KR101898529B1 - Ultraviolet ray-curable adhesive agent composition, adhesive film, and production method for adhesive film - Google Patents

Ultraviolet ray-curable adhesive agent composition, adhesive film, and production method for adhesive film Download PDF

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KR101898529B1
KR101898529B1 KR1020167033549A KR20167033549A KR101898529B1 KR 101898529 B1 KR101898529 B1 KR 101898529B1 KR 1020167033549 A KR1020167033549 A KR 1020167033549A KR 20167033549 A KR20167033549 A KR 20167033549A KR 101898529 B1 KR101898529 B1 KR 101898529B1
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meth
sensitive adhesive
acrylate
adhesive film
ultraviolet
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KR20170007326A (en
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마리코 츠나시마
마사유키 이와쿠보
야스오 오오지
게이지 츠나시마
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디아이씨 가부시끼가이샤
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    • C09J7/38—Pressure-sensitive adhesives [PSA]
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    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
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    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract

본 발명이 해결하려고 하는 과제는, 단차추종성 및 커팅성이 우수한 점착 필름이 얻어지는 자외선 경화형 점착제 조성물을 제공하는 것이다. 본 발명은, 수산기를 갖는 쇄신장제(a1-1) 및 그 밖의 폴리올을 포함하는, 수산기 당량이 400g/eq. 이하인 폴리올 조성물(a1), 폴리이소시아네이트(a2), 및, 이소시아네이트기 또는 수산기를 갖는 (메타)아크릴 화합물(a3)을 반응해서 얻어지는 우레탄(메타)아크릴레이트(A), 광중합개시제(B), 및, 유기 용제(C)를 함유하는 것을 특징으로 하는 자외선 경화형 점착제 조성물을 제공하는 것이다. 또한, 본 발명은, 상기 자외선 경화형 점착제 조성물을 건조 및 자외선 조사함에 의해 얻어지는 것을 특징으로 하는 점착 필름을 제공하는 것이다.An object to be solved by the present invention is to provide an ultraviolet-curable pressure-sensitive adhesive composition which can obtain an adhesive film excellent in step-following property and cutting property. (A1-1) having a hydroxyl group and other polyols having a hydroxyl equivalent of 400 g / eq. (Meth) acrylate (A) obtained by reacting a polyol composition (a1), a polyisocyanate (a2) and an isocyanate group or a hydroxyl group-containing (meth) acrylic compound (a3), a photopolymerization initiator , And an organic solvent (C). The present invention also provides an ultraviolet curable pressure-sensitive adhesive composition. The present invention also provides an adhesive film characterized by being obtained by drying and ultraviolet irradiation of the ultraviolet-curing pressure-sensitive adhesive composition.

Description

자외선 경화형 점착제 조성물, 점착 필름, 및, 점착 필름의 제조 방법{ULTRAVIOLET RAY-CURABLE ADHESIVE AGENT COMPOSITION, ADHESIVE FILM, AND PRODUCTION METHOD FOR ADHESIVE FILM}TECHNICAL FIELD The present invention relates to an ultraviolet curing pressure-sensitive adhesive composition, an ultraviolet curable pressure-sensitive adhesive composition, a pressure-sensitive adhesive film,

본 발명은, IT 관련 제품의 제조에 호적하게 사용할 수 있는 자외선 경화형 점착제 조성물에 관한 것이다.The present invention relates to an ultraviolet curing pressure-sensitive adhesive composition which can be suitably used in the manufacture of IT-related products.

전자수첩, 휴대전화 등의 소형 전자 단말에 마련되어 있는 화상 표시부로서는, 일반적으로, 화상 표시 모듈의 상부 또는 하부에, 상기 화상 표시 모듈을 보호하는 것 등을 목적으로 해서 투명한 화상 표시 패널이 적층된 것이 알려져 있다. 상기 화상 표시 패널에는, 의장성의 부여나, 차광성의 부여를 목적으로 해서 가식층(加飾層)이 마련되어 있는 경우가 많다.As an image display unit provided in a small electronic terminal such as an electronic notebook or a mobile phone, a transparent image display panel is generally stacked on the upper or lower portion of the image display module for the purpose of protecting the image display module It is known. In many cases, the image display panel is provided with a decorative layer (decorating layer) for the purpose of imparting designability and imparting a light shielding property.

상기 가식층이 마련된 개소에는, 화상 표시 패널의 표면에 대해서 약간 단차가 형성되어 있고, 화상 표시 패널을 고정하는 점착 시트(Optical Clear Adhesive, 이하 「OCA」라 약기한다)에는, 그 단차에 기포 등이 남지 않도록 높은 단차추종성이 요구되고 있다.In the position where the decorating layer is provided, a slight step is formed with respect to the surface of the image display panel. In the optical clear adhesive (hereinafter abbreviated as "OCA") for fixing the image display panel, It is required to follow high steps so as not to remain.

상기 OCA에 사용할 수 있는 자외선 경화형 점착제로서는, 예를 들면, 우레탄아크릴레이트, 아크릴 단량체 및 광중합개시제를 함유하는 무용제형 점착제 조성물을 사용해서 얻어진 점착제가 알려져 있다(예를 들면, 특허문헌 1을 참조).As an ultraviolet curable pressure sensitive adhesive that can be used for OCA, there is known a pressure sensitive adhesive obtained by using a solventless pressure sensitive adhesive composition containing, for example, urethane acrylate, an acrylic monomer and a photopolymerization initiator (see, for example, Patent Document 1) .

상기 점착제는, 자외선 경화 직후에 점착성을 발현할 수 있으므로 고생산성이 우수하고, 또한, 종래형의 점착제에 비해서 점착제층의 후막화가 용이하므로, 고기능화가 기대되는 등의 메리트를 갖고 있다.The above-mentioned pressure-sensitive adhesive has merits such as high productivity because it can exhibit tackiness immediately after curing with ultraviolet rays, and it is easy to form a pressure-sensitive adhesive layer thicker than conventional pressure-sensitive adhesives, and high performance is expected.

그러나, 상기 점착제와 같이 수지의 가교 밀도를 저하시키고, 유연성을 부여하는 방법에서는, 단차추종성은 양호해지지만, OCA를 재단할 때에 칼날에 풀이 부착하는 등 커팅성에는 개선이 요구되고 있었다.However, in the method of lowering the cross-linking density of the resin and imparting flexibility as in the case of the above-mentioned pressure-sensitive adhesive, the step-wise followability is improved. However, cutting property such as sticking to the blade at the time of cutting OCA has been required to be improved.

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

본 발명이 해결하려고 하는 과제는, 단차추종성 및 커팅성이 우수한 점착 필름이 얻어지는 자외선 경화형 점착제 조성물을 제공하는 것이다.An object to be solved by the present invention is to provide an ultraviolet-curable pressure-sensitive adhesive composition which can obtain an adhesive film excellent in step-following property and cutting property.

본 발명은, 수산기를 갖는 쇄신장제(a1-1) 및 그 밖의 폴리올을 포함하는, 수산기 당량이 400g/eq. 이하인 폴리올 조성물(a1), 폴리이소시아네이트(a2), 및, 이소시아네이트기 또는 수산기를 갖는 (메타)아크릴 화합물(a3)을 반응해서 얻어지는 우레탄(메타)아크릴레이트(A), 광중합개시제(B), 및, 유기 용제(C)를 함유하는 것을 특징으로 하는 자외선 경화형 점착제 조성물을 제공하는 것이다.(A1-1) having a hydroxyl group and other polyols having a hydroxyl equivalent of 400 g / eq. (Meth) acrylate (A) obtained by reacting a polyol composition (a1), a polyisocyanate (a2) and an isocyanate group or a hydroxyl group-containing (meth) acrylic compound (a3), a photopolymerization initiator , And an organic solvent (C). The present invention also provides an ultraviolet curable pressure-sensitive adhesive composition.

또한, 본 발명은, 상기 자외선 경화형 점착제 조성물을 건조 및 자외선 조사함에 의해 얻어지는 것을 특징으로 하는 점착 필름을 제공하는 것이다.The present invention also provides an adhesive film characterized by being obtained by drying and ultraviolet irradiation of the ultraviolet-curing pressure-sensitive adhesive composition.

또한, 본 발명은, 상기 자외선 경화형 점착제 조성물을 기재(基材)에 도공한 후에, 유기 용제(C)를 건조해서 자외선 경화형 점착 필름을 얻고, 다음으로, 당해 자외선 경화형 점착 필름의 점착층을 기재에 첩부(貼付)하고, 그 후 자외선 조사함에 의해 얻어지는 것을 특징으로 하는 점착 필름의 제조 방법을 제공하는 것이다.The present invention also relates to a method for producing an ultraviolet curing pressure-sensitive adhesive composition, which comprises applying the ultraviolet-curable pressure-sensitive adhesive composition onto a substrate, drying the organic solvent (C) And then irradiated with ultraviolet rays. The present invention also provides a method for producing a pressure-sensitive adhesive film.

본 발명의 자외선 경화형 점착제 조성물을 건조 및 자외선 조사함에 의해 얻어지는 점착 필름은, 단차추종성이 우수하고, 재단해도 풀 남음이 없어 커팅성이 우수한 것이고, 습열 조건 하에서 장시간 사용되어도 백화가 일어나기 어려운 것이다.The pressure-sensitive adhesive film obtained by drying and ultraviolet ray irradiation of the ultraviolet-curing pressure-sensitive adhesive composition of the present invention is excellent in step-following ability and excellent in cuttability because no residue is left after cutting.

또한, 상기 자외선 경화형 점착제 조성물을 건조해서 얻어지는 자외선 경화형 점착 필름은, 자외선 조사 전이어도 유동화하기 어려워, 작업성이 우수한 것이다.Furthermore, the ultraviolet curing type pressure-sensitive adhesive film obtained by drying the ultraviolet-curing pressure-sensitive adhesive composition is difficult to be fluidized even before ultraviolet irradiation, and is excellent in workability.

따라서, 본 발명의 자외선 경화형 점착제 조성물은, 광학 부재에 사용되는 점착제로서 호적하게 사용할 수 있고, 특히, 터치패널, 액정 디스플레이, 플라스마 디스플레이, 유기 EL, PC, 휴대전화, 전자수첩 등의 IT 관련 제품의 제조에 호적하게 사용할 수 있다.Therefore, the ultraviolet-curing pressure-sensitive adhesive composition of the present invention can be suitably used as a pressure-sensitive adhesive for use in an optical member, and can be used suitably for an IT related product such as a touch panel, liquid crystal display, plasma display, organic EL, PC, Can be suitably used for the production of

본 발명의 자외선 경화형 점착제 조성물은, 수산기를 갖는 쇄신장제(a1-1) 및 그 밖의 폴리올을 포함하는, 수산기 당량이 400g/eq. 이하인 폴리올 조성물(a1), 폴리이소시아네이트(a2), 및, 이소시아네이트기 또는 수산기를 갖는 (메타)아크릴 화합물(a3)을 반응해서 얻어지는 우레탄(메타)아크릴레이트(A), 광중합개시제(B), 및, 유기 용제(C)를 필수 성분으로서 함유하는 것이다.The ultraviolet-curable pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive composition containing a hydroxyl group-containing chain extender (a1-1) and other polyols having a hydroxyl equivalent of 400 g / eq. (Meth) acrylate (A) obtained by reacting a polyol composition (a1), a polyisocyanate (a2) and an isocyanate group or a hydroxyl group-containing (meth) acrylic compound (a3), a photopolymerization initiator , And an organic solvent (C) as essential components.

상기 수산기를 갖는 쇄신장제(a1-1)는, 단차추종성 및 커팅성이 우수한 점착 필름을 얻는데 필수의 성분이고, 수 평균 분자량이 50∼350의 범위의 것이다. 또, 상기 쇄신장제(a1-1)의 수 평균 분자량은, 겔·퍼미에이션·크로마토그래피(GPC)법에 의해, 하기 조건에서 측정한 값을 나타낸다.The hydroxyl-containing chain extender (a1-1) is an essential component for obtaining an adhesive film excellent in step traceability and cutability, and has a number average molecular weight of 50 to 350. The number average molecular weight of the chain extender (a1-1) shows a value measured by the gel permeation chromatography (GPC) under the following conditions.

