TW201821574A - Pressure-sensitive adhesive composition - Google Patents

Pressure-sensitive adhesive composition Download PDF

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TW201821574A
TW201821574A TW106132622A TW106132622A TW201821574A TW 201821574 A TW201821574 A TW 201821574A TW 106132622 A TW106132622 A TW 106132622A TW 106132622 A TW106132622 A TW 106132622A TW 201821574 A TW201821574 A TW 201821574A
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Taiwan
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meth
acrylate
adhesive layer
mass
adhesive composition
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TW106132622A
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Chinese (zh)
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TWI781113B (en
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淺津悠司
小橋亜依
薛明軒
竹田俊之
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日商住友化學股份有限公司
日商日本合成化學工業股份有限公司
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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
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • 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
    • 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
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Polarising Elements (AREA)

Abstract

A pressure-sensitive adhesive composition comprises a (meth)acrylic resin (A), a crosslinking agent (B) and a silane compound (C), wherein the (meth)acrylic resin (A) contains a structural unit derived from an acetoacetyl group-containing (meth)acrylate (a1) and a structural unit derived from a hydroxy group-containing (meth)acrylate (a2), and the mass ratio (a2)/(a1) of the structural unit is 0.5 to 5.

Description

黏著劑組成物  Adhesive composition  

本專利申請係根據日本專利申請第2016-186152號(申請日：2016年9月23日)以巴黎公約主張優先權，並於本說明書中參照該日本專利申請並於本說明書中援用其全部內容。 The present patent application claims priority from the Paris Convention in accordance with Japanese Patent Application No. 2016-186152 (Application Date: September 23, 2016), the entire disclosure of which is hereby incorporated by .

本發明係關於作為可利用於液晶顯示裝置等之光學構件為有用之黏著劑組成物、包含該黏著劑組成物之黏著劑層、含有該黏著劑層之附黏著劑層之光學膜及光學積層體、以及黏著劑組成物用(甲基)丙烯酸系樹脂。 The present invention relates to an adhesive composition which is useful as an optical member which can be used for a liquid crystal display device or the like, an adhesive layer containing the adhesive composition, an optical film and an optical laminate including an adhesive layer of the adhesive layer. A (meth)acrylic resin is used for the body and the adhesive composition.

以於偏光片單面或兩面積層貼合透明樹脂膜所成之偏光板為代表之光學膜，係廣泛使用作為構成液晶顯示裝置、有機EL顯示裝置等圖像顯示裝置之光學構件。如偏光板之光學膜常經由黏著劑層貼合於其他構件(例如液晶顯示裝置中的液晶單元等)而使用(參照專利文獻1)。因此，作為光學膜者，已知有於其一面預先設置黏著劑層的附黏著劑層之光學膜。 An optical film represented by a polarizing plate in which a transparent resin film is bonded to one side of a polarizing plate or a two-layered layer is widely used as an optical member constituting an image display device such as a liquid crystal display device or an organic EL display device. The optical film of the polarizing plate is often used by being bonded to another member (for example, a liquid crystal cell in a liquid crystal display device) via an adhesive layer (see Patent Document 1). Therefore, as an optical film, an optical film having an adhesive layer on which an adhesive layer is provided in advance is known.

[先前技術文獻]  [Previous Technical Literature]   [專利文獻]  [Patent Literature]  

專利文獻1：日本特開2010-229321號公報。 Patent Document 1: Japanese Laid-Open Patent Publication No. 2010-229321.

近年來，液晶顯示裝置、有機EL顯示裝置等圖像顯示裝置，係期以智慧型手機、平板型終端為代表之可攜式機器用途、和以汽車導航系統為代表之車載用機器用途發展。在如此用途中，可能暴露於與以往室內用TV用途相比為較嚴苛的環境，故提高裝置耐久性係成為課題。 In recent years, image display devices such as liquid crystal display devices and organic EL display devices have been developed for use in portable devices such as smart phones and tablet terminals, and in-vehicle use applications such as car navigation systems. In such an application, it may be exposed to a harsh environment as compared with the conventional indoor TV use. Therefore, it is a problem to improve the durability of the device.

對於構成圖像顯示裝置等之附黏著劑層之光學膜，亦同樣地要求耐久性。亦即，組裝於圖像顯示裝置等之黏著劑層會有放置於高溫或高溫高濕環境下、或放置於重複高溫與低溫之環境下之情形，而對於附黏著劑層之光學膜係要求在該等環境下亦可抑制黏著劑層與其所貼合的光學構件之界面處的浮翹和剝離、黏著劑層之發泡等不良，而且，亦要求光學特性不會劣化。特別是光學膜為偏光板時，在高溫環境下會有強收縮應力，故相較於一般光學膜，黏著劑層更要求高耐久性能。因提高上述圖像顯示裝置之耐久性的要求提升，故近來黏著劑層所要求之耐久性非常嚴苛。 Durability is also required for an optical film constituting an adhesive layer such as an image display device. That is, the adhesive layer assembled in an image display device or the like may be placed in a high-temperature or high-temperature high-humidity environment or placed in an environment of repeated high-temperature and low-temperature conditions, and the optical film system for the adhesive layer is required. In such an environment, defects such as buoyancy and peeling at the interface between the adhesive layer and the optical member to which it is bonded, foaming of the adhesive layer, and the like are also suppressed, and optical characteristics are not required to be deteriorated. In particular, when the optical film is a polarizing plate, there is a strong shrinkage stress in a high-temperature environment, so that the adhesive layer is required to have higher durability than the general optical film. Since the demand for improving the durability of the above image display device is increased, the durability required for the adhesive layer is very severe recently.

因此，本發明之目的係提供可形成即使在如此嚴苛的耐久條件下亦顯示優異的耐久性之黏著劑層之黏著劑組成物、包含該黏著劑組成物之黏著劑層、含有該黏著劑層之附黏著劑層之光學膜及光學積層體。 Accordingly, an object of the present invention is to provide an adhesive composition capable of forming an adhesive layer which exhibits excellent durability even under such severe durability conditions, an adhesive layer containing the adhesive composition, and the adhesive. An optical film and an optical laminate with an adhesive layer of the layer.

本發明之其他目的係提供可形成即使在上述嚴苛的耐久條件下亦顯示優異的耐久性之黏著劑層的黏著劑組成物用(甲基)丙烯酸系樹脂。 Another object of the present invention is to provide a (meth)acrylic resin for an adhesive composition which can form an adhesive layer which exhibits excellent durability even under the above-mentioned severe durability conditions.

本發明者為解決上述課題努力檢討，遂完成本發明。 The inventors of the present invention have made an effort to review the above problems and have completed the present invention.

亦即，本發明包括以下所述者。 That is, the present invention includes the following.

[1]一種黏著劑組成物，係含有(甲基)丙烯酸系樹脂(A)、交聯劑(B)及矽烷化合物(C)，前述(甲基)丙烯酸系樹脂(A)係包含源自於含有乙醯乙醯基之(甲基)丙烯酸酯(a1)之構成單元、及源自於含有羥基之(甲基)丙烯酸酯(a2)之構成單元，前述構成單元之質量比(a2)/(a1)為0.5至5。 [1] An adhesive composition comprising a (meth)acrylic resin (A), a crosslinking agent (B), and a decane compound (C), wherein the (meth)acrylic resin (A) is derived from The mass ratio of the constituent unit to the constituent unit of the (meth) acrylate (a1) containing the ethyl acetonitrile group and the constituent unit derived from the (meth) acrylate (a2) having a hydroxyl group (a2) /(a1) is from 0.5 to 5.

[2]如[1]所記載之黏著劑組成物，其中，(甲基)丙烯酸系樹脂(A)之重量平均分子量以聚苯乙烯換算為100萬以上。 [2] The adhesive composition according to [1], wherein the weight average molecular weight of the (meth)acrylic resin (A) is 1,000,000 or more in terms of polystyrene.

[3]如[1]或[2]所記載之黏著劑組成物，其中，(甲基)丙烯酸系樹脂(A)更包含源自於均聚物的玻璃轉移溫度未達0℃之丙烯酸烷酯(a3)之構成單元、及源自於均聚物的玻璃轉移溫度為0℃以上之丙烯酸烷酯(a4)之構成單元。 [3] The adhesive composition according to [1] or [2], wherein the (meth)acrylic resin (A) further comprises an alkyl acrylate derived from a homopolymer having a glass transition temperature of less than 0 ° C. The constituent unit of the ester (a3) and the constituent unit derived from the alkyl acrylate (a4) having a glass transition temperature of 0 ° C or higher derived from the homopolymer.

[4]如[1]至[3]中任一項所記載之黏著劑組成物，其中，源自於均聚物的玻璃轉移溫度未達0℃之丙烯酸烷酯(a3)之構成單元與源自於均聚物的玻璃轉移溫度為0℃以上之丙烯酸烷酯(a4)之構成單元的質量比(a3)/(a4)為0.1至4。 [4] The adhesive composition according to any one of [1] to [3] wherein the constituent unit of the alkyl acrylate (a3) derived from the homopolymer has a glass transition temperature of less than 0 ° C The mass ratio (a3)/(a4) of the constituent unit of the alkyl acrylate (a4) having a glass transition temperature of 0 ° C or more derived from a homopolymer is 0.1 to 4.

[5]如[1]至[4]中任一項所記載之黏著劑組成物，其中，相對於構成(甲基)丙烯酸系樹脂(A)之全部構成單元100質量份，(甲基)丙烯酸系樹脂(A)所包含之源自於含有羧基之(甲基)丙烯酸酯之構成單元的比例為1.0質量份以下。 The adhesive composition according to any one of the above [1] to [4], wherein (meth) is 100 parts by mass of all constituent units constituting the (meth)acrylic resin (A), (meth) The ratio of the constituent unit derived from the carboxyl group-containing (meth) acrylate contained in the acrylic resin (A) is 1.0 part by mass or less.

[6]如[1]至[5]中任一項所記載之黏著劑組成物，其中，(甲基)丙烯酸系樹脂(A)更含有源自於(甲基)丙烯醯胺系單體之構成單元。 [6] The adhesive composition according to any one of [1] to [5] wherein the (meth)acrylic resin (A) further contains a (meth)acrylamide monomer. The constituent unit.

[7]如[1]至[6]中任一項所記載之黏著劑組成物，其中，交聯劑(B)為異氰酸酯系化合物。 [7] The adhesive composition according to any one of [1] to [6] wherein the crosslinking agent (B) is an isocyanate compound.

[8]如[1]至[7]中任一項所記載之黏著劑組成物，其中，相對於(甲基)丙烯酸系樹脂(A)100質量份，交聯劑(B)之比例為0.01至10質量份。 [8] The adhesive composition according to any one of [1] to [7], wherein the ratio of the crosslinking agent (B) is 100 parts by mass based on the (meth)acrylic resin (A). 0.01 to 10 parts by mass.

[9]如[1]至[8]中任一項所記載之黏著劑組成物，其中，矽烷化合物(C)為下式(c1)所示矽烷化合物； (式中，B表示碳數3至20之烷二基或碳數3至20之二價脂環式烴基，構成前述烷二基及前述脂環式烴基之-CH2-可經取代為-O-或-CO-，R1表示碳數1至5之烷基，R2、R3、R4、R5及R6分別獨立表示碳數1至5之烷基或碳數1至5之烷氧基)。 [9] The adhesive composition according to any one of [1] to [8] wherein the decane compound (C) is a decane compound represented by the following formula (c1); (wherein, B represents an alkylenediyl group having 3 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and -CH 2 - constituting the aforementioned alkanediyl group and the aforementioned alicyclic hydrocarbon group may be substituted with - O- or -CO-, R 1 represents an alkyl group having 1 to 5 carbon atoms, and R 2 , R 3 , R 4 , R 5 and R 6 each independently represent an alkyl group having 1 to 5 carbon atoms or a carbon number of 1 to 5 Alkoxy).

[10]如[1]至[9]中任一項所記載之黏著劑組成物，其 中，相對於(甲基)丙烯酸系樹脂(A)100質量份，矽烷化合物(C)之比例為0.01至10質量份。 [10] The adhesive composition according to any one of [1] to [9], wherein the ratio of the decane compound (C) is 0.01% by mass based on 100 parts by mass of the (meth)acrylic resin (A). Up to 10 parts by mass.

[11]如[1]至[10]中任一項所記載之黏著劑組成物，其中，實質上不含有光聚合起始劑及其分解物。 [11] The adhesive composition according to any one of [1] to [10] wherein the photopolymerization initiator and the decomposition product thereof are substantially not contained.

[12]如[1]至[11]中任一項所記載之黏著劑組成物，其中進一步含有離子性化合物(D)。 [12] The adhesive composition according to any one of [1] to [11] further comprising an ionic compound (D).

[13]如[12]所記載之黏著劑組成物，其中，相對於(甲基)丙烯酸系樹脂(A)100質量份，離子性化合物(D)之比例為0.01至10質量份。 [13] The adhesive composition according to [12], wherein the ratio of the ionic compound (D) is 0.01 to 10 parts by mass based on 100 parts by mass of the (meth)acrylic resin (A).

[14]如[12]或[13]所記載之黏著劑組成物，其中，構成離子性化合物(D)之陰離子為由雙(三氟甲烷磺醯基)醯亞胺陰離子、雙(氟磺醯基)醯亞胺陰離子及四(五氟苯基)硼酸酯陰離子所成群組選出之至少1種。 [14] The adhesive composition according to [12] or [13] wherein the anion constituting the ionic compound (D) is an anion of bis(trifluoromethanesulfonyl) quinone imine, bis (fluorosulfonate) At least one selected from the group consisting of sulfhydryl anion and tetrakis(pentafluorophenyl) borate anion.

[15]一種黏著劑層，係含有[1]至[14]中任一項所記載之黏著劑組成物。 [15] An adhesive composition comprising the adhesive composition according to any one of [1] to [14].

[16]如[15]所記載之黏著劑層，其中，前述黏著劑層之膠化率為70至90%。 [16] The adhesive layer according to [15], wherein the adhesive layer has a gelation ratio of 70 to 90%.

[17]一種附黏著劑層之光學膜，係含有光學膜及於該光學膜的至少一面積層之黏著劑層，該黏著劑層係[15]或[16]所記載之黏著劑層。 [17] An optical film comprising an adhesive layer comprising an optical film and an adhesive layer on at least one area of the optical film, the adhesive layer being the adhesive layer described in [15] or [16].

[18]一種光學積層體，係含有[17]所記載之附黏著劑層之光學膜、及於該附黏著劑層之光學膜的黏著劑層側積層之基材。 [18] An optical layered product comprising the optical film having the adhesive layer described in [17] and a substrate laminated on the side of the adhesive layer of the optical film of the adhesive layer.

[19]一種黏著劑組成物用(甲基)丙烯酸系樹脂(A)，係 包含源自於含有乙醯乙醯基之(甲基)丙烯酸酯(a1)之構成單元、及源自於含有羥基之(甲基)丙烯酸酯(a2)之構成單元，前述構成單元之質量比(a2)/(a1)為0.5至5，且重量平均分子量以聚苯乙烯換算為100萬以上。 [19] A (meth)acrylic resin (A) for an adhesive composition, comprising a constituent unit derived from a (meth) acrylate (a1) containing an ethyl fluorene group, and derived from In the constituent unit of the hydroxy (meth) acrylate (a2), the mass ratio (a2)/(a1) of the structural unit is 0.5 to 5, and the weight average molecular weight is 1,000,000 or more in terms of polystyrene.

[20]如[19]所記載之黏著劑組成物用(甲基)丙烯酸系樹脂(A)，其中，(甲基)丙烯酸系樹脂(A)更包含源自於均聚物的玻璃轉移溫度未達0℃之丙烯酸烷酯(a3)之構成單元、及源自於均聚物的玻璃轉移溫度為0℃以上之丙烯酸烷酯(a4)之構成單元。 [20] The (meth)acrylic resin (A) for an adhesive composition according to [19], wherein the (meth)acrylic resin (A) further comprises a glass transition temperature derived from a homopolymer The constituent unit of the alkyl acrylate (a3) which is less than 0 ° C and the constituent unit derived from the alkyl acrylate (a4) having a glass transition temperature of 0 ° C or higher derived from the homopolymer.

[21]如[19]或[20]所記載之黏著劑組成物用(甲基)丙烯酸系樹脂(A)，其中，源自於均聚物的玻璃轉移溫度未達0℃之丙烯酸烷酯(a3)之構成單元與源自於均聚物的玻璃轉移溫度為0℃以上之丙烯酸烷酯(a4)之構成單元的質量比(a3)/(a4)為0.1至4。 [21] The (meth)acrylic resin (A) for an adhesive composition according to [19] or [20], wherein the alkyl acrylate derived from the homopolymer has a glass transition temperature of less than 0 ° C The mass ratio (a3)/(a4) of the constituent unit of (a3) and the constituent unit derived from the alkyl acrylate (a4) having a glass transition temperature of 0 ° C or higher derived from the homopolymer is 0.1 to 4.

[22]如[19]至[21]中任一項所記載之黏著劑組成物用(甲基)丙烯酸系樹脂(A)，其中，相對於構成(甲基)丙烯酸系樹脂(A)之全部構成單元100質量份，(甲基)丙烯酸系樹脂(A)所包含之源自於含有羧基之(甲基)丙烯酸酯之構成單元的比例為1.0質量份以下。 The (meth)acrylic resin (A) for an adhesive composition according to any one of [19] to [21], wherein, with respect to the (meth)acrylic resin (A) 100 parts by mass of all the constituent units, and the ratio of the constituent unit derived from the carboxyl group-containing (meth) acrylate contained in the (meth)acrylic resin (A) is 1.0 part by mass or less.

[23]如[19]至[22]中任一項所記載之黏著劑組成物用(甲基)丙烯酸系樹脂(A)，其中，(甲基)丙烯酸系樹脂(A)更含有源自於(甲基)丙烯醯胺系單體之構成單元。 [A] (meth)acrylic resin (A) for an adhesive composition according to any one of [19], wherein the (meth)acrylic resin (A) is further derived from A constituent unit of a (meth) acrylamide-based monomer.

根據本發明之黏著劑組成物，可形成即使 在嚴苛的耐久條件下亦具有優異的耐久性之黏著劑層、附該黏著劑層之光學膜及光學積層體。而且，根據含有本發明之黏著劑組成物用(甲基)丙烯酸系樹脂之黏著劑組成物，可形成即使在嚴苛的耐久條件下亦具有優異的耐久性之黏著劑層。 According to the adhesive composition of the present invention, an adhesive layer having excellent durability even under severe durability conditions, an optical film to which the adhesive layer is attached, and an optical laminate can be formed. Further, according to the adhesive composition containing the (meth)acrylic resin of the adhesive composition of the present invention, an adhesive layer having excellent durability even under severe durability conditions can be formed.

1、1a、1b‧‧‧附黏著劑層之光學膜 1, 1a, 1b‧‧‧ optical film with adhesive layer

2‧‧‧偏光片 2‧‧‧ polarizer

3‧‧‧第1樹脂膜 3‧‧‧1st resin film

4‧‧‧第2樹脂膜 4‧‧‧2nd resin film

5、6、7、8、9‧‧‧光學積層體 5, 6, 7, 8, 9‧‧‧ Optical laminates

10‧‧‧光學膜 10‧‧‧Optical film

10a、10b‧‧‧偏光板 10a, 10b‧‧‧ polarizing plate

20‧‧‧黏著劑層 20‧‧‧Adhesive layer

30‧‧‧金屬層 30‧‧‧metal layer

40‧‧‧基板 40‧‧‧Substrate

50‧‧‧樹脂層 50‧‧‧ resin layer

第1圖之示意剖面圖係表示本發明之附黏著劑層之光學膜之一例。 Fig. 1 is a schematic cross-sectional view showing an example of an optical film with an adhesive layer of the present invention.

第2圖之示意剖面圖係表示偏光板之層構成之一例。 Fig. 2 is a schematic cross-sectional view showing an example of a layer configuration of a polarizing plate.

第3圖之示意剖面圖係表示偏光板之層構成之其他例。 The schematic cross-sectional view of Fig. 3 shows another example of the layer configuration of the polarizing plate.

第4圖之示意剖面圖係表示本發明之光學積層體之一例。 Fig. 4 is a schematic cross-sectional view showing an example of the optical layered body of the present invention.

第5圖之示意剖面圖係表示本發明之光學積層體之其他例。 Fig. 5 is a schematic cross-sectional view showing another example of the optical layered body of the present invention.

第6圖之示意剖面圖係表示本發明之光學積層體之另一其他例。 Fig. 6 is a schematic cross-sectional view showing still another example of the optical layered body of the present invention.

第7圖之示意剖面圖係表示本發明之光學積層體之其他例。 Fig. 7 is a schematic cross-sectional view showing another example of the optical layered body of the present invention.

第8圖之示意剖面圖係表示本發明之光學積層體之另一其他例。 Fig. 8 is a schematic cross-sectional view showing still another example of the optical layered body of the present invention.

[1]黏著劑組成物 [1] Adhesive composition

本發明之黏著劑組成物係含有(甲基)丙烯酸系樹脂(A)、交聯劑(B)及矽烷化合物(C)。 The adhesive composition of the present invention contains a (meth)acrylic resin (A), a crosslinking agent (B), and a decane compound (C).

[1-1](甲基)丙烯酸系樹脂(A) [1-1] (Meth)acrylic resin (A)

(甲基)丙烯酸系樹脂(A)較佳為相對於構成(甲基)丙烯酸系樹脂(A)之全部構成單元100質量%含有源自於(甲基)丙烯酸系單體之構成單元50質量%以上的聚合物或共聚物，前述源自於(甲基)丙烯酸系單體之構成單元更佳為70質量%以上，又更佳為90質量%以上，且包含源自於含有乙醯乙醯基之(甲基)丙烯酸酯(a1)之構成單元及源自於含有羥基之(甲基)丙烯酸酯(a2)之構成單元，前述構成單元之質量比(a2)/(a1)為0.5至5。本發明之黏著劑組成物中，(甲基)丙烯酸系樹脂(A)係含有特定質量比之構成單元(a1)及(a2)，故可形成即使在高溫環境下亦具有優異的耐久性之黏著劑層。 The (meth)acrylic resin (A) preferably contains the mass of the constituent unit 50 derived from the (meth)acrylic monomer with respect to 100% by mass of all the constituent units constituting the (meth)acrylic resin (A). The polymer or copolymer of at least 100%, the constituent unit derived from the (meth)acrylic monomer is more preferably 70% by mass or more, still more preferably 90% by mass or more, and is contained in the group containing The constituent unit of the mercapto (meth) acrylate (a1) and the constituent unit derived from the hydroxyl group-containing (meth) acrylate (a2), wherein the mass ratio (a2)/(a1) of the constituent unit is 0.5. To 5. In the adhesive composition of the present invention, since the (meth)acrylic resin (A) contains the constituent units (a1) and (a2) having a specific mass ratio, it can be formed to have excellent durability even in a high temperature environment. Adhesive layer.

又，本說明書中，「(甲基)丙烯酸」意指「丙烯酸」或「甲基丙烯酸」，同樣地，「(甲基)丙烯酸酯」或「(甲基)丙烯醯基」等分別意指「丙烯酸酯」或「甲基丙烯酸酯」、「丙烯醯基」或「甲基丙烯醯基」。而且，本說明書中，耐久性是指例如在高溫環境下、高溫高濕環境下、重複高溫低溫境下等中可抑制黏著劑層和與其鄰接的光學構件之界面處的浮翹、剝離的特性(亦稱為抗剝離性)及可抑制黏著劑層之發泡等不良的特性(亦稱為抗發泡性)。再者，本說明書中，抗凝集破壞性是指可抑制黏著劑層之凝 集破壞(或破裂)的特性。 In the present specification, "(meth)acrylic acid" means "acrylic acid" or "methacrylic acid", and similarly, "(meth)acrylate" or "(meth)acrylylene group" means "Acrylate" or "methacrylate", "acrylonitrile" or "methacryl". In the present specification, the durability is such that, in a high-temperature environment, a high-temperature and high-humidity environment, a repeated high-temperature and low-temperature environment, etc., the characteristics of the floatation and peeling at the interface between the adhesive layer and the optical member adjacent thereto can be suppressed. (also known as peeling resistance) and properties (also referred to as anti-foaming properties) that can suppress defects such as foaming of the adhesive layer. Further, in the present specification, the anti-aggregation destructive property means a property of suppressing aggregation failure (or cracking) of the adhesive layer.

含有乙醯乙醯基之(甲基)丙烯酸酯(a1)可含有乙醯乙醯基以外之取代基，取代基可舉例如氰基等。含有乙醯乙醯基之(甲基)丙烯酸酯(a1)之具體例可列舉：例如(甲基)丙烯酸乙醯乙醯氧基烷酯，例如(甲基)丙烯酸乙醯乙醯氧基乙酯、(甲基)丙烯酸乙醯乙醯氧基丙酯、(甲基)丙烯酸乙醯乙醯氧基丁酯等(甲基)丙烯酸乙醯乙醯氧基C2-10烷酯；具有取代基之含有乙醯乙醯基之(甲基)丙烯酸酯，例如(甲基)丙烯酸2-氰基乙醯乙醯氧基乙酯等(甲基)丙烯酸氰基乙醯乙醯氧基C2-10烷酯等。從黏著劑層的耐久性、取得容易性之觀點來看，該等之中，較佳為(甲基)丙烯酸乙醯乙醯氧基乙酯、(甲基)丙烯酸乙醯乙醯氧基丙酯、(甲基)丙烯酸乙醯乙醯氧基丁酯，尤其該等中更佳為(甲基)丙烯酸2-乙醯乙醯氧基乙酯。該等含有乙醯乙醯基之(甲基)丙烯酸酯(a1)可單獨使用或組合二種以上使用。 The (meth) acrylate (a1) containing an acetamidine group may contain a substituent other than the acetamidine group, and examples of the substituent include a cyano group. Specific examples of the (meth) acrylate (a1) containing an ethyl acetonitrile group include, for example, ethoxylated alkyl (meth) acrylate, such as ethylene(meth)acrylate. Ethyl (meth) acrylate ethoxylated C 2-10 alkyl ester such as ester, ethoxylated propyl propyl (meth) acrylate or ethoxylated butyl butyl (meth) acrylate; a (meth) acrylate containing an ethyl acetonitrile group, such as 2-cyanoacetamidoethyl (meth)acrylate, such as cyanoacetoxyacetate (C ) -10 alkyl ester and the like. From the viewpoint of durability and ease of availability of the adhesive layer, among these, ethyl acetoacetate (meth) acrylate and acetamethylene methacrylate (meth) acrylate are preferred. The ester, acetamidine (meth) acrylate, in particular, more preferably 2-ethyl acetoxyethyl (meth) acrylate. These (meth) acrylate (meth) acrylates (a1) which may be used alone or in combination of two or more may be used.

