TWI789344B - Adhesive composition, adhesive member, optical member, and electronic member - Google Patents

Adhesive composition, adhesive member, optical member, and electronic member Download PDF

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TWI789344B
TWI789344B TW106102834A TW106102834A TWI789344B TW I789344 B TWI789344 B TW I789344B TW 106102834 A TW106102834 A TW 106102834A TW 106102834 A TW106102834 A TW 106102834A TW I789344 B TWI789344 B TW I789344B
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meth
adhesive composition
adhesive
acrylate
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TW201728725A (en
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佐佐木翔悟
徐創矢
設樂浩司
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日商日東電工股份有限公司
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives 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
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062Copolymers with monomers not covered by C09J133/06
    • C09J133/066Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives 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
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10Homopolymers or copolymers of methacrylic acid esters
    • C09J133/12Homopolymers or copolymers of methyl methacrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00Homopolymers 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
    • C08F120/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10Esters
    • C08F120/12Esters of monohydric alcohols or phenols
    • C08F120/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F120/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/20Applications use in electrical or conductive gadgets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Abstract

本發明提供一種形成應力分散性優異之黏著劑層之黏著劑組合物、具有由該黏著劑組合物形成之黏著劑層之黏著構件、具備該黏著構件之光學構件或電子構件。 本發明之黏著劑組合物包含具有源自(甲基)丙烯酸烷基酯之單體單元之聚合物(A),且將該黏著劑組合物硬化而形成之黏著劑層於-40℃~150℃之整個溫度區域中之損耗正切tanδ為0.10以上。The present invention provides an adhesive composition forming an adhesive layer excellent in stress dispersion, an adhesive member having an adhesive layer formed of the adhesive composition, and an optical member or an electronic member provided with the adhesive member. The adhesive composition of the present invention comprises a polymer (A) having a monomer unit derived from an alkyl (meth)acrylate, and the adhesive layer formed by hardening the adhesive composition is heated at -40°C to 150°C. The loss tangent tanδ in the entire temperature range of °C is 0.10 or more.

Description

黏著劑組合物、黏著構件、光學構件及電子構件Adhesive composition, adhesive member, optical member, and electronic member

本發明係關於一種黏著劑組合物、具有由該黏著劑組合物形成之黏著劑層之黏著構件、具備該黏著構件之光學構件或電子構件。The present invention relates to an adhesive composition, an adhesive member having an adhesive layer formed from the adhesive composition, and an optical member or an electronic member provided with the adhesive member.

為了對使用LCD之觸控面板、相機之透鏡部、電子設備等光學構件或電子構件賦予剛性或耐衝擊性,存在於露出面側貼附有黏著性膜之情況(例如專利文獻1)。此種黏著性膜通常具有基材層與黏著劑層。 對於此種光學構件或電子構件,於組裝時、加工時、輸送時、使用時等各種情形時,存在因壓入力而施加負荷之情況,產生因施加之負荷導致光學構件或電子構件發生破損之問題。 [先前技術文獻] [專利文獻] 專利文獻1:日本專利特開2014-234460號公報In order to impart rigidity or impact resistance to optical or electronic components such as touch panels using LCDs, lens units of cameras, and electronic equipment, an adhesive film may be attached to the exposed surface (eg, Patent Document 1). Such an adhesive film usually has a substrate layer and an adhesive layer. Such optical components or electronic components may be loaded due to press-fit force during assembly, processing, transportation, use, etc., and the optical components or electronic components may be damaged due to the applied load. question. [Prior Art Document] [Patent Document] Patent Document 1: Japanese Patent Laid-Open No. 2014-234460

[發明所欲解決之問題] 著眼於採用具有優異之應力分散性之應力分散膜作為黏著性膜,對設置於此種應力分散膜之黏著劑層之形成材料進行了研究。 本發明之課題在於提供一種形成應力分散性優異之黏著劑層之黏著劑組合物、具有由該黏著劑組合物形成之黏著劑層之黏著構件、具備該黏著構件之光學構件或電子構件。 [解決問題之技術手段] 本發明之黏著劑組合物包含具有源自(甲基)丙烯酸烷基酯之單體單元之聚合物(A),且 將該黏著劑組合物硬化而形成之黏著劑層於-40℃~150℃之整個溫度區域中之損耗正切tanδ為0.10以上。 於一實施形態中,上述源自(甲基)丙烯酸烷基酯之單體單元為源自具有碳數1~20之烷基作為烷基酯部分之(甲基)丙烯酸烷基酯的單體單元(I)。 於一實施形態中,上述聚合物(A)具有源自分子內具有OH基及/或COOH基之(甲基)丙烯酸酯的單體單元(II)。 於一實施形態中,本發明之黏著劑組合物包含2官能以上之有機多異氰酸酯系交聯劑及/或環氧系交聯劑。 於一實施形態中,係一種包含具有單體單元(I)與單體單元(II)之聚合物、以及2官能以上之有機多異氰酸酯系交聯劑及/或環氧系交聯劑之黏著劑組合物,該單體單元(I)源自具有碳數1~20之烷基作為烷基酯部分之(甲基)丙烯酸烷基酯,該單體單元(II)源自分子內具有OH基及/或COOH基之(甲基)丙烯酸酯;並且,將該黏著劑組合物中之NCO基之莫耳含有比率設為[NCO]、將該黏著劑組合物中之環氧基之莫耳含有比率設為[環氧基]、將該黏著劑組合物中之OH基之莫耳含有比率設為[OH]、將該黏著劑組合物中之COOH基之莫耳含有比率設為[COOH]時,0<([NCO]+[環氧基])/([OH]+[COOH])<0.05。 於一實施形態中,本發明之黏著劑組合物包含具有源自通式(1)所表示之含脂環式結構之(甲基)丙烯酸酯之單體單元、並且重量平均分子量為1000以上、未達30000的聚合物(B)。 CH2 =C(R1 )COOR2 …(1) (通式(1)中,R1 為氫原子或甲基,R2 為具有脂環式結構之烴基) 本發明之黏著構件具有由上述黏著劑組合物形成之黏著劑層。 本發明之光學構件具備上述黏著構件。 本發明之電子構件具備上述黏著構件。 [發明之效果] 根據本發明,能夠提供一種形成應力分散性優異之黏著劑層之黏著劑組合物、具有由該黏著劑組合物形成之黏著劑層之黏著構件、具備該黏著構件之光學構件或電子構件。[Problems to be Solved by the Invention] Focusing on the use of a stress-dispersing film having excellent stress-dispersing properties as an adhesive film, research has been conducted on materials for forming an adhesive layer provided on such a stress-dispersing film. An object of the present invention is to provide an adhesive composition forming an adhesive layer excellent in stress dispersion, an adhesive member having an adhesive layer formed of the adhesive composition, and an optical member or an electronic member provided with the adhesive member. [Means to Solve the Problems] The adhesive composition of the present invention comprises a polymer (A) having a monomer unit derived from an alkyl (meth)acrylate, and is formed by curing the adhesive composition. The loss tangent tanδ of the layer in the entire temperature range from -40°C to 150°C is 0.10 or more. In one embodiment, the monomer unit derived from an alkyl (meth)acrylate is a monomer derived from an alkyl (meth)acrylate having an alkyl group having 1 to 20 carbons as an alkyl ester portion. Unit (I). In one embodiment, the said polymer (A) has the monomer unit (II) derived from the (meth)acrylate which has OH group and/or COOH group in a molecule|numerator. In one embodiment, the adhesive composition of the present invention contains a bifunctional or higher organic polyisocyanate-based crosslinking agent and/or an epoxy-based crosslinking agent. In one embodiment, it is an adhesive comprising a polymer having a monomer unit (I) and a monomer unit (II), and an organic polyisocyanate-based crosslinking agent and/or an epoxy-based crosslinking agent having more than two functions. An agent composition, the monomer unit (I) is derived from an alkyl (meth)acrylate having an alkyl group having 1 to 20 carbon atoms as the alkyl ester part, and the monomer unit (II) is derived from an OH group having an OH group in the molecule group and/or COOH group (meth)acrylate; and, the molar content ratio of the NCO group in the adhesive composition is set to [NCO], and the molar content ratio of the epoxy group in the adhesive composition is The ear content ratio is [epoxy group], the molar content ratio of OH groups in the adhesive composition is [OH], and the molar content ratio of COOH groups in the adhesive composition is [ COOH], 0<([NCO]+[epoxy group])/([OH]+[COOH])<0.05. In one embodiment, the adhesive composition of the present invention contains a monomer unit derived from an alicyclic structure-containing (meth)acrylate represented by general formula (1), and has a weight average molecular weight of 1000 or more, Polymer (B) of less than 30,000. CH 2 =C(R 1 )COOR 2 ...(1) (In the general formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is a hydrocarbon group having an alicyclic structure) The adhesive member of the present invention has the above-mentioned Adhesive layer formed from the adhesive composition. The optical member of this invention is equipped with the said adhesive member. The electronic member of this invention is equipped with the said adhesive member. [Effects of the Invention] According to the present invention, it is possible to provide an adhesive composition forming an adhesive layer excellent in stress dispersion, an adhesive member having an adhesive layer formed of the adhesive composition, and an optical member including the adhesive member. or electronic components.

