또한, 경화에 필요한 광량으로서는, 예를 들면, 자외선에 의한 경화를 실시할 때에는, 0.1?20 J/㎠이 바람직하고, 0.5?10 J/㎠이 보다 바람직하다.In addition, as a quantity of light required for hardening, when hardening by an ultraviolet-ray, for example, 0.1-20 J / cm <2> is preferable and 0.5-10 J / cm <2> is more preferable.

본 발명에서 사용되는 우레탄 (메타)아크릴레이트계 화합물은, 분자 구조중에 방향환, 유황원자, 필요에 따라서 염소, 브롬, 요오드 등의 할로겐 원자를 갖기 때문에 고굴절률이며, 또한, 본 발명에서 사용되는 단관능 (메타)아크릴레이트계 화합물도, 분자 구조중에 방향환을 가져 고굴절률이기 때문에, 본 발명의 활성 에너지선경화성 조성물은 고굴절률을 갖는 경화물을 형성할 수 있다.The urethane (meth) acrylate compound used in the present invention has a high refractive index because it has an aromatic ring, a sulfur atom, and halogen atoms such as chlorine, bromine, iodine, etc. in the molecular structure, and is also used in the present invention. Since the monofunctional (meth) acrylate-based compound also has an aromatic ring in its molecular structure and has a high refractive index, the active energy ray-curable composition of the present invention can form a cured product having a high refractive index.

본 발명에서는, 이와 같은 경화물의 굴절률이 중요하고, 경화물의 굴절률은 1.58 이상인 것이 바람직하고, 보다 바람직하게는 1.58?1.64, 더욱은 1.59?1.63, 특히는 1.60?1.62인 것이 바람직하다. 경화물의 굴절률이 너무 낮으면 최근 고굴절률화의 요망에 대해 대응하는 것이 곤란해지고, 너무 높으면 아베수가 저하하는 경향이 있다. 또한, 본 발명에 있어서의 굴절률은, NaD선을 이용하여 23℃에서 측정되는 값이다.In this invention, the refractive index of such hardened | cured material is important, It is preferable that the refractive index of hardened | cured material is 1.58 or more, More preferably, it is 1.58-1.64, Furthermore, it is preferable that it is 1.59-1.63, Especially 1.60-1.62. When the refractive index of hardened | cured material is too low, it becomes difficult to respond to the request of high refractive index in recent years, and when too high, Abbe number tends to fall. In addition, the refractive index in this invention is a value measured at 23 degreeC using a NaD line.

본 발명에서는, 아베수도 중요하고, 바람직하게는 25이상, 보다 바람직하게는 25?40, 더욱 바람직하게는 26?35, 특히 바람직하게는 26?30이다. 아베수의 저하는 색분산의 증대를 의미하고, 너무 낮으면, 렌즈나 코트막에 색얼룩이 발생하기 쉬운 경향이 있다. 일반적으로, 아베수의 향상은 굴절률의 저하를 부르기 때문에, 성분(B)의 종류나 배합량을 적절히 선정할 필요가 있다. 예를 들면, 성분(B)로서 상기 중에서도 특히 비스페놀 A계의 화합물을 선택하거나 배합량이라고 하여도 성분(A)와 (B)의 합계 100 중량부에 대해서 10 중량부 이상 배합하거나 하는 등이 선택된다. 또한, 통상, 아베수의 상한값은 100이다.In this invention, Abbe number is also important, Preferably it is 25 or more, More preferably, it is 25-40, More preferably, it is 26-35, Especially preferably, it is 26-30. A decrease in Abbe's number means an increase in color dispersion, and if too low, color staining tends to occur on the lens and the coating film. In general, since the improvement of the Abbe number causes a decrease in the refractive index, it is necessary to appropriately select the kind or the blending amount of the component (B). For example, as a component (B), especially the bisphenol-A type compound is selected among the said, or even if it is a compounding quantity, 10 weight part or more is mix | blended with respect to a total of 100 weight part of components (A) and (B), etc. are selected. . In addition, the upper limit of Abbe's number is 100 normally.

본 발명에서, 사용되는 단관능 (메타)아크릴레이트계 화합물(B)는, 실온 부근에서 1 Pa?s이하로 저점도이며, 고점도인 우레탄 (메타)아크릴레이트계 화합물에 배합함으로써, 저점도인 조성물을 조제할 수 있다.In this invention, the monofunctional (meth) acrylate type compound (B) used is low viscosity below 1 Pa * s in the vicinity of room temperature, and is low viscosity by mix | blending with the high viscosity urethane (meth) acrylate type compound. The composition can be prepared.

여기서, 고점도인 우레탄 (메타)아크릴레이트계 화합물에 저점도의 단관능(메타)아크릴레이트계 화합물을 배합하는 것은 공지이다. 본 발명에서는, 높은 레벨로의 굴절률을 유지한 채로, 아베수의 저하도 없고, 저점도화를 달성할 수 있는 단관능 (메타)아크릴레이트계 화합물로서 상기 특정의 화학식 3 및/또는 4로 표시되는 화합물을 선택한 것에 최대의 특징이 있다. 예를 들면, 상기 특허 문헌 3의 단락 번호 0050 및 0051에 기재된 단관능 (메타)아크릴레이트계 화합물을 배합한 활성 에너지선 경화성 조성물에서는 본 발명의 효과를 얻을 수 없다.It is known to mix | blend a low viscosity monofunctional (meth) acrylate type compound with the high viscosity urethane (meth) acrylate type compound here. In the present invention, a monofunctional (meth) acrylate-based compound capable of achieving low viscosity without lowering Abbe's number while maintaining a high refractive index is represented by the above-mentioned specific formulas (3) and / or (4). The greatest feature is the selection of the compound. For example, the effect of this invention cannot be acquired in the active energy ray curable composition which mix | blended the monofunctional (meth) acrylate type compound of Paragraph No. 0050 and 0051 of the said patent document 3.

본 발명에서는, 이와 같은 활성 에너지선 경화성 조성물의 점도가 중요하고, 25℃에 있어서의 점도가 100 Pa?s이하인 것이 바람직하고, 보다 바람직하게는 1?90 Pa?s, 더욱은 2?80 Pa?s, 특히는 3?70 Pa?s인 것이 바람직하다. 점도가 너무 높으면, 무용제로 코팅하는 것이 곤란해지고, 너무 낮으면 2P 성형이나 나노임프린트 등의 미세 렌즈 제조 프로세스에 적용하는 것이 곤란해진다.In this invention, the viscosity of such an active energy ray curable composition is important, It is preferable that the viscosity in 25 degreeC is 100 Pa.s or less, More preferably, it is 1-90 Pa.s, Furthermore, it is 2-80 Pa. ? s, particularly preferably 3? 70 Pa? s. If the viscosity is too high, coating with a solvent will be difficult, and if too low, it will be difficult to apply to fine lens manufacturing processes such as 2P molding and nanoimprint.