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

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

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

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

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

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

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

칼럼 온도 : 40℃Column temperature: 40 DEG C

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

유속 : 1.0mL/분Flow rate: 1.0 mL / min

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

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

(표준 폴리스티렌)(Standard polystyrene)

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

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

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

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

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

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

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

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

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

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

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

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

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

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

상기 쇄신장제(a1-1)로서는, 예를 들면, 에틸렌글리콜, 1,2-프로판디올, 1,3-부탄디올, 1,4-부탄디올, 2,3-부탄디올, 3-메틸-1,5-펜탄디올, 1,6-헥산디올, 3,3'-디메틸올헵탄, 네오펜틸글리콜, 3,3-비스(히드록시메틸)헵탄, 디에틸렌글리콜, 디프로필렌글리콜, 폴리옥시프로필렌글리콜, 폴리옥시부틸렌글리콜, 글리세린, 트리메틸올프로판 등의 지방족 쇄신장제; 1,2-시클로부탄디올, 1,3-시클로펜탄디올, 1,4-시클로헥산디올, 시클로헵탄디올, 시클로옥탄디올, 1,4-시클로헥산디메탄올, 히드록시프로필시클로헥산올, 트리시클로[5.2.1.02,6]데칸-디메탄올, 비시클로[4.3.0]-노난디올, 디시클로헥산디올, 비시클로[4.3.0]노난디메탄올, 스피로[3.4]옥탄디올, 부틸시클로헥산디올, 1,1'-비시클로헥실리덴디올, 시클로헥산트리올, 수소 첨가 비스페놀A, 1,3-아다만탄디올 등의 지환 구조를 갖는 쇄신장제 등의 쇄신장제를 사용할 수 있다. 이들 쇄신장제는 단독으로 사용해도 되며 2종 이상을 병용해도 된다. 상기 쇄신장제(a1-1)로서는, 우수한 단차추종성을 유지하면서 점착 필름의 커팅성을 한층 더 향상할 수 있는 점으로부터, 지환 구조를 갖는 것을 사용하는 것이 바람직하고, 1,4-시클로헥산디메탄올을 사용하는 것이 보다 바람직하다.Examples of the chain extender (a1-1) include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, (Hydroxymethyl) heptane, diethylene glycol, dipropylene glycol, polyoxypropylene glycol, polyoxyethylene (meth) acrylate, polyoxyethylene Aliphatic extenders such as butylene glycol, glycerin and trimethylol propane; 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, bicyclo [4.3.0] nonanediol, spiro [3.4] octanediol, butylcyclohexanediol , Cyclohexanediol, cyclohexanetriol, hydrogenated bisphenol A, 1,3-adamantanediol, and the like can be used. These make-up preparations may be used alone or in combination of two or more. As the above-described chain extender (a1-1), those having an alicyclic structure are preferably used because they can further improve the cutting property of the pressure-sensitive adhesive film while maintaining an excellent step traceability, and 1,4-cyclohexanedimethanol Is more preferably used.

상기 쇄신장제(a1-1)의 사용량으로서는, 단차추종성 및 커팅성의 점으로부터, 폴리올 조성물(a1) 중 0.5∼40질량%의 범위인 것이 바람직하고, 3∼30질량%의 범위가 보다 바람직하다.The amount of the chain extender (a1-1) to be used is preferably in the range of 0.5 to 40% by mass, more preferably in the range of 3 to 30% by mass in the polyol composition (a1) from the viewpoint of step traceability and cutability.

상기 그 밖의 폴리올로서는, 예를 들면, 폴리에테르폴리올(a1-2), 폴리에스테르폴리올, 폴리카보네이트폴리올, 폴리아크릴폴리올, 폴리부타디엔폴리올, 수첨 폴리부타디엔폴리올, 다이머디올, 폴리이소프렌폴리올 등을 사용할 수 있다. 이들 폴리올은 단독으로 사용해도 되며 2종 이상을 병용해도 된다. 이들 중에서도, 유연성 및 내습열백화성을 한층 더 향상할 수 있는 점으로부터, 폴리에테르폴리올(a1-2)을 사용하는 것이 바람직하다.As other polyols, for example, polyether polyol (a1-2), polyester polyol, polycarbonate polyol, polyacrylic polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, dimer diol, polyisoprene polyol and the like can be used have. These polyols may be used alone or in combination of two or more. Among these, polyether polyol (a1-2) is preferably used because it can further improve flexibility and anti-wet heat resistance.

상기 폴리에테르폴리올(a1-2)로서는, 예를 들면, 폴리옥시에틸렌폴리올, 폴리옥시프로필렌폴리올, 폴리옥시테트라메틸렌폴리올, 폴리옥시에틸렌폴리옥시프로필렌폴리올, 폴리옥시에틸렌폴리옥시프로필렌폴리올, 폴리옥시프로필렌폴리옥시테트라메틸렌폴리올 등을 사용할 수 있다. 이들 폴리에테르폴리올은 단독으로 사용해도 되며 2종 이상을 병용해도 된다.Examples of the polyether polyol (a1-2) include polyoxyethylene polyol, polyoxypropylene polyol, polyoxytetramethylene polyol, polyoxyethylene polyoxypropylene polyol, polyoxyethylene polyoxypropylene polyol, polyoxypropylene Polyoxytetramethylene polyol and the like can be used. These polyether polyols may be used alone or in combination of two or more.

상기 폴리에테르폴리올(a1-2)을 사용할 경우의 사용량으로서는, 유연성 및 내습열백화성의 점으로부터, 폴리올 조성물(a1) 중 10∼99.5질량%의 범위인 것이 바람직하고, 40∼95질량%의 범위가 보다 바람직하다.The amount of the polyether polyol (a1-2) to be used is preferably 10 to 99.5 mass%, more preferably 40 to 95 mass%, of the polyol composition (a1), from the viewpoints of flexibility and anti- The range is more preferable.

상기 그 밖의 폴리올의 수 평균 분자량으로서는, 단차추종성, 커팅성, 점착물성 및 기계적 강도의 점으로부터, 400∼7,000의 범위인 것이 바람직하고, 700∼4,000의 범위가 보다 바람직하다. 또, 상기 그 밖의 폴리올의 수 평균 분자량은, 상기 쇄신장제(a1-1)의 수 평균 분자량과 마찬가지로 측정한 값을 나타낸다.The number average molecular weight of the other polyol is preferably in the range of 400 to 7,000, more preferably in the range of 700 to 4,000, from the viewpoint of step traceability, cutting property, adhesive property and mechanical strength. The number average molecular weight of the other polyols represents a value measured in the same manner as the number average molecular weight of the chain extender (a1-1).

상기 폴리올 조성물(a1)의 수산기 당량으로서는, 우수한 단차추종성과 커팅성을 양립하는데, 400g/eq. 이하인 것이 필수이다. 상기 폴리올 조성물(a1)의 수산기 당량의 값을 낮게 설정하는 것은, 통상 점착 필름을 딱딱하게 하는 방법이기 때문에 커팅성이 향상하는 것은 예측된 것이지만, 단차추종성도 우수한 점착 필름이 얻어진 것은 예상 외의 사항이었다. 상기 폴리올 조성물(a1)의 수산기 당량으로서는, 우수한 단차추종성을 유지하면서, 또한 커팅성 및 점착물성을 향상할 수 있는 점으로부터, 50∼390g/eq.의 범위인 것이 바람직하고, 200∼380g/eq.의 범위가 보다 바람직하다. 또, 상기 폴리올 조성물(a1)의 수산기 당량은, 상기 수산기를 갖는 쇄신장제(a1-1)를 포함하는 모든 폴리올의 투입량을, 각각의 쇄신장제 및 폴리올의 당량의 합계 값으로 나눈 값을 나타낸다.The hydroxyl equivalent of the polyol composition (a1) is preferably 400 g / eq. Or less. Setting the value of the hydroxyl group equivalent of the polyol composition (a1) to a low value is generally expected to improve the cuttability because the adhesive film is usually hardened, but it is expected that the pressure-sensitive adhesive film excellent in stepwise followability is obtained . The hydroxyl group equivalent of the polyol composition (a1) is preferably in the range of 50 to 390 g / eq., More preferably in the range of 200 to 380 g / eq, in view of improving the cutting property and the adhesive property while maintaining excellent step- The range of. The hydroxyl equivalent of the polyol composition (a1) represents a value obtained by dividing the amount of all the polyols containing the hydroxyl group-containing chain extender (a1-1) divided by the total value of the equivalents of the respective chain extender and the polyol.

상기 폴리이소시아네이트(a2)로서는, 예를 들면, 자일릴렌디이소시아네이트, 페닐렌디이소시아네이트, 톨릴렌디이소시아네이트, 디페닐메탄디이소시아네이트, 나프탈렌디이소시아네이트 등의 방향족 폴리이소시아네이트; 헥사메틸렌디이소시아네이트, 리신디이소시아네이트, 시클로헥산디이소시아네이트, 이소포론디이소시아네이트, 4,4'-디시클로헥실메탄디이소시아네이트, 디이소시아나토메틸시클로헥산, 테트라메틸자일릴렌디이소시아네이트 등의 지방족 또는 지환식 폴리이소시아네이트 등을 사용할 수 있다. 이들 폴리이소시아네이트는 단독으로 사용해도 되며 2종 이상을 병용해도 된다. 이들 중에서도, 커팅성 및 점착물성을 한층 더 향상할 수 있는 점으로부터, 지환식 폴리이소시아네이트를 사용하는 것이 바람직하고, 4,4'-디시클로헥실메탄디이소시아네이트, 이소포론디이소시아네이트, 시클로헥산디이소시아네이트 및 디이소시아나토메틸시클로헥산으로 이루어지는 군에서 선택되는 1종 이상의 폴리이소시아네이트를 사용하는 것이 보다 바람직하다.Examples of the polyisocyanate (a2) include aromatic polyisocyanates such as xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate and naphthalene diisocyanate; Alicyclic or alicyclic diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, diisocyanatomethylcyclohexane and tetramethyl xylylene diisocyanate; Polyisocyanate and the like can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, alicyclic polyisocyanates are preferably used from the viewpoint of further improving the cutting property and the adhesive property, and 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate And at least one polyisocyanate selected from the group consisting of diisocyanatomethylcyclohexane is more preferably used.

상기 이소시아네이트기 또는 수산기를 갖는 (메타)아크릴 화합물(a3)은, 우레탄(메타)아크릴레이트(A) 중에 (메타)아크릴로일기를 도입하는 목적으로 사용하는 것이다. 또, 본 발명에 있어서, 「(메타)아크릴」이란, 아크릴 및/또는 메타크릴을 나타내고, 「(메타)아크릴레이트」란, 아크릴레이트 및/또는 메타크릴레이트를 나타내고, 「(메타)아크릴로일」이란, 아크릴로일 및/또는 메타크릴로일을 나타낸다.The (meth) acrylic compound (a3) having an isocyanate group or a hydroxyl group is used for the purpose of introducing a (meth) acryloyl group into the urethane (meth) acrylate (A). In the present invention, the term "(meth) acryl" refers to acryl and / or methacryl, "(meth) acrylate" refers to acrylate and / or methacrylate, Acrylate " refers to acryloyl and / or methacryloyl.

또한, 상기 화합물(a3)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 화합물은 단독으로 사용해도 되며 2종 이상을 병용해도 된다. 이들 중에서도, 원료 입수의 용이성의 점으로부터, 2-(메타)아크릴로일옥시에틸이소시아네이트를 사용하는 것이 바람직하고, 자외선경화성의 점으로부터, 2-아크릴로일옥시에틸이소시아네이트를 사용하는 것이 보다 바람직하다.Examples of the (meth) acrylic compound having an isocyanate group that can be used as the compound (a3) include 2- (meth) acryloyloxyethyl isocyanate, 2- Oxy) ethyl isocyanate, and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate. These compounds may be used alone or in combination of two or more. Among them, it is preferable to use 2- (meth) acryloyloxyethyl isocyanate from the viewpoint of easiness of obtaining raw materials, and from the viewpoint of ultraviolet curing property, it is more preferable to use 2-acryloyloxyethyl isocyanate .

