TW202039732A - Polarizing film with adhesive layer, and image display device - Google Patents

Polarizing film with adhesive layer, and image display device Download PDF

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TW202039732A
TW202039732A TW108143758A TW108143758A TW202039732A TW 202039732 A TW202039732 A TW 202039732A TW 108143758 A TW108143758 A TW 108143758A TW 108143758 A TW108143758 A TW 108143758A TW 202039732 A TW202039732 A TW 202039732A
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adhesive layer
meth
group
polarizing film
aforementioned
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TW108143758A
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Chinese (zh)
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TWI839423B (en
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木村智之
石原康隆
外山雄祐
三田聰司
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日商日東電工股份有限公司
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • B32B7/023—Optical 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions 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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
    • 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
    • G02F1/133528—Polarisers
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

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  • Crystallography & Structural Chemistry (AREA)
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  • Nanotechnology (AREA)
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  • Adhesive Tapes (AREA)
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Abstract

This polarizing film with an adhesive layer comprises a polarizing film and an adhesive layer. The polarizing film comprises a polarizing element, a transparent protective film on only one surface of the polarizing element, and a conductive layer on the other one surface of the polarizing element with a transparent layer therebetween that is no more than 10 [mu]m thick and that is formed directly on the polarizing element. The adhesive layer is provided on the polarizing film with the aforementioned conductive layer interposed therebetween. Even in the case that a conductive layer is provided on the side of the polarizing element of the one-side-protected polarizing film, which has the transparent protective film on only one surface of the polarizing element, decoloration of the end part of the polarizing element in a humidified environment can be suppressed.

Description

附黏著劑層之偏光薄膜及影像顯示裝置Polarizing film with adhesive layer and image display device

本發明涉及附黏著劑層之偏光薄膜。且，本發明涉及應用有前述附黏著劑層之偏光薄膜的影像顯示面板、影像顯示裝置。The invention relates to a polarizing film with an adhesive layer. In addition, the present invention relates to an image display panel and an image display device to which the aforementioned polarizing film with an adhesive layer is applied.

以影像顯示面板、例如使用於液晶顯示裝置等之液晶面板來說，通常係於液晶單元兩側透過黏著劑層積層有偏光薄膜，該液晶單元係由配置於一對透明基板間的液晶層所形成。另一方面，製造影像顯示面板時，將前述附黏著劑層之偏光薄膜貼附於液晶單元時，會從附黏著劑層之偏光薄膜的黏著劑層剝離脫模薄膜，而剝離該脫模薄膜會產生靜電。如此產生的靜電會影響例如液晶顯示面板內部的液晶層之定向，導致不良。所以，例如藉由在偏光薄膜外面形成抗靜電層，可抑制靜電的產生。For image display panels, such as liquid crystal panels used in liquid crystal display devices, polarizing films are usually laminated on both sides of a liquid crystal cell through an adhesive layer. The liquid crystal cell is composed of a liquid crystal layer arranged between a pair of transparent substrates. form. On the other hand, when manufacturing an image display panel, when the aforementioned polarizing film with an adhesive layer is attached to a liquid crystal cell, the release film is peeled off from the adhesive layer of the polarizing film with the adhesive layer, and the release film is peeled off Will generate static electricity. The static electricity generated in this way affects, for example, the orientation of the liquid crystal layer inside the liquid crystal display panel, resulting in defects. Therefore, for example, by forming an antistatic layer on the outside of the polarizing film, the generation of static electricity can be suppressed.

為了抑制上述靜電發生，例如提出了一種抗靜電型附黏著劑層之光學薄膜，其於光學薄膜(例如偏光薄膜)之至少單面設置含有水溶性或水分散性導電聚合物之抗靜電層(導電層)，並於該抗靜電層上積層有黏著劑層(專利文獻1)。又，亦已知於黏著劑中添加離子性化合物作為抗靜電劑，可抑制靜電產生(專利文獻2)。In order to suppress the above-mentioned static electricity, for example, an antistatic optical film with an adhesive layer is proposed. An antistatic layer containing a water-soluble or water-dispersible conductive polymer is provided on at least one side of an optical film (such as a polarizing film). Conductive layer), and an adhesive layer is laminated on the antistatic layer (Patent Document 1). It is also known that adding an ionic compound as an antistatic agent to an adhesive can suppress the generation of static electricity (Patent Document 2).

先前技術文獻 專利文獻 專利文獻1：日本專利特開2004-338379號公報 專利文獻2：日本專利特開2009-251281號公報Prior art literature Patent literature Patent Document 1: Japanese Patent Laid-Open No. 2004-338379 Patent Document 2: Japanese Patent Laid-Open No. 2009-251281

發明欲解決之課題 根據專利文獻1、2中記載之具有抗靜電層的偏光薄膜，可抑制靜電產生。但已知，將專利文獻1記載之由導電聚合物形成之抗靜電層直接形成於單面保護偏光薄膜之偏光件時，前述導電聚合物會對偏光件造成不良影響，而偏光件端部在加濕環境下會褪色。且已知將專利文獻2記載之含有抗靜電劑之黏著劑層應用於單面保護偏光薄膜之偏光件時，會有在加濕環境下抗靜電劑進入偏光件內部而造成偏光件端部褪色，進而使黏著劑層之抗靜電機能降低之問題。Problems to be solved by the invention According to the polarizing film having an antistatic layer described in Patent Documents 1 and 2, the generation of static electricity can be suppressed. However, it is known that when the antistatic layer made of a conductive polymer described in Patent Document 1 is directly formed on a polarizer with a single-sided protective polarizing film, the aforementioned conductive polymer will adversely affect the polarizer, and the end of the polarizer is It will fade in humidified environment. It is also known that when the adhesive layer containing the antistatic agent described in Patent Document 2 is applied to a polarizer with a single-sided protective polarizing film, the antistatic agent may enter the inside of the polarizer in a humidified environment and cause the end of the polarizer to fade , Thereby reducing the antistatic function of the adhesive layer.

本發明之目的在於提供一種附黏著劑層之偏光薄膜，其即便在僅於偏光件之單面具有透明保護薄膜之單面保護偏光薄膜的前述偏光件側設有導電層之情形，仍可於加濕環境下抑制偏光件端部褪色。The object of the present invention is to provide a polarizing film with an adhesive layer, which can be used even if a conductive layer is provided on the polarizer side of the single-sided protective polarizing film with a transparent protective film on only one side of the polarizer. In a humidified environment, the end of the polarizer is suppressed from fading.

且，本發明之目的在於提供應用有前述附黏著劑層之偏光薄膜的影像顯示面板、影像顯示裝置。Moreover, the object of the present invention is to provide an image display panel and an image display device using the aforementioned polarizing film with an adhesive layer.

用以解決課題之方法 本發明人等為解決前述課題積極努力檢討後，發現了下述附黏著劑層之偏光薄膜，遂而完成本發明。Methods to solve the problem The inventors of the present invention made active efforts to solve the aforementioned problems and found the following polarizing film with an adhesive layer, and completed the present invention.

即，本發明係涉及一種附黏著劑層之偏光薄膜，其具有偏光薄膜及黏著劑層； 該附黏著劑層之偏光薄膜之特徵在於： 前述偏光薄膜具有偏光件、僅於前述偏光件之單面具有透明保護薄膜及於前述偏光件之另一面隔著透明層具有導電層，該透明層係直接形成於前述偏光件上且厚度為10μm以下，並且前述黏著劑層係隔著前述導電層設置。That is, the present invention relates to a polarizing film with an adhesive layer, which has a polarizing film and an adhesive layer; The characteristics of the polarizing film with adhesive layer are: The polarizing film has a polarizing member, a transparent protective film is provided on only one side of the polarizing member, and a conductive layer is provided on the other side of the polarizing member via a transparent layer. The transparent layer is directly formed on the polarizing member and has a thickness of 10 μm Hereinafter, the adhesive layer is provided via the conductive layer.

前述附黏著劑層之偏光薄膜中，作為前述透明層，可使用含有胺甲酸乙酯預聚物的形成材之硬化物，該胺甲酸乙酯預聚物係異氰酸酯化合物與多元醇的反應物。前述異氰酸酯化合物宜使用選自二異氰酸甲苯酯及二苯甲烷二異氰酸酯中之至少任一種。In the polarizing film with the adhesive layer, as the transparent layer, a cured product containing a forming material of a urethane prepolymer, which is a reaction product of an isocyanate compound and a polyol, can be used. It is preferable to use at least any one selected from the group consisting of toluene diisocyanate and diphenylmethane diisocyanate as the aforementioned isocyanate compound.

前述附黏著劑層之偏光薄膜中，前述透明層可含有環氧樹脂。In the polarizing film with the adhesive layer, the transparent layer may contain epoxy resin.

前述附黏著劑層之偏光薄膜中，前述透明層可使用下述樹脂組成物，該樹脂組成物包含： (a)聚合物，其係藉由將大於50重量份之丙烯酸系單體與大於0重量份且小於50重量份之下述通式(1)所示單體聚合而得者： [化學式1]

Figure 02_image001
(式中，X表示含有選自於由乙烯基、(甲基)丙烯醯基、苯乙烯基、(甲基)丙烯醯胺基、乙烯基醚基、環氧基、氧雜環丁烷基、羥基、胺基、醛基及羧基所構成群組中之至少1種反應性基的官能基，R1 及R2 分別獨立表示氫原子、可具有取代基之脂肪族烴基、可具有取代基之芳基或可具有取代基之雜環基，R1 及R2 可相互連結形成環)；及 (b)環氧樹脂；並且 前述聚合物(a)與環氧樹脂(b)之含有比例以重量比計為95：5~60：40或40：60~1：99。In the polarizing film with the adhesive layer, the transparent layer may use the following resin composition, the resin composition comprising: (a) a polymer, which is obtained by combining more than 50 parts by weight of acrylic monomer and more than 0 Part by weight and less than 50 parts by weight of the monomer represented by the following general formula (1) polymerized: [Chemical formula 1]
Figure 02_image001
(In the formula, X represents a group selected from vinyl, (meth)acryloyl, styryl, (meth)acrylamido, vinyl ether, epoxy, oxetanyl A functional group of at least one reactive group in the group consisting of, hydroxyl, amino, aldehyde, and carboxyl groups, R 1 and R 2 each independently represent a hydrogen atom, an aliphatic hydrocarbon group that may have a substituent, and a substituent that may have a substituent The aryl group or the heterocyclic group which may have a substituent, R 1 and R 2 may be connected to each other to form a ring); and (b) epoxy resin; and the content ratio of the aforementioned polymer (a) and epoxy resin (b) In terms of weight ratio, it is 95:5~60:40 or 40:60~1:99.

前述通式(1)中X所示官能基宜為下述通式(2)所示官能基： 通式(2)：Z-Y-(式中，Z表示含有選自於由乙烯基、(甲基)丙烯醯基、苯乙烯基、(甲基)丙烯醯胺基、乙烯基醚基、環氧基、氧雜環丁烷基、羥基、胺基、醛基及羧基所構成群組中之至少1種反應性基的官能基，Y表示有機基)。The functional group represented by X in the aforementioned general formula (1) is preferably a functional group represented by the following general formula (2): General formula (2): ZY-(In the formula, Z means containing selected from vinyl, (meth)acrylic acid group, styryl group, (meth)acrylic acid amino group, vinyl ether group, epoxy A functional group of at least one reactive group in the group consisting of a oxetanyl group, an oxetanyl group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group, and Y represents an organic group).

前述附黏著劑層之偏光薄膜中，前述導電層之厚度宜為1μm以下。In the aforementioned polarizing film with an adhesive layer, the thickness of the aforementioned conductive layer is preferably 1 μm or less.

前述附黏著劑層之偏光薄膜中，前述導電層宜含有導電性聚合物。In the polarizing film with the adhesive layer, the conductive layer preferably contains a conductive polymer.

前述附黏著劑層之偏光薄膜中，前述導電層宜含有選自聚噻吩、聚苯胺、奈米碳管中之至少1種。In the aforementioned polarizing film with an adhesive layer, the aforementioned conductive layer preferably contains at least one selected from polythiophene, polyaniline, and carbon nanotubes.

前述附黏著劑層之偏光薄膜中，前述黏著劑層可使用由含有(甲基)丙烯酸系聚合物(A)之黏著劑組成物所形成者。In the polarizing film with the adhesive layer, the adhesive layer may be formed of an adhesive composition containing (meth)acrylic polymer (A).

前述附黏著劑層之偏光薄膜中，前述黏著劑層可使用由含有(甲基)丙烯酸系聚合物(A)及離子性化合物(B)之黏著劑組成物所形成者。In the polarizing film with the adhesive layer, the adhesive layer may be formed of an adhesive composition containing a (meth)acrylic polymer (A) and an ionic compound (B).