含有羥基之(甲基)丙烯酸酯(a2)之具體例，可舉例如：(甲基)丙烯酸1-羥基甲酯、(甲基)丙烯酸1-羥基乙酯、(甲基)丙烯酸1-羥基丁酯、(甲基)丙烯酸1-羥基戊酯、(甲基)丙烯酸1-羥基庚酯等(甲基)丙烯酸1-羥基C1-8烷酯；(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2-羥基丁酯、(甲基)丙烯酸2-羥基戊酯、(甲基)丙烯酸2-羥基己酯等(甲基)丙烯酸2-羥基C2-9烷酯；(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸3-羥基戊酯、(甲基)丙烯酸3-羥基己酯、(甲 基)丙烯酸3-羥基庚酯等(甲基)丙烯酸3-羥基C3-10烷酯；(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸4-羥基戊酯、(甲基)丙烯酸4-羥基己酯、(甲基)丙烯酸4-羥基庚酯、(甲基)丙烯酸4-羥基辛酯等(甲基)丙烯酸4-羥基C4-11烷酯；(甲基)丙烯酸2-氯-2-羥基丙酯、(甲基)丙烯酸3-氯-2-羥基丙酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、(甲基)丙烯酸5-羥基戊酯、(甲基)丙烯酸5-羥基己酯、(甲基)丙烯酸5-羥基庚酯、(甲基)丙烯酸5-羥基辛酯、(甲基)丙烯酸5-羥基壬酯等(甲基)丙烯酸5-羥基C5-12烷酯；(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸6-羥基庚酯、(甲基)丙烯酸6-羥基辛酯、(甲基)丙烯酸6-羥基壬酯、(甲基)丙烯酸6-羥基癸酯等(甲基)丙烯酸6-羥基C6-13烷酯；(甲基)丙烯酸7-羥基庚酯、(甲基)丙烯酸7-羥基辛酯、(甲基)丙烯酸7-羥基壬酯、(甲基)丙烯酸7-羥基癸酯、(甲基)丙烯酸7-羥基十一酯等(甲基)丙烯酸7-羥基C7-14烷酯；(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸8-羥基壬酯、(甲基)丙烯酸8-羥基癸酯、(甲基)丙烯酸8-羥基十一酯、(甲基)丙烯酸8-羥基十二酯等(甲基)丙烯酸8-羥基C8-15烷酯；(甲基)丙烯酸9-羥基壬酯、(甲基)丙烯酸9-羥基癸酯、(甲基)丙烯酸9-羥基十一酯、(甲基)丙烯酸9-羥基十二酯、(甲基)丙烯酸9-羥基十三酯等(甲基)丙烯酸9-羥基C9-16烷酯；(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸10-羥基十一酯、(甲基)丙烯酸10-羥基十二酯、(甲基)丙烯酸10-羥基十三酯、(甲基)丙烯酸10-羥基十四酯等(甲基)丙烯酸10-羥基C10-17烷酯；(甲 基)丙烯酸11-羥基十一酯、(甲基)丙烯酸11-羥基十二酯、(甲基)丙烯酸11-羥基十三酯、(甲基)丙烯酸11-羥基十四酯、(甲基)丙烯酸11-羥基十五酯等(甲基)丙烯酸10-羥基C11-18烷酯；(甲基)丙烯酸12-羥基十二酯、(甲基)丙烯酸12-羥基十三酯、(甲基)丙烯酸12-羥基十四酯等(甲基)丙烯酸12-羥基C12-19烷酯；(甲基)丙烯酸13-羥基十五酯、(甲基)丙烯酸13-羥基十四酯、(甲基)丙烯酸13-羥基十五酯等(甲基)丙烯酸13-羥基C13-20烷酯；(甲基)丙烯酸14-羥基十四酯、(甲基)丙烯酸14-羥基十五酯等(甲基)丙烯酸14-羥基C14-21烷酯；(甲基)丙烯酸15-羥基十五酯、(甲基)丙烯酸15-羥基十七酯等(甲基)丙烯酸15-羥基C15-22烷酯等。 Specific examples of the hydroxyl group-containing (meth) acrylate (a2) include 1-hydroxymethyl (meth)acrylate, 1-hydroxyethyl (meth)acrylate, and 1-hydroxyl (meth)acrylate. 1-hydroxy C 1-8 alkyl (meth)acrylate such as butyl ester, 1-hydroxypentyl (meth)acrylate, 1-hydroxyheptyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate (2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate, 2-hydroxyhexyl (meth)acrylate, etc. (meth)acrylic acid 2-hydroxy C 2-9 alkyl ester; 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 3-hydroxypentyl (meth)acrylate, 3-(meth)acrylate 3-hydroxy C 3-10 alkyl (meth)acrylate such as hydroxyhexyl ester or 3-hydroxyheptyl (meth)acrylate; 4-hydroxybutyl (meth)acrylate; 4-hydroxypentyl (meth)acrylate a 4-hydroxy C 4-11 alkyl (meth)acrylate such as an ester, 4-hydroxyhexyl (meth)acrylate, 4-hydroxyheptyl (meth)acrylate or 4-hydroxyoctyl (meth)acrylate; 2-chloro-2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, (methyl)-propyl Acid 2-hydroxy-3-phenoxypropyl ester, 5-hydroxypentyl (meth)acrylate, 5-hydroxyhexyl (meth)acrylate, 5-hydroxyheptyl (meth)acrylate, (methyl) 5-hydroxy C 5-12 alkyl (meth)acrylate such as 5-hydroxyoctyl acrylate or 5-hydroxy decyl (meth)acrylate; 6-hydroxyhexyl (meth)acrylate, (meth)acrylic acid 6 -Hydroxyheptyl ester, 6-hydroxyoctyl (meth)acrylate, 6-hydroxydecyl (meth)acrylate, 6-hydroxydecyl (meth)acrylate, etc. 6-hydroxy C 6-13 (meth)acrylate Alkyl ester; 7-hydroxyheptyl (meth)acrylate, 7-hydroxyoctyl (meth)acrylate, 7-hydroxydecyl (meth)acrylate, 7-hydroxydecyl (meth)acrylate, (methyl) 7-hydroxy C 7-14 alkyl (meth)acrylate such as 7-hydroxyundecyl acrylate; 8-hydroxyoctyl (meth)acrylate, 8-hydroxydecyl (meth)acrylate, (methyl) (hydroxy) 8-hydroxydecyl acrylate, 8-hydroxyundecyl (meth) acrylate, 8-hydroxy C 8-15 alkyl (meth) acrylate, etc.; (methyl) 9-hydroxydecyl acrylate, 9-hydroxydecyl (meth)acrylate, 9-hydroxyundecyl (meth)acrylate, (methyl) propyl Acid 9-hydroxy dodecyl acrylate, (meth) acrylate, 9-hydroxy-tridecyl (meth) acrylate, 9-hydroxy C 9-16 alkyl acrylate; (meth) acrylate, 10-hydroxydecyl acrylate, (meth) 10-hydroxyundecyl acrylate, 10-hydroxydodecyl (meth)acrylate, 10-hydroxytridecyl (meth)acrylate, 10-hydroxytetradecyl (meth)acrylate, etc. (Meth)acrylic acid 10 - C 10-17 alkyl hydroxy acrylate; (meth) acrylate, 11-hydroxy eleven ester, (meth) acrylate, 11-hydroxy dodecyl acrylate, (meth) acrylate, 11-hydroxy-tridecyl acrylate, (meth) acrylic acid 11-hydroxytetradecylester, 11-hydroxypentadecyl (meth)acrylate, etc. 10-hydroxy C 11-18 alkyl (meth)acrylate; 12-hydroxydodecyl (meth)acrylate, (methyl) 12-hydroxy C 12-19 alkyl (meth)acrylate such as 12-hydroxytridecyl acrylate or 12-hydroxytetradecyl (meth)acrylate; 13-hydroxypentadecyl (meth)acrylate, (methyl) a 13-hydroxy C 13-20 alkyl (meth)acrylate such as 13-hydroxytetradecyl acrylate or 13-hydroxypentadecyl (meth) acrylate; 14-hydroxytetradecyl (meth) acrylate, (a) (meth)acrylic acid 14-hydroxypentadecyl ester and other (meth)acrylic acid 14-hydroxy C 14-21 alkyl ester; (methyl) A 15-hydroxy C 15-22 alkyl (meth)acrylate such as 15-hydroxypentadecyl acrylate or 15-hydroxyhexadecyl (meth)acrylate.

從黏著劑層之耐久性、取得容易性之觀點來看，該等之中較佳為(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2-羥基丁酯等(甲基)丙烯酸2-羥基C2-7烷酯；(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸3-羥基戊酯等(甲基)丙烯酸3-羥基C3-8烷酯；(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸4-羥基戊酯、(甲基)丙烯酸4-羥基己酯等(甲基)丙烯酸4-羥基C4-9烷酯；(甲基)丙烯酸5-羥基戊酯、(甲基)丙烯酸5-羥基己酯、(甲基)丙烯酸5-羥基庚酯、(甲基)丙烯酸5-羥基辛酯、(甲基)丙烯酸5-羥基壬酯等(甲基)丙烯酸5-羥基C5-9烷酯等，尤其該等之中更佳為(甲基)丙烯酸2-羥基乙酯。該等含有羥基之(甲基)丙烯酸酯(a2)可單獨使用或組合二種以上使用。 From the viewpoint of durability and ease of availability of the adhesive layer, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid are preferred among the above. 2-hydroxy C 2-7 alkyl (meth) acrylate such as 2-hydroxybutyl ester; 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 3-(meth)acrylate 3-hydroxy C 3-8 alkyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 4-hydroxypentyl (meth)acrylate, 4-hydroxyhexyl (meth)acrylate 4-hydroxy C 4-9 alkyl (meth)acrylate; 5-hydroxypentyl (meth)acrylate, 5-hydroxyhexyl (meth)acrylate, 5-hydroxyheptyl (meth)acrylate, a 5-hydroxy C 5-9 alkyl (meth)acrylate such as 5-hydroxyoctyl (meth)acrylate or 5-hydroxydecyl (meth)acrylate, and more preferably (meth) 2-hydroxyethyl acrylate. These hydroxyl group-containing (meth) acrylates (a2) may be used singly or in combination of two or more.

相對於構成(甲基)丙烯酸系樹脂之全部構成單元100質量份，源自於含有乙醯乙醯基之(甲基)丙烯酸酯(a1)之構成單元的比例較佳為0.01至10質量份，更佳為0.1至5質量份，又更佳為0.5至3質量份。而且，相對於構成(甲基)丙烯酸系樹脂之全部構成單元100質量份，源自於含有羥基之(甲基)丙烯酸酯(a2)之構成單元的比例較佳為0.01至20質量份，更佳為1至10質量份，又更佳為1.5至5質量份。該等構成單元之比例若為上述範圍，則可進一步提高黏著劑層之耐久性。 The ratio of the constituent unit derived from the (meth)acrylate (a1) containing an ethyl fluorene group is preferably 0.01 to 10 parts by mass based on 100 parts by mass of all the constituent units constituting the (meth)acrylic resin. More preferably, it is 0.1 to 5 parts by mass, and more preferably 0.5 to 3 parts by mass. In addition, the ratio of the constituent unit derived from the hydroxyl group-containing (meth) acrylate (a2) is preferably 0.01 to 20 parts by mass, based on 100 parts by mass of all the constituent units constituting the (meth)acrylic resin. It is preferably from 1 to 10 parts by mass, more preferably from 1.5 to 5 parts by mass. When the ratio of these constituent units is in the above range, the durability of the adhesive layer can be further improved.

源自於含有乙醯乙醯基之(甲基)丙烯酸酯(a1)之構成單元、及源自於含有羥基之(甲基)丙烯酸酯(a2)之構成單元之質量比(a2)/(a1)為0.5至5，較佳為0.7至4.5，更佳為1至4，又更佳為1.2至3.7，特佳為1.5至3.5。該等之質量比若為上述範圍，則可進一步提高黏著劑層之耐久性。 The mass ratio (a2)/(the constituent unit derived from the (meth) acrylate (a1) containing an ethyl acetonitrile group and the constituent unit derived from the (meth) acrylate (a2) having a hydroxyl group A1) is from 0.5 to 5, preferably from 0.7 to 4.5, more preferably from 1 to 4, still more preferably from 1.2 to 3.7, particularly preferably from 1.5 to 3.5. When the mass ratio is in the above range, the durability of the adhesive layer can be further improved.

(甲基)丙烯酸系樹脂(A)可進一步包含源自於均聚物的玻璃轉移溫度未達0℃之丙烯酸烷酯(a3)之構成單元、及源自於均聚物的玻璃轉移溫度為0℃以上之丙烯酸烷酯(a4)之構成單元。 The (meth)acrylic resin (A) may further comprise a constituent unit derived from an alkyl acrylate (a3) having a glass transition temperature of less than 0 ° C derived from a homopolymer, and a glass transition temperature derived from the homopolymer. A constituent unit of an alkyl acrylate (a4) of 0 ° C or higher.

均聚物的玻璃轉移溫度(Tg)未達0℃之丙烯酸烷酯(a3)可舉例如：丙烯酸乙酯、丙烯酸正丙酯及丙烯酸異丙酯、丙烯酸正丁酯及丙烯酸異丁酯、丙烯酸正戊酯、丙烯酸正己酯及丙烯酸異己酯、丙烯酸正庚酯、丙烯酸正辛酯及丙烯酸異辛酯、丙烯酸2-乙基己酯、丙烯酸正壬酯 及丙烯酸異壬酯、丙烯酸正癸酯及丙烯酸異癸酯、丙烯酸正十二酯等烷基的碳數為2至12左右之直鏈狀或支鏈狀丙烯酸烷酯等。丙烯酸烷酯(a3)可為具有脂環式構造之丙烯酸烷酯(丙烯酸環烷酯)，從對光學膜之追隨性、柔軟性或黏著性等觀點來看，較佳係碳數為2至10之丙烯酸烷酯，更佳係碳數為3至8之丙烯酸烷酯，又更佳係碳數為4至6之丙烯酸烷酯，特佳係丙烯酸正丁酯。若使用丙烯酸正丁酯則可提高追隨性，有利於例如抗剝離性等。該等丙烯酸烷酯(a3)可單獨使用或組合二種以上使用。 The alkyl acrylate (a3) having a glass transition temperature (Tg) of the homopolymer of less than 0 ° C may, for example, be ethyl acrylate, n-propyl acrylate and isopropyl acrylate, n-butyl acrylate and isobutyl acrylate, acrylic acid. N-amyl ester, n-hexyl acrylate and isohexyl acrylate, n-heptyl acrylate, n-octyl acrylate and isooctyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate and isodecyl acrylate, n-decyl acrylate and A linear or branched alkyl acrylate having an alkyl group such as isodecyl acrylate or n-dodecyl acrylate having a carbon number of 2 to 12 or the like. The alkyl acrylate (a3) may be an alkyl acrylate (cycloalkyl acrylate) having an alicyclic structure, and preferably has a carbon number of 2 to 2 from the viewpoints of followability, flexibility, or adhesion to an optical film. The alkyl acrylate of 10 is more preferably an alkyl acrylate having a carbon number of 3 to 8, and more preferably an alkyl acrylate having a carbon number of 4 to 6, particularly preferably n-butyl acrylate. When n-butyl acrylate is used, the followability can be improved, and it is advantageous, for example, in peeling resistance. These alkyl acrylates (a3) may be used singly or in combination of two or more.

作為均聚物Tg為0℃以上之丙烯酸烷酯(a4)，可舉出：丙烯酸甲酯、丙烯酸環烷酯(例如丙烯酸環己酯、丙烯酸異莰酯等)、丙烯酸硬脂酯、丙烯酸第三丁酯等，特佳為丙烯酸甲酯。若使用丙烯酸甲酯則可提升高溫耐久時的黏著劑層強度，例如可提高抗凝集破壞性。該等丙烯酸烷酯(a4)可單獨使用或組合二種以上使用。又，丙烯酸烷酯之均聚物Tg可參照例如POLYMER HANDBOOK(Wiley-Interscience)等文獻值。 Examples of the alkyl acrylate (a4) having a homopolymer Tg of 0 ° C or higher include methyl acrylate, a cycloalkyl acrylate (for example, cyclohexyl acrylate or isodecyl acrylate), stearyl acrylate, and acrylic acid. Tributyl ester, etc., particularly preferably methyl acrylate. If methyl acrylate is used, the strength of the adhesive layer at high temperature durability can be improved, for example, the anti-aggregation destructive property can be improved. These alkyl acrylates (a4) may be used singly or in combination of two or more. Further, the homopolymer Tg of the alkyl acrylate can be referred to, for example, literature values such as POLYMER HANDBOOK (Wiley-Interscience).

從黏著劑層之耐久性及重工(rework)性之觀點來看，相對於構成(甲基)丙烯酸系樹脂(A)之全部構成單元100質量份，源自於丙烯酸烷酯之構成單元(a3)及(a4)之合計比例例如可為40質量份以上。前述構成單元(a3)及(a4)之合計比例之下限值，較佳為50質量份，更佳為60質量份，又更佳為70質量份，特佳為75質量份。而且，前述構成單元(a3)及(a4)之合計比例之上限值較佳為98質 量份，更佳為95質量份，又更佳為90質量份。構成單元(a3)及(a4)之合計比例可為下限值與上限值之任意組合，例如可為50至98質量份，較佳為70至95質量份，更佳為75至95質量份。 From the viewpoint of durability and rework of the adhesive layer, the constituent unit derived from the alkyl acrylate (a3) is 100 parts by mass based on all the constituent units constituting the (meth)acrylic resin (A). The total ratio of (a4) and (a4) may be, for example, 40 parts by mass or more. The lower limit of the total ratio of the constituent units (a3) and (a4) is preferably 50 parts by mass, more preferably 60 parts by mass, still more preferably 70 parts by mass, and particularly preferably 75 parts by mass. Further, the upper limit of the total ratio of the constituent units (a3) and (a4) is preferably 98 parts by mass, more preferably 95 parts by mass, still more preferably 90 parts by mass. The total ratio of the constituent units (a3) and (a4) may be any combination of the lower limit value and the upper limit value, and may be, for example, 50 to 98 parts by mass, preferably 70 to 95 parts by mass, more preferably 75 to 95 parts by mass. Share.

若併用均聚物Tg未達0℃之丙烯酸烷酯(a3)與均聚物Tg為0℃以上之丙烯酸烷酯(a4)，則可兼顧抗凝集破壞性及追隨性(抗剝離性)，可提高對於光學膜(例如偏光板)的尺寸變化之耐久性。 When the alkyl acrylate (a3) having a homopolymer Tg of less than 0 ° C and the alkyl acrylate (a4) having a homopolymer Tg of 0 ° C or more are used in combination, the anti-aggregation destructive property and the followability (peeling resistance) can be achieved. The durability against dimensional changes of an optical film such as a polarizing plate can be improved.

源自於均聚物的玻璃轉移溫度未達0℃之丙烯酸烷酯(a3)之構成單元與源自於玻璃轉移溫度為0℃以上之丙烯酸烷酯(a4)之構成單元的質量比(a3)/(a4)，較佳為0.1至4，更佳為0.15至3.5，又更佳為0.2至2.5。該等質量比若為上述範圍，則可進一步提高黏著劑層之耐久性。源自於玻璃轉移溫度未達0℃之丙烯酸烷酯(a3)之構成單元的比例越大，則越提高追隨性，源自於玻璃轉移溫度為0℃以上之丙烯酸烷酯(a4)之構成單元的比例越大，則越提高抗凝集破壞性。而且，若以較均聚物的玻璃轉移溫度未達0℃之丙烯酸烷酯(a3)多的比例含有均聚物的玻璃轉移溫度為0℃以上之丙烯酸烷酯(a4)，則可進一步提高耐久性，即使在更嚴苛的耐久條件下亦可顯示優異的耐久性。 a mass ratio of a constituent unit derived from an alkyl acrylate (a3) having a glass transition temperature of less than 0 ° C to a constituent unit derived from an alkyl acrylate (a4) having a glass transition temperature of 0 ° C or higher (a3) And / (a4), preferably from 0.1 to 4, more preferably from 0.15 to 3.5, still more preferably from 0.2 to 2.5. When the mass ratio is in the above range, the durability of the adhesive layer can be further improved. The larger the proportion of the constituent units derived from the alkyl acrylate (a3) having a glass transition temperature of less than 0 ° C, the more the followability is improved, and the composition is derived from the alkyl acrylate (a4) having a glass transition temperature of 0 ° C or higher. The larger the proportion of the unit, the more the anti-aggregation destructive property is improved. Further, if the alkyl acrylate (a4) having a glass transition temperature of 0 ° C or higher in which the homopolymer has a glass transition temperature of less than 0 ° C in a ratio of more than 0 ° C is further increased, it can be further improved. Durability, even under more severe durability conditions, shows excellent durability.

(甲基)丙烯酸系樹脂(A)可進一步含有源自於含取代基之丙烯酸烷酯之構成單元。 The (meth)acrylic resin (A) may further contain a constituent unit derived from a substituent-containing alkyl acrylate.

含取代基之丙烯酸烷酯，可舉例如於前述丙烯酸烷酯(a3)及(a4)中的烷基導入有取代基(換言之，係 以取代基取代烷基之氫原子)之丙烯酸烷酯。該取代基例如可為芳基(例如苯基等)、芳氧基(例如苯氧基等)、烷氧基(例如甲氧基、乙氧基等)等。含取代基之丙烯酸烷酯，可舉例如：丙烯酸芳基烷酯(例如丙烯酸苯甲酯、丙烯酸苯乙酯等)、丙烯酸烷氧基烷酯(例如丙烯酸2-甲氧基乙酯、丙烯酸乙氧基甲酯等)、丙烯酸芳氧基烷酯(例如丙烯酸苯氧基乙酯等)、芳基氧聚烷二醇單丙烯酸酯、聚烷二醇單丙烯酸酯等。芳基氧聚烷二醇單丙烯酸酯及聚烷二醇單丙烯酸酯之伸烷基，例如可為亞甲基、伸乙基、伸丙基等C1-6伸烷基，較佳為伸乙基等，可適當選擇氧伸烷基之重複單元。伸烷基之重複單元例如可為1至7，較佳為1至5，特別是1或2。該等丙烯酸烷酯可單獨使用或組合二種以上使用。藉由包含含有芳基、芳氧基等芳香環之丙烯酸烷酯，可改善耐久試驗時的偏光板之露白。又，藉由含有含烷氧基或聚烷二醇構造等醚構造之丙烯酸烷酯，而可提高抗靜電性能。從露白性、抗靜電性、耐久性之平衡之觀點來看，較佳為包含丙烯酸芳氧基烷酯、芳基氧聚烷二醇丙烯酸酯。具體而言，可舉出丙烯酸苯氧基乙酯、苯氧基二乙二醇丙烯酸酯、苯氧基三乙二醇丙烯酸酯、苯氧基四乙二醇丙烯酸酯等。尤其較佳為使用丙烯酸苯氧基乙酯、苯氧基二乙二醇丙烯酸酯。 The alkyl acrylate containing a substituent may, for example, be an alkyl acrylate having a substituent introduced into the alkyl group of the alkyl acrylates (a3) and (a4) (in other words, a hydrogen atom of the alkyl group substituted by a substituent). The substituent may be, for example, an aryl group (e.g., a phenyl group), an aryloxy group (e.g., a phenoxy group), an alkoxy group (e.g., a methoxy group, an ethoxy group, etc.). The alkyl acrylate containing a substituent may, for example, be an aryl acrylate (for example, benzyl acrylate or phenylethyl acrylate) or an alkoxyalkyl acrylate (for example, 2-methoxyethyl acrylate or acrylic acid B). Oxymethyl ester or the like), aryloxyalkyl acrylate (for example, phenoxyethyl acrylate), aryloxypolyalkylene glycol monoacrylate, polyalkylene glycol monoacrylate, and the like. The alkyl group of the aryloxy polyalkylene glycol monoacrylate and the polyalkylene glycol monoacrylate may be, for example, a C 1-6 alkylene group such as a methylene group, an exoethyl group or a propyl group, preferably a stretching group. For the ethyl group or the like, a repeating unit of an oxygen-extended alkyl group can be appropriately selected. The repeating unit of the alkylene group may be, for example, 1 to 7, preferably 1 to 5, particularly 1 or 2. These alkyl acrylates may be used singly or in combination of two or more. By including an alkyl acrylate containing an aromatic ring such as an aryl group or an aryloxy group, the whitening of the polarizing plate during the endurance test can be improved. Further, the antistatic property can be improved by containing an alkyl acrylate having an ether structure such as an alkoxy group or a polyalkylene glycol structure. From the viewpoint of balance between whiteness, antistatic property and durability, it is preferred to contain an aryloxyalkyl acrylate or an aryloxypolyalkylene glycol acrylate. Specific examples thereof include phenoxyethyl acrylate, phenoxy diethylene glycol acrylate, phenoxy triethylene glycol acrylate, and phenoxytetraethylene glycol acrylate. It is especially preferred to use phenoxyethyl acrylate or phenoxy diethylene glycol acrylate.

相對於構成(甲基)丙烯酸系樹脂(A)之全部構成單元100質量份，源自於含有取代基之丙烯酸烷酯之構成單元的比例例如可為0至40質量份，較佳為3至30 質量份，又更佳為5至25質量份，尤其是可為7至21質量份。該比例若於上述範圍，則可進一步可提高上述露白性、抗靜電性、耐久性等特性。 The proportion of the constituent unit derived from the alkyl acrylate containing a substituent may be, for example, 0 to 40 parts by mass, preferably 3 to 100 parts by mass based on 100 parts by mass of all the constituent units constituting the (meth)acrylic resin (A). 30 parts by mass, more preferably 5 to 25 parts by mass, especially 7 to 21 parts by mass. When the ratio is in the above range, characteristics such as whiteness, antistatic property, and durability can be further improved.

(甲基)丙烯酸系樹脂(A)可含有源自於上述構成單元以外之其他單體之構成單元。其他單體可單獨使用或組合二種以上使用。其他單體可舉出：具有羥基以外之極性官能基之單體、(甲基)丙烯醯胺系單體、苯乙烯系單體、乙烯基系單體、分子內具有複數個(甲基)丙烯醯基之單體等。 The (meth)acrylic resin (A) may contain a constituent unit derived from a monomer other than the above constituent unit. The other monomers may be used singly or in combination of two or more. Examples of the other monomer include a monomer having a polar functional group other than a hydroxyl group, a (meth)acrylamide monomer, a styrene monomer, a vinyl monomer, and a plurality of (methyl) groups in the molecule. A monomer such as an acrylonitrile group.

具有羥基以外之極性官能基之單體，可舉出具有環氧基等雜環基、取代或未取代胺基、羧基等取代基之(甲基)丙烯酸酯。具體而言，可舉出：丙烯醯基嗎啉、乙烯基己內醯胺、N-乙烯基-2-吡咯啶酮、乙烯基吡啶、(甲基)丙烯酸四氫糠酯、己內酯改質丙烯酸四氫糠酯、(甲基)丙烯酸3,4-環氧環己基甲酯、(甲基)丙烯酸環氧丙酯、2,5-二氫呋喃等具有雜環基之單體；(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸二甲基胺基丙酯等具有取代或未取代胺基之單體；(甲基)丙烯酸、馬來酸、馬來酸酐、延胡索酸、巴豆酸、(甲基)丙烯酸羧基烷酯(例如(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯)等具有羧基之單體。該等單體可單獨使用或組合二種以上使用。又，從防止可積層於黏著劑層之分離膜的剝離性降低之觀點來看，較佳為實質上不含源自於具有胺基之單體之構成單元。又，實質上不含是指相對於構成(甲基) 丙烯酸系樹脂(A)之全部構成單元100質量份為未達1.0質量份。 Examples of the monomer having a polar functional group other than a hydroxyl group include a (meth) acrylate having a heterocyclic group such as an epoxy group, a substituted or unsubstituted amino group, or a substituent such as a carboxyl group. Specific examples include propylene decylmorpholine, vinyl caprolactam, N-vinyl-2-pyrrolidone, vinyl pyridine, tetrahydrofurfuryl (meth) acrylate, and caprolactone. a monomer having a heterocyclic group such as tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl (meth)acrylate or 2,5-dihydrofuran; a monomer having a substituted or unsubstituted amine group such as aminoethyl methacrylate, N,N-dimethylaminoethyl (meth)acrylate, or dimethylaminopropyl (meth)acrylate; (meth)acrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, carboxyalkyl (meth)acrylate (for example, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate), etc. Monomer. These monomers may be used singly or in combination of two or more. Moreover, from the viewpoint of preventing the peeling property of the separation membrane which can be deposited on the pressure-sensitive adhesive layer from being lowered, it is preferable that the constituent unit derived from the monomer having an amine group is substantially not contained. In addition, the term "substantially free" means that it is less than 1.0 part by mass based on 100 parts by mass of all the constituent units constituting the (meth)acrylic resin (A).