상기 화합물(a3)로서 사용할 수 있는 수산기를 갖는 (메타)아크릴 화합물로서는, 예를 들면, 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 3-히드록시프로필(메타)아크릴레이트, 3-히드록시부틸(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 6-히드록시헥실(메타)아크릴레이트, 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 화합물은 단독으로 사용해도 되며 2종 이상을 병용해도 된다. 이들 중에서도, 원료 입수의 용이성, 자외선경화성 및 점착물성의 점으로부터, 수산기를 갖는 아크릴산(메타)알킬에스테르를 사용하는 것이 바람직하고, 2-히드록시에틸아크릴레이트 및/또는 4-히드록시부틸아크릴레이트를 사용하는 것이 보다 바람직하다.Examples of the (meth) acrylic compound having a hydroxyl group that can be used as the compound (a3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Having a hydroxyl group such as (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate and hydroxyethyl acrylamide Alkyl (meth) acrylate; 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. These compounds may be used alone or in combination of two or more. Of these, acrylic acid (meth) alkyl esters having a hydroxyl group are preferably used from the viewpoints of ease of raw material acquisition, ultraviolet curing property and adhesive property, and 2-hydroxyethyl acrylate and / or 4-hydroxybutyl acrylate Is more preferable.

상기 화합물(a3)로서 이소시아네이트기를 갖는 (메타)아크릴 화합물을 사용할 경우의 우레탄(메타)아크릴레이트(A)의 제조 방법으로서는, 예를 들면, 무용제 하에서, 상기 폴리올(a1)과 상기 폴리이소시아네이트(a2)를 투입하고, 반응시킴에 의해서 수산기를 갖는 우레탄 프리폴리머를 얻고, 다음으로, 이소시아네이트기를 갖는 상기 (메타)아크릴 화합물(a3)을 공급하고, 혼합, 반응시킴에 의해서 제조하는 방법 등을 사용할 수 있다. 상기 반응은 어느 것에 있어서도, 예를 들면, 20∼120℃의 온도 조건 하에서, 30분∼24시간 행하는 것이 바람직하다.Examples of the method for producing the urethane (meth) acrylate (A) in the case of using the (meth) acrylic compound having an isocyanate group as the compound (a3) include a method in which the polyol (a1) and the polyisocyanate (Meth) acrylic compound (a3) having an isocyanate group is fed, mixed, and reacted with the isocyanate group-containing urethane prepolymer to obtain a urethane prepolymer having a hydroxyl group . It is preferable that the above reaction is carried out under temperature conditions of, for example, 20 to 120 캜 for 30 minutes to 24 hours.

상기 화합물(a3)로서 수산기를 갖는 (메타)아크릴 화합물을 사용할 경우의 상기 우레탄(메타)아크릴레이트(A)의 제조 방법으로서는, 예를 들면, 무용제 하에서, 상기 폴리올(a1)과 상기 (메타)아크릴 화합물(a3)을 반응계 중에 투입한 후에, 상기 폴리이소시아네이트(a2)를 공급하고, 혼합, 반응시킴에 의해서 제조하는 방법이나, 무용제 하에서, 상기 폴리올(a1)과 상기 폴리이소시아네이트(a2)를 반응시킴에 의해서 이소시아네이트기를 갖는 우레탄 프리폴리머를 얻고, 다음으로, 수산기를 갖는 상기 (메타)아크릴 화합물(a3)을 공급하고, 혼합, 반응시킴에 의해서 제조하는 방법 등을 사용할 수 있다. 상기 반응은 어느 것에 있어서도, 예를 들면, 20∼120℃의 온도 조건 하에서, 30분∼24시간 행하는 것이 바람직하다.Examples of the method for producing the urethane (meth) acrylate (A) in the case of using the (meth) acrylic compound having a hydroxyl group as the compound (a3) include a method in which the polyol (a1) (A1) and the polyisocyanate (a2) are reacted with each other in the absence of a solvent or by a method in which the acrylic compound (a3) is introduced into the reaction system and then the polyisocyanate (a2) A method in which a urethane prepolymer having an isocyanate group is obtained by a polymerization method and then the above (meth) acrylic compound (a3) having a hydroxyl group is supplied, mixed, and reacted. It is preferable that the above reaction is carried out under temperature conditions of, for example, 20 to 120 캜 for 30 minutes to 24 hours.

상기 우레탄(메타)아크릴레이트(A)의 제조는, 후술하는 유기 용제(C)의 존재 하에서 행해도 된다.The urethane (meth) acrylate (A) may be produced in the presence of an organic solvent (C) to be described later.

상기 화합물(a3)로서 수산기를 갖는 (메타)아크릴 화합물을 사용하는 경우에 있어서의, 상기 폴리올 조성물(a1)과 상기 폴리이소시아네이트(a2)와 상기 (메타)아크릴 화합물(a3)과의 반응은, 상기 폴리올 조성물(a1)이 갖는 수산기와 상기 (메타)아크릴 화합물(a3)이 갖는 수산기와의 합계량과, 폴리이소시아네이트(a2)가 갖는 이소시아네이트기와의 몰비[이소시아네이트기/수산기의 합계량]=0.75∼1의 범위에서 행하는 것이, 얻어지는 우레탄(메타)아크릴레이트(A)의 분자량을 제어하는데 바람직하고, 0.79∼0.995의 범위인 것이 보다 바람직하다. 또한, 상기 당량 비율이 1을 초과하는 경우에서 반응시켜도 되지만, 그 경우, 우레탄(메타)아크릴레이트(A)의 이소시아네이트기를 실활시키는 것을 목적으로 해서, 메탄올 등의 알코올을 사용하는 것이 바람직하다.The reaction of the polyol composition (a1), the polyisocyanate (a2) and the (meth) acrylic compound (a3) in the case of using the (meth) acrylic compound having a hydroxyl group as the compound (a3) (Molar ratio of isocyanate group / hydroxyl group) of the total amount of the hydroxyl group of the polyol composition (a1) and the hydroxyl group of the (meth) acrylic compound (a3) to the isocyanate group of the polyisocyanate (a2) = 0.75 to 1 Is preferable for controlling the molecular weight of the urethane (meth) acrylate (A) to be obtained, and it is more preferably in the range of 0.79 to 0.995. In this case, it is preferable to use an alcohol such as methanol for the purpose of deactivating the isocyanate group of the urethane (meth) acrylate (A).

또한, 상기 화합물(a3)로서 이소시아네이트를 갖는 (메타)아크릴 화합물을 사용하는 경우에 있어서의, 상기 폴리올 조성물(a1)과 상기 폴리이소시아네이트(a2)와 상기 (메타)아크릴 화합물(a3)과의 반응은, 상기 폴리올 조성물(a1)이 갖는 수산기와, 폴리이소시아네이트(a2) 및 (메타)아크릴 화합물(a3)이 갖는 이소시아네이트기의 합계와의 당량 비율[이소시아네이트기의 합계량/수산기]=0.75∼1의 범위에서 행하는 것이, 얻어지는 우레탄(메타)아크릴레이트(A)의 분자량을 제어하는데 바람직하고, 0.79∼0.995의 범위인 것이 보다 바람직하다. 또한, 상기 당량 비율이 1을 초과하는 경우에서 반응시켜도 되지만, 그 경우, 우레탄(메타)아크릴레이트(A)의 이소시아네이트기를 실활시키는 것을 목적으로 해서, 메탄올 등의 알코올을 사용하는 것이 바람직하다.The reaction of the polyol composition (a1) with the polyisocyanate (a2) and the (meth) acrylic compound (a3) in the case of using the (meth) acrylic compound having isocyanate as the compound (a3) (Total amount of isocyanate group / hydroxyl value) of the hydroxyl group of the polyol composition (a1) with the total of the isocyanate groups of the polyisocyanate (a2) and the (meth) acrylic compound (a3) Range is preferable for controlling the molecular weight of the urethane (meth) acrylate (A) to be obtained, and more preferably in the range of 0.79 to 0.995. In this case, it is preferable to use an alcohol such as methanol for the purpose of deactivating the isocyanate group of the urethane (meth) acrylate (A).

또한, 우레탄(메타)아크릴레이트(A)를 제조할 때에는, 필요에 따라서 중합금지제, 우레탄화 촉매 등을 사용해도 된다.When urethane (meth) acrylate (A) is produced, a polymerization inhibitor, an urethanation catalyst, or the like may be used if necessary.

상기 중합금지제로서는, 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. 이들 중합금지제는 단독으로 사용해도 되며 2종 이상을 병용해도 된다.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. These polymerization inhibitors may be used alone or in combination of two or more.

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. 이들 우레탄화 촉매는 단독으로 사용해도 되며 2종 이상을 병용해도 된다.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 tetraacetylacetonate, and the like can be used. These urethanation catalysts may be used alone or in combination of two or more.

상기 우레탄(메타)아크릴레이트(A)는, 광조사나 가열에 의해서 라디칼 중합을 진행시키는 (메타)아크릴로일기를 갖는 것이다. 상기 우레탄(메타)아크릴레이트(A)의 (메타)아크릴로일기 당량으로서는, 커팅성, 점착물성 및 단차추종성을 한층 더 향상할 수 있는 점으로부터, 1,000∼50,000g/eq.의 범위인 것이 바람직하고, 3,000∼50,000g/eq.의 범위가 보다 바람직하다. 또, 상기 (메타)아크릴로일기 당량은, 상기 폴리올(a1)과 폴리이소시아네이트(a2)와 (메타)아크릴 화합물(a3)과의 합계 질량을, 상기 우레탄(메타)아크릴레이트(A) 중에 존재하는 (메타)아크릴기의 당량으로 나눈 값을 나타낸다.The urethane (meth) acrylate (A) has a (meth) acryloyl group for promoting radical polymerization by light irradiation or heating. The (meth) acryloyl group equivalent of the urethane (meth) acrylate (A) is preferably in the range of 1,000 to 50,000 g / eq. From the viewpoint of further improving the cutting property, the adhesive property and the step- And more preferably in the range of 3,000 to 50,000 g / eq. The (meth) acryloyl group equivalent is preferably such that the total mass of the polyol (a1), the polyisocyanate (a2) and the (meth) acrylic compound (a3) is present in the urethane (meth) (Meth) acrylate group.

상기 우레탄(메타)아크릴레이트(A) 중의 우레탄 결합의 질량 비율로서는, 커팅성, 점착물성 및 단차추종성을 한층 더 향상할 수 있는 점으로부터, 우레탄(메타)아크릴레이트(A)의 전량 중 4∼20질량%의 범위인 것이 바람직하고, 5∼15질량%의 범위인 것이 보다 바람직하다. 또, 상기 우레탄(메타)아크릴레이트(A)의 우레탄 결합량은, 상기 폴리올(a1)과 상기 폴리이소시아네이트(a2)와 상기 (메타)아크릴 화합물(a3)과의 합계 질량에 대한, 상기 원료 중에 점유하는 우레탄 결합 구조의 질량 비율을 나타낸다.The mass ratio of the urethane bond in the urethane (meth) acrylate (A) is preferably in the range of 4 to 20 parts by mass based on the total amount of the urethane (meth) acrylate (A) from the viewpoint of further improving the cutting property, By mass to 20% by mass, and more preferably 5% by mass to 15% by mass. The urethane bonding amount of the urethane (meth) acrylate (A) is preferably within a range of from 1 to 100 parts by mass, based on the total mass of the polyol (a1), the polyisocyanate (a2) and the (meth) acrylic compound (a3) Represents the mass ratio of the occupied urethane bonding structure.

상기 우레탄(메타)아크릴레이트(A)의 중량 평균 분자량으로서는, 커팅성, 점착물성 및 단차추종성을 한층 더 향상할 수 있는 점으로부터, 5,000∼500,000의 범위인 것이 바람직하고, 15,000∼300,000의 범위가 보다 바람직하다. 또, 상기 우레탄(메타)아크릴레이트(A)의 중량 평균 분자량은, 상기 폴리카보네이트폴리올(a1-1)의 수 평균 분자량과 마찬가지로 측정해서 얻어진 값을 나타낸다.The weight average molecular weight of the urethane (meth) acrylate (A) is preferably in the range of from 5,000 to 500,000, more preferably in the range of from 15,000 to 300,000, from the viewpoint of further improving the cutting property, the adhesive property and the step- More preferable. The weight average molecular weight of the urethane (meth) acrylate (A) is a value obtained by measuring the number average molecular weight of the polycarbonate polyol (a1-1).