본 발명의 활성 에너지선 경화성 조성물은, 상기의 성분(A) 및 성분(B)를 함유하여 이루어지는 것이지만, 바람직하게는 더욱, 성분(C)로서 광중합 개시제를 함유한다.Although the active energy ray curable composition of this invention contains said component (A) and component (B), Preferably it contains a photoinitiator further as a component (C).

이와 같은 광중합 개시제로서는, 광의 작용에 의해 래디칼을 발생하는 것이면 좋고, 예를 들면, 4-페녹시디클로로아세트페논, 4-t-부틸디클로로아세트페논, 디에톡시아세트페논, 2-히드록시-2-메틸-1-페닐프로판-1-온, 1-(4-이소프로필렌페닐)-2-히드록시-2-메틸프로판-1-온, 1-(4-도데실페닐)-2-히드록시-2-메틸프로판-1-온, 4-(2-히드록시에톡시)-페닐(2-히드록시-2-프로필)케톤, 1-히드록시시클로헥실페닐케톤, 2-메틸-1-〔4-(메틸티오)페닐〕-2-몰포리노프로판-1, 벤조인, 벤조인메틸에테르, 벤조인에틸에테르, 벤조인이소프로필에테르, 벤조인이소부틸에테르, 벤질디메틸케탈, 벤조페논, 벤조일안식향산, 벤조일안식향산메틸, 4-페닐벤조페논, 히드록시벤조페논, 4-벤조일-4´-메틸디페닐설파이드, 3,3´-디메틸-4-메톡시벤조페논, 티옥산손, 2-크롤티옥산손, 2-메틸티옥산손, 2,4-디메틸티옥산손, 이소프로필티옥산손, 캠포퀴논(camphorquinone), 디벤조스베론, 2-에틸안스라퀴논, 4´,4˝-디에틸이소프탈로페논, 3,3´,4,4´-테트라(t-부틸퍼옥시카르보닐) 벤조페논, α-아실옥심에스테르, 아실포스핀옥사이드, 메틸페닐글리옥시레이트, 벤질, 9,10-페난스렌퀴논, 4-(2-히드록시에톡시)페닐-(2-히드록시-2-프로필)케톤 등을 들 수 있고, 그 중에서도 벤질디메틸케탈, 1-히드록시시클로헥실페닐케톤, 벤조일이소프로필에테르, 4-(2-히드록시에톡시)-페닐(2-히드록시-2-프로필)케톤, 2-히드록시-2-메틸-1-페닐프로판-1-온이 매우 적합하게 이용된다.As such a photoinitiator, what is necessary is just to generate | occur | produce a radical by the action of light, For example, 4-phenoxy dichloro acetphenone, 4-t- butyl dichloro acetphenone, diethoxy acetphenone, 2-hydroxy-2- Methyl-1-phenylpropan-1-one, 1- (4-isopropylenephenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy- 2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid , Methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-croti Oxoxone, 2-methylthio Acidone, 2,4-dimethylthioxone, isopropylthioxone, camphorquinone, dibenzoseveron, 2-ethyl anthraquinone, 4 ′, 4′-diethylisophthalophenone, 3, 3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, α-acyl oxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanslenquinone, 4- ( 2-hydroxyethoxy) phenyl- (2-hydroxy-2- propyl) ketone etc. are mentioned, Especially, benzyl dimethyl ketal, 1-hydroxy cyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2) -Hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one are suitably used.

성분(C)의 함유량은, 성분(A)와 성분(B)의 합계 100 중량부에 대해서 0.1?10 중량부인 것이 바람직하고, 보다 바람직하게는 0.2?5 중량부, 특히 바람직하게는 0.3?3 중량부이다. 이와 같은 함유량이 너무 적으면 경화 속도가 늦어지는 경향이 있고, 너무 많으면 경화물의 색상이 악화되는 경향이 있다.It is preferable that content of a component (C) is 0.1-10 weight part with respect to a total of 100 weight part of a component (A) and a component (B), More preferably, it is 0.2-5 weight part, Especially preferably, it is 0.3-3 Parts by weight. When such content is too small, there exists a tendency for hardening rate to become slow, and when too large, there exists a tendency for the color of hardened | cured material to deteriorate.

또한, 상기 광중합 개시제의 조제로서 예를 들면, 트리에탄올아민, 트리이소프로판올아민, 4,4´-디메틸아미노벤조페논(미히라케톤), 4,4´-디에틸아미노벤조페논, 2-디메틸아미노에틸안식향산, 4-디메틸아미노안식향산에틸, 4-디메틸아미노안식향산(n-부톡시)에틸, 4-디메틸아미노안식향산이소아밀, 4-디메틸아미노안식향산 2-에틸헥실, 2,4-디에틸옥산티옥산손, 2,4-디이소프로필티옥산손 등을 병용하는 것도 가능하다.Further, for example, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (mihiraketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethyl as preparations of the photopolymerization initiator. Benzoic acid, 4-dimethylamino benzoic acid, 4-dimethylamino benzoic acid (n-butoxy) ethyl, 4-dimethylamino benzoic acid isoamyl, 4-dimethylamino benzoic acid 2-ethylhexyl, 2,4-diethyloxane thioxane It is also possible to use together a hand, 2, 4- diisopropyl thioxane hand, etc.

또, 본 발명에 대해서는, 성분(C)에 더하여 연쇄 이동제로서 메르캅탄 화합물을 함유하는 것도 가능하다.Moreover, about this invention, it is also possible to contain a mercaptan compound as a chain transfer agent in addition to a component (C).

메르캅탄 화합물로서는, 분자 구조중에 복수의 티올기를 갖는 화합물이 바람직하다. 복수의 티올기를 갖는 화합물을 이용하는 것으로, 한층 더 고굴절률화나 표면 경도의 향상이 가능해진다.As the mercaptan compound, a compound having a plurality of thiol groups in the molecular structure is preferable. By using the compound which has a some thiol group, further high refractive index and the surface hardness can be improved.