前述附黏著劑層之偏光薄膜中，前述(甲基)丙烯酸系聚合物(A)宜含有(甲基)丙烯酸烷基酯(a1)及含醯胺基單體(a2)作為單體單元。In the polarizing film with the adhesive layer, the (meth)acrylic polymer (A) preferably contains an alkyl (meth)acrylate (a1) and an amide group-containing monomer (a2) as monomer units.

前述附黏著劑層之偏光薄膜中，前述含醯胺基單體(a2)宜為含N-乙烯基內醯胺系單體。In the aforementioned polarizing film with an adhesive layer, the aforementioned amide group-containing monomer (a2) is preferably an N-vinyl lactam-containing monomer.

前述附黏著劑層之偏光薄膜中，前述含醯胺基單體(a2)宜作為單體單元於前述(甲基)丙烯酸系聚合物(A)中含有0.1重量%以上。In the polarizing film with the adhesive layer, the amine group-containing monomer (a2) is preferably contained as a monomer unit in the (meth)acrylic polymer (A) at 0.1% by weight or more.

前述附黏著劑層之偏光薄膜中，前述離子性化合物(B)宜為鹼金屬鹽，且前述黏著劑層的表面電阻值宜為1×1010 ~1×1012 Ω/□。又，前述離子性化合物(B)宜為有機陽離子-陰離子鹽，且前述黏著劑層的表面電阻值宜為1×108 ~1×1010 Ω/□。In the polarizing film with the adhesive layer, the ionic compound (B) is preferably an alkali metal salt, and the surface resistance of the adhesive layer is preferably 1×10 10 to 1×10 12 Ω/□. In addition, the ionic compound (B) is preferably an organic cation-anion salt, and the surface resistance of the adhesive layer is preferably 1×10 8 to 1×10 10 Ω/□.

前述附黏著劑層之偏光薄膜中，前述離子性化合物(B)宜相對於前述(甲基)丙烯酸系聚合物(A)100重量份含有0.01重量份以上。In the polarizing film with the adhesive layer, the ionic compound (B) is preferably contained at least 0.01 parts by weight with respect to 100 parts by weight of the (meth)acrylic polymer (A).

前述附黏著劑層之偏光薄膜中，前述透明保護薄膜適於使用纖維素樹脂薄膜或(甲基)丙烯酸樹脂薄膜之情形。Among the aforementioned polarizing films with adhesive layers, the aforementioned transparent protective film is suitable for the case of using a cellulose resin film or a (meth)acrylic resin film.

又本發明涉及一種影像顯示面板，其特徵在於：具有前述附黏著劑層之偏光薄膜。前述影像顯示面板可應用具有液晶層及觸控感測器部之內嵌觸控感測機能之液晶單元上貼合有前述附黏著劑層之偏光薄膜的黏著劑層者。The present invention also relates to an image display panel, which is characterized by: a polarizing film with the aforementioned adhesive layer. The aforesaid image display panel can be applied to a liquid crystal cell with a liquid crystal layer and a touch sensor part with an in-cell touch sensing function and an adhesive layer with the polarizing film attached to the adhesive layer attached to the liquid crystal cell.

又本發明涉及一種影像顯示裝置，其特徵在於：具有前述影像顯示面板。The present invention also relates to an image display device, which is characterized by having the aforementioned image display panel.

發明效果 本發明附黏著劑層之偏光薄膜所用偏光薄膜為僅於偏光件之單面具有透明保護薄膜之單面保護偏光薄膜，其由薄型化、低成本化之觀點來看有利。另一方面，因於單面保護偏光薄膜之不具有透明保護薄膜之面具有導電層，故可抑制靜電產生。又，前述導電層係隔著透明層設於偏光件上，故導電層不會直接對偏光件造成影響，從而可抑制在加濕環境下偏光件之端部褪色。Invention effect The polarizing film used in the polarizing film with the adhesive layer of the present invention is a single-sided protective polarizing film with a transparent protective film on only one side of the polarizer, which is advantageous from the viewpoint of thinning and cost reduction. On the other hand, since the single-sided protective polarizing film has a conductive layer on the side that does not have a transparent protective film, it can suppress the generation of static electricity. In addition, the aforementioned conductive layer is provided on the polarizing member via the transparent layer, so the conductive layer will not directly affect the polarizing member, thereby preventing the end of the polarizing member from fading in a humidified environment.

又，雖前述導電層上設有黏著劑層，但製成為該黏著劑層中添加有離子性化合物之構成時，可藉由導電層與黏著劑層兩層來提升抗靜電性能。並且，即便製成為前述黏著劑層中添加有離子性化合物之構成時，可藉由前述透明層抑制前述黏著劑層所含離子性化合物偏析至偏光件，故即便於加濕環境下仍可抑制黏著劑層之電阻值上升。In addition, although an adhesive layer is provided on the aforementioned conductive layer, when an ionic compound is added to the adhesive layer, the antistatic performance can be improved by the conductive layer and the adhesive layer. In addition, even if it is made into a structure in which an ionic compound is added to the adhesive layer, the transparent layer can prevent the ionic compound contained in the adhesive layer from segregating to the polarizer, so it can be suppressed even in a humidified environment. The resistance value of the adhesive layer increases.

如以上所述，根據本發明附黏著劑層之偏光薄膜，可提供一種附黏著劑層之偏光薄膜，其即便使用有單面保護偏光薄膜，仍可抑制偏光件的光學可靠性劣化，為薄型且光學可靠性良好，且長時間抗靜電性優異。As described above, according to the polarizing film with an adhesive layer of the present invention, a polarizing film with an adhesive layer can be provided. Even if a single-sided protective polarizing film is used, the degradation of the optical reliability of the polarizer can be suppressed, and it is thin And the optical reliability is good, and the long-term antistatic property is excellent.

本發明附黏著劑層之偏光薄膜例如於圖1所示。如圖1所示，附黏著劑層之偏光薄膜1中使用有單面保護偏光薄膜11，該單面保護偏光薄膜11具有偏光件a、僅於前述偏光件a之單面具有透明保護薄膜b，並於前述偏光件a之另一面具有透明層c。前述單面保護偏光薄膜11中依序設有前述透明層c、導電層d、黏著劑層21。由可抑制偏光件在高溫高濕環境下之水分率上升之觀點，前述透明層c宜直接設於偏光件a。透明層c、d容後說明。For example, the polarizing film with the adhesive layer of the present invention is shown in FIG. 1. As shown in Fig. 1, a single-sided protective polarizing film 11 is used in the polarizing film 1 with an adhesive layer. The single-sided protective polarizing film 11 has a polarizer a and a transparent protective film b on only one side of the aforementioned polarizer a. , And has a transparent layer c on the other side of the aforementioned polarizer a. The single-sided protective polarizing film 11 is provided with the transparent layer c, the conductive layer d, and the adhesive layer 21 in this order. From the viewpoint of suppressing the increase in the moisture content of the polarizing member in a high temperature and high humidity environment, the aforementioned transparent layer c is preferably provided directly on the polarizing member a. The transparent layers c and d will be described later.

>附黏著劑層之偏光薄膜> 首先，就構成本發明附黏著劑層之偏光薄膜的各構件進行說明。>Polarizing film with adhesive layer> First, each member constituting the polarizing film of the adhesive layer of the present invention will be described.

偏光件並無特別限定，可使用各種偏光件。作為偏光件，可舉如使聚乙烯醇系薄膜、部分縮甲醛化聚乙烯醇系薄膜、乙烯-乙酸乙烯酯共聚物系部分皂化薄膜等親水性高分子薄膜吸附碘或二色性染料之二色性物質並進行單軸延伸者，以及聚乙烯醇之脫水處理物或聚氯乙烯之脫鹽酸處理物等多烯系定向薄膜等。該等之中又以由聚乙烯醇系薄膜與碘等的二色性物質構成之偏光件較適宜。該等偏光件之厚度無特別限制，一般在80μm左右以下。The polarizer is not particularly limited, and various polarizers can be used. Examples of polarizers include hydrophilic polymer films such as polyvinyl alcohol-based films, partially formalized polyvinyl alcohol-based films, and ethylene-vinyl acetate copolymer-based partially saponified films that adsorb iodine or dichroic dyes. Color materials and uniaxially stretched, and polyene-based oriented films such as dehydrated polyvinyl alcohol or dehydrated polyvinyl chloride. Among them, a polarizer composed of a dichroic substance such as a polyvinyl alcohol-based film and iodine is more suitable. The thickness of the polarizers is not particularly limited, and is generally below 80 μm.

又，偏光件可使用厚度10μm以下的薄型偏光件。從薄型化觀點來說，該厚度在1~7μm為宜。這種薄型偏光件因厚度參差少，視辨性佳，且尺寸變化少故耐久性優異，而且在作為偏光薄膜的厚度上亦能力求薄型化，就此等觀點來看較為理想。In addition, as the polarizer, a thin polarizer with a thickness of 10 μm or less can be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. Such a thin polarizer has less thickness variation, good visibility, and less dimensional changes, so it is excellent in durability, and can also be thinner in terms of thickness as a polarizing film, which is preferable from these viewpoints.

作為構成透明保護薄膜的材料，可使用例如透明性、機械強度、熱穩定性、抗濕性、各向同性等優異之熱塑性樹脂。所述熱塑性樹脂的具體例可舉例如三醋酸纖維素等之纖維素樹脂、聚酯樹脂、聚醚碸樹脂、聚碸樹脂、聚碳酸酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚烯烴樹脂、(甲基)丙烯酸樹脂、環狀聚烯烴樹脂(降莰烯系樹脂)、聚芳酯樹脂、聚苯乙烯樹脂、聚乙烯醇樹脂及該等之混合物。此外，在偏光件的單側，透明保護薄膜是藉由接著劑層而貼合，而在另一側，透明保護薄膜可使用(甲基)丙烯酸系、胺甲酸乙酯系、丙烯酸胺甲酸乙酯系、環氧系、聚矽氧系等熱硬化性樹脂或紫外線硬化型樹脂。As the material constituting the transparent protective film, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture resistance, isotropy, etc. can be used. Specific examples of the thermoplastic resin may include cellulose resins such as cellulose triacetate, polyester resins, polyether resins, polycarbonate resins, polycarbonate resins, polyamide resins, polyimide resins, and polyamide resins. Olefin resins, (meth)acrylic resins, cyclic polyolefin resins (norbornene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins and mixtures of these. In addition, on one side of the polarizer, the transparent protective film is bonded by the adhesive layer, and on the other side, the transparent protective film can be (meth)acrylic, urethane, or acrylic urethane Thermosetting resins such as ester-based, epoxy-based, and silicone-based resins or UV-curing resins.

前述透明保護薄膜之材料，由可將黏著劑層之表面電阻值的變動控制得較小來看以纖維素樹脂、(甲基)丙烯酸樹脂為佳。此外，(甲基)丙烯酸樹脂宜使用具有內酯環結構之(甲基)丙烯酸系樹脂。具有內酯環結構之(甲基)丙烯酸系樹脂可列舉日本特開2000-230016號公報、日本特開2001-151814號公報、日本特開2002-120326號公報、日本特開2002-254544號公報、日本特開2005-146084號公報等中記載之具有內酯環結構的(甲基)丙烯酸系樹脂。尤其是纖維素樹脂在會在單面保護偏光薄膜造成課題之抑制偏光件裂痕上較(甲基)丙烯酸樹脂更有效，就此觀點來看較佳。For the material of the aforementioned transparent protective film, cellulosic resin and (meth)acrylic resin are preferred because the variation of the surface resistance of the adhesive layer can be controlled to be small. In addition, as the (meth)acrylic resin, a (meth)acrylic resin having a lactone ring structure is preferably used. Examples of (meth)acrylic resins having a lactone ring structure include Japanese Patent Application Publication No. 2000-230016, Japanese Patent Application Publication No. 2001-151814, Japanese Patent Application Publication No. 2002-120326, and Japanese Patent Application Publication No. 2002-254544 A (meth)acrylic resin having a lactone ring structure described in JP 2005-146084 A, etc. In particular, cellulosic resin is more effective than (meth)acrylic resin in suppressing cracks in the polarizer, which can cause problems on one-sided protection of the polarizing film, and is preferable from this point of view.

前述透明保護薄膜之不接著偏光件的面上可設置硬塗層、抗反射層、抗黏著層、擴散層乃至防眩層等機能層。Functional layers such as hard coating, anti-reflection layer, anti-adhesion layer, diffusion layer and even anti-glare layer can be provided on the surface of the aforementioned transparent protective film that is not adhered to the polarizing member.

用於前述偏光件與透明保護薄膜的貼合之接著劑只要在光學上是透明的，則可無特別限制地使用水系、溶劑系、熱熔膠系、自由基硬化型、陽離子硬化型之各種形態的接著劑，惟水系接著劑或自由基硬化型接著劑較適宜。As long as the adhesive used for bonding the polarizer and the transparent protective film is optically transparent, various types of water-based, solvent-based, hot-melt adhesive-based, radical curing type, and cation curing type can be used without particular limitation. In the form of adhesives, only water-based adhesives or free radical hardening adhesives are more suitable.

