KR20150119027A - Ultraviolet light-curing adhesive agent composition and adhesive agent - Google Patents

Ultraviolet light-curing adhesive agent composition and adhesive agent Download PDF

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KR20150119027A
KR20150119027A KR1020157024459A KR20157024459A KR20150119027A KR 20150119027 A KR20150119027 A KR 20150119027A KR 1020157024459 A KR1020157024459 A KR 1020157024459A KR 20157024459 A KR20157024459 A KR 20157024459A KR 20150119027 A KR20150119027 A KR 20150119027A
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meth
acrylate
mass
sensitive adhesive
pressure
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KR101719536B1 (en
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게이지 츠나시마
야스오 오오지
고우지 사토
마리코 고니시
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디아이씨 가부시끼가이샤
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Abstract

본 발명이 해결하고자 하는 과제는, 점착력, 내습열백화성 및 내습열황변성이 뛰어난 자외선 경화형 점착제 조성물을 제공하는 것이다. 본 발명은, 폴리에틸렌글리콜(a1)을 포함하는 폴리올(a), 폴리이소시아네이트(b), 및, 수산기 또는 이소시아네이트기를 갖는 (메타)아크릴 화합물(c)을 반응시켜서 얻어지는 우레탄(메타)아크릴레이트(X), (메타)아크릴 단량체(Y), 및 광중합 개시제(Z)를 함유하는 것을 특징으로 하는 자외선 경화형 점착제 조성물 및 그것을 사용하여 얻어진 점착제를 제공하는 것이다. 본 발명의 자외선 경화형 점착제 조성물을 사용하여 얻어지는 점착제는, 광학 부재에 사용되는 점착제로서 호적하게 사용할 수 있다. 특히, 터치 패널, 액정 디스플레이, 플라스마 디스플레이, 유기 EL, PC, 휴대전화 등의 IT 관련 제품의 제조에 호적하게 사용할 수 있다.An object of the present invention is to provide an ultraviolet curing type pressure-sensitive adhesive composition which is excellent in adhesion, anti-wet heat-resistance and weathering resistance to moisture and heat. The present invention relates to a urethane (meth) acrylate (X) obtained by reacting a polyol (a) containing polyethylene glycol (a1), a polyisocyanate (b) and a (meth) acrylic compound having a hydroxyl group or an isocyanate group ), A (meth) acrylic monomer (Y), and a photopolymerization initiator (Z), and a pressure-sensitive adhesive obtained using the same. The pressure-sensitive adhesive obtained by using the ultraviolet curable pressure-sensitive adhesive composition of the present invention can be suitably used as a pressure-sensitive adhesive for use in an optical member. In particular, it can be suitably used for manufacturing IT related products such as touch panels, liquid crystal displays, plasma displays, organic EL, PCs, and mobile phones.

Description

자외선 경화형 점착제 조성물 및 점착제{ULTRAVIOLET LIGHT-CURING ADHESIVE AGENT COMPOSITION AND ADHESIVE AGENT}BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an ultraviolet curable pressure-

본 발명은, 점착력, 내습열백화성 및 내습열황변성이 뛰어난 자외선 경화형 점착제 조성물 및 점착제에 관한 것이다.The present invention relates to an ultraviolet curable pressure-sensitive adhesive composition and pressure-sensitive adhesive which are excellent in adhesive strength, anti-wet heat whitening property and anti-wet heat sulfur modification property.

아크릴계 점착제는, 종래부터 광범위한 용도에서 사용되고 있다. 특히 최근에는 박형 텔레비전 등의 IT 관련 제품에서의 용도가 확대하고 있어, 고성능, 고기능화가 진행되고 있다. 그러나, IT 관련 제품의 가격도 하락하고 있어, 고성능화뿐만 아니라 고생산성이 요구되고 있다.Acrylic pressure-sensitive adhesives have heretofore been used in a wide range of applications. Particularly recently, the use of IT-related products such as thin-type televisions is expanding, and high-performance and high-performance are progressing. However, the prices of IT-related products are also falling, and high productivity as well as high performance are required.

그러한 가운데, 종래형의 점착제(용제계, 수계)에서는 필수 공정이었던 용매의 건조 공정이나, 가공으로부터 성능이 발현될 때까지 필요한 에이징 시간 등이 불필요하므로, 고생산성을 기대할 수 있는 자외선 경화형 점착제가 주목되고 있다. 또한, 종래형의 점착제에 비하여 점착제층의 후막화가 용이하므로, 고기능화가 요구되는 등의 메리트를 들 수 있고, 앞으로의 신장이 기대되고 있다.In such a case, since an aging time and the like necessary from the drying step of the solvent, which was a necessary process in the conventional type pressure-sensitive adhesive (solvent system, water system), until the performance is developed from the processing are not required, the ultraviolet curing type pressure- . In addition, since the pressure-sensitive adhesive layer can be thickened more easily than conventional pressure-sensitive adhesives, there is a merit such as a demand for high-performance and the like.

상기 IT 관련 제품에서 사용 가능한 자외선 경화형 점착제로서는, 예를 들면, 불포화 이중 결합을 가지는 모노머 100질량부에 대하여, 우레탄 결합을 갖고, 또한, 폴리머 말단에 불포화 이중 결합을 갖는 중량 평균 분자량이 2만 이상의 고분자량체를 5질량부 이상, 200질량부 이하 포함하는 것을 특징으로 하는 점착제 조성물이 알려져 있다(예를 들면, 특허문헌 1을 참조).Examples of the ultraviolet curing type pressure-sensitive adhesive that can be used in the above-mentioned IT-related product include a pressure-sensitive adhesive having a urethane bond and an unsaturated double bond at the terminal of the polymer, with respect to 100 parts by mass of a monomer having an unsaturated double bond, A pressure-sensitive adhesive composition comprising a high molecular weight material in an amount of 5 parts by mass or more and 200 parts by mass or less is known (see, for example, Patent Document 1).

그러나, 상기 점착제에서는, 습열 조건하에서 점착제가 사용된 후에, 실온에서 방치되면 점착제 피막의 백화가 일어나거나, 경시적인 황변이 일어나는 등의 문제가 있었다.However, in the above-mentioned pressure-sensitive adhesive, when the pressure-sensitive adhesive is used under the moist heat condition and left at room temperature, whitening of the pressure-sensitive adhesive coating film occurs, and yellowing with time is caused.

일본국 특개2006-104296호 공보Japanese Patent Application Laid-Open No. 2006-104296

본 발명이 해결하고자 하는 과제는, 점착력, 내습열백화성 및 내습열황변성이 뛰어난 자외선 경화형 점착제 조성물을 제공하는 것이다.An object of the present invention is to provide an ultraviolet curing type pressure-sensitive adhesive composition which is excellent in adhesion, anti-wet heat-resistance and weathering resistance to moisture and heat.

본 발명자들은, 상기 과제를 해결하도록 예의 연구를 진행시키는 가운데, 우레탄(메타)아크릴레이트에 착목하여, 연구를 진행했다.The inventors of the present invention have conducted research while focusing on urethane (meth) acrylate while carrying out intensive studies to solve the above problems.

그 결과, 우레탄(메타)아크릴레이트의 원료로서 사용하는 폴리올로서, 폴리에틸렌글리콜을 필수로 포함함에 의해, 상기 과제를 해결할 수 있는 것을 알아내어, 본 발명을 완성하기에 이르렀다.As a result, it has been found out that polyethylene glycol is essentially contained as a polyol to be used as a raw material of urethane (meth) acrylate, and thus the above problems can be solved, and the present invention has been accomplished.

즉, 본 발명은, 폴리에틸렌글리콜(a1)을 포함하는 폴리올(a), 폴리이소시아네이트(b), 및, 수산기 또는 이소시아네이트기를 갖는 (메타)아크릴 화합물(c)을 반응시켜서 얻어지는 우레탄(메타)아크릴레이트(X), (메타)아크릴 단량체(Y), 및 광중합 개시제(Z)를 함유하는 것을 특징으로 하는 자외선 경화형 점착제 조성물 및 그것을 사용하여 얻어진 점착제를 제공하는 것이다.That is, the present invention relates to a urethane (meth) acrylate obtained by reacting a polyol (a) containing polyethylene glycol (a1), a polyisocyanate (b) and a hydroxyl group or an isocyanate group- (X), a (meth) acrylic monomer (Y), and a photopolymerization initiator (Z), and a pressure-sensitive adhesive obtained using the same.

본 발명의 자외선 경화형 점착제 조성물을 사용하여 얻어지는 점착제는, 뛰어난 점착력, 유지력, 내습열백화성 및 내습열황변성을 구비하는 것이다.The pressure-sensitive adhesive obtained by using the ultraviolet-curing pressure-sensitive adhesive composition of the present invention has excellent adhesive force, holding power, anti-wet heat and anti-wet heat sulfur.

본 발명의 자외선 경화형 점착제 조성물을 사용하여 얻어지는 점착제는, 광학 부재에 사용되는 점착제로서 호적하게 사용할 수 있다. 특히, 터치 패널, 액정 디스플레이, 플라스마 디스플레이, 유기 EL, PC, 휴대전화 등의 IT 관련 제품의 제조에 호적하게 사용할 수 있다.The pressure-sensitive adhesive obtained by using the ultraviolet curable pressure-sensitive adhesive composition of the present invention can be suitably used as a pressure-sensitive adhesive for use in an optical member. In particular, it can be suitably used for manufacturing IT related products such as touch panels, liquid crystal displays, plasma displays, organic EL, PCs, and mobile phones.

본 발명의 자외선 경화형 점착제 조성물은, 폴리에틸렌글리콜(a1)을 포함하는 폴리올(a), 폴리이소시아네이트(b), 및, 수산기 또는 이소시아네이트기를 갖는 (메타)아크릴 화합물(c)을 반응시켜서 얻어지는 우레탄(메타)아크릴레이트(X), (메타)아크릴 단량체(Y), 및 광중합 개시제(Z)를 함유하는 것이다.The ultraviolet curable pressure sensitive adhesive composition of the present invention is a UV curable pressure sensitive adhesive composition comprising urethane (meth) acrylate obtained by reacting a polyol (a) containing polyethylene glycol (a1), a polyisocyanate (b) ) Acrylate (X), (meth) acrylic monomer (Y), and a photopolymerization initiator (Z).

상기 폴리에틸렌글리콜(a1)은, 자외선 경화형 점착제 조성물의 친수성을 향상시키는 것이며, 점착제 피막이 습열 조건에서 폭로되었을 때에 습기나 수분을 균일하게 흡수할 수 있으므로, 점착제 피막의 내습열 후의 백화 억제에 기여하는 것이다. 또한, 상기 폴리에틸렌글리콜(a1)을 사용함에 의해, 황변하기 쉬운 (메타)아크릴 단량체의 사용량을 저감하거나, 또한 불사용할 수도 있으므로, 점착력을 유지하면서 뛰어난 내습열황변성도 부여할 수 있다.The polyethylene glycol (a1) improves the hydrophilicity of the ultraviolet curing pressure-sensitive adhesive composition, and when the pressure-sensitive adhesive coating is exposed under the humid conditions, moisture and moisture can be uniformly absorbed, thereby contributing to inhibition of whitening of the pressure- . Further, by using the polyethylene glycol (a1), the use amount of the (meth) acrylic monomer which is easily yellowed can be reduced or can be also used, so that excellent resistance to moisture and heat yellowing can be imparted while maintaining the adhesive strength.

상기 폴리에틸렌글리콜(a1)은, 우레탄(메타)아크릴레이트(X)의 원료로서 사용되지만, 점착력, 내습열백화성 및 내습열황변성의 점에서, 직쇄상의 것, 분기상의 것, 어느 쪽을 사용해도 되며, 상기 우레탄(메타)아크릴레이트(X) 중의 그래프트쇄로서도, 블록쇄로서도 존재해도 된다.The polyethylene glycol (a1) is used as a raw material for urethane (meth) acrylate (X), but from the viewpoints of adhesion, anti-wet heat resistance and anti-wet heat resistance, straight- , And it may be either a graft chain in the urethane (meth) acrylate (X) or a block chain.

상기 폴리에틸렌글리콜(a1)의 수평균 분자량으로서는, 내습열백화성 및 내습열황변성을 한층 더 향상할 수 있는 점에서, 200∼5,000의 범위인 것이 바람직하고, 또한 합성 시의 반응성 제어의 용이성이나 저온에서의 보존 안정성 등을 한층 더 향상할 수 있는 점에서, 200∼2,000의 범위가 보다 바람직하고, 200∼1,000의 범위가 더 바람직하다. 또, 상기 폴리에틸렌글리콜(a1)의 수평균 분자량은, 겔투과 크로마토그래피(GPC)법에 의해, 하기의 조건에서 측정한 값을 나타낸다.The number average molecular weight of the polyethylene glycol (a1) is preferably in the range of 200 to 5,000 from the viewpoint of further improving the anti-wet heat resistance and the anti-wet heat sulfur modification, and furthermore, More preferably in the range of 200 to 2,000 and more preferably in the range of 200 to 1,000 in view of further improving the storage stability at low temperatures and the like. The number average molecular weight of the polyethylene glycol (a1) is measured by gel permeation chromatography (GPC) under the following conditions.