복수의 티올기를 갖는 메르캅탄 화합물로서는, 예를 들면, 벤젠디티올, 자일렌디티올, 헥산디티올, 톨릴렌트리티올, 펜타에리스리톨테트라퀴스(β-티오프로피오네이트), 펜타에리스리톨테트라퀴스(티오글리코레이트), 트리메티롤프로판트리스(β-티오프로피오네이트), 트리메틸프로판트리스(티오글리코레이트), 디에틸렌글리콜비스(β-티오프로피오네이트), 디에틸렌글리콜비스(티오글리코레이트), 트리에틸렌글리콜비스(β-티오프로피오네이트), 트리에틸렌글리콜비스(티오글리코레이트), 디펜타에리스리톨헥사퀴스(β-티오프로피오네이트), 디펜타에리스리톨헥사퀴스(티오글리코레이트), 트리스［2-(β-티오프로피오닐옥시)에틸］트리이소시아누레이트, 트리스(2-티오글리콜옥시에틸)트리이소시아누레이트, 트리스［2-(β-티오프로피오닐옥시에톡시)에틸］트리이소시아누레이트, 트리스(2-티오글리코닐옥시에톡시에틸)트리이소시아누레이트, 트리스［3-(β-티오프로피오닐옥시)프로필］트리이소시아누레이트, 트리스(3-티오글리콜옥시프로필)트리이소시아누레이트 등을 들 수 있다.As a mercaptan compound which has a some thiol group, For example, benzenedithiol, xylenedithiol, hexanedithiol, tolylene thiol, pentaerythritol tetraquis ((beta) -thiopropionate), pentaerythritol tetraquis ( Thioglycolate), trimetholpropane tris (β-thiopropionate), trimethylpropane tris (thioglycorate), diethylene glycol bis (β-thiopropionate), diethylene glycol bis (thioglycorate) , Triethylene glycol bis (β-thiopropionate), triethylene glycol bis (thioglycorate), dipentaerythritol hexaquise (β-thiopropionate), dipentaerythritol hexaquise (thioglycorate), tris [2- (β-thiopropionyloxy) ethyl] triisocyanurate, tris (2-thioglycoloxyethyl) triisocyanurate, tris [2- (β-thiopropionyloxyethoxy) Ethyl] triisocyanurate, tris (2-thioglyconyloxyethoxyethyl) triisocyanurate, tris [3- (β-thiopropionyloxy) propyl] triisocyanurate, tris (3-thioglycoloxy Propyl) triisocyanurate etc. are mentioned.

또, 본 발명의 활성 에너지선경화성 조성물은, 필요에 따라서, 본 발명의 효과를 해치지 않는 범위 내에서 다른 공중합성 성분이나 각종 첨가제를 이용해도 좋다.Moreover, you may use the other copolymerizable component and various additives for the active energy ray curable composition of this invention in the range which does not impair the effect of this invention as needed.

다른 공중합 성분으로서는, 예를 들면, 에틸렌성 불포화 모노머(단, 성분(A), 성분(B)는 제외한다.)가 바람직하다. 이와 같은 에틸렌성 불포화 모노머로서는, 1 분자 중에 1개 이상의 에틸렌성 불포화기를 가지는 것이면 좋고, 단관능 모노머(단, 성분(B)는 제외한다.), 2 관능 모노머(단, 성분(A)는 제외한다.), 3 관능 이상의 모노머를 들 수 있다.As another copolymerization component, an ethylenically unsaturated monomer (a component (A) and a component (B) are excluded, for example) is preferable, for example. As such an ethylenically unsaturated monomer, what is necessary is just to have one or more ethylenically unsaturated groups in 1 molecule, and monofunctional monomer (except component (B) is excluded) and bifunctional monomer (except component (A). And trifunctional or higher functional monomers.

단관능 모노머로서는, 예를 들면, 스틸렌, 비닐톨루엔, 클로로스틸렌, α-메틸스틸렌, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 아크릴로니트릴, 초산비닐, 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 2-히드록시부틸(메타)아크릴레이트, 페녹시에틸(메타)아크릴레이트, 2-페녹시-2-히드록시프로필(메타)아크릴레이트, 2-히드록시-3-페녹시프로필(메타) 아크릴레이트, 3-클로로-2-히드록시프로필(메타)아크릴레이트, 글리세린모노(메타)아크릴레이트, 글리시딜(메타)아크릴레이트, 라우릴(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 트리시클로데카닐(메타)아크릴레이트, 디시클로펜테닐(메타)아크릴레이트, n-부틸(메타)아크릴레이트, 헥실(메타)아크릴레이트, 헵틸(메타)아크릴레이트, 옥틸(메타)아크릴레이트, 노닐(메타)아크릴레이트, 디실(메타)아크릴레이트, 이소디실(메타)아크릴레이트, 도데실(메타)아크릴레이트, n-스테아릴(메타)아크릴레이트, 벤질(메타)아크릴레이트, 페놀에틸렌옥사이드 변성(메타)아크릴레이트, 노닐페놀프로필렌옥사이드 변성(메타)아크릴레이트, 2-(메타)아크릴로일옥시-2-히드록시프로필프탈레이트 등의 프탈산 유도체의 하프 에스테르(메타)아크릴레이트, 퍼프릴(메타)아크릴레이트, 카르비톨(메타)아크릴레이트, 벤질(메타)아크릴레이트, 부톡시에틸(메타)아크릴레이트, 아릴(메타)아크릴레이트, 아크릴로일모르포린, 2-히드록시에틸아크릴아미드, N-메틸올(메타)아크릴아미드, N-비닐피롤리돈, 2-비닐피리딘, 2-(메타)아크릴로일옥시에틸애시드 인산염 모노에스테르 등을 들 수 있다.As the monofunctional monomer, for example, styrene, vinyltoluene, chlorostyrene, α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, vinyl acetate, 2-hydroxyethyl (meth ) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, Uryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, n-butyl (meth) acrylic Latex, hexyl (meth) acrylate, heptyl (meth) acrylic Yite, octyl (meth) acrylate, nonyl (meth) acrylate, disil (meth) acrylate, isodisyl (meth) acrylate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl Half ester of phthalic acid derivatives such as (meth) acrylate, phenol ethylene oxide modified (meth) acrylate, nonylphenol propylene oxide modified (meth) acrylate, and 2- (meth) acryloyloxy-2-hydroxypropyl phthalate (Meth) acrylate, perryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, aryl (meth) acrylate, acryloyl morpholine , 2-hydroxyethyl acrylamide, N-methylol (meth) acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, 2- (meth) acryloyloxyethyl acid phosphate monoester, etc. are mentioned. .