상기 광중합개시제(B)는, 광조사나 가열 등에 의해서 라디칼을 발생하고, 상기 우레탄(메타)아크릴레이트(A)의 라디칼 중합을 개시시키는 것이다.The photopolymerization initiator (B) generates a radical by light irradiation or heating to initiate radical polymerization of the urethane (meth) acrylate (A).

상기 광중합개시제(B)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=미힐러케톤), 4,4'-디에틸아미노벤조페논, α-아실옥심에스테르, 벤질, 메틸벤조일포르메이트(「바이아큐어55」), 2-에틸안트라퀴논 등의 안트라퀴논 화합물; 2,4,6-트리메틸벤조일디페닐포스핀옥사이드, 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드 등의 아실포스핀옥사이드 화합물; 3,3',4,4'-테트라(tert-부틸퍼옥시카르보닐)벤조페논, 아크릴화벤조페논 등을 사용할 수 있다. 이들 광중합개시제는 단독으로 사용해도 되며 2종 이상을 병용해도 된다.Examples of the photopolymerization initiator (B) 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 (alias: Michailler ketone), 4,4'-diethylaminobenzophenone,? -Acyloxime ester, benzyl, methylbenzoylformate Anthraquinone compounds such as ethyl anthraquinone; Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, and acrylated benzophenone. These photopolymerization initiators may be used alone or in combination of two or more.

상기 광중합개시제(B)로서는, 점착물성 및 자외선경화성을 한층 더 향상할 수 있는 점으로부터, 2-히드록시-2-메틸-1-페닐프로판-1-온, 1-히드록시시클로헥실페닐케톤, 2,4,6-트리메틸벤조일디페닐포스핀옥사이드 및 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드로 이루어지는 군에서 선택되는 1종 이상의 광중합개시제를 사용하는 것이 바람직하고, 1-히드록시시클로헥실페닐케톤, 2,4,6-트리메틸벤조일디페닐포스핀옥사이드가 보다 바람직하다.As the photopolymerization initiator (B), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, It is preferable to use at least one photopolymerization initiator selected from the group consisting of 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Hydroxycyclohexyl phenyl ketone, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are more preferable.

상기 광중합개시제(B)의 사용량으로서는, 자외선경화성을 한층 더 향상할 수 있는 점으로부터, 상기 우레탄(메타)아크릴레이트(A) 100질량부에 대해서, 0.1∼20질량부의 범위인 것이 바람직하고, 0.2∼15질량부의 범위가 보다 바람직하다.The amount of the photopolymerization initiator (B) to be used is preferably in the range of 0.1 to 20 parts by mass relative to 100 parts by mass of the urethane (meth) acrylate (A), more preferably 0.2 To 15 parts by mass is more preferable.

상기 유기 용제(C)로서는, 예를 들면, 톨루엔, 아세트산에틸, 아세트산부틸, 메틸에틸케톤, 헥산, 아세톤, 시클로헥산온, 3-펜탄온, 아세토니트릴, 프로피오니트릴, 이소부티로니트릴, 발레로니트릴, 디메틸설폭시드, 디메틸포름아미드 등을 사용할 수 있다. 이들 유기 용제는 단독으로 사용해도 되며 2종 이상을 병용해도 된다.Examples of the organic solvent (C) include toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, hexane, acetone, cyclohexanone, 3-pentanone, acetonitrile, propionitrile, isobutyronitrile, Rhenitrile, dimethylsulfoxide, dimethylformamide, and the like can be used. These organic solvents may be used alone or in combination of two or more.

상기 유기 용제(C)의 사용량으로서는, 건조성 및 도공성을 한층 더 향상할 수 있는 점으로부터, 자외선 경화형 점착제 조성물 중 70질량% 이하인 것이 바람직하고, 5∼60질량%의 범위가 보다 바람직하다.The amount of the organic solvent (C) to be used is preferably 70% by mass or less, more preferably 5 to 60% by mass in the ultraviolet-curable pressure-sensitive adhesive composition from the viewpoint of further improving drying and coating properties.

본 발명의 자외선 경화형 점착제 조성물은, 상기 우레탄(메타)아크릴레이트(A), 상기 광중합개시제(B) 및 상기 유기 용제(C)를 필수 성분으로서 함유하지만, 내습열백화성을 한층 더 향상할 수 있는 점으로부터, 2개 이상의 (메타)아크릴로일기를 갖는 (메타)아크릴 화합물(D)을 함유하는 것이 바람직하다.The ultraviolet curable pressure sensitive adhesive composition of the present invention contains the urethane (meth) acrylate (A), the photopolymerization initiator (B) and the organic solvent (C) as essential components, (Meth) acrylic compound (D) having two or more (meth) acryloyl groups.

상기 2개 이상의 (메타)아크릴로일기를 갖는 (메타)아크릴 화합물(D)로서는, 예를 들면, 에틸렌글리콜디(메타)아크릴레이트, 프로필렌글리콜디(메타)아크릴레이트, 테트라메틸렌글리콜디(메타)아크릴레이트, 트리메틸올프로판디(메타)아크릴레이트, 헥사메틸렌글리콜디(메타)아크릴레이트, 1,6-헥산디올디(메타)아크릴레이트, 1,9-노난디올디(메타)아크릴레이트, 1,10-데칸디올디(메타)아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, 펜타에리트리톨디(메타)아크릴레이트, 펜타에리트리톨트리(메타)아크릴레이트, 펜타에리트리톨테트라(메타)아크릴레이트, 디(트리메틸올프로판)디(메타)아크릴레이트, 디(트리메틸올프로판)트리(메타)아크릴레이트, 디(트리메틸올프로판)테트라(메타)아크릴레이트, 디펜타에리트리톨디(메타)아크릴레이트, 디펜타에리트리톨트리(메타)아크릴레이트, 디펜타에리트리톨테트라(메타)아크릴레이트, 디펜타에리트리톨펜타(메타)아크릴레이트, 디펜타에리트리톨헥사(메타)아크릴레이트 등의 지방족 다관능 (메타)아크릴레이트, 트리스(2-(메타)아크릴로일옥시에틸)이소시아누레이트 등의 이소시아누레이트 골격을 갖는 다관능 (메타)아크릴레이트 등을 사용할 수 있다. 이들 (메타)아크릴 화합물은 단독으로 사용해도 되며 2종 이상을 병용해도 된다. 이들 중에서도, 상기 우레탄(메타)아크릴레이트(A)와의 우수한 경화성에 의해 한층 더 향상한 내습열백화성이 얻어지는 점으로부터, 지방족 다관능 (메타)아크릴레이트 및 이소시아누레이트 골격을 갖는 다관능 (메타)아크릴레이트 골격을 갖는 다관능 (메타)아크릴레이트로 이루어지는 군에서 선택되는 1종 이상을 사용하는 것이 바람직하고, 펜타에리트리톨트리(메타)아크릴레이트, 펜타에리트리톨테트라(메타)아크릴레이트, 및, 트리스(2-(메타)아크릴로일옥시에틸)이소시아누레이트로 이루어지는 군에서 선택되는 1종 이상의 (메타)아크릴 화합물을 사용하는 것이 보다 바람직하다. 또, 상기 「다관능」이란, (메타)아크릴로일기를 바람직하게는 2∼8개의 범위, 보다 바람직하게는 2∼6개의 범위에서 갖는 것을 나타낸다.Examples of the (meth) acrylic compound (D) having two or more (meth) acryloyl groups include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetramethylene glycol di Acrylate, trimethylolpropane di (meth) acrylate, hexamethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9- Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, (Meth) acrylate, di (trimethylol propane) di (meth) acrylate, di (trimethylol propane) Acrylate, diphen (Meth) acrylate such as trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane tri (meth) acrylate, (Meth) acrylate having an isocyanurate skeleton such as tris (2- (meth) acryloyloxyethyl) isocyanurate, and the like can be used. These (meth) acrylic compounds may be used alone or in combination of two or more. Among these, polyfunctional (meth) acrylates having an aliphatic polyfunctional (meth) acrylate and isocyanurate skeleton are preferable because they can further improve anti-wet heat and whiteness due to excellent curability with the urethane (meth) (Meth) acrylate skeleton, and at least one selected from the group consisting of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, (Meth) acrylate, and tris (2- (meth) acryloyloxyethyl) isocyanurate is more preferably used. The above "polyfunctional" means that the (meth) acryloyl group is preferably in the range of 2 to 8, more preferably 2 to 6.

상기 (메타)아크릴 화합물(D)의 함유량으로서는, 내습열백화성을 한층 더 향상할 수 있는 점으로부터, 상기 우레탄(메타)아크릴레이트(A) 100질량부에 대해서, 1∼30질량부의 범위인 것이 바람직하고, 5∼20질량부의 범위가 보다 바람직하다.The content of the (meth) acrylic compound (D) is preferably in the range of 1 to 30 parts by mass per 100 parts by mass of the urethane (meth) acrylate (A) , More preferably from 5 to 20 parts by mass.

본 발명의 자외선 경화형 점착제 조성물은, 상기 우레탄(메타)아크릴레이트(A), 상기 광중합개시제(B) 및 상기 유기 용제(C)를 필수 성분으로 하고, 바람직하게는 상기 (메타)아크릴 화합물(D)을 함유하는 것이지만, 필요에 따라서 그 밖의 첨가제를 함유해도 된다.The ultraviolet-curing pressure-sensitive adhesive composition of the present invention preferably contains the urethane (meth) acrylate (A), the photopolymerization initiator (B) and the organic solvent (C) ), But other additives may be contained as necessary.

상기 그 밖의 첨가제로서는, 예를 들면, 산화방지제(E), 광안정제(F), 방청제, 실란커플링제, 틱소성 부여제, 증감제, 중합금지제, 레벨링제, 점착부여제, 대전방지제, 난연제 등을 사용할 수 있다. 이들 첨가제는 단독으로 사용해도 되며 2종 이상을 병용해도 된다. 이들 중에서도, 본 발명의 자외선 경화형 점착제 조성물이 높은 내습열황변성이 요구되는 용도에 사용되는 경우에는, 산화방지제(E) 및 광안정제(F)를 함유하는 것이 바람직하다.Examples of other additives include antioxidants (E), light stabilizers (F), rust inhibitors, silane coupling agents, thixotropic agents, sensitizers, polymerization inhibitors, leveling agents, tackifiers, antistatic agents, Flame retardants and the like can be used. These additives may be used alone or in combination of two or more. Among them, it is preferable that the ultraviolet curable pressure-sensitive adhesive composition of the present invention contains an antioxidant (E) and a light stabilizer (F) when it is used in applications requiring high resistance to moisture and heat sulfur.

상기 산화방지제(E)로서는, 열열화(熱劣化)로 발생하는 라디칼이 포착하는 힌더드페놀 화합물(1차 산화방지제), 및, 열열화로 발생하는 과산화물을 분해하는 인 화합물, 황 화합물(2차 산화방지제) 등을 사용할 수 있다.Examples of the antioxidant (E) include a hindered phenol compound (primary antioxidant) in which a radical generated by thermal deterioration is captured (primary antioxidant), a phosphorus compound which decomposes peroxide generated by thermal heating, a sulfur compound Antioxidant) or 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. 이들 화합물은 단독으로 사용해도 되며 2종 이상을 병용해도 된다.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- 1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro [5.5-undecane, 2,6-di-tert-butyl-4-methylphenol, 2,2'- Methylene bis (4-methyl-6-tert-butylphenol), 2,5-di- tert-amyl hydroquinone, and the like. These compounds may be used alone or in combination of two or more.