於本說明書中有「(甲基)丙烯酸」之表述之情形時,意指「丙烯酸及/或甲基丙烯酸」,有「(甲基)丙烯酸酯」之表述之情形時,意指「丙烯酸酯及/或甲基丙烯酸酯」。又,於本說明書中有「重量」之表述之情形時,亦可替換成作為表示重量之SI系單位而慣用之「質量」。 於本說明書中有「源自(a)之單體單元(A)」之表述之情形時,單體單元(A)為單體(a)具有之不飽和雙鍵因聚合發生斷鍵而形成之結構單元。再者,所謂不飽和雙鍵因聚合發生斷鍵而形成之結構單元係「RpRqC=CRrRs」之結構(Rp、Rq、Rr、Rs為以單鍵與碳原子鍵結之任意適當之基)之不飽和雙鍵「C=C」因聚合發生斷鍵而形成之「-RpRqC-CRrRs-」之結構單元。 於本說明書中,聚合物中之單體單元之含有比率例如可根據該聚合物之各種結構解析(例如NMR等)而獲知。又,即使不進行如上所述之各種結構解析,亦可將基於製造聚合物時使用之各種單體之使用量而算出之源自該各種單體之單體單元之含有比率作為聚合物中之單體單元之含有比率。即,可將製造聚合物時使用之全部單體成分中之某種單體(m)之含有比率作為該聚合物中之源自單體(m)之單體單元之含有比率進行處理。 ≪≪A.黏著劑組合物≫≫ 本發明之黏著劑組合物包含具有源自(甲基)丙烯酸烷基酯之單體單元的聚合物(A)。 本發明之黏著劑組合物中之上述聚合物(A)之含有比率較佳為80重量%~100重量%,更佳為85重量%~100重量%,進而較佳為90重量%~100重量%,尤佳為92.5重量%~100重量%,最佳為95重量%~100重量%。藉由使本發明之黏著劑組合物中之上述聚合物(A)之含有比率處於上述範圍內,能夠提供形成應力分散性更優異之黏著劑層之黏著劑組合物。 關於本發明之黏著劑組合物,將該黏著劑組合物硬化而形成之黏著劑層於-40℃~150℃之整個溫度區域中之損耗正切tanδ為0.10以上。藉由使-40℃~150℃之整個溫度區域中之上述損耗正切tanδ為0.10以上,能夠提供形成應力分散性優異之黏著劑層之黏著劑組合物。再者,上述損耗正切tanδ之測定方法於下文中進行敍述。 關於本發明之黏著劑組合物,將該黏著劑組合物硬化而形成之黏著劑層於-40℃~150℃之整個溫度區域中之損耗正切tanδ之上限較佳為2.40以下,更佳為2.20以下,進而較佳為2.00以下,尤佳為1.80以下。藉由使上述損耗正切tanδ之上限處於上述範圍內,能夠提供形成應力分散性更優異之黏著劑層之黏著劑組合物。 關於本發明之黏著劑組合物,將該黏著劑組合物硬化而形成之黏著劑層於-40℃~150℃之整個溫度區域中之損耗正切tanδ之下限較佳為0.12以上,更佳為0.14以上,進而較佳為0.16以上,尤佳為0.18以上。藉由使上述損耗正切tanδ之下限處於上述範圍內,能夠提供形成應力分散性更優異之黏著劑層之黏著劑組合物。 聚合物(A)具有源自(甲基)丙烯酸烷基酯之單體單元。聚合物(A)中之源自(甲基)丙烯酸烷基酯之單體單元可僅為1種,亦可為2種以上。 聚合物(A)中之源自(甲基)丙烯酸烷基酯之單體單元之含有比率較佳為90重量%~99.5重量%,更佳為91重量%~99重量%,進而較佳為92重量%~98.5重量%,尤佳為93重量%~98.2重量%,最佳為94重量%~98重量%。藉由使聚合物(A)中之源自(甲基)丙烯酸烷基酯之單體單元之含有比率處於上述範圍內,能夠提供形成應力分散性更優異之黏著劑層之黏著劑組合物。 上述源自(甲基)丙烯酸烷基酯之單體單元於無損本發明之效果之範圍內可採用任意適當之源自(甲基)丙烯酸烷基酯之單體單元。作為此種單體單元,就可進一步表現本發明之效果之方面而言,較佳為源自具有碳數1~20之烷基作為烷基酯部分之(甲基)丙烯酸烷基酯的單體單元(I)。 作為具有碳數1~20之烷基作為烷基酯部分之(甲基)丙烯酸烷基酯,例如可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸正十二烷基酯、(甲基)丙烯酸正十三烷基酯、(甲基)丙烯酸正十四烷基酯等。 聚合物(A)較佳為具有源自分子內具有OH基及/或COOH基之(甲基)丙烯酸酯的單體單元(II)。聚合物(A)中之源自分子內具有OH基及/或COOH基之(甲基)丙烯酸酯之單體單元(II)可僅為1種,亦可為2種以上。藉由使聚合物(A)具有源自分子內具有OH基及/或COOH基之(甲基)丙烯酸酯之單體單元(II),能夠提供形成應力分散性更優異之黏著劑層之黏著劑組合物。 聚合物(A)中之源自分子內具有OH基及/或COOH基之(甲基)丙烯酸酯之單體單元(II)之含有比率較佳為0.5重量%~10重量%,更佳為1重量%~9重量%,進而較佳為1.5重量%~8重量%,尤佳為1.8重量%~7重量%,最佳為2重量%~6重量%。藉由使聚合物(A)中之源自分子內具有OH基及/或COOH基之(甲基)丙烯酸酯之單體單元(II)之含有比率處於上述範圍內,能夠提供形成應力分散性更優異之黏著劑層之黏著劑組合物。 作為分子內具有OH基之(甲基)丙烯酸酯,例如可列舉:(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯、甲基丙烯酸(4-羥基甲基環己基)酯、N-羥甲基(甲基)丙烯醯胺、乙烯基醇、烯丙基醇、2-羥基乙基乙烯基醚、4-羥基丁基乙烯基醚、二乙二醇單乙烯基醚等。 作為分子內具有COOH基之(甲基)丙烯酸酯,例如可列舉:(甲基)丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、伊康酸、馬來酸、富馬酸、丁烯酸、異丁烯酸等。 聚合物(A)亦可具有源自其他單體之單體單元(III)。聚合物(A)中之源自其他單體之單體單元(III)可僅為1種,亦可為2種以上。 作為其他單體,例如可列舉:含氰基單體、乙烯基酯單體、芳香族乙烯基單體、含醯胺基單體、含醯亞胺基單體、含胺基單體、含環氧基單體、乙烯基醚單體、N-丙烯醯基嗎啉、含磺基單體、含磷酸基單體、含酸酐基單體等。 本發明之黏著劑組合物較佳為包含2官能以上之有機多異氰酸酯系交聯劑及/或環氧系交聯劑。本發明之黏著劑組合物所可包含之2官能以上之有機多異氰酸酯系交聯劑及/或環氧系交聯劑可僅為1種,亦可為2種以上。 本發明之黏著劑組合物中之上述2官能以上之有機多異氰酸酯系交聯劑及環氧系交聯劑之合計含有比率相對於聚合物(A)100重量份,較佳為0.001重量份~0.4重量份,更佳為0.0025重量份~0.3重量份,進而較佳為0.005重量份~0.2重量份,尤佳為0.0075重量份~0.15重量份,最佳為0.01重量份~0.1重量份。藉由使本發明之黏著劑組合物中之上述2官能以上之有機多異氰酸酯系交聯劑及環氧系交聯劑之合計含有比率相對於聚合物(A)100重量份處於上述範圍內,能夠提供形成應力分散性更優異之黏著劑層之黏著劑組合物。 作為2官能以上之有機多異氰酸酯系交聯劑,例如可列舉:伸丁基二異氰酸酯、六亞甲基二異氰酸酯等低級脂肪族多異氰酸酯類;伸環戊基二異氰酸酯、伸環己基二異氰酸酯、異佛爾酮二異氰酸酯等脂環族異氰酸酯類;2,4-甲苯二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、苯二甲基二異氰酸酯等芳香族異氰酸酯類;三羥甲基丙烷/甲苯二異氰酸酯三聚物加成物(例如,Nippon Polyurethane Industry Co.,Ltd.製造,商品名「CORONATE L」)、三羥甲基丙烷/六亞甲基二異氰酸酯三聚物加成物(例如,Nippon Polyurethane Industry Co.,Ltd.製造,商品名「CORONATE HL」)、六亞甲基二異氰酸酯之異氰尿酸酯體(例如,Nippon Polyurethane Industry Co.,Ltd.製造,商品名「CORONATE HX」)等異氰酸酯加成物等。 作為環氧系交聯劑,例如可列舉:雙酚A、表氯醇型環氧系樹脂、伸乙基縮水甘油醚、聚乙二醇二縮水甘油醚、甘油二縮水甘油醚、甘油三縮水甘油醚、1,6-己二醇縮水甘油醚、三羥甲基丙烷三縮水甘油醚、二縮水甘油基苯胺、二胺基縮水甘油基胺、N,N,N',N'-四縮水甘油基間苯二甲胺(例如,三菱瓦斯化學公司製造,商品名「TETRAD-X」)、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷(例如,三菱瓦斯化學公司製造,商品名「TETRAD-C」)等。 本發明之黏著劑組合物較佳為包含具有單體單元(I)與單體單元(II)之聚合物、以及2官能以上之有機多異氰酸酯系交聯劑及/或環氧系交聯劑,該單體單元(I)源自具有碳數1~20之烷基作為烷基酯部分之(甲基)丙烯酸烷基酯,該單體單元(II)源自分子內具有OH基及/或COOH基之(甲基)丙烯酸酯;並且,將該黏著劑組合物中之NCO基之莫耳含有比率設為[NCO]、將該黏著劑組合物中之環氧基之莫耳含有比率設為[環氧基]、將該黏著劑組合物中之OH基之莫耳含有比率設為[OH]、將該黏著劑組合物中之COOH基之莫耳含有比率設為[COOH]時,0<([NCO]+[環氧基])/([OH]+[COOH])<0.05。藉由使([NCO]+[環氧基])/([OH]+[COOH])處於上述範圍,能夠提供形成應力分散性更優異之黏著劑層之黏著劑組合物。 本發明之黏著劑組合物亦可包含具有源自通式(1)所表示之含脂環式結構之(甲基)丙烯酸酯之單體單元、並且重量平均分子量為1000以上、未達30000的聚合物(B)。 CH2 =C(R1 )COOR2 …(1) (通式(1)中,R1 為氫原子或甲基,R2 為具有脂環式結構之烴基) 聚合物(B)可僅為1種,亦可為2種以上。 聚合物(B)之重量平均分子量較佳為1000~30000,更佳為1250~25000,進而較佳為1500~20000,尤佳為1750~15000,最佳為2000~10000。藉由使聚合物(B)之重量平均分子量處於上述範圍內,即使增加交聯劑之量,亦可提供形成應力分散性更優異之黏著劑層之黏著劑組合物。 本發明之黏著劑組合物中之聚合物(B)之含有比率相對於聚合物(A)100重量份,較佳為0.5重量份~50重量份,更佳為1重量份~45重量份,進而較佳為2重量份~40重量份,尤佳為3重量份~35重量份,最佳為4重量份~30重量份。藉由使本發明之黏著劑組合物中之聚合物(B)之含有比率相對於聚合物(A)100重量份處於上述範圍內,即使增加交聯劑之量,亦可提供形成應力分散性更優異之黏著劑層之黏著劑組合物。 聚合物(B)中之源自通式(1)所表示之含脂環式結構之(甲基)丙烯酸酯之單體單元之含有比率較佳為40重量%~99.5重量%,更佳為42.5重量%~99重量%,進而較佳為45重量%~98.5重量%,尤佳為47.5重量%~98重量%,最佳為50重量%~97.5重量%。藉由使聚合物(B)中之源自通式(1)所表示之含脂環式結構之(甲基)丙烯酸酯之單體單元之含有比率處於上述範圍內,即使增加交聯劑之量,亦可提供形成應力分散性更優異之黏著劑層之黏著劑組合物。 作為上述通式(1)所表示之含脂環式結構之(甲基)丙烯酸酯,例如可列舉:(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊基酯、甲基丙烯酸二環戊氧基乙酯、丙烯酸二環戊氧基乙酯、甲基丙烯酸三環戊酯、丙烯酸三環戊酯、甲基丙烯酸1-金剛烷基酯、丙烯酸1-金剛烷基酯、甲基丙烯酸2-甲基-2-金剛烷基酯、丙烯酸2-甲基-2-金剛烷基酯、甲基丙烯酸2-乙基-2-金剛烷基酯、丙烯酸2-乙基-2-金剛烷基酯等。 聚合物(B)亦可具有源自其他單體之單體單元(IV)。聚合物(B)中之源自其他單體之單體單元(IV)可僅為1種,亦可為2種以上。 作為聚合物(B)所可包含之其他單體,例如可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸正十二烷基酯、(甲基)丙烯酸正十三烷基酯、(甲基)丙烯酸正十四烷基酯、丙烯酸、甲基丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊酯、伊康酸、馬來酸、富馬酸、丁烯酸、異丁烯酸等。 聚合物(A)、聚合物(B)於無損本發明之效果之範圍內,可藉由任意適當之方法來製造。作為此種製造方法,例如可列舉:溶液聚合、乳化聚合、塊狀聚合、懸浮聚合、光聚合(活性能量線聚合)等。該等製造方法之中,就成本或生產性之觀點而言,較佳為溶液聚合。所得之聚合物(A)可為無規共聚物、嵌段共聚物、交替共聚物、接枝共聚物等均可。所得之聚合物(B)可為無規共聚物、嵌段共聚物、交替共聚物、接枝共聚物等均可。 作為溶液聚合之方法,例如可列舉將單體成分、聚合起始劑等溶解於溶劑,進行加熱、聚合,從而獲得聚合物溶液之方法等。 作為溶液聚合中進行加熱聚合時之加熱溫度,例如可列舉50℃~90℃。作為溶液聚合中之加熱時間,例如可列舉1小時~24小時。 作為溶液聚合中可使用之溶劑,於無損本發明之效果之範圍內可使用任意適當之溶劑。作為此種溶劑,例如可列舉:甲苯、苯、二甲苯等芳香族烴類;乙酸乙酯、乙酸正丁酯等酯類;正己烷、正庚烷等脂肪族烴類;環己烷、甲基環己烷等脂環式烴類;甲基乙基酮、甲基異丁基酮等酮類等有機溶劑等。溶劑可僅為1種,亦可為2種以上。 於聚合物(A)、聚合物(B)之製造中可使用聚合起始劑。此種聚合起始劑可僅為1種,亦可為2種以上。作為此種聚合起始劑,例如可列舉:2,2'-偶氮二異丁腈、2,2'-偶氮雙(2-脒基丙烷)二鹽酸鹽、2,2'-偶氮雙[2-(5-甲基-2-咪唑啉-2-基)丙烷]二鹽酸鹽、2,2'-偶氮雙(2-甲基丙脒)二硫酸鹽、2,2'-偶氮雙(N,N'-二亞甲基異丁基脒)、2,2'-偶氮雙[N-(2-羧基乙基)-2-甲基丙脒]水合物(和光純藥公司製造,VA-057)等偶氮系起始劑;過硫酸鉀、過硫酸銨等過硫酸鹽;二(2-乙基己基)過氧化碳酸酯、二(4-第三丁基環己基)過氧化碳酸酯、二第二丁基過氧化碳酸酯、過氧化新癸酸第三丁酯、過氧化特戊酸第三己酯、過氧化特戊酸第三丁酯、過氧化二月桂醯、過氧化二正辛醯、過氧化-2-乙基己酸1,1,3,3-四甲基丁酯、過氧化二(4-甲基苯甲醯)、過氧化二苯甲醯、過氧化異丁酸第三丁酯、1,1-二(第三己基過氧化)環己烷、第三丁基過氧化氫、過氧化氫等過氧化物系起始劑;過硫酸鹽與亞硫酸氫鈉之組合、過氧化物與抗壞血酸鈉之組合等將過氧化物與還原劑組合而成之氧化還原系起始劑等。 聚合起始劑之用量於無損本發明之效果之範圍內,可採用任意適當之用量。作為此種用量,例如相對於單體成分100重量份,較佳為0.01重量份~5重量份。 於聚合物(A)、聚合物(B)之製造中,可使用鏈轉移劑。此種鏈轉移劑可僅為1種,亦可為2種以上。作為此種鏈轉移劑,例如可列舉:月桂基硫醇、縮水甘油基硫醇、巰基乙酸、2-巰基乙醇、硫代乙醇酸、硫代乙醇酸甲酯、硫代乙醇酸2-乙基己酯、2,3-二巰基-1-丙醇等。 鏈轉移劑之用量於無損本發明之效果之範圍內,可採用任意適當之用量。作為此種用量,例如相對於單體成分100重量份,較佳為0.01重量份~5重量份。 於聚合物(A)、聚合物(B)之製造中,可使用通常能夠在聚合反應中使用之其他任意適當之添加劑。 本發明之黏著劑組合物亦可包含交聯觸媒。作為交聯觸媒,於無損本發明之效果之範圍內可採用任意適當之交聯觸媒。作為此種交聯觸媒,例如可列舉:鈦酸四正丁酯、鈦酸四異丙酯、乙醯丙酮鐵、丁基氧化錫、二辛基二月桂酸錫等金屬系交聯觸媒(特別是錫系交聯觸媒)等。交聯觸媒可僅為1種,亦可為2種以上。 交聯觸媒之用量於無損本發明之效果之範圍內,可採用任意適當之用量。作為此種用量,例如相對於單體成分100重量份,較佳為0.001重量份~0.05重量份。 本發明之黏著劑組合物於無損本發明之效果之範圍內亦可含有任意適當之其他添加劑。作為此種其他添加劑,例如可列舉:矽烷偶合劑、交聯延遲劑、乳化劑、著色劑、顏料等粉體、染料、界面活性劑、塑化劑、黏著性賦予劑、表面潤滑劑、流平劑、軟化劑、抗氧化劑、防老化劑、光穩定劑、紫外線吸收劑、聚合抑制劑、無機填充劑、有機填充劑、金屬粉、顆粒狀、箔狀物等。此種其他添加劑可僅為1種,亦可為2種以上。 ≪≪B.黏著構件≫≫ 本發明之黏著構件具有由本發明之黏著劑組合物形成之黏著劑層。 本發明之黏著構件可僅包含黏著劑層,亦可包含黏著劑層與其他構件。 於本發明之黏著構件中,於黏著劑層作為最外層露出之形態之情形時,可於該露出面側設置任意適當之隔離膜(剝離片)。隔離膜(剝離片)亦可兼作下述基材。 黏著劑層係由本發明之黏著劑組合物形成。例如,將本發明之黏著劑組合物塗佈於任意適當之基材上,視需要進行乾燥而於基材上形成黏著劑層。然後,若剝離基材,則可獲得僅包含黏著劑層之本發明之黏著構件。又,例如,將本發明之黏著劑組合物塗佈於任意適當之基材上,視需要進行乾燥而於基材上形成黏著劑層,將基材原樣保留,藉此獲得包含黏著劑層與基材之黏著構件。又,例如,將本發明之黏著劑組合物塗佈於任意適當之基材上,視需要進行乾燥而於基材上形成黏著劑層,將剝離基材而獲得黏著劑層載置於其他構件(例如其他基材),藉此獲得包含黏著劑層與基材之黏著構件。又,例如,將本發明之黏著劑組合物塗佈於任意適當之基材上,視需要進行乾燥而於基材上形成黏著劑層,將在基材上形成黏著劑層轉印至其他構件(例如其他基材),藉此獲得包含黏著劑層與基材之黏著構件。 作為黏著劑組合物之塗佈方法,例如可列舉:輥塗、凹版塗佈、反向塗佈、輥刷、噴塗、氣刀塗佈法、利用模嘴塗佈機等之擠出塗佈等。 基材可為由單層形成者,亦可包含多層。基材可被延伸。 基材之厚度可根據用途設定為任意適當之厚度。就用以充分表現本發明之效果之觀點而言,基材之厚度較佳為4 μm~500 μm,更佳為10 μm~400 μm,進而較佳為15 μm~350 μm,尤佳為20 μm~300 μm。 作為基材之材料,根據用途可採用任意適當之材料。作為此種材料,例如可列舉:塑膠、紙、金屬膜、不織布等。此種材料之中,就可進一步表現本發明之效果之方面而言,較佳為塑膠。 作為上述塑膠,例如可列舉:聚酯系樹脂、聚烯烴系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂等。作為聚酯系樹脂,例如可列舉:聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯等。作為聚烯烴系樹脂,例如可列舉:烯烴單體之均聚物、烯烴單體之共聚物等。作為聚烯烴系樹脂,具體而言,例如可列舉:均聚丙烯;將乙烯成分作為共聚成分之嵌段系、無規系、接枝系等之丙烯系共聚物;反應性TPO;低密度、高密度、線性低密度、超低密度等之乙烯系聚合物;乙烯-丙烯共聚物、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸丁酯共聚物、乙烯-甲基丙烯酸共聚物、乙烯-甲基丙烯酸甲酯共聚物等乙烯系共聚物等。就可進一步表現本發明之效果之方面而言,作為上述塑膠,該等之中,較佳為聚酯系樹脂,更佳為聚對苯二甲酸乙二酯。 基材可視需要含有任意適當之添加劑。作為基材中所可含有之添加劑,例如可列舉:抗氧化劑、紫外線吸收劑、光穩定劑、抗靜電劑、填充劑、顏料等。基材中可含有之添加劑之種類、數目、量可根據目的適當地進行設定。 圖1係本發明之一實施形態之黏著構件之概略剖視圖。圖1中,本發明之黏著構件100包含基材10、黏著劑層20及隔離膜30。 ≪≪C.光學構件、電子構件≫≫ 本發明之黏著構件具有應力分散性優異之黏著劑層。因此,可適當地用作用於保護光學構件或電子構件免受來自外部之衝擊等之保護材料。即,本發明之光學構件具備本發明之黏著構件。又,本發明之電子構件具備本發明之黏著構件。 [實施例] 以下,藉由實施例具體地對本發明進行說明,但本發明不受該等實施例之任何限定。再者,實施例等中之試驗及評價方法如下所述。再者,記載為「份」之情形時,只要無特殊說明,則指「重量份」,記載為「%」之情形時,只要無特殊說明,則指「重量%」。 <重量平均分子量之測定> 聚合物之重量平均分子量(Mw)係使用TOSOH CORPORATION製造之GPC裝置(HLC-8220GPC)進行測定。再者,重量平均分子量(Mw)係利用聚苯乙烯換算值求出。 測定條件如下所述。 樣品濃度:0.2重量%(THF溶液) 樣品注入量:10 μl溶離液 THF流速:0.6 ml/分鐘 測定溫度:40℃ 樣品管柱:TSKguardcolumn SuperHZ-H(1根)+TSKgel Super HZM-H(2根) 參考管柱:TSKgel SuperH-RC(1根) 檢測器:示差折射計(RI) <黏著片之製作> 利用槽輥,將所得之黏著劑組合物以乾燥後之厚度成為50 μm之方式塗佈於單面經矽酮進行了剝離處理之厚度38 μm之聚酯膜(商品名:MRF,Mitsubishi Chemical Polyester Film股份有限公司製造)之剝離處理面,於乾燥溫度130℃、乾燥時間3分鐘之條件下進行固化、乾燥。如此,於基材上製作黏著劑層。繼而,將單面經矽酮對進行了剝離處理之厚度38 μm之聚酯膜(商品名:MRF,Mitsubishi Chemical Polyester Film股份有限公司製造)以該膜之剝離處理面成為黏著劑層側之方式被覆於黏著劑層之表面。如此,製作黏著片。 <玻璃轉移溫度(Tg)、儲存模數、損耗彈性模數、tanδ(損耗正切)之測定> 使用動態黏彈性測定裝置(Rheometrics公司製造,ARES),根據下述方法求出。 僅將黏著劑層自所得之黏著片取出,進行積層,形成約2 mm之厚度,將其衝壓為