또, 단관능 모노머로서 상기 외에 아크릴산의 미카엘 부가물 또는 2-아크릴로일옥시에틸디카르본산 모노 에스테르도 들 수 있고, 아크릴산의 미카엘 부가물로서는, 아크릴산 다이머, 메타크릴산 다이머, 아크릴산 트리머, 메타크릴산 트리머, 아크릴산 테트라머, 메타크릴산 테트라머 등을 들 수 있다. 또, 특정의 치환기를 갖는 카르본산인 2-아크릴로일옥시에틸디카르본산 모노에스테르로서는, 예를 들면 2-아크릴로일옥시에틸호박산 모노에스테르, 2-메타크릴로일옥시에틸호박산 모노에스텔, 2-아크릴로일옥시에틸프탈산 모노에스테르, 2-메타크릴록시에틸푸탈산 모노에테르, 2-아크릴로일옥시에틸헥사하이드로푸탈산 모노에스테르, 2-메타크릴록시에틸헥사하이드로후탈산 모노에스테르 등을 들 수 있다. 또한, 올리고 에스테르아크릴레이트도 들 수 있다.In addition to the above, the Michael addition product of acrylic acid or the 2-acryloyloxyethyldicarboxylic acid mono ester can also be mentioned as a monofunctional monomer, and the Michael addition product of acrylic acid is an acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, meta Methacrylate trimers, acrylic acid tetramers, methacrylic acid tetramers and the like. Moreover, as 2-acryloyloxyethyl dicarboxylic acid monoester which is a carboxylic acid which has a specific substituent, for example, 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinate monoester, 2-acryloyloxyethyl phthalate monoester, 2-methacryloxyethyl phthalate monoether, 2-acryloyloxyethyl hexahydrophthalic acid monoester, 2-methacryloxyethyl hexahydrofutal acid monoester, etc. Can be mentioned. Moreover, oligo ester acrylate is also mentioned.

2 관능 모노머로서는, 예를 들면, 에틸렌글리콜디(메타)아크릴레이트, 디에틸렌글리콜디(메타)아크릴레이트, 테트라에틸렌글리콜디(메타)아크릴레이트, 폴리에틸렌글리콜디(메타)아크릴레이트, 프로필렌글리콜디(메타)아크릴레이트, 디프로필렌글리콜디(메타)아크릴레이트, 폴리프로필렌글리콜디(메타)아크릴레이트, 부틸렌글리콜디(메타)아크릴레이트, 네오펜틸글리콜디(메타)아크릴레이트, 에틸렌옥사이드 변성 비스페놀 A형 디(메타)아크릴레이트, 프로필렌 옥사이드 변성 비스페놀 A형 디(메타)아크릴레이트, 1,6-헥산디올디(메타)아크릴레이트, 1,6-헥산디올에틸렌옥사이드 변성 디(메타)아크릴레이트, 글리세린 디(메타)아크릴레이트, 펜타에리스리톨 디(메타)아크릴레이트, 에틸렌글리콜디글리시딜에테르 디(메타)아크릴레이트, 디에틸렌글리콜디글리시딜에테르 디(메타)아크릴레이트, 푸탈산디글리시딜디에스테르 디(메타)아크릴레이트, 히드록시 피바린산 변성 네오펜틸글리콜디(메타)아크릴레이트, 이소시아누르산에틸렌옥사이드 변성 디아크릴레이트, 2-(메타)아크릴로일옥시 에틸애시드 인산염 디에스테르 등을 들 수 있다.As a bifunctional monomer, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propylene glycol di (Meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A-type di (meth) acrylate, propylene oxide modified bisphenol A-type di (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, 1,6-hexanediol ethylene oxide modified di (meth) acrylate , Glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol Glycidyl ether di (meth) acrylate, phthalic acid diglycidyl diester di (meth) acrylate, hydroxy pivaric acid modified neopentylglycol di (meth) acrylate, isocyanurate ethylene oxide modified diacrylate And 2- (meth) acryloyloxy ethyl acid phosphate diester.

3 관능 이상의 모노머로서는, 예를 들면, 트리메티롤프로판 트리(메타)아크릴레이트, 펜타에리스리톨 트리(메타)아크릴레이트, 펜타에리스리톨 테트라(메타) 아크릴레이트, 디펜타에리스리톨 펜타(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트, 트리(메타)아크릴로일옥시에톡시트리메티롤프로판, 글리세린폴리글리시딜에테르폴리(메타)아크릴레이트, 이소시아눌산에틸렌옥사이드 변성 트리아크릴레이트, 에틸렌옥사이드 변성 디펜타에리스리톨 펜타(메타)아크릴레이트, 에틸렌옥사이드 변성 디펜타에리스리톨 헥사(메타)아크릴레이트, 에틸렌옥사이드 변성 펜타에리스리톨 트리(메타)아크릴레이트, 에틸렌옥사이드 변성 펜타에리스리톨 테트라(메타)아크릴레이트, 호박산 변성 펜타에리스리톨 트리(메타)아크릴레이트 등을 들 수 있다.As a trifunctional or more than trifunctional monomer, For example, trimetholpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimetholpropane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified triacrylate, ethylene oxide modified Dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, succinic acid modified penta Erythritol tri (meth) acrylate, etc. are mentioned The.

상기 에틸렌성 불포화 모노머는 단독으로 이용할 수 있고, 2종 이상을 병용할 수도 있다.The said ethylenically unsaturated monomer can be used independently and can also use 2 or more types together.

상기 에틸렌성 불포화 모노머의 함유량은, 성분(A)와 성분(B)의 합계 100 중량부에 대해서, 30 중량부 이하가 바람직하고, 10 중량부 이하가 보다 바람직하다. 너무 많으면 굴절률이 저하되는 경향이 있다.30 weight part or less is preferable with respect to a total of 100 weight part of a component (A) and a component (B), and, as for content of the said ethylenically unsaturated monomer, 10 weight part or less is more preferable. When too much, there exists a tendency for a refractive index to fall.

또, 각종 첨가제로서는, 실란커플링제, 산화 방지제, 중합 금지제, 황변 방지제, 자외선 흡수제, 필러, 염안료, 기름, 가소제, 왁스류, 건조제, 분산제, 습윤제, 유화제, 겔화제, 안정제, 소포제, 레벨링제, 틱소트로피성(Thixotropie) 부여제, 난연제, 충전제, 보강제, 무광제, 가교제 등을 들 수 있다.Moreover, as various additives, a silane coupling agent, antioxidant, a polymerization inhibitor, a yellowing inhibitor, a ultraviolet absorber, a filler, a dye pigment, oil, a plasticizer, a wax, a drying agent, a dispersing agent, a wetting agent, an emulsifier, a gelling agent, a stabilizer, an antifoamer, Leveling agents, thixotropie imparting agents, flame retardants, fillers, reinforcing agents, matting agents, crosslinking agents and the like.

이렇게 하여 본 발명의 활성 에너지선 경화성 조성물은, 용제를 이용하지 않아도 저점도이며, 한편, 기재와의 밀착성이 뛰어난 고굴절률인 경화물을 형성할 수 있어 렌즈 형성 재료, 코팅제, 접착제 및 봉지제로서 매우 적합하게 사용된다.In this way, the active energy ray-curable composition of the present invention can form a high refractive index cured product having low viscosity even without using a solvent, and having excellent adhesion to a substrate, and thus, as a lens forming material, a coating agent, an adhesive, and an encapsulant. It is very suitably used.

