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KR20150095798A - Adhesive composition for optical film and surface-protective film - Google Patents

Adhesive composition for optical film and surface-protective film Download PDF

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Publication number
KR20150095798A
KR20150095798A KR1020157018415A KR20157018415A KR20150095798A KR 20150095798 A KR20150095798 A KR 20150095798A KR 1020157018415 A KR1020157018415 A KR 1020157018415A KR 20157018415 A KR20157018415 A KR 20157018415A KR 20150095798 A KR20150095798 A KR 20150095798A
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meth
sensitive adhesive
mass
acrylate
pressure
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KR1020157018415A
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KR101686761B1 (en
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겐이치 나카니시
가즈히로 사사키
유타 다케우치
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쇼와 덴코 가부시키가이샤
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J7/0239—
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C08K5/57—Organo-tin compounds
    • C09J2205/102—
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Paints Or Removers (AREA)

Abstract

본 발명의 광학 필름용 점착제 조성물은, (A) 중량 평균 분자량이 10 만 ∼ 60 만인 (메트)아크릴계 수지 65 ∼ 85 질량％ 와, (B) 수 평균 분자량이 500 ∼ 1500 인 폴리옥시알킬렌폴리올 10 ∼ 30 질량％ 와, (C) 폴리이소시아네이트 1.0 ∼ 5.0 질량％ 와, (D) 이온성 화합물 0.2 ∼ 1.0 질량％ 와, (E) 주석계 촉매 0.005 ∼ 0.1 질량％ 를 함유한다. 본 발명의 광학 필름용 점착제 조성물은 대전 방지성 및 투명성이 우수하여, 피착체에 대한 오염성 및 부식성이 낮다는 이점을 갖는다.The pressure-sensitive adhesive composition for an optical film of the present invention comprises (A) 65 to 85% by mass of a (meth) acrylic resin having a weight average molecular weight of 100,000 to 600,000 and (B) a polyoxyalkylene polyol having a number average molecular weight of 500 to 1,500 (D) an ionic compound in an amount of 0.2 to 1.0% by mass and (E) a tin-based catalyst in an amount of 0.005 to 0.1% by mass based on 100% by mass of the polyisocyanate. The pressure-sensitive adhesive composition for an optical film of the present invention has an advantage of being excellent in antistatic property and transparency, and low in staining property and corrosiveness to an adherend.

Description

광학 필름용 점착제 조성물 및 표면 보호 필름{ADHESIVE COMPOSITION FOR OPTICAL FILM AND SURFACE-PROTECTIVE FILM}TECHNICAL FIELD [0001] The present invention relates to a pressure-sensitive adhesive composition for optical films,

본 발명은 광학 필름용 점착제 조성물 및 표면 보호 필름에 관한 것이다.The present invention relates to a pressure-sensitive adhesive composition for an optical film and a surface protective film.

최근 광학 부품·전자 부품의 분야에서 표면 보호의 목적에서 폴리에틸렌, 폴리에스테르, 폴리프로필렌 등의 투명한 보호 시트 (투명 기재 시트) 와 점착제가 적층된 표면 보호 필름이 많이 사용되고 있다. 이 표면 보호 필름은 점착 시트로부터 이형 필름을 박리할 때 및 점착 시트를 피착체로부터 박리할 때, 정전기가 대전되어 버리면 주변의 먼지가 부착되어 광학 부품·전자 부품을 오염시켜 버리는 문제가 있다.BACKGROUND ART [0002] In recent years, in the field of optical components and electronic components, a surface protective film in which a transparent protective sheet (transparent substrate sheet) such as polyethylene, polyester, or polypropylene and a pressure-sensitive adhesive are laminated is widely used. When the release film is peeled off from the pressure sensitive adhesive sheet and the pressure sensitive adhesive sheet is peeled from the adherend, this surface protective film has a problem that when the static electricity is charged, the surrounding dust adheres to contaminate the optical and electronic parts.

그래서, 대전 방지성을 부여한 점착제가 개발되어 있고, 예를 들어, 특허문헌 1 및 2 에는 아크릴계 공중합체에 대전 방지제로서 폴리에테르폴리올을 첨가한 점착제가 개시되어 있다. 그러나, 대전 방지제로서 폴리에테르폴리올을 첨가한 점착제는 투명성에 문제가 있어, 품질 보증의 관점에서 투명성이 요구되는 표면 보호 필름에 사용할 수 없다.For example, Patent Documents 1 and 2 disclose a pressure-sensitive adhesive in which a polyether polyol is added to an acrylic copolymer as an antistatic agent. However, a pressure-sensitive adhesive to which a polyether polyol is added as an antistatic agent has a problem in transparency and can not be used in a surface protective film which requires transparency from the viewpoint of quality assurance.

또, 특허문헌 3 에는, 폴리에테르폴리올을 아크릴폴리머에 그래프트시킴으로써 대전 방지성과 투명성을 양립시킨 점착제가 개시되어 있다. 그러나, 이 점착제는 산가가 높은 점에서 ITO 필름과 같은 부식을 기피하는 광학 부재에 사용하기 어렵다는 등의 문제가 있었다.Patent Document 3 discloses a pressure-sensitive adhesive which combines antistatic properties and transparency by grafting a polyether polyol to an acrylic polymer. However, this pressure-sensitive adhesive has a problem that it is difficult to use in an optical member avoiding corrosion such as an ITO film because of high acid value.

일본 공개특허공보 평6-128539호Japanese Patent Application Laid-Open No. 6-128539 일본 공개특허공보 2005-325255호Japanese Laid-Open Patent Publication No. 2005-325255 일본 공개특허공보 2010-6980호Japanese Laid-Open Patent Publication No. 2010-6980

본 발명은 상기 종래 기술이 갖는 문제를 감안하여, 대전 방지성 및 투명성이 우수하고, 피착체에 대한 오염성 및 부식성이 낮은 광학 필름용 점착제 조성물 및 표면 보호 필름을 제공하는 것을 목적으로 한다.In view of the problems of the prior art, it is an object of the present invention to provide a pressure-sensitive adhesive composition for optical films and a surface protective film which are excellent in antistatic property and transparency and low in staining property and corrosion resistance to an adherend.

본 발명자들은 광학 필름용 점착제 조성물이 안고 있는 상기의 문제점을 배경으로 하여 예의 검토를 거듭한 결과, 특정 중량 평균 분자량의 (메트)아크릴계 수지, 특정 수 평균 분자량의 폴리옥시알킬렌폴리올, 폴리이소시아네이트, 이온성 화합물 및 주석계 촉매를 특정 중량 비율로 함유하는 광학 필름용 점착제 조성물이, 양호한 대전 방지성 및 투명성, 피착체에 대한 낮은 오염성 및 부식성을 나타내는 것을 알아내고, 이 지견에 기초하여 본 발명을 완성하였다.The present inventors have conducted intensive investigations with the background of the above-mentioned problems of the pressure-sensitive adhesive composition for an optical film. As a result, they have found that (meth) acrylic resin having a specific weight average molecular weight, polyoxyalkylene polyol having a specific number average molecular weight, Sensitive adhesive composition for an optical film containing an ionic compound and a tin-based catalyst in a specific weight ratio exhibits good antistatic properties and transparency, low staining properties to an adherend and corrosiveness, and based on this finding, Completed.

본 발명은 아래의 (1) ∼ (10) 으로 나타낸다.The present invention is represented by the following (1) to (10).

(1) (A) (메트)아크릴계 수지 65 ∼ 85 질량％ 와, (B) 폴리옥시알킬렌폴리올 10 ∼ 30 질량％ 와, (C) 폴리이소시아네이트 1.0 ∼ 5.0 질량％ 와, (D) 이온성 화합물 0.2 ∼ 1.0 질량％ 와, (E) 주석계 촉매 0.005 ∼ 0.1 질량％ 를 함유하는 광학 필름용 점착제 조성물로서, (A) (메트)아크릴계 수지의 중량 평균 분자량이 10 만 ∼ 60 만이고, 또한 (B) 폴리옥시알킬렌폴리올의 수 평균 분자량이 500 ∼ 1500 인 것을 특징으로 하는 광학 필름용 점착제 조성물.(1) A positive resist composition comprising (A) 65 to 85% by mass of a (meth) acrylic resin, (B) 10 to 30% by mass of a polyoxyalkylene polyol, (C) 1.0 to 5.0% by mass of a polyisocyanate, (A) 0.2 to 1.0% by mass of a compound (A) and 0.005 to 0.1% by mass of a tin catalyst (E), wherein the weight average molecular weight of the (meth) acrylic resin (B) the number average molecular weight of the polyoxyalkylene polyol is 500 to 1,500.