Figure 02_image001
7.9 mm,製作圓柱狀之顆粒,設為測定用樣品。將上述測定樣品固定於
Figure 02_image001
7.9 mm平行板之夾具,利用上述動態黏彈性測定裝置,對儲存模數G'、損耗彈性模數G''之溫度依存性進行測定,以tanδ=G''/G'之形式算出tanδ。再者,將所得之tanδ曲線成為極大時之溫度設為玻璃轉移溫度(Tg)(℃)。 測定條件如下所述。 測定:剪切模式 溫度範圍:-70℃~150℃ 升溫速度:5℃/分鐘 頻率:1 Hz [製造例1]:(甲基)丙烯酸系聚合物(1) 向具備攪拌翼、溫度計、氮氣導入管、冷凝器之四口燒瓶中添加丙烯酸2-乙基己酯(Nippon Shokubai Co., Ltd.製):100重量份、丙烯酸2-羥基乙酯(東亞合成公司製造):4重量份、作為聚合起始劑之2,2'-偶氮二異丁腈(和光純藥工業公司製造):0.2重量份、乙酸乙酯:156重量份,一面緩慢地攪拌,一面導入氮氣,將燒瓶內之液溫保持為65℃附近,進行6小時聚合反應,製備重量平均分子量55萬之(甲基)丙烯酸系聚合物(1)之溶液(40重量%)。 [製造例2]:(甲基)丙烯酸系聚合物(2) 向具備攪拌翼、溫度計、氮氣導入管、冷凝器之四口燒瓶中添加丙烯酸2-乙基己酯(Nippon Shokubai Co., Ltd.製):100重量份、丙烯酸4-羥基丁酯(大阪有機化學工業公司製造):10重量份、丙烯酸(東亞合成公司製造):0.02重量份、作為聚合起始劑之2,2'-偶氮二異丁腈(和光純藥工業公司製造):0.2重量份、乙酸乙酯:156重量份,一面緩慢地攪拌,一面導入氮氣,將燒瓶內之液溫保持為65℃附近,進行6小時聚合反應,製備重量平均分子量54萬之(甲基)丙烯酸系聚合物(2)之溶液(40重量%)。 [製造例3]:(甲基)丙烯酸系聚合物(3) 向具備攪拌翼、溫度計、氮氣導入管、冷凝器之四口燒瓶中添加丙烯酸丁酯(Nippon Shokubai Co., Ltd.製):99重量份、丙烯酸4-羥基丁酯(大阪有機化學工業公司製造):1重量份、作為聚合起始劑之2,2'-偶氮二異丁腈(和光純藥工業公司製造):1重量份、乙酸乙酯:156重量份,一面緩慢地攪拌,一面導入氮氣,將燒瓶內之液溫保持為60℃附近,進行7小時聚合反應,製備重量平均分子量160萬之(甲基)丙烯酸系聚合物(3)之溶液(39重量%)。 [製造例4]:(甲基)丙烯酸系聚合物(4) 向具備攪拌翼、溫度計、氮氣導入管、冷凝器之四口燒瓶中添加丙烯酸丁酯(Nippon Shokubai Co., Ltd.製):92重量份、N-丙烯醯基嗎啉(Kohjin co.,Ltd.製):5重量份、丙烯酸(東亞合成公司製造):2.9重量份、作為聚合起始劑之2,2'-偶氮二異丁腈(和光純藥工業公司製造):0.1重量份、乙酸乙酯:200重量份,一面緩慢地攪拌,一面導入氮氣,將燒瓶內之液溫保持為55℃附近,進行8小時聚合反應,製備重量平均分子量180萬之(甲基)丙烯酸系聚合物(4)之溶液(33重量%)。 [製造例5]:(甲基)丙烯酸系聚合物(5) 向具備攪拌翼、溫度計、氮氣導入管、冷凝器之四口燒瓶中添加丙烯酸丁酯(Nippon Shokubai Co., Ltd.製):95重量份、丙烯酸(東亞合成公司製造):5重量份、作為聚合起始劑之2,2'-偶氮二異丁腈(和光純藥工業公司製造):0.2重量份、乙酸乙酯:156重量份,一面緩慢地攪拌,一面導入氮氣,將燒瓶內之液溫保持為63℃附近,進行10小時聚合反應,製備重量平均分子量70萬之(甲基)丙烯酸系聚合物(5)之溶液(40重量%)。 [製造例6]:含脂環式結構之(甲基)丙烯酸系聚合物(6) 將作為單體成分之甲基丙烯酸環己酯[均聚物(聚甲基丙烯酸環己酯)之玻璃轉移溫度:66℃]:95重量份、丙烯酸:5重量份、作為鏈轉移劑之2-巰基乙醇:3重量份、作為聚合起始劑之2,2'-偶氮二異丁腈:0.2重量份、及作為聚合溶劑之甲苯:103.2重量份投入至可分離式燒瓶中,一面導入氮氣,一面攪拌1小時。如此,將聚合體系內之氧氣去除後,升溫至70℃,使其反應3小時,進而,於75℃下反應2小時,獲得重量平均分子量4000之(甲基)丙烯酸系聚合物(6)之溶液(50重量%)。 [製造例6]:含脂環式結構之(甲基)丙烯酸系聚合物(7) 向具備攪拌翼、溫度計、氮氣導入管、冷凝器、滴液漏斗之四口燒瓶中投入甲苯:100重量份、甲基丙烯酸二環戊酯(DCPMA)(商品名:FA-513M,日立化成工業公司製造):60重量份、甲基丙烯酸甲酯(MMA):40重量份、及作為鏈轉移劑之硫代乙醇酸甲酯:3.5重量份。然後,於70℃、氮氣環境下攪拌1小時後,投入作為聚合起始劑之2,2'-偶氮二異丁腈:0.2重量份,使其於70℃下反應2小時,繼而於80℃下反應4小時後,於90℃下反應1小時,獲得重量平均分子量4000之(甲基)丙烯酸系聚合物(7)之溶液(51重量%)。 [實施例1] 對(甲基)丙烯酸系聚合物(1)之溶液,以相對於(甲基)丙烯酸系聚合物(1)之溶液之固形物成分100重量份,全部固形物成分成為25重量%之方式利用乙酸乙酯進行稀釋,利用分散機攪拌,獲得包含丙烯酸系樹脂之黏著劑組合物(1)。將結果示於表1。 [實施例2] 向(甲基)丙烯酸系聚合物(1)之溶液中加入:相對於(甲基)丙烯酸系聚合物(1)之溶液之固形物成分100重量份,以固形物成分換算計為0.01重量份之作為交聯劑之CORONATE L(Nippon Polyurethane Industry Co.,Ltd.製)、以固形物成分換算計為0.005重量份之作為交聯觸媒之乙醯丙酮鐵(日本化學產業公司製造),並以全部固形物成分成為25重量%之方式利用乙酸乙酯進行稀釋,利用分散機攪拌,獲得包含丙烯酸系樹脂之黏著劑組合物(2)。將結果示於表1。 [實施例3] 向(甲基)丙烯酸系聚合物(1)之溶液中加入:相對於(甲基)丙烯酸系聚合物(1)之溶液之固形物成分100重量份,以固形物成分換算計為0.1重量份之作為交聯劑之CORONATE L(Nippon Polyurethane Industry Co.,Ltd.製)、以固形物成分換算計為0.005重量份之作為交聯觸媒之乙醯丙酮鐵(日本化學產業公司製造),並以全部固形物成分成為25重量%之方式利用乙酸乙酯進行稀釋,利用分散機攪拌,獲得包含丙烯酸系樹脂之黏著劑組合物(3)。將結果示於表1。 [實施例4] 向(甲基)丙烯酸系聚合物(1)之溶液中加入:相對於(甲基)丙烯酸系聚合物(1)之溶液之固形物成分100重量份,以固形物成分換算計為0.05重量份之作為交聯劑之CORONATE L(Nippon Polyurethane Industry Co.,Ltd.製)、以固形物成分換算計為0.005重量份之作為交聯觸媒之乙醯丙酮鐵(日本化學產業公司製造)、以固形物成分換算計為5重量份之(甲基)丙烯酸系聚合物(6)之溶液,並以全部固形物成分成為25重量%之方式利用乙酸乙酯進行稀釋,利用分散機攪拌,獲得包含丙烯酸系樹脂之黏著劑組合物(4)。將結果示於表1。 [實施例5] 向(甲基)丙烯酸系聚合物(1)之溶液中加入:相對於(甲基)丙烯酸系聚合物(1)之溶液之固形物成分100重量份,以固形物成分換算計為0.1重量份之作為交聯劑之CORONATE L(Nippon Polyurethane Industry Co.,Ltd.製)、以固形物成分換算計為0.005重量份之作為交聯觸媒之乙醯丙酮鐵(日本化學產業公司製造)、以固形物成分換算計為5重量份之(甲基)丙烯酸系聚合物(6)之溶液,並以全部固形物成分成為25重量%之方式利用乙酸乙酯進行稀釋,利用分散機攪拌,獲得包含丙烯酸系樹脂之黏著劑組合物(5)。將結果示於表1。 [實施例6] 向(甲基)丙烯酸系聚合物(1)之溶液中加入:相對於(甲基)丙烯酸系聚合物(1)之溶液之固形物成分100重量份,以固形物成分換算計為0.3重量份之作為交聯劑之CORONATE L(Nippon Polyurethane Industry Co.,Ltd.製)、以固形物成分換算計為0.005重量份之作為交聯觸媒之乙醯丙酮鐵(日本化學產業公司製造)、以固形物成分換算計為5重量份之(甲基)丙烯酸系聚合物(6)之溶液,並以全部固形物成分成為25重量%之方式利用乙酸乙酯進行稀釋,利用分散機攪拌,獲得包含丙烯酸系樹脂之黏著劑組合物(6)。將結果示於表1。 [實施例7] 向(甲基)丙烯酸系聚合物(1)之溶液中加入:相對於(甲基)丙烯酸系聚合物(1)之溶液之固形物成分100重量份,以固形物成分換算計為0.1重量份之作為交聯劑之CORONATE L(Nippon Polyurethane Industry Co.,Ltd.製)、以固形物成分換算計為0.005重量份之作為交聯觸媒之乙醯丙酮鐵(日本化學產業公司製造)、以固形物成分換算計為5重量份之(甲基)丙烯酸系聚合物(7)之溶液,並以全部固形物成分成為25重量%之方式利用乙酸乙酯進行稀釋,利用分散機攪拌,獲得包含丙烯酸系樹脂之黏著劑組合物(7)。將結果示於表1。 [實施例8] 向(甲基)丙烯酸系聚合物(1)之溶液中加入:相對於(甲基)丙烯酸系聚合物(1)之溶液之固形物成分100重量份,以固形物成分換算計為0.3重量份之作為交聯劑之CORONATE L(Nippon Polyurethane Industry Co.,Ltd.製)、以固形物成分換算計為0.005重量份之作為交聯觸媒之乙醯丙酮鐵(日本化學產業公司製造)、以固形物成分換算計為5重量份之(甲基)丙烯酸系聚合物(7)之溶液,並以全部固形物成分成為25重量%之方式利用乙酸乙酯進行稀釋,利用分散機攪拌,獲得包含丙烯酸系樹脂之黏著劑組合物(8)。將結果示於表1。 [實施例9] 對(甲基)丙烯酸系聚合物(2)之溶液,以相對於(甲基)丙烯酸系聚合物(2)之溶液之固形物成分100重量份,全部固形物成分成為25重量%之方式利用乙酸乙酯進行稀釋,利用分散機攪拌,獲得包含丙烯酸系樹脂之黏著劑組合物(9)。將結果示於表1。 [實施例10] 向(甲基)丙烯酸系聚合物(2)之溶液中加入:相對於(甲基)丙烯酸系聚合物(2)之溶液之固形物成分100重量份,以固形物成分換算計為0.1重量份之作為交聯劑之CORONATE L(Nippon Polyurethane Industry Co.,Ltd.製)、以固形物成分換算計為0.05重量份之TETRAD-C(三菱瓦斯化學公司製造)、以固形物成分換算計為0.005重量份之作為交聯觸媒之乙醯丙酮鐵(日本化學產業公司製造),並以全部固形物成分成為25重量%之方式利用乙酸乙酯進行稀釋,利用分散機攪拌,獲得包含丙烯酸系樹脂之黏著劑組合物(10)。將結果示於表1。 [實施例11] 向(甲基)丙烯酸系聚合物(3)之溶液中加入:相對於(甲基)丙烯酸系聚合物(3)之溶液之固形物成分100重量份,以固形物成分換算計為0.02重量份之作為交聯劑之CORONATE L(Nippon Polyurethane Industry Co.,Ltd.製)、以固形物成分換算計為0.005重量份之作為交聯觸媒之乙醯丙酮鐵(日本化學產業公司製造),並以全部固形物成分成為25重量%之方式利用乙酸乙酯進行稀釋,利用分散機攪拌,獲得包含丙烯酸系樹脂之黏著劑組合物(11)。將結果示於表1。 [實施例12] 向(甲基)丙烯酸系聚合物(4)之溶液中加入:相對於(甲基)丙烯酸系聚合物(4)之溶液之固形物成分100重量份,以固形物成分換算計為0.3重量份之作為交聯劑之CORONATE L(Nippon Polyurethane Industry Co.,Ltd.製)、以固形物成分換算計為0.005重量份之作為交聯觸媒之乙醯丙酮鐵(日本化學產業公司製造),並以全部固形物成分成為25重量%之方式利用乙酸乙酯進行稀釋,利用分散機攪拌,獲得包含丙烯酸系樹脂之黏著劑組合物(12)。將結果示於表1。 [實施例13] 向(甲基)丙烯酸系聚合物(5)之溶液中加入:相對於(甲基)丙烯酸系聚合物(5)之溶液之固形物成分100重量份,以固形物成分換算計為0.075重量份之作為交聯劑之TETRAD-C(三菱瓦斯化學公司製造)、以固形物成分換算計為0.005重量份之作為交聯觸媒之乙醯丙酮鐵(日本化學產業公司製造),並以全部固形物成分成為25重量%之方式利用乙酸乙酯進行稀釋,利用分散機攪拌,獲得包含丙烯酸系樹脂之黏著劑組合物(13)。將結果示於表1。 [實施例14] 向(甲基)丙烯酸系聚合物(5)之溶液中加入:相對於(甲基)丙烯酸系聚合物(5)之溶液之固形物成分100重量份,以固形物成分換算計為0.075重量份之作為交聯劑之TETRAD-C(三菱瓦斯化學股份有限公司製造)、以固形物成分換算計為0.005重量份之作為交聯觸媒之乙醯丙酮鐵(日本化學產業公司製造)、以固形物成分換算計為20重量份之(甲基)丙烯酸系聚合物(6)之溶液,並以全部固形物成分成為25重量%之方式利用乙酸乙酯進行稀釋,利用分散機攪拌,獲得包含丙烯酸系樹脂之黏著劑組合物(14)。將結果示於表1。 [比較例1] 向(甲基)丙烯酸系聚合物(1)之溶液中加入:相對於(甲基)丙烯酸系聚合物(1)之溶液之固形物成分100重量份,以固形物成分換算計為0.5重量份之作為交聯劑之CORONATE L(Nippon Polyurethane Industry Co.,Ltd.製)、以固形物成分換算計為0.005重量份之作為交聯觸媒之乙醯丙酮鐵(日本化學產業公司製造),並以全部固形物成分成為25重量%之方式利用乙酸乙酯進行稀釋,利用分散機攪拌,獲得包含丙烯酸系樹脂之黏著劑組合物(C1)。將結果示於表1。 [比較例2] 向(甲基)丙烯酸系聚合物(2)之溶液中加入:相對於(甲基)丙烯酸系聚合物(2)之溶液之固形物成分100重量份,以固形物成分換算計為0.45重量份之作為交聯劑之CORONATE L(Nippon Polyurethane Industry Co.,Ltd.製)、以固形物成分換算計為0.3重量份之TETRAD-C(三菱瓦斯化學公司製造)、以固形物成分換算計為0.005重量份之作為交聯觸媒之乙醯丙酮鐵(日本化學產業公司製造),並以全部固形物成分成為25重量%之方式利用乙酸乙酯進行稀釋,利用分散機攪拌,獲得包含丙烯酸系樹脂之黏著劑組合物(C2)。將結果示於表1。 [表1]
Figure 106102834-A0304-0001
[實施例15] 將聚酯膜自由實施例1中獲得之黏著劑組合物(1)形成之黏著片之一面剝離,貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有黏著片之光學構件。 [實施例16] 將聚酯膜自由實施例2中獲得之黏著劑組合物(2)形成之黏著片之一面剝離,貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有黏著片之光學構件。 [實施例17] 將聚酯膜自由實施例4中獲得之黏著劑組合物(4)形成之黏著片之一面剝離,貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有黏著片之光學構件。 [實施例18] 將聚酯膜自由實施例7中獲得之黏著劑組合物(7)形成之黏著片之一面剝離,貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有黏著片之光學構件。 [實施例19] 將聚酯膜自由實施例9中獲得之黏著劑組合物(9)形成之黏著片之一面剝離,貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有黏著片之光學構件。 [實施例20] 將聚酯膜自由實施例10中獲得之黏著劑組合物(10)形成之黏著片之一面剝離,貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有黏著片之光學構件。 [實施例21] 將聚酯膜自由實施例11中獲得之黏著劑組合物(11)形成之黏著片之一面剝離,貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有黏著片之光學構件。 [實施例22] 將聚酯膜自由實施例12中獲得之黏著劑組合物(12)形成之黏著片之一面剝離,貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有黏著片之光學構件。 [實施例23] 將聚酯膜自由實施例13中獲得之黏著劑組合物(13)形成之黏著片之一面剝離,貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有黏著片之光學構件。 [實施例24] 將聚酯膜自由實施例14中獲得之黏著劑組合物(14)形成之黏著片之一面剝離,貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有黏著片之光學構件。 [實施例25] 將聚酯膜自由實施例1中獲得之黏著劑組合物(1)形成之黏著片之一面剝離,貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有黏著片之電子構件。 [實施例26] 將聚酯膜自由實施例2中獲得之黏著劑組合物(2)形成之黏著片之一面剝離,貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有黏著片之電子構件。 [實施例27] 將聚酯膜自由實施例4中獲得之黏著劑組合物(4)形成之黏著片之一面剝離,貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有黏著片之電子構件。 [實施例28] 將聚酯膜自由實施例7中獲得之黏著劑組合物(7)形成之黏著片之一面剝離,貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有黏著片之電子構件。 [實施例29] 將聚酯膜自由實施例9中獲得之黏著劑組合物(9)形成之黏著片之一面剝離,貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有黏著片之電子構件。 [實施例30] 將聚酯膜自由實施例10中獲得之黏著劑組合物(10)形成之黏著片之一面剝離,貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有黏著片之電子構件。 [實施例31] 將聚酯膜自由實施例11中獲得之黏著劑組合物(11)形成之黏著片之一面剝離,貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有黏著片之電子構件。 [實施例32] 將聚酯膜自由實施例12中獲得之黏著劑組合物(12)形成之黏著片之一面剝離,貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有黏著片之電子構件。 [實施例33] 將聚酯膜自由實施例13中獲得之黏著劑組合物(13)形成之黏著片之一面剝離,貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有黏著片之電子構件。 [實施例34] 將聚酯膜自由實施例14中獲得之黏著劑組合物(14)形成之黏著片之一面剝離,貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有黏著片之電子構件。 [產業上之可利用性] 具有由本發明之黏著劑組合物形成之黏著劑層之黏著構件例如可適當地用作用於保護光學構件或電子構件免受來自外部之衝擊等之保護材料。When there is an expression "(meth)acrylic acid" in this specification, it means "acrylic acid and/or methacrylic acid", and when there is an expression "(meth)acrylate", it means "acrylate and/or methacrylate". In addition, when there is an expression of "weight" in this specification, it may be replaced with "mass" which is commonly used as the SI system unit for expressing weight. When the expression "monomer unit (A) derived from (a)" is used in this specification, the monomer unit (A) is formed by breaking the unsaturated double bond of the monomer (a) due to polymerization. the structural unit. Furthermore, the so-called unsaturated double bond is a structural unit formed by bond breaking due to polymerization. The unsaturated double bond "C=C" is a structural unit of "-RpRqC-CRrRs-" formed by bond breaking due to polymerization. In this specification, the content ratio of the monomer unit in a polymer can be known from various structural analysis (for example, NMR etc.) of the said polymer, for example. In addition, even without performing various structural analyzes as described above, the content ratio of monomer units derived from various monomers calculated based on the amount of various monomers used in the production of the polymer can be used as the content ratio in the polymer. The content ratio of the monomer unit. That is, the content rate of a certain monomer (m) in all the monomer components used in the production of the polymer can be treated as the content rate of the monomer unit derived from the monomer (m) in the polymer. ≪≪A. Adhesive composition≫≫ The adhesive composition of the present invention contains a polymer (A) having a monomer unit derived from an alkyl (meth)acrylate. The content ratio of the polymer (A) in the adhesive composition of the present invention is preferably 80% by weight to 100% by weight, more preferably 85% by weight to 100% by weight, further preferably 90% by weight to 100% by weight %, preferably 92.5% by weight to 100% by weight, most preferably 95% by weight to 100% by weight. By making the content ratio of the said polymer (A) in the adhesive composition of this invention into the said range, the adhesive composition which forms the adhesive layer more excellent in stress dispersion property can be provided. Regarding the adhesive composition of the present invention, the loss tangent tan δ of the adhesive layer formed by curing the adhesive composition in the entire temperature range from -40°C to 150°C is 0.10 or more. By setting the loss tangent tanδ in the entire temperature range from -40°C to 150°C to be 0.10 or more, it is possible to provide an adhesive composition that forms an adhesive layer excellent in stress dispersibility. In addition, the method of measuring the above-mentioned loss tangent tanδ is described below. Regarding the adhesive composition of the present invention, the upper limit of the loss tangent tanδ of the adhesive layer formed by curing the adhesive composition in the entire temperature range of -40°C to 150°C is preferably 2.40 or less, more preferably 2.20 or less, more preferably 2.00 or less, particularly preferably 1.80 or less. By making the upper limit of the said loss tangent tanδ into the said range, the adhesive composition which forms the adhesive layer more excellent in stress dispersion property can be provided. Regarding the adhesive composition of the present invention, the lower limit of the loss tangent tanδ of the adhesive layer formed by curing the adhesive composition in the entire temperature range of -40°C to 150°C is preferably 0.12 or more, more preferably 0.14 or more, more preferably 0.16 or more, particularly preferably 