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-제삼부틸-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. 이들 화합물은 단독으로 사용해도 되며 2종 이상을 병용해도 된다.Examples of the phosphorus compound include triphenylphosphine, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl = phosphite, triphenylphosphite, trisnonylphenylphosphite, tris (2,4-dibutylphenyl) phosphite, tris (2,4-dibutyl-5-methylphenyl) phosphite, tris [2- (Tridecyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, octyldiphenyl phosphite, di (decyl) monophenyl phosphite, Pentaerythritol diphosphite, bis (2,4-dibutylphenyl) pentaerythritol diphosphite, bis (2,6-dibutyl-4-methylphenyl) pentaerythritol diphosphite, (2,4,6-tributylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetra (tridecyl) iso (Tridecyl) -4,4'-n-butylidenebis (2-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2,4-dibutylphenyl) biphenylene diphosphonite, 9,10-dihydro-9-oxa-10 (2-methyl- (4,6-butylphenyl) -2-ethylhexylphosphite, 2,2'-methylenebis (4,6-butylphenyl) -octa Tris (2, 4, 8, 10-tetrakisbutyldibenzo [d, f] decylphosphite, 2,2'-ethylidenebis (4,6-dibutylphenyl) fluorophosphite, [1.3.2] dioxaphosphper-6-yl) oxy] ethyl) amine, 2-ethyl-2-butylpropylene glycol and a phosphite of 2,4,6-tributylphenol. These compounds may be used alone or in combination of two or more.

상기 황 화합물로서는, 예를 들면, 디도데실-3,3'-티오프로피오네이트, 디라우릴-3,3'-티오디프로피오네이트, 디라우릴티오디티오네이트, 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. 이들 화합물은 단독으로 사용해도 되며 2종 이상을 병용해도 된다.Examples of the sulfur compound include, for example, titanyl-3,3'-thiopropionate, dilauryl-3,3'-thiodipropionate, dilauryl thiodidonate, 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. These compounds may be used alone or in combination of two or more.

이들 중에서도, 점착력 및 내습열황변성을 한층 더 향상할 수 있는 점으로부터, 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 산화방지제를 사용하는 것이 보다 바람직하고, 트리페닐포스핀, 비스(2,4-디-tert-부틸-6-메틸페닐)=에틸=포스피트를 사용하는 것이 보다 바람직하다.Among them, it is preferable to use a phosphorus compound from the viewpoint of further improving the adhesion and the resistance to moisture and heat sulfur sulfur, and it is preferable to use a phosphorus compound such as triphenylphosphine and 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 ethylphosphite is more preferably used.

상기 산화방지제(E)를 사용할 경우의 사용량으로서는, 내습열황변성을 한층 더 향상할 수 있는 점으로부터, 상기 우레탄(메타)아크릴레이트(A) 100질량부에 대해서, 0.01∼10질량부의 범위인 것이 바람직하다.The amount of the antioxidant (E) to be used is preferably 0.01 to 10 parts by mass per 100 parts by mass of the urethane (meth) acrylate (A) .

상기 광안정제(F)는, 광열화로 발생하는 라디칼을 포착하는 것이며, 예를 들면, 티올 화합물, 티오에테르 화합물, 힌더드아민 화합물 등의 라디칼 포착제; 벤조페논 화합물, 벤조에이트 화합물 등의 자외선흡수제 등을 사용할 수 있다. 이들 광안정제는 단독으로 사용해도 되며 2종 이상을 병용해도 된다. 이들 중에서도, 내습열황변성을 한층 더 향상할 수 있는 점으로부터, 힌더드아민 화합물을 사용하는 것이 바람직하다.The light stabilizer (F) captures radicals generated by photo-thermalization and includes, for example, radical scavengers such as thiol compounds, thioether compounds and hindered amine compounds; Benzophenone compounds, benzoate compounds and the like can be used. These light stabilizers may be used alone or in combination of two or more. Among them, it is preferable to use a hindered amine compound from the viewpoint of further improving 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-디메틸에틸히드로퍼옥시드와 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-아세틸계힌더드아민 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, 숙신산디메틸·1-(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. 이들 화합물은 단독으로 사용해도 되며 2종 이상을 병용해도 된다.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 the reaction product of ethyl hydroperoxide and octane; 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- Tetramethylpiperidine polycondensate, propanedioic acid [(4-methoxyphenyl) methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidyl) Alkyl hindered amine compounds and the like can be used. These compounds may be used alone or in combination of two or more.

상기 광안정제(F)를 사용할 경우의 사용량으로서는, 내습열황변성을 한층 더 향상할 수 있는 점으로부터, 상기 우레탄(메타)아크릴레이트(A) 100질량부에 대해서, 0.01∼10질량부의 범위인 것이 바람직하다.The amount of the light stabilizer (F) to be used is preferably in the range of 0.01 to 10 parts by mass per 100 parts by mass of the urethane (meth) acrylate (A) .

본 발명의 자외선 경화형 점착제 조성물의 점도로서는, 도공성 및 작업성의 점으로부터, 500∼30,000mPa·s의 범위인 것이 바람직하고, 1,000∼20,000mPa·s의 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 30,000 mPa · s and more preferably in the range of 1,000 to 20,000 mPa · s, from the viewpoints of coatability and workability. The viscosity is a value measured by a B-type viscometer at 25 캜.

다음으로, 본 발명의 점착 필름의 제조 방법에 대하여 설명한다.Next, a method for producing the pressure-sensitive adhesive film of the present invention will be described.

상기 점착 필름은, 상기 자외선 경화형 점착제 조성물 중의 유기 용제(C)를 건조하는 공정, 및, 자외선을 조사해서 조성물을 경화시키는 공정을 거침에 의해 얻어진다.The pressure-sensitive adhesive film is obtained by a step of drying the organic solvent (C) in the ultraviolet-curing pressure-sensitive adhesive composition and a step of curing the composition by irradiating ultraviolet rays.

또한, 상기 점착 필름의 제조 방법으로서는, 단차추종성이 우수한 점착 필름이 얻어지는 점으로부터, 상기 자외선 경화형 점착제 조성물을 기재에 도공한 후에, 유기 용제(C)를 건조해서 자외선 경화형 점착 필름을 얻고, 다음으로, 당해 자외선 경화형 점착 필름의 점착층을 기재에 첩부하고, 그 후 자외선 조사함에 의해 점착 필름을 얻는 방법을 사용하는 것이 바람직하다. 이 방법에 따르면, 자외선 경화 전의 상기 자외선 경화형 점착 필름에 대해서, 그 후에 첩부되는 기재로서 인쇄 단차 등의 단차를 갖는 것을 사용했을 경우에, 당해 단차 부분에 공극을 남기지 않고 상기 자외선 경화형 점착 필름을 첩부할 수 있기 때문에, 단차추종성이 우수한 점착 필름을 얻을 수 있다.As a method of producing the above adhesive film, an ultraviolet-curable adhesive film is obtained by drying the organic solvent (C) after coating the base material with the ultraviolet-curing pressure-sensitive adhesive composition from the viewpoint of obtaining an adhesive film excellent in step- , A method of pasting the adhesive layer of the ultraviolet-curable adhesive film to the substrate and then irradiating ultraviolet rays to obtain an adhesive film. According to this method, when the ultraviolet-curable adhesive film before curing is cured with a step such as a printed step as a substrate to be pasted thereafter, the ultraviolet curing-type adhesive film is adhered without leaving a gap in the stepped portion, It is possible to obtain an adhesive film excellent in step-following property.

또, 본 발명에 있어서는, 유기 용제 건조 후, 자외선 경화 전의 상태를 「자외선 경화형 점착 필름」이라 하며, 자외선 경화 후의 상태를 「점착 필름」이라 한다.In the present invention, the state after the organic solvent is dried and before the ultraviolet curing is referred to as an " ultraviolet curable adhesive film ", and the state after the ultraviolet curing is referred to as an " adhesive film ".

상기 기재로서는, 예를 들면, 플라스틱 기재, 플렉서블 프린트 기재, 유리 기재, 이들 기재에 이형(離型) 처리를 실시한 기재나 ITO(산화인듐주석)를 증착한 기재 등을 사용할 수 있다. 또, 점착층의 양면에는 각각 동일한 기재를 사용해도 되며 별개의 기재를 사용해도 된다.As the above substrate, for example, a plastic substrate, a flexible printed substrate, a glass substrate, a substrate obtained by subjecting these substrates to a releasing treatment, a substrate obtained by depositing ITO (indium tin oxide), or the like can be used. Further, the same substrate may be used for both sides of the adhesive layer, or a separate substrate may be used.

상기 플라스틱 기재로서는, 예를 들면, 아크릴 수지, PC(폴리카보네이트), PBT(폴리부틸렌테레프탈레이트), PPS(폴리페닐렌설파이드), 변성 PPE(폴리페닐렌에테르), PET(폴리에틸렌테레프탈레이트), COP(시클로올레핀 폴리머), TAC(트리아세틸셀룰로오스) 등을 원료로 해서 얻어지는 플라스틱 필름, 반사 방지 필름, 방오 필름, 터치패널을 구성하는 투명 도전막의 필름 등을 사용할 수 있다.Examples of the plastic substrate include acrylic resin, PC (polycarbonate), PBT (polybutylene terephthalate), PPS (polyphenylene sulfide), modified PPE (polyphenylene ether), PET (polyethylene terephthalate) , An antireflection film, an antifouling film, a film of a transparent conductive film constituting a touch panel, or the like can be used, which are obtained by using, as a raw material, COP (cycloolefin polymer) and TAC (triacetylcellulose)

상기 자외선 경화형 점착제 조성물을 상기 기재에 도공하는 방법으로서는, 예를 들면, 애플리케이터, 롤 코터, 나이프 코터, 그라비어 코터 등을 사용해서 도포하는 방법을 들 수 있다. 상기 도공 후는, 얻어진 적층체를 건조기 등에 넣고, 온도 50∼130℃의 범위에서, 1∼30분 건조시킴에 의해 유기 용제(C)를 건조시킴에 의해, 자외선 경화 전의 자외선 경화형 점착 필름이 얻어진다.As a method of applying the ultraviolet-curable pressure-sensitive adhesive composition to the substrate, a method of applying the ultraviolet-curable pressure-sensitive adhesive composition using an applicator, a roll coater, a knife coater, a gravure coater or the like can be used. After the coating, the obtained laminate is dried in the dryer or the like at a temperature in the range of 50 to 130 캜 for 1 to 30 minutes to dry the organic solvent (C) to obtain an ultraviolet curing type pressure-sensitive adhesive film Loses.

상기 자외선 경화형 점착 필름으로서는, 단차추종성을 한층 더 향상할 수 있는 점으로부터, 60℃에 있어서의 저장 탄성률이, 주파수 1Hz에서 측정했을 경우에 3×105Pa 미만인 것이 바람직하고, 1×103 이상 3×105Pa 미만인 것이 바람직하다. 또, 상기 자외선 경화형 점착 필름의 저장 탄성률의 측정 방법은 실시예에 기재한다.The ultraviolet curing type pressure-sensitive adhesive film preferably has a storage elastic modulus at 60 ° C of less than 3 x 10 5 Pa when measured at a frequency of 1 Hz, more preferably not less than 1 x 10 3 Preferably less than 3 x 10 < 5 > Pa. The method for measuring the storage elastic modulus of the ultraviolet-curable adhesive film is described in Examples.

또한, 상기 자외선 경화형 점착 필름으로서는, 또한 커팅성 및 단차추종성을 한층 더 향상할 수 있는 점으로부터, 30℃에 있어서의 저장 탄성률이, 주파수 1Hz에서 측정했을 경우에 5×104Pa 이상인 것이 바람직하고, 5×104∼5×106Pa의 범위가 보다 바람직하다.The ultraviolet curing type pressure-sensitive adhesive film also preferably has a storage modulus at 30 DEG C of 5 x 10 < 4 > Pa or more when measured at a frequency of 1 Hz from the viewpoint of further improving the cutting property and step- , And more preferably in the range of 5 × 10 4 to 5 × 10 6 Pa.

상기 자외선 경화형 점착 필름으로서는, 또한 커팅성 및 단차추종성을 한층 더 향상할 수 있는 점으로부터, 80℃에 있어서의 저장 탄성률이, 주파수 1Hz에서 측정했을 경우에 1×102∼5×105Pa의 범위인 것이 바람직하다.The ultraviolet curing type pressure-sensitive adhesive film can further improve the cutting property and the step-following property, so that the storage elastic modulus at 80 캜 is preferably from 1 × 10 2 to 5 × 10 5 Pa .