>透明層> 以下就透明層詳細說明。>Transparent layer> The transparent layer will be described in detail below.

由薄層化及光學可靠性之觀點，透明層之厚度宜為10μm以下，且5μm以下為佳，3μm以下更佳，更宜為1.5μm以下，又更宜為1μm以下。透明層過厚時，偏光薄膜之厚度會變厚，進而有使偏光件之光學可靠性降低之虞。另一方面，由將黏著劑層之表面電阻值的變動比抑制地較小之觀點來看，透明層之厚度宜為0.1μm以上，更宜為0.2μm以上，又更宜為0.3μm以上。From the viewpoint of thinning and optical reliability, the thickness of the transparent layer is preferably 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less, more preferably 1.5 μm or less, and even more preferably 1 μm or less. When the transparent layer is too thick, the thickness of the polarizing film will become thicker, which may reduce the optical reliability of the polarizer. On the other hand, from the viewpoint of suppressing the variation ratio of the surface resistance of the adhesive layer to a small extent, the thickness of the transparent layer is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

形成前述透明層之材料可使用具有透明性且可抑制導電層對偏光件之影響者。所述材料可舉例如含有屬異氰酸酯化合物與多元醇的反應物之胺甲酸乙酯預聚物(a)的形成材。The material for forming the aforementioned transparent layer can be transparent and can suppress the influence of the conductive layer on the polarizer. The material may be, for example, a material containing a urethane prepolymer (a) which is a reactant of an isocyanate compound and a polyol.

異氰酸酯化合物例如宜為多官能異氰酸酯化合物，具體可舉多官能芳香族系異氰酸酯化合物、脂環族系異氰酸酯、脂肪族系異氰酸酯化合物或該等之二聚物等。The isocyanate compound is preferably, for example, a polyfunctional isocyanate compound, and specific examples include polyfunctional aromatic isocyanate compounds, alicyclic isocyanates, aliphatic isocyanate compounds, or dimers of these.

多官能芳香族系異氰酸酯化合物例如可舉二異氰酸伸苯酯、2,4-異氰酸甲苯酯、2,6-二異氰酸甲苯酯、2,2’-二苯甲烷二異氰酸酯、4,4’-二苯甲烷二異氰酸酯、4,4’-甲苯胺二異氰酸酯、4,4’-二苯基醚二異氰酸酯、4,4’-二苯基二異氰酸酯、1,5-萘二異氰酸酯、伸茬基二異氰酸酯、亞甲基雙4-苯基異氰酸酯、二異氰酸對伸苯酯等。Examples of polyfunctional aromatic isocyanate compounds include phenylene diisocyanate, 2,4-toluene isocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate Isocyanate, diisocyanate, methylene bis 4-phenyl isocyanate, p-phenylene diisocyanate, etc.

多官能脂環族系異氰酸酯化合物例如可舉1,3-環戊烯二異氰酸酯、1,3-環己烷二異氰酸酯、1,4-環己烷二異氰酸酯、1,3-雙異氰酸基甲基環己烷、異佛酮二異氰酸酯、加氫二苯甲烷二異氰酸酯、加氫伸茬基二異氰酸酯、加氫二異氰酸甲苯酯、加氫四甲基伸茬基二異氰酸酯等。Examples of polyfunctional alicyclic isocyanate compounds include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, and 1,3-diisocyanate Methyl cyclohexane, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethyl diisocyanate, etc.

多官能脂肪族系異氰酸酯化合物例如可舉三亞甲基二異氰酸酯、四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、五亞甲基二異氰酸酯、1,2-伸丙基二異氰酸酯、1,3-伸丁基二異氰酸酯、十二亞甲基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯等。The polyfunctional aliphatic isocyanate compound includes, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3 -Butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc.

又，多官能異氰酸酯化合物可舉如參(6-異氰酸酯基己基)三聚異氰酸酯等具有三個以上異氰酸酯基者。In addition, examples of the polyfunctional isocyanate compound include those having three or more isocyanate groups such as ginseng (6-isocyanatohexyl) trimer isocyanate.

多元醇例如可舉乙二醇、二乙二醇、1,3-丁二醇、1,4-丁二醇、新戊二醇、3-甲-1,5-戊二醇、2-丁-2-乙-1,3-丙二醇、2,4-二乙基-1,5-戊二醇、1,2-己二醇、1,6-己二醇、1,8-辛二醇、1,9-壬二醇、2-甲-1,8-辛二醇、1,8-癸二醇、十八烷二醇、丙三醇、三羥甲丙烷、新戊四醇、己三醇、聚丙二醇等。Polyols include, for example, ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butanediol -2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol , 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerol, trimethylolpropane, neopentaerythritol, hexane Triol, polypropylene glycol, etc.

作為前述胺甲酸乙酯預聚物(a)，在本發明中宜使用在分子結構上，環狀結構(苯環、三聚氰酸酯環、三聚異氰酸酯環等)在結構中所占比率大之剛性結構者。舉例而言，前述多官能異氰酸酯化合物可單獨使用一種或併用兩種以上，但由抑制水分混入前述偏光件之觀點，以芳香族系異氰酸酯化合物為宜。其他多官能異氰酸酯化合物亦可併用芳香族系異氰酸酯化合物。而在芳香族系異氰酸酯化合物之中，前述異氰酸酯化合物尤宜使用選自二異氰酸甲苯酯及二苯甲烷二異氰酸酯中之至少任一種。As the aforementioned urethane prepolymer (a), it is suitable to use in the present invention in the molecular structure, the ratio of cyclic structure (benzene ring, cyanurate ring, isocyanurate ring, etc.) in the structure Large rigid structure. For example, the aforementioned polyfunctional isocyanate compound may be used singly or in combination of two or more, but from the viewpoint of suppressing the incorporation of moisture into the aforementioned polarizer, an aromatic isocyanate compound is preferred. Other polyfunctional isocyanate compounds can also be used in combination with aromatic isocyanate compounds. Among the aromatic isocyanate compounds, it is particularly preferable to use at least any one selected from the group consisting of toluene diisocyanate and diphenylmethane diisocyanate as the aforementioned isocyanate compound.

胺甲酸乙酯預聚物(a)宜使用三羥甲丙烷-三-異氰酸甲苯酯、三羥甲丙烷-三-二苯甲烷二異氰酸酯。此外，前述胺甲酸乙酯預聚物(a)為具有末端異氰酸酯基之化合物，例如可藉由混合異氰酸酯化合物與多元醇後進行攪拌使其反應而得。通常宜以使異氰酸酯基相對於多元醇之羥基呈過剩之方式將異氰酸酯化合物與多元醇混合。The urethane prepolymer (a) preferably uses trimethylolpropane-tris-toluene isocyanate and trimethylolpropane-tris-diphenylmethane diisocyanate. In addition, the aforementioned urethane prepolymer (a) is a compound having a terminal isocyanate group, and can be obtained, for example, by mixing an isocyanate compound and a polyol and then stirring and reacting. It is generally suitable to mix the isocyanate compound with the polyol in such a way that the isocyanate group becomes excessive relative to the hydroxyl group of the polyol.

另，前述胺甲酸乙酯預聚物(a)亦可使用已對末端異氰酸酯基賦予保護基者。保護基有肟及內醯胺等。保護異氰酸酯基者係透過加熱使保護基自異氰酸酯基解離，而使異氰酸酯基進行反應。In addition, as the aforementioned urethane prepolymer (a), a terminal isocyanate group has been provided with a protective group. The protecting groups include oxime and lactam. The isocyanate group is protected by heating to dissociate the protective group from the isocyanate group, thereby allowing the isocyanate group to react.

形成透明層之形成材除前述胺甲酸乙酯預聚物(a)外，還可含有化合物(b)，該化合物(b)具有至少2個具有與異氰酸酯基具反應性之活性氫的官能基。具有與異氰酸酯基具反應性之活性氫的官能基可舉羥基、胺基等。前述化合物(b)具有的具活性氫之官能基的個數愈多，與胺甲酸乙酯預聚物(a)之異氰酸酯基的反應點便會變得愈多而更易於形成硬化物，因此前述官能基之個數宜為3以上。In addition to the aforementioned urethane prepolymer (a), the forming material for forming the transparent layer may also contain a compound (b) having at least two functional groups with active hydrogen reactive with isocyanate groups . The functional group having active hydrogen reactive with the isocyanate group includes a hydroxyl group and an amino group. The more the number of functional groups with active hydrogen in the aforementioned compound (b), the more reaction points with the isocyanate group of the urethane prepolymer (a), and the easier it is to form a hardened product. The number of the aforementioned functional groups is preferably 3 or more.

又，化合物(b)將其分子量除以前述官能基之個數所得值宜為350以下。藉由如所述方式定義分子量與官能基之個數的關係，可確保化合物(b)與胺甲酸乙酯預聚物(a)之異氰酸酯基的反應性。In addition, the value obtained by dividing the molecular weight of the compound (b) by the number of the aforementioned functional groups is preferably 350 or less. By defining the relationship between the molecular weight and the number of functional groups as described above, the reactivity of the compound (b) with the isocyanate group of the urethane prepolymer (a) can be ensured.

又，前述化合物(b)之分子量宜為1000以下。化合物(b)之分子量設為1000以下之範圍者由與胺甲酸乙酯預聚物(a)一同以溶液形態調製形成材時之相溶性的觀點來看較佳。In addition, the molecular weight of the aforementioned compound (b) is preferably 1,000 or less. It is preferable that the molecular weight of the compound (b) is in the range of 1000 or less from the viewpoint of compatibility when preparing the forming material in the form of a solution together with the urethane prepolymer (a).

前述化合物(b)可例示如多元醇、多元胺、於分子內具有羥基與胺基之化合物等。Examples of the aforementioned compound (b) include polyols, polyamines, and compounds having a hydroxyl group and an amino group in the molecule.

多元醇可舉例如乙二醇、二乙二醇、1,3-丁二醇、1,4-丁二醇、新戊二醇、3-甲基-1,5-戊二醇、2-丁基-2-乙基-1,3-丙二醇、2,4-二乙基-1,5-戊二醇、1,2-己二醇、1,6-己二醇、1,8-辛二醇、1,9-壬二醇、2-甲基-1,8-辛二醇、1,8-癸二醇、十八烷二醇、聚丙二醇等2官能醇；甘油、三羥甲丙烷等3官能醇；新戊四醇、己三醇、山梨醇等4官能醇等；其他還可舉聚氧伸丙基甘油醚、聚氧伸丙基三羥甲丙烷醚、聚氧伸丙基山梨醇醚等對前述多元醇加成環氧烷(例如環氧丙烷)加成物等。Polyols include, for example, ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2- Butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8- Difunctional alcohols such as octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, polypropylene glycol, etc.; glycerin, trihydroxy Trifunctional alcohols such as methyl propane; 4-functional alcohols such as neopentyl erythritol, hexanetriol, sorbitol, etc.; others can also include polyoxypropylene glycerol ether, polyoxypropylene trimethylolpropane ether, polyoxypropylene Propyl sorbitol ether and the like add alkylene oxide (for example, propylene oxide) adducts and the like to the aforementioned polyol.

多元胺可舉例如伸乙二胺、伸丙二胺、六亞甲基二胺、二伸乙三胺、三伸乙四胺、異佛酮二胺、二環己基甲烷-4,4'-二胺、二聚物二胺等。Polyamines include, for example, ethylene diamine, propylene diamine, hexamethylene diamine, diethylene triamine, ethylene tetramine, isophorone diamine, dicyclohexylmethane-4,4'- Diamine, dimer diamine, etc.

又，於分子內具有羥基與胺基之化合物可舉例如2-羥乙基伸乙二胺、2-羥乙基伸丙二胺、二-2-羥乙基伸乙二胺、二-2-羥乙基伸丙二胺、2-羥丙基伸乙二胺、二-2-羥丙基伸乙二胺等於分子內具有羥基之二胺類；乙醇胺、二乙醇胺、三乙醇胺等烷醇胺類。In addition, compounds having a hydroxyl group and an amino group in the molecule include, for example, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, and di-2-hydroxyethyl Propylene diamine, 2-hydroxypropyl ethylene diamine, and di-2-hydroxypropyl ethylene diamine are equal to diamines with hydroxyl groups in the molecule; alkanolamines such as ethanolamine, diethanolamine, and triethanolamine.

前述化合物(b)由防止偏光件之光學可靠性惡化的觀點來看使用多元醇較佳，尤其三羥甲丙烷由與胺甲酸乙酯預聚物(a)之反應性的觀點來看較佳。The aforementioned compound (b) is preferably a polyol from the standpoint of preventing deterioration of the optical reliability of the polarizer, especially trimethylolpropane is preferable from the standpoint of the reactivity with the urethane prepolymer (a) .