0.18 or more. By setting the lower limit of the loss tangent tan δ within the above range, it is possible to provide an adhesive composition that forms an adhesive layer more excellent in stress dispersion properties. The polymer (A) has a monomer unit derived from an alkyl (meth)acrylate. The monomer unit derived from the alkyl (meth)acrylate in a polymer (A) may be only 1 type, and may be 2 or more types. The content ratio of the monomer unit derived from an alkyl (meth)acrylate in the polymer (A) is preferably from 90% by weight to 99.5% by weight, more preferably from 91% by weight to 99% by weight, and still more preferably 92% by weight to 98.5% by weight, more preferably 93% by weight to 98.2% by weight, most preferably 94% by weight to 98% by weight. When the content rate of the monomer unit derived from the alkyl (meth)acrylate in a polymer (A) exists in the said range, the adhesive composition which forms the adhesive layer more excellent in stress dispersion property can be provided. As the above-mentioned alkyl (meth)acrylate-derived monomer unit, any appropriate alkyl (meth)acrylate-derived monomer unit can be adopted within the range that does not impair the effects of the present invention. As such a monomer unit, a monomer derived from an alkyl (meth)acrylate having an alkyl group having 1 to 20 carbon atoms as the alkyl ester moiety is preferable in terms of further expressing the effects of the present invention. Body unit (I). Examples of the alkyl (meth)acrylate having an alkyl group having 1 to 20 carbon atoms as the alkyl ester moiety include methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic acid n-Butyl, Second-butyl (meth)acrylate, Tertiary-butyl (meth)acrylate, Isobutyl (meth)acrylate, Hexyl (meth)acrylate, 2-Ethyl (meth)acrylate Hexyl ester, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, (meth)acrylate base) isodecyl acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, etc. The polymer (A) preferably has a monomer unit (II) derived from a (meth)acrylate having an OH group and/or a COOH group in the molecule. The monomer unit (II) derived from the (meth)acrylate which has OH group and/or COOH group in a molecule|numerator in a polymer (A) may be only 1 type, and may be 2 or more types. By making the polymer (A) have a monomer unit (II) derived from a (meth)acrylate having an OH group and/or a COOH group in the molecule, it is possible to provide an adhesive that forms an adhesive layer with better stress dispersion properties. agent composition. The content rate of the monomer unit (II) derived from (meth)acrylate having an OH group and/or COOH group in the polymer (A) is preferably 0.5% by weight to 10% by weight, more preferably 1% by weight to 9% by weight, more preferably 1.5% by weight to 8% by weight, particularly preferably 1.8% by weight to 7% by weight, most preferably 2% by weight to 6% by weight. By setting the content ratio of the monomer unit (II) derived from (meth)acrylate having OH group and/or COOH group in the polymer (A) within the above range, it is possible to provide stress dispersion Adhesive composition for a more excellent adhesive layer. Examples of (meth)acrylates having an OH group in the molecule include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. , 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4 -Hydroxymethylcyclohexyl) ester, N-hydroxymethyl(meth)acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, di Ethylene glycol monovinyl ether, etc. Examples of (meth)acrylates having a COOH group in the molecule include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, Fumaric acid, crotonic acid, methacrylic acid, etc. The polymer (A) may also have monomer units (III) derived from other monomers. The monomer unit (III) derived from another monomer in a polymer (A) may be only 1 type, and may be 2 or more types. Examples of other monomers include cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, amide group-containing monomers, amide imide group-containing monomers, amine group-containing monomers, Epoxy monomers, vinyl ether monomers, N-acryl morpholine, sulfo-containing monomers, phosphoric acid-containing monomers, anhydride-containing monomers, etc. The adhesive composition of the present invention preferably contains a bifunctional or higher organic polyisocyanate-based crosslinking agent and/or an epoxy-based crosslinking agent. The bifunctional or more functional organic polyisocyanate-based crosslinking agent and/or epoxy-based crosslinking agent that may be included in the adhesive composition of the present invention may be only one type, or may be two or more types. In the adhesive composition of the present invention, the total content ratio of the above-mentioned organic polyisocyanate-based crosslinking agent with more than two functions and epoxy-based crosslinking agent is preferably 0.001 parts by weight to 100 parts by weight of the polymer (A). 0.4 parts by weight, more preferably 0.0025 parts by weight to 0.3 parts by weight, more preferably 0.005 parts by weight to 0.2 parts by weight, especially preferably 0.0075 parts by weight to 0.15 parts by weight, most preferably 0.01 parts by weight to 0.1 parts by weight. By making the total content ratio of the above-mentioned organic polyisocyanate crosslinking agent with more than two functions and epoxy-type crosslinking agent in the adhesive composition of the present invention fall within the above-mentioned range with respect to 100 parts by weight of the polymer (A), It is possible to provide an adhesive composition that forms an adhesive layer that is more excellent in stress dispersion. Examples of bifunctional or higher organic polyisocyanate crosslinking agents include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, Alicyclic isocyanate such as isophorone diisocyanate; Aromatic isocyanate such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate; Trimethylolpropane / toluene diisocyanate trimer adduct (for example, manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "CORONATE L"), trimethylolpropane/hexamethylene diisocyanate trimer adduct ( For example, manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "CORONATE HL"), isocyanurate body of hexamethylene diisocyanate (for example, manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "CORONATE HL"), HX") and other isocyanate adducts, etc. Examples of epoxy-based crosslinking agents include bisphenol A, epichlorohydrin-type epoxy-based resins, ethylidene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, and glycerin triglycidyl ether. Glyceryl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, diamino glycidyl amine, N,N,N',N'-tetraglycidyl ether Glyceryl m-xylylenediamine (for example, manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD-X"), 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (for example, Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD-C") and the like. The adhesive composition of the present invention preferably comprises a polymer having a monomer unit (I) and a monomer unit (II), and an organic polyisocyanate-based crosslinking agent and/or an epoxy-based crosslinking agent having more than two functions , the monomer unit (I) is derived from an alkyl (meth)acrylate having an alkyl group having 1 to 20 carbon atoms as an alkyl ester part, and the monomer unit (II) is derived from an OH group and/or or COOH-based (meth)acrylate; and, the molar content ratio of the NCO group in the adhesive composition is set to [NCO], the molar content ratio of the epoxy group in the adhesive composition When [epoxy group] is used, the molar content ratio of OH groups in the adhesive composition is [OH], and the molar content ratio of COOH groups in the adhesive composition is [COOH] , 0<([NCO]+[epoxy group])/([OH]+[COOH])<0.05. By making ([NCO]+[epoxy group])/([OH]+[COOH]) in the said range, the adhesive composition which forms the adhesive layer more excellent in stress dispersion property can be provided. The adhesive composition of the present invention may also contain a monomer unit derived from an alicyclic structure-containing (meth)acrylate represented by general formula (1) and have a weight average molecular weight of 1,000 or more and less than 30,000 Polymer (B). CH 2 =C(R 1 )COOR 2 ...(1) (In the general formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is a hydrocarbon group with an alicyclic structure) The polymer (B) can be only 1 type, or 2 or more types. The weight average molecular weight of the polymer (B) is preferably 1,000-30,000, more preferably 1,250-25,000, further preferably 1,500-20,000, especially preferably 1,750-15,000, most preferably 2,000-10,000. By making the weight average molecular weight of a polymer (B) into the said range, even if it increases the quantity of a crosslinking agent, the adhesive composition which forms the adhesive layer more excellent in stress dispersion property can be provided. The content ratio of the polymer (B) in the adhesive composition of the present invention is preferably 0.5 to 50 parts by weight, more preferably 1 to 45 parts by weight, based on 100 parts by weight of the polymer (A). Furthermore, it is preferably 2 parts by weight to 40 parts by weight, particularly preferably 3 parts by weight to 35 parts by weight, most preferably 4 parts by weight to 30 parts by weight. By setting the content ratio of the polymer (B) in the adhesive composition of the present invention within the above-mentioned range with respect to 100 parts by weight of the polymer (A), even if the amount of the crosslinking agent is increased, it is possible to provide stress dispersion Adhesive composition for a more excellent adhesive layer. The content ratio of the monomer unit derived from the alicyclic structure-containing (meth)acrylate represented by the general formula (1) in the polymer (B) is preferably from 40% by weight to 99.5% by weight, more preferably 42.5% by weight to 99% by weight, more preferably 45% by weight to 98.5% by weight, particularly preferably 47.5% by weight to 98% by weight, most preferably 50% by weight to 97.5% by weight. By making the content ratio of the monomer unit derived from the alicyclic structure-containing (meth)acrylate represented by the general formula (1) in the polymer (B) within the above-mentioned range, even if the amount of the crosslinking agent is increased, The amount can also provide an adhesive composition that forms an adhesive layer with better stress dispersion. Examples of (meth)acrylates having an alicyclic structure represented by the general formula (1) include: cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, methacrylic acid Dicyclopentyloxyethyl ester, dicyclopentyloxyethyl acrylate, tricyclopentyl methacrylate, tricyclopentyl acrylate, 1-adamantyl methacrylate, 1-adamantyl acrylate, methyl 2-methyl-2-adamantyl acrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, 2-ethyl-2- Adamantyl esters, etc. The polymer (B) may also have monomer units (IV) derived from other monomers. The monomer unit (IV) derived from another monomer in a polymer (B) may be only 1 type, and may be 2 or more types. Examples of other monomers that may be included in the polymer (B) include: methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second (meth)acrylate Butyl, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate , Isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, (meth) n-dodecyl acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, Ikon acid, maleic acid, fumaric acid, crotonic acid, methacrylic acid, etc. Polymer (A) and polymer (B) can be produced by any appropriate method in the range which does not impair the effect of this invention. As such a manufacturing method, solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, photopolymerization (active energy ray polymerization), etc. are mentioned, for example. Among these production methods, solution polymerization is preferred from the viewpoint of cost or