얻어진 자외선 경화형 점착 필름을 상기 기재에 첩부한 후는, 양자를 압착시키고, 필요에 따라서 오토클레이브 처리를 실시해도 된다.After the obtained ultraviolet-curable pressure-sensitive adhesive film is attached to the substrate, the ultraviolet-curable pressure-sensitive adhesive film may be pressed and subjected to autoclave processing, if necessary.

그 후, 자외선 조사함에 의해 점착 필름이 얻어지지만, 상기 자외선 조사하는 방법으로서는, 예를 들면, 제논 램프, 제논-수은 램프, 메탈할라이드 램프, 고압 수은 램프, 저압 수은 램프 등의 공지의 자외선 광조사 장치를 사용하는 방법을 들 수 있다.Thereafter, ultraviolet ray irradiation is performed to obtain a pressure-sensitive adhesive film. Examples of the ultraviolet ray irradiation method include a known ultraviolet light irradiation such as a xenon lamp, a xenon-mercury lamp, a metal halide lamp, a high pressure mercury lamp, And a method of using the device.

상기 자외선의 조사량으로서는, 바람직하게는 0.05∼5J/㎠, 보다 바람직하게는 0.1∼3J/㎠, 특히 바람직하게는 0.3∼1.5J/㎠의 범위인 것이 좋다. 또, 자외선의 조사량은, GS유아사가부시키가이샤제 UV체커 「UVR-N1」을 사용해서 300∼390㎚의 파장역에 있어서 측정한 값을 기준으로 한다.The irradiation dose of the ultraviolet ray 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 irradiation amount of ultraviolet ray is based on the value measured in a wavelength range of 300 to 390 nm using a UV checker "UVR-N1" manufactured by GS Kasei Co., Ltd.

이상의 방법으로 해서 얻어지는 점착 필름의 두께로서는, 사용되는 용도에 따라서 적의(適宜) 결정되지만, 대략 10∼500㎛의 범위인 것이 바람직하다.The thickness of the pressure-sensitive adhesive film obtained by the above method is appropriately determined depending on the intended use, but is preferably in the range of approximately 10 to 500 占 퐉.

또한, 상기 점착 필름으로서는, 커팅성을 한층 더 향상할 수 있는 점으로부터, 30℃에 있어서의 저장 탄성률이, 주파수 1Hz에서 측정했을 경우에 1×104Pa 이상인 것이 바람직하고, 1×104∼5×107Pa의 범위가 보다 바람직하다. 또, 상기 점착 필름의 저장 탄성률의 측정 방법은 실시예에 기재한다.Further, as the adhesive film, the storage modulus in the cutting property in, 30 ℃ from a point that even be further improved, and it is preferably not less than 1 × 10 4 Pa when measured at a frequency 1Hz, 1 × 10 4 ~ More preferably in the range of 5 x 10 < 7 > Pa. The method for measuring the storage modulus of the adhesive film is described in Examples.

또한, 상기 점착 필름으로서는, 단차추종성을 한층 더 향상할 수 있는 점으로부터, 80℃에 있어서의 저장 탄성률이, 주파수 1Hz에서 측정했을 경우에 1×104Pa 이상인 것이 바람직하고, 1×104∼1×107Pa의 범위가 보다 바람직하다.Further, as the adhesive film, the step following property from the point that even further improved, and the storage elastic modulus at 80 ℃, and preferably not less than 1 × 10 4 Pa when measured at a frequency 1Hz, 1 × 10 4 ~ 1 x 10 < 7 > Pa.

또한, 상기 점착 필름으로서는, 단차추종성을 한층 더 향상할 수 있는 점으로부터, 100℃에 있어서의 저장 탄성률이, 주파수 1Hz에서 측정했을 경우에 1×104Pa 이상인 것이 바람직하고, 1×104∼1×106Pa의 범위가 보다 바람직하다.The pressure-sensitive adhesive film preferably has a storage elastic modulus at 100 ° C of 1 x 10 4 Pa or more when measured at a frequency of 1 Hz, more preferably 1 x 10 4 to 10 x 10 4 Pa, More preferably in the range of 1 x 10 < 6 > Pa.

이상, 본 발명의 자외선 경화형 점착제 조성물을 사용해서 얻어지는 점착 필름은, 재단해도 풀 남음이 없고, 커팅성이 우수한 것이다. 또한, 상기 특정의 제조 방법을 사용한 경우에는, 또한 단차추종성이 우수한 점착 필름을 얻을 수 있다.As described above, the pressure-sensitive adhesive film obtained by using the ultraviolet-curing pressure-sensitive adhesive composition of the present invention is excellent in cutting property without leaving any residue on cutting. In addition, when the above specific production method is used, an adhesive film excellent in step-following property can be obtained.

따라서, 본 발명의 자외선 경화형 점착제 조성물은, 광학 부재에 사용되는 점착제로서 호적하게 사용할 수 있고, 특히, 터치패널, 액정 디스플레이, 플라스마 디스플레이, 유기 EL, PC, 휴대전화 등의 IT 관련 제품의 제조에 호적하게 사용할 수 있다.Therefore, 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, and can be used suitably for the production of IT related products such as touch panels, liquid crystal displays, plasma displays, organic EL, It can be used for personal use.

(실시예) (Example)

이하, 실시예를 사용해서, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail using examples.

[합성예 1][Synthesis Example 1]

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

교반기, 환류 냉각관, 질소 도입관, 온도계를 구비한 반응 용기에, 폴리프로필렌글리콜(수 평균 분자량; 1,000, 이하 「PPG1000」이라 약기한다)을 61.64질량부, 2,6-디-tert-부틸-크레졸을 0.3질량부, p-메톡시페놀 0.05질량부를 첨가했다. 반응 용기 내 온도가 40℃로 될 때까지 승온한 후, 이소포론디이소시아네이트(이하, 「IPDI」라 약기한다) 28.57질량부 첨가했다. 거기서, 디옥틸주석디네오데카네이트 0.1질량부 첨가하고, 1시간 걸쳐서 80℃까지 승온했다. 그 후, 80℃에서 3시간 홀드하고, 1,4-시클로헥산디메탄올(이하, 「CHDM」이라 약기한다)을 9.41질량부 첨가하고, 80℃에서 12시간 홀드했다. 모든 수산기가 소실해 있는 것을 확인 후, 2-히드록시에틸아크릴레이트(이하, 「HEA」라 약기한다) 0.39질량부 첨가하고, 80℃에서 5시간 홀드하고, 모든 이소시아네이트기가 소실해 있는 것을 확인 후, 냉각하여 우레탄아크릴레이트(A-1)를 얻었다. 얻어진 우레탄아크릴레이트(A-1)는, 아크릴로일기의 당량이 30,000g/eq.(유효 숫자 2자리로 반올림. 2-히드록시에틸아크릴레이트의 분자량은 116.1로 했다. 이하, 같다), 중량 평균 분자량이 99,000이었다. 또한, 폴리올 조성물의 수산기 당량은, 280g/eq.였다.61.64 parts by mass of polypropylene glycol (number average molecular weight: 1,000, hereinafter abbreviated as "PPG1000") was added to a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer, -Cresol and 0.05 parts by mass of p-methoxyphenol were added. After the temperature in the reaction vessel was raised to 40 캜, 28.57 parts by mass of isophorone diisocyanate (hereinafter abbreviated as &quot; IPDI &quot;) was added. Thereafter, 0.1 part by mass of dioctyltin dinneodecanate was added, and the temperature was elevated to 80 DEG C over 1 hour. Thereafter, the mixture was held at 80 DEG C for 3 hours, 9.41 parts by mass of 1,4-cyclohexanedimethanol (hereinafter abbreviated as &quot; CHDM &quot;) was added, and the mixture was held at 80 DEG C for 12 hours. After confirming that all hydroxyl groups were lost, 0.39 parts by mass of 2-hydroxyethyl acrylate (hereinafter abbreviated as "HEA") was added, and the mixture was held at 80 ° C. for 5 hours. After confirming that all the isocyanate groups were lost , And cooled to obtain urethane acrylate (A-1). The resulting urethane acrylate (A-1) had an equivalent weight of acryloyl group of 30,000 g / eq. (Rounded to two significant digits, the molecular weight of 2-hydroxyethyl acrylate was 116.1, The average molecular weight was 99,000. The hydroxyl equivalent of the polyol composition was 280 g / eq.

[합성예 2][Synthesis Example 2]

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

교반기, 환류 냉각관, 질소 도입관, 온도계를 구비한 반응 용기에, PPG1000을 70.86질량부, 2,6-디-tert-부틸-크레졸을 0.3질량부, p-메톡시페놀 0.05질량부를 첨가했다. 반응 용기 내 온도가 40℃로 될 때까지 승온한 후, IPDI를 28.78질량부 첨가했다. 거기서, 디옥틸주석디네오데카네이트 0.1질량부 첨가하고, 1시간 걸쳐서 80℃까지 승온했다. 그 후, 80℃에서 3시간 홀드하고, CHDM을 4.97질량부 첨가하고, 80℃에서 12시간 홀드했다. 모든 수산기가 소실해 있는 것을 확인 후, HEA를 0.39질량부 첨가하고, 80℃에서 5시간 홀드하고, 모든 이소시아네이트기가 소실해 있는 것을 확인 후, 냉각하여 우레탄아크릴레이트(A-2)를 얻었다. 얻어진 우레탄아크릴레이트(A-2)는, 아크릴로일기의 당량이 31,000g/eq., 중량 평균 분자량이 100,000이었다. 또한, 폴리올 조성물의 수산기 당량은, 360g/eq.였다.70.86 parts by mass of PPG1000, 0.3 parts by mass of 2,6-di-tert-butyl-cresol and 0.05 parts by mass of p-methoxyphenol were added to a reaction vessel equipped with a stirrer, a reflux condenser, . After the temperature in the reaction vessel was raised to 40 캜, 28.78 parts by mass of IPDI was added. Thereafter, 0.1 part by mass of dioctyltin dinneodecanate was added, and the temperature was elevated to 80 DEG C over 1 hour. Thereafter, the mixture was held at 80 DEG C for 3 hours, 4.97 parts by mass of CHDM was added, and the mixture was held at 80 DEG C for 12 hours. After confirming that all of the hydroxyl groups had disappeared, 0.39 parts by mass of HEA was added, and the mixture was held at 80 占 폚 for 5 hours. After confirming that all the isocyanate groups disappeared, the mixture was cooled to obtain urethane acrylate (A-2). The resulting urethane acrylate (A-2) had an equivalent of acryloyl group of 31,000 g / eq. And a weight average molecular weight of 100,000. The hydroxyl equivalent of the polyol composition was 360 g / eq.

[합성예3][Synthesis Example 3]

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

교반기, 환류 냉각관, 질소 도입관, 온도계를 구비한 반응 용기에, PPG1000을 56.46질량부, 2,6-디-tert-부틸-크레졸을 0.3질량부, p-메톡시페놀 0.05질량부를 첨가했다. 반응 용기 내 온도가 40℃로 될 때까지 승온한 후, IPDI를 30.94질량부 첨가했다. 거기서, 디옥틸주석디네오데카네이트 0.1질량부 첨가하고, 1시간 걸쳐서 80℃까지 승온했다. 그 후, 80℃에서 3시간 홀드하고, CHDM을 11.44질량부 첨가하고, 80℃에서 12시간 홀드했다. 모든 수산기가 소실해 있는 것을 확인 후, HEA를 1.16질량부 첨가하고, 80℃에서 5시간 홀드하고, 모든 이소시아네이트기가 소실해 있는 것을 확인 후, 냉각하여 우레탄아크릴레이트(A-3)를 얻었다. 얻어진 우레탄아크릴레이트(A-3)는, 아크릴로일기의 당량이 10,000g/eq., 중량 평균 분자량이 24,300이었다. 또한, 폴리올 조성물의 수산기 당량은, 250g/eq.였다.56.46 parts by mass of PPG1000, 0.3 parts by mass of 2,6-di-tert-butyl-cresol and 0.05 parts by mass of p-methoxyphenol were added to a reaction vessel equipped with a stirrer, a reflux condenser, . After the temperature in the reaction vessel was raised to 40 캜, 30.94 parts by mass of IPDI was added. Thereafter, 0.1 part by mass of dioctyltin dinneodecanate was added, and the temperature was elevated to 80 DEG C over 1 hour. Thereafter, the mixture was held at 80 DEG C for 3 hours, 11.44 parts by mass of CHDM was added, and the mixture was held at 80 DEG C for 12 hours. After confirming that all of the hydroxyl groups had disappeared, 1.16 parts by mass of HEA was added and the mixture was held at 80 캜 for 5 hours. After confirming that all the isocyanate groups were lost, the mixture was cooled to obtain urethane acrylate (A-3). The obtained urethane acrylate (A-3) had an equivalent number of acryloyl groups of 10,000 g / eq. And a weight average molecular weight of 24,300. The hydroxyl group equivalent of the polyol composition was 250 g / eq.