本發明中，即使不含有被認為會增加ITO腐蝕性之源自於具有羧基之單體之構成單元(亦稱為源自於含有羧基之(甲基)丙烯酸酯之構成單元)亦顯示高耐久性，故可兼顧耐久性及耐ITO腐蝕性。 In the present invention, even if it does not contain a constituent unit derived from a monomer having a carboxyl group (also referred to as a constituent unit derived from a carboxyl group-containing (meth) acrylate) which is considered to increase ITO corrosion resistance, it exhibits high durability. Sexuality, so it can balance durability and ITO corrosion resistance.

另一方面，若含有源自於具有羧基之單體之構成單元[源自於含有羧基之(甲基)丙烯酸酯之構成單元]，則可進一步提高耐久性。本發明中，即使源自於含有羧基之(甲基)丙烯酸酯之構成單元的比例少，亦可有效地提高耐久性，故藉由含有少量的源自於含有羧基之(甲基)丙烯酸酯之構成單元，可抑制ITO之腐蝕，並可進一步提高耐久性。 On the other hand, when a constituent unit derived from a monomer having a carboxyl group [derived from a constituent unit of a carboxyl group-containing (meth) acrylate] is contained, durability can be further improved. In the present invention, even if the proportion of the constituent unit derived from the carboxyl group-containing (meth) acrylate is small, the durability can be effectively improved, so that a small amount of the (meth) acrylate derived from the carboxyl group is contained. The constituent unit can suppress corrosion of ITO and further improve durability.

相對於構成(甲基)丙烯酸系樹脂之全部構成單元100質量份，源自於含有羧基之(甲基)丙烯酸酯之構成單元的比例為1.0質量份以下。源自於含有羧基之(甲基)丙烯酸酯之構成單元的比例之上限值較佳為0.8質量份，更佳為0.5質量份，又更佳為0.3質量份，特佳為0.2質量份，尤佳為0.15質量份。源自於含有羧基之(甲基)丙烯酸酯之構成單元的比例之下限值較佳為0質量份，更佳為0.001質量份，又更佳為0.005質量份，特佳為0.01質量份，尤佳為0.05質量份。源自於含有羧基之(甲基)丙烯酸酯之構成單元的比例可為該等上限值與下限值之任意組合，例如可為0至1質量份，較佳為0至0.8質量份，更佳為0.001至0.5質量份，又更佳為0.005至0.3質量份， 特佳為0.01至0.2質量份，尤佳為0.05至0.15質量份。源自於含有羧基之(甲基)丙烯酸酯之構成單元的比例若為上限值以下，則可抑制ITO腐蝕性，若為下限值以上，則可提高耐久性。 The ratio of the constituent unit derived from the carboxyl group-containing (meth) acrylate is 1.0 part by mass or less based on 100 parts by mass of all the constituent units constituting the (meth)acrylic resin. The upper limit of the ratio of the constituent unit derived from the carboxyl group-containing (meth) acrylate is preferably 0.8 parts by mass, more preferably 0.5 parts by mass, still more preferably 0.3 parts by mass, particularly preferably 0.2 parts by mass, More preferably, it is 0.15 parts by mass. The lower limit of the ratio of the constituent unit derived from the carboxyl group-containing (meth) acrylate is preferably 0 parts by mass, more preferably 0.001 part by mass, still more preferably 0.005 part by mass, particularly preferably 0.01 part by mass, More preferably, it is 0.05 parts by mass. The ratio of the constituent unit derived from the carboxyl group-containing (meth) acrylate may be any combination of the above upper limit value and the lower limit value, and may be, for example, 0 to 1 part by mass, preferably 0 to 0.8 part by mass, More preferably, it is 0.001 to 0.5 parts by mass, still more preferably 0.005 to 0.3 parts by mass, particularly preferably 0.01 to 0.2 parts by mass, particularly preferably 0.05 to 0.15 parts by mass. When the ratio of the constituent unit derived from the carboxyl group-containing (meth) acrylate is at most the upper limit value, ITO corrosion resistance can be suppressed, and when it is at least the lower limit value, durability can be improved.

(甲基)丙烯醯胺系單體可舉例如N-羥甲基丙烯醯胺、N-(2-羥基乙基)丙烯醯胺、N-(3-羥基丙基)丙烯醯胺、N-(4-羥基丁基)丙烯醯胺、N-(5-羥基戊基)丙烯醯胺、N-(6-羥基己基)丙烯醯胺、N,N-二甲基丙烯醯胺、N,N-二乙基丙烯醯胺、N-異丙基丙烯醯胺、N-(3-二甲基胺基丙基)丙烯醯胺、N-(1,1-二甲基-3-側氧基丁基)丙烯醯胺、N-〔2-(2-側氧基-1-咪唑啶基)乙基〕丙烯醯胺、2-丙烯醯基胺基-2-甲基-1-丙烷磺酸、N-(甲氧基甲基)丙烯醯胺、N-(乙氧基甲基)丙烯醯胺、N-(丙氧基甲基)丙烯醯胺、N-(1-甲基乙氧基甲基)丙烯醯胺、N-(1-甲基丙氧基甲基)丙烯醯胺、N-(2-甲基丙氧基甲基)丙烯醯胺〔別名：N-(異丁氧基甲基)丙烯醯胺〕、N-(丁氧基甲基)丙烯醯胺、N-(1,1-二甲基乙氧基甲基)丙烯醯胺、N-(2-甲氧基乙基)丙烯醯胺、N-(2-乙氧基乙基)丙烯醯胺、N-(2-丙氧基乙基)丙烯醯胺、N-〔2-(1-甲基乙氧基)乙基〕丙烯醯胺、N-〔2-(1-甲基丙氧基)乙基〕丙烯醯胺、N-〔2-(2-甲基丙氧基)乙基〕丙烯醯胺〔別名：N-(2-異丁氧基乙基)丙烯醯胺〕、N-(2-丁氧基乙基)丙烯醯胺、N-〔2-(1,1-二甲基乙氧基)乙基〕丙烯醯胺等。藉由含有源自於(甲基)丙烯醯胺系單體之構造單元，可進一步提高黏著劑層之耐久性。尤其，該等之中較佳為N-(甲氧基 甲基)丙烯醯胺、N-(乙氧基甲基)丙烯醯胺、N-(丙氧基甲基)丙烯醯胺、N-(丁氧基甲基)丙烯醯胺、N-(2-甲基丙氧基甲基)丙烯醯胺等。 The (meth)acrylamide monomer may, for example, be N-methylol acrylamide, N-(2-hydroxyethyl) acrylamide, N-(3-hydroxypropyl) acrylamide, N- (4-hydroxybutyl) acrylamide, N-(5-hydroxypentyl) acrylamide, N-(6-hydroxyhexyl) acrylamide, N,N-dimethyl decylamine, N,N - diethyl acrylamide, N-isopropyl acrylamide, N-(3-dimethylaminopropyl) acrylamide, N-(1,1-dimethyl-3-oxirane Butyl) acrylamide, N-[2-(2-o-oxy-1-imidazolidinyl)ethyl]propenylamine, 2-propenylamino-2-methyl-1-propane sulfonic acid , N-(methoxymethyl)propenylamine, N-(ethoxymethyl)propenylamine, N-(propoxymethyl)propenylamine, N-(1-methylethoxy Methyl) acrylamide, N-(1-methylpropoxymethyl) acrylamide, N-(2-methylpropoxymethyl) acrylamide [alias: N-(isobutoxy) Methyl) acrylamide], N-(butoxymethyl)propenylamine, N-(1,1-dimethylethoxymethyl)propenylamine, N-(2-methoxyB Acrylamide, N-(2-ethoxyethyl)propenamide, N-(2-propoxyethyl)propenamide, N-[2-(1-methylethoxy) Ethyl]propenylamine, N-[2-(1-methylpropoxy)ethyl]propenylamine, N-[2-(2-methylpropoxy)ethyl]propenylamine [alias: N-(2-isobutoxyethyl) acrylamide], N-(2-butoxyethyl) acrylamide, N-[2-(1,1-dimethylethoxy) Ethyl) acrylamide and the like. The durability of the adhesive layer can be further improved by containing a structural unit derived from a (meth)acrylamide monomer. In particular, among these, N-(methoxymethyl)propenylamine, N-(ethoxymethyl)propenylamine, N-(propoxymethyl)propenylamine, N- are preferred. (butoxymethyl) acrylamide, N-(2-methylpropoxymethyl) acrylamide, and the like.

相對於構成(甲基)丙烯酸系樹脂之全部構成單元100質量份，源自於(甲基)丙烯醯胺系單體之構成單元的比例為5質量份以下。源自於(甲基)丙烯醯胺系單體之構成單元的比例之上限值較佳為3質量份，更佳為2質量份，又更佳為1質量份。源自於(甲基)丙烯醯胺系單體之構成單元的比例之下限值較佳為0質量份，更佳為0.001質量份，又更佳為0.01質量份，特佳為0.1質量份。源自於(甲基)丙烯醯胺系單體之構成單元的比例可為該等上限值與下限值之任意組合，例如可為0至5質量份，較佳為0.001至3質量份，更佳為0.01至2質量份，又更佳為0.1至1質量份。源自於(甲基)丙烯醯胺系單體之構成單元的比例若為上述範圍，則可進一步提高黏著劑層之耐久性。 The ratio of the constituent units derived from the (meth)acrylamide monomer is 5 parts by mass or less based on 100 parts by mass of all the constituent units constituting the (meth)acrylic resin. The upper limit of the ratio of the constituent unit derived from the (meth)acrylamide monomer is preferably 3 parts by mass, more preferably 2 parts by mass, still more preferably 1 part by mass. The lower limit of the ratio of the constituent unit derived from the (meth)acrylamide monomer is preferably 0 parts by mass, more preferably 0.001 part by mass, still more preferably 0.01 part by mass, particularly preferably 0.1 part by mass. . The ratio of the constituent units derived from the (meth)acrylamide monomer may be any combination of the above upper limit and lower limit, and may be, for example, 0 to 5 parts by mass, preferably 0.001 to 3 parts by mass. More preferably, it is 0.01 to 2 parts by mass, and still more preferably 0.1 to 1 part by mass. When the ratio of the constituent unit derived from the (meth)acrylamide monomer is in the above range, the durability of the adhesive layer can be further improved.

苯乙烯系單體可舉例如：苯乙烯；甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、二乙基苯乙烯、三乙基苯乙烯、丙基苯乙烯、丁基苯乙烯、己基苯乙烯、庚基苯乙烯、辛基苯乙烯等烷基苯乙烯；氟苯乙烯、氯苯乙烯、溴苯乙烯、二溴苯乙烯、碘苯乙烯等鹵化苯乙烯；硝基苯乙烯；乙醯基苯乙烯；甲氧基苯乙烯；二乙烯基苯等。 Examples of the styrene monomer include styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, and propyl styrene. An alkyl styrene such as butyl styrene, hexyl styrene, heptyl styrene or octyl styrene; a halogenated styrene such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene or iodine styrene; Nitrostyrene; ethoxylated styrene; methoxystyrene; divinylbenzene.

乙烯基系單體可舉例如：乙酸乙烯酯、丙 酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、月桂酸乙烯酯等脂肪酸乙烯酯；氯乙烯、溴乙烯等鹵化乙烯；偏二氯乙烯等鹵化亞乙烯；乙烯基吡啶、乙烯基吡咯啶酮、乙烯基咔唑等含氮芳香族乙烯；丁二烯、異戊二烯、氯丁二烯等共軛二烯單體；丙烯腈、甲基丙烯腈等不飽和腈等。 Examples of the vinyl monomer include vinyl acetate such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, and vinyl laurate; and halogenated ethylene such as vinyl chloride or vinyl bromide; a vinylidene halide such as vinylidene chloride; a nitrogen-containing aromatic vinyl such as vinylpyridine, vinylpyrrolidone or vinylcarbazole; or a conjugated diene monomer such as butadiene, isoprene or chloroprene An unsaturated nitrile such as acrylonitrile or methacrylonitrile.

分子內具有複數個(甲基)丙烯醯基之單體可舉例如：1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯等分子內具有2個(甲基)丙烯醯基之單體；三羥甲基丙烷三(甲基)丙烯酸酯等分子內具有3個(甲基)丙烯醯基之單體等。 The monomer having a plurality of (meth) acrylonitrile groups in the molecule may, for example, be 1,4-butanediol di(meth)acrylate or 1,6-hexanediol di(meth)acrylate, , 9-decanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, three a monomer having two (meth) acrylonitrile groups in a molecule such as propylene glycol di(meth)acrylate; and three (meth) acrylonitrile groups in a molecule such as trimethylolpropane tri(meth)acrylate Monomers, etc.

為了進一步提高黏著劑層之耐久性，(甲基)丙烯酸系樹脂(A)之凝膠滲透層析法GPC之標準聚苯乙烯換算重量平均分子量(Mw)較佳為100萬以上。Mw之下限值更佳為110萬，又更佳為120萬，特佳為130萬。而且，Mw之上限值並無特別限制，惟從將黏著劑組成物加工為例如薄片狀(塗佈於基材)時之塗佈性之觀點來看，較佳為250萬，更佳為220萬，又更佳為200萬。Mw可為該等上限值與下限值之任意組合，例如可為100至250萬，更佳為110萬至220萬，又更佳為120至200萬。而且，以重量平均分子量Mw與數量平均分子量Mn之比(Mw/Mn)表示之分子量分布通常為1至10，較佳為2至8，又更佳為3至6。 In order to further improve the durability of the pressure-sensitive adhesive layer, the standard polystyrene-equivalent weight average molecular weight (Mw) of the gel permeation chromatography GPC of the (meth)acrylic resin (A) is preferably 1,000,000 or more. The lower limit of Mw is better at 1.1 million, and more preferably 1.2 million, and particularly good at 1.3 million. Further, the upper limit of the Mw is not particularly limited, but is preferably 2.5 million, more preferably from the viewpoint of coating properties of the adhesive composition into, for example, a sheet form (coated on a substrate). 2.2 million, and better 2 million. Mw may be any combination of the upper limit value and the lower limit value, and may be, for example, 100 to 2.5 million, more preferably 1.1 million to 2.2 million, and still more preferably 1.2 to 2 million. Further, the molecular weight distribution expressed by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw/Mn) is usually from 1 to 10, preferably from 2 to 8, more preferably from 3 to 6.

而且，(甲基)丙烯酸系樹脂(A)較佳為在GPC流出曲線上之Mw於1000至250萬的範圍具有單一譜峰。若使用該譜峰數為1之(甲基)丙烯酸系樹脂(A)，則有利於提高黏著劑層、附黏著劑層之光學膜及含有其之光學積層體之耐久性。 Further, the (meth)acrylic resin (A) preferably has a single peak in the range of 1,000 to 2.5 million in Mw on the GPC elution curve. When the (meth)acrylic resin (A) having the number of peaks of 1 is used, it is advantageous in improving the durability of the adhesive layer, the optical film with the adhesive layer, and the optical laminate containing the same.

所得之流出曲線於上述範圍「具有單一譜峰」係意指Mw於1000至250萬之範圍中僅具1個極大值。本說明書中，GPC流出曲線中係將S/N比為30以上者定義為譜峰。又，GPC流出曲線之譜峰數目及(甲基)丙烯酸系樹脂(A)之Mw及Mn可依實施例處所記載之GPC測定條件求得。 The resulting outflow curve in the above range "having a single peak" means that Mw has only one maximum value in the range of 1,000 to 2.5 million. In the present specification, a GPC outflow curve is defined as a peak in which the S/N ratio is 30 or more. Further, the number of peaks of the GPC elution curve and the Mw and Mn of the (meth)acrylic resin (A) can be determined by the GPC measurement conditions described in the examples.

(甲基)丙烯酸系樹脂(A)在溶解於乙酸乙酯並成為濃度20質量%之溶液時，在25℃的黏度較佳為3萬mPa‧s以下，更佳為100至2萬mPa‧s。若為上述範圍之黏度，則從將黏著劑組成物塗佈於基材時之塗佈性之觀點來看係屬有利。又，黏度可藉由布氏(Brookfield)黏度計測定。 When the (meth)acrylic resin (A) is dissolved in ethyl acetate to have a concentration of 20% by mass, the viscosity at 25 ° C is preferably 30,000 mPa ‧ or less, more preferably 100 to 20,000 mPa ‧ s. When the viscosity is in the above range, it is advantageous from the viewpoint of coatability when the adhesive composition is applied to a substrate. Also, the viscosity can be measured by a Brookfield viscometer.

(甲基)丙烯酸系樹脂(A)之玻璃轉移溫度(Tg)例如可為-60至20℃，較佳為-50至10℃，又更佳為-40至0℃。若玻璃轉移溫度為上述範圍，則有利於提高黏著劑層之耐久性。又，玻璃轉移溫度可藉由示差掃描熱量計(DSC)測定。 The glass transition temperature (Tg) of the (meth)acrylic resin (A) may be, for example, -60 to 20 ° C, preferably -50 to 10 ° C, and more preferably -40 to 0 ° C. If the glass transition temperature is in the above range, it is advantageous to improve the durability of the adhesive layer. Also, the glass transition temperature can be measured by a differential scanning calorimeter (DSC).

(甲基)丙烯酸系樹脂(A)例如可藉由溶液聚合法、塊狀聚合法、懸浮聚合法、乳化聚合法等公知方法 而製造，尤其較佳為溶液聚合法。溶液聚合法可舉例如下述方法：將單體及有機溶媒混合，在氮環境下添加熱聚合起始劑，於40至90℃，較佳為50至80℃左右之溫度條件下攪拌3至15小時左右。為了調控反應，可在聚合中連續地或間歇地添加單體、熱聚合起始劑。該單體、熱起始劑可為已添加於有機溶媒之狀態。 The (meth)acrylic resin (A) can be produced, for example, by a known method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method or an emulsion polymerization method, and a solution polymerization method is particularly preferable. The solution polymerization method may be, for example, a method in which a monomer and an organic solvent are mixed, and a thermal polymerization initiator is added under a nitrogen atmosphere, and stirred at a temperature of 40 to 90 ° C, preferably about 50 to 80 ° C, for 3 to 15 Hours or so. In order to modulate the reaction, a monomer or a thermal polymerization initiator may be continuously or intermittently added in the polymerization. The monomer and the hot starter may be in a state of being added to the organic solvent.

聚合起始劑係使用熱聚合起始劑、光聚合起始劑等。光聚合起始劑可舉例如：4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮等。熱聚合起始劑可舉例如：2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2-甲基丁腈)、1,1’-偶氮雙(環己烷-1-甲腈)、2,2’-偶氮雙(2,4-二甲基戊腈)、2,2’-偶氮雙(2,4-二甲基-4-甲氧基戊腈)、二甲基-2,2’-偶氮雙(2-甲基丙酸酯)、2,2’-偶氮雙(2-羥基甲基丙腈)等偶氮系化合物；月桂基過氧化物、第三丁基過氧化氫、過氧化苯甲醯、過氧化苯甲酸第三丁酯、異丙苯過氧化氫、過氧化二碳酸二異丙酯、過氧化二碳酸二丙酯、過氧化第三丁基新癸酸酯、過氧化第三丁基新戊酸酯、(3,5,5-三甲基己醯基)過氧化物等有機過氧化物；過硫酸鉀、過硫酸銨、過氧化氫等無機過氧化物等。而且，亦可使用併用過氧化物與還原劑之氧化還原系起始劑等。 As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, or the like is used. The photopolymerization initiator may, for example, be 4-(2-hydroxyethoxy)phenyl (2-hydroxy-2-propyl) ketone or the like. The thermal polymerization initiator may, for example, be 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane) -1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxypenta Azo compound such as nitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-hydroxymethylpropionitrile); lauryl Peroxide, tert-butyl hydroperoxide, benzammonium peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate , organic peroxides such as perbutyl tert- phthalate, tributyl pivalate peroxide, (3,5,5-trimethylhexyl) peroxide; potassium persulfate, An inorganic peroxide such as ammonium persulfate or hydrogen peroxide. Further, a redox initiator such as a peroxide and a reducing agent may be used in combination.

相對於構成(甲基)丙烯酸系樹脂(A)之單體總量100質量份，聚合起始劑之比例為0.001至5質量份左右。(甲基)丙烯酸系樹脂(A)之聚合，可使用藉由活性能量射線之聚合法，例如藉由紫外線等之聚合法。 The ratio of the polymerization initiator is about 0.001 to 5 parts by mass based on 100 parts by mass of the total of the monomers constituting the (meth)acrylic resin (A). As the polymerization of the (meth)acrylic resin (A), a polymerization method by an active energy ray, for example, a polymerization method by ultraviolet rays or the like can be used.

有機溶媒可舉例如：甲苯、二甲苯等芳香族烴類；乙酸乙酯、乙酸丁酯等酯類；丙醇、異丙醇等脂肪族醇類；丙酮、甲基乙酮、甲基異丁酮等酮類等。 Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propanol and isopropanol; acetone, methyl ethyl ketone, and methyl isobutylene. Ketones such as ketones.

[1-2]交聯劑(B) [1-2] Crosslinking agent (B)

本發明之黏著劑組成物係含有交聯劑(B)。該交聯劑(B)只要為可與(甲基)丙烯酸系樹脂(A)中含有羥基或乙醯乙醯基之極性官能基反應者即可。本發明中，導入於(甲基)丙烯酸系樹脂(A)的側鏈之羥基或乙醯乙醯基會與交聯劑(B)反應，而形成有利於耐久性(例如黏著劑層之抗發泡性、抗剝離性及抗凝集破壞性等)之交聯構造。 The adhesive composition of the present invention contains a crosslinking agent (B). The crosslinking agent (B) may be any one which can react with a polar functional group having a hydroxyl group or an ethyl oxime group in the (meth)acrylic resin (A). In the present invention, the hydroxyl group or the ethyl oxime group introduced into the side chain of the (meth)acrylic resin (A) reacts with the crosslinking agent (B) to form a favorable durability (for example, an adhesive layer resistance). Crosslinked structure of foaming property, peeling resistance, and anti-aggregation destructive property, etc.).

交聯劑(B)可舉出慣用的交聯劑，例如可舉出異氰酸酯系化合物、環氧化合物、氮丙啶化合物、金屬螫合物化合物、過氧化物等，尤其是從黏著劑組成物之適用期(pot life)和交聯速度之觀點、及附黏著劑層之光學膜和光學積層體之耐久性等觀點來看，較佳為異氰酸酯系化合物。 The crosslinking agent (B) may, for example, be a conventional crosslinking agent, and examples thereof include an isocyanate compound, an epoxy compound, an aziridine compound, a metal chelate compound, a peroxide, and the like, particularly from an adhesive composition. From the viewpoints of the pot life and the crosslinking speed, and the durability of the optical film and the optical layered body with the adhesive layer, an isocyanate compound is preferable.

異氰酸酯系化合物較佳為分子內具有至少2個異氰酸基(-NCO)之化合物，可舉例如：脂肪族異氰酸酯系化合物(例如六亞甲基二異氰酸酯等)、脂環族異氰酸酯系化合物(例如異佛酮二異氰酸酯、氫化伸苯二甲基二異氰酸酯、氫化二苯基甲烷二異氰酸酯等)、芳香族異氰酸酯系化合物(例如甲伸苯基二異氰酸酯、伸苯二甲基二異氰酸酯、二苯基甲烷二異氰酸酯、萘二異氰酸酯、三苯基甲烷三異氰酸酯等)等。而且，交聯劑(B)可為前述異氰酸酯系 化合物之多元醇化合物之加成物(加成體)[例如甘油、三羥甲基丙烷等之加成物]、三聚異氰酸酯化物、縮二脲型化合物、聚醚多元醇、聚酯多元醇、丙烯酸多元醇、聚丁二烯多元醇、聚異戊二烯多元醇等與經加成反應之胺甲酸乙酯預聚物型之異氰酸酯化合物等的衍生物。交聯劑(B)可單獨使用或組合二種以上使用。該等中，可舉出具代表性的芳香族異氰酸酯系化合物(例如甲伸苯基二異氰酸酯、伸苯二甲基二異氰酸酯等)、脂肪族異氰酸酯系化合物(例如六亞甲基二異氰酸酯等)或該等之多元醇化合物(例如甘油、三羥甲基丙烷等)加成物。交聯劑(B)若為芳香族異氰酸酯系化合物及/或該等之多元醇化合物加成物，則可提高附黏著劑層之光學膜之耐久性。尤其，若為甲伸苯基二異氰酸酯系化合物及/或該等多元醇化合物之加成物，則亦可進一步提高耐久性。 The isocyanate compound is preferably a compound having at least two isocyanato groups (-NCO) in the molecule, and examples thereof include an aliphatic isocyanate compound (for example, hexamethylene diisocyanate) and an alicyclic isocyanate compound ( For example, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc., aromatic isocyanate compounds (for example, methylphenyl diisocyanate, benzoyl diisocyanate, diphenyl) Methane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc.). Further, the crosslinking agent (B) may be an adduct (adduct) of a polyol compound of the above isocyanate compound (for example, an adduct of glycerin or trimethylolpropane), a trimer isocyanate, or a dimer. Isocyanate compound of urea type prepolymer type with urea compound, polyether polyol, polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene polyol, etc. Derivatives of etc. The crosslinking agent (B) may be used singly or in combination of two or more. Among these, a typical aromatic isocyanate compound (for example, methylphenylene diisocyanate or benzoyl diisocyanate) or an aliphatic isocyanate compound (for example, hexamethylene diisocyanate) or An adduct of such a polyol compound (e.g., glycerin, trimethylolpropane, etc.). When the crosslinking agent (B) is an aromatic isocyanate compound and/or a polyol compound adduct, the durability of the optical film with the adhesive layer can be improved. In particular, if it is a methyl phenyl diisocyanate compound and/or an adduct of these polyol compounds, durability can be further improved.

相對於(甲基)丙烯酸系樹脂(A)100質量份，交聯劑(B)之比例較佳為0.01至10質量份，更佳為0.1至5質量份，又更佳為0.15至1質量份，尤佳為0.2至0.5質量份。交聯劑(B)之比例若為上述上限值以下，則有利於提高抗剝離性，若為上述下限值以上，則有利於提高抗發泡性、重工性。 The ratio of the crosslinking agent (B) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, still more preferably 0.15 to 1 part by mass based on 100 parts by mass of the (meth)acrylic resin (A). It is especially preferably 0.2 to 0.5 parts by mass. When the ratio of the crosslinking agent (B) is at most the above upper limit value, it is advantageous in improving the peeling resistance, and when it is at least the above lower limit value, it is advantageous in improving the foaming resistance and the reworkability.

[1-3]矽烷化合物(C) [1-3] decane compound (C)

黏著劑組成物係含有矽烷化合物(C)。藉由含有該矽烷化合物(C)，可提高黏著劑層與基材(例如金屬層、透明電極、玻璃基板等)等之密著性(或接著性)。矽烷化合物(C) 只要為可與(甲基)丙烯酸系樹脂(A)之反應性基(例如羥基、乙醯乙醯基)鍵結之矽烷化合物即可，可舉例如：乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基參(2-甲氧基乙氧基)矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基乙氧基二甲基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、1,3-雙(3’-三甲氧基丙基)尿素等。 The adhesive composition contains a decane compound (C). By containing the decane compound (C), the adhesion (or adhesion) of the adhesive layer to a substrate (for example, a metal layer, a transparent electrode, a glass substrate, or the like) can be improved. The decane compound (C) may be a decane compound which can be bonded to a reactive group (for example, a hydroxyl group or an ethyl fluorenyl group) of the (meth)acrylic resin (A), and examples thereof include a vinyltrimethoxy group. Decane, vinyltriethoxydecane, vinyl ginseng (2-methoxyethoxy)decane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethyl Oxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylethoxydimethyl decane, 2-(3,4-epoxycyclohexyl Ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropylidene Trimethoxy decane, 1,3-bis(3'-trimethoxypropyl) urea, and the like.