productivity. The obtained polymer (A) may be a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, or the like. The obtained polymer (B) may be a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, or the like. As a method of solution polymerization, the method of dissolving a monomer component, a polymerization initiator, etc. in a solvent, heating, and superposing|polymerizing, and obtaining a polymer solution etc. are mentioned, for example. As heating temperature at the time of performing thermal polymerization in solution polymerization, 50 degreeC - 90 degreeC is mentioned, for example. As heating time in solution polymerization, 1 hour - 24 hours are mentioned, for example. As a solvent usable for solution polymerization, any appropriate solvent can be used within the range which does not impair the effect of this invention. Examples of such solvents include: aromatic hydrocarbons such as toluene, benzene, and xylene; esters such as ethyl acetate and n-butyl acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; Cyclohexane and other alicyclic hydrocarbons; organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone, etc. Only 1 type may be sufficient as a solvent, and 2 or more types may be sufficient as it. A polymerization initiator can be used for the production of the polymer (A) and the polymer (B). Such a polymerization initiator may be only 1 type, and may be 2 or more types. Examples of such polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'- Azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis(2-methylpropionamidine) disulfate, 2,2 '-Azobis(N,N'-dimethyleneisobutylamidine), 2,2'-Azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate ( Manufactured by Wako Pure Chemical Industries, Ltd., azo initiators such as VA-057); persulfates such as potassium persulfate and ammonium persulfate; bis(2-ethylhexyl) peroxycarbonate, bis(4-tertiary butyl) Cyclohexyl peroxycarbonate, di-butyl peroxycarbonate, tertiary butyl peroxyneodecanoate, tertiary hexyl peroxypivalate, tertiary butyl peroxypivalate, peroxypivalate Dilauroyl peroxide, dioctyl peroxide, 1,1,3,3-tetramethylbutyl peroxide, di(4-methylbenzoyl) peroxide, peroxide Peroxide initiators such as dibenzoyl, tert-butyl peroxyisobutyrate, 1,1-bis(tert-hexylperoxy)cyclohexane, tert-butyl hydroperoxide, hydrogen peroxide, etc. ; The combination of persulfate and sodium bisulfite, the combination of peroxide and sodium ascorbate, etc. Redox system initiators made by combining peroxide and reducing agent, etc. The amount of the polymerization initiator used can be any appropriate amount within the range that does not impair the effect of the present invention. As such a usage-amount, for example, 0.01 weight part - 5 weight part is preferable with respect to 100 weight part of monomer components. A chain transfer agent can be used in the production of the polymer (A) and the polymer (B). Such a chain transfer agent may be only 1 type, and may be 2 or more types. As such a chain transfer agent, for example, lauryl mercaptan, glycidyl mercaptan, thioglycolic acid, 2-mercaptoethanol, thioglycolic acid, methyl thioglycolate, 2-ethyl thioglycolate Hexyl ester, 2,3-dimercapto-1-propanol, etc. The chain transfer agent can be used in any appropriate amount within the range that does not impair the effect of the present invention. As such a usage-amount, for example, 0.01 weight part - 5 weight part is preferable with respect to 100 weight part of monomer components. In the production of the polymer (A) and the polymer (B), other arbitrary appropriate additives that can usually be used in a polymerization reaction can be used. The adhesive composition of the present invention may also contain a crosslinking catalyst. As a crosslinking catalyst, any appropriate crosslinking catalyst can be used within the range which does not impair the effect of this invention. Examples of such crosslinking catalysts include metal-based crosslinking catalysts such as tetra-n-butyl titanate, tetraisopropyl titanate, iron acetylacetonate, butyltin oxide, and dioctyltin dilaurate. (especially tin-based cross-linking catalyst), etc. The crosslinking catalyst may be only 1 type, and may be 2 or more types. The amount of the crosslinking catalyst can be used in any appropriate amount within the range that does not impair the effects of the present invention. Such an amount used is preferably, for example, 0.001 to 0.05 parts by weight with respect to 100 parts by weight of monomer components. The adhesive composition of the present invention may contain any other appropriate additives within the range that does not impair the effects of the present invention. Examples of such other additives include: silane coupling agents, crosslinking retarders, emulsifiers, colorants, powders such as pigments, dyes, surfactants, plasticizers, adhesion imparting agents, surface lubricants, fluids, etc. Leveling agent, softener, antioxidant, anti-aging agent, light stabilizer, ultraviolet absorber, polymerization inhibitor, inorganic filler, organic filler, metal powder, granular, foil, etc. Such other additives may be only one type, or may be two or more types. ≪≪B. Adhesive member≫≫ The adhesive member of the present invention has an adhesive layer formed from the adhesive composition of the present invention. The adhesive member of the present invention may only include an adhesive layer, or may include an adhesive layer and other members. In the adhesive member of the present invention, when the adhesive layer is exposed as the outermost layer, any appropriate release film (release sheet) may be provided on the exposed surface side. A separator (peeling sheet) may also serve as the base material described below. The adhesive layer is formed from the adhesive composition of the present invention. For example, the adhesive composition of the present invention is coated on any appropriate substrate, and dried as necessary to form an adhesive layer on the substrate. Then, when the substrate is peeled off, the adhesive member of the present invention including only the adhesive layer can be obtained. Also, for example, the adhesive composition of the present invention is coated on any suitable substrate, dried if necessary to form an adhesive layer on the substrate, and the substrate is left as it is, thereby obtaining a composite material comprising the adhesive layer and the substrate. Substrate adhesive member. Also, for example, the adhesive composition of the present invention is coated on any appropriate substrate, dried as necessary to form an adhesive layer on the substrate, and the adhesive layer obtained by peeling off the substrate is mounted on another member. (such as other substrates), thereby obtaining an adhesive member comprising an adhesive layer and a substrate. Also, for example, the adhesive composition of the present invention is coated on any appropriate substrate, dried as necessary to form an adhesive layer on the substrate, and the adhesive layer formed on the substrate is transferred to other members (such as other substrates), thereby obtaining an adhesive member comprising an adhesive layer and a substrate. Examples of coating methods for the adhesive composition include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, extrusion coating using a die coater, etc. . The substrate may be formed of a single layer or may include multiple layers. The substrate can be extended. The thickness of the substrate can be set to any appropriate thickness according to the application. From the viewpoint of fully expressing the effect of the present invention, the thickness of the substrate is preferably 4 μm to 500 μm, more preferably 10 μm to 400 μm, further preferably 15 μm to 350 μm, and especially preferably 20 μm. μm~300μm. As the material of the base material, any appropriate material can be adopted according to the application. As such a material, plastic, paper, a metal film, a nonwoven fabric, etc. are mentioned, for example. Among such materials, plastic is preferred in terms of further exhibiting the effects of the present invention. Examples of the plastics include polyester resins, polyolefin resins, polyamide resins, and polyimide resins. As a polyester resin, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc. are mentioned, for example. As a polyolefin resin, the homopolymer of an olefin monomer, the copolymer of an olefin monomer, etc. are mentioned, for example. Specific examples of polyolefin-based resins include: homopolypropylene; block-, random-, and graft-based propylene-based copolymers containing ethylene as a copolymer component; reactive TPO; low-density, Ethylene polymers of high density, linear low density, ultra-low density, etc.; ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid Ethylene-based copolymers such as butyl ester copolymers, ethylene-methacrylic acid copolymers, and ethylene-methyl methacrylate copolymers, etc. In terms of further expressing the effects of the present invention, among these plastics, polyester-based resins are preferred, and polyethylene terephthalate is more preferred. The base material may optionally contain any appropriate additives. Examples of additives that may be contained in the substrate include antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fillers, pigments, and the like. The kind, number, and amount of additives that can be contained in the base material can be appropriately set according to the purpose. Fig. 1 is a schematic sectional view of an adhesive member according to an embodiment of the present invention. In FIG. 1 , an adhesive member 100 of the present invention includes a substrate 10 , an adhesive layer 20 and a separator 30 . ≪≪C. Optical member, electronic member≫≫ The adhesive member of the present invention has an adhesive layer excellent in stress dispersibility. Therefore, it can be used suitably as a protective material for protecting an optical member or an electronic member from external impact, etc. That is, the optical member of this invention is equipped with the adhesive member of this invention. Moreover, the electronic member of this invention is equipped with the adhesive member of this invention. EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples. In addition, the test and evaluation method in an Example etc. are as follows. In addition, when described as "part", it means "weight part" unless otherwise specified, and when described as "%", unless otherwise specified, it means "weight%". <Measurement of weight average molecular weight> The weight average molecular weight (Mw) of a polymer was measured using the GPC apparatus (HLC-8220GPC) manufactured by TOSOH CORPORATION. In addition, weight average molecular weight (Mw) was calculated|required using the polystyrene conversion value. The measurement conditions are as follows. Sample concentration: 0.2% by weight (THF solution) Sample injection volume: 10 μl Eluent THF Flow rate: 0.6 ml/min Measurement temperature: 40°C Sample column: TSKguardcolumn SuperHZ-H (1 piece) + TSKgel Super HZM-H (2 pieces ) Reference column: TSKgel SuperH-RC (1 piece) Detector: Differential refractometer (RI) <Preparation of adhesive sheet> Using a grooved roller, apply the obtained adhesive composition so that the thickness after drying becomes 50 μm Clothed on the peeled surface of a polyester film with a thickness of 38 μm (trade name: MRF, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) that has been peeled with silicone on one side, dried at 130°C for 3 minutes. Conditions for curing and drying. In this way, an adhesive layer is produced on the base material. Next, a polyester film with a thickness of 38 μm (trade name: MRF, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) that has been peeled off with silicone on one side is placed so that the peeled side of the film becomes the adhesive layer side. Coated on the surface of the adhesive layer. In this way, an adhesive sheet was produced. <Measurement of glass transition temperature (Tg), storage modulus, loss elastic modulus, and tan δ (loss tangent)> Using a dynamic viscoelasticity measuring device (manufactured by Rheometrics, ARES), it was determined by the following method. Only the adhesive layer was taken out from the obtained adhesive sheet, laminated to form a thickness of about 2 mm, and punched into