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

칼럼 : 도소 가부시키가이샤제의 하기의 칼럼을 직렬로 접속하여 사용했다.Column: The following columns of Tosoh Corporation were connected in series and used.

「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(시차 굴절계)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 사용하여 검량선을 작성했다.Standard sample: A calibration curve was prepared using the following standard polystyrene.

(표준 폴리스티렌)(Standard polystyrene)

도소 가부시키가이샤제 「TSKgel 표준 폴리스티렌 A-500」Quot; TSKgel Standard Polystyrene A-500 " manufactured by Tosoh Corporation

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

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

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

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

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

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

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

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

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

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

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

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

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

상기 폴리에틸렌글리콜(a1)의 사용량으로서는, 점착력, 유지력, 내습열백화성 및 내습열황변성을 한층 더 향상할 수 있는 점에서, 상기 폴리올(a) 중 1∼60질량%의 범위인 것이 바람직하고, 3∼50질량%의 범위가 보다 바람직하고, 5∼40질량%의 범위가 더 바람직하고, 10.5∼33질량%의 범위가 특히 바람직하다.The amount of the polyethylene glycol (a1) to be used is preferably in the range of 1 to 60% by mass of the polyol (a) from the viewpoint of further improving the adhesive force, the holding power, the anti-wet heat resistance and the anti- , More preferably from 3 to 50 mass%, still more preferably from 5 to 40 mass%, and particularly preferably from 10.5 to 33 mass%.

또한, 우레탄(메타)아크릴레이트(X) 중의 상기 폴리에틸렌글리콜(a1)의 함유량으로서는, 점착력, 유지력, 내습열백화성 및 내습열황변성을 한층 더 향상할 수 있는 점에서, 0.1∼50질량%의 범위인 것이 바람직하고, 5∼35질량%의 범위가 보다 바람직하고, 9∼25질량%의 범위가 더 바람직하다.The content of the polyethylene glycol (a1) in the urethane (meth) acrylate (X) is preferably from 0.1 to 50 mass%, more preferably from 0.1 to 50 mass%, from the viewpoint of further improving the adhesive force, By mass, more preferably in the range of 5 to 35% by mass, and further preferably in the range of 9 to 25% by mass.

상기 폴리에틸렌글리콜(a1) 이외에 사용할 수 있는 상기 폴리올(a)로서는, 예를 들면, 폴리에틸렌글리콜 이외의 폴리에테르폴리올, 폴리에스테르폴리올, 폴리카보네이트폴리올, 아크릴폴리올, 부타디엔폴리올 등을 사용할 수 있다. 이들의 폴리올은 단독으로 사용해도 2종 이상을 병용해도 된다. 이들 중에서도, 점착력, 유지력, 내습열백화성 및 내습열황변성을 한층 더 향상할 수 있는 점에서, 상기 폴리에테르폴리올, 폴리카보네이트폴리올을 사용하는 것이 바람직하다.Examples of the polyol (a) which can be used in addition to the polyethylene glycol (a1) include polyether polyols other than polyethylene glycol, polyester polyols, polycarbonate polyols, acryl polyols, butadiene polyols and the like. These polyols may be used singly or in combination of two or more. Among these, polyether polyol and polycarbonate polyol are preferably used in view of further improving adhesion, holding power, anti-wet heat whitening resistance and anti-wet heat sulfur modification.

상기 폴리에테르폴리올로서는, 예를 들면, 에틸렌옥사이드, 프로필렌옥사이드, 부틸렌옥사이드 등의 알킬렌옥사이드의 1종 또는 2종 이상을, 2개 이상의 활성 수소를 갖는 화합물에 부가 중합시켜 얻어진 생성물이나, 테트라히드로퓨란을 개환 중합하여 얻어지는 폴리테트라메틸렌글리콜, 테트라히드로퓨란과 알킬 치환 테트라히드로퓨란을 공중합시킨 변성 폴리테트라메틸렌글리콜이나, 네오펜틸글리콜과 테트라히드로퓨란을 공중합시킨 변성 폴리테트라메틸렌글리콜 등을 사용할 수 있다.Examples of the polyether polyol include products obtained by subjecting one or two or more alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to an addition polymerization with a compound having two or more active hydrogens, Polytetramethylene glycol obtained by ring-opening polymerization of hydrofuran, modified polytetramethylene glycol obtained by copolymerizing tetrahydrofuran and alkyl-substituted tetrahydrofuran, modified polytetramethylene glycol obtained by copolymerizing neopentyl glycol and tetrahydrofuran, or the like can be used have.

상기 2개 이상의 활성 수소를 갖는 화합물로서는, 예를 들면 에틸렌글리콜, 디에틸렌글리콜, 트리에틸렌글리콜, 테트라에틸렌글리콜, 1,2-프로판디올, 1,3-프로판디올, 디프로필렌글리콜, 트리프로필렌글리콜, 1,2-부탄디올, 1,3-부탄디올, 1,4-부탄디올, 2,3-부탄디올, 1,5-펜탄디올, 1,5-헥산디올, 1,6-헥산디올, 2,5-헥산디올, 1,7-헵탄디올, 1,8-옥탄디올, 1,9-노난디올, 1,10-데칸디올, 1,11-운데칸디올, 1,12-도데칸디올, 2-메틸-1,3-프로판디올, 네오펜틸글리콜, 2-부틸-2-에틸-1,3-프로판디올, 3-메틸-1,5-펜탄디올, 2-에틸-1,3-프로판디올, 3-메틸-1,5-펜탄디올, 2-에틸-1,3-헥산디올, 2-메틸-1,8-옥탄디올, 하이드로퀴논, 레조르신, 비스페놀A, 비스페놀F, 4,4'-비스페놀 등의 비교적 저분자량의 디히드록시 화합물; 1,2-시클로부탄디올, 1,3-시클로펜탄디올, 1,4-시클로헥산디올, 시클로헵탄디올, 시클로옥탄디올, 1,4-시클로헥산디메탄올, 히드록시프로필시클로헥산올, 트리시클로[5,2,1,0,2,6]데칸-디메탄올, 비시클로[4,3,0]-노난디올, 디시클로헥산디올, 트리시클로[5,3,1,1]도데칸디올, 비시클로[4,3,0]노난디메탄올, 트리시클로[5,3,1,1]도데칸-디에탄올, 히드록시프로필트리시클로[5,3,1,1]도데칸올, 스피로[3,4]옥탄디올, 부틸시클로헥산디올, 1,1'-비시클로헥실리덴디올, 시클로헥산트리올, 수소 첨가 비스페놀A, 1,3-아다만탄디올 등의 지환식 폴리올; 폴리에틸렌글리콜, 폴리프로필렌글리콜, 폴리테트라메틸렌글리콜 등의 폴리에테르폴리올; 폴리헥사메틸렌아디페이트, 폴리헥사메틸렌숙시네이트, 폴리카프로락톤 등의 폴리에스테르폴리올 등을 사용할 수 있다.Examples of the compound having two or more active hydrogens include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol , 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, Hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-propanediol, 3-propanediol, Methyl-1,8-octanediol, hydroquinone, resorcin, bisphenol A, bisphenol F, 4,4'-bisphenol A relatively low molecular weight dihydroxy compound such as a dihydroxy compound; 1,2-cyclobutanediol, 1,3-cyclopentanediol, 1,4-cyclohexanediol, cycloheptanediol, cyclooctanediol, 1,4-cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo [ 5,2,1,0,2,6] decane-dimethanol, bicyclo [4,3,0] -nonanediol, dicyclohexanediol, tricyclo [5,3,1,1] dodecanediol, Dicyclo [5,3,1] dodecanol, bicyclo [4,3,0] nonanediol, tricyclo [5,3,1,1] dodecane-diethanol, hydroxypropyltricyclo [ , 4] octanediol, butylcyclohexanediol, 1,1'-bicyclohexylidenediol, cyclohexanetriol, hydrogenated bisphenol A and 1,3-adamantanediol; Polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; And polyester polyols such as polyhexamethylene adipate, polyhexamethylene succinate, and polycaprolactone.

상기 폴리에테르폴리올의 수평균 분자량으로서는, 200∼3,000의 범위가 바람직하고, 500∼2,000의 범위가 보다 바람직하고, 500∼1,500의 범위가 더 바람직하다. 또, 상기 폴리에테르폴리올의 수평균 분자량은, 상기 폴리에틸렌글리콜(a1)의 수평균 분자량과 같이 측정하여 얻어진 값을 나타낸다.The number average molecular weight of the polyether polyol is preferably in the range of 200 to 3,000, more preferably in the range of 500 to 2,000, and still more preferably in the range of 500 to 1,500. The number average molecular weight of the polyether polyol represents a value obtained by measuring the number average molecular weight of the polyethylene glycol (a1).

상기 폴리카보네이트폴리올로서는, 예를 들면, 탄산에스테르 및/또는 포스겐과, 상기 2개 이상의 활성 수소를 갖는 화합물을 반응시켜서 얻어지는 것을 사용할 수 있다.As the polycarbonate polyol, for example, those obtained by reacting carbonic acid ester and / or phosgene with a compound having two or more active hydrogens may be used.

상기 탄산에스테르로서는, 예를 들면, 메틸카보네이트, 디메틸카보네이트, 에틸카보네이트, 디에틸카보네이트, 시클로카보네이트, 디페닐카보네이트 등을 사용할 수 있다.As the carbonic ester, for example, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used.

상기 폴리카보네이트폴리올의 수산기가로서는, 점착력을 한층 더 향상할 수 있는 점에서, 30∼230㎎KOH/g의 범위인 것이 바람직하고, 50∼230㎎KOH/g의 범위가 보다 바람직하다. 또, 상기 폴리카보네이트폴리올의 수산기가는, JISK0070-1992에 준거하여 측정을 행한 값을 나타낸다.The hydroxyl group value of the polycarbonate polyol is preferably in the range of 30 to 230 mgKOH / g, more preferably in the range of 50 to 230 mgKOH / g, from the viewpoint of further improving the adhesive force. The hydroxyl value of the above polycarbonate polyol indicates the value measured in accordance with JIS K0070-1992.

상기 폴리이소시아네이트(b)로서는, 예를 들면, 자일릴렌디이소시아네이트, 페닐렌디이소시아네이트, 톨릴렌디이소시아네이트, 디페닐메탄디이소시아네이트, 나프탈렌디이소시아네이트 등의 방향족 디이소시아네이트; 헥사메틸렌디이소시아네이트, 리신디이소시아네이트, 시클로헥산디이소시아네이트, 이소포론디이소시아네이트, 4,4'-디시클로헥실메탄디이소시아네이트, 디이소시아나토메틸시클로헥산, 테트라메틸자일릴렌디이소시아네이트 등의 지방족 또는 지환 구조를 갖는 디이소시아네이트 등을 사용할 수 있다. 이들의 폴리이소시아네이트는 단독으로 사용해도 2종 이상을 병용해도 된다. 이들 중에서도, 점착력, 유지력 및 내습열황변성을 한층 더 향상할 수 있는 점에서, 지환 구조를 갖는 디이소시아네이트를 사용하는 것이 바람직하고, 4,4'-디시클로헥실메탄디이소시아네이트, 이소포론디이소시아네이트, 시클로헥산디이소시아네이트, 디이소시아나토메틸시클로헥산을 사용하는 것이 보다 바람직하다.Examples of the polyisocyanate (b) include aromatic diisocyanates such as xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate and naphthalene diisocyanate; Alicyclic or alicyclic structures such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, diisocyanatomethylcyclohexane, tetramethyl xylylene diisocyanate, And the like can be used. These polyisocyanates may be used singly or in combination of two or more. Of these, diisocyanates having an alicyclic structure are preferably used in view of further improving adhesion, retention, and resistance to moisture-wet heat sulfur, and 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate , Cyclohexane diisocyanate, and diisocyanatomethylcyclohexane are more preferably used.

상기 수산기 또는 이소시아네이트기를 갖는 (메타)아크릴 화합물(c)은, 우레탄(메타)아크릴레이트(X) 중에 (메타)아크릴로일기를 도입할 목적으로 사용하는 것이다.The (meth) acrylic compound (c) having a hydroxyl group or an isocyanate group is used for the purpose of introducing a (meth) acryloyl group into urethane (meth) acrylate (X).