(2) 상기 (A) (메트)아크릴계 수지가 공중합 성분으로서 수산기 함유 (메트)아크릴계 모노머를 0.5 ∼ 10 ㏖％ 함유하는 것을 특징으로 하는 (1) 에 기재된 광학 필름용 점착제 조성물.(2) The pressure-sensitive adhesive composition for an optical film according to (1), wherein the (A) (meth) acrylic resin contains 0.5 to 10% by mol of a hydroxyl group-containing (meth) acrylic monomer as a copolymerization component.

(3) 상기 수산기 함유 (메트)아크릴계 모노머가 2-하이드록시에틸(메트)아크릴레이트인 것을 특징으로 하는 (2) 에 기재된 광학 필름용 점착제 조성물.(3) The pressure-sensitive adhesive composition for an optical film according to (2), wherein the hydroxyl group-containing (meth) acrylic monomer is 2-hydroxyethyl (meth) acrylate.

(4) 상기 (A) (메트)아크릴계 수지가, 공중합 성분으로서 메틸(메트)아크릴레이트를 15 ∼ 50 ㏖％ 함유하는 것을 특징으로 하는 (1) ∼ (3) 중 어느 1 항에 기재된 광학 필름용 점착제 조성물.(4) The optical film according to any one of (1) to (3), wherein the (A) (meth) acrylic resin contains 15 to 50 mol% of methyl (meth) acrylate as a copolymerization component. Sensitive adhesive composition.

(5) 산가가 0 ∼ 5 ㎎KOH/g 인 것을 특징으로 하는 (1) ∼ (4) 중 어느 1 항에 기재된 광학 필름용 점착제 조성물.(5) The pressure-sensitive adhesive composition for an optical film according to any one of (1) to (4), wherein the acid value is 0 to 5 mgKOH / g.

(6) 상기 (D) 이온성 화합물이 알칼리 금속염인 것을 특징으로 하는 (1) ∼ (5) 중 어느 1 항에 기재된 광학 필름용 점착제 조성물.(6) The pressure-sensitive adhesive composition for an optical film according to any one of (1) to (5), wherein the ionic compound (D) is an alkali metal salt.

(7) 상기 (E) 주석계 촉매가 디옥틸주석디라우레이트인 것을 특징으로 하는 (1) ∼ (6) 중 어느 1 항에 기재된 광학 필름용 점착제 조성물.(7) The pressure-sensitive adhesive composition for an optical film according to any one of (1) to (6), wherein the (E) tin catalyst is dioctyltin dilaurate.

(8) 투명 기재 상의 편면에, (1) ∼ (7) 중 어느 1 항에 기재된 광학 필름용 점착제 조성물을 경화시켜 얻어지는 점착제층이 형성되어 있는 것을 특징으로 하는 표면 보호 필름.(8) A surface protective film comprising a pressure-sensitive adhesive layer formed by curing a pressure-sensitive adhesive composition for an optical film according to any one of (1) to (7)

(9) 표면 고유 저항값이 1.0 × 1010 Ω/□ 이하이고, 또한 헤이즈가 1.2 이하인 것을 특징으로 하는 (8) 에 기재된 표면 보호 필름.(9) The surface protective film according to (8), wherein the surface resistivity is 1.0 10 10 ? /? Or less and the haze is 1.2 or less.

(10) 상기 투명 기재가 두께 5 ∼ 200 ㎛ 의, 폴리에틸렌테레프탈레이트, 폴리에틸렌, 폴리프로필렌, 폴리스티렌, 폴리이미드, 폴리비닐알코올, 폴리염화비닐 또는 셀룰로오스인 것을 특징으로 하는 (8) 또는 (9) 에 기재된 표면 보호 필름.(10) The electrophotographic toner according to (8) or (9), wherein the transparent substrate is a polyethylene terephthalate, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride or cellulose having a thickness of 5 to 200 μm ≪ / RTI >

본 발명에 의하면, 대전 방지성 및 투명성이 우수하여, 피착체에 대한 오염성 및 부식성이 낮은 광학 필름용 점착제 조성물 및 표면 보호 필름을 제공할 수 있다.INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a pressure-sensitive adhesive composition for an optical film and a surface protective film which are excellent in antistatic property and transparency and low in staining property and corrosion resistance to an adherend.

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

본 발명의 광학 필름용 점착제 조성물은, (A) (메트)아크릴계 수지와, (B) 폴리옥시알킬렌폴리올과, (C) 폴리이소시아네이트와, (D) 이온성 화합물과, (E) 주석계 촉매를 함유하는 것이다.The pressure-sensitive adhesive composition for an optical film of the present invention comprises (A) a (meth) acrylic resin, (B) a polyoxyalkylene polyol, (C) a polyisocyanate, (D) Catalyst.

본 발명에 있어서의 (메트)아크릴계 수지란 아크릴계 수지 또는 메타크릴계 수지를 말하고, 또 (메트)아크릴레이트란 아크릴레이트 또는 메타크릴레이트를 말한다. 또한, (메트)아크릴레이트계 수지는 전체 구성 모노머의 80 ㏖％ 이상이 (메트)아크릴레이트계 모노머인 폴리머를 가리킨다.The (meth) acrylic resin in the present invention refers to acrylic resin or methacrylic resin, and (meth) acrylate refers to acrylate or methacrylate. The (meth) acrylate-based resin refers to a polymer in which at least 80 mol% of all the constituent monomers are (meth) acrylate-based monomers.

(A) (메트)아크릴계 수지(A) a (meth) acrylic resin

본 발명에 있어서의 (A) (메트)아크릴계 수지의 중합에 사용되는 (메트)아크릴계 모노머로는 특별히 한정은 없지만, 카르복실기 (화학식 : -COOH) 를 함유하지 않는 것이 바람직하다. (메트)아크릴계 모노머의 예로는, 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, n-프로필(메트)아크릴레이트, 이소프로필(메트)아크릴레이트, n-부틸(메트)아크릴레이트, tert-부틸(메트)아크릴레이트, 이소부틸(메트)아크릴레이트, n-헥실(메트)아크릴레이트, 2-에틸헥실(메트)아크릴레이트, 이소옥틸(메트)아크릴레이트, 라우릴(메트)아크릴레이트, 이소데실(메트)아크릴레이트, 스테아릴(메트)아크릴레이트, 트리데실(메트)아크릴레이트, 이소스테아릴(메트)아크릴레이트 등의 알킬(메트)아크릴레이트, 시클로헥실(메트)아크릴레이트, 노르보르닐(메트)아크릴레이트, 이소보르닐(메트)아크릴레이트, 노르보르나닐(메트)아크릴레이트, 디시클로펜테닐(메트)아크릴레이트, 디시클로펜테닐옥시에틸(메트)아크릴레이트, 디시클로펜타닐(메트)아크릴레이트, 디시클로펜타닐옥시에틸(메트)아크릴레이트, 트리시클로데칸디메틸올디(메트)아크릴레이트 등의 고리형 알킬(메트)아크릴레이트, 메톡시에틸(메트)아크릴레이트, 에톡시에틸(메트)아크릴레이트, 부톡시에틸(메트)아크릴레이트, 2-메톡시에톡시에틸(메트)아크릴레이트, 2-에톡시에톡시에틸(메트)아크릴레이트 등의 알콕시알킬(메트)아크릴레이트, 메톡시디에틸렌글리콜(메트)아크릴레이트, 에톡시디에틸렌글리콜(메트)아크릴레이트, 메톡시디프로필렌글리콜(메트)아크릴레이트 등의 알콕시(폴리)알킬렌글리콜(메트)아크릴레이트, 옥타플루오로펜틸(메트)아크릴레이트 등의 불소화 알킬(메트)아크릴레이트, N,N-디메틸아미노에틸(메트)아크릴레이트, N,N-디에틸아미노에틸(메트)아크릴레이트 등의 디알킬아미노알킬(메트)아크릴레이트, (메트)아크릴아미드, 다이아세톤(메트)아크릴아미드 등의 아미드기 함유 (메트)아크릴레이트, 글리시딜(메트)아크릴레이트 등의 에폭시기 함유 (메트)아크릴레이트, 실리콘 변성 (메트)아크릴레이트, 폴리에틸렌글리콜디(메트)아크릴레이트, 디에틸렌글리콜디(메트)아크릴레이트, 네오펜틸글리콜디(메트)아크릴레이트, 트리에틸렌글리콜디(메트)아크릴레이트, 트리프로필렌글리콜디(메트)아크릴레이트 등의 다관능성 (메트)아크릴레이트 등을 들 수 있다. 이들은 단독으로 사용해도 되고, 2 종류 이상을 조합하여 사용해도 된다.The (meth) acrylic monomer used in the polymerization of the (A) (meth) acrylic resin in the present invention is not particularly limited, but preferably contains no carboxyl group (-COOH). Examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate such as isooctyl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate and isostearyl Acrylate, norbornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl Cyclopentanyl (meth) acrylate (Meth) acrylate such as dicyclopentanyloxyethyl (meth) acrylate and tricyclodecane dimethylol (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl Alkoxyalkyl (meth) acrylates such as butoxyethyl (meth) acrylate, 2-methoxyethoxyethyl (meth) acrylate and 2-ethoxyethoxyethyl (meth) acrylate, (Meth) acrylate, octafluoropentyl (meth) acrylate, etc., such as ethoxydiethylene glycol (meth) acrylate and methoxydipropylene glycol (meth) (Meth) acrylate such as fluorinated alkyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate, Arc Amide and diacetone (meth) acrylamide, epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate, silicone modified (meth) acrylates, polyethylene glycol di Acrylates such as di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tripropylene glycol di ) Acrylate, and the like. These may be used alone or in combination of two or more.