Figure 02_image001
7.9 mm, make cylindrical particles, and set it as a sample for measurement. The above-mentioned samples were fixed in
Figure 02_image001
For the fixture of 7.9 mm parallel plates, use the above-mentioned dynamic viscoelasticity measuring device to measure the temperature dependence of storage modulus G' and loss elastic modulus G'', and calculate tanδ in the form of tanδ=G''/G'. In addition, let the temperature at which the obtained tanδ curve becomes a maximum be glass transition temperature (Tg) (degreeC). The measurement conditions are as follows. Measurement: shear mode Temperature range: -70°C to 150°C Heating rate: 5°C/min Frequency: 1 Hz [Manufacturing example 1]: (Meth)acrylic polymer (1) equipped with stirring blade, thermometer, nitrogen gas Add 2-ethylhexyl acrylate (manufactured by Nippon Shokubai Co., Ltd.): 100 parts by weight, 2-hydroxyethyl acrylate (manufactured by Toagosei Co., Ltd.): 4 parts by weight, As a polymerization initiator, 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.): 0.2 parts by weight, ethyl acetate: 156 parts by weight, while stirring slowly, introducing nitrogen into the flask, The liquid temperature was maintained at around 65° C., and the polymerization reaction was carried out for 6 hours to prepare a solution (40% by weight) of (meth)acrylic polymer (1) with a weight average molecular weight of 550,000. [Production Example 2]: (Meth)acrylic polymer (2) Add 2-ethylhexyl acrylate (Nippon Shokubai Co., Ltd. .manufactured): 100 parts by weight, 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.): 10 parts by weight, acrylic acid (manufactured by Toagosei Co.): 0.02 parts by weight, 2,2'- Azobisisobutyronitrile (manufactured by Wako Pure Chemical Industry Co., Ltd.): 0.2 parts by weight, ethyl acetate: 156 parts by weight, while slowly stirring, nitrogen gas was introduced, and the liquid temperature in the flask was kept at around 65°C. After 1 hour of polymerization reaction, a solution (40% by weight) of (meth)acrylic polymer (2) with a weight average molecular weight of 540,000 was prepared. [Production Example 3]: (meth)acrylic polymer (3) Add butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a condenser: 99 parts by weight, 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.): 1 part by weight, 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator: 1 Parts by weight, ethyl acetate: 156 parts by weight, while slowly stirring, introduce nitrogen gas, keep the liquid temperature in the flask at around 60°C, and carry out polymerization reaction for 7 hours to prepare (meth)acrylic acid with a weight average molecular weight of 1.6 million It is a solution (39% by weight) of polymer (3). [Production Example 4]: (meth)acrylic polymer (4) Add butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a condenser: 92 parts by weight, N-acrylmorpholine (manufactured by Kohjin co., Ltd.): 5 parts by weight, acrylic acid (manufactured by Toagosei Co.): 2.9 parts by weight, 2,2'-azo as a polymerization initiator Diisobutyronitrile (manufactured by Wako Pure Chemical Industry Co., Ltd.): 0.1 parts by weight, ethyl acetate: 200 parts by weight, while slowly stirring, nitrogen gas was introduced, and the liquid temperature in the flask was kept at around 55°C, and polymerization was carried out for 8 hours. Reaction was carried out to prepare a solution (33% by weight) of a (meth)acrylic polymer (4) having a weight average molecular weight of 1.8 million. [Manufacturing Example 5]: (meth)acrylic polymer (5) Add butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a condenser: 95 parts by weight, acrylic acid (manufactured by Toagosei Co.): 5 parts by weight, 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator: 0.2 parts by weight, ethyl acetate: 156 parts by weight, while slowly stirring, introduce nitrogen gas, keep the liquid temperature in the flask at around 63°C, and carry out polymerization reaction for 10 hours to prepare (meth)acrylic polymer (5) with a weight average molecular weight of 700,000 solution (40% by weight). [Manufacturing Example 6]: (meth)acrylic polymer (6) containing alicyclic structure Transition temperature: 66°C]: 95 parts by weight, acrylic acid: 5 parts by weight, 2-mercaptoethanol as a chain transfer agent: 3 parts by weight, 2,2'-azobisisobutyronitrile as a polymerization initiator: 0.2 Parts by weight, and toluene as a polymerization solvent: 103.2 parts by weight were put into a separable flask, and stirred for 1 hour while introducing nitrogen gas. In this way, after the oxygen in the polymerization system was removed, the temperature was raised to 70°C, and it was reacted for 3 hours, and then reacted at 75°C for 2 hours to obtain a (meth)acrylic polymer (6) with a weight average molecular weight of 4000. solution (50% by weight). [Manufacturing Example 6]: (Meth)acrylic polymer (7) containing alicyclic structure Toluene was put into a four-necked flask equipped with stirring blades, a thermometer, a nitrogen gas introduction tube, a condenser, and a dropping funnel: 100 wt. Parts, dicyclopentanyl methacrylate (DCPMA) (trade name: FA-513M, manufactured by Hitachi Chemical Industry Co., Ltd.): 60 parts by weight, methyl methacrylate (MMA): 40 parts by weight, and as a chain transfer agent Methyl thioglycolate: 3.5 parts by weight. Then, after stirring for 1 hour at 70°C under a nitrogen atmosphere, 2,2'-azobisisobutyronitrile: 0.2 parts by weight was added as a polymerization initiator, and it was reacted at 70°C for 2 hours, followed by 80 After reacting at °C for 4 hours, it reacted at 90 °C for 1 hour to obtain a solution (51% by weight) of a (meth)acrylic polymer (7) with a weight average molecular weight of 4000. [Example 1] With respect to the solution of the (meth)acrylic polymer (1), the total solid content was 25 parts by weight relative to 100 parts by weight of the solid content of the solution of the (meth)acrylic polymer (1). % by weight was diluted with ethyl acetate and stirred with a disperser to obtain an adhesive composition (1) containing an acrylic resin. The results are shown in Table 1. [Example 2] To the solution of the (meth)acrylic polymer (1), add: 100 parts by weight of the solid content relative to the solution of the (meth)acrylic polymer (1), in terms of solid content 0.01 parts by weight of CORONATE L (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a crosslinking agent, and 0.005 parts by weight of iron acetylacetonate (Nippon Chemical Industry Co., Ltd.) as a crosslinking catalyst in terms of solid content company), and diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred with a disperser to obtain an adhesive composition (2) containing an acrylic resin. The results are shown in Table 1. [Example 3] To the solution of the (meth)acrylic polymer (1), add: 100 parts by weight of the solid content relative to the solution of the (meth)acrylic polymer (1), in terms of solid content 0.1 part by weight of CORONATE L (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a crosslinking agent, and 0.005 parts by weight of iron acetylacetonate as a crosslinking catalyst (Nippon Chemical Industry Co., Ltd. company), was diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred with a disperser to obtain an adhesive composition (3) containing an acrylic resin. The results are shown in Table 1. [Example 4] To the solution of the (meth)acrylic polymer (1), add: 100 parts by weight of the solid content relative to the solution of the (meth)acrylic polymer (1), in terms of solid content 0.05 parts by weight of CORONATE L (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a crosslinking agent, and 0.005 parts by weight of iron acetylacetonate (Nippon Chemical Industry Co., Ltd.) as a crosslinking catalyst in terms of solid content manufactured by the company) and a solution of 5 parts by weight of (meth)acrylic polymer (6) in terms of solid content, diluted with ethyl acetate so that the total solid content became 25% by weight, and dispersed by stirring with a machine to obtain an adhesive composition (4) comprising an acrylic resin. The results are shown in Table 1. [Example 5] To the solution of the (meth)acrylic polymer (1), add: 100 parts by weight of the solid content relative to the solution of the (meth)acrylic polymer (1), in terms of solid content 0.1 part by weight of CORONATE L (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a crosslinking agent, and 0.005 parts by weight of iron acetylacetonate as a crosslinking catalyst (Nippon Chemical Industry Co., Ltd. manufactured by the company) and a solution of 5 parts by weight of (meth)acrylic polymer (6) in terms of solid content, diluted with ethyl acetate so that the total solid content became 25% by weight, and dispersed by stirring with a machine to obtain an adhesive composition (5) comprising an acrylic resin. The results are shown in Table 1. [Example 6] To the solution of the (meth)acrylic polymer (1), add: 100 parts by weight of the solid content relative to the solution of the (meth)acrylic polymer (1), in terms of solid content 0.3 parts by weight of CORONATE L (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a crosslinking agent, 0.005 parts by weight of iron acetylacetonate as a crosslinking catalyst (Nippon Chemical Industry Co., Ltd. manufactured by the company) and a solution of 5 parts by weight of (meth)acrylic polymer (6) in terms of solid content, diluted with ethyl acetate so that the total solid content became 25% by weight, and dispersed by stirring with a machine to obtain an adhesive composition (6) comprising an acrylic resin. The results are shown in Table 1. [Example 7] To the solution of the (meth)acrylic polymer (1), add: 100 parts by weight of the solid content relative to the solution of the (meth)acrylic polymer (1), in terms of solid content 0.1 part by weight of CORONATE L (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a crosslinking agent, and 0.005 parts by weight of iron acetylacetonate as a crosslinking catalyst (Nippon Chemical Industry Co., Ltd. manufactured by the company) and a solution of 5 parts by weight of (meth)acrylic polymer (7) in terms of solid content, diluted with ethyl acetate so that the total solid content became 25% by weight, and dispersed by stirring with a machine to obtain an adhesive composition (7) comprising an acrylic resin. The results are shown in Table 1. [Example 8] To the solution of the (meth)acrylic polymer (1), add: 100 parts by weight of the solid content relative to the solution of the (meth)acrylic polymer (1), in terms of solid content 0.3 parts by weight of CORONATE L (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a crosslinking agent, 0.005 parts by weight of iron acetylacetonate as a crosslinking catalyst (Nippon Chemical Industry Co., Ltd. manufactured by the company) and a solution of 5 parts by weight of (meth)acrylic polymer (7) in terms of solid content, diluted with ethyl acetate so that the total solid content became 25% by weight, and dispersed by stirring with a machine to obtain an adhesive composition (8) comprising an acrylic resin. The results are shown in Table 1. [Example 9] For the solution of the (meth)acrylic polymer (2), the total solid content was 25 parts by weight relative to 100 parts by weight of the solid content of the solution of the (meth)acrylic polymer (2). % by weight was diluted with ethyl acetate and stirred with a disperser to obtain an adhesive composition (9) containing an acrylic resin. The results are shown in Table 1. [Example 10] To the solution of the (meth)acrylic polymer (2), add: 100 parts by weight