상기 화합물(c)로서 사용할 수 있는 상기 수산기를 갖는 (메타)아크릴 화합물로서는, 예를 들면, 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 3-히드록시프로필아크릴레이트, 3-히드록시부틸(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 6-히드록시헥실아크릴레이트, 히드록시에틸아크릴아미드 등의 수산기를 갖는 (메타)아크릴산알킬에스테르; 트리메틸올프로판디(메타)아크릴레이트, 펜타에리트리톨트리(메타)아크릴레이트, 디펜타에리트리톨펜타(메타)아크릴레이트 등의 수산기를 갖는 다관능 (메타)아크릴레이트; 폴리에틸렌글리콜모노아크릴레이트, 폴리프로필렌글리콜모노아크릴레이트 등을 사용할 수 있다. 이들 중에서도, 자외선에 의한 경화성이 한층 더 향상하는 점에서, 수산기를 갖는 아크릴 화합물을 사용하는 것이 보다 바람직하고, 원료 입수의 용이함, 경화성 및 점착 물성을 한층 더 향상할 수 있는 점에서, 수산기를 갖는 아크릴산알킬에스테르를 사용하는 것이 더 바람직하고, 2-히드록시에틸아크릴레이트, 4-히드록시부틸아크릴레이트를 사용하는 것이 특히 바람직하다.Examples of the (meth) acrylic compound having a hydroxyl group which can be used as the compound (c) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) (Meth) acrylic acid alkyl ester having a hydroxyl group such as propyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl acrylate and hydroxyethyl acrylamide ; Polyfunctional (meth) acrylates having a hydroxyl group such as trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate; Polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, and the like. Of these, acrylic compounds having a hydroxyl group are more preferably used in view of further improving the curability due to ultraviolet rays, and from the viewpoint that the raw material can be easily obtained, the curability and the adhesive property can be further improved, Acrylic acid alkyl ester is more preferably used, and it is particularly preferable to use 2-hydroxyethyl acrylate or 4-hydroxybutyl acrylate.

또한, 상기 화합물(c)로서 사용할 수 있는 이소시아네이트기를 갖는 (메타)아크릴 화합물로서는, 예를 들면, 2-(메타)아크릴로일옥시에틸이소시아네이트, 2-(2-(메타)아크릴로일옥시에틸옥시)에틸이소시아네이트, 1,1-비스((메타)아크릴로일옥시메틸)에틸이소시아네이트 등을 사용할 수 있다. 이들 중에서도, 원료 입수의 용이성의 점에서, 2-(메타)아크릴로일옥시에틸이소시아네이트를 사용하는 것이 바람직하고, 2-아크릴로일옥시에틸이소시아네이트가 보다 바람직하다.Examples of the (meth) acrylic compound having an isocyanate group which can be used as the compound (c) include 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethyl Oxy) ethyl isocyanate, and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate. Among them, it is preferable to use 2- (meth) acryloyloxyethyl isocyanate from the viewpoint of easiness of obtaining raw materials, and 2-acryloyloxyethyl isocyanate is more preferable.

상기 화합물(c)로서 수산기를 갖는 (메타)아크릴 화합물을 사용하는 경우의 상기 우레탄(메타)아크릴레이트(X)의 제조 방법으로서는, 예를 들면, 무용제하에서, 상기 폴리올(a)과 상기 (메타)아크릴 화합물(c)을 반응계 중에 투입한 후에, 상기 폴리이소시아네이트(b)를 공급하고, 혼합, 반응시킴에 의해 제조하는 방법이나, 무용제하에서, 상기 폴리올(a)과 상기 폴리이소시아네이트(b)를 반응시킴에 의해 이소시아네이트기를 갖는 우레탄 프리폴리머를 얻고, 이어서, 수산기를 갖는 상기 (메타)아크릴 화합물(c)을 공급하고, 혼합, 반응시킴에 의해 제조하는 방법 등을 사용할 수 있다. 상기 반응은 어느 것에 있어서도, 20∼120℃의 조건하에서 약 30분∼24시간 정도 행하는 것이 바람직하다.Examples of the method for producing the urethane (meth) acrylate (X) in the case of using the (meth) acrylic compound having a hydroxyl group as the compound (c) include a method in which the polyol (a) (A) and the polyisocyanate (b) are reacted in the presence of a solvent and a method in which the acrylic compound (c) is introduced into the reaction system and then the polyisocyanate (b) A method in which a urethane prepolymer having an isocyanate group is obtained by the reaction and then the above (meth) acrylic compound (c) having a hydroxyl group is supplied, mixed, and reacted. In all of the above reactions, it is preferable to conduct the reaction for about 30 minutes to 24 hours under the condition of 20 to 120 캜.

또한, 상기 화합물(c)로서 이소시아네이트기를 갖는 (메타)아크릴 화합물을 사용하는 경우의 우레탄(메타)아크릴레이트(X)의 제조 방법으로서는, 예를 들면, 무용제하에서, 상기 폴리올(a)과 상기 폴리이소시아네이트(b)를 투입하고, 반응시킴에 의해 수산기를 갖는 우레탄 프리폴리머를 얻고, 이어서, 이소시아네이트기를 갖는 상기 (메타)아크릴 화합물(c)을 공급하고, 혼합, 반응시킴에 의해 제조하는 방법 등을 사용할 수 있다. 상기 반응은 어느 것에 있어서도, 20∼120℃의 조건하에서 약 30분∼24시간 정도 행하는 것이 바람직하다.Examples of the method for producing the urethane (meth) acrylate (X) in the case of using the (meth) acrylic compound having an isocyanate group as the compound (c) include a method in which the polyol (Meth) acrylic compound (c) having an isocyanate group is obtained by adding an isocyanate (b) and reacting the mixture to obtain a urethane prepolymer having a hydroxyl group, followed by mixing and reacting . In all of the above reactions, it is preferable to conduct the reaction for about 30 minutes to 24 hours under the condition of 20 to 120 캜.

상기 우레탄(메타)아크릴레이트(X)의 제조는, 유기 용제나 수계 매체의 존재하에서 행해도 된다. 또한, 유기 용제나 수계 매체 대신에, 후술하는 (메타)아크릴 단량체(Y) 존재하에서 제조해도 된다.The urethane (meth) acrylate (X) may be produced in the presence of an organic solvent or an aqueous medium. Further, it may be produced in the presence of a (meth) acrylic monomer (Y) described later instead of an organic solvent or an aqueous medium.

상기 폴리올(a)과 상기 폴리이소시아네이트(b)와 상기 (메타)아크릴 화합물(c)과의 반응은, 상기 폴리올(a)이 갖는 수산기와 상기 (메타)아크릴 화합물(c)이 갖는 수산기의 합계량과, 폴리이소시아네이트(b)가 갖는 이소시아네이트기와의 당량 비율 [이소시아네이트기/수산기의 합계량]=0.75∼1의 범위에서 행하는 것이, 얻어지는 우레탄(메타)아크릴레이트(X)의 분자량을 제어하기 위해 바람직하고, 0.79∼0.995의 범위인 것이 보다 바람직하다. 또한, 상기 당량 비율이 1을 초과하는 경우에 반응시켜도 되지만, 그 경우, 우레탄(메타)아크릴레이트(X)의 이소시아네이트기를 실활(失活)시키는 것을 목적으로 하여, 메탄올 등의 알코올을 사용하는 것이 바람직하다. 그 경우에는, 상기 폴리올(a)이 갖는 수산기와 상기 (메타)아크릴 화합물(dc)이 갖는 수산기와 알코올이 갖는 수산기의 합계량과, 상기 폴리이소시아네이트기와의 당량 비율 [이소시아네이트기/수산기의 합계량]이 상기 범위 내가 되도록 조정하는 것이 바람직하다.The reaction of the polyol (a) with the polyisocyanate (b) and the (meth) acrylic compound (c) is carried out in such a manner that the total amount of the hydroxyl groups of the polyol (a) (Isocyanate group / hydroxyl group) = 0.75 to 1 is preferable in order to control the molecular weight of the urethane (meth) acrylate (X) to be obtained, and the isocyanate group of the polyisocyanate , And more preferably in the range of 0.79 to 0.995. When the equivalent ratio is more than 1, the reaction may be carried out. In this case, for the purpose of inactivating the isocyanate group of urethane (meth) acrylate (X), use of an alcohol such as methanol desirable. In this case, the ratio of the total amount of the hydroxyl group of the polyol (a) and the hydroxyl group of the hydroxyl group and the alcohol of the (meth) acrylic compound (dc) to the polyisocyanate group [isocyanate group / hydroxyl group total amount] It is preferable to adjust it to be within the above range.

또한, 상기 우레탄(메타)아크릴레이트(X)의 이소시아네이트기를 실활시키는 것을 목적으로 하여 사용 가능한 알코올로서는, 예를 들면, 메탄올, 에탄올, 프로판올, 부탄올 등의 1관능 알코올이나, 1,2-프로필렌글리콜이나 1,3-부틸렌글리콜 등의 1급과 2급의 수산기로 이루어지는 2관능 알코올 등을 사용해도 된다.Examples of usable alcohols for the purpose of deactivating the isocyanate group of the urethane (meth) acrylate (X) include monofunctional alcohols such as methanol, ethanol, propanol and butanol, and 1,2- Or a bifunctional alcohol having primary and secondary hydroxyl groups such as 1,3-butylene glycol may be used.

또한, 우레탄(메타)아크릴레이트(X)를 제조할 때에는, 필요에 따라 중합 금지제나 우레탄화 촉매 등을 사용해도 된다.In addition, when urethane (meth) acrylate (X) is produced, a polymerization inhibitor or urethanization catalyst may be used if necessary.

상기 중합 금지제로서는, 예를 들면, 3,5-비스tert-부틸-4-히드록시톨루엔, 하이드로퀴논, 메틸하이드로퀴논, 하이드로퀴논모노메틸에테르(메토퀴논), 파라tert-부틸카테콜메톡시페놀, 2,6-디tert-부틸크레졸, 페노티아진, 테트라메틸티우람디설피드, 디페닐아민, 디니트로벤젠 등을 사용할 수 있다.Examples of the polymerization inhibitor include 3,5-bis tert-butyl-4-hydroxytoluene, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether (methoquinone), para tert- butyl catechol methoxyphenol , 2,6-ditert-butylcresol, phenothiazine, tetramethylthiuram disulfide, diphenylamine, dinitrobenzene and the like can be used.

상기 우레탄화 촉매로서는, 예를 들면, 트리에틸아민, 트리에틸렌디아민, N-메틸모르폴린 등의 함질소 화합물, 아세트산칼륨, 스테아르산아연, 옥틸산주석 등의 금속염, 디부틸틴라우레이트, 지르코늄테트라아세틸아세토네이트 등의 유기 금속 화합물 등을 사용할 수 있다.Examples of the urethanization catalyst include nitrogen-containing compounds such as triethylamine, triethylenediamine and N-methylmorpholine, metal salts such as potassium acetate, zinc stearate and tin octylate, dibutyltin laurate, zirconium And organic metal compounds such as tetraacetyl acetonate.

상기 우레탄(메타)아크릴레이트(X)는, 광조사나 가열 등에 의해 라디칼 중합을 진행시키는 (메타)아크릴로일기를 갖는 것이다. 상기 (메타)아크릴로일기의 당량으로서는, 점착력이나 단차 추종성 등을 한층 더 향상할 수 있는 점에서, 1,000∼200,000g/eq.의 범위인 것이 바람직하고, 5,000∼100,000g/eq.의 범위가 보다 바람직하다. 또, 상기 (메타)아크릴로일기의 당량은, 상기 폴리올(a)과 폴리이소시아네이트(b)와 (메타)아크릴 화합물(d)과의 합계 질량을, 상기 우레탄(메타)아크릴레이트(X) 중에 존재하는 (메타)아크릴기의 당량으로 나눈 값을 나타낸다. 또한, 본 발명에 있어서, 「(메타)아크릴 화합물」이란, 메타크릴 화합물과 아크릴 화합물의 한쪽 또는 양쪽을 말하고, 「(메타)아크릴레이트」란, 메타크릴레이트와 아크릴레이트의 한쪽 또는 양쪽을 말하고, 「(메타)아크릴로일기」란, 메타크릴로일기와 아크릴로일기의 한쪽 또는 양쪽을 말하고, 「(메타)아크릴산」이란, 메타크릴산과 아크릴산의 한쪽 또는 양쪽을 말하고, 「(메타)아크릴 단량체」란, 메타크릴 단량체와 아크릴 단량체의 한쪽 또는 양쪽을 말한다.The urethane (meth) acrylate (X) has a (meth) acryloyl group for promoting radical polymerization by optical irradiation or heating. The equivalent weight of the (meth) acryloyl group is preferably in the range of 1,000 to 200,000 g / eq., More preferably in the range of 5,000 to 100,000 g / eq., In view of further improving the adhesion and step- More preferable. The equivalent weight of the (meth) acryloyl group is preferably set such that the total mass of the polyol (a), the polyisocyanate (b) and the (meth) acrylic compound (d) Represents the value divided by the equivalent of the (meth) acrylic group present. In the present invention, the term "(meth) acrylic compound" refers to one or both of a methacrylic compound and an acrylic compound, and "(meth) acrylate" refers to one or both of methacrylate and acrylate (Meth) acryloyl group "refers to one or both of a methacryloyl group and an acryloyl group, and the term" (meth) acrylic acid "refers to one or both of methacrylic acid and acrylic acid, Monomers "refers to one or both of a methacrylic monomer and an acrylic monomer.