前述形成材含有前述胺甲酸乙酯預聚物(a)作為主成分。胺甲酸乙酯預聚物(a)宜含有形成材之固體成分的50重量%以上。The aforementioned forming material contains the aforementioned urethane prepolymer (a) as a main component. The urethane prepolymer (a) preferably contains 50% by weight or more of the solid content of the forming material.

相對於前述胺甲酸乙酯預聚物(a)與前述化合物(b)之合計100重量%(固體成分比率)，前述化合物(b)相對於前述胺甲酸乙酯預聚物(a)之摻混比率宜為5重量%以上。由提升膜強度之觀點，前述化合物(b)之摻混比率宜為10重量%以上。另一方面，前述化合物(b)之摻混比率若變多，有時會造成偏光件之光學可靠性惡化，因此前述化合物(b)之摻混比率宜為80重量%以下，且50重量%以下更佳。With respect to the total 100% by weight (solid content ratio) of the aforementioned urethane prepolymer (a) and the aforementioned compound (b), the aforementioned compound (b) is blended with respect to the aforementioned urethane prepolymer (a) The mixing ratio is preferably 5% by weight or more. From the viewpoint of improving the film strength, the blending ratio of the aforementioned compound (b) is preferably 10% by weight or more. On the other hand, if the blending ratio of the aforementioned compound (b) increases, the optical reliability of the polarizer may sometimes deteriorate. Therefore, the blending ratio of the aforementioned compound (b) is preferably 80% by weight or less, and 50% by weight The following is better.

前述形成材更可為了提高異氰酸酯基之反應性而使用反應觸媒。反應觸媒並無特別限制，惟理想的是錫系觸媒或胺系觸媒。反應觸媒可使用1種或2種以上。反應觸媒的使用量，通常係以相對於100重量份之胺甲酸乙酯預聚物(a)為5重量份以下來使用。一旦反應觸媒量多，交聯反應速度即會變快而使形成材發泡。而使用發泡後的形成材則無法獲得充分的接著性。通常，使用反應觸媒時，宜為0.01~5重量份，更宜為0.05~4重量份。The aforementioned forming material may further use a reaction catalyst in order to increase the reactivity of the isocyanate group. The reaction catalyst is not particularly limited, but it is desirably a tin-based catalyst or an amine-based catalyst. One type or two or more types of reaction catalysts can be used. The amount of the reaction catalyst used is usually 5 parts by weight or less with respect to 100 parts by weight of the urethane prepolymer (a). Once the amount of reaction catalyst is large, the crosslinking reaction speed will increase and the forming material will foam. On the other hand, the foamed forming material cannot obtain sufficient adhesiveness. Generally, when the reaction catalyst is used, it is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 4 parts by weight.

更可為了提高異氰酸酯基之反應性而使用反應觸媒。反應觸媒並無特別限制，惟理想的是錫系觸媒或胺系觸媒。反應觸媒可使用1種或2種以上。反應觸媒的使用量，通常係以相對於100重量份之胺甲酸乙酯預聚物為5重量份以下來使用。一旦反應觸媒量多，交聯反應速度即會變快而使形成材發泡。而使用發泡後的形成材則無法獲得充分的接著性。通常，使用反應觸媒時，宜為0.01~5重量份，更宜為0.05~4重量份。In order to improve the reactivity of isocyanate groups, a reaction catalyst can be used. The reaction catalyst is not particularly limited, but it is desirably a tin-based catalyst or an amine-based catalyst. One type or two or more types of reaction catalysts can be used. The usage amount of the reaction catalyst is usually 5 parts by weight or less with respect to 100 parts by weight of the urethane prepolymer. Once the amount of reaction catalyst is large, the crosslinking reaction speed will increase and the forming material will foam. On the other hand, the foamed forming material cannot obtain sufficient adhesiveness. Generally, when the reaction catalyst is used, it is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 4 parts by weight.

錫系觸媒可使用無機系、有機系之任一種，惟以有機系為宜。無機系錫系觸媒可舉例如氯化亞錫、氯化錫等。有機系錫系觸媒宜具有至少1個下述有機基：具甲基、乙基、醚基、酯基等骨架之脂肪族基、脂環族基等。可舉例如四-正丁錫、乙酸三-正丁錫、三氯化正丁錫、氫氧化三甲錫、二氯化二甲錫、二月桂酸二丁錫等。The tin-based catalyst can be either inorganic or organic, but organic is preferred. Examples of the inorganic tin-based catalyst include stannous chloride and tin chloride. The organic tin-based catalyst preferably has at least one of the following organic groups: aliphatic groups and alicyclic groups with a skeleton such as methyl, ethyl, ether, and ester groups. Examples include tetra-n-butyl tin, tri-n-butyl tin acetate, n-butyl tin trichloride, trimethyl tin hydroxide, dimethyl tin dichloride, and dibutyl tin dilaurate.

又，作為胺系觸媒並無特別限制。宜為例如具有至少1個

Figure 108143758-A0101-12-0018-1
啶、脒類、二氮雜雙環十一烯等脂環族基等有機基者。除此以外，胺系觸媒還可舉三乙胺等。另外，前述以外之反應觸媒可例示環烷酸鈷、氫氧化苄基三甲銨等。In addition, there are no particular limitations on the amine catalyst. It is suitable for example to have at least 1
Figure 108143758-A0101-12-0018-1
Organic groups such as pyridine, amidines, diazabicycloundecene and other alicyclic groups. In addition to this, triethylamine and the like can be mentioned as an amine catalyst. In addition, examples of reaction catalysts other than the foregoing include cobalt naphthenate and benzyltrimethylammonium hydroxide.

前述形成材一般係以含有前述胺甲酸乙酯預聚物(a)及前述化合物(b)之溶液形態作使用。溶液可為溶劑系，亦可為乳液、膠體分散液、水溶液等水系。The aforementioned forming material is generally used in the form of a solution containing the aforementioned urethane prepolymer (a) and the aforementioned compound (b). The solution may be a solvent system, or an aqueous system such as emulsion, colloidal dispersion, and aqueous solution.

有機溶劑只要不具有具有與異氰酸酯基具反應性之活性氫的官能基，且可均勻溶解構成形成材的前述胺甲酸乙酯預聚物(a)及前述化合物(b)，即無特別限制。有機溶劑可使用1種或組合2種以上來使用。又，前述有機溶劑可分別對前述胺甲酸乙酯預聚物(a)及前述化合物(b)使用不同溶劑。此時，可在調製各溶液後混合各溶液藉此來調製形成材。並可於調製出的形成材中進而添加有機溶劑來調整形成材之黏度。並且於為已溶解於有機溶劑之溶劑系溶液時，亦可使其含有下述例示之醇類或水等作為溶劑。The organic solvent is not particularly limited as long as it does not have a functional group having an active hydrogen reactive with an isocyanate group and can uniformly dissolve the urethane prepolymer (a) and the compound (b) constituting the forming material. An organic solvent can be used 1 type or in combination of 2 or more types. In addition, the aforementioned organic solvent may use different solvents for the aforementioned urethane prepolymer (a) and the aforementioned compound (b). In this case, after preparing each solution, each solution can be mixed to prepare a forming material. An organic solvent can be added to the prepared material to adjust the viscosity of the material. In addition, when it is a solvent-based solution that has been dissolved in an organic solvent, it may contain alcohols, water, and the like exemplified below as a solvent.

有機溶劑可舉如甲苯、二甲苯等芳香族烴類)；乙酸乙酯、乙酸丁酯等酯類；己烷、環己烷、甲基環己烷等脂肪族或脂環式烴類；1,2-二氯乙烷等鹵烷類；甲基三級丁基醚等醚類；甲基乙基酮、甲基異丁基酮、環己酮、環戊酮、乙醯丙酮等酮類等。Examples of organic solvents include aromatic hydrocarbons such as toluene and xylene); esters such as ethyl acetate and butyl acetate; aliphatic or alicyclic hydrocarbons such as hexane, cyclohexane, and methylcyclohexane; 1 ,2-Dichloroethane and other halogenated alkanes; methyl tertiary butyl ether and other ethers; methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, acetone and other ketones Wait.

此外，在作成水系溶液時，亦可摻混例如正丁醇、異丙醇等醇類、丙酮等酮類。在作成水系溶液時，可藉由使用分散劑來進行，或者藉由對胺甲酸乙酯預聚物導入羧酸鹽、磺酸鹽、四級銨鹽等與異氰酸酯基之反應性低的官能基、或聚乙二醇等水分散性成分來進行。In addition, when making an aqueous solution, alcohols such as n-butanol and isopropanol, and ketones such as acetone may also be blended. When preparing an aqueous solution, it can be carried out by using a dispersant, or by introducing functional groups with low reactivity with isocyanate groups such as carboxylate, sulfonate, and quaternary ammonium salt to the urethane prepolymer , Or polyethylene glycol and other water-dispersible ingredients.

>環氧樹脂> 又，用以形成前述透明層之材料可舉環氧樹脂。 環氧樹脂可使用任意適當之環氧樹脂。環氧樹脂較佳可使用具有芳香族環之環氧樹脂。藉由使用環氧樹脂，可抑制黏著劑層之表面電阻值的歷時性變化，與偏光件之密著性更優異，而可防止從偏光件端部褪色。並且，於透明層上形成有黏著劑層時，可提升黏著劑層之投錨力。具有芳香族環之環氧樹脂可舉例如雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂等雙酚型環氧樹脂；苯酚酚醛環氧樹脂、甲酚酚醛環氧樹脂、羥苯甲醛苯酚酚醛環氧樹脂等酚醛型環氧樹脂；四羥苯甲烷之環氧丙基醚、四羥基二苯基酮之環氧丙基醚、環氧化聚乙烯苯酚等多官能型環氧樹脂、萘酚型環氧樹脂、萘型環氧樹脂、聯苯型環氧樹脂等。較佳可使用雙酚A型環氧樹脂、聯苯型環氧樹脂、雙酚F型環氧樹脂。藉由使用該等環氧樹脂，可更防止從偏光件端部褪色。環氧樹脂可僅使用1種亦可組合2種以上來使用。>Epoxy resin> In addition, the material used to form the aforementioned transparent layer can be epoxy resin. Any appropriate epoxy resin can be used as the epoxy resin. As the epoxy resin, an epoxy resin having an aromatic ring can preferably be used. By using epoxy resin, the temporal change of the surface resistance value of the adhesive layer can be suppressed, the adhesion to the polarizer is more excellent, and the discoloration from the end of the polarizer can be prevented. Moreover, when an adhesive layer is formed on the transparent layer, the anchoring force of the adhesive layer can be improved. Examples of epoxy resins having aromatic rings include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin; phenol novolac epoxy resin, cresol Novolac epoxy resin, paraben phenol novolac epoxy resin, etc.; glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxydiphenyl ketone, epoxidized polyethylene phenol, etc. Multifunctional epoxy resin, naphthol epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, etc. Preferably, bisphenol A type epoxy resin, biphenyl type epoxy resin, and bisphenol F type epoxy resin can be used. By using these epoxy resins, color fading from the end of the polarizer can be more prevented. The epoxy resin may be used by only 1 type or in combination of 2 or more types.

環氧樹脂宜為重量平均分子量(Mw)為20,000以上，且宜為30,000以上，更宜為37,000以上。藉由環氧樹脂之重量平均分子量為上述範圍，可更防止從偏光件端部褪色。重量平均分子量例如可藉由GPC來測定。The epoxy resin preferably has a weight average molecular weight (Mw) of 20,000 or more, and preferably 30,000 or more, and more preferably 37,000 or more. Since the weight average molecular weight of the epoxy resin is in the above range, discoloration from the end of the polarizer can be prevented more. The weight average molecular weight can be measured by GPC, for example.

又，形成前述透明層之材料可使用例如包含聚合物(a)(以下亦稱聚合物(a))與環氧樹脂(b)之組成物，該聚合物(a)係藉由將大於50重量份之丙烯酸系單體與大於0重量份且小於50重量份之下述通式(1)所示單體聚合而得者。前述聚合物(a)與環氧樹脂(b)之含有比例以重量比計宜為95：5~60：40、或40：60~1：99。 [化學式2]

Figure 02_image001
(式中，X表示含有選自於由乙烯基、(甲基)丙烯醯基、苯乙烯基、(甲基)丙烯醯胺基、乙烯基醚基、環氧基、氧雜環丁烷基、羥基、胺基、醛基及羧基所構成群組中之至少1種反應性基的官能基，R1 及R2 分別獨立表示氫原子、可具有取代基之脂肪族烴基、可具有取代基之芳基或可具有取代基之雜環基，R1 及R2 可相互連結形成環)。In addition, the material for forming the aforementioned transparent layer can be, for example, a composition containing polymer (a) (hereinafter also referred to as polymer (a)) and epoxy resin (b), and the polymer (a) is made by reducing the amount of Part by weight of acrylic monomer and more than 0 parts by weight and less than 50 parts by weight of monomer represented by the following general formula (1) are polymerized. The content ratio of the aforementioned polymer (a) and epoxy resin (b) is preferably 95:5~60:40 or 40:60~1:99 in terms of weight ratio. [Chemical formula 2]
Figure 02_image001
(In the formula, X represents a group selected from vinyl, (meth)acryloyl, styryl, (meth)acrylamido, vinyl ether, epoxy, oxetanyl A functional group of at least one reactive group in the group consisting of, hydroxyl, amino, aldehyde, and carboxyl groups, R 1 and R 2 each independently represent a hydrogen atom, an aliphatic hydrocarbon group that may have a substituent, and a substituent that may have a substituent The aryl group or the heterocyclic group which may have a substituent, R 1 and R 2 may be connected to each other to form a ring).