of the solid content relative to the solution of the (meth)acrylic polymer (2), in terms of solid content 0.1 parts by weight of CORONATE L (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a crosslinking agent, 0.05 parts by weight of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) in terms of solid content Component conversion is 0.005 parts by weight of iron acetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a crosslinking catalyst, and diluted with ethyl acetate so that the total solid content becomes 25% by weight, and stirred by a disperser, An adhesive composition (10) containing an acrylic resin was obtained. The results are shown in Table 1. [Example 11] To the solution of the (meth)acrylic polymer (3), add: 100 parts by weight of the solid content relative to the solution of the (meth)acrylic polymer (3), in terms of solid content 0.02 parts by weight of CORONATE L (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a crosslinking agent, and 0.005 parts by weight of iron acetylacetonate (Nippon Chemical Industry Co., Ltd.) as a crosslinking catalyst in terms of solid content company), and diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred with a disperser to obtain an adhesive composition (11) containing an acrylic resin. The results are shown in Table 1. [Example 12] To the solution of the (meth)acrylic polymer (4), add: 100 parts by weight of the solid content relative to the solution of the (meth)acrylic polymer (4), in terms of solid content 0.3 parts by weight of CORONATE L (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a crosslinking agent, 0.005 parts by weight of iron acetylacetonate as a crosslinking catalyst (Nippon Chemical Industry Co., Ltd. company), and diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred with a disperser to obtain an adhesive composition (12) containing an acrylic resin. The results are shown in Table 1. [Example 13] To the solution of the (meth)acrylic polymer (5), add: 100 parts by weight of the solid content relative to the solution of the (meth)acrylic polymer (5), in terms of solid content 0.075 parts by weight of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a crosslinking agent, and 0.005 parts by weight of iron acetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a crosslinking catalyst in terms of solid content , and diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred with a disperser to obtain an adhesive composition (13) containing an acrylic resin. The results are shown in Table 1. [Example 14] To the solution of the (meth)acrylic polymer (5), add: 100 parts by weight of the solid content relative to the solution of the (meth)acrylic polymer (5), in terms of solid content 0.075 parts by weight of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a crosslinking agent, 0.005 parts by weight of iron acetylacetonate (Nippon Chemical Industry Co., Ltd.) as a crosslinking catalyst in terms of solid content ) and a solution of 20 parts by weight of a (meth)acrylic polymer (6) in terms of solid content, diluted with ethyl acetate so that the total solid content becomes 25% by weight, and used in a disperser Stir to obtain an adhesive composition (14) containing an acrylic resin. The results are shown in Table 1. [Comparative Example 1] To the solution of the (meth)acrylic polymer (1), add: 100 parts by weight of the solid content relative to the solution of the (meth)acrylic polymer (1), in terms of solid content 0.5 parts by weight of CORONATE L (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a crosslinking agent, and 0.005 parts by weight of iron acetylacetonate as a crosslinking catalyst (Nippon Chemical Industry Co., Ltd. company), and diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred with a disperser to obtain an adhesive composition (C1) containing an acrylic resin. The results are shown in Table 1. [Comparative Example 2] To the solution of the (meth)acrylic polymer (2), add: 100 parts by weight of the solid content relative to the solution of the (meth)acrylic polymer (2), in terms of solid content 0.45 parts by weight of CORONATE L (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a crosslinking agent, 0.3 parts by weight of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) in terms of solid content Component conversion is 0.005 parts by weight of iron acetylacetonate (manufactured by Nippon Chemical Industry Co., Ltd.) as a crosslinking catalyst, and diluted with ethyl acetate so that the total solid content becomes 25% by weight, and stirred by a disperser, An adhesive composition (C2) containing an acrylic resin was obtained. The results are shown in Table 1. [Table 1]
Figure 106102834-A0304-0001
[Example 15] One side of the adhesive sheet formed from the polyester film obtained from the adhesive composition (1) obtained in Example 1 was peeled off, and attached to a polarizing plate as an optical member (manufactured by Nitto Denko Co., Ltd., trade name "TEG1465DUHC"), an optical component with an adhesive sheet attached. [Example 16] One side of the adhesive sheet formed from the polyester film obtained from the adhesive composition (2) obtained in Example 2 was peeled off, and attached to a polarizing plate as an optical member (manufactured by Nitto Denko Co., Ltd., trade name "TEG1465DUHC"), an optical component with an adhesive sheet attached. [Example 17] One side of the adhesive sheet formed from the polyester film obtained from the adhesive composition (4) obtained in Example 4 was peeled off, and attached to a polarizing plate as an optical member (manufactured by Nitto Denko Co., Ltd., trade name "TEG1465DUHC"), an optical component with an adhesive sheet attached. [Example 18] One side of the adhesive sheet formed from the polyester film obtained from the adhesive composition (7) obtained in Example 7 was peeled off, and attached to a polarizing plate as an optical member (manufactured by Nitto Denko Co., Ltd., trade name "TEG1465DUHC"), an optical component with an adhesive sheet attached. [Example 19] One side of the adhesive sheet formed from the polyester film obtained from the adhesive composition (9) obtained in Example 9 was peeled off, and attached to a polarizing plate as an optical member (manufactured by Nitto Denko Co., Ltd., trade name "TEG1465DUHC"), an optical component with an adhesive sheet attached. [Example 20] One side of the adhesive sheet formed from the polyester film obtained from the adhesive composition (10) obtained in Example 10 was peeled off, and attached to a polarizing plate as an optical member (manufactured by Nitto Denko Co., Ltd., trade name "TEG1465DUHC"), an optical component with an adhesive sheet attached. [Example 21] One side of the adhesive sheet made of the polyester film obtained from the adhesive composition (11) obtained in Example 11 was peeled off, and attached to a polarizing plate as an optical member (manufactured by Nitto Denko Co., Ltd., trade name "TEG1465DUHC"), an optical component with an adhesive sheet attached. [Example 22] One side of the adhesive sheet formed from the polyester film obtained from the adhesive composition (12) obtained in Example 12 was peeled off, and attached to a polarizing plate as an optical member (manufactured by Nitto Denko Co., Ltd., trade name "TEG1465DUHC"), an optical component with an adhesive sheet attached. [Example 23] One side of the adhesive sheet formed from the polyester film obtained from the adhesive composition (13) obtained in Example 13 was peeled off, and attached to a polarizing plate as an optical member (manufactured by Nitto Denko Co., Ltd., trade name "TEG1465DUHC"), an optical component with an adhesive sheet attached. [Example 24] One side of the adhesive sheet formed from the polyester film obtained from the adhesive composition (14) obtained in Example 14 was peeled off, and attached to a polarizing plate as an optical member (manufactured by Nitto Denko Co., Ltd., trade name "TEG1465DUHC"), an optical component with an adhesive sheet attached. [Example 25] One side of the adhesive sheet formed from the polyester film obtained from the adhesive composition (1) obtained in Example 1 was peeled off, and attached to a conductive film (manufactured by Nitto Denko Co., Ltd., commercial product) as an electronic component. Named "ELECRYSTA V270L-TFMP"), an electronic component with an adhesive sheet was obtained. [Example 26] One side of the adhesive sheet formed from the polyester film obtained from the adhesive composition (2) obtained in Example 2 was peeled off, and attached to a conductive film (manufactured by Nitto Denko Co., Ltd., commercial product) as an electronic component. Named "ELECRYSTA V270L-TFMP"), an electronic component with an adhesive sheet was obtained. [Example 27] One side of the adhesive sheet formed from the polyester film obtained from the adhesive composition (4) obtained in Example 4 was peeled off, and attached to a conductive film (manufactured by Nitto Denko Co., Ltd., commercial product) as an electronic component. Named "ELECRYSTA V270L-TFMP"), an electronic component with an adhesive sheet was obtained. [Example 28] One side of the adhesive sheet formed from the polyester film obtained from the adhesive composition (7) obtained in Example 7 was peeled off, and attached to a conductive film (manufactured by Nitto Denko Co., Ltd., commercial product) as an electronic component. Named "ELECRYSTA V270L-TFMP"), an electronic component with an adhesive sheet was obtained. [Example 29] One side of the adhesive sheet formed from the polyester film obtained from the adhesive composition (9) obtained in Example 9 was peeled off, and attached to a conductive film (manufactured by Nitto Denko Co., Ltd., commercial product) as an electronic component. Named "ELECRYSTA V270L-TFMP"), an electronic component with an adhesive sheet was obtained. [Example 30] One side of the adhesive sheet formed from the polyester film obtained from the adhesive composition (10) obtained in Example 10 was peeled off, and attached to a conductive film (manufactured by Nitto Denko Co., Ltd., commercial product) as an electronic component. Named "ELECRYSTA V270L-TFMP"), an electronic component with an adhesive sheet was obtained. [Example 31] One side of the adhesive sheet formed of the polyester film obtained from the adhesive composition (11) obtained in Example 11 was peeled off, and attached to a conductive film (manufactured by Nitto Denko Co., Ltd., commercial product) as an electronic component. Named "ELECRYSTA V270L-TFMP"), an electronic component with an adhesive sheet was obtained. [Example 32] One side of the adhesive sheet formed from the polyester film obtained from the adhesive composition (12) obtained in Example 12 was peeled off, and attached to a conductive film (manufactured by Nitto Denko Co., Ltd., commercial product) as an electronic component. Named "ELECRYSTA V270L-TFMP"), an electronic component with an adhesive sheet was obtained. [Example 33] One side of the adhesive sheet formed of the polyester film obtained from the adhesive composition (13) obtained in Example 13 was peeled off, and attached to a conductive film (manufactured by Nitto Denko Co., Ltd., commercial product) as an electronic component. Named "ELECRYSTA V270L-TFMP"), an electronic component with an adhesive sheet was obtained. [Example 34] One side of the adhesive sheet formed of the polyester film from the adhesive composition (14) obtained in Example 14 was peeled off, and attached to a conductive film (manufactured by Nitto Denko Co., Ltd., commercial product) as an electronic component. Named "ELECRYSTA V270L-TFMP"), an electronic component with an adhesive sheet was obtained. [Industrial Applicability] An adhesive member having an adhesive layer formed from the adhesive composition of the present invention can be suitably used as a protective material for protecting an optical member or an electronic member from external impact or the like, for example.