상기 우레탄(메타)아크릴레이트(X)의 중량 평균 분자량으로서는, 뛰어난 점착력과 유지력을 양립할 수 있고, 또한, 양호한 도공 작업성을 부여할 수 있는 관점에서, 5,000∼200,000의 범위인 것이 바람직하고, 10,000∼100,000의 범위가 보다 바람직하다. 또, 상기 우레탄(메타)아크릴레이트(X)의 중량 평균 분자량은, 상기 폴리에틸렌글리콜(a1)의 수평균 분자량과 마찬가지로 측정하여 얻어진 값을 나타낸다.The weight average molecular weight of the urethane (meth) acrylate (X) is preferably in the range of 5,000 to 200,000 from the viewpoints of both excellent adhesive force and holding force, and in addition, And more preferably in the range of 10,000 to 100,000. The weight-average molecular weight of the urethane (meth) acrylate (X) is a value obtained by measuring the number average molecular weight of the polyethylene glycol (a1).

상기 (메타)아크릴 단량체(Y)로서는, 예를 들면, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 프로필(메타)아크릴레이트, 이소프로필(메타)아크릴레이트, 부틸(메타)아크릴레이트, sec-부틸(메타)아크릴레이트, 이소부틸(메타)아크릴레이트, 2-에틸부틸(메타)아크릴레이트, n-펜틸(메타)아크릴레이트, 헥실(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 헵틸(메타)아크릴레이트, 옥틸(메타)아크릴레이트, 노닐(메타)아크릴레이트, 도데실(메타)아크릴레이트, 3-메틸부틸(메타)아크릴레이트, 이소옥틸(메타)아크릴레이트, 라우릴(메타)아크릴레이트, 트리데실(메타)아크릴레이트, 스테아릴(메타)아크릴레이트, 네오펜틸(메타)아크릴레이트, 헥사데실(메타)아크릴레이트, 이소아밀(메타)아크릴레이트 등의 지방족 (메타)아크릴레이트; 이소보로닐(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 테트라히드로푸르푸릴(메타)아크릴레이트 등의 지환식 (메타)아크릴레이트; 3-메톡시부틸(메타)아크릴레이트), 2-메톡시에틸(메타)아크릴레이트, 3-메톡시프로필(메타)아크릴레이트, 2-메톡시부틸(메타)아크릴레이트, 옥시에틸렌의 부가 몰수가 1∼15의 범위의 메톡시폴리에틸렌글리콜아크릴레이트, 에톡시-디에틸렌글리콜(메타)아크릴레이트, 에틸카르비톨(메타)아크릴레이트 등의 에테르기를 갖는 (메타)아크릴레이트; 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트 등의 수산기를 갖는 (메타)아크릴레이트; 벤질(메타)아크릴레이트, 벤질(메타)아크릴레이트, 페녹시에틸(메타)아크릴레이트, 페녹시폴리에틸렌글리콜아크릴레이트, 페닐(메타)아크릴레이트, 2-히드록시-3-페녹시프로필(메타)아크릴레이트 등의 방향족 (메타)아크릴레이트; (메타)아크릴아미드, 디메틸(메타)아크릴아미드, 아크릴로일모르폴린, 디메틸아미노프로필(메타)아크릴아미드, 이소프로필(메타)아크릴아미드, 디에틸(메타)아크릴아미드, 히드록시에틸(메타)아크릴아미드, 디아세톤(메타)아크릴아미드 등의 질소 원자를 갖는 (메타)아크릴 단량체 등을 사용할 수 있다. 이들의 (메타)아크릴 단량체는 단독으로 사용해도 2종 이상을 병용해도 된다.Examples of the (meth) acrylic monomer (Y) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) (meth) acrylate, isobutyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n-pentyl (Meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (Meth) acrylate such as lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, neopentyl (meth) acrylate, hexadecyl Aliphatic (meth) acrylates; Alicyclic (meth) acrylates such as isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate; Methoxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 2- (Meth) acrylate having an ether group such as methoxypolyethylene glycol acrylate, ethoxy-diethylene glycol (meth) acrylate, ethylcarbitol (meth) acrylate and the like in the range of 1 to 15; (Meth) acrylates having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; Benzyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol acrylate, phenyl (meth) acrylate, 2- Aromatic (meth) acrylates such as acrylate; (Meth) acrylamide, diethyl (meth) acrylamide, hydroxyethyl (meth) acrylamide, dimethyl (meth) acrylamide, acryloylmorpholine, dimethylaminopropyl (meth) acrylamide, (Meth) acryl monomers having a nitrogen atom such as acrylamide, diacetone (meth) acrylamide and the like can be used. These (meth) acrylic monomers may be used singly or in combination of two or more kinds.

또, 상기 (메타)아크릴 단량체(Y)로서, 뛰어난 내습열백화성을 부여하기 위해서, 상기 질소 원자를 갖는 (메타)아크릴 단량체를 사용하는 경우가 있다. 그 경우, 내습열황변성이 저하하는 경우가 있기 때문에, 첨가량은 적은 편이 바람직하고, 상기 (메타)아크릴 단량체(Y) 전량에 대하여 40질량% 이하인 것이 바람직하고, 35질량% 이하인 것이 보다 바람직하다. 본 발명에 있어서는, 상기 폴리에틸렌글리콜(a1)을 사용함으로써 점착제 피막의 친수성을 향상할 수 있기 때문에, 적은 첨가량으로 내습열백화성을 발현할 수 있다.As the (meth) acrylic monomer (Y), a (meth) acrylic monomer having the nitrogen atom may be used in order to impart excellent anti-wet heat resistance. In this case, the addition amount is preferably small, preferably 40 mass% or less, more preferably 35 mass% or less based on the total amount of the (meth) acrylic monomer (Y) . In the present invention, since the hydrophilic property of the pressure-sensitive adhesive film can be improved by using the polyethylene glycol (a1), anti-wet heat whitening property can be exhibited with a small addition amount.

상기 (메타)아크릴 단량체(Y)의 사용량으로서는, 점착력의 점에서, 상기 우레탄(메타)아크릴레이트(X) 100질량부에 대하여, 30∼200질량부의 범위에서 사용하는 것이 바람직하고, 50∼150질량부의 범위가 보다 바람직하고, 70∼130질량부의 범위가 특히 바람직하다.The amount of the (meth) acrylic monomer (Y) to be used is preferably in the range of 30 to 200 parts by mass, more preferably 50 to 150 parts by mass with respect to 100 parts by mass of the urethane (meth) acrylate (X) More preferably in the range of 70 to 130 parts by mass.

상기 광중합 개시제(Z)는, 광조사나 가열 등에 의해 라디칼을 발생하고, 상기 우레탄(메타)아크릴레이트(X)나 상기 (메타)아크릴 단량체(Y)의 라디칼 중합을 개시시키는 것이다.The photopolymerization initiator (Z) generates a radical by light irradiation or heating to initiate radical polymerization of the urethane (meth) acrylate (X) or the (meth) acrylic monomer (Y).

상기 광중합 개시제(Z)로서는, 예를 들면, 4-페녹시디클로로아세토페논, 디에톡시아세토페논, 2-히드록시-2-메틸-1-페닐프로판-1-온, 1-(4-이소프로필페닐)-2-히드록시-2-메틸프로판-1-온, 1-히드록시시클로헥실페닐케톤, 4-(2-히드록시에톡시)-페닐(2-히드록시-2-프로필)케톤, 2-메틸-[4-(메틸티오)페닐]-2-모르폴리노-1-프로판온, 2,2-디메톡시-2-페닐아세토페논 등의 아세토페논 화합물; 벤조인, 벤조인메틸에테르, 벤조인이소에틸에테르, 벤조인이소프로필에테르, 벤조인이소부틸에테르 등의 벤조인 화합물; 벤조페논, 벤조일벤조산, 벤조일벤조산메틸, 4-페닐벤조페논, 히드록시벤조페논, 4-벤조일-4'-메틸디페닐설파이드, 3,3'-디메틸-4-메톡시벤조페논 등의 벤조페논 화합물; 티오잔톤, 2-클로로티오잔톤, 2,4-디클로로티오잔톤, 2-메틸티오잔톤, 2,4-디메틸티오잔톤, 2,4-디에틸티오잔톤, 이소프로필티오잔톤, 2,4-디이소프로필티오잔톤 등의 티오잔톤 화합물; 4,4'-디메틸아미노티오잔톤(별명=미네라즈케톤), 4,4'-디에틸아미노벤조페논, α-아실옥심에스테르, 벤질, 메틸벤조일포르메이트(「바이아큐아55」), 2-에틸안트라퀴논 등의 안트라퀴논 화합물; 2,4,6-트리메틸벤조일디페닐포스핀옥사이드(「루시린TPO」), 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드(「IRGACURE819」) 등의 아실포스핀옥사이드 화합물; 3,3',4,4'-테트라(tert-부티로퍼옥시카르보닐)벤조페논[니혼유시 가부시키가이샤제의 「BTTB」], 아크릴화벤조페논 등을 사용할 수 있다.Examples of the photopolymerization initiator (Z) include 4-phenoxydichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan- Phenyl) -2-hydroxy-2-methylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 4- (2-hydroxyethoxy) -phenyl (2- Acetophenone compounds such as 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone and 2,2-dimethoxy-2-phenylacetophenone; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin isoethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenylsulfide and 3,3'-dimethyl- compound; Thioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-di Thioxanthone compounds such as isopropyl thioxanthone; (4-aminobenzoic acid), 4,4'-dimethylaminothioxanthone (aka Mineraz ketone), 4,4'-diethylaminobenzophenone,? -Acyloxime ester, benzyl, methylbenzoylformate Anthraquinone compounds such as ethyl anthraquinone; Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide ("Lucillin TPO") and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide ("IRGACURE819"); 3,3 ', 4,4'-tetra (tert-butyroperoxycarbonyl) benzophenone ("BTTB" manufactured by Nippon Oil & Fats Co., Ltd.), and acrylated benzophenone.

상기 광중합 개시제(Z)로서는, 점착력, 유지력, 내습열황변성 및 경화성을 한층 더 향상할 수 있는 점에서, 2-히드록시-2-메틸-1-페닐프로판-1-온, 1-히드록시시클로헥실페닐케톤, 2,4,6-트리메틸벤조일디페닐포스핀옥사이드, 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드를 사용하는 것이 바람직하다.As the photopolymerization initiator (Z), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy Cyclohexyl phenyl ketone, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, and bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide are preferably used.

상기 광중합 개시제(Z)의 사용량은, 상기 우레탄(메타)아크릴레이트(X) 100질량부에 대하여, 0.1∼20질량부의 범위에서 사용하는 것이 바람직하고, 0.5∼15질량부의 범위가 보다 바람직하고, 1∼5질량부의 범위가 특히 바람직하다.The photopolymerization initiator (Z) is preferably used in an amount of 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, per 100 parts by mass of the urethane (meth) acrylate (X) And particularly preferably in the range of 1 to 5 parts by mass.

본 발명의 자외선 경화형 점착제 조성물은, 상기 우레탄(메타)아크릴레이트(X), 상기 (메타)아크릴 단량체(Y) 및 상기 광중합 개시제(Z)를 필수 성분으로서 함유하지만, 필요에 따라 그 외의 첨가제를 함유해도 된다.The ultraviolet curable pressure sensitive adhesive composition of the present invention contains the urethane (meth) acrylate (X), the (meth) acrylic monomer (Y) and the photopolymerization initiator (Z) as essential components, .