而且，矽烷化合物(C)可為聚矽氧寡聚物型化合物，若將該聚矽氧寡聚物以單體彼此的組合表示，則可舉例如：3-巰基丙基二甲氧基矽烷或3-巰基丙基三甲氧基矽烷/四甲氧基矽烷寡聚物、3-巰基甲基二甲氧基矽烷或3-巰基甲基三甲氧基矽烷/四乙氧基矽烷寡聚物、3-巰基丙基二乙氧基矽烷或3-巰基丙基三乙氧基矽烷/四甲氧基矽烷寡聚物、3-巰基甲基二乙氧基矽烷或3-巰基甲基三乙氧基矽烷/四乙氧基矽烷寡聚物等含巰基烷基之寡聚物；將該含巰基烷基之寡聚物的巰基烷基置換為其他取代基[例如3-環氧丙氧基丙基、(甲基)丙烯醯氧基丙基、乙烯基、胺基等]之寡聚物等。 Further, the decane compound (C) may be a polyoxyxene oligomer type compound, and if the polyoxy oxy oligomer is represented by a combination of monomers, for example, 3-mercaptopropyldimethoxydecane may be mentioned. Or 3-mercaptopropyltrimethoxydecane/tetramethoxydecane oligomer, 3-mercaptomethyldimethoxydecane or 3-mercaptomethyltrimethoxydecane/tetraethoxydecane oligomer, 3-mercaptopropyldiethoxydecane or 3-mercaptopropyltriethoxydecane/tetramethoxydecane oligomer, 3-mercaptomethyldiethoxydecane or 3-mercaptomethyltriethoxylate a mercaptoalkyl group-containing oligomer such as a decane/tetraethoxydecane oligomer; a mercaptoalkyl group-containing oligomer of a mercaptoalkyl group substituted with another substituent [eg 3-epoxypropoxypropane An oligomer such as a (meth)acryloxypropyl group, a vinyl group, an amine group or the like.

矽烷化合物(C)較佳可為下式(c1)所示之矽烷化合物。黏著劑組成物若含有下式(c1)所示之矽烷化合物，則可進一步提高密著性(或接著性)，故可形成抗剝離 性優異之黏著劑層。又，該黏著劑層重工性亦優異。尤其在高溫環境下將黏著劑層應用(或積層)於透明電極(例如ITO基板等)時，亦可維持密著性(或接著性)並顯示高耐久性。 The decane compound (C) is preferably a decane compound represented by the following formula (c1). When the oxime compound represented by the following formula (c1) is contained in the adhesive composition, the adhesion (or adhesion) can be further improved, so that an adhesive layer excellent in peeling resistance can be formed. Further, the adhesive layer is also excellent in workability. In particular, when an adhesive layer is applied (or laminated) to a transparent electrode (for example, an ITO substrate) in a high-temperature environment, adhesion (or adhesion) can be maintained and high durability can be exhibited.

(式中，B表示碳數1至20之烷二基或碳數3至20之二價脂環式烴基，構成前述烷二基及前述脂環式烴基之-CH2-可經取代為-O-或-CO-，R1表示碳數1至5之烷基，R2、R3、R4、R5及R6分別獨立表示碳數1至5之烷基或碳數1至5之烷氧基) (wherein, B represents an alkylenediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and -CH 2 - constituting the aforementioned alkanediyl group and the aforementioned alicyclic hydrocarbon group may be substituted with - O- or -CO-, R 1 represents an alkyl group having 1 to 5 carbon atoms, and R 2 , R 3 , R 4 , R 5 and R 6 each independently represent an alkyl group having 1 to 5 carbon atoms or a carbon number of 1 to 5 Alkoxy)

式(c1)中，B表示例如：亞甲基、伸乙基、三亞甲基、四亞甲基、六亞甲基、七亞甲基、八亞甲基等碳數1至20之烷二基；伸環丁基(例如1,2-伸環丁基)、伸環戊基(例如1,2-伸環戊基)、伸環己基(例如1,2-伸環己基)、伸環辛基(例如1,2-伸環辛基)等碳數3至20之二價脂環式烴基；或構成該等烷二基及前述脂環式烴基之-CH2-取代為-O-或-CO-之基。較佳之B為碳數1至10之烷二基。R1表示例如甲基、乙基、丙基、異丙基、丁基、第二丁基、第三丁基、戊基等碳數1至5之烷基，R2、R3、R4、R5及R6分別獨立表示例如前述R1所例示的碳數1至5之烷基；或例如甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、第 二丁氧基、第三丁氧基等碳數1至5之烷氧基。較佳之R2、R3、R4、R5及R6為碳數1至5之烷氧基。該等矽烷化合物(C)可單獨使用或組合二種以上使用。 In the formula (c1), B represents, for example, a methylene group, an exoethyl group, a trimethylene group, a tetramethylene group, a hexamethylene group, a hepethylene group, an octamethyl group or the like having 1 to 20 carbon atoms. a cyclobutyl group (for example, 1,2-cyclopentene butyl), a cyclopentyl group (for example, 1,2-cyclopentyl), a cyclohexyl group (for example, 1,2-extended cyclohexyl), a ring a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms such as an octyl group (e.g., 1,2-cyclooctyl); or a -CH 2 - constituting the alkanediyl group and the aforementioned alicyclic hydrocarbon group is -O- Or the base of -CO-. Preferably, B is an alkanediyl group having 1 to 10 carbon atoms. R 1 represents an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a t-butyl group or a pentyl group, and R 2 , R 3 and R 4 . And R 5 and R 6 each independently represent, for example, the alkyl group having 1 to 5 carbon atoms exemplified in the above R 1 ; or, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, second Alkoxy group having 1 to 5 carbon atoms such as a butoxy group and a third butoxy group. Preferably, R 2 , R 3 , R 4 , R 5 and R 6 are alkoxy groups having 1 to 5 carbon atoms. These decane compounds (C) may be used singly or in combination of two or more.

具體之矽烷化合物(c1)可舉例如：(三甲氧基矽基)甲烷、1,2-雙(三甲氧基矽基)乙烷、1,2-雙(三乙氧基矽基)乙烷、1,3-雙(三甲氧基矽基)丙烷、1,3-雙(三乙氧基矽基)丙烷、1,4-雙(三甲氧基矽基)丁烷、1,4-雙(三乙氧基矽基)丁烷、1,5-雙(三甲氧基矽基)戊烷、1,5-雙(三乙氧基矽基)戊烷、1,6-雙(三甲氧基矽基)己烷、1,6-雙(三乙氧基矽基)己烷、1,6-雙(三丙氧基矽基)己烷、1,8-雙(三甲氧基矽基)辛烷、1,8-雙(三乙氧基矽基)辛烷、1,8-雙(三丙氧基矽基)辛烷等雙(三C1-5烷氧基矽基)C1-10烷烴；雙(二甲氧基甲基矽基)甲烷、1,2-雙(二甲氧基甲基矽基)乙烷、1,2-雙(二甲氧基乙基矽基)乙烷、1,4-雙(二甲氧基甲基矽基)丁烷、1,4-雙(二甲氧基乙基矽基)丁烷、1,6-雙(二甲氧基甲基矽基)己烷、1,6-雙(二甲氧基乙基矽基)己烷、1,8-雙(二甲氧基甲基矽基)辛烷、1,8-雙(二甲氧基乙基矽基)辛烷等雙(二C1-5烷氧基C1-5烷基矽基)C1-10烷烴；1,6-雙(甲氧基二甲基矽基)己烷、1,8-雙(甲氧基二甲基矽基)辛烷等雙(單C1-5烷氧基-二C1-5烷基矽基)C1-10烷烴等。該等之中，因為可有效地提高抗剝離性等，故較佳為1,2-雙(三甲氧基矽基)乙烷、1,3-雙(三甲氧基矽基)丙烷、1,4-雙(三甲氧基矽基)丁烷、1,5-雙(三甲氧基矽基)戊烷、1,6-雙(三甲氧基矽基)己烷、1,8-雙(三甲氧基矽基)辛烷等雙(三C1-3烷氧基矽 基)C1-10烷烴，尤佳為1,6-雙(三甲氧基矽基)己烷、1,8-雙(三甲氧基矽基)辛烷。該等矽烷化合物(c1)可單獨使用或組合二種以上使用。 Specific examples of the decane compound (c1) include (trimethoxyindenyl)methane, 1,2-bis(trimethoxyindenyl)ethane, and 1,2-bis(triethoxyindenyl)ethane. , 1,3-bis(trimethoxyindenyl)propane, 1,3-bis(triethoxyindenyl)propane, 1,4-bis(trimethoxydecyl)butane, 1,4-double (triethoxyindenyl)butane, 1,5-bis(trimethoxydecyl)pentane, 1,5-bis(triethoxydecyl)pentane, 1,6-bis (trimethoxy) Hexyl, hexyl, 1,6-bis(triethoxyindenyl)hexane, 1,6-bis(tripropoxydecyl)hexane, 1,8-bis(trimethoxyindenyl) Bis(tri-C 1-5 alkoxyfluorenyl) C such as octane, 1,8-bis(triethoxyindenyl)octane, 1,8-bis(tripropoxydecyl)octane 1-10 alkane; bis(dimethoxymethylindenyl)methane, 1,2-bis(dimethoxymethylindenyl)ethane, 1,2-bis(dimethoxyethylhydrazino) Ethane, 1,4-bis(dimethoxymethylindenyl)butane, 1,4-bis(dimethoxyethylindenyl)butane, 1,6-bis(dimethoxy) Methylmercapto)hexane, 1,6-bis(dimethoxyethylindenyl)hexane, 1,8-bis(dimethoxymethylindenyl)octane, 1,8-bis ( Dimethoxyethyl decyl)octane C 1-5 alkoxy-C 1-5 alkyl silicon based) C 1-10 alkanes; 1,6-bis (methoxymethyl silicon based dimethyl) hexane, 1,8-bis (methoxymethyl two A bis(mono C 1-5 alkoxy-di C 1-5 alkyl fluorenyl) C 1-10 alkane such as methylmercapto)octane. Among these, 1,2-bis(trimethoxyindenyl)ethane, 1,3-bis(trimethoxyindenyl)propane, and 1, are preferable because the peeling resistance and the like can be effectively improved. 4-bis(trimethoxyindenyl)butane, 1,5-bis(trimethoxydecyl)pentane, 1,6-bis(trimethoxydecyl)hexane, 1,8-bis (trimethyl) Bis(tri-C 1-3 alkoxyfluorenyl) C 1-10 alkane such as oxyindenyl)octane, especially preferably 1,6-bis(trimethoxyindenyl)hexane, 1,8-double (trimethoxyindenyl)octane. These decane compounds (c1) may be used singly or in combination of two or more.

相對於(甲基)丙烯酸系樹脂(A)100質量份，矽烷化合物(C)之比例較佳為0.01至10質量份，更佳為0.05至3質量份，又更佳為0.1至1質量份，特佳為0.2至0.5質量份。矽烷化合物(C)之比例若為上述上限值以下，則有利於抑制矽烷化合物(C)從黏著劑層滲出，若為上述下限值以上，則容易提高黏著劑層與基材(例如金屬層、玻璃基板等)之密著性(或接著性)，亦有利於提高抗剝離性等。 The proportion of the decane compound (C) is preferably from 0.01 to 10 parts by mass, more preferably from 0.05 to 3 parts by mass, still more preferably from 0.1 to 1 part by mass, per 100 parts by mass of the (meth)acrylic resin (A). It is particularly preferably from 0.2 to 0.5 parts by mass. When the ratio of the decane compound (C) is at most the above upper limit, it is advantageous for suppressing the decane compound (C) from oozing out of the adhesive layer, and if it is at least the above lower limit, it is easy to increase the adhesive layer and the substrate (for example, metal). The adhesion (or adhesion) of the layer, the glass substrate, and the like is also advantageous for improving the peeling resistance and the like.

[1-4]抗靜電劑 [1-4]Antistatic agent

本發明之黏著劑組成物可進一步含有抗靜電劑。藉由含有抗靜電劑，可提高黏著劑層之抗靜電性，例如可抑制將脫模膜、保護膜等剝離時產生的靜電所造成之不良等。抗靜電劑可舉出慣用者，較佳為離子性抗靜電劑(離子性化合物(D))。構成離子性抗靜電劑(離子性化合物(D))之陽離子可舉出有機陽離子、無機陽離子等。有機陽離子可舉例如：吡啶鎓陽離子、咪唑鎓陽離子、銨陽離子、鋶陽離子、鏻陽離子等。無機陽離子可舉例如：鋰陽離子、鉀陽離子、鈉陽離子、銫陽離子等鹼金屬陽離子；鎂陽離子、鈣陽離子等鹼土金屬陽離子等。構成離子性抗靜電劑(離子性化合物(D))之陰離子，可為無機陰離子及有機陰離子中之任一者，惟就抗靜電性能優異之點而言，較佳為含有氟原子之 陰離子。含有氟原子之陰離子可舉例如：六氟磷酸鹽陰離子(PF6 -)、雙(三氟甲烷磺醯基)醯亞胺陰離子[(CF3SO2)2N-]、雙(氟磺醯基)醯亞胺陰離子[(FSO2)2N-]、四(五氟苯基)硼酸酯陰離子[(C6F5)4B-]等。該等抗靜電劑可單獨使用或組合二種以上使用。尤佳為由雙(三氟甲烷磺醯基)醯亞胺陰離子[(CF3SO2)2N-]、雙(氟磺醯基)醯亞胺陰離子[(FSO2)2N-]及四(五氟苯基)硼酸酯陰離子[(C6F5)4B-]所成群組選出之至少1種。就黏著劑組成物之抗靜電性能的經時安定性優異之點而言，較佳為於室溫為固體之離子性抗靜電劑(離子性化合物(D))。而且，離子性化合物(D)較佳為包含含有氟原子之陰離子與有機陽離子之離子性化合物。 The adhesive composition of the present invention may further contain an antistatic agent. By containing an antistatic agent, the antistatic property of the adhesive layer can be improved, and for example, the defects caused by static electricity generated when the release film or the protective film is peeled off can be suppressed. The antistatic agent is exemplified, and an ionic antistatic agent (ionic compound (D)) is preferred. The cation constituting the ionic antistatic agent (ionic compound (D)) may, for example, be an organic cation or an inorganic cation. The organic cation may, for example, be a pyridinium cation, an imidazolium cation, an ammonium cation, a phosphonium cation or a phosphonium cation. Examples of the inorganic cation include an alkali metal cation such as a lithium cation, a potassium cation, a sodium cation or a phosphonium cation; an alkaline earth metal cation such as a magnesium cation or a calcium cation. The anion which constitutes the ionic antistatic agent (ionic compound (D)) may be either an inorganic anion or an organic anion, and is preferably an anion containing a fluorine atom from the viewpoint of excellent antistatic properties. The anion containing a fluorine atom may, for example, be a hexafluorophosphate anion (PF 6 - ), a bis(trifluoromethanesulfonyl) quinone imine [(CF 3 SO 2 ) 2 N - ], or a bis(fluorosulfonate) a quinone imine anion [(FSO 2 ) 2 N - ], a tetrakis(pentafluorophenyl) borate anion [(C 6 F 5 ) 4 B - ] or the like. These antistatic agents may be used singly or in combination of two or more. Particularly preferred is bis(trifluoromethanesulfonyl) anthracene anion [(CF 3 SO 2 ) 2 N - ], bis(fluorosulfonyl) quinone imine [(FSO 2 ) 2 N - ] and At least one selected from the group consisting of tetrakis(pentafluorophenyl) borate anion [(C 6 F 5 ) 4 B - ]. The ionic antistatic agent (ionic compound (D)) which is solid at room temperature is preferred in terms of the stability of the antistatic property of the adhesive composition. Further, the ionic compound (D) is preferably an ionic compound containing an anion containing a fluorine atom and an organic cation.

相對於(甲基)丙烯酸系樹脂(A)100質量份，離子性抗靜電劑(離子性化合物(D))之比例例如可為0.01至10質量份，較佳為0.1至5質量份，更佳為1至3質量份。 The ratio of the ionic antistatic agent (ionic compound (D)) to the (meth)acrylic resin (A) may be, for example, 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, more preferably 100 parts by mass of the (meth)acrylic resin (A). It is preferably 1 to 3 parts by mass.

[1-5]其他成分 [1-5] Other ingredients

本發明之黏著劑組成物可含有溶劑、交聯觸媒、紫外線吸收劑、耐候安定劑、賦黏劑(tackifier)、塑化劑、軟化劑、染料、顏料、無機填料、光散射性微粒子等添加劑之單獨或二種以上。而且，亦可於黏著劑組成物調配紫外線硬化性化合物，並在形成黏著劑層後照射紫外線而使硬化，而形成更硬的黏著劑層。交聯觸媒可舉例如：六亞甲基二胺、伸乙二胺、聚乙烯亞 胺、六亞甲基四胺、二伸乙三胺、三伸乙四胺、異佛酮二胺、三亞甲基二胺、多胺基樹脂及三聚氰胺樹脂等胺系化合物等。 The adhesive composition of the present invention may contain a solvent, a crosslinking catalyst, an ultraviolet absorber, a weathering stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, a light-scattering fine particle, etc. The additive may be used alone or in combination of two or more. Further, an ultraviolet curable compound may be blended in the adhesive composition, and after the adhesive layer is formed, ultraviolet rays are irradiated to be hardened to form a harder adhesive layer. The cross-linking catalyst may, for example, be hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, An amine compound such as trimethylene diamine, polyamine based resin or melamine resin.

從提高黏著劑層、附黏著劑層之光學膜及含有該等之光學積層體的抗金屬腐蝕性之觀點來看，本發明之黏著劑組成物可含有防鏽劑。防鏽劑可舉例如：苯并***系化合物等***系化合物；苯并噻唑系化合物等噻唑系化合物；苯甲基咪唑系化合物等咪唑系化合物；咪唑啉系化合物；喹啉系化合物；吡啶系化合物；嘧啶系化合物；吲哚系化合物；胺系化合物；尿素系化合物；苯甲酸鈉；苯甲基硫醇系化合物；二-第二丁基硫化物；及二苯基亞碸等。 The adhesive composition of the present invention may contain a rust preventive agent from the viewpoint of improving the adhesive layer, the optical film with the adhesive layer, and the metal corrosion resistance of the optical laminate. Examples of the rust preventive agent include a triazole compound such as a benzotriazole compound; a thiazole compound such as a benzothiazole compound; an imidazole compound such as a benzylimidazole compound; an imidazoline compound; and a quinoline compound; a pyridine compound; a pyrimidine compound; an anthraquinone compound; an amine compound; a urea compound; a sodium benzoate; a benzylthiol compound; a di-second butyl sulfide;

較佳態樣中，本發明之黏著劑組成物實質上不含有光聚合起始劑及其分解物。其原因係黏著劑組成物中的光聚合起始劑及其分解物會有阻礙耐久性優異的黏著劑層形成之虞。在此，實質上不含有意指相對於黏著劑組成物100質量份為1.0質量份以下，較佳為0.1質量份以下，更佳為0.01質量份以下，又更佳為0.001質量份以下，尤其最佳為0質量份。 In a preferred embodiment, the adhesive composition of the present invention contains substantially no photopolymerization initiator and its decomposition product. The reason for this is that the photopolymerization initiator and the decomposition product thereof in the adhesive composition have a tendency to prevent the formation of an adhesive layer excellent in durability. Here, the substantially no content means 1.0 part by mass or less, preferably 0.1 part by mass or less, more preferably 0.01 part by mass or less, still more preferably 0.001 part by mass or less, and particularly preferably 0.001 part by mass or less, based on 100 parts by mass of the adhesive composition. The optimum is 0 parts by mass.

如上述，本發明之黏著劑組成物係含有特定(甲基)丙烯酸系樹脂(A)、交聯劑(B)及矽烷化合物(C)，故可提高由該黏著劑組成物所構成的黏著劑層之耐久性，即使在高溫環境，亦可有效地抑制界面處之剝離(或浮翹)及發泡。而且，即使產生強收縮應力，黏著劑層亦可有效 地緩和該應力，故可防止伴隨光學膜(例如偏光板)收縮所產生之露白。推測其原因如下：本發明之黏著劑組成物所含之(甲基)丙烯酸系樹脂(A)係於側鏈具有反應性相異之二個官能基，亦即，於側鏈具有羥基及乙醯乙醯基，且以特定之質量比含有具有各個官能基之構成單元，故黏著劑組成物可形成黏著劑層，該黏著劑層係具有最適於展現優異的耐久性之交聯構造和交聯密度。 As described above, the adhesive composition of the present invention contains the specific (meth)acrylic resin (A), the crosslinking agent (B), and the decane compound (C), so that the adhesion composed of the adhesive composition can be improved. The durability of the agent layer can effectively suppress peeling (or floating) and foaming at the interface even in a high temperature environment. Further, even if a strong shrinkage stress is generated, the adhesive layer can effectively alleviate the stress, so that whitening caused by shrinkage of an optical film (e.g., a polarizing plate) can be prevented. The reason is presumed to be as follows: The (meth)acrylic resin (A) contained in the adhesive composition of the present invention is a functional group having two reactive groups which are reactive in the side chain, that is, having a hydroxyl group and a side chain in the side chain. The urethane group contains a constituent unit having a respective functional group at a specific mass ratio, so that the adhesive composition can form an adhesive layer having a crosslinked structure and a cross which are most suitable for exhibiting excellent durability. Joint density.

[2]黏著劑層及附黏著劑層之光學膜以及該等之製造方法 [2] Adhesive layer and optical film with adhesive layer and manufacturing method thereof

本發明係包括包含前述黏著劑組成物之黏著劑層。該黏著劑層係例如可藉由將前述黏著劑組成物作成溶解或分散於溶劑而含有溶劑之黏著劑組成物，接著將之於光學膜或脫模膜表面進行塗佈、乾燥而形成。 The present invention includes an adhesive layer comprising the aforementioned adhesive composition. The pressure-sensitive adhesive layer can be formed, for example, by applying the above-mentioned pressure-sensitive adhesive composition to a solvent composition containing a solvent dissolved or dispersed in a solvent, followed by coating and drying the surface of the optical film or the release film.

而且，本發明亦包括一種附黏著劑層之光學膜，係含有光學膜、及於該光學膜的至少一面積層之前述黏著劑層。 Moreover, the present invention also includes an optical film with an adhesive layer comprising an optical film and the aforementioned adhesive layer on at least one area of the optical film.

本發明之黏著劑層及該附黏著劑層之光學膜係由前述黏著劑組成物所形成，故在嚴苛的耐久條件(例如100℃以上之耐久條件)中亦具有優異的耐久性。 The adhesive layer of the present invention and the optical film of the adhesive layer are formed of the above-mentioned adhesive composition, and therefore have excellent durability in severe durability conditions (for example, durability conditions of 100 ° C or more).

第1圖之示意剖面圖表示本發明之附黏著劑層之光學膜的一例。第1圖所示之附黏著劑層之光學膜1係積層有光學膜10、及於該光學膜單面之黏著劑層20。該黏著劑層20通常直接積層於光學膜10的表面。又，黏著劑層20可積層於光學膜10的兩面。 Fig. 1 is a schematic cross-sectional view showing an example of an optical film with an adhesive layer of the present invention. The optical film 1 with an adhesive layer shown in Fig. 1 is composed of an optical film 10 and an adhesive layer 20 on one side of the optical film. The adhesive layer 20 is usually laminated directly on the surface of the optical film 10. Further, the adhesive layer 20 can be laminated on both surfaces of the optical film 10.

將黏著劑層20積層於光學膜10的表面時，較佳為在光學膜10之貼合面及/或黏著劑層20之貼合面形成底塗層(primer layer)、或實施前述表面活性化處理(例如電漿處理、電暈處理等)，尤佳為實施電暈處理。 When the adhesive layer 20 is laminated on the surface of the optical film 10, it is preferred to form a primer layer on the bonding surface of the optical film 10 and/or the bonding surface of the adhesive layer 20, or to perform the aforementioned surface activity. For the treatment (for example, plasma treatment, corona treatment, etc.), it is particularly preferable to carry out corona treatment.

光學膜10為如第2圖所示之單面保護偏光板時，黏著劑層20通常係於偏光片面，亦即於偏光片2中與第1樹脂膜3為相反側的面積層(較佳為直接積層)。光學膜10為如第3圖所示之兩面保護偏光板時，黏著劑層20可積層於第1、第2樹脂膜3、4中之任一者之外面，也可積層於兩者之外面。 When the optical film 10 is a single-sided protective polarizing plate as shown in Fig. 2, the adhesive layer 20 is usually applied to the polarizing plate surface, that is, the area layer on the opposite side of the polarizing film 2 from the first resin film 3 (preferably For direct accumulation). When the optical film 10 is a double-sided protective polarizing plate as shown in FIG. 3, the adhesive layer 20 may be laminated on the outer surface of either of the first and second resin films 3 and 4, or may be laminated on both surfaces. .

在光學膜10與黏著劑層20之間可另外設置抗靜電層。抗靜電層可使用：聚矽氧烷等矽系材料，摻錫氧化銦、摻錫氧化銻等無機金屬系材料，聚噻吩、聚苯乙烯磺酸、聚苯胺等有機高分子系材料。 An antistatic layer may be additionally disposed between the optical film 10 and the adhesive layer 20. As the antistatic layer, an anthracene-based material such as polyoxyalkylene oxide, an inorganic metal-based material such as tin-doped indium oxide or tin-doped cerium oxide, or an organic polymer-based material such as polythiophene, polystyrenesulfonic acid or polyaniline may be used.

附黏著劑層之光學膜1可含有積層於黏著劑層20之外面之分離膜(剝離膜)。該分離膜通常係在使用黏著劑層20時(例如積層至透明導電極、玻璃基板時)被剝離去除。分離膜可係在例如由聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚碳酸酯、聚芳酯等各種樹脂所構成的膜之要形成黏著劑層20的面經實施聚矽氧處理等脫模處理者。 The optical film 1 with an adhesive layer may contain a separation film (release film) laminated on the outer surface of the adhesive layer 20. The separation membrane is usually peeled off when the adhesive layer 20 is used (for example, when laminated to a transparent conductive electrode or a glass substrate). The separation membrane may be formed on the surface of the film composed of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, or polyarylate to form the adhesive layer 20. Demolding treatment such as polyoxygen treatment.

藉由將構成上述黏著劑組成物之各成分溶解或分散於溶劑而作成含有溶劑之黏著劑組成物，接著將其於光學膜10表面進行塗佈、乾燥而形成黏著劑層20， 可獲得附黏著劑層之光學膜1。而且，藉由於分離膜之脫模處理面以與上述相同方式形成黏著劑層20，並將該黏著劑層20積層(轉印)於光學膜10的表面，亦可獲得附黏著劑層之光學膜1。 An adhesive composition containing a solvent is prepared by dissolving or dispersing the components constituting the above-mentioned adhesive composition in a solvent, and then coating and drying the surface of the optical film 10 to form an adhesive layer 20, thereby obtaining an adhesive. Optical film 1 of the adhesive layer. Further, by forming the adhesive layer 20 in the same manner as described above by the release-treated surface of the separation film, and laminating (transferring) the adhesive layer 20 on the surface of the optical film 10, the optical layer with the adhesive layer can also be obtained. Membrane 1.

黏著劑層之厚度通常為2至40μm，從附黏著劑層之光學膜之耐久性、附黏著劑層之光學膜之重工性等觀點來看，較佳為5至30μm，更佳為10至25μm。若黏著劑層之厚度為上限值以下，則重工性良好，若為下限值以上，則對於光學膜的尺寸變化之黏著劑層追隨性(或跟隨性)良好。 The thickness of the adhesive layer is usually 2 to 40 μm, preferably 5 to 30 μm, more preferably 10 to 10, from the viewpoint of the durability of the optical film with the adhesive layer and the reworkability of the optical film with the adhesive layer. 25 μm. When the thickness of the adhesive layer is less than or equal to the upper limit, the workability is good, and if it is at least the lower limit, the adhesive layer followability (or followability) with respect to the dimensional change of the optical film is good.