(A) (메트)아크릴계 수지와 (B) 폴리옥시알킬렌폴리올의 상용성, 즉 광학 필름용 점착제 조성물을 경화시켜 얻어지는 점착제층의 투명성을 고려하면, (A) (메트)아크릴계 수지의 공중합 성분으로서 메틸아크릴레이트 또는 메틸메타크릴레이트가 15 ∼ 50 ㏖％ 함유되는 것이 바람직하고, 25 ∼ 45 ㏖％ 함유되는 것이 보다 바람직하다.Considering the compatibility of the (A) (meth) acrylic resin and (B) the polyoxyalkylene polyol, that is, the transparency of the pressure-sensitive adhesive layer obtained by curing the pressure-sensitive adhesive composition for an optical film, , It is preferable that methyl acrylate or methyl methacrylate is contained in an amount of 15 to 50 mol%, more preferably 25 to 45 mol%.

또, 본 발명에 있어서의 (A) (메트)아크릴계 수지는, 폴리이소시아네이트를 개재하여 폴리옥시알킬렌폴리올과 반응시켜 일체화시킬 수 있다 (투명성이 향상된다) 는 관점에서, 공중합 성분으로서 수산기 함유 (메트)아크릴계 모노머를 함유하는 것이 바람직하다. 수산기 함유 (메트)아크릴계 모노머의 예로는, 2-하이드록시에틸(메트)아크릴레이트, 2-하이드록시프로필(메트)아크릴레이트, 4-하이드록시부틸(메트)아크릴레이트, 1,3-부탄디올(메트)아크릴레이트, 1,4-부탄디올(메트)아크릴레이트, 1,6-헥산디올(메트)아크릴레이트, 3-메틸펜탄디올(메트)아크릴레이트 등의 수산기 함유 (메트)아크릴레이트 등을 들 수 있다. 그 중에서도, 공중합성 및 반응성면에서 2-하이드록시에틸(메트)아크릴레이트가 바람직하다. 수산기 함유 (메트)아크릴계 모노머는 (A) (메트)아크릴계 수지의 공중합 성분으로서 0.5 ∼ 10 ㏖％ 함유되는 것이 바람직하고, 0.6 ∼ 8.0 ㏖％ 함유되는 것이 보다 바람직하다.From the viewpoint that the (A) (meth) acrylic resin of the present invention can be integrated with the polyoxyalkylene polyol through a polyisocyanate to improve the transparency, the content of the hydroxyl group-containing Meth) acryl-based monomer. Examples of the hydroxyl group-containing (meth) acrylic monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Containing (meth) acrylates such as 1,4-butanediol (meth) acrylate, 1,6-hexanediol (meth) acrylate and 3-methylpentanediol (meth) . Among them, 2-hydroxyethyl (meth) acrylate is preferable in view of copolymerization and reactivity. The hydroxyl group-containing (meth) acrylic monomer is preferably contained in an amount of 0.5 to 10 mol%, more preferably 0.6 to 8.0 mol%, as a copolymerization component of the (A) (meth) acrylic resin.

또, 본 발명에 있어서의 (A) (메트)아크릴계 수지에는 중합성을 해치지 않는 범위에서, 공중합 성분으로서 그 밖의 중합성 모노머를 사용할 수 있다. 그러한 중합성 모노머의 예로는, 아크릴로니트릴, 메타크릴로니트릴, 스티렌, α-메틸스티렌, 아세트산비닐, 프로피온산비닐, 스테아르산비닐, 염화비닐, 염화비닐리덴, 알킬비닐에테르, 비닐톨루엔, 비닐피리딘, 비닐피롤리돈, 이타콘산디알킬에스테르, 푸마르산디알킬에스테르, 알릴알코올, 아크릴클로라이드, 메틸비닐케톤, N-아크릴아미드메틸트리메틸암모늄클로라이드, 알릴트리메틸암모늄클로라이드, 디메틸알릴비닐케톤 등을 들 수 있다.Further, other polymerizable monomers may be used as the copolymerization component in the (A) (meth) acrylic resin of the present invention within a range that does not impair the polymerizability. Examples of such polymerizable monomers include acrylonitrile, methacrylonitrile, styrene,? -Methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, vinyl pyridine , Vinyl pyrrolidone, dialkyl itaconate, dialkyl fumarate, allyl alcohol, acryl chloride, methyl vinyl ketone, N-acrylamidomethyltrimethyl ammonium chloride, allyltrimethyl ammonium chloride, dimethyl allyl vinyl ketone and the like .

본 발명에 있어서의 (A) (메트)아크릴계 수지는 중량 평균 분자량이 10 만 ∼ 60 만일 필요가 있고, 바람직하게는 15 만 ∼ 50 만, 보다 바람직하게는 20 만 ∼ 40 만이다. 중량 평균 분자량이 10 만보다 작은 경우에는, 응집력이 작아짐으로써 점착제의 잔류를 일으킨다. 한편, 중량 평균 분자량이 60 만보다 큰 경우에는, (A) (메트)아크릴계 수지와 (B) 폴리옥시알킬렌폴리올의 상용성이 나빠져, 얻어지는 점착제층의 투명성이 나빠진다.The (A) (meth) acrylic resin in the present invention should have a weight average molecular weight of 100,000 to 60, preferably 150,000 to 500,000, and more preferably 200,000 to 400,000. When the weight-average molecular weight is less than 100,000, the cohesive force is decreased, thereby causing the adhesive to remain. On the other hand, when the weight average molecular weight is more than 60,000, the compatibility of the (A) (meth) acrylic resin and the polyoxyalkylene polyol (B) deteriorates and the transparency of the resultant pressure-sensitive adhesive layer deteriorates.

여기서 중량 평균 분자량은 겔·퍼미에이션·크로마토그래피 (쇼와 전공 주식회사 제조, 쇼덱스 (등록상표) GPC-101) 를 사용하여, 하기 조건에서 상온에서 측정하고, 폴리스티렌 환산에 의해서 산출되는 것이다.Here, the weight average molecular weight is determined by gel permeation chromatography (manufactured by Showa Denko KK, Shodex (registered trademark) GPC-101) at room temperature under the following conditions and calculated by polystyrene conversion.

칼럼 : 쇼와 전공 주식회사 제조, 쇼덱스 (등록상표) LF-804Column: Shodex (registered trademark) LF-804 manufactured by Showa Denko KK

칼럼 온도 : 40 ℃ Column temperature: 40 DEG C

시료 : 공중합체의 0.2 질량％ 테트라하이드로푸란 용액Sample: 0.2% by mass of a tetrahydrofuran solution of the copolymer

유량 : 1 ㎖/분Flow rate: 1 ml / min

용리액 : 테트라하이드로푸란Eluent: tetrahydrofuran

또, 본 발명에 있어서의 (A) (메트)아크릴계 수지의 유리 전이 온도 (Tg) 는 -80 ∼ 0 ℃ 인 것이 바람직하고, 보다 바람직하게는 -70 ∼ -10 ℃ 이다. Tg 가 0 ℃ 보다 높은 경우에는, 피착체에 대한 젖음성이 나빠져 바람직하지 않다. 한편, Tg 가 -80 ℃ 보다 낮은 경우에는, 응집력이 작아짐으로써 점착제의 잔류를 발생시킬 가능성이 있어 바람직하지 않다. 또한, (A) (메트)아크릴계 수지의 Tg 는 사용하는 모노머 성분이나 조성비를 적절히 변경함으로써 조정할 수 있다.The glass transition temperature (Tg) of the (A) (meth) acrylic resin in the present invention is preferably -80 to 0 占 폚, more preferably -70 to -10 占 폚. When the Tg is higher than 0 占 폚, the wettability to an adherend becomes poor, which is not preferable. On the other hand, when the Tg is lower than -80 占 폚, the cohesive force is decreased, which may cause the residual of the pressure-sensitive adhesive. The Tg of the (A) (meth) acrylic resin can be adjusted by appropriately changing the monomer components or the composition ratio to be used.