상기 외의 첨가제로서는, 예를 들면, 실란커플링제, 산화 방지제, 광안정제, 용매, 방청제, 틱소 부여제, 증감제, 중합 금지제, 레벨링제, 점착 부여제, 대전 방지제, 난연제 등을 사용할 수 있다. 이들 중에서도, 내습열 후의 점착 물성을 한층 더 향상할 수 있는 점에서, 실란커플링제를 함유하는 것이 바람직하다. 또한, 내습열황변성 등을 한층 더 향상할 수 있는 점에서, 산화 방지제, 광안정제를 함유하는 것이 바람직하다.As other additives, for example, a silane coupling agent, an antioxidant, a light stabilizer, a solvent, a rust inhibitor, a thixotropic agent, a sensitizer, a polymerization inhibitor, a leveling agent, a tackifier, an antistatic agent, . Among them, it is preferable to contain a silane coupling agent in order to further improve the adhesive property after heat-resistant heat treatment. Further, it is preferable to contain an antioxidant and a light stabilizer in order to further improve the resistance to moisture-wet heat sulfur and the like.

상기 실란커플링제로서는, 예를 들면, 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필트리에톡시실란, 3-글리시독시프로필메틸디에톡시실란, 3-글리시독시프로필메틸디메톡시실란 등의 에폭시기를 갖는 실란커플링제; 2-(3,4-에폭시시클로헥실)에틸트리에톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란, 2-(3,4-에폭시시클로헥실)에틸메틸디메톡시실란, 2-(3,4-에폭시시클로헥실)에틸메틸디에톡시실란, 2-(3,4-에폭시시클로헥실)프로필트리메톡시실란, 2-(3,4-에폭시시클로헥실)프로필메틸디메톡시실란, 2-(3,4-에폭시시클로헥실)프로필트리에톡시실란, 2-(3,4-에폭시시클로헥실)프로필메틸디에톡시실란 등의 지환 에폭시기를 갖는 실란커플링제; 비닐트리클로로실란, 비닐트리메톡시실란, 비닐트리에톡시실란, p-스티릴트리메톡시실란, 3-메타크릴옥시프로필메틸디메톡시실란, 3-메타크릴옥시프로필트리메톡시실란, 3-메타크릴옥시프로필메틸디에톡시실란, 3-메타크릴옥시프로필트리에톡시실란, 3-아크릴옥시프로필트리메톡시실란, 3-메르캅토프로필메틸디메톡시실란, 3-메르캅토프로필트리메톡시실란, 실리콘알콕시 올리고머 등을 사용할 수 있다. 이들의 실란커플링제는 단독으로 사용해도 2종 이상을 병용해도 된다. 이들 중에서도, 내습열 후의 점착력 등을 한층 더 향상할 수 있는 점에서, 에폭시기를 갖는 실란커플링제, 지환 에폭시기를 갖는 실란커플링제를 사용하는 것이 바람직하고, 2-(3,4-에폭시시클로헥실)에틸트리에톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란, 3-글리시독시프로필트리메톡시실란 및 3-글리시독시프로필트리에톡시실란으로 이루어지는 군에서 선택되는 1종 이상을 사용하는 것이 보다 바람직하다.Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyl A silane coupling agent having an epoxy group such as dimethoxysilane; (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- , 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 2- Silane coupling agents having an alicyclic epoxy group such as silane, 2- (3,4-epoxycyclohexyl) propyltriethoxysilane and 2- (3,4-epoxycyclohexyl) propylmethyldiethoxysilane; Vinyl trichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, Silicon alkoxy oligomers, and the like. These silane coupling agents may be used singly or in combination of two or more. Among them, it is preferable to use a silane coupling agent having an epoxy group and a silane coupling agent having an alicyclic epoxy group, from the viewpoint of further improving the adhesion force after heat resistance to moisture and the like, and 2- (3,4-epoxycyclohexyl) Ethyl triethoxysilane, ethyl triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl trimethoxysilane, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane. It is more preferable to use at least one of them.

상기 실란커플링제의 사용량으로서는, 내습열 후의 점착력을 한층 더 향상할 수 있는 점에서, 상기 우레탄(메타)아크릴레이트(X) 100질량부에 대하여, 0.01∼10질량부의 범위에서 사용하는 것이 바람직하고, 0.05∼5질량부의 범위가 보다 바람직하고, 0.05∼1질량부의 범위가 더 바람직하다.The amount of the silane coupling agent used is preferably in the range of 0.01 to 10 parts by mass based on 100 parts by mass of the urethane (meth) acrylate (X) from the viewpoint of further improving the adhesion after heat- , More preferably 0.05 to 5 parts by mass, and still more preferably 0.05 to 1 part by mass.

상기 산화 방지제로서는, 열열화(熱劣化)로 발생하는 라디칼을 포착하는 힌더드페놀 화합물(1차 산화 방지제), 및 열열화로 발생하는 과산화물을 분해하는 인 화합물, 황 화합물(2차 산화 방지제) 등을 사용할 수 있다.Examples of the antioxidant include hindered phenol compounds (primary antioxidants) that capture radicals generated by thermal degradation (thermal deterioration), phosphorus compounds that decompose peroxides generated by thermal heating, sulfur compounds (secondary antioxidants), and the like Can be used.

상기 힌더드페놀 화합물로서는, 예를 들면, 트리에틸렌글리콜-비스-[3-(3-t-부틸-5-메틸-4히드록시페닐)프로피오네이트], 펜타에리트리톨테트라키스[3-(3,5-디-tert-부틸-4-히드록시페닐)프로피오네이트, 옥타데실[3-(3,5-디-tert-부틸-4-히드록시페닐)프로피오네이트, 티오디에틸렌비스[3-(3,5-디-tert-부틸-4-히드록시페닐)프로피오네이트], 벤젠프로판산-3,5-비스(1,1-디메틸에틸)-4-히드록시-C7-C9 측쇄 알킬에스테르, 4,6-비스(도데실티오메틸)-o-크레졸, N-페닐벤젠아민과 2,4,4-트리메틸펜텐과의 반응 생성물, 2-t-부틸-6-(3-t-부틸-2-히드록시-5-메틸벤질)-4-메틸페닐아크릴레이트, 3,9-비스[2-[3-(t-부틸-4-히드록시-5-메틸페닐)프로피오닐옥시]-1,1-디메틸에틸]2,4,8,10-테트라옥사스피로[5·5]운데칸, 2,6-디-tert-부틸-4-메틸페놀, 2,2'-메틸렌비스(4-메틸-6-tert-부틸페놀), 2,5-디-tert-아밀하이드로퀴논 등을 사용할 수 있다.Examples of the hindered phenol compound include triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, octadecyl [3- [3- (3,5-di -tert- butyl-4-hydroxyphenyl) propionate], benzene propanoic acid 3,5-bis (1,1-dimethylethyl) -4-hydroxy--C 7 -C 9 branched alkyl esters, 4,6-bis (dodecyl thiomethyl) -o- cresol, N- amine reaction product of benzene and 2,4,4-trimethyl pentene, 2-butyl-6-t- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 3,9- Octyloxy] -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro [5.5] undecane, 2,6-di-tert- Methylene bis (4-methyl-6-tert-butylphenol), 2,5-di- Wheat hydroquinone and the like can be used.

상기 인 화합물로서는, 예를 들면, 트리페닐포스핀, 비스(2,4-디-tert-부틸-6-메틸페닐)=에틸=포스피트, 트리페닐포스파이트, 트리스노닐페닐포스파이트, 트리스(2,4-디부틸페닐)포스파이트, 트리스(2,4-디부틸-5-메틸페닐)포스파이트, 트리스[2-제3부틸-4-(3-부틸-4-히드록시-5-메틸페닐티오)-5-메틸페닐]포스파이트, 트리스(2,4-디-tert-부틸페닐)포스파이트, 트리데실포스파이트, 옥틸디페닐포스파이트, 디(데실)모노페닐포스파이트, 디(트리데실)펜타에리트리톨디포스파이트, 디(노닐페닐)펜타에리트리톨디포스파이트, 비스(2,4-디부틸페닐)펜타에리트리톨디포스파이트, 비스(2,6-디부틸-4-메틸페닐)펜타에리트리톨디포스파이트, 비스(2,4,6-트리부틸페닐)펜타에리트리톨디포스파이트, 비스(2,4-디쿠밀페닐)펜타에리트리톨디포스파이트, 테트라(트리데실)이소프로필리덴디페놀디포스파이트, 테트라(트리데실)-4,4'-n-부틸리덴비스(2-부틸-5-메틸페놀)디포스파이트, 헥사(트리데실)-1,1,3-트리스(2-메틸-4-히드록시-5-부틸페닐)부탄트리포스파이트, 테트라키스(2,4-디부틸페닐)비페닐렌디포스포나이트, 9,10-디하이드로-9-옥사-10-포스파페난트렌-10-옥사이드, 2,2'-메틸렌비스(4,6-부틸페닐)-2-에틸헥실포스파이트, 2,2'-메틸렌비스(4,6-부틸페닐)-옥타데실포스파이트, 2,2'-에틸리덴비스(4,6-디부틸페닐)플루오로포스파이트, 트리스(2-[(2,4,8,10-테트라키스부틸디벤조[d,f][1,3,2]디옥사포스페핀-6-일)옥시]에틸)아민, 2-에틸-2-부틸프로필렌글리콜과 2,4,6-트리부틸페놀의 포스파이트 등을 사용할 수 있다.Examples of the phosphorus compound include triphenylphosphine, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl = phosphite, triphenylphosphite, trisnonylphenylphosphite, tris (2,4-dibutyl-5-methylphenyl) phosphite, tris [2- tert -butyl-4- (3-butyl- (2,4-di-tert-butylphenyl) phosphite, tridecylphosphite, octyldiphenylphosphite, di (decyl) monophenyl phosphite, di ) Pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-dibutylphenyl) pentaerythritol diphosphite, bis (2,6-dibutyl-4-methylphenyl) pentaerythritol (2,4,6-tributylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isoprop (Tridecyl) -4,1'-n-butylidenebis (2-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2,4-dibutylphenyl) biphenylene diphosphonite, 9,10-dihydro-9-oxa-10- (4,6-butylphenyl) -2-ethylhexylphosphite, 2,2'-methylenebis (4,6-butylphenyl) -octadecyl (4, 6-dibutylphenyl) fluorophosphite, tris (2 - [(2,4,8,10-tetrakisbutyldibenzo [d, f] 1,3,2] dioxaphosphper-6-yl) oxy] ethyl) amine, 2-ethyl-2-butylpropylene glycol and a phosphite of 2,4,6-tributylphenol.

상기 황 화합물로서는, 예를 들면, 디도데실-3,3'-티오프로피오네이트, 디라우릴-3,3'-티오디프로피오네이트, 라우디릴티오디티오네이트, 디트리데실-3,3'-티오디프로피오네이트, 디미리스틸-3,3'-티오디프로피오네이트, 디스테아릴-3,3'-티오디프로피오네이트, 테트라키스-메틸렌-3-라우릴티오프로피오네이트메탄, 디스테아릴-3,3'-메틸-3,3'-티오디프로피오네이트, 라우릴스테아릴-3,3'-티오디프로피오네이트, 비스[2-메틸-4-(3-n-알킬티오프로피오닐옥시)-5-t-부틸페닐]설피드, β-라우릴티오프로피오네이트, 2-메르캅토벤조이미다졸, 2-메르캅토-5-메틸벤조이미다졸, 디옥타데실-3,3'-티오디프로티오네이트 등을 사용할 수 있다.As the sulfur compound, for example, there can be mentioned, for example, didodecyl-3,3'-thiopropionate, dilauryl-3,3'-thiodipropionate, lauryldithiothionate, Thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, tetrakis-methylene-3-laurylthiopropionate 3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, bis [2-methyl-4- ( 3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide,? -Laurylthiopropionate, 2- mercaptobenzoimidazole, 2- mercapto- Dioctadecyl-3,3'-thiodipropionate, and the like.

이들 중에서도, 점착력 및 내습열황변성을 한층 더 향상할 수 있는 점에서, 인 화합물을 사용하는 것이 바람직하고, 트리페닐포스핀, 비스(2,4-디-tert-부틸-6-메틸페닐)=에틸=포스피트 및 트리스(2,4-디-tert-부틸페닐)포스파이트로 이루어지는 군에서 선택되는 1종 이상의 산화 방지제를 사용하는 것이 보다 바람직하고, 트리페닐포스핀, 비스(2,4-디-tert-부틸-6-메틸페닐)=에틸=포스피트를 사용하는 것이 특히 바람직하다.Among them, phosphorus compounds are preferably used, and triphenylphosphine, bis (2,4-di-tert-butyl-6-methylphenyl) It is more preferable to use at least one antioxidant selected from the group consisting of trimethyl phosphine, ethyl phosphite and tris (2,4-di-tert-butylphenyl) phosphite, Di-tert-butyl-6-methylphenyl) ethyl = phosphite is particularly preferably used.