黏著劑層較佳為在23至80℃之溫度範圍顯示0.1至5MPa之儲藏彈性模數者。藉此，可更有效地提高附黏著劑層之光學膜之耐久性。「在23至80℃之溫度範圍顯示0.1至5MPa之儲藏彈性模數」意指在該範圍中之任一溫度的儲藏彈性模數皆為上述範圍內的值。儲藏彈性模數通常是隨著溫度上升而漸減，故若在23℃及80℃之儲藏彈性模數皆於上述範圍內，則可假設在該範圍溫度顯示上述範圍內之儲藏彈性模數。黏著劑層之儲藏彈性模數可使用市售的黏彈性測定裝置，例如REOMETRIC公司製之黏彈性測定裝置「DYNAMIC ANALYZERRDA II」而測定。 The adhesive layer is preferably one which exhibits a storage elastic modulus of 0.1 to 5 MPa in a temperature range of 23 to 80 °C. Thereby, the durability of the optical film with the adhesive layer can be more effectively improved. "The storage elastic modulus of 0.1 to 5 MPa in the temperature range of 23 to 80 ° C" means that the storage elastic modulus at any one of the ranges is a value within the above range. The storage elastic modulus generally decreases as the temperature rises. Therefore, if the storage elastic modulus at 23 ° C and 80 ° C is within the above range, it can be assumed that the storage elastic modulus in the above range is displayed in the range temperature. The storage elastic modulus of the adhesive layer can be measured using a commercially available viscoelasticity measuring device such as a viscoelasticity measuring device "DYNAMIC ANALYZERRDA II" manufactured by REOMETRIC.

作為交聯密度之一指標可使用膠化率。本發明之黏著劑層具有預定的交聯密度，故顯示預定的膠化率。亦即，本發明之黏著劑層之膠化率例如可為70至90質量%，較佳為75至90質量%，又更佳為75至85質量%。 若膠化率為下限值以上，則有利於黏著劑層之抗發泡性、重工性，若膠化率為上限值以下，則有利於抗剝離性。又，膠化率可藉由實施例處所記載之方法測定。 As an indicator of the crosslink density, a gelation rate can be used. The adhesive layer of the present invention has a predetermined crosslink density, so that a predetermined gelation rate is exhibited. That is, the gelation rate of the adhesive layer of the present invention may be, for example, 70 to 90% by mass, preferably 75 to 90% by mass, and still more preferably 75 to 85% by mass. When the gelation rate is at least the lower limit value, the foaming resistance and the reworkability of the pressure-sensitive adhesive layer are favored, and if the gelation ratio is at most the upper limit value, the peeling resistance is favored. Further, the gelation rate can be measured by the method described in the examples.

本發明之黏著劑層係具有預定的黏著力。亦即，於玻璃基板貼合前述黏著劑層，在溫度23℃、相對濕度50%之條件下，24小時後之前述黏著劑層之黏著力在剝離速度300mm/分鐘時，較佳為0.5至25N，更佳為0.5至20N，又更佳為0.5至15N，特佳為1至10N，尤佳為1.5至10N。黏著力若為下限值以上，則有利於重工性。又，黏著力可藉由實施例處所記載之方法而測定。 The adhesive layer of the present invention has a predetermined adhesive force. That is, the adhesive layer is bonded to the glass substrate, and the adhesive force of the adhesive layer after 24 hours at a temperature of 23 ° C and a relative humidity of 50% is preferably 0.5 to a peeling speed of 300 mm/min. 25N, more preferably 0.5 to 20N, still more preferably 0.5 to 15N, particularly preferably 1 to 10N, and particularly preferably 1.5 to 10N. If the adhesion is above the lower limit, it is advantageous for heavy work. Further, the adhesion can be measured by the method described in the examples.

[2-1]光學膜 [2-1] Optical film

構成附黏著劑層之光學膜1的光學膜10可為能組裝於於液晶顯示裝置等圖像顯示裝置之各種光學膜(具有光學特性的膜)。該光學膜10可為單層構造(例如偏光片、相位差膜、增亮膜、防眩膜、抗反射膜、擴散膜、聚光膜等光學功能性膜等)，也可為多層構造(例如偏光板、相位差板等)。光學膜10較佳為偏光板、偏光片、相位差板或相位差膜，尤其較佳為偏光板或偏光片。又，本說明書中，光學膜意指用以發揮顯示圖像(顯示畫面等)之功能的膜(例如用以發揮提高影像易見性之功能的膜)。而且，本說明書中，偏光板意指在偏光片至少一面積層有樹脂膜或樹脂層者，相位差板意指於相位差膜的至少一面積層有樹脂膜或樹脂層者。 The optical film 10 constituting the optical film 1 with an adhesive layer can be various optical films (films having optical characteristics) that can be incorporated in an image display device such as a liquid crystal display device. The optical film 10 may have a single layer structure (for example, a polarizer, a retardation film, a brightness enhancement film, an anti-glare film, an anti-reflection film, a diffusion film, an optical functional film such as a light-concentrating film, or the like), or may have a multilayer structure ( For example, a polarizing plate, a phase difference plate, etc.). The optical film 10 is preferably a polarizing plate, a polarizing plate, a phase difference plate or a retardation film, and particularly preferably a polarizing plate or a polarizing plate. In the present specification, the optical film means a film (for example, a film for exhibiting a function of improving image visibility) for displaying a function of displaying an image (display screen or the like). Further, in the present specification, the polarizing plate means a resin film or a resin layer in at least one area of the polarizing plate, and the phase difference plate means a resin film or a resin layer in at least one area of the retardation film.

[2-2]偏光板 [2-2] Polarizer

第2圖及第3圖係表示偏光板之層構成的例之示意剖面圖。第2圖所示之偏光板10a係於偏光片2的一面積層(或積層貼合)有第1樹脂膜3之單面保護偏光板，第3圖所示之偏光板10b係於偏光片2另一面進一步積層(或積層貼合)有第2樹脂膜4之兩面保護偏光板。第1、第2樹脂膜3、4可經由未於圖中顯示之接著劑層、黏著劑層而貼合於偏光片2。又，偏光板10a、10b可包含第1、第2樹脂膜3、4以外之其他膜、層。 2 and 3 are schematic cross-sectional views showing an example of a layer configuration of a polarizing plate. The polarizing plate 10a shown in Fig. 2 is a single-sided protective polarizing plate in which one layer of the polarizing plate 2 is laminated (or laminated) with the first resin film 3, and the polarizing plate 10b shown in Fig. 3 is attached to the polarizing plate 2. On the other surface, a double-sided protective polarizing plate having a second resin film 4 is further laminated (or laminated). The first and second resin films 3 and 4 can be bonded to the polarizer 2 via an adhesive layer or an adhesive layer which is not shown in the drawing. Further, the polarizing plates 10a and 10b may include other films and layers other than the first and second resin films 3 and 4.

偏光片2具有以下性質：吸收具有與其吸收軸平行之振動面的線性偏光，並穿透具有與吸收軸垂直相交(與穿透軸平行)之振動面的線性偏光。例如可使用在聚乙烯醇系樹脂膜吸附配向有二色性色素的膜。二色性色素可舉例如：碘、二色性有機染料等。 The polarizer 2 has a property of absorbing linear polarized light having a vibrating surface parallel to its absorption axis and penetrating linearly polarized light having a vibrating surface perpendicularly intersecting the absorption axis (parallel to the transmission axis). For example, a film in which a dichroic dye is adsorbed and adsorbed on a polyvinyl alcohol-based resin film can be used. The dichroic dye may, for example, be iodine or a dichroic organic dye.

聚乙烯醇系樹脂可藉由將聚乙酸乙烯酯系樹脂皂化而獲得。聚乙酸乙烯酯系樹脂可舉例如：乙酸乙烯酯之均聚物的聚乙酸乙烯酯、可與乙酸乙烯酯共聚合之單體(例如不飽和羧酸、烯烴、乙烯基醚、不飽和磺酸、具有銨基之(甲基)丙烯醯胺等)與乙酸乙烯酯之共聚物等。 The polyvinyl alcohol-based resin can be obtained by saponifying a polyvinyl acetate-based resin. Examples of the polyvinyl acetate-based resin include polyvinyl acetate which is a homopolymer of vinyl acetate, and a monomer copolymerizable with vinyl acetate (for example, an unsaturated carboxylic acid, an olefin, a vinyl ether, an unsaturated sulfonic acid). A copolymer of a (meth)acrylamide or the like having an ammonium group and a vinyl acetate.

聚乙烯醇系樹脂之皂化度通常為85至100莫耳%，較佳為98莫耳%以上。聚乙烯醇系樹脂可經改質，例如可為以醛類改質之聚乙烯醇甲醛或聚乙烯醇縮醛等。聚乙烯醇系樹脂之平均聚合度通常為1000至10000，較佳為1500至5000。又，聚乙烯醇系樹脂之平均聚合度可根據JIS K 6726求得。 The degree of saponification of the polyvinyl alcohol-based resin is usually from 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, and may be, for example, polyvinyl alcohol formaldehyde or polyvinyl acetal modified with an aldehyde. The average degree of polymerization of the polyvinyl alcohol-based resin is usually from 1,000 to 10,000, preferably from 1,500 to 5,000. Further, the average degree of polymerization of the polyvinyl alcohol-based resin can be determined in accordance with JIS K 6726.

通常將聚乙烯醇系樹脂所製膜者使用作為偏光片2之原料膜。聚乙烯醇系樹脂可以公知的方法製膜。原料膜之厚度通常為1至150μm，若考慮延伸容易度等，則較佳為10μm以上。 Usually, a film formed of a polyvinyl alcohol resin is used as a raw material film of the polarizer 2. The polyvinyl alcohol-based resin can be formed into a film by a known method. The thickness of the raw material film is usually from 1 to 150 μm, and is preferably 10 μm or more in consideration of easiness of elongation and the like.

偏光片2係例如可對原料膜實施單軸延伸步驟、以二色性色素將膜染色使吸附該二色性色素之步驟、以硼酸水溶液處理膜之步驟及水洗膜之步驟，最後進行乾燥而製造。偏光片2之厚度通常為1至30μm，從附黏著劑層之光學膜1之薄膜化的觀點來看，較佳為20μm以下，更佳為15μm以下，尤其是10μm以下。 The polarizer 2 is, for example, a step of performing a uniaxial stretching step on the raw material film, a step of dyeing the film with a dichroic dye to adsorb the dichroic dye, a step of treating the film with an aqueous solution of boric acid, and a step of washing the film, and finally drying. Manufacturing. The thickness of the polarizer 2 is usually from 1 to 30 μm, and is preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm or less from the viewpoint of film formation of the optical film 1 with an adhesive layer.

於聚乙烯醇系樹脂膜吸附配向二色性色素所成之偏光片2，係使用聚乙烯醇系樹脂膜之單獨膜作為原料膜，除了對該膜實施單軸延伸處理及二色性色素的染色處理之方法(設為方法(1))獲得以外，亦可藉由於基材膜塗佈含有聚乙烯醇系樹脂之塗佈液(水溶液等)，使乾燥而獲得具有聚乙烯醇系樹脂層之基材膜後，對每個基材膜進行單軸延伸，並對延伸後之聚乙烯醇系樹脂層實施二色性色素之染色處理，接著剝離去除基材膜之方法(設為方法(2))獲得。基材膜可使用由與可構成後述第1、第2樹脂膜3、4之熱塑性樹脂相同之熱塑性樹脂所構成的膜，較佳為由聚對苯二甲酸乙二酯等聚酯系樹脂、聚碳酸酯系樹脂、三乙酸纖維素等纖維素系樹脂、降莰烯系樹脂等環狀聚烯烴系樹脂、聚苯乙烯系樹脂等所構成的膜。若利用上述方法(2)，則容易製作薄膜之偏光片2，亦容易製作厚度7μm 以下偏光片2。 In the polarizing plate 2 obtained by adsorbing a dichroic dye to a polyvinyl alcohol-based resin film, a single film of a polyvinyl alcohol-based resin film is used as a raw material film, and the film is subjected to uniaxial stretching treatment and dichroic dye. In addition to the method of the dyeing treatment (the method (1)), the coating liquid (such as an aqueous solution) containing a polyvinyl alcohol-based resin may be applied to the base film to be dried to obtain a polyvinyl alcohol-based resin layer. After the base film, the base film is uniaxially stretched, and the stretched polyvinyl alcohol-based resin layer is subjected to a dyeing treatment of the dichroic dye, followed by peeling off the substrate film (the method is 2)) Obtained. As the base film, a film composed of a thermoplastic resin similar to the thermoplastic resin which can constitute the first and second resin films 3 and 4 to be described later can be used, and a polyester resin such as polyethylene terephthalate or preferably A film made of a polycarbonate resin such as a polycarbonate resin or a cellulose acetate such as triacetate, a cyclic polyolefin resin such as a norbornene resin, or a polystyrene resin. According to the above method (2), it is easy to produce the polarizer 2 of the film, and it is also easy to produce the polarizer 2 having a thickness of 7 μm or less.

第1、第2樹脂膜3、4係分別獨立並具有透光性，較佳為包含光學性透明之熱塑性樹脂的膜，例如可為：由鏈狀聚烯烴系樹脂(例如聚乙烯系樹脂、聚丙烯系樹脂等)、環狀聚烯烴系樹脂(例如降莰烯系樹脂等)等聚烯烴系樹脂；纖維素系樹脂(例如纖維素酯系樹脂等)；聚酯系樹脂(例如聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯等)；聚碳酸酯系樹脂(例如2,2-雙(4-羥基苯基)丙烷等雙酚所衍生之聚碳酸酯等)；(甲基)丙烯酸系樹脂；聚苯乙烯系樹脂；聚醚醚酮系樹脂；聚碸系樹脂、或該等之混合物、共聚物等所構成的膜。該等之中，第1、第2樹脂膜3、4分別係以由環狀聚烯烴系樹脂、聚碳酸酯系樹脂、纖維素系樹脂、聚酯系樹脂及(甲基)丙烯酸系樹脂等所構成的膜為較佳，以由纖維素系樹脂及環狀聚烯烴系樹脂等所構成的膜為更佳。 The first and second resin films 3 and 4 are each independently light transmissive, and are preferably a film containing an optically transparent thermoplastic resin, and may be, for example, a chain polyolefin resin (for example, a polyethylene resin, a polyolefin-based resin such as a polypropylene resin or a cyclic polyolefin resin (for example, a decene-based resin); a cellulose-based resin (for example, a cellulose ester-based resin); and a polyester-based resin (for example, a poly-pair) Ethylene phthalate, polyethylene naphthalate, polybutylene terephthalate, etc.; polycarbonate resin (for example, bisphenol such as 2,2-bis(4-hydroxyphenyl)propane (Derivative polycarbonate, etc.); (meth)acrylic resin; polystyrene resin; polyetheretherketone resin; polyfluorene-based resin, or a mixture of such a mixture or a copolymer. Among these, the first and second resin films 3 and 4 are made of a cyclic polyolefin resin, a polycarbonate resin, a cellulose resin, a polyester resin, a (meth)acrylic resin, or the like. The film to be formed is preferably a film composed of a cellulose resin or a cyclic polyolefin resin or the like.

鏈狀聚烯烴系樹脂可舉例如：聚乙烯樹脂、聚丙烯樹脂等鏈狀烯烴之均聚物，包含2種以上鏈狀烯烴之共聚物等。 The chain-like polyolefin resin may, for example, be a homopolymer of a chain olefin such as a polyethylene resin or a polypropylene resin, or a copolymer containing two or more kinds of chain olefins.

環狀聚烯烴系樹脂係以降莰烯、四環十二烯(別名：二甲橋八氫萘)或該等之衍生物為代表例之含有環狀烯烴作為聚合單元之樹脂的總稱。環狀聚烯烴系樹脂可舉出：環狀烯烴之開環(共)聚合物及其氫化物，環狀烯烴之加成聚合物，環狀烯烴與乙烯、丙烯等鏈狀烯烴或具有乙烯基之芳香族化合物的共聚物以及該等經不飽和羧酸 或其衍生物改質之改質(共)聚合物等。該等之中，較佳為使用降莰烯、多環降莰烯系單體等降莰烯系單體作為環狀烯烴的降莰烯系樹脂。 The cyclic polyolefin-based resin is a general term for a resin containing a cyclic olefin as a polymerization unit, which is a representative example of norbornene, tetracyclododecene (alias: dimethicone) or such derivatives. Examples of the cyclic polyolefin-based resin include a ring-opened (co)polymer of a cyclic olefin and a hydrogenated product thereof, an addition polymer of a cyclic olefin, a cyclic olefin, and a chain olefin such as ethylene or propylene or a vinyl group. A copolymer of an aromatic compound and a modified (co)polymer modified with the unsaturated carboxylic acid or a derivative thereof. Among these, a norbornene-based resin having a norbornene-based monomer such as a norbornene or a polycyclic norbornene-based monomer as a cyclic olefin is preferably used.

纖維素系樹脂較佳為纖維素酯系樹脂，亦即，纖維素之部分或完全酯化物等，可舉例如：纖維素之乙酸酯、丙酸酯、丁酸酯、該等之混合酯等。該等之中，較佳為三乙酸纖維素、二乙酸纖維素、乙酸丙酸纖維素、乙酸丁酸纖維素等。 The cellulose resin is preferably a cellulose ester resin, that is, a partially or fully esterified cellulose, and the like, and examples thereof include cellulose acetate, propionate, butyrate, and mixed esters thereof. Wait. Among these, cellulose triacetate, cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate, and the like are preferable.

聚酯系樹脂係具有酯鍵之上述纖維素酯系樹脂以外之樹脂，一般係由多元羧酸或其衍生物與多元醇之聚縮合體所構成者。聚酯系樹脂可舉例如：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、聚萘二甲酸丁二酯、聚對苯二甲酸丙二酯、聚萘二甲酸丙二酯、聚對苯二甲酸環己二甲酯、聚萘二甲酸環己二甲酯等。 The polyester-based resin is a resin other than the cellulose ester-based resin having an ester bond, and is generally composed of a polycondensate of a polyvalent carboxylic acid or a derivative thereof and a polyhydric alcohol. Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polytrimethylene terephthalate. Polypropylene naphthalate, cyclohexanedimethylene terephthalate, cyclohexanedimethylene naphthalate, and the like.

聚碳酸酯系樹脂係由碳酸與甘醇或雙酚所形成之聚酯。該等之中，從耐熱性、耐候性及耐酸性之觀點來看，較佳為在分子鏈具有二苯基烷烴之芳香族聚碳酸酯。聚碳酸酯可舉例如：2,2-雙(4-羥基苯基)丙烷(別名雙酚A)、2,2-雙(4-羥基苯基)丁烷、1,1-雙(4-羥基苯基)環己烷、1,1-雙(4-羥基苯基)異丁烷、1,1-雙(4-羥基苯基)乙烷等由雙酚衍生之聚碳酸酯等。 The polycarbonate resin is a polyester formed of carbonic acid and glycol or bisphenol. Among these, from the viewpoint of heat resistance, weather resistance, and acid resistance, an aromatic polycarbonate having a diphenyl alkane in a molecular chain is preferred. The polycarbonate may, for example, be 2,2-bis(4-hydroxyphenyl)propane (alias bisphenol A), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4- A bisphenol-derived polycarbonate or the like such as hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)isobutane or 1,1-bis(4-hydroxyphenyl)ethane.

可構成第1、第2樹脂膜3、4之(甲基)丙烯酸系樹脂，可為以源自於甲基丙烯酸酯之構成單元為主體(例如其係含有50質量%以上)之聚合物，較佳為有其他共 聚合成分與之共聚合的共聚物。(甲基)丙烯酸系樹脂可含有二種以上源自於甲基丙烯酸酯之構成單元。甲基丙烯酸酯可舉出：甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯等甲基丙烯酸之C1至C4烷酯。 The (meth)acrylic resin which can constitute the first and second resin films 3 and 4 can be a polymer mainly composed of a constituent unit derived from methacrylate (for example, it contains 50% by mass or more). It is preferred to have a copolymer in which other copolymerization components are copolymerized. The (meth)acrylic resin may contain two or more constituent units derived from methacrylate. The methacrylate may, for example, be a C 1 to C 4 alkyl methacrylate such as methyl methacrylate, ethyl methacrylate or butyl methacrylate.

作為可與甲基丙烯酸酯共聚合之共聚合成分，可舉出丙烯酸酯。丙烯酸酯較佳為丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯等丙烯酸之C1至C8烷酯。其他的共聚合成分之具體例可舉出：(甲基)丙烯酸等不飽和酸類；苯乙烯、鹵化苯乙烯、α-甲基苯乙烯、乙烯基甲苯等芳香族乙烯基化合物；(甲基)丙烯腈等乙烯基氰化合物；馬來酸酐、檸康酸酐等不飽和酸酐；苯基馬來醯亞胺、環己基馬來醯亞胺等不飽和醯亞胺等於分子內具有1個聚合性碳-碳雙鍵之丙烯酸酯以外的化合物。亦可使用於分子內具有2個以上聚合性碳-碳雙鍵之化合物作為共聚合成分。共聚合成分可單獨使用或組合二種以上使用。 An acrylate is mentioned as a copolymerization component copolymerizable with a methacrylate. The acrylate is preferably a C 1 to C 8 alkyl ester of acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate. Specific examples of the other copolymerization component include unsaturated acids such as (meth)acrylic acid; aromatic vinyl compounds such as styrene, halogenated styrene, α-methylstyrene, and vinyltoluene; Vinyl cyanide compound such as acrylonitrile; unsaturated acid anhydride such as maleic anhydride or citraconic anhydride; unsaturated quinone imine such as phenyl maleimide or cyclohexylmaleimine is equal to one polymerizable carbon in the molecule - A compound other than the acrylate of the carbon double bond. A compound having two or more polymerizable carbon-carbon double bonds in the molecule may also be used as a copolymerization component. The copolymerization components may be used singly or in combination of two or more.

就可提高膜之耐久性之點而言，(甲基)丙烯酸系樹脂可在高分子主鏈具有環構造。環構造較佳為環狀酸酐構造、環狀醯亞胺構造、內酯環構造等雜環構造。環狀酸酐構造之具體例可舉出：戊二酸酐構造、琥珀酸酐構造等，環狀醯亞胺構造之具體例可舉出：戊二醯亞胺構造、琥珀醯亞胺構造等，內酯環構造之具體例可舉出：丁內酯環構造、戊內酯環構造等。 The (meth)acrylic resin may have a ring structure in the polymer main chain in terms of improving the durability of the film. The ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic quinone imine structure, or a lactone ring structure. Specific examples of the cyclic acid anhydride structure include a glutaric anhydride structure and a succinic anhydride structure, and specific examples of the cyclic quinone imine structure include a glutarinium structure and an amber quinone structure, and a lactone. Specific examples of the ring structure include a butyrolactone ring structure and a valerolactone ring structure.

從作成膜之製膜性、膜之耐衝撃性等觀點來看，(甲基)丙烯酸系樹脂可含有丙烯酸系橡膠粒子。丙烯酸系橡膠粒子是指將以丙烯酸酯為主體之彈性聚合物作為必要成分的粒子，可舉出實質上僅包含彈性聚合物之單層構造者、以彈性聚合物為一個層之多層構造者。彈性聚合物之例可舉出：交聯彈性共聚物，係以丙烯酸烷酯為主成分且共聚有可與其共聚合之其他乙烯基單體及交聯性單體者。彈性聚合物之主成分之丙烯酸烷酯可舉例如：丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯等丙烯酸之C1至C8烷酯。烷基的碳數較佳為4以上。 The (meth)acrylic resin may contain acrylic rubber particles from the viewpoints of film forming properties of the film formation, impact resistance of the film, and the like. The acrylic rubber particles are particles in which an elastic polymer mainly composed of acrylate is used as an essential component, and a single layer structure including only an elastic polymer and a multilayer structure having one layer of an elastic polymer are mentioned. Examples of the elastic polymer include a crosslinked elastic copolymer mainly composed of an alkyl acrylate and copolymerized with another vinyl monomer and a crosslinkable monomer copolymerizable therewith. The alkyl acrylate of the main component of the elastic polymer may, for example, be a C 1 to C 8 alkyl acrylate such as methyl acrylate, ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate. The alkyl group preferably has 4 or more carbon atoms.

作為可與丙烯酸烷酯共聚合之其他乙烯基單體，可舉出分子內具有1個聚合性碳-碳雙鍵之化合物，更具體而言，可舉出如甲基丙烯酸甲酯之甲基丙烯酸酯、如苯乙烯之芳香族乙烯基化合物、如(甲基)丙烯腈之乙烯基氰化合物等。交聯性單體可舉出於分子內具有至少2個聚合性碳-碳雙鍵之交聯性化合物，更具體而言，可舉出乙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯等多元醇之(甲基)丙烯酸酯、(甲基)丙烯酸烯丙酯等(甲基)丙烯酸之烯酯、二乙烯基苯等。 Examples of the other vinyl monomer copolymerizable with the alkyl acrylate include a compound having one polymerizable carbon-carbon double bond in the molecule, and more specifically, a methyl group such as methyl methacrylate. An acrylate, an aromatic vinyl compound such as styrene, a vinyl cyanide compound such as (meth)acrylonitrile, or the like. The crosslinkable monomer may be a crosslinkable compound having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically, ethylene glycol di(meth)acrylate or butanediol (meth)acrylate of a polyhydric alcohol such as di(meth)acrylate, (meth)acrylic acid ester such as allyl (meth)acrylate, divinylbenzene or the like.

相對於(甲基)丙烯酸系樹脂100質量份，丙烯酸系橡膠粒子之含量較佳為5質量份以上，更佳為10質量份以上。若丙烯酸系橡膠粒子之含量過多，則會降低膜的表面硬度，而且，在對膜實施表面處理時，會降低對表面處理劑中的有機溶劑之耐溶劑性。因此，相對於(甲基) 丙烯酸系樹脂100質量份，丙烯酸系橡膠粒子之含量通常為80質量份以下，較佳為60質量份以下。 The content of the acrylic rubber particles is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, based on 100 parts by mass of the (meth)acrylic resin. When the content of the acrylic rubber particles is too large, the surface hardness of the film is lowered, and when the film is subjected to surface treatment, the solvent resistance to the organic solvent in the surface treatment agent is lowered. Therefore, the content of the acrylic rubber particles is usually 80 parts by mass or less, preferably 60 parts by mass or less, based on 100 parts by mass of the (meth)acrylic resin.

第1、第2樹脂膜3、4可含有本發明技術領域中通常的添加劑。添加劑可舉例如：紫外線吸收劑、紅外線吸收劑、有機系染料、顏料、無機系色素、抗氧化劑、抗靜電劑、界面活性劑、滑劑、分散劑、熱安定劑等。紫外線吸收劑可舉出水楊酸酯化合物、二苯基酮化合物、苯并***化合物、三化合物、(甲基)丙烯酸氰基酯化合物、鎳錯鹽等。 The first and second resin films 3 and 4 may contain additives generally used in the technical field of the present invention. Examples of the additive include an ultraviolet absorber, an infrared ray absorbing agent, an organic dye, a pigment, an inorganic dye, an antioxidant, an antistatic agent, a surfactant, a slip agent, a dispersant, and a heat stabilizer. Examples of the ultraviolet absorber include a salicylate compound, a diphenylketone compound, a benzotriazole compound, and three A compound, a cyanoacrylate (meth) acrylate compound, a nickel salt or the like.

第1、第2樹脂膜3、4分別可為未延伸膜、或是經單軸或雙軸延伸之膜中之任一者。第1樹脂膜3及/或第2樹脂膜4可為擔任保護偏光片2之角色的保護膜，也可為兼具如後述相位差膜之光學功能的保護膜。又，第1樹脂膜3及第2樹脂膜4可為相同或相異之膜。 Each of the first and second resin films 3 and 4 may be either an unstretched film or a film that is uniaxially or biaxially stretched. The first resin film 3 and/or the second resin film 4 may be a protective film that functions as a protective polarizer 2, or may be a protective film that has an optical function as a retardation film to be described later. Further, the first resin film 3 and the second resin film 4 may be the same or different films.