본 발명의 활성 에너지선 경화성 조성물을 렌즈 형성 재료로서 사용하는 경우, 렌즈 형성의 수법은 특히 한정되지 않지만, 예를 들면, 주형 성형이나 2P 성형 등 공지의 수법이 이용된다.When using the active energy ray curable composition of this invention as a lens formation material, the method of lens formation is not specifically limited, For example, well-known methods, such as mold shaping | molding and 2P shaping | molding, are used.

또한, 여기서 말하는 렌즈란, 프리즘 렌즈, 프레넬 렌즈(Fresnel screen), 마이크로 렌즈 어레이 등의 광을 굴절, 회절, 간섭시키는 것이면 한정되지 않고, 수지 필름이나 유리 등의 기재상에, 프리즘 형태의 미소한 요철을 주기적 또는 랜덤으로 형성한 렌즈 필름 등도 매우 적합한 사용예로서 들 수 있다. 특히, 본 발명의 매우 적합한 사용예로서 고휘도화 필름을 들 수 있다. 고휘도화 필름은, 수지 필름상에 100㎛ 사이즈의 프리즘을 배열한 것이며, 디스플레이의 휘도 향상이나 소비 전력화를 위해서, 광원으로부터의 확산광을 어느 정도 집광하여 전면에 출사시키는 기능을 갖는 광학 필름이다.In addition, the lens here is not limited as long as it refracts, diffracts, or interferes light, such as a prism lens, a Fresnel screen, and a microlens array, and is a microscopic prism form on a base material, such as a resin film or glass. A lens film in which one unevenness is formed periodically or randomly is also a very suitable use example. In particular, a high brightness film is mentioned as a very suitable use example of this invention. The high brightness film is an optical film having a prism of 100 µm in size on a resin film, and has an optical film having a function of condensing diffused light from a light source to some extent and emitting it to the entire surface for improving brightness of the display and increasing power consumption.

고휘도화 필름을 2P 성형으로 제조하려면, 먼저 활성 에너지선 경화성 조성물을, 표면이 미세한 프리즘 형상에 가공된 모형으로 유연하여, 조성물의 상부에 투명 수지 필름을 씌운 후, 수지 필름의 상부로부터 활성 에너지선을 조사하여 조성물을 경화시키고, 이 프리즘 형상을 갖는 경화물을 수지 필름마다 모형으로부터 박리함으로써 제조된다. 모형으로서는, 금형, 유리형, 수지형 등을 이용할 수 있다. 수지 필름으로서는, 예를 들면, 폴리올레핀계 필름, 폴리에스테르계 필름, 폴리카보네이트계 필름, 아크릴계 필름 등을 들 수 있다.In order to manufacture the high brightness film by 2P molding, first, the active energy ray curable composition is cast into a model processed into a prismatic shape having a fine surface, and a transparent resin film is covered on the top of the composition, and then the active energy ray is formed from the top of the resin film. It is manufactured by irradiating and hardening a composition and peeling the hardened | cured material which has this prism shape from a model for every resin film. As the model, a mold, a glass mold, a resin mold, or the like can be used. As a resin film, a polyolefin type film, a polyester type film, a polycarbonate film, an acryl type film etc. are mentioned, for example.

활성 에너지선으로서는, 원자외선, 자외선, 근자외선, 가시광선, 적외선 등의 광선, X선,γ선 등의 전자파 이외, 전자선, 프로톤선, 중성자선 등을 이용할 수 있지만, 경화 속도, 조사 장치의 입수의 용이함, 가격 등으로부터 자외선 조사에 의한 경화가 유리하다.As the active energy ray, electron beams, proton rays, neutron rays, etc. can be used in addition to electromagnetic waves such as ultraviolet rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, visible rays, infrared rays, X-rays, γ-rays, and the like. Curing by ultraviolet irradiation is advantageous from the availability, price and the like.

자외선 조사에 의해 경화시키는 방법으로서는, 150?450nm 파장역의 광을 발하는 고압 수은 램프, 초고압 수은 등, 카본 아크 등, 메탈할라이드 램프, 크세논 램프, 케미컬 램프 등을 이용하고, 0.1?10J/㎠ 정도의 자외선을 조사하면 좋다. 자외선 조사 후는, 필요에 따라서 가열을 하여 경화의 완전을 도모할 수도 있다.As a method of hardening by ultraviolet irradiation, about 0.1-10J / cm <2> is used, using the high pressure mercury lamp which emits light of 150-450 nm wavelength range, the ultrahigh pressure mercury lamp, carbon arc lights, a metal halide lamp, a xenon lamp, a chemical lamp, etc. It is good to irradiate ultraviolet rays. After ultraviolet irradiation, you may heat as needed and can complete hardening.

본 발명의 활성 에너지선 경화성 조성물을 코팅제로서 사용하는 경우, 코팅의 수법은 특히 한정되지 않지만, 예를 들면, 스핀 코트, 딥 코트, 바 코트, 그라비아 코트 등 공지의 수법이 이용된다.When using the active energy ray curable composition of this invention as a coating agent, the method of coating is not specifically limited, For example, well-known methods, such as a spin coat, a dip coat, a bar coat, a gravure coat, are used.

코팅제로서 사용하는 경우, 본 발명의 주지로부터 용제 희석은 바람직하지 않지만, 핸들링성의 향상을 목적으로, 소량의 용제를 첨가하는 것도 가능하다. 이 경우, 용제로서는, 예를 들면, 톨루엔, 자일렌 등의 방향족 탄화수소류, 초산에틸, 초산 부틸, 프로필렌글리콜모노메틸 에테르 아세테이트 등의 에스테르류, n-프로필 알코올, 이소-프로필 알코올 등의 알코올류, 아세톤, 메틸에틸케톤, 시클로헥사논 등의 케톤류 등의 공지의 유기용제를 들 수 있다.In the case of using as a coating agent, solvent dilution is not preferable from the main point of the present invention, but it is also possible to add a small amount of solvent for the purpose of improving handling properties. In this case, examples of the solvent include aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate, alcohols such as n-propyl alcohol and iso-propyl alcohol. And well-known organic solvents, such as ketones, such as acetone, methyl ethyl ketone, and cyclohexanone, are mentioned.