상기 산화 방지제의 사용량으로서는, 내습열황변성을 한층 더 향상할 수 있는 점에서, 상기 우레탄(메타)아크릴레이트(X) 100질량부에 대하여, 0.01∼10질량부의 범위인 것이 바람직하다.The amount of the antioxidant to be used is preferably in the range of 0.01 to 10 parts by mass based on 100 parts by mass of the urethane (meth) acrylate (X) from the viewpoint of further improving resistance to moisture and heat sulfur.

상기 광안정제는, 광열화(光劣化)로 발생하는 라디칼을 포착하는 것이며, 예를 들면, 티올 화합물, 티오에테르 화합물, 힌더드아민 화합물 등의 라디칼 포착제, 및 벤조페논 화합물, 벤조에이트 화합물 등의 자외선 흡수제 등을 사용할 수 있다. 이들 중에서도, 내습열황변성을 한층 더 향상할 수 있는 점에서, 힌더드아민 화합물을 사용하는 것이 바람직하다.The light stabilizer captures radicals generated by photo-degradation (photodegradation), and examples thereof include radical scavengers such as thiol compounds, thioether compounds, and hindered amine compounds, and benzophenone compounds, benzoate compounds, Of ultraviolet absorber and the like can be used. Among them, it is preferable to use a hindered amine compound in order to further improve resistance to moisture-wet heat sulfur.

상기 힌더드아민 화합물로서는, 예를 들면, 시클로헥산과 과산화N-부틸2,2,6,6-테트라메틸-4-피페리딘아민-2,4,6-트리클로로1,3,5-트리아진과의 반응 생성물과 2-아미노에탄올과의 반응 생성물, 데칸이산비스(2,2,6,6-테트라메틸-1-(옥틸옥시)-4-피페리디닐)에스테르, 1,1-디메틸에틸히드로퍼옥사이드와 옥탄의 반응 생성물 등의 아미노에테르기를 갖는 힌더드아민 화합물; N-아세틸-3-도데실-1-(2,2,6,6-테트라메틸-4-피페리디닐)피롤리딘-2,5-디온 등의 N-아세틸계 힌더드아민 화합물; 비스(1,2,2,6,6-펜타메틸-4-피페리딜)=데칸디오에이트, 비스(1,2,2,6,6,-펜타메틸-4-피페리딜){[3,5-비스(1,1-디메틸에틸)-4-히드록시페닐]메틸}부틸말로네이트, 숙신산디메틸1-(2-히드록시에틸)-4-히드록시-2,2,6,6-테트라메틸피페리딘 중축합물, 프로판디오익애시드[{4-메톡시페닐}메틸렌]-비스(1,2,2,6,6-펜타메틸-4-피페리딜)에스테르의 N-알킬힌더드아민 화합물 등을 사용할 수 있다.Examples of the hindered amine compound include cyclohexane and N-butyl peroxide 2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro-1,3,5- (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, 1,1-dimethyl A hindered amine compound having an amino ether group such as a reaction product of ethyl hydroperoxide and octane; N-acetyl-type hindered amine compounds such as N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione; Bis (1,2,2,6,6-pentamethyl-4-piperidyl) = decanedioate, bis (1,2,2,6,6, (1,1-dimethylethyl) -4-hydroxyphenyl] methyl} butyl malonate, succinic acid dimethyl 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6 -Tetramethylpiperidine polycondensate, N-alkyl of propanedioic acid [{4-methoxyphenyl} methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidyl) Hindered amine compounds and the like can be used.

상기 광안정제의 사용량으로서는, 내습열황변성을 한층 더 향상할 수 있는 점에서, 상기 우레탄(메타)아크릴레이트(X) 100질량부에 대하여, 0.01∼10질량부의 범위인 것이 바람직하다.The amount of the light stabilizer used is preferably in the range of 0.01 to 10 parts by mass based on 100 parts by mass of the urethane (meth) acrylate (X) from the viewpoint of further improving resistance to moisture and heat sulfur.

본 발명의 자외선 경화형 점착제 조성물의 점도로서는, 양호한 도공성, 및 도공 시의 점착제 용액의 취급의 용이함의 점에서, 500∼20,000mPas의 범위인 것이 바람직하고, 1,000∼15,000mPas의 범위가 보다 바람직하다. 또, 상기 점도는, 25℃에서 B형 점도계로 측정한 값을 나타낸다.The viscosity of the ultraviolet curing pressure-sensitive adhesive composition of the present invention is preferably in the range of 500 to 20,000 mPas, more preferably in the range of 1,000 to 15,000 mPas, from the viewpoints of good coatability and ease of handling of the pressure- . The viscosity is a value measured by a B-type viscometer at 25 캜.

본 발명의 자외선 경화형 점착제 조성물은, 자외선 등의 에너지선의 조사에 의해 경화를 진행시킬 수 있다.The ultraviolet curing pressure-sensitive adhesive composition of the present invention can promote curing by irradiation with energy rays such as ultraviolet rays.

본 발명의 자외선 경화형 점착제 조성물을 경화시키는 방법으로서는, 예를 들면, 제논 램프, 제논-수은 램프, 메탈 할라이드 램프, 고압 수은 램프, 저압 수은 램프 등의 공지의 자외선 광조사 장치를 사용하여 소정의 자외선을 조사함에 의해 경화시킬 수 있다.As a method of curing the ultraviolet curable pressure-sensitive adhesive composition of the present invention, a known ultraviolet light irradiation apparatus such as a xenon lamp, a xenon-mercury lamp, a metal halide lamp, a high pressure mercury lamp, To cure it.

상기 자외선의 조사는, 바람직하게는 0.05∼5J/㎠, 보다 바람직하게는 0.1∼3J/㎠, 특히 바람직하게는 0.3∼1.5J/㎠의 범위인 것이 된다. 또, 자외선 조사량은, UV 체커 UVR-N1(GS유아사 가부시키가이샤제)을 사용하여 300∼390㎚의 파장역에 있어서 측정한 값을 기준으로 했다.The irradiation of ultraviolet rays is preferably in the range of 0.05 to 5 J / cm 2, more preferably 0.1 to 3 J / cm 2, particularly preferably 0.3 to 1.5 J / cm 2. The ultraviolet irradiation dose was based on a value measured in a wavelength range of 300 to 390 nm using a UV Checker UVR-N1 (manufactured by GS Yuasa K.K.).

본 발명의 자외선 경화형 점착제 조성물을 도포하여 점착제층을 형성할 수 있는 기재로서는, 플라스틱 기재, 플렉서블 프린트 기재, 유리 기재 및 이들의 기재에 ITO를 증착한 기재 등을 사용할 수 있다.As the substrate on which the pressure-sensitive adhesive layer can be formed by applying the ultraviolet curable pressure-sensitive adhesive composition of the present invention, a plastic substrate, a flexible print substrate, a glass substrate, a substrate obtained by depositing ITO on these substrates, or the like can be used.

상기 플라스틱 기재로서는, 일반적으로 사용되는 아크릴 수지 등으로 이루어지는 기재나 PC(폴리카보네이트), PBT(폴리부틸렌테레프탈레이트), PPS(폴리페닐렌설파이드), 변성 PPE(폴리페닐렌에테르), PET(폴리에틸렌테레프탈레이트), COP(시클로올레핀 폴리머), TAC(트리아세틸셀룰로오스)나 반사 방지 필름, 방오 필름, 터치 패널을 구성하는 투명 도전막의 필름 등을 사용할 수 있다.Examples of the plastic substrate include a substrate made of a generally used acrylic resin or the like, a substrate made of polycarbonate (PC), PBT (polybutylene terephthalate), PPS (polyphenylene sulfide), modified PPE (polyphenylene ether) Polyethylene terephthalate), COP (cycloolefin polymer), TAC (triacetylcellulose), an antireflection film, an antifouling film, and a film of a transparent conductive film constituting a touch panel.

[실시예][Example]

이하, 실시예를 사용하여, 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.

[합성예1][Synthesis Example 1]

<우레탄아크릴레이트(X-1)의 합성>&Lt; Synthesis of urethane acrylate (X-1) >

교반기, 환류 냉각관, 질소 도입관, 온도계를 구비한 반응 용기에, 폴리테트라메틸렌글리콜(수평균 분자량; 1,000, 이하 「PTMG1000」이라고 약기함)을 410질량부, 폴리에틸렌글리콜(수평균 분자량; 400, 이하 「PEG-1」이라고 약기함)을 27.5질량부, 2-히드록시에틸아크릴레이트(이하, 「HEA」라고 약기함) 6.1질량부, 2,6-디-tert-부틸-크레졸을 2질량부, p-메톡시페놀 0.3질량부를 첨가했다. 반응 용기 내 온도가 40℃가 될 때까지 승온한 후, 이소포론디이소시아네이트(이하, 「IPDI」라고 약기함) 105질량부 첨가했다. 그래서, 디옥틸주석디네오데카네이트 0.1질량부 첨가하여, 1시간 걸쳐서 80℃까지 승온했다. 그 후, 80℃에서 12시간 홀드하고, 모든 이소시아네이트기가 소실하여 있는 것을 확인 후, 냉각하여 우레탄아크릴레이트(X-1)를 얻었다. 얻어진 우레탄아크릴레이트(X-1)는, 아크릴로일기의 당량이 10,441(소수점 이하 반올림. 2-히드록시에틸아크릴레이트의 분자량은 116.1로 했다. 이하, 동일), 중량 평균 분자량이 30,000이었다.410 parts by mass of polytetramethylene glycol (number average molecular weight: 1,000, hereinafter abbreviated as &quot; PTMG1000 &quot;) was added to a reaction vessel equipped with a stirrer, a reflux condenser, , 6.1 parts by mass of 2-hydroxyethyl acrylate (hereinafter abbreviated as &quot; HEA &quot;), 2,6-di-tert-butyl-cresol by 2 , And 0.3 parts by mass of p-methoxyphenol were added. After the temperature in the reaction vessel was raised to 40 캜, 105 parts of isophorone diisocyanate (hereinafter abbreviated as &quot; IPDI &quot;) was added. Thus, 0.1 part by mass of dioctyltin dinneodecanate was added, and the temperature was raised to 80 占 폚 over 1 hour. Thereafter, the mixture was held at 80 DEG C for 12 hours, and it was confirmed that all of the isocyanate groups disappeared and then cooled to obtain urethane acrylate (X-1). The urethane acrylate (X-1) thus obtained had an equivalent number of acryloyl groups of 10,441 (rounded off to a decimal point and a molecular weight of 2-hydroxyethyl acrylate of 116.1, the same applies hereinafter) and a weight average molecular weight of 30,000.

[합성예2][Synthesis Example 2]

<우레탄아크릴레이트(X-2)의 합성>&Lt; Synthesis of urethane acrylate (X-2) >

교반기, 환류 냉각관, 질소 도입관, 온도계를 구비한 반응 용기에, 폴리카보네이트폴리올(「듀라놀 T-5651」 아사히가세이케미컬 가부시키가이샤제, 수평균 분자량; 1000) 390질량부, 폴리에틸렌글리콜(수평균 분자량; 600, 이하 「PEG-2」라고 약기함)을 43.4질량부, HEA 9질량부, 2,6-디-tert-부틸-크레졸을 2질량부, p-메톡시페놀 0.3질량부를 첨가했다. 반응 용기 내 온도가 40℃가 될 때까지 승온한 후, IPDI를 102질량부 첨가했다. 그래서, 디옥틸주석디네오데카네이트 0.1질량부 첨가하여, 1시간 걸쳐서 80℃까지 승온했다. 그 후, 80℃에서 12시간 홀드하고, 모든 이소시아네이트기가 소실하여 있는 것을 확인 후, 냉각하여 우레탄아크릴레이트(X-2)를 얻었다. 얻어진 우레탄아크릴레이트(X-2)는, 아크릴로일기의 당량이 7,023, 중량 평균 분자량이 19,000이었다.390 parts by mass of a polycarbonate polyol (&quot; DYRANOL T-5651 &quot; manufactured by Asahi Chemical Industry Co., Ltd., number average molecular weight: 1000), 20 parts by mass of polyethylene glycol , 43.4 parts by mass of polyoxyethylene (number average molecular weight: 600, hereinafter abbreviated as "PEG-2"), 9 parts by mass of HEA, 2 parts by mass of 2,6- &Lt; / RTI &gt; After the temperature in the reaction vessel was raised to 40 캜, 102 parts of IPDI was added. Thus, 0.1 part by mass of dioctyltin dinneodecanate was added, and the temperature was raised to 80 占 폚 over 1 hour. Thereafter, the mixture was held at 80 DEG C for 12 hours to confirm that all the isocyanate groups were lost, and then cooled to obtain urethane acrylate (X-2). The resulting urethane acrylate (X-2) had an equivalent number of acryloyl groups of 7,023 and a weight average molecular weight of 19,000.