而且，第1樹脂膜3及/或第2樹脂膜4係可於其外面(與偏光片2為相反側之表面)具備硬塗層、防眩層、抗反射層、光擴散層、抗靜電層、防汙層、導電層等表面處理層(塗覆層)。該第1樹脂膜3及第2樹脂膜4之厚度分別通常為1至150μm，較佳為5至100μm，更佳為5至60μm，又更佳為50μm以下(例如1至40μm)，尤其為30μm以下(例如5至25μm)。 Further, the first resin film 3 and/or the second resin film 4 may have a hard coat layer, an antiglare layer, an antireflection layer, a light diffusion layer, and an antistatic layer on the outer surface (the surface opposite to the polarizer 2). a surface treatment layer (coating layer) such as a layer, an antifouling layer, or a conductive layer. The thickness of the first resin film 3 and the second resin film 4 is usually 1 to 150 μm, preferably 5 to 100 μm, more preferably 5 to 60 μm, still more preferably 50 μm or less (for example, 1 to 40 μm), and particularly Below 30 μm (for example, 5 to 25 μm).

尤其在智慧型手機、平板型終端等中小型取向之偏光板中，係要求薄膜化，故較常使用厚度30μm以下之較薄者作為第1樹脂膜3及/或第2樹脂膜4，惟如 此之偏光板係偏光片2的收縮力之抑制力較弱，且耐久性容易變得不充分。即使在將此種偏光板使用作為光學膜10時，本發明之附黏著劑層之光學膜1仍具有良好的耐久性。 In particular, in a small-sized orientated polarizing plate such as a smart phone or a tablet terminal, thin film formation is required. Therefore, a thinner one having a thickness of 30 μm or less is used as the first resin film 3 and/or the second resin film 4, but only In such a polarizing plate, the contracting force of the polarizer 2 is weak, and durability is likely to be insufficient. Even when such a polarizing plate is used as the optical film 10, the optical film 1 of the adhesive layer of the present invention has good durability.

第1、第2樹脂膜3、4可經由接著劑層、黏著劑層貼合於偏光片2。可使用水系接著劑或活性能量射線硬化性接著劑作為形成接著劑層之接著劑。 The first and second resin films 3 and 4 can be bonded to the polarizer 2 via an adhesive layer or an adhesive layer. A water-based adhesive or an active energy ray-curable adhesive can be used as an adhesive for forming an adhesive layer.

作為水系接著劑，可舉出慣用的水系接著劑(例如：由聚乙烯醇系樹脂水溶液所構成之接著劑、水系二液型胺甲酸乙酯系乳液接著劑、醛化合物、環氧化合物、三聚氰胺系化合物、羥甲基化合物、異氰酸酯化合物、胺化合物、多價金屬鹽等交聯劑等)。該等之中，可適合使用由聚乙烯醇系樹脂水溶液所構成之水系接著劑。又，使用水系接著劑時，在貼合偏光片2與第1、第2樹脂膜3、4後，為了去除水系接著劑中所含的水，較佳為實施乾燥步驟。乾燥步驟後，例如可設置在20至45℃左右溫度熟化之熟化步驟。 The water-based adhesive agent is a conventional water-based adhesive (for example, an adhesive composed of a polyvinyl alcohol-based resin aqueous solution, an aqueous two-component urethane-based emulsion adhesive, an aldehyde compound, an epoxy compound, or a melamine). A compound, a methylol compound, an isocyanate compound, an amine compound, a crosslinking agent such as a polyvalent metal salt, or the like). Among these, a water-based adhesive composed of a polyvinyl alcohol-based resin aqueous solution can be suitably used. Moreover, when a water-based adhesive is used, after the polarizer 2 and the first and second resin films 3 and 4 are bonded, it is preferred to carry out a drying step in order to remove water contained in the water-based adhesive. After the drying step, for example, a curing step of aging at a temperature of about 20 to 45 ° C may be provided.

上述活性能量射線硬化性接著劑，是指藉由照射紫外線、電子射線等活性能量射線而硬化之接著劑，可舉例如：含有聚合性化合物及光聚合起始劑之硬化性組成物、含有光反應性樹脂之硬化性組成物、含有黏合劑樹脂及光反應***聯劑之硬化性組成物等，較佳為紫外線硬化性接著劑。 The active energy ray-curable adhesive agent is an adhesive which is cured by irradiation with active energy rays such as ultraviolet rays and electron beams, and examples thereof include a curable composition containing a polymerizable compound and a photopolymerization initiator, and light. The curable composition of the reactive resin, the curable composition containing the binder resin and the photoreactive crosslinking agent, and the like are preferably an ultraviolet curable adhesive.

使用活性能量射線硬化性接著劑時，係在貼合偏光片2與第1、第2樹脂膜3、4後，視需要進行乾 燥步驟，接著進行藉由照射活性能量射線而使活性能量射線硬化性接著劑硬化之硬化步驟。活性能量射線之光源並無特別限定，但較佳為在波長400nm以下具有發光分布之紫外線。 When the active energy ray-curable adhesive is used, after the polarizer 2 and the first and second resin films 3 and 4 are bonded, a drying step is performed as needed, and then the active energy ray is hardened by irradiation of the active energy ray. The hardening step of the hardening of the adhesive. The light source of the active energy ray is not particularly limited, but is preferably an ultraviolet ray having a light-emitting distribution at a wavelength of 400 nm or less.

貼合偏光片2與第1、第2樹脂膜3、4之方法，可舉出於該等之至少任一貼合面實施皂化處理、電暈處理、電漿處理等表面活性化處理之方法等。於偏光片2的兩面貼合樹脂膜時，用以貼合該等樹脂膜之接著劑可為同種接著劑也可為不同種接著劑。 The method of bonding the polarizer 2 and the first and second resin films 3 and 4 may be performed by performing surface activation treatment such as saponification treatment, corona treatment, or plasma treatment on at least one of the bonding surfaces. Wait. When the resin film is bonded to both surfaces of the polarizer 2, the adhesive for bonding the resin films may be the same kind of adhesive or a different type of adhesive.

偏光板10a、10b可進一步含有其他膜或層。其具體例在後述之相位差膜以外，有增亮膜、防眩膜、抗反射膜、擴散膜、聚光膜、黏著劑層20以外之黏著劑層、塗覆層、保護膜等。保護膜係以保護偏光板等光學膜10的表面免於受傷、髒污為目的而使用之膜，若以附黏著劑層之光學膜1為例，則通常的例子係貼合於例如金屬層、基板上之後被剝離去除。 The polarizing plates 10a, 10b may further contain other films or layers. Specific examples thereof include a brightness enhancement film, an anti-glare film, an anti-reflection film, a diffusion film, a light-concentrating film, an adhesive layer other than the adhesive layer 20, a coating layer, a protective film, and the like, in addition to the retardation film to be described later. The protective film is a film which is used for the purpose of protecting the surface of the optical film 10 such as a polarizing plate from damage or contamination. When the optical film 1 with an adhesive layer is used as an example, a general example is attached to, for example, a metal layer. After being removed from the substrate, it is peeled off.

保護膜通常係由基材膜及積層於基材膜上之黏著劑層所構成。基材膜可以熱塑性樹脂構成，例如：可以聚乙烯系樹脂、聚丙烯系樹脂等聚烯烴系樹脂；聚對苯二甲酸乙二酯和聚萘二甲酸乙二酯等聚酯系樹脂；聚碳酸酯系樹脂；(甲基)丙烯酸系樹脂等構成。 The protective film is usually composed of a base film and an adhesive layer laminated on the base film. The base film may be composed of a thermoplastic resin, for example, a polyolefin resin such as a polyethylene resin or a polypropylene resin; a polyester resin such as polyethylene terephthalate or polyethylene naphthalate; and polycarbonate. An ester resin; a (meth)acrylic resin or the like.

[2-3]相位差板 [2-3] phase difference plate

如上所述，相位差板所含之相位差膜係顯示光學異向性之光學膜，可為下述延伸膜：將樹脂膜延伸至1.01至6 倍左右而獲得之延伸膜，該樹脂膜係除了作為可使用於第1、第2樹脂膜3、4者而於上文例示的熱塑性樹脂以外，還包含例如聚乙烯醇系樹脂、聚芳酯系樹脂、聚醯亞胺系樹脂、聚醚碸系樹脂、聚偏二氟乙烯/聚甲基丙烯酸甲酯系樹脂、液晶聚酯系樹脂、乙烯/乙酸乙烯酯共聚物皂化物、聚氯化乙烯系樹脂等。該等之中，較佳為將聚碳酸酯系樹脂膜、環狀烯烴系樹脂膜、(甲基)丙烯酸系樹脂膜或纖維素系樹脂膜進行單軸延伸或雙軸延伸之延伸膜。而且，本說明書中，相位差膜亦包括零延遲(Zero retardation)膜。但是，零延遲膜亦可使用作為保護膜。此外，稱為單軸性相位差膜、廣視角相位差膜、低光彈性模數相位差膜等之膜亦可應用作為相位差膜。 As described above, the retardation film contained in the retardation film is an optical film exhibiting an optical anisotropy, and may be a stretched film obtained by extending a resin film to about 1.01 to 6 times, which is obtained by stretching the resin film. In addition to the thermoplastic resin exemplified above, which can be used for the first and second resin films 3 and 4, for example, a polyvinyl alcohol-based resin, a polyarylate-based resin, a polyimide-based resin, or a polyether is included. A lanthanum resin, a polyvinylidene fluoride/polymethyl methacrylate resin, a liquid crystal polyester resin, an ethylene/vinyl acetate copolymer saponified product, a polychlorinated vinyl resin, or the like. Among these, a polycarbonate film, a cyclic olefin resin film, a (meth)acrylic resin film, or a cellulose resin film is preferably a stretch film which is uniaxially stretched or biaxially stretched. Moreover, in the present specification, the retardation film also includes a zero retardation film. However, a zero retardation film can also be used as a protective film. Further, a film called a uniaxial retardation film, a wide viewing angle retardation film, or a low photoelastic modulus retardation film can also be used as the retardation film.

零延遲膜是指面內相位差值Re及厚度方向相位差值Rth皆為-15至15nm之膜。該相位差膜適合使用於IPS模式的液晶顯示裝置。面內相位差值Re及厚度方向相位差值Rth較佳係皆為-10至10nm，更佳係皆為-5至5nm。在此所述之面內相位差值Re及厚度方向相位差值Rth係於波長590nm的值。 Zero means the retardation film in-plane retardation value R e and R th retardation value in the thickness direction are both -15 to 15nm of the film. This retardation film is suitable for use in an IPS mode liquid crystal display device. The in-plane phase difference value R e and the thickness direction phase difference R th are preferably from -10 to 10 nm, more preferably from -5 to 5 nm. The in-plane phase difference value R e and the thickness direction phase difference value R th described herein are values at a wavelength of 590 nm.

面內相位差值Re及厚度方向相位差值Rth分別以下式定義。 The in-plane phase difference value R e and the thickness direction phase difference value R th are respectively defined by the following equations.

Re=(nx-ny)×d R e =(n x -n y )×d

Rth=〔(nx+ny)/2-nz〕×d式中，nx係膜面內慢軸方向(x軸方向)之折射率，ny係膜面內快軸方向(於面內與x軸垂直相交之y軸方向)之折射 率，nz係膜厚度方向(於膜面垂直之z軸方向)之折射率，d係膜的厚度。 R th =[(n x +n y )/2-n z ]×d where the refractive index of the n x -type film in the in-plane slow axis direction (x-axis direction) and the n y-type film in-plane fast axis direction ( refractive index in the plane perpendicular to the x-axis intersects a y-axis direction) of, n z based film thickness direction (z-axis perpendicular to the film surface direction), the film thickness d based.

零延遲膜中，例如可使用由纖維素系樹脂、鏈狀聚烯烴系樹脂及環狀聚烯烴系樹脂等聚烯烴系樹脂、聚對苯二甲酸乙二酯系樹脂或(甲基)丙烯酸系樹脂所構成之樹脂膜。尤其，就容易調控相位差值且容易取得來看，較佳為使用纖維素系樹脂、聚烯烴系樹脂或(甲基)丙烯酸系樹脂。 For the zero retardation film, for example, a polyolefin resin such as a cellulose resin, a chain polyolefin resin or a cyclic polyolefin resin, a polyethylene terephthalate resin or a (meth)acrylic acid can be used. A resin film composed of a resin. In particular, it is preferable to use a cellulose resin, a polyolefin resin, or a (meth)acrylic resin in order to easily adjust the phase difference and to easily obtain it.

而且，相位差膜亦可使用藉由液晶性化合物之塗佈/配向而表現光學異向性之膜、藉由無機層狀化合物之塗佈而表現光學異向性之膜。此種相位差膜有稱為溫度補償型相位差膜者、或由JX日礦日石能源股份有限公司以「NH FILM」之商品名販售之棒狀液晶為傾斜配向之膜、由Fujifilm股份有限公司以「WV FILM」之商品名販售之圓盤狀液晶為傾斜配向之膜、由住友化學股份有限公司以「VAC FILM」之商品名販售之完全雙軸配向型之膜、同為由住友化學股份有限公司以「new VAC FILM」之商品名販售之雙軸配向型之膜等。又，於相位差膜的至少一面積層之樹脂膜，例如可為上述保護膜。 Further, as the retardation film, a film which exhibits optical anisotropy by coating/alignment of a liquid crystal compound or a film which exhibits optical anisotropy by application of an inorganic layered compound can be used. Such a retardation film is a film which is called a temperature-compensated retardation film or a rod-shaped liquid crystal which is sold under the trade name of "NH FILM" by JX Nippon Mining & Energy Co., Ltd., and is a film of the oblique alignment. The disc-shaped liquid crystal sold by the company under the trade name "WV FILM" is a film with a tilting alignment, and a completely biaxial alignment film sold by Sumitomo Chemical Co., Ltd. under the trade name "VAC FILM". A biaxially oriented film sold by Sumitomo Chemical Co., Ltd. under the trade name "new VAC FILM". Further, the resin film of at least one area layer of the retardation film may be, for example, the above protective film.

[3]光學積層體 [3] Optical laminate

本發明係包括一種光學積層體，係含有前述附黏著劑層之光學膜、及於該附黏著劑層之光學膜的黏著劑層側積層之基材。本發明之光學積層體，因黏著劑層係由前述黏著劑組成物所形成，故即便在嚴苛的耐久條件(例如100℃ 以上之耐久條件)中亦具有優異的耐久性。 The present invention includes an optical laminate comprising a substrate comprising the above-mentioned optical film with an adhesive layer and an adhesive layer side layer of the optical film of the adhesive layer. In the optical layered body of the present invention, since the adhesive layer is formed of the above-mentioned adhesive composition, it has excellent durability even under severe durability conditions (for example, durability conditions of 100 ° C or more).

基材可舉出慣用的基材，例如玻璃基板、ITO(摻錫氧化銦)基板、塑膠膜、有機導電膜、金屬層、保護塗層(overcoat)樹脂層等。 The base material may, for example, be a conventional substrate such as a glass substrate, an ITO (tin-doped indium oxide) substrate, a plastic film, an organic conductive film, a metal layer, an overcoat resin layer or the like.

第4至8圖之示意剖面圖係表示本發明之光學積層體的例子。 The schematic cross-sectional views of Figs. 4 to 8 show examples of the optical layered body of the present invention.

第4圖所示之光學積層體5，係將於基板40上積層之金屬層30(或金屬配線層30)積層於前述附黏著劑層之光學膜1a(或附黏著劑層之偏光板1a)的黏著劑層側之面者。前述附黏著劑層之光學膜1a係於前述偏光板10a之偏光片2側的面積層有黏著劑層20者。 The optical layered body 5 shown in Fig. 4 is formed by laminating a metal layer 30 (or a metal wiring layer 30) laminated on the substrate 40 to the optical film 1a (or the polarizing plate 1a with an adhesive layer) to which the adhesive layer is attached. ) The side of the adhesive layer side. The optical film 1a with the adhesive layer is attached to the polarizer layer 20 on the side of the polarizer 2 on the side of the polarizing plate 10a.

第5圖所示之光學積層體6，係將於基板40上積層之金屬層30積層於附黏著劑層之光學膜1b(或附黏著劑層之偏光板1b)的黏著劑層側之面者。前述附黏著劑層之光學膜1b係於前述偏光板10b之第2樹脂膜4側的面積層有黏著劑層20的光學膜。 The optical layered body 6 shown in Fig. 5 is formed by laminating a metal layer 30 laminated on the substrate 40 on the side of the adhesive layer of the optical film 1b (or the polarizing plate 1b with the adhesive layer) to which the adhesive layer is attached. By. The optical film 1b with the pressure-sensitive adhesive layer is an optical film having an adhesive layer 20 in an area layer on the side of the second resin film 4 of the polarizing plate 10b.

可藉由在積層於基板40上之金屬層30經由黏著劑層20貼合附黏著劑層之光學膜(1a、1b)而獲得光學積層體5、6。 The optical laminates 5 and 6 can be obtained by bonding the optical films (1a, 1b) with the adhesive layer to the metal layer 30 laminated on the substrate 40 via the adhesive layer 20.

於基板40上形成金屬層30之方法，可舉例如濺鍍法等。基板40可為構成觸碰輸入元件所含之液晶單元之透明基板，較佳為玻璃基板。該玻璃基板之材料，可使用鈉鈣玻璃、低鹼玻璃、無鹼玻璃等。金屬層30可形成於基板40的整面，也可形成於基板40的一部分。 A method of forming the metal layer 30 on the substrate 40 may be, for example, a sputtering method. The substrate 40 may be a transparent substrate constituting a liquid crystal cell included in the touch input element, and is preferably a glass substrate. As the material of the glass substrate, soda lime glass, low alkali glass, alkali-free glass, or the like can be used. The metal layer 30 may be formed on the entire surface of the substrate 40 or may be formed on a portion of the substrate 40.

金屬層30例如可為含有由鋁、銅、銀、鐵、錫、鋅、鎳、鉬、鉻、鎢、鉛及含有該等中之2種以上金屬的合金所選出之至少1種金屬元素的層。從導電性的觀點來看，該等之中，較佳為含有由鋁、銅、銀及金所選出之至少1種金屬元素的層，從導電性及成本之觀點來看，更佳為含有鋁元素的層，又更佳為含有鋁元素作為主成分(構成金屬層30之全部金屬成分之50質量%以上)的層。 The metal layer 30 may be, for example, at least one metal element selected from the group consisting of aluminum, copper, silver, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead, and an alloy containing two or more of these metals. Floor. From the viewpoint of conductivity, among these, a layer containing at least one metal element selected from aluminum, copper, silver, and gold is preferable, and it is more preferable from the viewpoint of conductivity and cost. Further, the layer of the aluminum element is more preferably a layer containing an aluminum element as a main component (constituting 50% by mass or more of all the metal components of the metal layer 30).

金屬層30例如可為ITO等透明電極層，可具有金屬層30且同時具有由ITO等金屬氧化物所構成之透明電極層。又，也可使用於基板上配置有細線金屬配線層之金屬網和於黏合劑中添加有金屬奈米粒子、金屬奈米線的層。 The metal layer 30 may be, for example, a transparent electrode layer such as ITO, and may have a metal layer 30 and a transparent electrode layer made of a metal oxide such as ITO. Further, a metal mesh on which a fine metal wiring layer is disposed on a substrate and a layer in which metal nanoparticles or metal nanowires are added to the adhesive may be used.

金屬層30之調製方法並無特別限定，可為金屬箔，也可為藉由真空蒸鍍法、濺鍍法、離子鍍法、噴墨印刷法、凹板印刷法所形成者，惟較佳為藉由濺鍍法、噴墨印刷法、凹板印刷法所形成之金屬層，更佳為藉由濺鍍所形成之金屬層。金屬層30之厚度並無特別限定，但通常為3μm以下，較佳為1μm以下，更佳為0.8μm以下，通常為0.01μm以上。又，金屬層30為金屬配線層(例如金屬網)時，該金屬配線之線寬通常為10μm以下，較佳為5μm以下，又更佳為3μm以下，通常為0.5μm以上。 The method of preparing the metal layer 30 is not particularly limited, and may be a metal foil, or may be formed by a vacuum deposition method, a sputtering method, an ion plating method, an inkjet printing method, or a gravure printing method. The metal layer formed by the sputtering method, the inkjet printing method, or the gravure printing method is more preferably a metal layer formed by sputtering. The thickness of the metal layer 30 is not particularly limited, but is usually 3 μm or less, preferably 1 μm or less, more preferably 0.8 μm or less, and usually 0.01 μm or more. When the metal layer 30 is a metal wiring layer (for example, a metal mesh), the line width of the metal wiring is usually 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less, and usually 0.5 μm or more.

第6圖所示之光學積層體7，係於基板40上積層有前述附黏著劑層之光學膜1的黏著劑層20者。 The optical layered body 7 shown in Fig. 6 is an adhesive layer 20 on which the optical film 1 with the adhesive layer is laminated on the substrate 40.

第7圖所示之光學積層體8，係於基板40 上積層有金屬層30之面上(與基板40為相反側的面上)積層樹脂層50，並進一步將所積層之樹脂層50積層於前述附黏著劑層之光學膜1的黏著劑層20側的面者。形成樹脂層50之樹脂可舉例如構成前述例示之第1或第2樹脂膜之樹脂等。 The optical layered body 8 shown in Fig. 7 is formed by laminating a resin layer 50 on the surface of the substrate 40 on which the metal layer 30 is laminated (the surface opposite to the substrate 40), and further laminating the resin layer 50 of the laminated layer. On the side of the adhesive layer 20 of the optical film 1 with the adhesive layer described above. The resin forming the resin layer 50 may, for example, be a resin constituting the first or second resin film exemplified above.

第8圖所示之光學積層體9，除了是於基板40上將複數個金屬層30在縱橫方向隔以預定的間隔而積層，並於該複數個金屬層30之間(或空隙間)且是該金屬層30之面上(與基板40為相反側的面上)形成(或積層)樹脂層50以外，係與光學積層體7相同。為該光學積層體9之形態(金屬層30圖案化為預定的形狀之形態)時，金屬層30可為例如觸碰輸入式液晶顯示裝置所具有的觸碰輸入元件之金屬配線層(亦即電極層)。 The optical layered body 9 shown in FIG. 8 is formed by laminating a plurality of metal layers 30 on the substrate 40 at a predetermined interval in the longitudinal and lateral directions, and between the plurality of metal layers 30 (or between the gaps). The optical layer body 7 is the same as the optical layered body 7 except that the resin layer 50 is formed (or laminated) on the surface of the metal layer 30 (the surface opposite to the substrate 40). In the form of the optical laminate 9 (the metal layer 30 is patterned into a predetermined shape), the metal layer 30 may be, for example, a metal wiring layer that touches a touch input element of an input liquid crystal display device (ie, Electrode layer).

光學積層體9中，複數個金屬層30可整體性或局部性地與黏著劑層20接觸，也可不接觸。而且，金屬層30可為含有上述金屬或合金之連續膜。又，亦可省略樹脂層50。 In the optical laminate 9, a plurality of metal layers 30 may be in contact with the adhesive layer 20 integrally or partially, or may not be in contact. Moreover, the metal layer 30 may be a continuous film containing the above metal or alloy. Further, the resin layer 50 may be omitted.

將附黏著劑層之光學膜(1、1a、1b)與基板40(玻璃基板、透明基板等)或金屬層30(透明電極層)進行黏貼並製作光學積層體後，當有任何不良時，有需要進行所謂重工作業，亦即將附黏著劑層之光學膜由基板40或金屬層30剝離並將其他附黏著劑層之光學膜1重貼於基板40或金屬層30之情形。本發明之附黏著劑層之光學膜1係不容易在剝離後之玻璃基板或透明電極的表面產生模 糊、殘膠等，係重工性優異。 After the optical film (1, 1a, 1b) with the adhesive layer is adhered to the substrate 40 (glass substrate, transparent substrate, etc.) or the metal layer 30 (transparent electrode layer) to form an optical layered body, when there is any defect, There is a need to perform a so-called heavy work, in which the optical film with the adhesive layer is peeled off from the substrate 40 or the metal layer 30 and the other optical film 1 with the adhesive layer is attached to the substrate 40 or the metal layer 30. The optical film 1 with an adhesive layer of the present invention is less likely to cause blurring or residual glue on the surface of the glass substrate or the transparent electrode after peeling, and is excellent in reworkability.

[4]圖像顯示裝置 [4] Image display device

本發明之黏著劑層、附黏著劑層之光學膜及光學積層體可使用於液晶顯示裝置、有機EL顯示裝置等圖像顯示裝置，該圖像顯示裝置係具有優異的耐久性。 The pressure-sensitive adhesive layer of the present invention, the optical film with an adhesive layer, and the optical laminate can be used for an image display device such as a liquid crystal display device or an organic EL display device, and the image display device has excellent durability.

液晶顯示裝置可為具有觸控面板功能之觸碰輸入式液晶顯示裝置。觸碰輸入式液晶顯示裝置係具備含有液晶單元之觸碰輸入元件及背光。觸控面板之構成可為公知方式(例如Out-cell型、On-cell型、In-cell型等)，而且觸控面板之運作方式可為公知方式，例如可為電阻膜方式、靜電容量方式(表面型靜電容量方式、投射型靜電容量方式)等。本發明之附黏著劑層之光學膜可配置於觸碰輸入元件(液晶單元)之觀視側，也可配置於背光側，亦可配置於觀視側與背光側兩者。液晶單元之驅動方式可為TN方式、VA方式、IPS方式、多區域(multidomain)方式、OCB方式等以往公知之任何方式。又，前述液晶顯示裝置中，具有光學積層體之基板40可為上述液晶單元所含有之基板(典型為玻璃基板)。 The liquid crystal display device can be a touch input type liquid crystal display device having a touch panel function. The touch input type liquid crystal display device includes a touch input element including a liquid crystal cell and a backlight. The configuration of the touch panel can be a well-known method (for example, an Out-cell type, an On-cell type, an In-cell type, etc.), and the operation mode of the touch panel can be a well-known manner, for example, a resistive film method or an electrostatic capacity method. (Surface type electrostatic capacitance method, projection type electrostatic capacitance method), etc. The optical film with the adhesive layer of the present invention may be disposed on the viewing side of the touch input element (liquid crystal cell), may be disposed on the backlight side, or may be disposed on both the viewing side and the backlight side. The driving method of the liquid crystal cell may be any conventionally known method such as a TN method, a VA method, an IPS method, a multi-domain method, or an OCB method. Further, in the liquid crystal display device, the substrate 40 having the optical layered body may be a substrate (typically a glass substrate) included in the liquid crystal cell.

而且，本發明之附黏著劑層之光學膜可配置於有機EL顯示裝置之觀視側。 Further, the optical film of the adhesive layer of the present invention can be disposed on the viewing side of the organic EL display device.

有機EL顯示裝置，例如可為具備下述構成者：在基板上所形成各像素內，由基板側算起，積層有下部電極、藉由具有光學效果之物質開始運作之部位的有機EL層、及上部電極。藉由來自於在有機EL層流通電流而發光之 有機EL的光至少通過電極中的一電極(透光性導電膜)而得以確認。 In the organic EL display device, for example, an organic EL layer in which a lower electrode and a portion having an optical effect start to operate are stacked in each pixel formed on the substrate, and the substrate is formed on the substrate side. And the upper electrode. The light from the organic EL which emits light by flowing a current through the organic EL layer is confirmed by at least one electrode (translucent conductive film) in the electrode.

[5]黏著劑組成物用(甲基)丙烯酸系樹脂(A) [5] (meth)acrylic resin (A) for adhesive composition

本發明包含黏著劑組成物用(甲基)丙烯酸系樹脂(A)。該黏著劑組成物用(甲基)丙烯酸系樹脂(A)係與上述(甲基)丙烯酸系樹脂(A)相同者，構成(甲基)丙烯酸系樹脂(A)之較佳構成單元及該構成單元之較佳比例等亦與上述(甲基)丙烯酸系樹脂(A)相同。而且，該黏著劑組成物用(甲基)丙烯酸系樹脂(A)較佳為可使用於附黏著劑層之光學膜所使用之黏著劑組成物用(甲基)丙烯酸系樹脂。而且，應用黏著劑組成物用(甲基)丙烯酸系樹脂(A)之黏著劑組成物並無特別限定，惟較佳可舉出上述[1]所記載之黏著劑組成物。 The present invention comprises a (meth)acrylic resin (A) for an adhesive composition. The (meth)acrylic resin (A) is the same as the (meth)acrylic resin (A), and the preferred constituent unit of the (meth)acrylic resin (A) and the adhesive composition are the same. The preferred ratio of the constituent units and the like are also the same as those of the above (meth)acrylic resin (A). Further, the (meth)acrylic resin (A) for the adhesive composition is preferably a (meth)acrylic resin for an adhesive composition which can be used for an optical film to which an adhesive layer is applied. In addition, the adhesive composition of the (meth)acrylic resin (A) to which the adhesive composition is applied is not particularly limited, and the adhesive composition described in the above [1] is preferable.