前述組成物中聚合物(a)與環氧樹脂(b)之含有比例以重量比計為95：5~60：40、或40：60~1：99。藉由聚合物(a)與環氧樹脂(b)之含有比例為上述範圍，可獲得可抑制黏著劑層之表面電阻值的歷時性變化，與偏光件之密著性更優異，而可防止從偏光件端部褪色之透明層用樹脂組成物。並且，藉由聚合物(a)與環氧樹脂(b)之含有比例為上述範圍，於透明層上形成有黏著劑層時，可提升黏著劑層之投錨力。結果，可獲得兼顧偏光件與透明層之密著性、及與形成於透明層上之黏著劑層的投錨力之偏光板(附透明層之單面保護偏光薄膜)。聚合物(a)與環氧樹脂(b)之含有比例以重量比計宜為95：5~80：20或20：80~5：95，更宜為90：10~70：30或30：70~10：90。聚合物(a)與環氧樹脂(b)之含有比例愈接近等分(50：50)，愈有保護層白化之虞。The content ratio of the polymer (a) and the epoxy resin (b) in the aforementioned composition is 95:5 to 60:40 or 40:60 to 1:99 in terms of weight ratio. When the content ratio of the polymer (a) and the epoxy resin (b) is in the above range, the temporal change of the surface resistance value of the adhesive layer can be suppressed, the adhesion to the polarizer is more excellent, and it can prevent A resin composition for the transparent layer that fades from the end of the polarizer. Moreover, when the content ratio of the polymer (a) and the epoxy resin (b) is in the above range, when the adhesive layer is formed on the transparent layer, the anchoring force of the adhesive layer can be improved. As a result, it is possible to obtain a polarizing plate (single-sided protective polarizing film with a transparent layer) that has both the adhesion between the polarizer and the transparent layer and the anchoring force with the adhesive layer formed on the transparent layer. The content ratio of polymer (a) and epoxy resin (b) is preferably 95:5~80:20 or 20:80~5:95, more preferably 90:10~70:30 or 30 by weight ratio: 70~10:90. The closer the content ratio of the polymer (a) to the epoxy resin (b) is (50:50), the more likely the protective layer is to whiten.

>聚合物(a)> 前述聚合物(a)可藉由將大於50重量份之丙烯酸系單體與大於0重量份且小於50重量份之前述通式(1)所示單體進行聚合而得。>Polymer(a)> The aforementioned polymer (a) can be obtained by polymerizing more than 50 parts by weight of acrylic monomer and more than 0 parts by weight and less than 50 parts by weight of the monomer represented by the aforementioned general formula (1).

前述聚合物(a)代表上具有下述式所示結構。藉由將前述通式(1)所示單體與丙烯酸系單體成分進行聚合，聚合物(a)可具有於側鏈包含硼之取代基(例如下述式中k之重複單元)。藉此，可提升偏光件與使用前述樹脂組成物形成之層(透明層)之密著性。該包含硼之取代基可以與聚合物連接來含有，亦可以無規來含有。 前述聚合物(a)可僅使用1種亦可組合2種以上來使用。 [化學式3]

Figure 02_image004
(式中、R6 表示任意官能基，j及k表示1以上之整數)。The aforementioned polymer (a) typically has a structure represented by the following formula. By polymerizing the monomer represented by the aforementioned general formula (1) with the acrylic monomer component, the polymer (a) may have a substituent containing boron in the side chain (for example, the repeating unit of k in the following formula). Thereby, the adhesion between the polarizer and the layer (transparent layer) formed using the aforementioned resin composition can be improved. The boron-containing substituent may be linked to the polymer to be contained, or it may be contained randomly. The aforementioned polymer (a) may be used alone or in combination of two or more kinds. [Chemical formula 3]
Figure 02_image004
(In the formula, R 6 represents an arbitrary functional group, and j and k represent an integer of 1 or more).

前述聚合物(a)之重量平均分子量宜為10,000以上，且宜為20,000以上，更宜為35,000以上，尤宜為50,000以上。又，聚合物(a)之重量平均分子量宜為250,000以下，且宜為200,000以下，更宜為150,000以下。藉由聚合物(a)之重量平均分子量為上述範圍，可提升使用前述樹脂組成物形成之層(透明層)之耐裂痕性。重量平均分子量例如可藉由GPC(溶劑：二甲基甲醯胺(DMF))來測定。The weight average molecular weight of the aforementioned polymer (a) is preferably 10,000 or more, and preferably 20,000 or more, more preferably 35,000 or more, and particularly preferably 50,000 or more. In addition, the weight average molecular weight of the polymer (a) is preferably 250,000 or less, more preferably 200,000 or less, and more preferably 150,000 or less. When the weight average molecular weight of the polymer (a) is in the above range, the crack resistance of the layer (transparent layer) formed using the aforementioned resin composition can be improved. The weight average molecular weight can be measured by GPC (solvent: dimethylformamide (DMF)), for example.

前述聚合物(a)之玻璃轉移溫度宜為50℃以上，且宜為60℃以上，較佳為80℃以上。又，聚合物(a)之玻璃轉移溫度宜為300℃以下。藉由玻璃轉移溫度為上述範圍，可提升使用前述樹脂組成物形成之層(透明層)之耐裂痕性。The glass transition temperature of the aforementioned polymer (a) is preferably 50°C or higher, preferably 60°C or higher, and more preferably 80°C or higher. In addition, the glass transition temperature of the polymer (a) is preferably 300°C or lower. When the glass transition temperature is in the above range, the crack resistance of the layer (transparent layer) formed using the aforementioned resin composition can be improved.

前述聚合物(a)可藉由將包含大於50重量份之丙烯酸系單體、大於0重量份且小於50重量份之通式(1)所示單體、聚合引發劑與任意他單體之單體組成物以任意適當之聚合方法進行聚合而得。聚合方法可適宜使用溶液聚合。藉由溶液聚合將聚合物(a)聚合，藉此可獲得更高分子量之聚合物。The aforementioned polymer (a) can be obtained by combining acrylic monomers of more than 50 parts by weight, monomers represented by general formula (1) of more than 0 parts by weight and less than 50 parts by weight, polymerization initiators, and any other monomers. The monomer composition is obtained by polymerizing by any appropriate polymerization method. As the polymerization method, solution polymerization can be suitably used. Polymer (a) is polymerized by solution polymerization to obtain a higher molecular weight polymer.

≪丙烯酸系單體≫ 前述丙烯酸系單體可使用任意適當之丙烯酸系單體。可舉例如具有直鏈或支鏈結構之(甲基)丙烯酸酯系單體、及具有環狀結構之(甲基)丙烯酸酯系單體。本說明書中，(甲基)丙烯酸意指丙烯酸及/或甲基丙烯酸。≪Acrylic monomers≫ Any appropriate acrylic monomer can be used as the aforementioned acrylic monomer. Examples include (meth)acrylate monomers having a linear or branched structure and (meth)acrylate monomers having a cyclic structure. In this specification, (meth)acrylic acid means acrylic acid and/or methacrylic acid.

具有直鏈或支鏈結構之(甲基)丙烯酸酯系單體可舉例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸甲基2-乙基己酯、(甲基)丙烯酸2-羥乙酯等。較佳可使用(甲基)丙烯酸甲酯。(甲基)丙烯酸酯系單體可僅使用1種亦可組合2種以上來使用。The (meth)acrylate-based monomers having a linear or branched structure include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth)acrylic acid Isopropyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, methyl 2-ethylhexyl (meth)acrylate, (methyl) 2-hydroxyethyl acrylate and the like. Preferably, methyl (meth)acrylate can be used. The (meth)acrylate-based monomer may be used alone or in combination of two or more kinds.

具有環狀結構之(甲基)丙烯酸酯系單體可舉例如(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸1-金剛烷基酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧乙酯、(甲基)丙烯酸二環戊酯、聯苯(甲基)丙烯酸酯、鄰聯苯氧乙基(甲基)丙烯酸酯、鄰聯苯氧基乙氧乙基(甲基)丙烯酸酯、間聯苯氧乙基丙烯酸酯、對聯苯氧乙基(甲基)丙烯酸酯、鄰聯苯氧基-2-羥丙基(甲基)丙烯酸酯、對聯苯氧基-2-羥丙基(甲基)丙烯酸酯、間聯苯氧基-2-羥丙基(甲基)丙烯酸酯、N-(甲基)丙烯醯氧基乙基-鄰聯苯＝胺甲酸酯、N-(甲基)丙烯醯氧基乙基-對聯苯＝胺甲酸酯、N-(甲基)丙烯醯氧基乙基-間聯苯＝胺甲酸酯、鄰苯基苯酚環氧丙基醚丙烯酸酯等含聯苯基單體、三苯(甲基)丙烯酸酯、鄰三苯氧乙基(甲基)丙烯酸酯等。較佳可使用(甲基)丙烯酸1-金剛烷基酯、(甲基)丙烯酸二環戊酯。藉由使用該等單體可獲得玻璃轉移溫度高之聚合物。該等單體可僅使用1種亦可組合2種以上來使用。此外，本說明書中，所謂(甲基)丙烯醯是指丙烯醯基及/或甲基丙烯醯基。The (meth)acrylate monomers having a cyclic structure include, for example, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, 1- Adamantyl ester, dicyclopentenyl (meth)acrylate, dicyclopentenoxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, biphenyl (meth)acrylate, ortho-linked Phenoxyethyl (meth)acrylate, o-biphenoxyethoxyethyl (meth)acrylate, m-biphenoxyethyl acrylate, p-biphenoxyethyl (meth)acrylate, o-biphenoxyethyl (meth)acrylate Phenoxy-2-hydroxypropyl (meth)acrylate, p-biphenoxy-2-hydroxypropyl (meth)acrylate, m-biphenoxy-2-hydroxypropyl (meth)acrylate , N-(meth)acryloyloxyethyl-o-biphenyl=carbamate, N-(meth)acryloyloxyethyl-p-biphenyl=carbamate, N-(methyl) Acrylic oxyethyl-m-biphenyl = urethane, o-phenylphenol glycidyl ether acrylate and other biphenyl-containing monomers, triphenyl (meth)acrylate, o-tamoxifen (Meth)acrylate etc. Preferably, 1-adamantyl (meth)acrylate and dicyclopentyl (meth)acrylate can be used. By using these monomers, a polymer with a high glass transition temperature can be obtained. These monomers may be used by only 1 type or in combination of 2 or more types. In addition, in this specification, the (meth)acryloyl group means an acryloyl group and/or a methacryloyl group.

又，亦可使用具有(甲基)丙烯醯基之矽倍半氧烷化合物取代上述(甲基)丙烯酸酯系單體。藉由使用矽倍半氧烷化合物，可獲得玻璃轉移溫度高之丙烯酸系聚合物。矽倍半氧烷化合物已知有具有各種骨架結構例如籠型結構、梯型結構、無規結構等之骨架者。矽倍半氧烷化合物可為僅具有1種該等結構者，亦可為具有2種以上者。矽倍半氧烷化合物可僅使用1種亦可組合2種以上來使用。In addition, a silsesquioxane compound having a (meth)acryloyl group may be used in place of the (meth)acrylate monomer. By using a silsesquioxane compound, an acrylic polymer with a high glass transition temperature can be obtained. Silsesquioxane compounds are known to have various framework structures such as cage structures, ladder structures, random structures, and the like. The silsesquioxane compound may have only one type of these structures, or may have two or more types. The silsesquioxane compound may be used alone or in combination of two or more kinds.

具有(甲基)丙烯醯基之矽倍半氧烷化合物可使用例如東亞合成股份公司SQ系列之MAC grade及AC grade。MAC grade為具有甲基丙烯醯基之矽倍半氧烷化合物，具體可舉例如MAC-SQ TM-100、MAC-SQ　SI-20、MAC-SQ HDM等。AC grade為具有丙烯醯基之矽倍半氧烷化合物，具體可舉例如AC-SQ TA-100、AC-SQ SI-20等。For the silsesquioxane compound having a (meth)acrylic acid group, for example, MAC grade and AC grade of Toagosei SQ series can be used. MAC grade is a silsesquioxane compound having a methacrylic acid group, and specific examples include MAC-SQ TM-100, MAC-SQ "SI-20, MAC-SQ HDM and the like. AC grade is a silsesquioxane compound having an acryl group, and specific examples include AC-SQ TA-100 and AC-SQ SI-20.