[합성예3][Synthesis Example 3]

<우레탄아크릴레이트(X-3)의 합성>&Lt; Synthesis of urethane acrylate (X-3) >

교반기, 환류 냉각관, 질소 도입관, 온도계를 구비한 반응 용기에, PTMG1000을 351질량부, PEG-1을 51.4질량부, HEA를 5.7질량부, 2,6-디-tert-부틸-크레졸을 2질량부, p-메톡시페놀 0.3질량부를 첨가했다. 반응 용기 내 온도가 40℃가 될 때까지 승온한 후, IPDI를 104질량부 첨가했다. 그래서, 디옥틸주석디네오데카네이트 0.1질량부 첨가하여, 1시간 걸쳐서 80℃까지 승온했다. 그 후, 80℃에서 12시간 홀드하고, 모든 이소시아네이트기가 소실하여 있는 것을 확인 후, 냉각하여 우레탄아크릴레이트(X-3)를 얻었다. 얻어진 우레탄아크릴레이트(X-3)는, 아크릴로일기의 당량이 10,431, 중량 평균 분자량이 21,000이었다.351 parts by mass of PTMG1000, 51.4 parts by mass of PEG-1, 5.7 parts by mass of HEA, and 2,6-di-tert-butyl-cresol were added to a reaction vessel equipped with a stirrer, a reflux condenser, 2 parts by mass, and 0.3 part by mass of p-methoxyphenol were added. After raising the temperature in the reaction vessel to 40 占 폚, 104 parts by mass of IPDI was added. Thus, 0.1 part by mass of dioctyltin dinneodecanate was added, and the temperature was raised to 80 占 폚 over 1 hour. Thereafter, the mixture was held at 80 DEG C for 12 hours, and it was confirmed that all the isocyanate groups had disappeared, followed by cooling to obtain urethane acrylate (X-3). The obtained urethane acrylate (X-3) had an equivalent number of acryloyl groups of 10,431 and a weight average molecular weight of 21,000.

[합성예4][Synthesis Example 4]

<우레탄아크릴레이트(X-4)의 합성>&Lt; Synthesis of urethane acrylate (X-4) >

교반기, 환류 냉각관, 질소 도입관, 온도계를 구비한 반응 용기에, 폴리프로필렌글리콜(수평균 분자량; 3,000, 이하, 「PPG3000」라고 약기함)을 180질량부, PTMG1000을 143질량부, PEG-1을 109질량부, HEA를 6질량부, 2,6-디-tert-부틸-크레졸을 2질량부, p-메톡시페놀 0.3질량부를 첨가했다. 반응 용기 내 온도가 40℃가 될 때까지 승온한 후, IPDI를 105질량부 첨가했다. 그래서, 디옥틸주석디네오데카네이트 0.1질량부 첨가하여, 1시간 걸쳐서 80℃까지 승온했다. 그 후, 80℃에서 12시간 홀드하고, 모든 이소시아네이트기가 소실하여 있는 것을 확인 후, 냉각하여 우레탄아크릴레이트(X-4)를 얻었다. 얻어진 우레탄아크릴레이트(X-4)는, 아크릴로일기의 당량이 10,507, 중량 평균 분자량이 26,000이었다.180 parts by mass of polypropylene glycol (number average molecular weight: 3,000, hereinafter abbreviated as &quot; PPG3000 &quot;) and 143 parts by mass of PTMG1000 were charged in a reaction vessel equipped with a stirrer, a reflux condenser, 1, 109 parts by mass of HEA, 6 parts by mass of HEA, 2 parts by mass of 2,6-di-tert-butyl-cresol and 0.3 parts by mass of p-methoxyphenol were added. After raising the temperature in the reaction vessel to 40 占 폚, 105 parts by mass of IPDI was added. Thus, 0.1 part by mass of dioctyltin dinneodecanate was added, and the temperature was raised to 80 占 폚 over 1 hour. Thereafter, the mixture was held at 80 DEG C for 12 hours, and it was confirmed that all of the isocyanate groups had disappeared, followed by cooling to obtain urethane acrylate (X-4). The obtained urethane acrylate (X-4) had an equivalent number of acryloyl groups of 10,507 and a weight average molecular weight of 26,000.

[합성예5][Synthesis Example 5]

<우레탄아크릴레이트(X-5)의 합성>&Lt; Synthesis of urethane acrylate (X-5) >

교반기, 환류 냉각관, 질소 도입관, 온도계를 구비한 반응 용기에, 듀라놀 T-5652를 442질량부, 폴리에틸렌글리콜(「Ymer N120」 Perstorp사제, 수평균 분자량; 1,000)을 246질량부, HEA를 9.5질량부, 2,6-디-tert-부틸-크레졸을 2질량부, p-메톡시페놀 0.3질량부를 첨가했다. 반응 용기 내 온도가 40℃가 될 때까지 승온한 후, IPDI를 102질량부 첨가했다. 그래서, 디옥틸주석디네오데카네이트 0.1질량부 첨가하여, 1시간 걸쳐서 80℃까지 승온했다. 그 후, 80℃에서 12시간 홀드하고, 모든 이소시아네이트기가 소실하여 있는 것을 확인 후, 냉각하여 우레탄아크릴레이트(X-5)를 얻었다. 얻어진 우레탄아크릴레이트(X-5)는, 아크릴로일기의 당량이 9,771, 중량 평균 분자량이 20,000이었다.442 parts by mass of Duranol T-5652, 246 parts by mass of polyethylene glycol ("Ymer N120" manufactured by Perstorp Co., Ltd., number average molecular weight: 1,000) and 30 parts by mass of HEA , 2 parts by mass of 2,6-di-tert-butyl-cresol and 0.3 parts by mass of p-methoxyphenol were added. After the temperature in the reaction vessel was raised to 40 캜, 102 parts of IPDI was added. Thus, 0.1 part by mass of dioctyltin dinneodecanate was added, and the temperature was raised to 80 占 폚 over 1 hour. Thereafter, the mixture was held at 80 DEG C for 12 hours, and it was confirmed that all the isocyanate groups had disappeared and then cooled to obtain urethane acrylate (X-5). The resulting urethane acrylate (X-5) had an equivalent number of acryloyl groups of 9,771 and a weight average molecular weight of 20,000.

[합성예6][Synthesis Example 6]

<우레탄아크릴레이트(X-6)의 합성>&Lt; Synthesis of urethane acrylate (X-6) >

교반기, 환류 냉각관, 질소 도입관, 온도계를 구비한 반응 용기에, 듀라놀 T-5651을 467질량부, HEA를 9.6질량부, 2,6-디-tert-부틸-크레졸을 2질량부, p-메톡시페놀 0.3질량부를 첨가했다. 반응 용기 내 온도가 40℃가 될 때까지 승온한 후, IPDI를 101질량부 첨가했다. 그래서, 디옥틸주석디네오데카네이트 0.1질량부 첨가하여, 1시간 걸쳐서 80℃까지 승온했다. 그 후, 80℃에서 12시간 홀드하고, 모든 이소시아네이트기가 소실하여 있는 것을 확인 후, 냉각하여 우레탄아크릴레이트(X-6)를 얻었다. 얻어진 우레탄아크릴레이트(X-6)는, 아크릴로일기의 당량이 6,985, 중량 평균 분자량이 19,000이었다.467 parts by mass of Duranol T-5651, 9.6 parts by mass of HEA, 2 parts by mass of 2,6-di-tert-butyl-cresol, and 0.3 parts by mass of p-methoxyphenol were added. After raising the temperature in the reaction vessel to 40 캜, 101 parts of IPDI was added. Thus, 0.1 part by mass of dioctyltin dinneodecanate was added, and the temperature was raised to 80 占 폚 over 1 hour. Thereafter, the mixture was held at 80 DEG C for 12 hours, and it was confirmed that all the isocyanate groups had disappeared, followed by cooling to obtain urethane acrylate (X-6). The resulting urethane acrylate (X-6) had an equivalent number of acryloyl groups of 6,985 and a weight average molecular weight of 19,000.

[합성예7][Synthesis Example 7]

<우레탄아크릴레이트(X-7)의 합성>&Lt; Synthesis of urethane acrylate (X-7) >

교반기, 환류 냉각관, 질소 도입관, 온도계를 구비한 반응 용기에, PTMG1000을 460질량부, HEA를 6.5질량부, 2,6-디-tert-부틸-크레졸을 2질량부, p-메톡시페놀 0.3질량부를 첨가했다. 반응 용기 내 온도가 40℃가 될 때까지 승온한 후, IPDI를 105질량부 첨가했다. 그래서, 디옥틸주석디네오데카네이트 0.1질량부 첨가하여, 1시간 걸쳐서 80℃까지 승온했다. 그 후, 80℃에서 12시간 홀드하고, 모든 이소시아네이트기가 소실하여 있는 것을 확인 후, 냉각하여 우레탄아크릴레이트(X-7)를 얻었다. 얻어진 우레탄아크릴레이트(X-7)는, 아크릴로일기의 당량이 10,208, 중량 평균 분자량이 22,000이었다.460 parts by mass of PTMG1000, 6.5 parts by mass of HEA, 2 parts by mass of 2,6-di-tert-butyl-cresol, p-methoxy And 0.3 parts by mass of phenol were added. After raising the temperature in the reaction vessel to 40 占 폚, 105 parts by mass of IPDI was added. Thus, 0.1 part by mass of dioctyltin dinneodecanate was added, and the temperature was raised to 80 占 폚 over 1 hour. Thereafter, the mixture was held at 80 DEG C for 12 hours to confirm that all of the isocyanate groups were lost, and then cooled to obtain urethane acrylate (X-7). The resulting urethane acrylate (X-7) had an equivalent number of acryloyl groups of 10,208 and a weight average molecular weight of 22,000.

[실시예1][Example 1]

<자외선 경화형 점착제 조성물의 조제>&Lt; Preparation of UV-curable pressure-sensitive adhesive composition >

교반기, 환류 냉각관, 온도계를 구비한 반응 용기에, 상기 우레탄아크릴레이트(X-1) 100질량부, 부틸아크릴레이트(이하, 「BA」라고 약기함) 105질량부, 디메틸아크릴아미드(이하, 「DMAA」라고 약기함) 10질량부를 투입하고, 80℃에서 균일해질 때까지 교반했다. 그 후, 실온까지 냉각하고, 교반하에서 2,4,6-트리메틸벤조일페닐포스핀옥사이드 3질량부, 데칸이산비스(2,2,6,6-테트라메틸-1-(옥틸옥시)-4-피페리디닐)에스테르 0.5질량부, 트리페닐포스핀 0.5질량부, 3-글리시독시프로필트리에톡시실란 0.1질량부를 첨가하여, 균일해질 때까지 교반했다. 그 후, 200메시 금망(金網)으로 여과하여, 자외선 경화형 점착제 조성물을 얻었다.A reaction vessel equipped with a stirrer, a reflux condenser and a thermometer was charged with 100 parts by mass of the urethane acrylate (X-1), 105 parts by mass of butyl acrylate (hereinafter abbreviated as "BA"), Quot; DMAA &quot;) were charged, and the mixture was stirred at 80 DEG C until uniform. Thereafter, the mixture was cooled to room temperature, and 3 parts by mass of 2,4,6-trimethylbenzoylphenylphosphine oxide, 2 parts by mass of decanedic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4- 0.5 part by mass of triphenylphosphine, and 0.1 part by mass of 3-glycidoxypropyltriethoxysilane were added to the mixture, and the mixture was stirred until homogeneous. Thereafter, the mixture was filtered through a 200 mesh net to obtain an ultraviolet curable pressure sensitive adhesive composition.

[실시예2∼6, 비교예1∼2][Examples 2 to 6, Comparative Examples 1 to 2]

사용하는 우레탄(메타)아크릴레이트, (메타)아크릴 단량체의 종류 및 양을 표 1에 나타내는 바와 같이 변경한 이외에는, 실시예1과 같이 하여 자외선 경화형 점착제 조성물을 얻었다.An ultraviolet curing pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that the type and amount of the urethane (meth) acrylate and (meth) acrylic monomer used were changed as shown in Table 1.