유기용제의 배합량은, 활성 에너지선 경화성 조성물 100 중량부에 대해서, 바람직하게는 20 중량부 이하, 보다 바람직하게는 10 중량부 이하, 더욱 바람직하게는 5 중량부 이하이다. 너무 많으면 건조 부하가 증대되는 경향이 있다.The compounding quantity of an organic solvent is 20 weight part or less, More preferably, it is 10 weight part or less, More preferably, it is 5 weight part or less with respect to 100 weight part of active energy ray curable compositions. Too much tends to increase the drying load.

본 발명의 코팅제는, 이것을 기재에 코팅하여, 필요에 따라서 용제 건조한 후, 활성 에너지선을 조사함으로써 경화된다. 이와 같은 기재로서는, 특히 한정되지 않고, 예를 들면, 폴리올레핀계 필름, 폴리에스테르계 필름, 폴리카보네이트계 필름, 아크릴계 필름 등의 수지 필름, 유리 등을 들 수 있다.The coating agent of this invention is hardened | cured by irradiating an active energy ray after coating this on a base material and drying a solvent as needed. It does not specifically limit as such a base material, For example, resin films, such as a polyolefin film, a polyester film, a polycarbonate film, and an acryl-type film, glass, etc. are mentioned.

이상과 같이, 본 발명의 활성 에너지선 경화성 조성물은, 저점도이며, 고굴절률로 또한, 기재로의 밀착성이 뛰어난 경화물을 형성할 수 있어 렌즈 형성 재료, 코팅제, 접착제, 봉지제, 점착제, 도료, 잉크, 코팅 바인더 등의 여러 가지의 용도에 유용하다. 그 중에서도, 기재상에, 프레네 렌즈나 마이크로 렌즈 어레이 등의 미소 렌즈를 형성하는 렌즈 형성제로서 매우 적합하게 사용된다.As mentioned above, the active-energy-ray-curable composition of this invention can form hardened | cured material with low viscosity, high refractive index, and excellent adhesiveness to a base material, lens forming material, coating agent, adhesive agent, sealing agent, adhesive agent, coating material It is useful for various uses, such as an ink, a coating binder, and the like. Especially, it is used suitably as a lens former which forms microlenses, such as a Frene lens and a microlens array, on a base material.

(실시 예)(Example)

이하, 실시 예를 들어 본 발명을 더욱 구체적으로 설명하지만, 본 발명은 그 요지를 넘지 않는 한 이하의 실시 예로 한정되는 것은 아니다.Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded.

또한, 실시 예 중 「부」, 「%」는 특별한 언급이 없는 한 중량 기준을 의미한다. 각 특성의 측정 조건은 이하와 같다.In addition, "part" and "%" in an Example mean a basis of weight unless there is particular notice. The measurement conditions of each characteristic are as follows.

(1) 점도(1) viscosity

도쿄계기사 제조 E형 점토계를 이용하여, 25℃, 회전수 5 rpm(EMD3°콘)으로 측정하였다.It measured at 25 degreeC and rotation amount of 5 rpm (EMD3 degree cone) using the Tokyo-type E-type clay meter made from Tokyo Corporation.

(2) 굴절률(2) refractive index

아타고사 제조의 「아베 굴절계 1 T(NaD선)」를 이용하여 25℃에서 측정하였다.It measured at 25 degreeC using the "Abe refractometer 1T (NaD line)" by the Atago company.

(3) 아베수(3) Abesu

아타고사 제조의 「아베 굴절계 1 T」를 이용하여 25℃에서 측정하였다.It measured at 25 degreeC using the "Abe refractometer 1T" by the Atago company.

(4) 밀착성(4) Adhesion

JIS K 5600-5-6에 준하여, 피르테스트(박리 속도 10 ㎝/초)를 실시하여, 코트층이 폴리에틸렌 테레프탈레이트(PET) 기재로부터 벗겨진 것을 ×, 벗겨지지 않았던 것을 ○로 하였다.According to JIS K 5600-5-6, Pyr test (peel rate 10 cm / sec) was performed, and what peeled off the polyethylene terephthalate (PET) base material by the thing which peeled off from a polyethylene terephthalate (PET) base material was made into (circle).

〔우레탄 (메타)아크릴레이트계 화합물(A)의 제조〕[Manufacture of urethane (meth) acrylate type compound (A)]

적하 로트, 온도계, 교반기, 수냉 콘덴서, 질소 가스 취입구를 구비한 4구 플라스크에, 2-이소시아나토에틸아크릴레이트 52g(0.37 몰), 디부틸주석디라우레이트 0.02g를 넣고, 또한, 적하 로트에 4,4＇-비스〔β-히드록시에틸티오〕디페닐술폰 66.7g(0.18 몰)과 THF(테트라하이드로퓨란) 700g의 균일한 용액을 준비하였다. 플라스크 내를 60℃로 온도 상승한 후, 적하 로트에서 370g/시간에 용액을 적하하여 반응을 실시하여, 잔존 이소시아네이트기가 0.1%가 된 시점에서 반응을 종료하였다. 그 후, 중합 금지제로서 하이드로퀴논 메틸에테르 0.4g을 더하여 용제를 제거하고, 우레탄 (메타)아크릴레이트계 화합물(A)을 얻었다. 얻어진 우레탄 (메타) 아크릴레이트계 화합물(A)의 점도는 1640 Pa?s이었다.Into a four-necked flask equipped with a dropping lot, a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 52 g (0.37 mol) of 2-isocyanatoethyl acrylate and 0.02 g of dibutyltin dilaurate were further added. A lot of 66.7 g (0.18 mol) of 4,4'-bis [(beta) -hydroxyethylthio] diphenyl sulfone and 700 g of THF (tetrahydrofuran) was prepared for the lot. After raising the temperature in a flask to 60 degreeC, the solution was dripped at 370g / hour in the dropping lot, and reaction was performed, and reaction was complete when the remaining isocyanate group became 0.1%. Then, 0.4 g of hydroquinone methyl ether was added as a polymerization inhibitor, the solvent was removed, and the urethane (meth) acrylate type compound (A) was obtained. The viscosity of the obtained urethane (meth) acrylate compound (A) was 1640 Pa.s.

또, 얻어진 우레탄 (메타)아크릴레이트계 화합물(A)의 13C-NMR, 1H-NMR, 적외 차트로부터, 이 우레탄 (메타)아크릴레이트계 화합물(A)의 구조는 하기와 같다.Moreover, the structure of this urethane (meth) acrylate type compound (A) is as follows from 13 C-NMR, 1 H-NMR of an obtained urethane (meth) acrylate type compound (A), and an infrared chart.