[합성예4][Synthesis Example 4]

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

교반기, 환류 냉각관, 질소 도입관, 온도계를 구비한 반응 용기에, PPG1000을 43.33질량부, 2,6-디-tert-부틸-크레졸을 0.3질량부, p-메톡시페놀 0.05질량부를 첨가했다. 반응 용기 내 온도가 40℃로 될 때까지 승온한 후, IPDI를 42.49질량부 첨가했다. 거기서, 디옥틸주석디네오데카네이트 0.1질량부 첨가하고, 1시간 걸쳐서 80℃까지 승온했다. 그 후, 80℃에서 3시간 홀드하고, 1,4-부탄디올(이하, 「BG」라 약기한다)을 13.02질량부 첨가하고, 80℃에서 12시간 홀드했다. 모든 수산기가 소실해 있는 것을 확인 후, HEA를 1.16질량부 첨가하고, 80℃에서 5시간 홀드하고, 모든 이소시아네이트기가 소실해 있는 것을 확인 후, 냉각하여 우레탄아크릴레이트(A-4)를 얻었다. 얻어진 우레탄아크릴레이트(A-4)는, 아크릴로일기의 당량이 10,000g/eq., 중량 평균 분자량이 26,700이었다. 또한, 폴리올 조성물의 수산기 당량은, 150g/eq.였다.43.33 parts by mass of PPG1000, 0.3 parts by mass of 2,6-di-tert-butyl-cresol and 0.05 parts by mass of p-methoxyphenol were added to a reaction vessel equipped with a stirrer, a reflux condenser, . After the temperature in the reaction vessel was raised to 40 캜, 42.49 parts by mass of IPDI was added. Thereafter, 0.1 part by mass of dioctyltin dinneodecanate was added, and the temperature was elevated to 80 DEG C over 1 hour. Thereafter, the mixture was held at 80 DEG C for 3 hours, 13.02 parts by mass of 1,4-butanediol (hereinafter abbreviated as "BG") was added, and the mixture was held at 80 DEG C for 12 hours. After confirming that all of the hydroxyl groups had disappeared, 1.16 parts by mass of HEA was added, and the mixture was held at 80 ° C for 5 hours. After confirming that all of the isocyanate groups were lost, the mixture was cooled to obtain urethane acrylate (A-4). The obtained urethane acrylate (A-4) had an equivalent number of acryloyl groups of 10,000 g / eq. And a weight average molecular weight of 26,700. The hydroxyl equivalent of the polyol composition was 150 g / eq.

[비교합성예 1][Comparative Synthesis Example 1]

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

교반기, 환류 냉각관, 질소 도입관, 온도계를 구비한 반응 용기에, 폴리프로필렌글리콜(수 평균 분자량; 2,000, 이하 「PPG2000」이라 약기한다)을 37.03질량부, 폴리옥시테트라메틸렌글리콜(수 평균 분자량; 650, 이하, 「PTMG650」이라 약기한다)을 30.3질량부, 폴리에틸렌글리콜(수 평균 분자량; 400, 이하, 「PEG400」이라 약기한다)을 11.88질량부, HEA를 0.55질량부, 2,6-디-tert-부틸-크레졸을 0.3질량부, p-메톡시페놀 0.05질량부를 첨가했다. 반응 용기 내 온도가 40℃로 될 때까지 승온한 후, IPDI를 20.23질량부 첨가했다. 그 후 80℃에서 12시간 홀드하고, 모든 이소시아네이트기가 소실해 있는 것을 확인 후, 냉각하여 우레탄아크릴레이트(A'-1)를 얻었다. 얻어진 우레탄아크릴레이트(A'-1)는, 아크릴로일기의 당량이 21,000g/eq., 중량 평균 분자량이 27,000이었다. 또한, 폴리올 조성물의 수산기 당량은, 423g/eq.였다.37.03 parts by mass of polypropylene glycol (number average molecular weight: 2,000, hereinafter abbreviated as &quot; PPG2000 &quot;) was added to a reaction vessel equipped with a stirrer, a reflux condenser tube, a nitrogen introducing tube, and a thermometer, polyoxytetramethylene glycol (Hereinafter abbreviated as &quot; PEG400 &quot;), 0.55 parts by mass of HEA, 0.5 part by mass of 2,6- 0.3 part by mass of di-tert-butyl-cresol and 0.05 part by mass of p-methoxyphenol were added. After the temperature in the reaction vessel was raised to 40 캜, 20.23 parts by mass of IPDI was added. 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 (A'-1). The resulting urethane acrylate (A'-1) had an equivalent number of acryloyl groups of 21,000 g / eq. And a weight average molecular weight of 27,000. The hydroxyl group equivalent of the polyol composition was 423 g / eq.

[실시예 1][Example 1]

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

교반기, 환류 냉각관, 온도계를 구비한 반응 용기를 용기 내 온도 80℃로 데우고, 상기 우레탄아크릴레이트(A-1) 100질량부, 아세트산에틸 122질량부를 넣고 균일해질 때까지 교반했다. 그 후, 실온까지 냉각하고, 교반 하에서 펜타에리트리톨트리아크릴레이트와 펜타에리트리톨테트라아크릴레이트의 혼합물(도아고세이가부시키가이샤제 「아로닉스M-305」, 이하, 「(D-1)」이라 약기한다) 10질량부, 2,4,6-트리메틸벤조일디페닐-포스핀옥사이드(이하, 「(B-1)」이라 약기한다)를 0.3질량부, 데칸이산비스(2,2,6,6-테트라메틸-1-(옥틸옥시)-4-피페리디닐)에스테르를 0.5질량부, 트리페닐포스핀 0.5질량부를 순차 첨가하고, 균일해질 때까지 교반했다. 그 후, 200메시 철망으로 여과하여, 자외선 경화형 점착제 조성물을 얻었다.A reaction vessel equipped with a stirrer, a reflux condenser and a thermometer was heated to 80 DEG C in the vessel temperature, 100 parts by mass of the urethane acrylate (A-1) and 122 parts by mass of ethyl acetate were added and stirred until uniform. Thereafter, the mixture was cooled to room temperature, and a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Aronix M-305, hereinafter referred to as "(D-1)", manufactured by Toagosei Co., , 0.3 parts by mass of 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide (hereinafter abbreviated as "(B-1)"), 10 parts by mass of decanedic acid bis (2,2,6 , 0.5 part by mass of 6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester and 0.5 part by mass of triphenylphosphine were added successively, and the mixture was stirred until uniform. Thereafter, the mixture was filtered through a 200-mesh wire netting to obtain an ultraviolet curable pressure-sensitive adhesive composition.

[실시예 2∼4, 비교예 1][Examples 2 to 4 and Comparative Example 1]

사용하는 우레탄(메타)아크릴레이트(A), (메타)아크릴 화합물(D)의 종류 및/또는 양을 표 1에 나타내는 바와 같이 변경한 것 이외는 실시예 1과 마찬가지로 해서 자외선 경화형 점착제 조성물을 얻었다.An ultraviolet curing pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that kinds and / or amounts of urethane (meth) acrylate (A) and (meth) acrylic compound (D) used were changed as shown in Table 1 .

[자외선 경화형 점착 필름의 제작 방법][Method of producing ultraviolet curable adhesive film]

표면에 이형 처리된 두께 50㎛의 폴리에틸렌테레프탈레이트 필름(이형 PET50)의 표면에, 유기 용제 건조 후의 막두께가 100㎛로 되도록 실시예 및 비교예에서 얻어진 자외선 경화형 점착제 조성물을 도포하고, 80℃ 건조기 중에서 5분간 건조시켜서 자외선 경화형 점착 필름을 얻었다.The ultraviolet curable pressure sensitive adhesive composition obtained in Examples and Comparative Examples was coated on the surface of a polyethylene terephthalate film (release PET50) having a thickness of 50 占 퐉 which had been subjected to release treatment on the surface so that the film thickness after drying of the organic solvent became 100 占 퐉, For 5 minutes to obtain an ultraviolet curing type pressure-sensitive adhesive film.

[커팅성의 평가 방법][Evaluation method of cutting property]

상기 자외선 경화형 점착 필름을 추가로 이형 PET50에 첩합(貼合)했다. 다음으로, UV-A 영역의 파장의 적산 광량이 1J/㎠로 되도록 자외선 조사하여, 점착 필름을 갖는 적층체를 얻었다. 얻어진 적층체를 재단기에 의해 재단, 재단기의 칼날에의 풀 남음의 유무를 목시로 관찰했다. 또, 풀 남음이 확인되지 않은 경우는 「T」, 풀 남음이 확인된 경우는 「F」라 평가했다.The ultraviolet curing type pressure-sensitive adhesive film was further adhered (bonded) to the release PET 50. Next, ultraviolet light was irradiated so that the accumulated light quantity of the wavelength of the UV-A region was 1 J / cm 2 to obtain a laminate having an adhesive film. The obtained laminate was observed with a cutting machine to determine whether or not a paste was left on the blade of the cutting and cutting machine by a cutting machine. In addition, when the pool remnant was not confirmed, it was evaluated as "T", and when the pool remnant was confirmed, it was evaluated as "F".

[단차추종성의 평가 방법][Evaluation method of stepwise followability]

상기 자외선 경화형 점착 필름을, 두께 100㎛의 폴리에틸렌테레프탈레이트 필름(PET100)에 첩합하여, 편면에 PET100이 첩합된 점착 필름을 제작했다. 이것을 세로 50㎜, 가로 40㎜로 재단한 것을 시험편으로 했다. 이것과는 별개로, PET50으로부터 세로 40㎜, 가로 30㎜, 폭 5㎜의 프레임을 재단했다. 이 두께 50㎛의 프레임을 유리판 상에 두고, 그 위로부터 상기 시험편을 2㎏ 롤×2왕복해서, PET100과 시험편으로 상기 두께 50㎛의 프레임을 사이에 끼우도록 첩부했다. 이것을, 50℃, 0.5MPa의 조건 하에서 20분간 오토클레이브 처리했다. 그 후, 유리판측으로부터 유리판 투하 후의 UV-A 영역의 파장의 적산 광량이 1J/㎠로 되도록 자외선 조사하여, 점착 필름을 갖는 적층체를 얻었다. 얻어진 적층체를 80℃ 분위기 하에서 24시간 방치하고, 두께 50㎛의 프레임의 내측 부분을 목시로 관찰하고, 50㎛의 단차에 대한 추종성을 이하와 같이 평가했다.The ultraviolet curing type pressure-sensitive adhesive film was laminated to a polyethylene terephthalate film (PET100) having a thickness of 100 占 퐉 to prepare an adhesive film in which PET100 was stuck on one side. The test piece was cut into a length of 50 mm and a width of 40 mm. Apart from this, a frame of 40 mm in length, 30 mm in width and 5 mm in width was cut from PET50. The frame having a thickness of 50 탆 was placed on a glass plate, and the test piece was reciprocated by 2 kg rolls × 2 from above, and the PET 100 was stuck with a test piece so that the 50 탆 thick frame was interposed therebetween. This was autoclaved for 20 minutes under the conditions of 50 占 폚 and 0.5 MPa. Thereafter, ultraviolet light was radiated from the glass plate side so that the accumulated light quantity of the wavelength of the UV-A region after the glass plate was dropped to 1 J / cm 2 to obtain a laminate having an adhesive film. The obtained laminate was allowed to stand in an atmosphere at 80 캜 for 24 hours, and the inside of the frame with a thickness of 50 탆 was observed with a naked eye, and the followability to a step of 50 탆 was evaluated as follows.