[점착 필름의 제작 방법][Production method of adhesive film]

표면에 이형 처리된 두께 50㎛의 폴리에틸렌테레프탈레이트 필름(이형 PET50)의 표면에, UV 조사 후에 있어서의 막두께가 175㎛가 되도록 실시예 및 비교예에서 얻어진 자외선 경화형 점착제 조성물을 도포하여, 이형 PET50을 첩합했다. 그 후, UV 조사 장치에서, 이형 PET50 투과 후의 UV-A 영역의 파장의 적산 광량이 1J/㎠가 되도록 UV 조사하여, 점착 필름을 제작했다.The ultraviolet curable pressure sensitive adhesive composition obtained in Examples and Comparative Examples was coated on the surface of a 50 占 퐉 -thick polyethylene terephthalate film (release PET50) having a thickness of 175 占 퐉 after UV irradiation, . Thereafter, in the UV irradiator, UV irradiation was performed so that the accumulated light quantity of the wavelength of the UV-A region after permeation of the releasing PET 50 was 1 J / cm 2, thereby producing an adhesive film.

[점착력의 측정 방법][Measurement method of adhesive strength]

상술의 방법으로 제작한 점착 필름의 편면을, 두께 75㎛의 폴리에틸렌테레프탈레이트 필름(PET75)에 첩합하여, 편면에 PET75 기재가 첩합된 점착 필름을 제작했다. 이것을 25㎜ 폭으로 자른 것을 시험편으로 했다. 당해 시험편을 2㎏ 롤×2왕복으로 피착체인 유리판, 폴리카보네이트(PC)판에 각각 첩부했다. 첩부 1시간 후에 23℃, 습도 50%의 분위기하에서 180℃ 박리 강도를 측정하여, 점착력으로 했다.The one side of the pressure-sensitive adhesive film produced by the method described above was bonded to a polyethylene terephthalate film (PET75) having a thickness of 75 占 퐉 to produce an adhesive film in which a PET75 base material was adhered to one side. The test piece was cut into a width of 25 mm. The test piece was attached to a glass plate and a polycarbonate (PC) plate, which were adhered to each other, with reciprocating 2 kg rolls. One hour after the attachment, the peel strength at 180 캜 was measured in an atmosphere of 23 캜 and 50% humidity to obtain the adhesive strength.

[내습열백화성의 평가 방법][Evaluation method of anti-wet heat whitening property]

상술의 방법으로 제작한 점착 필름의 편면을, 두께 100㎛의 폴리에틸렌테레프탈레이트 필름(PET100)에 첩합하여, 편면에 PET100 기재가 첩합된 점착 필름을 제작했다. 이것을 종 50㎜, 횡 40㎜로 자르고, 유리판에 2㎏ 롤×2왕복으로 첩부한 것을 시험편으로 했다. 그 시험편을, 탁도계 「NDH5000」(니혼덴쇼쿠고교(주)제)로, JISK7361-1-1997에 준하여 헤이즈(%)를 측정하여, 이 값을 초기값으로 했다. 다음으로, 이 시험편을 85℃, 습도 85%의 분위기하에 10분 방치한 후 취출하고, 취출 후 10분 이내에 헤이즈(%)를 탁도계 「NDH5000」(니혼덴쇼쿠고교(주)제)로, JISK7361-1-1997에 준하여 측정했다.The one side of the pressure-sensitive adhesive film produced by the above method was bonded to a polyethylene terephthalate film (PET100) having a thickness of 100 占 퐉 to prepare an adhesive film in which a PET100 base material was bonded to one side. The specimen was cut into 50 mm long and 40 mm wide and attached to a glass plate with 2 kg rolls × 2 reciprocations. The haze (%) of the test piece was measured with a turbidimeter "NDH5000" (manufactured by Nihon Denshoku Kogyo Co., Ltd.) in accordance with JIS K 7361-1-1997, and this value was used as an initial value. Next, the test piece was allowed to stand in an atmosphere at 85 캜 and a humidity of 85% for 10 minutes and taken out. The haze (%) was measured with a turbidity meter "NDH5000" (manufactured by Nihon Denshoku Kogyo K.K.) -1-1997.

[내습열황변성의 평가 방법][Evaluation method of moisture resistance and yellowing resistance]

상술의 방법으로 제작한 점착 필름의 편면을 유리판에 첩부하고, 또 다른 1매의 이형 PET50을 박리한 것을 시험편으로 했다. 그 시험편을, 광원C, 시야 2°, 분광 측색계 「CM-5000d」(코니카미놀타센신구 가부시키가이샤제)로, JISK7105-1981에 준하여 황변도(b*)를 측정했다. 또한, 상기 시험편을 80℃, 습도 85%의 분위기하에서 500시간 방치한 후에, 마찬가지로 황변도(b*)를 측정했다.One side of the adhesive film produced by the above method was attached to a glass plate, and another piece of the release PET 50 was peeled off. (B *) was measured by a light source C, a visual field 2 °, and a spectroscopic colorimeter CM-5000d (manufactured by Konica Minolta Sensing Co., Ltd.) in accordance with JIS K7105-1981. Further, after the test piece was allowed to stand in an atmosphere at 80 캜 and a humidity of 85% for 500 hours, the yellowing degree (b *) was similarly measured.

[표 1][Table 1]

Figure pct00001
Figure pct00001

또, 표 1∼2 중의 역어(譯語)에 대해서 설명한다.In addition, the inverse terms in Tables 1 and 2 will be described.

ACMO; 아크릴로일모르폴린ACMO; Acryloylmorpholine

NOA; n-옥틸아크릴레이트NOA; n-octyl acrylate

IOA; 이소옥틸아크릴레이트IOA; Isooctyl acrylate

TDA; 트리데실아크릴레이트TDA; Tridecyl acrylate

CHA; 시클로헥실아크릴레이트CHA; Cyclohexyl acrylate

IBXA; 이소보르닐아크릴레이트IBXA; Isobornyl acrylate

본 발명의 자외선 경화형 점착제 조성물을 사용하여 얻어진 점착제는, 점착력, 내습열백화성 및 내습열황변성이 뛰어난 것을 알 수 있었다.The pressure-sensitive adhesive obtained by using the ultraviolet curable pressure-sensitive adhesive composition of the present invention was found to be excellent in adhesive strength, anti-wet heat whitening property and anti-wet heat sulfur modification property.

한편, 비교예1은, 우레탄(메타)아크릴레이트의 원료로서 폴리에틸렌글리콜을 사용하지 않는 태양이지만, 내습열백화성이 불량인 것을 알 수 있었다.On the other hand, in Comparative Example 1, although polyethylene glycol was not used as a raw material of urethane (meth) acrylate, it was found that the anti-wet heat resistance was poor.

비교예2는, 우레탄(메타)아크릴레이트의 원료로서 폴리에틸렌글리콜을 사용하지 않고, 또한, (메타)아크릴 단량체로서 황변성이 높은 ACMO를 다량으로 사용한 태양이지만, 내습열황변성이 불량인 것을 알 수 있었다.Comparative Example 2 is a case in which polyethylene glycol is not used as a raw material of urethane (meth) acrylate, and a large amount of ACMO having a high sulfur-modifying property is used as the (meth) acrylic monomer. However, I could.

Claims (5)

폴리에틸렌글리콜(a1)을 포함하는 폴리올(a), 폴리이소시아네이트(b), 및, 수산기 또는 이소시아네이트기를 갖는 (메타)아크릴 화합물(c)을 반응시켜서 얻어지는 우레탄(메타)아크릴레이트(X), (메타)아크릴 단량체(Y), 및 광중합 개시제(Z)를 함유하는 것을 특징으로 하는 자외선 경화형 점착제 조성물.(Meth) acrylate (X), (meth) acrylate (meth) acrylate obtained by reacting a polyol (a) containing a polyethylene glycol (a1), a polyisocyanate (b) and a (meth) acrylic compound having a hydroxyl group or an isocyanate group ) An acrylic monomer (Y), and a photopolymerization initiator (Z). 제1항에 있어서,
상기 폴리에틸렌글리콜(a1)의 수평균 분자량이 200∼5,000의 범위인 자외선 경화형 점착제 조성물.The method according to claim 1,
Wherein the polyethylene glycol (a1) has a number average molecular weight of 200 to 5,000. 제1항에 있어서,
상기 폴리에틸렌글리콜(a1)의 사용량이 상기 폴리올(a) 중 1∼60질량%의 범위인 자외선 경화형 점착제 조성물.The method according to claim 1,
The amount of the polyethylene glycol (a1) to be used is in the range of 1 to 60 mass% of the polyol (a). 제1항에 있어서,
상기 (메타)아크릴 단량체(Y) 중에 있어서의 질소 원자를 갖는 (메타)아크릴 단량체의 함유량이 40질량% 이하인 자외선 경화형 점착제 조성물.The method according to claim 1,
Wherein the content of the (meth) acrylic monomer having a nitrogen atom in the (meth) acrylic monomer (Y) is 40 mass% or less. 제1항 내지 제4항 중 어느 한 항에 기재된 자외선 경화형 점착제 조성물을 사용하여 얻어진 것을 특징으로 하는 점착제.A pressure-sensitive adhesive obtained by using the ultraviolet-curable pressure-sensitive adhesive composition according to any one of claims 1 to 4.
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Families Citing this family (11)

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KR101874867B1 (en) * 2013-12-25 2018-07-05 디아이씨 가부시끼가이샤 Ultraviolet curable adhesive composition, adhesive film and method for producing adhesive film
JP5822051B1 (en) * 2013-12-25 2015-11-24 Dic株式会社 UV-curable adhesive composition, adhesive film, and method for producing adhesive film
JP6753038B2 (en) * 2015-04-07 2020-09-09 三菱ケミカル株式会社 Photocurable composition
WO2016190361A1 (en) * 2015-05-26 2016-12-01 デンカ株式会社 Composition
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CN105754538A (en) * 2016-03-23 2016-07-13 烟台信友新材料股份有限公司 Ultraviolet curing adhesive allowing heating curing and preparation method
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JP6502295B2 (en) * 2016-08-10 2019-04-17 株式会社有沢製作所 UV curable resin composition
TW201823413A (en) * 2016-12-20 2018-07-01 日商荒川化學工業股份有限公司 Ultraviolet-curable adhesive, cured object and adhesive sheet wherein the ultraviolet-curable adhesive is substantially a solvent-free transparent adhesive that is not whitened due to high heat and high humidity
JP7073814B2 (en) * 2018-03-16 2022-05-24 三菱ケミカル株式会社 An active energy ray-curable resin composition, a coating agent using the same, and a sheet.
CN109185804A (en) * 2018-09-07 2019-01-11 扬州金源灯饰有限公司 Environmentally friendly LED street lamp

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000038547A (en) * 1998-07-24 2000-02-08 Mitsubishi Rayon Co Ltd Photocuring adhesive composition and optical member using same
JP2006104296A (en) 2004-10-04 2006-04-20 Nitto Denko Corp Adhesive composition, adhesive layer and adhesive sheet manufactured using the adhesive composition
JP2007084727A (en) * 2005-09-22 2007-04-05 Dainippon Printing Co Ltd Ultraviolet-curable adhesive for forming optical sheet and optical sheet

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3316040B2 (en) * 1993-07-02 2002-08-19 三菱レイヨン株式会社 Photocurable resin composition
JP4112223B2 (en) * 2001-12-21 2008-07-02 日本合成化学工業株式会社 Active energy ray-curable pressure-sensitive adhesive composition
JP2008007694A (en) * 2006-06-30 2008-01-17 Sanyo Chem Ind Ltd Photosensitive composition for adhesive agent
JP5069662B2 (en) * 2007-11-12 2012-11-07 リンテック株式会社 Adhesive sheet
US20120282427A1 (en) * 2009-12-02 2012-11-08 Nipponkayaku Kabushikikaisha Ultraviolet-Curable Resin Composition For Optical Disc And Cured Product Thereof
JP5542029B2 (en) * 2010-11-08 2014-07-09 ディーエイチ・マテリアル株式会社 (Meth) acryloyl group-containing polyurethane, method for producing (meth) acryloyl group-containing polyurethane, radical polymerizable resin composition, cured product
JP5630256B2 (en) * 2010-12-24 2014-11-26 Dic株式会社 UV-curable adhesive resin composition, adhesive and laminate
TWI454548B (en) * 2012-08-01 2014-10-01 Eternal Materials Co Ltd Dual curable adhesive composition
CN103012728B (en) * 2012-12-11 2014-10-29 广东工业大学 Method for preparing ultraviolet light cured pressure sensitive adhesive

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000038547A (en) * 1998-07-24 2000-02-08 Mitsubishi Rayon Co Ltd Photocuring adhesive composition and optical member using same
JP2006104296A (en) 2004-10-04 2006-04-20 Nitto Denko Corp Adhesive composition, adhesive layer and adhesive sheet manufactured using the adhesive composition
JP2007084727A (en) * 2005-09-22 2007-04-05 Dainippon Printing Co Ltd Ultraviolet-curable adhesive for forming optical sheet and optical sheet

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