여기서, Tg 는 아래의 방법에서 구해진 것을 가리킨다. (A) (메트)아크릴계 수지로부터 10 ㎎ 의 시료를 채취하고, 시차 주사 열량계 (DSC) 를 사용하여, 10 ℃/분의 승온 속도로 -80 ℃ 에서부터 200 ℃ 까지 온도를 변화시켜 시차 주사 열량을 측정하고, 유리 전이에 의한 흡열 개시 온도를 Tg 로 한다. 또한, Tg 가 2 개 관찰된 경우에는, 2 개의 Tg 의 평균치를 취하는 것으로 한다.Here, Tg indicates that obtained by the following method. A 10 mg sample was taken from the (A) (meth) acrylic resin and the temperature was changed from -80 ° C to 200 ° C at a heating rate of 10 ° C / minute using a differential scanning calorimeter (DSC) , And the endothermic initiation temperature due to the glass transition is defined as Tg. When two Tg are observed, it is assumed that the average value of two Tg is taken.

본 발명에 있어서의 (A) (메트)아크릴계 수지의 중합 방법은 특별히 제한되는 것이 아니고, 용액 중합, 유화 중합, 괴상 중합, 현탁 중합, 교호 공중합 등의 공지된 방법에 의해서 중합할 수 있다. 그 중에서도 용액 중합이 특히 바람직하다.The polymerization method of the (A) (meth) acrylic resin in the present invention is not particularly limited, and can be polymerized by a known method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, alternating copolymerization and the like. Among them, solution polymerization is particularly preferable.

또, 얻어지는 공중합체는 랜덤 공중합체, 블록 공중합체 등 어느 것이어도 된다.The resulting copolymer may be a random copolymer, a block copolymer, or the like.

(A) (메트)아크릴계 수지의 중합시에 사용되는 중합 개시제는 특별히 한정되지 않고, 공지된 것 중에서 적절히 선택하여 사용할 수 있다. 예를 들어, 2,2'-아조비스(이소부티로니트릴), 2,2'-아조비스(4-메톡시-2,4-디메틸발레로니트릴), 2,2'-아조비스(2,4-디메틸발레로니트릴), 2,2'-아조비스(2-메틸부티로니트릴), 1,1'-아조비스(시클로헥산-1-카르보니트릴), 2,2'-아조비스(2,4,4-트리메틸펜탄), 디메틸-2,2'-아조비스(2-메틸프로피오네이트) 등의 아조계 중합 개시제；벤조일퍼옥사이드, t-부틸하이드로퍼옥사이드, 디-t-부틸퍼옥사이드, t-부틸퍼옥시벤조에이트, 디쿠밀퍼옥사이드, 1,1-비스(t-부틸퍼옥시)-3,3,5-트리메틸시클로헥산, 1,1-비스(t-부틸퍼옥시)시클로도데칸 등의 과산화물계 중합 개시제 등의 유용성 (油溶性) 중합 개시제가 바람직하게 예시된다. 이들 중합 개시제는 단독으로 사용해도 되고, 2 종 이상을 조합하여 사용해도 된다. 중합 개시제의 사용량은 통상적인 사용량이면 되고, 예를 들어 모노머 100 질량부에 대해서 0.01 ∼ 5 질량부 정도의 범위에서 선택할 수 있고, 0.02 ∼ 4 질량부의 범위인 것이 바람직하며, 0.03 ∼ 3 질량부인 것이 보다 바람직하다.The polymerization initiator used in the polymerization of the (A) (meth) acrylic resin is not particularly limited and may be appropriately selected from known ones. Azo compounds such as 2,2'-azobis (isobutyronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) , 4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis Azo-based polymerization initiators such as benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl (2-methylpropionate) T-butyl peroxybenzoate, dicumyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- And an oil-soluble polymerization initiator such as peroxide-based polymerization initiator such as cyclododecane. These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator to be used is not particularly limited and may be selected within a range of, for example, 0.01 to 5 parts by mass based on 100 parts by mass of the monomer, preferably 0.02 to 4 parts by mass and 0.03 to 3 parts by mass More preferable.

또한, 용액 중합에서는 각종 일반적인 용제를 사용할 수 있다. 이와 같은 용제로는 아세트산에틸, 아세트산n-프로필, 아세트산n-부틸 등의 에스테르류, 톨루엔, 벤젠 등의 방향족 탄화수소류, n-헥산, n-헵탄 등의 지방족 탄화수소류, 시클로헥산, 메틸시클로헥산 등의 지환식 탄화수소류, 메틸에틸케톤, 메틸이소부틸케톤 등의 케톤류 등의 유기 용제를 들 수 있다. 이들 용제는 단독으로 사용해도 되고, 2 종 이상을 조합하여 사용해도 된다.In solution polymerization, various general solvents can be used. Such solvents include esters such as ethyl acetate, n-propyl acetate and n-butyl acetate, aromatic hydrocarbons such as toluene and benzene, aliphatic hydrocarbons such as n-hexane and n-heptane, aliphatic hydrocarbons such as cyclohexane and methylcyclohexane And organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone. These solvents may be used alone, or two or more solvents may be used in combination.

또, 본 발명에 있어서의 (A) (메트)아크릴계 수지의 배합량으로는 65 ∼ 85 질량％ 일 필요가 있고, 보다 바람직하게는 70 ∼ 85 질량％ 이다. 배합량이 65 질량％ 보다 적은 경우에는 피착체를 오염시키고, 한편, 배합량이 85 질량％ 를 초과하는 경우에는 충분한 대전 특성이 얻어지지 않는다.The amount of the (A) (meth) acrylic resin in the present invention should be 65 to 85% by mass, and more preferably 70 to 85% by mass. When the blending amount is less than 65% by mass, the adherend is contaminated. On the other hand, when the blending amount exceeds 85% by mass, sufficient charging property can not be obtained.

(B) 폴리옥시알킬렌폴리올(B) a polyoxyalkylene polyol

본 발명에 있어서의 (B) 폴리옥시알킬렌폴리올로는 에테르기를 갖는 폴리머폴리올이면 특별히 한정되지 않고, 공지된 폴리머폴리올을 적절히 사용할 수 있다. (B) 폴리옥시알킬렌폴리올의 예로는, 폴리에틸렌글리콜, 폴리프로필렌글리콜, 폴리테트라메틸렌에테르글리콜 및 이들의 유도체 또는 공중합체 등을 들 수 있다. 그 중에서도, (메트)아크릴계 수지와의 상용성을 조정하기 쉽다는 이유에서 폴리프로필렌글리콜이 바람직하다. 이들은 단독으로 사용해도 되고, 2 종 이상을 혼합하여 사용해도 된다.The polyoxyalkylene polyol (B) in the present invention is not particularly limited as long as it is a polymer polyol having an ether group, and a known polymer polyol can be suitably used. Examples of the polyoxyalkylene polyol (B) include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and derivatives and copolymers thereof. Among them, polypropylene glycol is preferable because it is easy to adjust the compatibility with the (meth) acrylic resin. These may be used alone or in combination of two or more.

본 발명에 있어서의 (B) 폴리옥시알킬렌폴리올은 수 평균 분자량이 500 ∼ 1500 일 필요가 있고, 바람직하게는 800 ∼ 1200 이다. 수 평균 분자량이 1500 을 초과하는 경우에는, 점착제층의 투명성이 나빠진다. 한편, 수 평균 분자량이 500 보다 작은 경우에는, 점착제의 잔류를 일으킬 가능성이 있어 바람직하지 않다. 수 평균 분자량은 GPC (겔·퍼미에이션·크로마토그래피) 에 의해서 측정하여 얻어진 것을 말한다.The polyoxyalkylene polyol (B) in the present invention needs to have a number average molecular weight of 500 to 1500, preferably 800 to 1200. When the number average molecular weight exceeds 1,500, the transparency of the pressure-sensitive adhesive layer is deteriorated. On the other hand, when the number average molecular weight is less than 500, there is a possibility that the pressure-sensitive adhesive may remain, which is not preferable. The number average molecular weight refers to a value obtained by measurement by GPC (gel permeation chromatography).

또, 본 발명에 있어서의 (B) 폴리옥시알킬렌폴리올의 배합량으로는 10 ∼ 30 질량％ 일 필요가 있고, 보다 바람직하게는 15 ∼ 25 질량％ 이다. 배합량이 10 질량％ 보다 적은 경우에는 충분한 대전 특성이 얻어지지 않고, 한편, 배합량이 30 질량％ 를 초과하는 경우에는 피착체를 오염시킨다.The blending amount of the polyoxyalkylene polyol (B) in the present invention is required to be 10 to 30 mass%, and more preferably 15 to 25 mass%. When the blending amount is less than 10 mass%, sufficient charging property is not obtained, while when the blending amount exceeds 30 mass%, the adherend is contaminated.