丙烯酸系單體可使用大於50重量份。丙烯酸系單體係以與前述通式(1)所示單體之合計可成為100重量份之方式作使用。The acrylic monomer can be used more than 50 parts by weight. The acrylic single system can be used so that the sum of the monomers represented by the aforementioned general formula (1) can be 100 parts by weight.

≪通式(1)所示單體≫ 藉由使用通式(1)所示單體，可於聚合物(a)之側鏈導入含硼之取代基。因此，代表上可提升以PVA系樹脂構成之偏光件與使用前述樹脂組成物形成之層(透明層)之密著性。且，使用前述樹脂組成物形成之層(透明層)本身之耐水性亦會提升，而可防止從偏光件端部褪色。單體可僅使用1種亦可組合2種以上來使用。 [化學式4]

Figure 02_image001
(式中，X表示含有選自於由乙烯基、(甲基)丙烯醯基、苯乙烯基、(甲基)丙烯醯胺基、乙烯基醚基、環氧基、氧雜環丁烷基、羥基、胺基、醛基及羧基所構成群組中之至少1種反應性基的官能基，R1 及R2 分別獨立表示氫原子、可具有取代基之脂肪族烴基、可具有取代基之芳基或可具有取代基之雜環基，R1 及R2 可相互連結形成環)。≪Monomer represented by general formula (1)≫ By using the monomer represented by general formula (1), a boron-containing substituent can be introduced into the side chain of polymer (a). Therefore, representatively, the adhesion between the polarizer made of PVA-based resin and the layer (transparent layer) made of the aforementioned resin composition can be improved. In addition, the water resistance of the layer (transparent layer) formed using the aforementioned resin composition is also improved, and the color fading from the end of the polarizer can be prevented. A monomer may use only 1 type, and may use 2 or more types in combination. [Chemical formula 4]
Figure 02_image001
(In the formula, X represents a group selected from vinyl, (meth)acryloyl, styryl, (meth)acrylamido, vinyl ether, epoxy, oxetanyl A functional group of at least one reactive group in the group consisting of, hydroxyl, amino, aldehyde, and carboxyl group, R 1 and R 2 each independently represent a hydrogen atom, an aliphatic hydrocarbon group that may have a substituent, and a substituent that may have The aryl group or the heterocyclic group which may have a substituent, R 1 and R 2 may be connected to each other to form a ring).

上述脂肪族烴基可舉可具有取代基之碳數1~20直鏈或支鏈烷基、可具有取代基之碳數3~20環狀烷基、碳數2~20烯基。上述芳基可舉可具有取代基之碳數6~20苯基、可具有取代基之碳數10~20萘基等。雜環基可舉可具有取代基之至少包含1個雜原子的5員環基或6員環基。此外，R1 及R2 可相互連結形成環。R1 及R2 宜為氫原子或碳數1~3直鏈或支鏈烷基，較宜為氫原子。The aliphatic hydrocarbon group may include a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms, which may have a substituent. Examples of the aryl group include a phenyl group having 6 to 20 carbon atoms, which may have a substituent, and a naphthyl group having 10 to 20 carbon atoms that may have a substituent. Examples of the heterocyclic group include a 5-membered ring group or a 6-membered ring group containing at least one heteroatom which may have a substituent. In addition, R 1 and R 2 may be connected to each other to form a ring. R 1 and R 2 are preferably hydrogen atoms or straight or branched chain alkyl groups with 1 to 3 carbon atoms, more preferably hydrogen atoms.

上述X所示官能基所含反應性基係選自於由乙烯基、(甲基)丙烯醯基、苯乙烯基、(甲基)丙烯醯胺基、乙烯基醚基、環氧基、氧雜環丁烷基、羥基、胺基、醛基及羧基所構成群組中之至少1種。較理想的是反應性基為(甲基)丙烯醯基及/或(甲基)丙烯醯胺基。藉由具有該等反應性基，可提升偏光件與使用前述樹脂組成物形成之層(透明層)之密著性。The reactive groups contained in the functional groups indicated by X are selected from vinyl groups, (meth)acrylic groups, styryl groups, (meth)acrylic acid amino groups, vinyl ether groups, epoxy groups, and oxygen groups. At least one of the group consisting of a heterocyclobutane group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group. It is preferable that the reactive group is a (meth)acrylic acid group and/or a (meth)acrylic acid amino group. By having these reactive groups, the adhesion between the polarizer and the layer (transparent layer) formed using the aforementioned resin composition can be improved.

於一實施形態中，上述X所示官能基宜為下述通式(2)所示官能基： 通式(2)：Z-Y-(式中，Z表示含有選自於由乙烯基、(甲基)丙烯醯基、苯乙烯基、(甲基)丙烯醯胺基、乙烯基醚基、環氧基、氧雜環丁烷基、羥基、胺基、醛基及羧基所構成群組中之至少1種反應性基的官能基，Y表示有機基)。前述有機基具體而言意指可具有取代基之碳數1~20有機基，更具體可舉例如碳數1~20之可具有取代基之直鏈或支鏈伸烷基、碳數3~20之可具有取代基之環狀伸烷基、碳數6~20之可具有取代基的伸苯基、碳數10~20之可具有取代基的伸萘基等。In one embodiment, the functional group represented by X is preferably a functional group represented by the following general formula (2): General formula (2): ZY-(In the formula, Z means containing selected from vinyl, (meth)acrylic acid group, styryl group, (meth)acrylic acid amino group, vinyl ether group, epoxy A functional group of at least one reactive group in the group consisting of a oxetanyl group, an oxetanyl group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group, and Y represents an organic group). The aforementioned organic group specifically means an organic group with 1 to 20 carbons that may have a substituent, and more specifically includes, for example, a linear or branched alkylene group with 1 to 20 carbons and optionally a substituent, and a carbon number of 3 to Cyclic alkylene group of 20 which may have substituents, phenylene group of which may have substituents of carbon number of 6-20, naphthylene group of which may have substituents of carbon number of 10-20, etc.

前述通式(1)所示單體具體來說可使用以下化合物。 [化學式5]

Figure 02_image007
Specifically, the following compounds can be used as the monomer represented by the aforementioned general formula (1). [Chemical formula 5]
Figure 02_image007

通式(1)所示單體除了前述舉例之化合物以外，也可舉例如羥乙基丙烯醯胺與硼酸之酯、羥甲基丙烯醯胺與硼酸之酯、丙烯酸羥乙酯與硼酸之酯、及丙烯酸羥丁酯與硼酸之酯等(甲基)丙烯酸酯與硼酸之酯。The monomer represented by the general formula (1), in addition to the compounds exemplified above, may also include, for example, ester of hydroxyethyl acrylamide and boric acid, ester of hydroxymethacrylamide and boric acid, and ester of hydroxyethyl acrylate and boric acid. , And esters of (meth)acrylate and boric acid such as hydroxybutyl acrylate and boric acid.

前述通式(1)所示單體可以大於0重量份且小於50重量份之含量來使用。較佳為0.01重量份以上且小於50重量份，且宜為0.05重量份~20重量份，更宜為0.1重量份~10重量份。單體含量若大於50重量份，則易發生從端部褪色。The monomer represented by the aforementioned general formula (1) can be used in a content greater than 0 parts by weight and less than 50 parts by weight. It is preferably 0.01 parts by weight or more and less than 50 parts by weight, and preferably 0.05 parts by weight to 20 parts by weight, and more preferably 0.1 parts by weight to 10 parts by weight. If the monomer content is more than 50 parts by weight, discoloration from the end is likely to occur.

≪聚合引發劑≫ 聚合引發劑可使用任意適當之聚合引發劑。可舉例如苯甲醯基過氧化物、月桂醯基過氧化物、過氧化鈉等過氧化物；三級丁基過氧化氫、過氧化氫異丙苯等過氧化氫；偶氮雙異丁腈等偶氮化合物。聚合引發劑可僅使用1種亦可使用2種以上。≪Polymerization initiator≫ Any appropriate polymerization initiator can be used as the polymerization initiator. Examples include peroxides such as benzyl peroxide, lauryl peroxide, and sodium peroxide; hydrogen peroxide such as tertiary butyl hydroperoxide and cumene hydroperoxide; azobisisobutyl Azo compounds such as nitriles. A polymerization initiator may use only 1 type, and may use 2 or more types.

聚合引發劑之含量可使用任意適當之量。聚合引發劑之含量宜為0.1重量份~5重量份，較宜為0.3重量份~2重量份。Any appropriate amount can be used for the content of the polymerization initiator. The content of the polymerization initiator is preferably 0.1 to 5 parts by weight, more preferably 0.3 to 2 parts by weight.

≪聚合方法≫ 如上述，聚合物(a)較佳可藉由將丙烯酸系單體及通式(1)所示單體等單體成分進行溶液聚合來獲得。溶液聚合所使用之溶劑可使用任意適當之溶劑。可舉例如水；甲醇、乙醇、異丙醇等醇；苯、甲苯、二甲苯、環己烷、正己烷等芳香族或脂肪族烴；乙酸乙酯等酯化合物；丙酮、甲基乙基酮等酮化合物；四氫呋喃、二㗁烷等環狀醚化合物等。該等溶劑可僅使用1種亦可組合2種以上來使用。且，亦可併用有機溶劑與水。≪Aggregation method≫ As described above, the polymer (a) is preferably obtained by solution polymerization of monomer components such as acrylic monomers and monomers represented by the general formula (1). Any appropriate solvent can be used for the solvent used in the solution polymerization. Examples include water; alcohols such as methanol, ethanol, and isopropanol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and n-hexane; ester compounds such as ethyl acetate; acetone, methyl ethyl ketone, etc. Ketone compounds; cyclic ether compounds such as tetrahydrofuran and dioxane. These solvents may be used alone or in combination of two or more kinds. Furthermore, an organic solvent and water may be used in combination.

聚合反應可以任意適當之溫度及時間進行。例如，可於50℃~100℃、較佳為於60℃~80℃之範圍下進行聚合反應。又，反應時間例如為1小時~8小時，且宜為3小時~5小時。The polymerization reaction can be carried out at any appropriate temperature and time. For example, the polymerization reaction can be carried out in the range of 50°C to 100°C, preferably 60°C to 80°C. In addition, the reaction time is, for example, 1 hour to 8 hours, and preferably 3 hours to 5 hours.

>環氧樹脂(b)> 環氧樹脂(b)可使用任意適當之環氧樹脂。環氧樹脂(b)較佳可使用具有芳香族環之環氧樹脂。藉由使用具有芳香族環之環氧樹脂作為環氧樹脂(b)，可獲得與偏光件之密著性更優異而可防止從偏光件端部褪色之透明層用樹脂組成物。並且，於透明層上形成有黏著劑層時，可提升黏著劑層之投錨力。具有芳香族環之環氧樹脂可舉例如雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂等雙酚型環氧樹脂；苯酚酚醛環氧樹脂、甲酚酚醛環氧樹脂、羥苯甲醛苯酚酚醛環氧樹脂等酚醛型環氧樹脂；四羥苯甲烷之環氧丙基醚、四羥基二苯基酮之環氧丙基醚、環氧化聚乙烯苯酚等多官能型環氧樹脂、萘酚型環氧樹脂、萘型環氧樹脂、聯苯型環氧樹脂等。較佳可使用雙酚A型環氧樹脂、聯苯型環氧樹脂、雙酚F型環氧樹脂。藉由使用該等環氧樹脂，可更防止從偏光件端部褪色。環氧樹脂可僅使用1種亦可組合2種以上來使用。>Epoxy resin(b)> Any appropriate epoxy resin can be used for the epoxy resin (b). As the epoxy resin (b), it is preferable to use an epoxy resin having an aromatic ring. By using an epoxy resin having an aromatic ring as the epoxy resin (b), it is possible to obtain a resin composition for a transparent layer that has more excellent adhesion to the polarizer and can prevent discoloration from the end of the polarizer. Moreover, when an adhesive layer is formed on the transparent layer, the anchoring force of the adhesive layer can be improved. Examples of epoxy resins having aromatic rings include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin; phenol novolac epoxy resin, cresol Novolac epoxy resin, paraben phenol novolac epoxy resin, etc.; glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxydiphenyl ketone, epoxidized polyethylene phenol, etc. Multifunctional epoxy resin, naphthol epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, etc. Preferably, bisphenol A type epoxy resin, biphenyl type epoxy resin, and bisphenol F type epoxy resin can be used. By using these epoxy resins, color fading from the end of the polarizer can be more prevented. The epoxy resin may be used by only 1 type or in combination of 2 or more types.