「A」 : 단차로부터의 들뜸이 없고, 기포의 혼입 없음 "A": No lifting from the step, no mixing of bubbles

「B」 : 단차로부터의 들뜸이 없지만, 기포의 혼입이 일부 확인됨 "B": There is no lift from the step, but the presence of air bubbles is partially confirmed

「C」 : 기포의 혼입이 눈에 띔 &Quot; C &quot;

[자외선 경화형 점착 필름(자외선 조사전)의 저장 탄성률의 측정 방법][Method of measuring storage elastic modulus of ultraviolet curing type adhesive film (ultraviolet curing dictionary)] [

상기 자외선 경화형 점착 필름의 점착층을 차광 하에서 두께 1㎜로 될 때까지 중첩해서 시험편으로 했다. 얻어진 시험편을 ARES 점탄성 측정 장치(티·에이·인스투르먼트·재팬가부시키가이샤제)를 사용해서, 승온 속도 2℃/분, 측정 주파수 1Hz, 온도 범위; 0∼100℃, 변형; 0.5%의 조건에서 측정했다.The pressure-sensitive adhesive layer of the ultraviolet-curing type pressure-sensitive adhesive film was superimposed on the test piece until the thickness became 1 mm under light shielding. The obtained test piece was measured with an ARES viscoelasticity measuring apparatus (manufactured by TA Instruments Instruments Co., Ltd.) at a heating rate of 2 캜 / min, a measuring frequency of 1 Hz, 0 to 100 캜, strain; 0.5%.

[점착 필름(자외선 조사 후)의 저장 탄성률의 측정 방법][Method of measuring the storage elastic modulus of an adhesive film (after ultraviolet irradiation)] [

상기 [커팅성의 평가 방법]에서 얻어진 점착 필름을 두께 1㎜로 될 때까지 중첩해서 시험편으로 했다. 얻어진 시험편을 ARES 점탄성 측정 장치(티·에이·인스투르먼트·재팬가부시키가이샤제)를 사용해서, 승온 속도 2℃/분, 측정 주파수 1Hz, 온도 범위; 0∼100℃, 변형; 0.5%의 조건에서 측정했다.The pressure-sensitive adhesive film obtained in the above-mentioned [evaluation method of cutting property] was superimposed until a thickness of 1 mm was used as a test piece. The obtained test piece was measured with an ARES viscoelasticity measuring apparatus (manufactured by TA Instruments Instruments Co., Ltd.) at a heating rate of 2 캜 / min, a measuring frequency of 1 Hz, 0 to 100 캜, strain; 0.5%.

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

상기 자외선 경화형 점착 필름을, 두께 100㎛의 폴리에틸렌테레프탈레이트 필름(PET100)에 첩합하고, 편면에 PET100이 첩합된 점착 필름을 제작했다. 이것을 세로 50㎜, 가로 40㎜로 재단, 이형 PET50을 벗기고, 유리판에 첩부한 것을 시험편으로 했다. 얻어진 시험편의 유리판측으로부터 유리판 투과 후의 UV-A 영역의 파장의 적산 광량이 1J/㎠으로 되도록 자외선 조사하여, 점착 필름을 갖는 적층체를 얻었다. 이것을 니혼덴쇼쿠고교가부시키가이샤제 탁도계 「NDH5000」을 사용해서 헤이즈(헤이즈 1)를 측정한 후, 85℃, 습도 85%의 분위기 하에서 100시간 방치하고, 23℃, 습도 50%의 분위기 하에서 취출했다. 취출한 후, 10분 이내에 점착 필름의 헤이즈(헤이즈 2)를 니혼덴쇼쿠고교가부시키가이샤제 탁도계 「NDH5000」을 사용해서, JISK7361-1-1997에 준거해서 측정했다. 또, 상기 헤이즈 1과 헤이즈 2와의 차가 0.5% 이하인 경우에는 「A」, 0.5%를 초과하고 1% 미만인 경우에는 「B」, 1%를 초과하는 경우에는 「C」로 평가했다.The ultraviolet curing type pressure-sensitive adhesive film was laminated to a polyethylene terephthalate film (PET100) having a thickness of 100 占 퐉 to prepare an adhesive film in which PET100 was adhered to one side. This was cut to a length of 50 mm and a width of 40 mm, and the release PET 50 was peeled off and attached to a glass plate. Ultraviolet light was irradiated from the glass plate side of the obtained test piece so that the accumulated light quantity of the wavelength of the UV-A region after passing through the glass plate became 1 J / cm 2 to obtain a laminate having an adhesive film. The haze (haze 1) was measured using a turbidimeter &quot; NDH5000 &quot; manufactured by Nippon Denshoku Chemical Co., Ltd., and then left for 100 hours in an atmosphere at 85 캜 and a humidity of 85%. Under an atmosphere of 23 캜 and a humidity of 50% I took it out. The haze (haze 2) of the adhesive film was measured in accordance with JIS K 7361-1-1997 using a turbidimeter "NDH5000" manufactured by Nippon Denshoku Chemical Industries, Ltd. within 10 minutes after the removal. When the difference between the haze 1 and the haze 2 was 0.5% or less, it was evaluated as "A". When the difference was more than 0.5%, less than 1%, "B"

[표 1] [Table 1]

Figure 112016117351784-pct00001
Figure 112016117351784-pct00001

본 발명의 점착 필름은, 커팅성, 내습열백화성 및 단차추종성이 우수한 것을 알 수 있었다.It was found that the pressure-sensitive adhesive film of the present invention is excellent in cutting property, anti-wet heat heating ability and step-following property.

한편, 비교예 1은, 폴리올의 수산기 당량이 본 발명에서 규정하는 범위를 초과하는 태양이지만, 커팅성이 불량이었다.On the other hand, in Comparative Example 1, the hydroxyl equivalent of the polyol exceeded the range specified in the present invention, but the cutting property was poor.

Claims (13)

수산기를 갖는 쇄신장제(a1-1) 및 그 밖의 폴리올을 포함하는, 수산기 당량이 400g/eq. 이하인 폴리올 조성물(a1), 폴리이소시아네이트(a2), 및, 이소시아네이트기 또는 수산기를 갖는 (메타)아크릴 화합물(a3)을 반응해서 얻어지는 우레탄(메타)아크릴레이트(A), 광중합개시제(B), 및, 유기 용제(C)를 함유하고,
상기 폴리올 조성물(a1)에 있어서, 쇄신장제(a1-1)의 사용량이, 0.5∼40질량%의 범위인 것을 특징으로 하는 자외선 경화형 점착제 조성물.(A1-1) having a hydroxyl group and other polyols having a hydroxyl equivalent of 400 g / eq. (Meth) acrylate (A) obtained by reacting a polyol composition (a1), a polyisocyanate (a2) and an isocyanate group or a hydroxyl group-containing (meth) acrylic compound (a3), a photopolymerization initiator , And an organic solvent (C)
Wherein the amount of the chain extender (a1-1) used in the polyol composition (a1) is in the range of 0.5 to 40 mass%. 제1항에 있어서,
상기 수산기를 갖는 쇄신장제(a1-1)가, 지환 구조를 갖는 것인 자외선 경화형 점착제 조성물.The method according to claim 1,
Wherein the hydroxyl group-containing chain extender (a1-1) has an alicyclic structure. 제1항에 있어서,
상기 그 밖의 폴리올이, 폴리에테르폴리올(a1-2)인 자외선 경화형 점착제 조성물.The method according to claim 1,
Wherein the other polyol is a polyether polyol (a1-2). 제1항에 있어서,
상기 우레탄(메타)아크릴레이트(A)의 (메타)아크릴로일기 당량이, 1,000∼50,000g/eq.의 범위인 자외선 경화형 점착제 조성물.The method according to claim 1,
Wherein the (meth) acryloyl group equivalent of the urethane (meth) acrylate (A) is in the range of 1,000 to 50,000 g / eq. 제1항에 있어서,
또한, 2개 이상의 (메타)아크릴로일기를 갖는 (메타)아크릴 화합물(D)을 함유하는 것인 자외선 경화형 점착제 조성물.The method according to claim 1,
(D) having at least two (meth) acryloyl groups. The pressure-sensitive adhesive composition according to claim 1, wherein the (meth) acrylic compound (D) 제5항에 있어서,
상기 (메타)아크릴 화합물(D)의 함유량이, 상기 우레탄(메타)아크릴레이트(A) 100질량부에 대해서, 1∼30질량부의 범위인 자외선 경화형 점착제 조성물.6. The method of claim 5,
Wherein the content of the (meth) acrylic compound (D) is in the range of 1 to 30 parts by mass based on 100 parts by mass of the urethane (meth) acrylate (A). 제5항에 있어서,
상기 (메타)아크릴 화합물(D)이, 지방족 다관능 (메타)아크릴레이트 및 이소시아누레이트 골격을 갖는 다관능 (메타)아크릴레이트 골격을 갖는 다관능 (메타)아크릴레이트로 이루어지는 군에서 선택되는 1종 이상인 자외선 경화형 점착제 조성물.6. The method of claim 5,
Wherein the (meth) acrylic compound (D) is selected from the group consisting of an aliphatic polyfunctional (meth) acrylate and a polyfunctional (meth) acrylate having a polyfunctional (meth) acrylate skeleton having an isocyanurate skeleton At least one ultraviolet curable pressure-sensitive adhesive composition. 제1항 내지 제7항 중 어느 한 항에 기재된 자외선 경화형 점착제 조성물을 건조 및 자외선 조사함에 의해 얻어지는 것을 특징으로 하는 점착 필름.A pressure-sensitive adhesive film obtained by drying and irradiating ultraviolet rays of the ultraviolet-curable pressure-sensitive adhesive composition according to any one of claims 1 to 7. 제8항에 있어서,
상기 점착 필름의 30℃에 있어서의 저장 탄성률이, 주파수 1Hz에서 측정했을 경우에, 1×104Pa 이상인 점착 필름.9. The method of claim 8,
Wherein the adhesive film has a storage elastic modulus at 30 DEG C of 1 x 10 &lt; 4 &gt; Pa or more when measured at a frequency of 1 Hz. 제1항 내지 제7항 중 어느 한 항에 기재된 자외선 경화형 점착제 조성물을 기재에 도공한 후에, 유기 용제(C)를 건조해서 자외선 경화형 점착 필름을 얻고, 다음으로, 당해 자외선 경화형 점착 필름의 점착층을 기재에 첩부(貼付)하고, 그 후 자외선 조사함에 의해 얻어지는 것을 특징으로 하는 점착 필름의 제조 방법.An ultraviolet curing pressure-sensitive adhesive composition according to any one of claims 1 to 7, which is applied onto a substrate, drying the organic solvent (C) to obtain an ultraviolet-curable pressure-sensitive adhesive film, Is adhered to a base material, and then irradiated with ultraviolet rays, thereby obtaining a pressure-sensitive adhesive film. 제10항에 있어서,
상기 자외선 경화형 점착 필름의 점착층을 첩부하는 기재(基材)가, 단차를 갖는 것인 점착 필름의 제조 방법.11. The method of claim 10,
Wherein the substrate (base material) to which the pressure-sensitive adhesive layer of the ultraviolet-curable pressure-sensitive adhesive film is applied has a step. 제10항에 있어서,
상기 자외선 경화형 점착 필름의 60℃에 있어서의 저장 탄성률이, 주파수 1Hz에서 측정했을 경우에 3×105Pa 미만인 점착 필름의 제조 방법.11. The method of claim 10,
Wherein the ultraviolet curing type pressure-sensitive adhesive film has a storage elastic modulus at 60 ° C of less than 3 x 10 5 Pa when measured at a frequency of 1 Hz. 제10항에 있어서,
상기 점착 필름의 100℃에 있어서의 저장 탄성률이, 주파수 1Hz에서 측정했을 경우에 1×104Pa 이상인 점착 필름의 제조 방법.11. The method of claim 10,
Wherein the storage elastic modulus of the adhesive film at 100 deg. C is 1 x 10 &lt; 4 &gt; Pa or more when measured at a frequency of 1 Hz.
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