(C) 폴리이소시아네이트(C) Polyisocyanate

본 발명에 있어서의 (C) 폴리이소시아네이트로는 방향족계, 지방족계, 지환식계 등의 폴리이소시아네이트를 들 수 있다. (C) 폴리이소시아네이트의 예로는, 1,4-테트라메틸렌디이소시아네이트, 1,6-헥사메틸렌디이소시아네이트 (HDI), 2-메틸-1,5-펜탄디이소시아네이트, 3-메틸-1,5-펜탄디이소시아네이트, 트리메틸헥사메틸렌디이소시아네이트, 이소포론디이소시아네이트, 시클로헥실디이소시아네이트, 톨릴렌디이소시아네이트 (TDI), 수소 첨가 톨릴렌디이소시아네이트, 디페닐메탄디이소시아네이트, 수소 첨가 디페닐메탄디이소시아네이트, 폴리페닐메탄폴리이소시아네이트, 자일렌디이소시아네이트, 수소 첨가 자일렌디이소시아네이트, 테트라메틸자일릴렌디이소시아네이트, 노르보르넨디이소시아네이트, 나프탈렌디이소시아네이트, 트리메틸올프로판/톨릴렌디이소시아네이트 삼량체 부가물, 트리메틸올프로판/헥사메틸렌디이소시아네이트 삼량체 부가물, 헥사메틸렌디이소시아네이트의 이소시아누레이트체 등의 이소시아네이트 부가물, 폴리에테르폴리이소시아네이트, 폴리에스테르폴리이소시아네이트 등을 들 수 있다. 이들은 단독으로 사용해도 되고, 2 종 이상을 조합하여 사용해도 된다.Examples of the polyisocyanate (C) in the present invention include polyisocyanates such as aromatic, aliphatic, alicyclic and the like. Examples of the polyisocyanate (C) include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 2-methyl-1,5-pentane diisocyanate, (TDI), hydrogenated tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, polyphenylmethane diisocyanate, polyphenylmethane diisocyanate, diisocyanate diisocyanate, Polyisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, tetramethyl xylene diisocyanate, norbornene diisocyanate, naphthalene diisocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct, trimethylolpropane / hexamethylene diisocyanate trimer S body adduct, hexamethylene di An isocyanate adduct such as an isocyanurate of isocyanate, a polyether polyisocyanate, and a polyester polyisocyanate. These may be used alone or in combination of two or more.

또, 본 발명에 있어서의 (C) 폴리이소시아네이트의 배합량으로는 1.0 ∼ 5.0 질량％ 일 필요가 있고, 보다 바람직하게는 2.0 ∼ 4.0 질량％ 이다. 배합량이 1.0 질량％ 보다 적은 경우에는 충분한 응집력이 얻어지지 않고, 한편, 배합량이 5.0 질량％ 를 초과하는 경우에는 점착층이 지나치게 경화되어 피착체에 대한 젖음성이 나빠진다.The amount of the polyisocyanate (C) in the present invention should be 1.0 to 5.0% by mass, and more preferably 2.0 to 4.0% by mass. When the blending amount is less than 1.0% by mass, a sufficient cohesive force can not be obtained. On the other hand, when the blending amount exceeds 5.0% by mass, the pressure-sensitive adhesive layer is excessively cured and the wettability to the adherend is deteriorated.

(D) 이온성 화합물(D) an ionic compound

본 발명에 사용되는 (D) 이온성 화합물로는 아니온과 카티온으로 이루어지는, 25 ℃ 에서 액체상 또는 고체상인 이온성 화합물을 들 수 있다. 구체적으로는 알칼리 금속염, 이온성 액체 (25 ℃ 에서 액체상), 계면 활성제 등을 들 수 있다. 그 중에서도, 피착체를 잘 오염시키지 않는다는 이유에서 알칼리 금속염이 바람직하다.Examples of the ionic compound (D) used in the present invention include ionic compounds comprising anions and cations, which are liquid or solid at 25 占 폚. Specifically, an alkali metal salt, an ionic liquid (liquid at 25 占 폚), and a surfactant can be given. Among them, an alkali metal salt is preferable because it does not contaminate the adherend well.

알칼리 금속염으로는 리튬, 나트륨, 칼륨 등의 알칼리 금속 카티온과, 아니온으로 이루어지는 화합물을 들 수 있고, 구체적으로는, 염화나트륨, 염화칼륨, 염화리튬, 과염소산리튬, 염소산칼륨, 질산칼륨, 질산나트륨, 탄산나트륨, 티오시안산나트륨, LiBr, LiI, LiBF4, LiPF6, LiSCN, 아세트산나트륨, 알긴산나트륨, 리그닌술폰산나트륨, 톨루엔술폰산나트륨, LiCF3SO3, Li(CF3SO2)2N, Li(C2F5SO2)2N, Li(CF3SO2)3C 등을 들 수 있다. 이들 알칼리 금속염은 단독으로 사용해도 되고, 2 종 이상을 조합하여 사용해도 된다.Examples of the alkali metal salt include alkali metal cation such as lithium, sodium and potassium and compounds comprising anion. Specific examples thereof include sodium chloride, potassium chloride, lithium chloride, lithium perchlorate, potassium chlorate, potassium nitrate, sodium nitrate, sodium carbonate, sodium thiocyanate, sodium, LiBr, LiI, LiBF 4, LiPF 6, LiSCN, sodium acetate, sodium alginate, lignin sulfonate, toluene sulfonate, LiCF 3 SO 3, Li ( CF 3 SO 2) 2 N, Li ( C 2 F 5 SO 2 ) 2 N, Li (CF 3 SO 2) 3 C, and the like. These alkali metal salts may be used alone or in combination of two or more.

또, 본 발명에 있어서의 (D) 이온성 화합물의 배합량으로는 0.2 ∼ 1.0 질량％ 일 필요가 있고, 보다 바람직하게는 0.3 ∼ 0.8 질량％ 이다. 배합량이 0.2 질량％ 보다 적은 경우에는 충분한 대전 특성이 얻어지지 않고, 한편, 배합량이 1.0 질량％ 를 초과하는 경우에는 피착체를 오염시킨다.The amount of the ionic compound (D) in the present invention should be from 0.2 to 1.0% by mass, and more preferably from 0.3 to 0.8% by mass. If the blending amount is less than 0.2 mass%, sufficient charging property can not be obtained. On the other hand, when the blending amount exceeds 1.0 mass%, the adherend is contaminated.

(E) 주석계 촉매(E) Tin catalyst

본 발명에 있어서의 (E) 주석계 촉매로는, 디부틸주석디라우레이트, 디부틸주석디에틸헥소에이트, 디옥틸주석디라우레이트 등을 들 수 있다. 그 중에서도, (C) 폴리이소시아네이트의 경화성이 양호하고 또한 안전성이 높다는 이유에서, 디옥틸주석디라우레이트가 바람직하다.Examples of the (E) tin catalyst in the present invention include dibutyltin dilaurate, dibutyltin diethylhexoate, and dioctyltin dilaurate. Among them, dioctyltin dilaurate is preferable because (C) the polyisocyanate has good curability and high safety.

또, 본 발명에 있어서의 (E) 주석계 촉매의 배합량으로는 0.005 ∼ 0.1 질량％ 일 필요가 있고, 보다 바람직하게는 0.01 ∼ 0.05 질량％ 이다. 배합량이 0.005 질량％ 보다 적은 경우에는 충분한 응집력이 얻어지지 않고, 한편, 배합량이 0.1 질량％ 를 초과하는 경우에는 (메트)아크릴계 수지의 안정성이 나빠져 포트 라이프가 짧아진다.The amount of the (E) tin-based catalyst in the present invention should be 0.005 to 0.1% by mass, and more preferably 0.01 to 0.05% by mass. If the blending amount is less than 0.005 mass%, sufficient cohesive strength can not be obtained. On the other hand, when the blending amount exceeds 0.1 mass%, the stability of the (meth) acrylic resin becomes poor and the pot life becomes short.