10‧‧‧基材 20‧‧‧黏著劑層 30‧‧‧隔離膜 100‧‧‧黏著構件10‧‧‧Substrate 20‧‧‧adhesive layer 30‧‧‧Isolation film 100‧‧‧adhesive components

圖1係本發明之一實施形態之黏著構件之概略剖視圖。Fig. 1 is a schematic sectional view of an adhesive member according to an embodiment of the present invention.

10‧‧‧基材 10‧‧‧Substrate

20‧‧‧黏著劑層 20‧‧‧adhesive layer

30‧‧‧隔離膜 30‧‧‧Isolation film

100‧‧‧黏著構件 100‧‧‧adhesive components

Claims (5)

一種黏著劑組合物,其係包含具有源自(甲基)丙烯酸烷基酯之單體單元之聚合物(A)者,該黏著劑組合物中之該聚合物(A)之含有比率為95重量%~100重量%,該源自(甲基)丙烯酸烷基酯之單體單元為源自具有碳數1~20之烷基作為烷基酯部分之(甲基)丙烯酸烷基酯的單體單元(I),該聚合物(A)具有源自分子內具有OH基及/或COOH基之(甲基)丙烯酸酯的單體單元(II),該黏著劑組合物包含2官能以上之有機多異氰酸酯系交聯劑及/或環氧系交聯劑,由該黏著劑組合物形成之黏著劑層於-40℃~150℃之整個溫度區域中之損耗正切tanδ為0.10以上,且該黏著劑組合物係包含具有單體單元(I)與單體單元(II)之聚合物、以及2官能以上之有機多異氰酸酯系交聯劑及/或環氧系交聯劑者,該單體單元(I)源自具有碳數1~20之烷基作為烷基酯部分之(甲基)丙烯酸烷基酯,該單體單元(II)源自分子內具有OH基及/或COOH基之(甲基)丙烯酸酯;並且,將該黏著劑組合物中之NCO基之莫耳含有比率設為[NCO]、將該黏著劑組合物中之環氧基之莫耳含有比率設為[環氧基]、將該黏著劑組合物中之OH基之莫耳含有比率設為[OH]、將該黏著劑組合物中之COOH基之莫耳含有比率設為[COOH]時,0<([NCO]+[環氧基])/([OH]+[COOH])<0.05。 An adhesive composition comprising a polymer (A) having a monomer unit derived from an alkyl (meth)acrylate, the content ratio of the polymer (A) in the adhesive composition being 95% % by weight to 100% by weight, the monomer unit derived from an alkyl (meth)acrylate is a unit derived from an alkyl (meth)acrylate having an alkyl group having 1 to 20 carbons as the alkyl ester part A monomer unit (I), the polymer (A) has a monomer unit (II) derived from a (meth)acrylate having an OH group and/or a COOH group in the molecule, and the adhesive composition includes two or more functional Organic polyisocyanate-based crosslinking agent and/or epoxy-based crosslinking agent, the loss tangent tanδ of the adhesive layer formed from the adhesive composition in the entire temperature range from -40°C to 150°C is 0.10 or more, and the The adhesive composition is composed of a polymer having a monomer unit (I) and a monomer unit (II), and an organic polyisocyanate-based crosslinking agent and/or an epoxy-based crosslinking agent with more than two functions. The unit (I) is derived from an alkyl (meth)acrylate having an alkyl group having 1 to 20 carbons as the alkyl ester part, and the monomer unit (II) is derived from an alkyl group having an OH group and/or a COOH group in the molecule. (meth)acrylate; and, the molar content ratio of the NCO group in the adhesive composition is set to [NCO], and the molar content ratio of the epoxy group in the adhesive composition is set to [ring oxygen group], when the molar content ratio of the OH group in the adhesive composition is [OH], and the molar content ratio of the COOH group in the adhesive composition is [COOH], 0<( [NCO]+[epoxy group])/([OH]+[COOH])<0.05. 如請求項1之黏著劑組合物,其包含具有源自通式(1)所表示之含脂環式結構之(甲基)丙烯酸酯之單體單元、並且重量平均分子量為1000以上、未達30000的聚合物(B),CH2=C(R1)COOR2...(1)(通式(1)中,R1為氫原子或甲基,R2為具有脂環式結構之烴基)。 The adhesive composition according to claim 1, which comprises monomer units derived from (meth)acrylic acid esters with an alicyclic structure represented by general formula (1), and has a weight average molecular weight of 1000 or more and less than 1000. 30000 polymer (B), CH 2 =C(R 1 )COOR 2 ... (1) (in the general formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is an alicyclic structure Hydrocarbyl). 一種黏著構件,其具有由如請求項1或2之黏著劑組合物形成之黏著劑層。 An adhesive member having an adhesive layer formed from the adhesive composition according to claim 1 or 2. 一種光學構件,其具備如請求項3之黏著構件。 An optical member comprising the adhesive member according to claim 3. 一種電子構件,其具備如請求項3之黏著構件。 An electronic component comprising the adhesive component according to claim 3.
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