環氧樹脂(b)宜為重量平均分子量(Mw)為20,000以上，且宜為30,000以上，更宜為37,000以上。藉由環氧樹脂(b)之重量平均分子量為上述範圍，可更防止從偏光件端部褪色。重量平均分子量例如可藉由GPC來測定。The epoxy resin (b) preferably has a weight average molecular weight (Mw) of 20,000 or more, and preferably 30,000 or more, more preferably 37,000 or more. Since the weight average molecular weight of the epoxy resin (b) is in the above-mentioned range, discoloration from the end of the polarizer can be prevented more. The weight average molecular weight can be measured by GPC, for example.

>其他成分> 透明層用樹脂組成物除了前述環氧樹脂、上述聚合物(a)及環氧樹脂(b)外，還可包含有任意適當之其他成分。其他成分可舉例如溶劑及添加劑。溶劑可使用可用於將上述聚合物(a)進行溶液聚合時之溶劑，亦可使用其他溶劑。其他溶劑可適宜使用乙酸乙酯、甲苯、甲基乙基酮、環戊酮等。該等溶劑可僅使用1種亦可組合2種以上來使用。>Other ingredients> In addition to the aforementioned epoxy resin, the aforementioned polymer (a), and the aforementioned epoxy resin (b), the resin composition for a transparent layer may contain any appropriate other components. Examples of other components include solvents and additives. As the solvent, a solvent that can be used for solution polymerization of the above-mentioned polymer (a) can be used, and other solvents can also be used. As other solvents, ethyl acetate, toluene, methyl ethyl ketone, cyclopentanone, etc. can be suitably used. These solvents may be used alone or in combination of two or more kinds.

添加劑可使用任意適當之添加劑。可舉例如界面活性劑、紫外線吸收劑、抗氧化劑、增黏劑等。添加劑可僅使用1種亦可組合2種以上來使用。該等添加劑可以任意適當之量來使用。Any appropriate additives can be used as additives. Examples include surfactants, ultraviolet absorbers, antioxidants, and thickeners. Additives may be used alone or in combination of two or more kinds. These additives can be used in any appropriate amount.

>透明層用樹脂組成物之調製方法> 透明層用樹脂組成物可以任意適當之方法來調製。例如，可藉由於任意適當之溶劑中混合聚合物(a)、環氧樹脂(b)及因應需要之任意適當之添加劑來調製。又，將聚合物(a)以溶液聚合方式進行聚合時，亦可藉由於聚合物(a)之聚合溶液中添加環氧樹脂(b)及任意適當之添加劑並混合來調製。>Preparation method of resin composition for transparent layer> The resin composition for the transparent layer can be prepared by any appropriate method. For example, it can be prepared by mixing the polymer (a), the epoxy resin (b) and any appropriate additives as needed in any appropriate solvent. In addition, when the polymer (a) is polymerized by solution polymerization, it can also be prepared by adding and mixing the epoxy resin (b) and any appropriate additives to the polymerization solution of the polymer (a).

除含有前述胺甲酸乙酯預聚物(a)之形成材、含有前述環氧樹脂之形成材、包含前述聚合物(a)與環氧樹脂(b)之組成物的形成材外，形成透明層之材料可舉例如氰基丙烯酸酯系形成材、環氧系形成材、胺甲酸乙酯丙烯酸酯系形成材等。Except for the forming material containing the aforementioned urethane prepolymer (a), the forming material containing the aforementioned epoxy resin, and the forming material containing the composition of the aforementioned polymer (a) and epoxy resin (b), it is transparent Examples of the material of the layer include cyanoacrylate-based forming materials, epoxy-based forming materials, and urethane acrylate-based forming materials.

前述透明層之形成可依前述形成材之種類作適當選擇，舉例而言可透過將該形成材塗佈於偏光件等後進行硬化來進行，而可以塗佈層之形態製得透明層。一般而言，係藉由於前述塗佈後，在30~100℃左右、更宜在50~80℃下乾燥0.5~15分鐘左右使硬化層形成來進行。另外，當前述形成材含有異氰酸酯成分時，為了促進反應，可在30~100℃左右、更宜在50~80℃下進行0.5~24小時左右之退火處理。The formation of the aforementioned transparent layer can be appropriately selected according to the type of the aforementioned forming material. For example, it can be carried out by coating the forming material on a polarizer or the like and then curing, and a transparent layer can be obtained in the form of a coating layer. Generally speaking, it is performed by drying at about 30-100°C, more preferably at 50-80°C, for about 0.5-15 minutes after the aforementioned coating to form a hardened layer. In addition, when the aforementioned forming material contains an isocyanate component, in order to promote the reaction, an annealing treatment may be carried out at about 30 to 100°C, more preferably at 50 to 80°C, for about 0.5 to 24 hours.

>導電層> 由表面電阻值之穩定性及與黏著劑層21之密著性之觀點來看，前述導電層d之厚度宜為1μm以下，且0.01~0.5μm為佳，0.01~0.2μm較佳，0.01~0.1μm更佳。又，由抗靜電機能之觀點來看，前述導電層d之表面電阻值宜為1×108 ~1×1012 Ω/□，且以1×108 ~1×1011 Ω/□為佳，1×108 ~1×1010 Ω更佳。>Conductive layer> From the viewpoint of the stability of the surface resistance value and the adhesion to the adhesive layer 21, the thickness of the aforementioned conductive layer d is preferably 1μm or less, and 0.01~0.5μm is better, 0.01~0.2μm is more Better, 0.01~0.1μm is more preferable. Also, from the viewpoint of antistatic function, the surface resistance value of the aforementioned conductive layer d is preferably 1×10 8 ~1×10 12 Ω/□, and preferably 1×10 8 ~1×10 11 Ω/□ , 1×10 8 ~1×10 10 Ω is better.

導電層可由各種抗靜電劑組成物形成。形成導電層之抗靜電劑可使用離子性界面活性劑系、導電性聚合物、導電性微粒子、奈米碳管等。The conductive layer can be formed of various antistatic agent compositions. As the antistatic agent for forming the conductive layer, ionic surfactants, conductive polymers, conductive fine particles, carbon nanotubes, etc. can be used.

從光學特性、外觀、抗靜電效果及抗靜電效果於加熱時、加濕時之穩定性的觀點來看，該等抗靜電劑中又宜使用導電性聚合物、奈米碳管。尤其宜使用聚苯胺、聚噻吩等導電性聚合物。導電性聚合物可適當使用有機溶劑可溶性、水溶性、水分散性者，惟宜使用水溶性導電性聚合物或水分散性導電性聚合物。因為水溶性導電性聚合物或水分散性導電性聚合物可將形成抗靜電層時的塗佈液調製成水溶液或水分散液，該塗佈液無須使用非水系有機溶劑，即可抑制光學薄膜基材因該有機溶劑變質的情況。又，水溶液或水分散液可含有水以外的水系溶劑。可舉如甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、二級丁醇、三級丁醇、正戊醇、異戊醇、二級戊醇、三級戊醇、1-乙基-1-丙醇、2-甲基-1-丁醇、正己醇、環己醇等醇類。From the viewpoint of optical properties, appearance, antistatic effect, and stability of the antistatic effect during heating and humidification, conductive polymers and carbon nanotubes are suitable for these antistatic agents. In particular, conductive polymers such as polyaniline and polythiophene are preferably used. As the conductive polymer, those soluble in organic solvents, water-soluble, or water-dispersible can be suitably used, but water-soluble conductive polymers or water-dispersible conductive polymers are preferably used. Because the water-soluble conductive polymer or the water-dispersible conductive polymer can prepare the coating liquid when forming the antistatic layer into an aqueous solution or a water dispersion, the coating liquid does not need to use a non-aqueous organic solvent to suppress the optical film The substrate is deteriorated by the organic solvent. In addition, the aqueous solution or aqueous dispersion may contain an aqueous solvent other than water. Examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, n-pentanol, isoamyl alcohol, secondary pentanol, and tertiary pentanol , 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol and other alcohols.

又，前述聚苯胺、聚噻吩等水溶性導電性聚合物或水分散性導電性聚合物宜於分子中具有親水性官能基。親水性官能基可舉如磺酸基、胺基、醯胺基、亞胺基、四級銨鹽基、羥基、巰基、肼基、羧基、硫酸酯基、磷酸酯基或該等之鹽等。因為分子內具有親水性官能基，可輕易溶於水或可以微粒子狀輕易地分散於水中，而可易調製出前述水溶性導電性聚合物或水分散性導電性聚合物。In addition, the aforementioned water-soluble conductive polymer or water-dispersible conductive polymer such as polyaniline and polythiophene preferably has a hydrophilic functional group in the molecule. Hydrophilic functional groups can include sulfonic acid groups, amino groups, amide groups, imine groups, quaternary ammonium salt groups, hydroxyl groups, sulfhydryl groups, hydrazine groups, carboxyl groups, sulfate ester groups, phosphate ester groups or their salts, etc. . Since the molecule has a hydrophilic functional group, it can be easily dissolved in water or can be easily dispersed in water in the form of fine particles, and the aforementioned water-soluble conductive polymer or water-dispersible conductive polymer can be easily prepared.

就水溶性導電聚合物之市售物例子來說，可列舉聚苯胺磺酸(Mitsubishi Rayon Co., Ltd.製，聚苯乙烯換算所得重量平均分子量150000)等。就水分散性導電聚合物之市售物例子來說，可列舉聚噻吩系導電性聚合物(Nagase ChemteX Co.製、商品名Denatron系列)等。Examples of commercially available water-soluble conductive polymers include polyaniline sulfonic acid (manufactured by Mitsubishi Rayon Co., Ltd., a weight average molecular weight of 150,000 in terms of polystyrene). Examples of commercially available water-dispersible conductive polymers include polythiophene-based conductive polymers (manufactured by Nagase ChemteX Co., trade name Denatron series) and the like.

又，就導電層之形成材料而言，在提升抗靜電劑之皮膜形成性、對光學薄膜之密著性等目的下，亦可連同前述抗靜電劑還添加黏結劑成分。抗靜電劑為水溶性導電性聚合物或水分散性導電性聚合物之水系材料時，使用水溶性或水分散性之黏結劑成分。黏結劑之例子可舉如含

Figure 108143758-A0304-12-0059-1
唑啉基聚合物、聚胺甲酸乙酯系樹脂、聚酯系樹脂、丙烯酸系樹脂、聚醚系樹脂、纖維素系樹脂、聚乙烯醇系樹脂、環氧樹脂、聚乙烯基吡咯啶酮、聚苯乙烯系樹脂、聚乙二醇、新戊四醇等。尤其以聚胺甲酸乙酯系樹脂、聚酯系樹脂、丙烯酸系樹脂為宜。該等黏結劑可依其用途適當使用1種或2種以上。In addition, for the conductive layer forming material, for the purpose of improving the film forming property of the antistatic agent and the adhesion to the optical film, a binder component can be added together with the antistatic agent. When the antistatic agent is a water-based material of a water-soluble conductive polymer or a water-dispersible conductive polymer, use a water-soluble or water-dispersible binder component. Examples of binders can include
Figure 108143758-A0304-12-0059-1
Oxazoline-based polymers, polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, epoxy resins, polyvinylpyrrolidone, Polystyrene resin, polyethylene glycol, neopentyl erythritol, etc. In particular, polyurethane resins, polyester resins, and acrylic resins are suitable. One kind or two or more kinds of these binders can be appropriately used according to the application.

抗靜電劑、黏結劑之使用量依該等之種類而定，惟宜控制成以使所得導電層之表面電阻值成為1×108 ~1×1012 Ω/□。The amount of antistatic agent and adhesive used depends on these types, but should be controlled so that the surface resistance of the resulting conductive layer becomes 1×10 8 to 1×10 12 Ω/□.

>黏著劑層> 前述黏著劑層係由黏著劑形成。黏著劑可使用各種黏著劑，可舉例如橡膠系黏著劑、丙烯酸系黏著劑、聚矽氧系黏著劑、胺甲酸乙酯系黏著劑、乙烯基烷基醚系黏著劑、聚乙烯基吡咯啶酮系黏著劑、聚丙烯醯胺系黏著劑、纖維素系黏著劑等。可因應前述黏著劑的種類來選擇黏著性的基底聚合物。前述黏著劑中，就光學透明性佳、展現適當濕潤性、凝集性與接著性之黏著特性且耐候性及耐熱性等優異之觀點來看，宜使用丙烯酸系黏著劑。>Adhesive layer> The aforementioned adhesive layer is formed of an adhesive. Various adhesives can be used as the adhesive. Examples include rubber adhesives, acrylic adhesives, silicone adhesives, urethane adhesives, vinyl alkyl ether adhesives, and polyvinylpyrrolidine. Ketone-based adhesives, polyacrylamide-based adhesives, cellulose-based adhesives, etc. The adhesive base polymer can be selected according to the type of the aforementioned adhesive. Among the aforementioned adhesives, it is preferable to use an acrylic adhesive from the viewpoints of excellent optical transparency, exhibiting adhesive properties such as proper wettability, aggregation and adhesion, and excellent weather resistance and heat resistance.