본 발명의 광학 필름용 점착제 조성물은 산가가 0 ∼ 5 ㎎KOH/g 인 것이 바람직하고, 0 ∼ 1 ㎎KOH/g 인 것이 보다 바람직하며, 0 ∼ 0.3 ㎎KOH/g 인 것이 더욱 보다 바람직하고, 0 ∼ 0.1 ㎎KOH/g 인 것이 가장 바람직하다. 산가가 5 ㎎KOH/g 보다 높으면 ITO 필름 등의 부식을 기피하는 재료에 대해서 사용이 곤란해진다. 또한, 조성물의 산가는 JIS K 0070 에 준거하여 측정한 값이다. 예를 들어, 아래와 같이 측정한다.The pressure-sensitive adhesive composition for an optical film of the present invention preferably has an acid value of 0 to 5 mgKOH / g, more preferably 0 to 1 mgKOH / g, still more preferably 0 to 0.3 mgKOH / g, And most preferably 0 to 0.1 mgKOH / g. If the acid value is higher than 5 mgKOH / g, it becomes difficult to use the material for avoiding corrosion such as ITO film. The acid value of the composition is a value measured in accordance with JIS K 0070. For example, measure as follows.

정밀 천칭으로 100 ㎖ 삼각 플라스크에 시료 약 2 g 정도를 정밀 칭량하고, 이것에 에탄올/디에틸에테르 = 1/1 (질량비) 의 혼합 용매 10 ㎖ 를 첨가하여 용해시킨다. 또한, 이 용기에 지시약으로서 페놀프탈레인에탄올 용액을 1 ∼ 3 방울 첨가하고, 시료가 균일해질 때까지 충분히 교반한다. 이것을, 0.1 N 수산화칼륨-에탄올 용액으로 적정하고, 지시약의 엷은 홍색이 30 초간 계속되었을 때를 중화의 종점으로 한다. 그 결과로부터, 하기의 일반식 (1) 을 사용하여 얻은 값을 조성물의 산가로 한다.Precisely weighed about 2 g of a sample in a 100 ml Erlenmeyer flask with a precision balance, and 10 ml of a mixed solvent of ethanol / diethyl ether = 1/1 (mass ratio) is added to dissolve. Further, 1 to 3 drops of a phenolphthalein ethanol solution as an indicator is added to the container, and sufficiently stirred until the sample becomes uniform. This is titrated with a 0.1 N potassium hydroxide-ethanol solution, and when the light pink of the indicator has continued for 30 seconds, this is taken as the end point of neutralization. From the result, the value obtained by using the following general formula (1) is the acid of the composition.

[수학식 1][Equation 1]

산가 (㎎KOH/g) ＝ [B × f × 5.611]/S (1)(MgKOH / g) = [B x f x 5.611] / S (1)

상기 식 중, B 는 0.1N 수산화칼륨-에탄올 용액의 사용량 (㎖) 이고, f 는 0.1 N 수산화칼륨-에탄올 용액의 팩터이고, S 는 시료의 채취량 (g) 이다.Wherein B is the amount (ml) of 0.1 N potassium hydroxide-ethanol solution, f is a factor of 0.1 N potassium hydroxide-ethanol solution and S is the amount of sample (g).

또, 본 발명의 광학 필름용 점착제 조성물에는 투명성을 저해하지 않는 범위에서 공지된 각종 첨가제를 필요에 따라서 첨가해도 된다. 첨가제로는 가소제, 표면 윤활제, 레벨링제, 연화제, 산화 방지제, 노화 방지제, 광 안정제, 자외선 흡수제, 중합 금지제, 벤조트리아졸계 등의 광 안정제, 인산에스테르계 및 그 밖의 난연제, 계면 활성제와 같은 대전 방지제 등을 들 수 있다.Various known additives may be added to the pressure-sensitive adhesive composition for an optical film of the present invention as long as they do not impair transparency. Examples of additives include additives such as plasticizers, surface lubricants, leveling agents, softeners, antioxidants, antioxidants, light stabilizers, ultraviolet absorbers, light stabilizers such as polymerization inhibitors and benzotriazole, phosphoric esters and other flame retardants, And the like.

또, 본 발명의 광학 필름용 점착제 조성물은 도포시의 점도 조정을 목적으로 유기 용매를 사용하여 희석시켜도 된다. 사용할 수 있는 유기 용매로는, 예를 들어 메틸에틸케톤, 아세톤, 아세트산에틸, 테트라하이드로푸란, 디옥산, 시클로헥사논, n-헥산, 톨루엔, 자일렌, n-프로판올, 이소프로판올, 아세트산n-프로필 등을 들 수 있다. 이들 유기 용매는 단독으로 사용해도 되고, 2 종 이상을 혼합하여 사용해도 된다.The pressure-sensitive adhesive composition for an optical film of the present invention may be diluted with an organic solvent for the purpose of viscosity adjustment at the time of application. Examples of the organic solvent that can be used include organic solvents such as methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, n-propanol, isopropanol, And the like. These organic solvents may be used alone or in combination of two or more.

본 발명의 표면 보호 필름은, 투명 기재 상의 편면에 상기한 광학 필름용 점착제 조성물을 경화시켜 얻어지는 점착제층이 형성되어 있는 것이다. 점착제층의 두께는 통상적으로 3 ∼ 100 ㎛ 이고, 바람직하게는 5 ∼ 50 ㎛ 이다.In the surface protective film of the present invention, a pressure-sensitive adhesive layer obtained by curing the above-mentioned pressure-sensitive adhesive composition for an optical film is formed on one surface of a transparent substrate. The thickness of the pressure-sensitive adhesive layer is usually 3 to 100 占 퐉, preferably 5 to 50 占 퐉.

투명 기재로는 예를 들어, 폴리에틸렌테레프탈레이트, 폴리에틸렌, 폴리프로필렌, 폴리스티렌, 폴리이미드, 폴리비닐알코올, 폴리염화비닐, 셀룰로오스 등을 들 수 있다. 투명 기재의 두께는 통상적으로 5 ∼ 200 ㎛, 바람직하게는 10 ∼ 100 ㎛ 정도이다.Examples of the transparent substrate include polyethylene terephthalate, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, cellulose and the like. The thickness of the transparent substrate is usually from 5 to 200 mu m, preferably from 10 to 100 mu m.

또한, 투명 기재의 편면에는 필요에 따라서 실리콘계, 불소계, 장사슬 알킬계 등의 이형제에 의한 이형 처리 및 방오 처리, 산 처리, 알칼리 처리, 프라이머 처리, 코로나 처리, 플라즈마 처리, 자외선 처리 등의 용이한 접착 처리를 행할 수도 있다.If desired, one side of the transparent substrate may be subjected to a releasing treatment with a releasing agent such as a silicone system, a fluorine system or a long chain alkyl system, an easy processing such as an antifouling treatment, an acid treatment, an alkali treatment, a primer treatment, a corona treatment, a plasma treatment, It is also possible to carry out an adhesion treatment.

또, 투명 기재로는 대전 방지 처리되어 있는 것이 보다 바람직하게 사용된다. 투명 기재에 행해지는 대전 방지 처리로는 특별히 한정되지 않지만, 일반적으로 사용되는 투명 기재의 적어도 편면에 대전 방지층을 형성하는 방법, 또는 투명 기재에 대전 방지제를 반죽하여 이겨 넣는 방법을 사용할 수 있다.It is more preferable to use an antistatic treatment for the transparent substrate. The antistatic treatment to be performed on the transparent substrate is not particularly limited, but a method of forming an antistatic layer on at least one side of a generally used transparent substrate or a method of kneading an antistatic agent and kneading the antistatic agent may be used.

또한, 본 발명의 표면 보호 필름에 있어서의 점착제층의 형성에는 공지된 코팅법 (도포법) 을 사용할 수 있고, 관용의 코터, 예를 들어 그라비아 롤 코터, 리버스 롤 코터, 키스 롤 코터, 딥 롤 코터, 바 코터, 나이프 코터, 스프레이 코터, 콤마 코터, 다이렉트 코터 등을 사용하여 코팅할 수 있다.For forming the pressure-sensitive adhesive layer in the surface protective film of the present invention, a known coating method (coating method) can be used, and a coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, A coater, a bar coater, a knife coater, a spray coater, a comma coater, a direct coater, or the like.

본 발명의 표면 보호 필름에는 필요에 따라서 점착면을 보호할 목적에서 점착제층 표면에 세퍼레이터를 첩합 (貼合) 할 수 있다. 세퍼레이터를 구성하는 기재로는 종이나 플라스틱 필름이 있는데, 표면 평활성이 우수한 점에서 플라스틱 필름이 바람직하게 사용된다. 그 필름으로는 상기한 점착제층을 보호할 수 있는 필름이면 특별히 한정되지 않고, 예를 들어 폴리에틸렌 필름, 폴리프로필렌 필름, 폴리에틸렌테레프탈레이트 필름, 폴리부텐 필름 등을 들 수 있다.In the surface protective film of the present invention, a separator may be bonded to the surface of the pressure-sensitive adhesive layer for the purpose of protecting the pressure-sensitive adhesive surface, if necessary. As the base material constituting the separator, there are paper and plastic films, and plastic films are preferably used because of their excellent surface smoothness. The film is not particularly limited as long as it can protect the above-mentioned pressure-sensitive adhesive layer, and examples thereof include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, and a polybutene film.