[화학식 9][Chemical Formula 9]

Figure pct00009
Figure pct00009

〔활성 에너지선 경화성 조성물의 제조〕[Production of Active Energy Ray Curable Composition]

상기에서 얻어진 우레탄 (메타)아크릴레이트계 화합물(A), 단관능 (메타)아크릴레이트(B)로서 2-(o-페닐페녹시)에틸아크릴레이트(신나카무라 가카쿠 고교 가부시키가이샤 제조 NK에스테르 「A-LEN-10」), 2-페닐-2＇-(β-(메타) 아크릴로일옥시에톡시페닐)프로판(신나카무라 가카구고교 가부시키가이샤 제조 NK에스테르 「A-CMP-1 E」), 또는 (B) 성분에 해당하지 않는 단관능 (메타)아크릴레이트로서 2-히드록시-3-페녹시프로필아크릴레이트(신나카무라 가카구고교 가부시키가이샤 제조 NK에스테르 「702 A」), 광중합 개시제(C)로서 2-히드록시-2-메틸-1-페닐-프로판-1-온(치바?스페셜티?케미컬즈사 제조, 「다로큐아 1173」(상품명))을, 각각 표 1에 나타내는 양을 배합하여, 실온으로 1시간 균일하게 될 때까지 교반하여 활성 에너지선 경화성 조성물을 조제하였다. 얻어진 각 조성물의 점도는 표 1에 나타내는 대로이다.2- (o-phenylphenoxy) ethyl acrylate (Shin-Nakamura Kakaku Kogyo Co., Ltd. NK ester) as a urethane (meth) acrylate type compound (A) obtained above, and monofunctional (meth) acrylate (B) "A-LEN-10"), 2-phenyl-2 '-(β- (meth) acryloyloxyethoxyphenyl) propane (Shin-Nakamura Kakagugyo Co., Ltd. make NK ester "A-CMP-1E" Or 2-hydroxy-3-phenoxypropyl acrylate (NK ester "702A" manufactured by Shin-Nakamura Chemical Industries, Ltd.) as a monofunctional (meth) acrylate which does not correspond to (B) component, The amount which shows 2-hydroxy-2-methyl-1-phenyl-propane-1-one (Ciba-Specialty Chemicals make, "Darokyu 1173" (brand name)) as a photoinitiator (C) in Table 1, respectively. Was mixed, and it stirred until it became uniform at room temperature for 1 hour, and prepared the active energy ray curable composition. The viscosity of each obtained composition is as showing in Table 1.

〔코트층의 형성〕[Formation of Coat Layer]

상기에서 얻어지는 활성 에너지선 경화성 조성물을, 두께 10㎛의 PET 필름상에, 바 코트 하였다(막 두께 판정을 위해 판면의 일부에 테이프를 붙여 마스킹하였다). 고압 수은등 램프 80W, 1등을 이용하고, 13㎝의 높이로부터 4.3m/min의 컨베이어 속도로 1 패스의 자외선 조사(적산 조사량 1 J/㎠)를 실시하여, 두께 10㎛의 코트층을 형성하였다. 얻어진 코트층의 굴절률, 아베수를 측정하였다. 또, 상기 평가방법에 근거해 밀착성을 평가하였다. 결과를 표 1에 맞추어 나타낸다.The active energy ray curable composition obtained above was bar-coated on a 10-micrometer-thick PET film (a tape was masked on a part of plate surface for film thickness determination). Using a high-pressure mercury lamp lamp 80W and one lamp, UV radiation (integrated irradiation amount of 1 J / cm 2) in one pass was performed at a conveyor speed of 4.3 m / min from a height of 13 cm to form a coat layer having a thickness of 10 μm. . The refractive index and Abbe's number of the obtained coat layer were measured. Moreover, adhesiveness was evaluated based on the said evaluation method. The results are shown in Table 1 below.

Figure pct00010
Figure pct00010

조성물 No. 1?4는 본 발명의 실시 예이며, 조성물 No. 5, 6은 비교예이다.Composition No. 1 to 4 are examples of the present invention, and the composition No. 5 and 6 are comparative examples.

단관능 모노머로서 화학식 3으로 표시되는 화합물에 속하는 2-(o-페닐 페녹시) 에틸아크릴레이트를 배합한 조성물 No. 1?3, 화학식 4로 표시되는 화합물에 속하는 2-페닐-2＇-(β-((메타)아크릴로일옥시에톡시페닐)프로판을 배합한 조성물 No. 4에서는, 모두 저점도의 조성물로 핸들링성이 뛰어난 것이며, 또한 얻어지는 경화물은, 굴절률 1.58 이상으로 높고, 아베수도 26?30으로 매우 양호한 값이었다. 또, 조성물 No. 1?4로부터 얻어지는 경화물에는, 모두 밀착성이 뛰어났다.The composition No. which mix | blended 2- (o-phenyl phenoxy) ethylacrylate which belongs to the compound represented by General formula (3) as a monofunctional monomer. In composition No. 4 which mix | blended 2-phenyl-2 '-((beta)-((meth) acryloyloxyethoxyphenyl) propane which belongs to the compound represented by 1-3 and the general formula (4), all are the composition of low viscosity It was excellent in handling property, and the hardened | cured material obtained was high in refractive index 1.58 or more, and the Abbe number was also a very favorable value in 26-30. Moreover, the hardened | cured material obtained from composition No. 1-4 was all excellent in adhesiveness.

한편, 조성물 No. 6은, 특허 문헌 3에서 예시되고 있었던 단관능(메타)아크릴레이트를 배합한 것이다. 단관능 (메타)아크릴레이트의 배합량을 No.4와 동량으로 함으로써, 점도를 No. 4로 동일한 정도로까지 저하할 수 있었지만, 굴절률이 1.563으로 조성물 No.1?4보다 낮고, 렌즈 형성제 등의 광학적 용도의 재료로서 부적당하다. 따라서, 특정 구조를 갖는 단관능 (메타)아크릴레이트를 이용했을 경우(No. 1?4)로 한정하여, 성분(A)으로서의 우레탄 (메타)아크릴레이트의 고굴절률을 손상시키지 않고, 점도 저감을 달성할 수 있다는 것을 알 수 있다.On the other hand, composition No. 6 mix | blended the monofunctional (meth) acrylate illustrated by patent document 3. As shown in FIG. By making the compounding quantity of monofunctional (meth) acrylate the same amount as No. 4, a viscosity is No. Although it could fall to the same grade as 4, refractive index is 1.563, lower than Composition No. 1-4, and it is unsuitable as a material for optical uses, such as a lens former. Therefore, when monofunctional (meth) acrylate which has a specific structure is used (No. 1-4), viscosity reduction is carried out without damaging the high refractive index of the urethane (meth) acrylate as a component (A). It can be seen that it can be achieved.