本發明之較佳態樣中，黏著劑組成物用(甲基)丙烯酸系樹脂(A)係包含源自於含有乙醯乙醯基之(甲基)丙烯酸酯(a1)之構成單元、及源自於含有羥基之(甲基)丙烯酸酯(a2)之構成單元，前述構成單元之質量比(a2)/(a1)為0.5至5，且重量平均分子量(Mw)以聚苯乙烯換算為100萬以上。此種黏著劑組成物用(甲基)丙烯酸系樹脂(A)可形成即使在高溫環境(例如100℃以上之高溫環境)亦具有優異的耐久性及良好的重工性之黏著劑層。 In a preferred embodiment of the present invention, the (meth)acrylic resin (A) for an adhesive composition comprises a constituent unit derived from a (meth) acrylate (a1) containing an ethyl acetonitrile group, and The constituent unit derived from the hydroxyl group-containing (meth) acrylate (a2), wherein the mass ratio (a2)/(a1) of the constituent unit is 0.5 to 5, and the weight average molecular weight (Mw) is expressed in terms of polystyrene. More than 1 million. The (meth)acrylic resin (A) of such an adhesive composition can form an adhesive layer which has excellent durability and good reworkability even in a high temperature environment (for example, a high temperature environment of 100 ° C or higher).

(實施例)  (Example)  

以下以實施例及比較例進一步具體說明本 發明，但本發明並不限定於該等例。以下表示使用量、含量之份及%為質量基準。 Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the examples. The following indicates the amount of use, the amount of content, and % as the mass basis.

<製造例1：黏著劑層用(甲基)丙烯酸系樹脂(A-1)之製造> <Production Example 1: Production of (meth)acrylic resin (A-1) for adhesive layer>

於具備冷卻管、氮導入管、溫度計及攪拌機之反應容器中加入將表1所示之組成(表1之數值為質量份)之單體與乙酸乙酯80份、丙酮40份、偶氮雙異丁腈0.012份混合所得的溶液。以氮氣取代反應容器內空氣後，提升內溫並以回流溫度反應3.5小時，之後加入乙酸乙酯並以使聚合物的濃度成為20%之方式進行調整，而獲得(甲基)丙烯酸系樹脂(A-1)之乙酸乙酯/丙酮溶液。所得之(甲基)丙烯酸系樹脂(A-1)之重量平均分子量Mw為139萬，重量平均分子量Mw與數量平均分子量Mn的比(Mw/Mn)為3.9。 Into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, a monomer having a composition shown in Table 1 (the mass of which is shown in Table 1) and 80 parts of ethyl acetate, 40 parts of acetone, and azobis were added. The resulting solution was mixed with 0.012 parts of isobutyronitrile. After replacing the air in the reaction vessel with nitrogen, the internal temperature was raised and reacted at a reflux temperature for 3.5 hours, and then ethyl acetate was added and adjusted so that the concentration of the polymer became 20%, thereby obtaining a (meth)acrylic resin ( A-1) ethyl acetate / acetone solution. The weight average molecular weight Mw of the obtained (meth)acrylic resin (A-1) was 1.39 million, and the ratio (Mw/Mn) of the weight average molecular weight Mw to the number average molecular weight Mn was 3.9.

<製造例2-14：黏著劑層用(甲基)丙烯酸系樹脂(A-2至14)之製造> <Production Example 2-14: Production of (meth)acrylic resin (A-2 to 14) for an adhesive layer>

除了單體組成為表1所示之組成以外，以與製造例1相同方式獲得(甲基)丙烯酸系樹脂(A-2至14)之乙酸乙酯/丙酮溶液(樹脂濃度：20%)。所得之(甲基)丙烯酸系樹脂(A-2至14)之重量平均分子量Mw皆為130萬至150萬之範圍，Mw/Mn為3至6之範圍。 An ethyl acetate/acetone solution (resin concentration: 20%) of the (meth)acrylic resin (A-2 to 14) was obtained in the same manner as in Production Example 1, except that the monomer composition was the composition shown in Table 1. The weight average molecular weight Mw of the obtained (meth)acrylic resin (A-2 to 14) is in the range of 1.3 million to 1,500,000, and Mw/Mn is in the range of 3 to 6.

以上製造例中，重量平均分子量Mw及數量平均分子量Mn係於高速液相層析儀(日本Waters公司製，「Waters 2695(本體)」與「Waters 2414(檢測器)」)將管柱：Shodex GPC KF-806L(排除極限分子量：2×107，分離範圍： 100至2×107，理論段數：10,000段/支，充填劑材質：苯乙烯/二乙烯基苯共聚物，充填劑粒徑：10μm)3根進行串聯配置，使用四氫呋喃作為溶析液，以試料濃度1mg/mL、試料導入量100μL、溫度35℃、流速1mL/分鐘之條件藉由標準聚苯乙烯換算而測定。獲得GPC之流出曲線時之條件亦與此相同。 In the above production examples, the weight average molecular weight Mw and the number average molecular weight Mn are based on a high-speed liquid chromatography ("Waters 2695 (main body)" and "Waters 2414 (detector)" manufactured by Waters, Japan). GPC KF-806L (excluding the limit molecular weight: 2 × 10 7 , separation range: 100 to 2 × 10 7 , theoretical number of stages: 10,000 segments / support, filler material: styrene / divinylbenzene copolymer, filler particles Three diameters: 10 μm) were placed in series, and tetrahydrofuran was used as the elution solution, and the sample concentration was 1 mg/mL, the sample introduction amount was 100 μL, the temperature was 35 ° C, and the flow rate was 1 mL/min. The measurement was carried out by standard polystyrene conversion. The conditions for obtaining the GPC outflow curve are also the same.

玻璃轉移溫度Tg，係使用SII NanoTechnology股份有限公司製之示差掃描熱量計(DSC)「EXSTAR DSC6000」，在氮環境下以測定溫度範圍-80至50℃、升溫速度10℃/分鐘之條件進行測定。 The glass transition temperature Tg was measured using a differential scanning calorimeter (DSC) "EXSTAR DSC6000" manufactured by SII NanoTechnology Co., Ltd. under a nitrogen atmosphere at a measurement temperature range of -80 to 50 ° C and a temperature increase rate of 10 ° C / min. .

將各製造例中單體之組成(表1之數值為質量份)、所得(甲基)丙烯酸樹脂之重量平均分子量及分子量分布(Mw/Mn)示於表1。 The composition of the monomer in each production example (the numerical value in Table 1 is a part by mass), the weight average molecular weight (Mw/Mn) of the obtained (meth)acrylic resin, and the molecular weight distribution (Mw/Mn) are shown in Table 1.

表1之「單體組成」欄中之簡稱是指以下單體。 The abbreviation in the column of "monomer composition" in Table 1 means the following monomers.

BA：丙烯酸正丁酯(均聚物的玻璃轉移溫度：-54℃) BA: n-butyl acrylate (glass transition temperature of homopolymer: -54 ° C)

MA：丙烯酸甲酯(均聚物的玻璃轉移溫度：10℃) MA: methyl acrylate (glass transition temperature of homopolymer: 10 ° C)

AAEM：甲基丙烯酸乙醯乙醯氧基乙酯(a1) AAEM: Ethyl ethoxide ethyl methacrylate (a1)

HEA：丙烯酸2-羥基乙酯(a2) HEA: 2-hydroxyethyl acrylate (a2)

PEA：丙烯酸苯氧基乙酯 PEA: phenoxyethyl acrylate

PEA2：苯氧基二乙二醇丙烯酸酯 PEA2: phenoxy diethylene glycol acrylate

BMAA：丁氧基甲基丙烯醯胺 BMAA: Butoxymethyl propylene amide

AA：丙烯酸 AA: Acrylic

<實施例1至9、比較例1至7> <Examples 1 to 9, Comparative Examples 1 to 7>

(1)黏著劑組成物之調製 (1) Modulation of adhesive composition

於上述製造例所得之(甲基)丙烯酸系樹脂之乙酸乙酯溶液(樹脂濃度：20%)中，混合相對於該溶液之固體成分100份為表2所示的量(質量份)之交聯劑(B)及矽烷化合物(C)，進一步以使固體成分濃度成為14%之方式添加乙酸乙酯，獲得黏著劑組成物。在所使用之商品含有溶劑等時，表2所示之各調配成分之調配量為其所含有的有效成分之質量份數。 In the ethyl acetate solution (resin concentration: 20%) of the (meth)acrylic resin obtained in the above production example, 100 parts of the solid component of the solution was mixed and the amount (parts by mass) shown in Table 2 was added. Further, the crosslinking agent (B) and the decane compound (C) were further added with ethyl acetate so that the solid content concentration became 14% to obtain an adhesive composition. When the product to be used contains a solvent or the like, the blending amount of each of the blending components shown in Table 2 is the mass fraction of the active ingredient contained therein.

表2中，簡稱所示之各調配成分詳如下述。 In Table 2, each of the compounding components shown by the abbreviation is as follows.

(交聯劑) (crosslinking agent)

B-1：甲伸苯基二異氰酸酯之三羥甲基丙烷加成物之乙酸乙酯溶液(固體成分濃度75%)，由東曹股份有限公司所得之商品名「CORONATE L」。 B-1: an ethyl acetate solution (solid content: 75%) of a trimethylolpropane adduct of methyl phenyl diisocyanate, which is commercially available from Tosoh Corporation as "CORONATE L".

(矽烷化合物) (decane compound)

C-1：1,6-雙(三甲氧基矽基)己烷。 C-1:1,6-bis(trimethoxyindenyl)hexane.

(2)黏著劑層之製作 (2) Production of adhesive layer

使用塗佈器，將上述(1)所調製之各黏著劑組成物以乾燥後的厚度成為20μm之方式塗佈於經實施脫模處理之由聚對苯二甲酸乙二酯膜所構成之分離膜〔LINTEC股份有限公司所得之商品名「PLR-382051」〕之脫模處理面，並 以100℃乾燥1分鐘，製作黏著劑層(黏著劑薄片)。 The adhesive composition prepared in the above (1) was applied to the separation of the polyethylene terephthalate film subjected to mold release treatment by a thickness of 20 μm after drying using an applicator. The release treated surface of the film (trade name "PLR-382051" obtained by LINTEC Co., Ltd.) was dried at 100 ° C for 1 minute to prepare an adhesive layer (adhesive sheet).

(3)附黏著劑層之光學膜(P-1)之製作 (3) Production of optical film (P-1) with adhesive layer

將平均聚合度約2400、皂化度99.9莫耳%、厚度60μm之聚乙烯醇膜〔Kuraray股份有限公司製之商品名「Kuraray Vinylon VF-PE#6000」〕浸漬於37℃純水後，於含有碘及碘化鉀之水溶液(碘/碘化鉀/水(質量比)=0.04/1.5/100)中以30℃浸漬。其後，於含有碘化鉀及硼酸之水溶液(碘化鉀/硼酸/水(質量比)=12/3.6/100)中以56.5℃浸漬。將膜以10℃純水洗淨後，以85℃乾燥，獲得於聚乙烯醇吸附配向有碘之厚度約23μm之偏光片。延伸主要在碘染色及硼酸處理之步驟進行，總延伸倍率為5.3倍。 A polyvinyl alcohol film (Kuraray Vinylon VF-PE #6000, manufactured by Kuraray Co., Ltd.) having an average polymerization degree of about 2400, a saponification degree of 99.9 mol%, and a thickness of 60 μm was immersed in pure water at 37 ° C, and then contained therein. An aqueous solution of iodine and potassium iodide (iodine/potassium iodide/water (mass ratio) = 0.04/1.5/100) was impregnated at 30 °C. Thereafter, it was impregnated at 56.5 ° C in an aqueous solution containing potassium iodide and boric acid (potassium iodide / boric acid / water (mass ratio) = 12 / 3.6 / 100). The film was washed with pure water at 10 ° C, and then dried at 85 ° C to obtain a polarizer having a thickness of about 23 μm in the form of iodine adsorbed on the polyvinyl alcohol. The extension is mainly carried out in the steps of iodine dyeing and boric acid treatment, and the total stretching ratio is 5.3 times.

於所得之偏光片之單面經由由聚乙烯醇系樹脂水溶液所構成之接著劑而貼合厚度25μm之由三乙酸纖維素膜所構成之透明保護膜〔KONICA MINOLTA OPTO股份有限公司製之商品名「KC2UA」〕。接著，在上述偏光片之與三乙酸纖維素膜為相反側的面，經由由聚乙烯醇系樹脂水溶液所構成之接著劑而貼合厚度23μm之由環狀聚烯烴系樹脂所構成之零位相差膜〔日本ZEON股份有限公司製之商品名「ZEONOR」〕，而製作偏光板。接著，於零位相差膜之與接於偏光片的面為相反側的面實施用以提高密著性之電暈放電處理後，將上述(2)所製作之黏著劑層中與分離膜為相反側的面(黏著劑層面)以積層機貼合後，以溫度23℃、相對濕度65%之條件熟化7天，獲得附黏著劑層之光學膜(P-1)。 A transparent protective film made of a cellulose triacetate film (a trade name of KONICA MINOLTA OPTO Co., Ltd.) having a thickness of 25 μm was bonded to one surface of the obtained polarizer via a binder composed of a polyvinyl alcohol-based resin aqueous solution. "KC2UA"]. Then, on the surface of the polarizer opposite to the cellulose triacetate film, a zero-position of a cyclic polyolefin resin having a thickness of 23 μm was bonded through an adhesive composed of a polyvinyl alcohol-based resin aqueous solution. A phase difference film (trade name "ZEONOR" manufactured by ZEON Co., Ltd., Japan) was used to produce a polarizing plate. Next, after the corona discharge treatment for improving the adhesion is performed on the surface of the zero-order phase difference film opposite to the surface of the polarizing film, the adhesive layer prepared in the above (2) and the separation film are The surface on the opposite side (adhesive layer) was bonded by a laminator, and then aged for 7 days under the conditions of a temperature of 23 ° C and a relative humidity of 65% to obtain an optical film (P-1) with an adhesive layer.

(4)附黏著劑層之光學膜之耐久性評估 (4) Durability evaluation of optical film with adhesive layer

將上述(3)所製作附黏著劑層之光學膜(P-1)以偏光板之延伸軸方向成為長邊之方式裁切為300mm×220mm之大小，並剝離分離膜，將露出之黏著劑層面貼合於玻璃基板。將所得之貼附於玻璃基板之試驗片(貼附於玻璃基板之附黏著劑層之光學膜)於高壓釜中以溫度50℃、壓力5kg/cm2(490.3kPa)加壓20分鐘。玻璃基板係使用康寧公司製之無鹼玻璃，商品名為「Eagle XG」。 The optical film (P-1) having the adhesive layer produced in the above (3) is cut into a size of 300 mm × 220 mm so that the direction of the extension axis of the polarizing plate becomes a long side, and the separation film is peeled off to expose the adhesive. The layer is attached to the glass substrate. The obtained test piece attached to the glass substrate (optical film attached to the adhesive layer of the glass substrate) was pressurized in an autoclave at a temperature of 50 ° C and a pressure of 5 kg/cm 2 (490.3 kPa) for 20 minutes. The glass substrate was made of an alkali-free glass made by Corning, and the product name was "Eagle XG".

對所得之光學積層體實施於溫度105℃之乾燥條件下保持250小時之耐熱試驗。 The obtained optical laminate was subjected to a heat resistance test under a drying condition of a temperature of 105 ° C for 250 hours.

目視觀察各試驗後之光學積層體，以目視觀察黏著劑層有無浮翹、剝離、發泡等外觀變化，並根據下述評估基準評估耐久性。結果示於表3。 The optical laminate after each test was visually observed to visually observe the appearance change of the adhesive layer such as floatation, peeling, foaming, and the durability was evaluated according to the following evaluation criteria. The results are shown in Table 3.

5：完全未觀察到浮翹、剝離、發泡等外觀變化。 5: No change in appearance such as floatation, peeling, and foaming was observed at all.

4：幾乎未觀察到浮翹、剝離、發泡等外觀變化。 4: Appearance changes such as floatation, peeling, and foaming were hardly observed.

3：稍微觀察到浮翹、剝離、發泡等外觀變化。 3: Appearance changes such as floatation, peeling, and foaming were slightly observed.

2：觀察到浮翹、剝離、發泡等外觀變化。 2: Appearance changes such as floatation, peeling, and foaming were observed.

1：明顯確認到浮翹、剝離、發泡等外觀變化。 1: Apparent changes such as floatation, peeling, and foaming were clearly confirmed.

(5)附黏著劑層之光學膜之黏著力評估 (5) Evaluation of adhesion of optical film with adhesive layer

將上述(3)所製作之附黏著劑層之光學膜(P-1)裁切為25mm×150mm大小之試驗片。由試驗片剝離分隔片，並將其黏著劑面貼附於玻璃基板。將所得之貼附於玻璃基板之試驗片(貼附於玻璃基板之附黏著劑層之光學膜)於高壓釜 中，以溫度50℃、壓力5kg/cm2(490.3kPa)加壓20分鐘。於溫度23℃、相對濕度50%之環境中保管24小時之後，由試驗片將光學膜與黏著劑層一起以300mm/分鐘之速度往180°方向剝離。剝離時之平均剝離力係作為黏著力示於表3。黏著力為15N以下時係重工性優異，而且又，為0.5N以上時，由偏光板端部受到衝撃時亦不易產生剝離。 The optical film (P-1) with the adhesive layer prepared in the above (3) was cut into a test piece having a size of 25 mm × 150 mm. The separator was peeled off from the test piece, and the adhesive surface was attached to the glass substrate. The obtained test piece attached to the glass substrate (optical film attached to the adhesive layer of the glass substrate) was pressurized in an autoclave at a temperature of 50 ° C and a pressure of 5 kg/cm 2 (490.3 kPa) for 20 minutes. After storage for 24 hours in an environment of a temperature of 23 ° C and a relative humidity of 50%, the optical film and the adhesive layer were peeled off from the test piece at a speed of 300 mm/min in a 180° direction. The average peeling force at the time of peeling is shown in Table 3 as the adhesive force. When the adhesive force is 15 N or less, the workability is excellent, and when it is 0.5 N or more, peeling is less likely to occur when the end portion of the polarizing plate is washed.

[光學積層體之ITO腐蝕性評估] [Evaluation of ITO Corrosion of Optical Laminates]

以低電阻率計〔Mitsubishi Chemical Analytech股份有限公司製之商品名「Loresta-AX」〕測定附有ITO層之玻璃基板的ITO層表面之表面電阻(試驗前表面電阻值)。接著，將形成有上述(3)所製作的黏著劑層之偏光板裁切為20mm×40mm大小之試驗片。由所得試驗片剝離分隔片，經由黏著劑層黏貼於玻璃基板之ITO層側。將所得之光學積層體於溫度60℃、相對濕度90%之烘箱中保管500小時後，於溫度23℃、相對濕度50%之環境下將ITO層與黏著劑層之間剝離。測定剝離後ITO層之表面電阻(試驗後表面電阻值)。以下式算出試驗前後之電阻變化率並用以下基準進行評估。電阻變化率越小，則ITO腐蝕性越低。結果示於表3。 The surface resistance (surface resistance value before the test) of the surface of the ITO layer of the glass substrate with the ITO layer was measured by a low resistivity meter (trade name "Loresta-AX" manufactured by Mitsubishi Chemical Analytech Co., Ltd.). Next, the polarizing plate on which the adhesive layer prepared in the above (3) was formed was cut into a test piece having a size of 20 mm × 40 mm. The separator was peeled off from the obtained test piece, and adhered to the ITO layer side of the glass substrate via the adhesive layer. The obtained optical laminate was stored in an oven at a temperature of 60 ° C and a relative humidity of 90% for 500 hours, and then the ITO layer and the adhesive layer were peeled off in an environment of a temperature of 23 ° C and a relative humidity of 50%. The surface resistance (surface resistance value after the test) of the ITO layer after peeling was measured. The resistance change rate before and after the test was calculated by the following formula and evaluated by the following criteria. The smaller the rate of change in resistance, the lower the corrosion of ITO. The results are shown in Table 3.

電阻變化率(%)=[(試驗後表面電阻值)-(試驗前表面電阻值)]/[試驗前表面電阻值]×100 Resistance change rate (%) = [(surface resistance value after test) - (surface resistance value before test)] / [surface resistance value before test] × 100

<ITO腐蝕性之評估基準> <Evaluation criteria for ITO corrosion>

○：電阻變化率未達50%，為ITO腐蝕性良好之光學積層體。 ○: The optical layered body having a low resistance change rate of less than 50% and having excellent ITO corrosion resistance.

×：電阻變化率為50%以上，光學積層體之ITO腐蝕性不良。 X: The rate of change in resistance was 50% or more, and the ITO corrosion resistance of the optical layered body was poor.

〔黏著劑薄片之膠化率〕 [gelation rate of adhesive sheet]

說明本發明之黏著劑薄片之膠化率評估方法。膠化率越大則黏著劑中進行越多交聯反應，可作為交聯密度之判斷依據。膠化率係根據以下(a)至(d)所測定之值。 A method for evaluating the gelation rate of the adhesive sheet of the present invention will be described. The greater the gelation rate, the more cross-linking reaction is carried out in the adhesive, which can be used as a basis for judging the crosslink density. The gelation rate is a value measured according to the following (a) to (d).

(a)將約8cm×約8cm的面積之黏著劑薄片與約10cm×約10cm之SUS304所構成的金屬網(其質量設為Wm)進行貼合。 (a) An adhesive sheet having an area of about 8 cm × about 8 cm is bonded to a metal mesh (having a mass of Wm) of SUS304 of about 10 cm × about 10 cm.

(b)秤量上述(1)所得貼合物，並設其質量為Ws，繼而以包入黏著劑薄片之方式折4次並以訂書機(stapler)固定後秤量，設其質量為Wb。 (b) The composition obtained in the above (1) was weighed and set to have a mass of Ws, and then folded four times in the form of an adhesive sheet and fixed by a stapler, and the mass was set to Wb.

(c)將上述(2)中經訂書機固定之網放入玻璃容器，加入乙酸乙酯60mL並浸漬後，將該玻璃容器於室溫保管3天。 (c) The net fixed by the stapler in the above (2) was placed in a glass container, and 60 mL of ethyl acetate was added thereto and immersed, and the glass container was stored at room temperature for 3 days.

(d)由玻璃容器取出網，於120℃乾燥24小時後進行秤量，設其質量為Wa，根據下式計算膠化率。 (d) The net was taken out from the glass container, dried at 120 ° C for 24 hours, weighed, and the mass was Wa, and the gelation rate was calculated according to the following formula.

膠化率(質量%)=〔{Wa-(Wb-Ws)-Wm}/(Ws-Wm)〕×100 Gelation rate (% by mass) = [{Wa-(Wb-Ws)-Wm}/(Ws-Wm)] × 100

如表3所示，(甲基)丙烯酸系樹脂之成分中AAEM(a1)與HEA(a2)之質量比(a2)/(a1)為0.5至5的範圍內之實施例1至9之光學積層體係顯示較該質量比為0.5至5的範圍外之比較例1至7之光學積層體優異的耐久性。而且，(甲基)丙烯酸系樹脂之成分中，含有0.1質量份AA之實施例4及含有0.5質量份BMAA之實施例5之光學積層體係顯示更優異之耐久性。 As shown in Table 3, the optical compositions of Examples 1 to 9 in the range of 0.5 to 5 in which the mass ratio (a2)/(a1) of AAEM(a1) to HEA(a2) in the component of the (meth)acrylic resin was 0.5 to 5 The laminated system showed excellent durability against the optical laminates of Comparative Examples 1 to 7 outside the range of the mass ratio of 0.5 to 5. Further, among the components of the (meth)acrylic resin, Example 4 containing 0.1 part by mass of AA and the optical layered system of Example 5 containing 0.5 part by mass of BMAA exhibited more excellent durability.

<製造例15-17：黏著劑層用(甲基)丙烯酸系樹脂(A-15)至(A-17)之製造> <Production Example 15-17: Production of (meth)acrylic resin (A-15) to (A-17) for an adhesive layer>

除了單體之組成為表4所示組成以外，以與製造例1 相同方式獲得(甲基)丙烯酸系樹脂(A-15)至(A-17)之乙酸乙酯/丙酮溶液(樹脂濃度：20%)。所得之(甲基)丙烯酸系樹脂(A-15)至(A-17)之重量平均分子量Mw皆為110萬至150萬之範圍，Mw/Mn為3至6之範圍。重量平均分子量Mw及數量平均分子量Mn係以上述所記載之方法測定。 The ethyl acetate/acetone solution of the (meth)acrylic resins (A-15) to (A-17) was obtained in the same manner as in Production Example 1, except that the composition of the monomers was the composition shown in Table 4 (resin concentration: 20%). The weight average molecular weight Mw of the obtained (meth)acrylic resins (A-15) to (A-17) is in the range of 1.1 million to 1,500,000, and Mw/Mn is in the range of 3 to 6. The weight average molecular weight Mw and the number average molecular weight Mn were measured by the methods described above.

表4之「單體組成」欄之簡稱係意指以下單體。 The abbreviation of "monomer composition" in Table 4 means the following monomers.

BA：丙烯酸正丁酯(均聚物的玻璃轉移溫度：-54℃) BA: n-butyl acrylate (glass transition temperature of homopolymer: -54 ° C)

MA：丙烯酸甲酯(均聚物的玻璃轉移溫度：10℃) MA: methyl acrylate (glass transition temperature of homopolymer: 10 ° C)

AAEM：甲基丙烯酸乙醯乙醯氧基乙酯(a1) AAEM: Ethyl ethoxide ethyl methacrylate (a1)

HEA：丙烯酸2-羥基乙酯(a2) HEA: 2-hydroxyethyl acrylate (a2)

PEA：丙烯酸苯氧基乙酯 PEA: phenoxyethyl acrylate

PEA2：苯氧基二乙二醇丙烯酸酯 PEA2: phenoxy diethylene glycol acrylate

BMAA：丁氧基甲基丙烯醯胺 BMAA: Butoxymethyl propylene amide

AA：丙烯酸 AA: Acrylic

<實施例10-12> <Example 10-12>

(6)黏著劑組成物之調製 (6) Modulation of adhesive composition

於上述製造例15-17所得之(甲基)丙烯酸系樹脂之乙酸乙酯溶液(樹脂濃度：20%)中，混合相對於該溶液之固體成分100份為表5所示量(質量份)之交聯劑(B)及矽烷化合物(C)，進一步以固體成分濃度成為14%之方式添加乙酸乙酯，而獲得黏著劑組成物。在所使用商品含有溶劑等時，表5所示之各調配成分之調配量為其所含有的有效成分之質量份數。 In the ethyl acetate solution (resin concentration: 20%) of the (meth)acrylic resin obtained in the above Production Example 15-17, 100 parts by weight of the solid component of the solution was mixed and the amount shown in Table 5 (parts by mass). Further, the cross-linking agent (B) and the decane compound (C) were further added with ethyl acetate so that the solid content concentration became 14%, thereby obtaining an adhesive composition. When the product to be used contains a solvent or the like, the blending amount of each of the blending components shown in Table 5 is the mass fraction of the active ingredient contained therein.

表5中，簡稱所示之各調配成分係詳述如下。 In Table 5, each of the formulated components shown by the abbreviation is detailed below.