상기와 같이 구성한 본 발명의 표면 보호 필름은, 점착면의 표면 고유 저항값이 1.0 × 1010 Ω/□ 이하이고, 또한 헤이즈가 1.2 이하이기 때문에 정전기가 발생되기 쉬운 플라스틱 제품 등에 사용된다. 그 중에서도, 액정 디스플레이 등에 사용되는 편광판, 파장판, 위상차판, 광학 보상 필름, 반사 시트, 휘도 향상 필름 등의 광학 부재 표면을 보호할 목적에서 사용되는 표면 보호 필름으로서 바람직하게 사용할 수 있다.The surface protective film of the present invention constituted as described above is used for a plastic product which is liable to generate static electricity because its surface resistivity is 1.0 10 10 ? /? Or less and its haze is 1.2 or less. Among them, it can be suitably used as a surface protective film used for the purpose of protecting the surface of an optical member such as a polarizing plate, a wave plate, a retardation plate, an optical compensation film, a reflection sheet, and a brightness enhancement film used for a liquid crystal display or the like.

실시예 Example

이하에 실시예 및 비교예에 의해서 본 발명을 보다 구체적으로 설명하지만, 본 발명은 이들 예에 의해서 전혀 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited at all by these examples.

＜(메트)아크릴계 수지 (A-1) ∼ (A-3) 의 합성＞<Synthesis of (meth) acrylic resins (A-1) to (A-3)

냉각관, 질소 도입관, 온도계 및 교반 장치를 구비한 반응 용기에, 아세트산n-프로필 500 질량부, 2-에틸헥실아크릴레이트 265 질량부 (0.53 ㏖), 이소보르닐아크릴레이트 41 질량부 (0.07 ㏖), 메틸메타크릴레이트 105 질량부 (0.39 ㏖), 2-하이드록시에틸아크릴레이트 2 질량부 (0.007 ㏖) 및 2,2'-아조비스(이소부티로니트릴) 0.4 질량부를 넣고, 질소 기류 중에서 95 ℃ 에서 8 시간 중합하고, 유리 전이 온도 -30 ℃, 중량 평균 분자량 25 만의 (메트)아크릴계 수지 (A-1) 을 얻었다. 또한, (메트)아크릴계 수지의 유리 전이 온도 및 중량 평균 분자량의 측정은 앞서 설명한 방법에 의해서 행하였다.500 parts by mass of n-propyl acetate, 265 parts by mass (0.53 mol) of 2-ethylhexyl acrylate and 41 parts by mass of isobornyl acrylate (0.07 part by mass) were added to a reaction vessel equipped with a thermometer, 105 parts by mass (0.39 mol) of methyl methacrylate, 2 parts by mass (0.007 mol) of 2-hydroxyethyl acrylate and 0.4 part by mass of 2,2'-azobis (isobutyronitrile) At 95 캜 for 8 hours to obtain a (meth) acrylic resin (A-1) having a glass transition temperature of -30 캜 and a weight average molecular weight of 250,000. The glass transition temperature and the weight average molecular weight of the (meth) acrylic resin were measured by the method described above.

또, (메트)아크릴계 수지 (A-2) 및 (메트)아크릴계 수지 (A-3) 은, 사용하는 모노머를 표 1 과 같이 변경한 것 이외에는, (메트)아크릴계 수지 (A-1) 과 동일하게 하여 합성하였다. (메트)아크릴계 수지 (A-2) ∼ (A-3) 에 대해서도 유리 전이 온도 및 중량 평균 분자량을 측정하였다. 결과를 표 1 에 나타낸다.The (meth) acrylic resin (A-2) and the (meth) acrylic resin (A-3) were the same as the (meth) acrylic resin (A-1) except that the monomers used were changed as shown in Table 1 Respectively. The glass transition temperature and the weight average molecular weight of the (meth) acrylic resins (A-2) to (A-3) were also measured. The results are shown in Table 1.

＜실시예 1 ∼ 2 및 비교예 1 ∼ 7＞&Lt; Examples 1 to 2 and Comparative Examples 1 to 7 &gt;

표 2 에 나타내는 조성에서 (메트)아크릴계 수지, 폴리옥시알킬렌폴리올, 폴리이소시아네이트, 이온성 화합물 및 주석계 촉매를 배합하고, 또한, 아세트산에틸로 고형분 농도를 50 질량％ 로 조절하고, 실온 하에서 디스퍼저를 사용하여 혼합함으로써 광학 필름용 점착제 조성물 용액을 얻었다. 이 용액을, 두께 38 ㎛ 의 폴리에틸렌테레프탈레이트 (PET) 필름의 편면에 박리 처리가 행해져 이루어지는 세퍼레이터의 박리 처리면 상에, 건조 후의 두께가 50 ㎛ 가 되도록 유연 도포하고, 50 ℃ 에서 5 분간 및 110 ℃ 에서 3 분간 가열 건조시키고, 그리고 두께 50 ㎛ 의 PET 필름을 첩합하여 점착 시트를 제작하였다.(Meth) acrylic resin, a polyoxyalkylene polyol, a polyisocyanate, an ionic compound and a tin-based catalyst were mixed in the composition shown in Table 2, the solid content concentration was adjusted to 50 mass% with ethyl acetate, To obtain a pressure-sensitive adhesive composition solution for an optical film. This solution was applied on the peeled surface of the separator made by peeling a polyethylene terephthalate (PET) film having a thickness of 38 占 퐉 on one side so as to have a thickness of 50 占 퐉 after drying and baked at 50 占 폚 for 5 minutes and 110 占 폚 Deg.] C for 3 minutes, and a PET film having a thickness of 50 [mu] m was laminated to produce a pressure-sensitive adhesive sheet.

＜산가＞<Acid value>

상기 방법으로 각 조성물의 산가를 측정하였다. 결과를 표 2 에 나타낸다.The acid value of each composition was measured by the above method. The results are shown in Table 2.

＜표면 고유 저항값＞&Lt; Surface resistivity value &gt;

얻어진 점착 시트를 40 × 40 ㎜ 의 크기로 절단한 후, 이것을 온도 23 ℃ 및 상대 습도 65 ％ 의 환경 하에 3 시간 방치하고 습도를 조정한 후, 세퍼레이터를 벗겨내고, JIS K 6911 에 기재된 방법으로 점착면의 표면 고유 저항을 측정하였다. 결과를 표 2 에 나타낸다. 또한, 표면 고유 저항값이 작을수록 대전 방지 성능이 높은 것을 의미한다.The resulting pressure-sensitive adhesive sheet was cut into a size of 40 mm × 40 mm and left for 3 hours in an environment of a temperature of 23 ° C. and a relative humidity of 65% to adjust the humidity. Thereafter, the separator was peeled off and adhered by the method described in JIS K 6911 The surface resistivity of the surface was measured. The results are shown in Table 2. Also, the smaller the surface resistivity value, the higher the antistatic performance.

＜투명성＞<Transparency>

얻어진 점착 시트를 30 ㎜ × 30 ㎜ 의 크기에 잘라내고, 점착 시트의 세퍼레이터를 벗겨내어 유리판에 첩합한 것을 측정용 샘플로 하였다. 측정용 샘플에 대해서, 주식회사 무라카미 색채 기술 연구소 제조 「HR-100 형」을 사용하고, 헤이즈미터 NM-150 (주식회사 무라카미 색채 기술 연구소 제조) 을 사용하여 헤이즈를 측정하였다. 헤이즈 (％) 는 확산 투과율을 전광선 투과율로 나누고, 100 을 곱하여 산출하였다. 또한, n 수는 3 회로 하고, 그 평균치를 채용하였다. 전광선 투과율 (％) 을 측정하였다. 결과를 표 2 에 나타낸다. 또한, 헤이즈값은 값이 작을수록 투명성이 높은 것을 의미한다.The resulting pressure-sensitive adhesive sheet was cut into a size of 30 mm x 30 mm, the separator of the pressure-sensitive adhesive sheet was peeled off, and the pressure-sensitive adhesive sheet was attached to a glass plate. The measurement sample was measured for haze using "HR-100 type" manufactured by Murakami Color Research Laboratory Co., Ltd. and using a haze meter NM-150 (manufactured by Murakami Color Research Laboratory Co., Ltd.). The haze (%) was calculated by dividing the diffuse transmittance by the total light transmittance and multiplying by 100. In addition, the number of n was three, and the average value was adopted. The total light transmittance (%) was measured. The results are shown in Table 2. Further, the haze value means that the smaller the value, the higher the transparency.