조성물 No. 5는, 희석용 단관능 모노머를 포함하지 않는 경우이다. 화학식 1로 표시되는 우레탄 (메타)아크릴레이트 화합물(A)에 근거하여, 굴절률을 어느 정도 높일 수 있었던 경화물을 얻을 수 있었지만, 단관능 모노머도 용제도 포함하지 않기 때문에, 고점도로 코트성에 뒤떨어지는 것이 되며, 또한, 밀착성도 뒤떨어지고 있었다.Composition No. 5 is a case where the difunctional monofunctional monomer is not included. Based on the urethane (meth) acrylate compound (A) represented by General formula (1), the hardened | cured material which could raise the refractive index to some extent was obtained, but since a monofunctional monomer does not contain a solvent, it is inferior to coatability with high viscosity. Moreover, adhesiveness was inferior.

(산업상의 이용 가능성)(Industrial availability)

본 발명의 활성 에너지선 경화성 조성물은, 저점도로, 고굴절률이면서, 기재로의 밀착성이 뛰어난 경화물을 형성할 수 있다. 렌즈 형성 재료, 코팅제, 접착제, 봉지제, 점착제, 도료, 잉크, 코팅 바인더 등, 각종의 피막 형성 재료로서 유용하고, 안에서도, 디스플레이용의 기판이나 광학 필름, 렌즈, 태양전지나 메모리 디스크 등의 코팅제로서 이용하는데 매우 유용하다. 특히, 기재상에, 프레넬 렌즈나 마이크로 렌즈 어레이 등의 미소 렌즈를 형성하는 렌즈 형성제로서 매우 적합하게 사용된다.
The active energy ray curable composition of this invention can form hardened | cured material excellent in the adhesiveness to a base material with a low viscosity and high refractive index. It is useful as various film forming materials, such as a lens forming material, a coating agent, an adhesive, an encapsulant, an adhesive, a paint, an ink, and a coating binder, and also as a coating agent, such as a board | substrate for display, an optical film, a lens, a solar cell, a memory disk, etc. inside. Very useful to use. In particular, it is used suitably as a lens former which forms microlenses, such as a Fresnel lens and a microlens array, on a base material.

Claims (9)

(A) 하기 화학식 1 및/또는 2로 표시되는 우레탄 (메타)아크릴레이트계 화합물；및
(B) 하기 화학식 3 및/또는 4로 표시되는 단관능 (메타)아크릴레이트계 화합물을 함유하는 활성 에너지선 경화성 조성물.
[화학식 1]
Figure pct00011

[화학식 2]
Figure pct00012

[화학식 3]
Figure pct00013

[화학식 4]
Figure pct00014

(식1 중, R1, R2는 수소 또는 메틸기, R3, R4는 탄소수 1?3의 탄화수소기, X는 염소, 브롬, 또는 요오드, a와 b는 같거나 다르게 0?4의 정수, Y는 산소 또는 유황이며, 식2 중, R5, R6는 수소 또는 메틸기, R7, R8는 탄소수 1?3의 탄화수소기, Z는 염소, 브롬, 또는 요오드, c는 0?4의 정수, W는 산소 또는 유황이며, 식3 중, R9는 수소 또는 메틸기, R10는 탄소수 1?3의 탄화수소기이며, 식4 중, R11은 수소 또는 메틸기, R12는 탄소수 1?3의 탄화수소기이다.(A) a urethane (meth) acrylate type compound represented by the following general formula (1) and / or 2; and
(B) The active energy ray curable composition containing the monofunctional (meth) acrylate type compound represented by following General formula (3) and / or 4.
[Formula 1]
Figure pct00011

(2)
Figure pct00012

(3)
Figure pct00013

[Chemical Formula 4]
Figure pct00014

(In Formula 1, R 1 and R 2 are hydrogen or methyl groups, R 3 and R 4 are hydrocarbon groups having 1 to 3 carbon atoms, X is chlorine, bromine or iodine, and a and b are integers equal to or different from 0 to 4). And Y is oxygen or sulfur, in which R 5 and R 6 are hydrogen or methyl, R 7 and R 8 are hydrocarbon groups having 1 to 3 carbon atoms, Z is chlorine, bromine or iodine, and c is 0 to 4 Is an integer of W, W is oxygen or sulfur, and in formula 3, R <9> is hydrogen or a methyl group, R <10> is a C1-C3 hydrocarbon group, In formula, R <11> is hydrogen or a methyl group and R <12> is C1-C? 3 is a hydrocarbon group. 청구항 1에 있어서,
(C) 광중합 개시제를 더욱 함유하는 것을 특징으로 하는 활성 에너지선 경화성 조성물.The method according to claim 1,
(C) An active energy ray curable composition further containing a photoinitiator. 청구항 1 또는 2에 있어서,
25℃에 있어서의 점도가 100 Pa?s 이하인 것을 특징으로 하는 활성 에너지선 경화성 조성물.The method according to claim 1 or 2,
The viscosity in 25 degreeC is 100 Pa * s or less, The active energy ray curable composition characterized by the above-mentioned. 청구항 1 내지 3 중 어느 한 항에 있어서,
경화물의 굴절률이 1.58 이상인 것을 특징으로 하는 활성 에너지선 경화성 조성물.4. The method according to any one of claims 1 to 3,
The refractive index of hardened | cured material is 1.58 or more, The active energy ray curable composition characterized by the above-mentioned. 청구항 1 내지 4 중 어느 한 항에 기재된 활성 에너지선 경화성 조성물의 활성 에너지선 조사에 의해 얻어지는 경화물이며, 굴절률이 1.58 이상인 것을 특징으로 하는 경화물.It is hardened | cured material obtained by active energy ray irradiation of the active energy ray curable composition of any one of Claims 1-4, and refractive index is 1.58 or more, Cured | curing material characterized by the above-mentioned. 청구항 1 내지 4 중 어느 한 항에 기재된 활성 에너지선 경화성 조성물로 이루어지는 것을 특징으로 하는 렌즈 형성제.A lens former comprising the active energy ray curable composition according to any one of claims 1 to 4. 청구항 1 내지 4 중 어느 한 항에 기재된 활성 에너지선 경화성 조성물로 이루어지는 것을 특징으로 하는 코팅제.The coating agent which consists of an active-energy-ray-curable composition of any one of Claims 1-4. 청구항 1 내지 4 중 어느 한 항에 기재된 활성 에너지선 경화성 조성물로 이루어지는 것을 특징으로 하는 접착제.It consists of the active energy ray curable composition of any one of Claims 1-4, The adhesive agent characterized by the above-mentioned. 청구항 1 내지 4 중 어느 한 항에 기재된 활성 에너지선 경화성 조성물로 이루어지는 것을 특징으로 하는 발광 다이오드의 봉지제.It consists of the active energy ray curable composition of any one of Claims 1-4, The sealing agent of the light emitting diode characterized by the above-mentioned.
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