(交聯劑) (crosslinking agent)

B-1：甲伸苯基二異氰酸酯之三羥甲基丙烷加成體之乙酸乙酯溶液(固體成分濃度75%)，東曹股份有限公司所得之商品名「CORONATE L」。 B-1: Ethyl acetate solution of trimethylolpropane adduct of methyl phenyl diisocyanate (solid content: 75%), and the trade name "CORONATE L" obtained by Tosoh Corporation.

(矽烷化合物) (decane compound)

C-1：1,6-雙(三甲氧基矽基)己烷。 C-1:1,6-bis(trimethoxyindenyl)hexane.

(7)黏著劑層之製作 (7) Production of adhesive layer

除了以上述(6)所調製之各黏著劑組成物取代黏著劑組成物以外，係以與上述「(2)黏著劑層之製作」相同方法製作黏著劑層(黏著劑薄片)。 An adhesive layer (adhesive sheet) was produced in the same manner as in the above-mentioned "(2) Preparation of Adhesive Layer", except that each of the adhesive compositions prepared in the above (6) was used in place of the adhesive composition.

(8)附黏著劑層之光學膜(P-2)之製作 (8) Production of optical film (P-2) with adhesive layer

除了以上述(7)所製作之黏著劑層取代黏著劑層以外，係以與上述「(3)附黏著劑層之光學膜(P-1)之製作」相同方法製作附黏著劑層之光學膜(P-2)。 The optical layer of the adhesive layer was produced in the same manner as in the above-mentioned "(3) Production of optical film (P-1) with adhesive layer" except that the adhesive layer prepared in the above (7) was used in place of the adhesive layer. Membrane (P-2).

(9)附黏著劑層之光學膜之耐久性評估 (9) Durability evaluation of optical film with adhesive layer

將上述(8)所製作之附黏著劑層之光學膜(P-2)以偏光板之延伸軸方向成為長邊之方式裁切為300mm×220mm的大小並剝離分離膜，將露出之黏著劑層面貼合於玻璃基板。將所得之貼附於玻璃基板之試驗片(貼附於玻璃基板之附黏著劑層之光學膜)於高壓釜中，以溫度50℃、壓力5kg/cm2(490.3kPa)加壓20分鐘。玻璃基板係使用康寧公司製之無鹼玻璃，商品名「Eagle XG」。 The optical film (P-2) with the adhesive layer produced in the above (8) is cut into a size of 300 mm × 220 mm so that the direction of the extension axis of the polarizing plate becomes a long side, and the separation film is peeled off to expose the adhesive. The layer is attached to the glass substrate. The obtained test piece attached to the glass substrate (optical film attached to the adhesive layer of the glass substrate) was pressurized in an autoclave at a temperature of 50 ° C and a pressure of 5 kg/cm 2 (490.3 kPa) for 20 minutes. The glass substrate was made of an alkali-free glass made by Corning Co., Ltd. under the trade name "Eagle XG".

對所得之光學積層體實施於溫度105℃之乾燥條件下保持500小時之耐熱試驗。 The obtained optical laminate was subjected to a heat resistance test under a drying condition of a temperature of 105 ° C for 500 hours.

目視觀察各試驗後之光學積層體，以目視觀察黏著劑層有無浮翹、剝離、發泡等外觀變化，根據評估基準評估耐久性。結果示於表6。 The optical laminate after each test was visually observed to visually observe the appearance change of the adhesive layer such as floatation, peeling, foaming, etc., and the durability was evaluated based on the evaluation criteria. The results are shown in Table 6.

5：完全未觀察到浮翹、剝離、發泡等外觀變化。 5: No change in appearance such as floatation, peeling, and foaming was observed at all.

4：幾乎未觀察到浮翹、剝離、發泡等外觀變化。 4: Appearance changes such as floatation, peeling, and foaming were hardly observed.

3：稍微觀察到浮翹、剝離、發泡等外觀變化。 3: Appearance changes such as floatation, peeling, and foaming were slightly observed.

2：觀察到浮翹、剝離、發泡等外觀變化。 2: Appearance changes such as floatation, peeling, and foaming were observed.

1：明顯確認到浮翹、剝離、發泡等外觀變化。 1: Apparent changes such as floatation, peeling, and foaming were clearly confirmed.

(10)附黏著劑層之光學膜之黏著力評估 (10) Evaluation of adhesion of optical film with adhesive layer

除了以上述(8)所製作附黏著劑層之光學膜(P-2)取代附黏著劑層之光學膜以外，係以與上述「(5)附黏著劑層之光學膜之黏著力評估」相同方法評估附黏著劑層之光學膜(P-2)之黏著力。結果示於表6。 In addition to the optical film (P-2) with the adhesive layer prepared in the above (8), the optical film of the adhesive layer is replaced with the above-mentioned "(5) Adhesion evaluation of the optical film with the adhesive layer" The adhesion of the optical film (P-2) with the adhesive layer was evaluated in the same manner. The results are shown in Table 6.

[光學積層體之ITO腐蝕性評估] [Evaluation of ITO Corrosion of Optical Laminates]

除了以上述(8)所製作附黏著劑層之光學膜(P-2)取代附黏著劑層之光學膜以外，係以與上述所記載之方法相同方法製作積層有ITO之光學積層體，並評估以上述所記載之方法得到的光學積層體之ITO腐蝕性。結果示於表6。又，評估基準亦與上述相同。 An optical layered body in which ITO was laminated was produced in the same manner as described above except that the optical film (P-2) having the adhesive layer formed in the above (8) was used instead of the optical film with the adhesive layer. The ITO corrosion resistance of the optical layered body obtained by the method described above was evaluated. The results are shown in Table 6. Also, the evaluation criteria are the same as above.

[黏著劑薄片之膠化率] [Gelification rate of adhesive sheet]

以上述所記載方法測定上述(7)所製作之黏著劑薄片之膠化率。結果示於表6。 The gelation rate of the adhesive sheet produced in the above (7) was measured by the method described above. The results are shown in Table 6.

如表6所示，(甲基)丙烯酸系樹脂之成分中AAEM(a1)與HEA(a2)之質量比(a2)/(a1)為0.5至5的範圍內之實施例係顯示較該質量比為0.5至5範圍外之比較例之光學積層體優異的耐久性。而且，(甲基)丙烯酸系樹脂之成分中，若較均聚物的玻璃轉移溫度未達0℃之丙烯酸烷酯(a3)多之比例含有均聚物Tg為0℃以上之丙烯酸烷酯(a4)，則即使在更嚴苛耐久性試驗亦顯示良好耐久性。 As shown in Table 6, in the composition of the (meth)acrylic resin, the embodiment in which the mass ratio (a2)/(a1) of AAEM (a1) to HEA (a2) is in the range of 0.5 to 5 shows that the mass is higher than the mass. The optical laminate of the comparative example having a ratio of 0.5 to 5 is excellent in durability. Further, among the components of the (meth)acrylic resin, an alkyl acrylate having a homopolymer Tg of 0 ° C or more is contained in a ratio of a polyalkyl acrylate (a3) having a glass transition temperature of less than 0 ° C. A4) shows good durability even in more severe durability tests.

<實施例13-15、比較例8> <Examples 13-15, Comparative Example 8>

(11)黏著劑組成物之調製 (11) Modulation of adhesive composition

於上述製造例2-4、13所得之(甲基)丙烯酸系樹脂之乙酸乙酯溶液(樹脂濃度：20%)中，混合相對於該溶液之固體成分100份為表7所示量(質量份)之交聯劑(B)、矽烷化合物(C)及離子性化合物(D)，進一步以固體成分濃度成為14%之方式添加乙酸乙酯，而獲得黏著劑組成物。在所使用商品含有溶劑等時，表7所示之各調配成分之調配量為其所含有的有效成分之質量份數。 In the ethyl acetate solution (resin concentration: 20%) of the (meth)acrylic resin obtained in the above Production Examples 2-4 and 13, 100 parts of the solid component with respect to the solution was mixed and the amount shown in Table 7 (mass) The cross-linking agent (B), the decane compound (C), and the ionic compound (D) were further added with ethyl acetate so that the solid content concentration was 14%, and the adhesive composition was obtained. When the product to be used contains a solvent or the like, the blending amount of each of the blending components shown in Table 7 is the mass fraction of the active ingredient contained therein.

表7中簡稱所示各調配成分之詳細如下。 The details of the respective components shown in the abbreviation in Table 7 are as follows.

(交聯劑) (crosslinking agent)

B-1：甲伸苯基二異氰酸酯之三羥甲基丙烷加成體之乙酸乙酯溶液(固體成分濃度75%)，東曹股份有限公司所得之商品名「CORONATE L」。 B-1: Ethyl acetate solution of trimethylolpropane adduct of methyl phenyl diisocyanate (solid content: 75%), and the trade name "CORONATE L" obtained by Tosoh Corporation.

(矽烷化合物) (decane compound)

C-1：1,6-雙(三甲氧基矽基)己烷。 C-1:1,6-bis(trimethoxyindenyl)hexane.

(離子性化合物) (ionic compound)

D-1：N-癸基吡啶鎓雙(氟磺醯基)醯亞胺。 D-1: N-decylpyridinium bis(fluorosulfonyl) quinone imine.

(12)黏著劑層之製作 (12) Production of adhesive layer

除了以上述(11)所調製之各黏著劑組成物取代黏著劑組成物以外，係以與上述「(2)黏著劑層之製作」相同方法製作黏著劑層。 An adhesive layer was produced in the same manner as in the above-mentioned "(2) Preparation of Adhesive Layer" except that each of the adhesive compositions prepared in the above (11) was used in place of the adhesive composition.

(13)附黏著劑層之光學膜(P-3)之製作 (13) Production of optical film (P-3) with adhesive layer

將平均聚合度2400、皂化度99.9莫耳%、厚度30μm之聚乙烯醇膜(Kuraray股份有限公司製商品名〔Kuraray poval-film VF-PE#3000〕)浸漬於37℃純水後，於含有碘及碘化鉀之水溶液(碘/碘化鉀/水(重量比)=0.04/1.5/100)中 以30℃浸漬。其後，於含有碘化鉀及硼酸之水溶液(碘化鉀/硼酸/水(重量比)=12/3.6/100)中以56.5℃浸漬。接著將膜以10℃的純水洗淨後，於85℃乾燥，獲得於聚乙烯醇吸附配向有碘之厚度約12μm之偏光片A。延伸主要是在碘染色及硼酸處理步驟進行，總延伸倍率為5.3倍。 A polyvinyl alcohol film (Kuraray poval-film VF-PE #3000, manufactured by Kuraray Co., Ltd.) having an average degree of polymerization of 2,400, a saponification degree of 99.9 mol%, and a thickness of 30 μm was immersed in pure water at 37 ° C, and then contained therein. An aqueous solution of iodine and potassium iodide (iodine/potassium iodide/water (weight ratio) = 0.04/1.5/100) was impregnated at 30 °C. Thereafter, it was impregnated at 56.5 ° C in an aqueous solution containing potassium iodide and boric acid (potassium iodide / boric acid / water (weight ratio) = 12 / 3.6 / 100). Subsequently, the film was washed with pure water at 10 ° C, and then dried at 85 ° C to obtain a polarizing plate A having a thickness of about 12 μm in the form of iodine adsorbed on the polyvinyl alcohol. The extension is mainly carried out in the steps of iodine dyeing and boric acid treatment, and the total stretching ratio is 5.3 times.

於所得之偏光膜A的單面，經由由聚乙烯醇系樹脂水溶液所構成之接著劑貼合在厚度25μm之三乙醯基纖維素膜附加7μm硬塗層而得之透明保護膜(凸版印刷股份有限公司製之商品名〔25KCHCN-TC〕)。接著，於偏光膜A之與貼合有透明保護膜之面為相反側的面，經由由聚乙烯醇系樹脂水溶液所構成之接著劑貼合厚度23μm之環烯烴系樹脂膜(日本ZEON股份有限公司製之商品名〔ZF14-023〕)，獲得偏光板A。接著，在環烯烴系樹脂膜中與偏光片接觸面為相反側的面實施用以提高密著性之電暈放電處理後，藉由積層機貼合在上述(12)所製作之黏著劑層之與分離膜為相反側的面(黏著劑層面)後，以溫度23℃、相對濕度65%之條件熟化7天，獲得附黏著劑層之光學膜(P-3)。 On one surface of the obtained polarizing film A, a transparent protective film (tapped printing) was obtained by laminating a 3 μm-thick cellulose film having a thickness of 25 μm on a single surface of a polarizing film A made of a polyvinyl alcohol-based resin solution with a 7 μm hard coat layer. The trade name of the company limited by shares (25KCHCN-TC)). Then, a cycloolefin resin film having a thickness of 23 μm is bonded to the surface of the polarizing film A on the side opposite to the surface on which the transparent protective film is bonded, and an adhesive composed of a polyvinyl alcohol-based resin aqueous solution (Japanese ZEON Co., Ltd.) The company name (ZF14-023) is obtained by the company, and the polarizing plate A is obtained. Then, after the corona discharge treatment for improving the adhesion is performed on the surface of the cycloolefin resin film opposite to the contact surface of the polarizer, the adhesive layer produced in the above (12) is bonded to the surface of the adhesive layer by the laminator. After the surface (adhesive layer) on the opposite side to the separation membrane, the film was aged at a temperature of 23 ° C and a relative humidity of 65% for 7 days to obtain an optical film (P-3) with an adhesive layer.

(14)附黏著劑層之光學膜之耐久性評估 (14) Durability evaluation of optical film with adhesive layer

除了以上述(13)所製作之附黏著劑層之光學膜(P-3)取代附黏著劑層之光學膜以外，係以與上述「(4)附黏著劑層之光學膜之耐久性評估」相同方法評估附黏著劑層之光學膜之耐久性。結果示於表8。又，評估基準亦與上述相同。 In addition to the optical film (P-3) with the adhesive layer prepared in the above (13), the optical film of the adhesive layer is replaced with the durability of the optical film of the above (4) adhesive layer. The same method was used to evaluate the durability of the optical film with the adhesive layer. The results are shown in Table 8. Also, the evaluation criteria are the same as above.

(15)附黏著劑層之光學膜之黏著力評估 (15) Evaluation of adhesion of optical film with adhesive layer

除了以上述(13)所製作之附黏著劑層之光學膜(P-3)取代附黏著劑層之光學膜以外，係以與上述「(5)附黏著劑層之光學膜之黏著力評估」相同方法評估附黏著劑層之光學膜(P-3)之黏著力。結果示於表8。 In addition to the optical film (P-3) with the adhesive layer prepared in the above (13), the optical film of the adhesive layer is replaced by the adhesion of the optical film of the above (5) adhesive layer. The same method was used to evaluate the adhesion of the optical film (P-3) with the adhesive layer. The results are shown in Table 8.

[光學積層體之ITO腐蝕性評估] [Evaluation of ITO Corrosion of Optical Laminates]

除了以上述(13)所製作之附黏著劑層之光學膜(P-3)取代附黏著劑層之光學膜以外，係以與上述所記載之方法相同方法製作積層有ITO之光學積層體，並評估上述所記載之方法所得光學積層體之ITO腐蝕性。結果示於表8。又，評估基準亦與上述相同。 An optical layered body in which ITO is laminated is produced in the same manner as described above except that the optical film (P-3) with an adhesive layer produced in the above (13) is used instead of the optical film with an adhesive layer. The ITO corrosion resistance of the optical laminate obtained by the method described above was evaluated. The results are shown in Table 8. Also, the evaluation criteria are the same as above.

[黏著劑薄片之膠化率] [Gelification rate of adhesive sheet]

以上述所記載之方法測定上述(12)所製作黏著劑薄片之膠化率。結果示於表8。 The gelation rate of the adhesive sheet prepared in the above (12) was measured by the method described above. The results are shown in Table 8.

將上述(13)所製作之附黏著劑層之光學膜(P-3)之分隔片剝離後，藉由表面固有電阻測定裝置〔三菱化學股份有限公司製之「Hiresta-up MCP-HT450」(商品名)〕測定黏著劑之表面電阻值。以施加電壓250V、施加時間10秒之測定條件實施測定。若表面電阻值為1.0×1012Ω/□以下，則可獲得良好的抗靜電性。 The separator of the optical film (P-3) with the adhesive layer produced in the above (13) was peeled off, and the surface specific resistance measuring device [Hiresta-up MCP-HT450 (manufactured by Mitsubishi Chemical Corporation) was used. Trade name)] Determine the surface resistance of the adhesive. The measurement was carried out under the measurement conditions of an applied voltage of 250 V and an application time of 10 seconds. When the surface resistance value is 1.0 × 10 12 Ω / □ or less, good antistatic properties can be obtained.

Claims (23)

一種黏著劑組成物，係含有(甲基)丙烯酸系樹脂(A)、交聯劑(B)及矽烷化合物(C)；前述(甲基)丙烯酸系樹脂(A)係包含源自於含有乙醯乙醯基之(甲基)丙烯酸酯(a1)之構成單元、及源自於含有羥基之(甲基)丙烯酸酯(a2)之構成單元，前述構成單元之質量比(a2)/(a1)為0.5至5。  An adhesive composition comprising a (meth)acrylic resin (A), a crosslinking agent (B), and a decane compound (C); and the (meth)acrylic resin (A) is derived from a a constituent unit of the (meth) acrylate (a1) and a constituent unit derived from a hydroxyl group-containing (meth) acrylate (a2), and the mass ratio of the constituent unit (a2)/(a1) ) is 0.5 to 5.   如申請專利範圍第1項所述之黏著劑組成物，其中，(甲基)丙烯酸系樹脂(A)之重量平均分子量以聚苯乙烯換算為100萬以上。  The adhesive composition according to the first aspect of the invention, wherein the weight average molecular weight of the (meth)acrylic resin (A) is 1,000,000 or more in terms of polystyrene.   如申請專利範圍第1或2項所述之黏著劑組成物，其中，(甲基)丙烯酸系樹脂(A)更包含源自於均聚物的玻璃轉移溫度未達0℃之丙烯酸烷酯(a3)之構成單元、及源自於均聚物的玻璃轉移溫度為0℃以上之丙烯酸烷酯(a4)之構成單元。  The adhesive composition according to claim 1 or 2, wherein the (meth)acrylic resin (A) further comprises an alkyl acrylate derived from a homopolymer having a glass transition temperature of less than 0 ° C ( The constituent unit of a3) and the constituent unit derived from the alkyl acrylate (a4) having a glass transition temperature of 0 ° C or higher derived from a homopolymer.   如申請專利範圍第1至3項中任一項所述之黏著劑組成物，其中，源自於均聚物的玻璃轉移溫度未達0℃之丙烯酸烷酯(a3)之構成單元與源自於均聚物的玻璃轉移溫度為0℃以上之丙烯酸烷酯(a4)之構成單元的質量比(a3)/(a4)為0.1至4。  The adhesive composition according to any one of claims 1 to 3, wherein the constituent unit of the alkyl acrylate (a3) derived from the homopolymer has a glass transition temperature of less than 0 ° C and is derived from The mass ratio (a3)/(a4) of the constituent unit of the alkyl acrylate (a4) having a glass transition temperature of 0 ° C or more in the homopolymer is 0.1 to 4.   如申請專利範圍第1至4項中任一項所述之黏著劑組成物，其中，相對於構成(甲基)丙烯酸系樹脂(A)之全部構成單元100質量份，(甲基)丙烯酸系樹脂(A)所包含之源自於含有羧基之(甲基)丙烯酸酯之構成單元的 比例為1.0質量份以下。  The adhesive composition according to any one of the first to fourth aspects of the present invention, wherein the (meth)acrylic acid is 100 parts by mass based on all the constituent units constituting the (meth)acrylic resin (A). The ratio of the constituent unit derived from the carboxyl group-containing (meth) acrylate contained in the resin (A) is 1.0 part by mass or less.   如申請專利範圍第1至5項中任一項所述之黏著劑組成物，其中，(甲基)丙烯酸系樹脂(A)更含有源自於(甲基)丙烯醯胺系單體之構成單元。  The adhesive composition according to any one of claims 1 to 5, wherein the (meth)acrylic resin (A) further contains a composition derived from a (meth)acrylamide monomer. unit.   如申請專利範圍第1至6項中任一項所述之黏著劑組成物，其中，交聯劑(B)為異氰酸酯系化合物。  The adhesive composition according to any one of claims 1 to 6, wherein the crosslinking agent (B) is an isocyanate compound.   如申請專利範圍第1至7項中任一項所述之黏著劑組成物，其中，相對於(甲基)丙烯酸系樹脂(A)100質量份，交聯劑(B)之比例為0.01至10質量份。  The adhesive composition according to any one of claims 1 to 7, wherein the ratio of the crosslinking agent (B) is 0.01 to 100 parts by mass of the (meth)acrylic resin (A). 10 parts by mass.   如申請專利範圍第1至8項中任一項所述之黏著劑組成物，其中，矽烷化合物(C)為下式(c1)所示矽烷化合物； 式中，B表示碳數3至20之烷二基或碳數3至20之二價脂環式烴基，構成前述烷二基及前述脂環式烴基之-CH 2-可經取代為-O-或-CO-，R 1表示碳數1至5之烷基，R 2、R 3、R 4、R 5及R 6分別獨立表示碳數1至5之烷基或碳數1至5之烷氧基。 The adhesive composition according to any one of claims 1 to 8, wherein the decane compound (C) is a decane compound represented by the following formula (c1); Wherein B represents a C3 to 20 alkanediyl group or a C3 to 20 divalent alicyclic hydrocarbon group, and the -CH 2 - constituting the aforementioned alkanediyl group and the aforementioned alicyclic hydrocarbon group may be substituted with -O - or -CO-, R 1 represents an alkyl group having 1 to 5 carbon atoms, and R 2 , R 3 , R 4 , R 5 and R 6 each independently represent an alkyl group having 1 to 5 carbon atoms or a carbon number of 1 to 5 Alkoxy. 如申請專利範圍第1至9項中任一項所述之黏著劑組成物，其中，相對於(甲基)丙烯酸系樹脂(A)100質量份，矽烷化合物(C)之比例為0.01至10質量份。  The adhesive composition according to any one of claims 1 to 9, wherein the ratio of the decane compound (C) is 0.01 to 10 with respect to 100 parts by mass of the (meth)acrylic resin (A). Parts by mass.   如申請專利範圍第1至10項中任一項所述之黏著劑組 成物，其實質上不含有光聚合起始劑及其分解物。  The adhesive composition according to any one of claims 1 to 10, which does not substantially contain a photopolymerization initiator and a decomposition product thereof.   如申請專利範圍第1至11項中任一項所述之黏著劑組成物，更含有離子性化合物(D)。  The adhesive composition according to any one of claims 1 to 11, further comprising an ionic compound (D).   如申請專利範圍第12項所述之黏著劑組成物，其中，相對於(甲基)丙烯酸系樹脂(A)100質量份，離子性化合物(D)之比例為0.01至10質量份。  The adhesive composition according to claim 12, wherein the ratio of the ionic compound (D) is 0.01 to 10 parts by mass based on 100 parts by mass of the (meth)acrylic resin (A).   如申請專利範圍第12或13項所述之黏著劑組成物，其中，構成離子性化合物(D)之陰離子係由雙(三氟甲烷磺醯基)醯亞胺陰離子、雙(氟磺醯基)醯亞胺陰離子及四(五氟苯基)硼酸酯陰離子所成群組選出之至少1種。  The adhesive composition according to claim 12 or 13, wherein the anion which constitutes the ionic compound (D) is an bis(trifluoromethanesulfonyl) sulfinium anion, bis(fluorosulfonyl) At least one selected from the group consisting of a quinone imine anion and a tetrakis(pentafluorophenyl) borate anion.   一種黏著劑層，係含有申請專利範圍第1至14項中任一項所述之黏著劑組成物。  An adhesive composition comprising the adhesive composition according to any one of claims 1 to 14.   如申請專利範圍第15項所述之黏著劑層，其中，前述黏著劑層之膠化率為70至90%。  The adhesive layer according to claim 15, wherein the adhesive layer has a gelation ratio of 70 to 90%.   一種附黏著劑層之光學膜，係含有光學膜及於該光學膜的至少一面積層之黏著劑層，該黏著劑層係申請專利範圍第15或16項所述之黏著劑層。  An optical film with an adhesive layer comprising an optical film and an adhesive layer on at least one area of the optical film, the adhesive layer being the adhesive layer of claim 15 or 16.   一種光學積層體，係含有申請專利範圍第17項所記載之附黏著劑層之光學膜、及於該附黏著劑層之光學膜的黏著劑層側積層之基材。  An optical layered product comprising the optical film with an adhesive layer described in claim 17 and a substrate laminated on the side of the adhesive layer of the optical film of the adhesive layer.   一種黏著劑組成物用(甲基)丙烯酸系樹脂(A)，係包含源自於含有乙醯乙醯基之(甲基)丙烯酸酯(a1)之構成單元、及源自於含有羥基之(甲基)丙烯酸酯(a2)之構成單元，前述構成單元之質量比(a2)/(a1)為0.5至5，且 重量平均分子量以聚苯乙烯換算為100萬以上。  The (meth)acrylic resin (A) for an adhesive composition comprising a constituent unit derived from a (meth) acrylate (a1) containing an ethyl ethane group and derived from a hydroxyl group ( The structural unit of the methyl acrylate (a2) has a mass ratio (a2)/(a1) of 0.5 to 5, and a weight average molecular weight of 1,000,000 or more in terms of polystyrene.   如申請專利範圍第19項所記載之黏著劑組成物用(甲基)丙烯酸系樹脂(A)，其中，(甲基)丙烯酸系樹脂(A)更包含源自於均聚物的玻璃轉移溫度未達0℃之丙烯酸烷酯(a3)之構成單元、及源自於均聚物的玻璃轉移溫度為0℃以上之丙烯酸烷酯(a4)之構成單元。  The (meth)acrylic resin (A) for an adhesive composition according to claim 19, wherein the (meth)acrylic resin (A) further comprises a glass transition temperature derived from a homopolymer. The constituent unit of the alkyl acrylate (a3) which is less than 0 ° C and the constituent unit derived from the alkyl acrylate (a4) having a glass transition temperature of 0 ° C or higher derived from the homopolymer.   如申請專利範圍第19或20項所記載之黏著劑組成物用(甲基)丙烯酸系樹脂(A)，其中，源自於均聚物的玻璃轉移溫度未達0℃之丙烯酸烷酯(a3)之構成單元與源自於均聚物的玻璃轉移溫度為0℃以上之丙烯酸烷酯(a4)之構成單元的質量比(a3)/(a4)為0.1至4。  The (meth)acrylic resin (A) for an adhesive composition according to claim 19 or 20, wherein the alkyl acrylate (a3) derived from a homopolymer has a glass transition temperature of less than 0 ° C (a3) The mass ratio (a3)/(a4) of the constituent unit of the alkyl acrylate (a4) having a glass transition temperature of 0 ° C or higher derived from the homopolymer is 0.1 to 4.   如申請專利範圍第19至21項中任一項所述之黏著劑組成物用(甲基)丙烯酸系樹脂(A)，其中，相對於構成(甲基)丙烯酸系樹脂(A)之全部構成單元100質量份，(甲基)丙烯酸系樹脂(A)所包含之源自於含有羧基之(甲基)丙烯酸酯之構成單元的比例為1.0質量份以下。  The (meth)acrylic resin (A) for an adhesive composition according to any one of claims 19 to 21, wherein all of the constituents of the (meth)acrylic resin (A) are formed. The ratio of the constituent unit derived from the carboxyl group-containing (meth) acrylate contained in the (meth)acrylic resin (A) is 1.0 part by mass or less based on 100 parts by mass of the unit.   如申請專利範圍第19至22項中任一項所述之黏著劑組成物用(甲基)丙烯酸系樹脂(A)，其中，(甲基)丙烯酸系樹脂(A)更含有源自於(甲基)丙烯醯胺系單體之構成單元。  The (meth)acrylic resin (A) for an adhesive composition according to any one of claims 19 to 22, wherein the (meth)acrylic resin (A) is further contained ( A constituent unit of a methyl methacrylate monomer.  
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