＜점착 시트의 점착력 측정＞&Lt; Measurement of Adhesive Force of Adhesive Sheet &gt;

얻어진 점착 시트를 25 ㎜ × 100 ㎜ 의 크기에 잘라내고, 점착 시트의 세퍼레이터를 벗겨내어 점착면 (측정면) 을 시험판에 첩부하고, 2 ㎏ 의 고무 롤러 (폭 : 약 50 ㎜) 를 1 왕복시켜 측정용 샘플을 제작하였다. 시험판으로서 유리판을 사용하였다. 얻어진 측정용 샘플을 온도 23 ℃ 및 상대 습도 50 ％ 의 환경 하에 24 시간 방치한 후, JIS Z 0237 에 준하여 박리 속도 300 ㎜/분으로 180°방향의 인장 시험을 행하여 점착 시트의 유리판에 대한 점착력 (N/25 ㎜) 을 측정하였다. 얻어진 측정치를 점착력으로 하였다. 결과를 표 2 에 나타낸다.The obtained pressure sensitive adhesive sheet was cut into a size of 25 mm x 100 mm, the separator of the pressure sensitive adhesive sheet was peeled off, the pressure sensitive adhesive surface (measurement surface) was attached to the test plate, and a 2 kg rubber roller (width: about 50 mm) A sample for measurement was prepared. A glass plate was used as a test plate. The obtained measurement sample was allowed to stand for 24 hours under an environment of a temperature of 23 캜 and a relative humidity of 50% and then subjected to a tensile test in the direction of 180 占 at a peeling speed of 300 mm / min according to JIS Z 0237 to determine the adhesive strength N / 25 mm) was measured. The obtained measurement value was regarded as adhesive force. The results are shown in Table 2.

＜피착체로의 오염성＞&Lt; Contamination to adherend &gt;

위에서 얻어진 점착 시트를 50 ㎜ × 50 ㎜ 의 크기로 잘라내고, 세퍼레이터를 벗겨내어 유리판에 붙였다. 이 샘플을 70 ℃ 에서 5 일간 방치한 후, 점착 시트를 벗겨내어 유리 표면으로의 오염성을 육안으로 확인하고, 하기 기준으로 평가하였다. 결과를 표 2 에 나타낸다.The pressure-sensitive adhesive sheet obtained above was cut into a size of 50 mm x 50 mm, and the separator was peeled off and attached to the glass plate. The sample was allowed to stand at 70 占 폚 for 5 days, and then the pressure-sensitive adhesive sheet was peeled off to visually confirm the stain on the glass surface. The results are shown in Table 2.

○ : 첩합 전의 유리 표면과 비교하여 변화 없음.○: No change compared to the glass surface before bonding.

× : 유리 표면에 점착제의 잔류가 확인된다.X: Residual of the pressure-sensitive adhesive on the glass surface is confirmed.

Figure pct00001
Figure pct00001

Figure pct00002
Figure pct00002

Claims (10)

(A) (메트)아크릴계 수지 65 ∼ 85 질량％ 와,
(B) 폴리옥시알킬렌폴리올 10 ∼ 30 질량％ 와,
(C) 폴리이소시아네이트 1.0 ∼ 5.0 질량％ 와,
(D) 이온성 화합물 0.2 ∼ 1.0 질량％ 와,
(E) 주석계 촉매 0.005 ∼ 0.1 질량％
를 함유하는 광학 필름용 점착제 조성물로서,
(A) (메트)아크릴계 수지의 중량 평균 분자량이 10 만 ∼ 60 만이고, 또한 (B) 폴리옥시알킬렌폴리올의 수 평균 분자량이 500 ∼ 1500 인 것을 특징으로 하는 광학 필름용 점착제 조성물.(A) from 65 to 85% by mass of a (meth) acrylic resin,
(B) 10 to 30% by mass of a polyoxyalkylene polyol,
(C) 1.0 to 5.0% by mass of a polyisocyanate,
(D) 0.2 to 1.0% by mass of an ionic compound,
(E) tin catalyst 0.005 to 0.1 mass%
Sensitive adhesive composition for an optical film,
Wherein the weight average molecular weight of the (A) (meth) acrylic resin is 100,000 to 600,000, and the number average molecular weight of the polyoxyalkylene polyol (B) is 500 to 1,500. 제 1 항에 있어서,
상기 (A) (메트)아크릴계 수지가 공중합 성분으로서 수산기 함유 (메트)아크릴계 모노머를 0.5 ∼ 10 ㏖％ 함유하는 것을 특징으로 하는 광학 필름용 점착제 조성물.The method according to claim 1,
Sensitive adhesive composition for an optical film, wherein the (A) (meth) acrylic resin contains 0.5 to 10 mol% of a hydroxyl group-containing (meth) acrylic monomer as a copolymerization component. 제 2 항에 있어서,
상기 수산기 함유 (메트)아크릴계 모노머가 2-하이드록시에틸(메트)아크릴레이트인 것을 특징으로 하는 광학 필름용 점착제 조성물.3. The method of claim 2,
Wherein the hydroxyl group-containing (meth) acrylic monomer is 2-hydroxyethyl (meth) acrylate. 제 1 항 내지 제 3 항 중 어느 한 항에 있어서,
상기 (A) (메트)아크릴계 수지가, 공중합 성분으로서 메틸(메트)아크릴레이트를 15 ∼ 50 ㏖％ 함유하는 것을 특징으로 하는 광학 필름용 점착제 조성물.4. The method according to any one of claims 1 to 3,
Sensitive adhesive composition for an optical film, wherein the (A) (meth) acrylic resin contains 15 to 50 mol% of methyl (meth) acrylate as a copolymerization component. 제 1 항 내지 제 4 항 중 어느 한 항에 있어서,
산가가 0 ∼ 5 ㎎KOH/g 인 것을 특징으로 하는 광학 필름용 점착제 조성물.5. The method according to any one of claims 1 to 4,
And an acid value of 0 to 5 mgKOH / g. 제 1 항 내지 제 5 항 중 어느 한 항에 있어서,
상기 (D) 이온성 화합물이 알칼리 금속염인 것을 특징으로 하는 광학 필름용 점착제 조성물.6. The method according to any one of claims 1 to 5,
Wherein the ionic compound (D) is an alkali metal salt. 제 1 항 내지 제 6 항 중 어느 한 항에 있어서,
상기 (E) 주석계 촉매가 디옥틸주석디라우레이트인 것을 특징으로 하는 광학 필름용 점착제 조성물.7. The method according to any one of claims 1 to 6,
Wherein the (E) tin catalyst is dioctyltin dilaurate. 투명 기재 상의 편면에, 제 1 항 내지 제 7 항 중 어느 한 항에 기재된 광학 필름용 점착제 조성물을 경화시켜 얻어지는 점착제층이 형성되어 있는 것을 특징으로 하는 표면 보호 필름.A surface protective film comprising a pressure-sensitive adhesive layer formed by curing a pressure-sensitive adhesive composition for an optical film according to any one of claims 1 to 7 on one side of a transparent substrate. 제 8 항에 있어서,
표면 고유 저항값이 1.0 × 1010 Ω/□ 이하이고 또한 헤이즈가 1.2 이하인 것을 특징으로 하는 표면 보호 필름.9. The method of claim 8,
The surface resistance value of 1.0 × 10 10 Ω / □ or less and also the surface-protective film, characterized in that the haze value less than 1.2. 제 8 항 또는 제 9 항에 있어서,
상기 투명 기재가 두께 5 ∼ 200 ㎛ 의 폴리에틸렌테레프탈레이트, 폴리에틸렌, 폴리프로필렌, 폴리스티렌, 폴리이미드, 폴리비닐알코올, 폴리염화비닐 또는 셀룰로오스인 것을 특징으로 하는 표면 보호 필름.10. The method according to claim 8 or 9,
Wherein the transparent substrate is polyethylene terephthalate, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride or cellulose having a thickness of 5 to 200 占 퐉.
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WO2020116288A1 (en) * 2018-12-05 2020-06-11 リンテック株式会社 Composite sheet for protective film formation and method for producing semiconductor chip
CN111534248B (en) * 2020-05-25 2023-04-21 中国乐凯集团有限公司 Pressure-sensitive adhesive, preparation method thereof, surface protective film and element
CN113583282B (en) * 2021-09-10 2023-01-17 中国科学技术大学先进技术研究院 Antistatic optical film, preparation method thereof and display panel
WO2024080146A1 (en) * 2022-10-14 2024-04-18 日東電工株式会社 Adhesive composition, adhesive sheet and reinforcement film

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CN104870592B (en) 2016-10-12
TWI510584B (en) 2015-12-01

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