前述丙烯酸系黏著劑係由含有(甲基)丙烯酸系聚合物(A)之黏著劑組成物調製而成。以下，說明該黏著劑組成物。The aforementioned acrylic adhesive is prepared from an adhesive composition containing (meth)acrylic polymer (A). Hereinafter, the adhesive composition will be described.

(甲基)丙烯酸系聚合物(A)含有(甲基)丙烯酸烷基酯(a1)為主成分作為單體單元。另，(甲基)丙烯酸酯係指丙烯酸酯及/或甲基丙烯酸酯，本發明之(甲基)亦為同義。The (meth)acrylic polymer (A) contains an alkyl (meth)acrylate (a1) as a main component as a monomer unit. In addition, (meth)acrylate refers to acrylate and/or methacrylate, and (meth) in the present invention also has the same meaning.

構成(甲基)丙烯酸系聚合物(A)之主骨架的(甲基)丙烯酸烷基酯，可以例示直鏈狀或支鏈狀烷基碳數1~18者。例如前述烷基可例示如甲基、乙基、丙基、異丙基、丁基、異丁基、戊基、己基、環己基、庚基、2-乙基己基、異辛基、壬基、癸基、異癸基、十二基、異肉豆蔻基、月桂基、十三基、十五基、十六基、十七基、十八基等。該等可單獨使用或可組合來使用。該等烷基的平均碳數宜為3~9。The (meth)acrylic acid alkyl ester constituting the main skeleton of the (meth)acrylic polymer (A) may be a linear or branched alkyl group having 1 to 18 carbon atoms. For example, the aforementioned alkyl group can be exemplified as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl, isooctyl, nonyl , Decyl, isodecyl, dodecyl, isomyristyl, lauryl, thirteen, fifteen, sixteen, seventeen, octadecyl, etc. These can be used alone or in combination. The average carbon number of these alkyl groups is preferably 3-9.

(甲基)丙烯酸烷基酯(a1)之重量比率，作為單體單元於構成(甲基)丙烯酸系聚合物(A)之總構成單體(100重量%)之重量比率中宜為70重量%以上。(甲基)丙烯酸烷基酯(a1)之重量比率可視為其他共聚單體之剩餘部分來考量。將(甲基)丙烯酸烷基酯(a1)之重量比率設在前述範圍內，於確保接著性上為佳。The weight ratio of the alkyl (meth)acrylate (a1) is preferably 70 weight in the weight ratio of the monomer unit to the total monomer (100% by weight) constituting the (meth)acrylic polymer (A) %the above. The weight ratio of the alkyl (meth)acrylate (a1) can be considered as the remainder of other comonomers. The weight ratio of the alkyl (meth)acrylate (a1) is set within the aforementioned range to ensure adhesiveness.

為了改善接著性及耐熱性，除前述(甲基)丙烯酸烷基酯(a1)之單體單元外，還可於前述(甲基)丙烯酸系聚合物(A)中，藉由共聚來導入1種以上具有具(甲基)丙烯醯基或乙烯基等不飽和雙鍵之聚合性官能基的共聚單體。In order to improve adhesiveness and heat resistance, in addition to the monomer units of the aforementioned alkyl (meth)acrylate (a1), the aforementioned (meth)acrylic polymer (A) can also be introduced by copolymerization. One or more kinds of comonomers having polymerizable functional groups having unsaturated double bonds such as (meth)acrylic groups or vinyl groups.

前述共聚單體可舉例如含醯胺基單體、含羧基單體、含羥基單體等含官能基單體。該等中，含醯胺基單體(a2)適於後述摻混離子性化合物(B)之情形。Examples of the aforementioned comonomer include functional group-containing monomers such as amide group-containing monomers, carboxyl group-containing monomers, and hydroxyl group-containing monomers. Among these, the amide group-containing monomer (a2) is suitable for the case of blending the ionic compound (B) described later.

用於形成前述黏著劑層的黏著劑組成物中，在有被導入基底聚合物之(甲基)丙烯酸系聚合物(A)中之側鏈的醯胺基存在時，藉由該醯胺基之存在，即使在加濕環境下仍能抑制藉由摻混離子性化合物(B)而經調整的黏著劑層的表面電阻值變動而大增，從而可維持在所期望之值的範圍內，由此看來較佳。吾等認為藉由作為共聚單體之官能基被導入(甲基)丙烯酸系聚合物(A)中之側鏈的醯胺基之存在，能提高(甲基)丙烯酸系聚合物(A)與離子性化合物(B)的相溶性。In the adhesive composition used to form the aforementioned adhesive layer, when there is a side chain amide group introduced into the (meth)acrylic polymer (A) of the base polymer, the amide group The existence of it can suppress the change and increase of the surface resistance of the adhesive layer adjusted by mixing the ionic compound (B) even in a humidified environment, so that it can be maintained within the desired value range. From this it seems better. We believe that by introducing the functional group of the comonomer into the side chain of the (meth)acrylic polymer (A), the presence of the amino group in the side chain can improve the (meth)acrylic polymer (A) and Compatibility of ionic compound (B).

又，前述黏著劑層在有被導入基底聚合物之(甲基)丙烯酸系聚合物(A)中之側鏈的醯胺基存在時，對玻璃及透明導電層(ITO層等)的耐久性皆良好，而可抑制在貼附於液晶面板之狀態下發生剝落或浮凸等。且，在加濕環境下(加濕可靠性試驗後)依舊可滿足耐久性。In addition, the adhesive layer has durability against glass and transparent conductive layers (ITO layers, etc.) when there are side chains of amide groups introduced into the base polymer (meth)acrylic polymer (A) All are good, and can suppress peeling or embossing in the state of being attached to the liquid crystal panel. Moreover, durability can still be satisfied in a humidified environment (after humidification reliability test).

含醯胺基單體(a2)係一於其結構中含有醯胺基且含有(甲基)丙烯醯基、乙烯基等聚合性不飽和雙鍵之化合物。含醯胺基單體(a2)之具體例可舉(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-異丙基丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-己基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥甲基-N-丙烷(甲基)丙烯醯胺、胺甲基(甲基)丙烯醯胺、胺乙基(甲基)丙烯醯胺、巰甲基(甲基)丙烯醯胺、巰乙基(甲基)丙烯醯胺等丙烯醯胺系單體；N-(甲基)丙烯醯基嗎福林、N-(甲基)丙烯醯基哌啶、N-(甲基)丙烯醯基吡咯啶等N-丙烯醯基雜環單體；N-乙烯基吡咯啶酮、N-乙烯基-ε-己內醯胺等含N-乙烯基內醯胺系單體等。含醯胺基單體(a2)在可抑制表面電阻值隨時間(尤其是在加濕環境下)上升、滿足耐久性來看為佳。尤其在含醯胺基單體(a2)之中，又以含N-乙烯基內醯胺系單體由可抑制表面電阻值隨時間(尤其是在加濕環境下)上升、滿足對透明導電層(觸控感測器層)之耐久性來看尤佳。另，前述雖未示例，不過具有羥基之含醯胺基單體在與離子性化合物(B)組合時，有導電性上升之傾向，而且使用比率一多，與偏光薄膜(光學薄膜)之投錨力及與透明導電層(觸控感測器層)之重工性會出問題，故不宜使用。The amide group-containing monomer (a2) is a compound containing an amide group in its structure and a polymerizable unsaturated double bond such as a (meth)acryloyl group and a vinyl group. Specific examples of the amine group-containing monomer (a2) include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, and N,N-diethyl(meth)acrylamide Amine, N-isopropyl acrylamide, N-methyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-hydroxymethyl (Meth)acrylamide, N-hydroxymethyl-N-propane (meth)acrylamide, aminomethyl(meth)acrylamide, aminoethyl(meth)acrylamide, mercaptomethyl (Meth)acrylamide, mercaptoethyl (meth)acrylamide and other acrylamide monomers; N-(meth)acrylamide mopholin, N-(meth)acrylamide piper N-acryloyl heterocyclic monomers such as pyridine, N-(meth)acryloylpyrrolidine; N-vinylpyrrolidone, N-vinyl-ε-caprolactone, etc. containing N-vinyl Amide-based monomers, etc. The amide group-containing monomer (a2) is preferable in terms of suppressing the increase in surface resistance value over time (especially in a humidified environment) and satisfying durability. Especially among the monomers (a2) containing amide groups, the use of N-vinyl lactam-containing monomers can suppress the increase in surface resistance over time (especially in humidified environments) and meet the requirements for transparent conductivity. The durability of the layer (touch sensor layer) is particularly good. In addition, although not shown in the foregoing, the amine group-containing monomer having a hydroxyl group tends to increase in conductivity when combined with the ionic compound (B), and the usage ratio is high. It is used as an anchor for polarizing films (optical films). There will be problems with the reworkability of the transparent conductive layer (touch sensor layer) and it is not suitable for use.

由可抑制表面電阻值隨時間(特別是在加濕環境下)上升之觀點來看，含醯胺基單體(a2)之前述重量比率宜為0.1重量%以上。前述重量比率宜為0.3重量%以上，更宜為0.5重量%以上。另一方面，前述重量比率太大有對偏光薄膜等基材薄膜之投錨性降低之傾向，所以前述重量比率宜為35重量%以下，較宜為30重量%以下，更宜為25重量%以下。From the viewpoint of suppressing the surface resistance value from increasing with time (especially in a humidified environment), the aforementioned weight ratio of the amide group-containing monomer (a2) is preferably 0.1% by weight or more. The aforementioned weight ratio is preferably 0.3% by weight or more, more preferably 0.5% by weight or more. On the other hand, if the aforementioned weight ratio is too large, it tends to reduce the anchoring property of the substrate film such as polarizing film. Therefore, the aforementioned weight ratio is preferably 35% by weight or less, more preferably 30% by weight or less, and more preferably 25% by weight or less .

含羧基單體係一於其結構中含有羧基且含有(甲基)丙烯醯基、乙烯基等聚合性不飽和雙鍵之化合物。含羧基單體之具體例可舉例如(甲基)丙烯酸、(甲基)丙烯酸羧乙酯、(甲基)丙烯酸羧戊酯、伊康酸、馬來酸、延胡索酸、巴豆酸等。從共聚性、價格及黏著特性的觀點來看，前述含羧基單體中以丙烯酸為宜。The carboxyl group-containing single system is a compound that contains a carboxyl group in its structure and contains polymerizable unsaturated double bonds such as (meth)acrylic acid groups and vinyl groups. Specific examples of the carboxyl group-containing monomer include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like. From the viewpoint of copolymerization, price, and adhesive properties, acrylic acid is preferred among the aforementioned carboxyl group-containing monomers.

含羥基單體係一於其結構中含有羥基且含有(甲基)丙烯醯基、乙烯基等聚合性不飽和雙鍵之化合物。含羥基單體的具體例可舉例如(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸6-羥己酯、(甲基)丙烯酸8-羥辛酯、(甲基)丙烯酸10-羥癸酯、(甲基)丙烯酸12-羥月桂酯等(甲基)丙烯酸羥基烷基酯或(4-羥甲基環己基)-甲基丙烯酸酯等。由耐久性之觀點，前述含羥基單體中宜為(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸4-羥丁酯，尤以(甲基)丙烯酸4-羥丁酯為佳。The hydroxyl-containing single system is a compound containing a hydroxyl group in its structure and a polymerizable unsaturated double bond such as a (meth)acryloyl group and a vinyl group. Specific examples of hydroxyl-containing monomers include, for example, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyethyl (meth)acrylate Hydroxyhexyl ester, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate and other hydroxyalkyl (meth)acrylates or (4- Hydroxymethylcyclohexyl)-methacrylate and the like. From the viewpoint of durability, among the aforementioned hydroxyl-containing monomers, 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferred, and 4-hydroxybutyl (meth)acrylate is particularly preferred. .

含羧基單體、含羥基單體在黏著劑組成物含有交聯劑時會成為其與交聯劑的反應點。含羧基單體、含羥基單體在分子間與交聯劑之反應性佳，故適宜用於提升所得黏著劑層之凝集性及耐熱性。又，就兼具耐久性與重工性之觀點而言，含羧基單體較為理想，而就重工性之觀點而言，以含羥基單體較為理想。The carboxyl group-containing monomer and the hydroxyl group-containing monomer become the reaction point of the crosslinking agent when the adhesive composition contains the crosslinking agent. The carboxyl group-containing monomer and the hydroxyl group-containing monomer have good reactivity with the crosslinking agent between the molecules, so they are suitable for improving the cohesiveness and heat resistance of the resulting adhesive layer. In addition, from the viewpoint of having both durability and heavy workability, a carboxyl group-containing monomer is preferable, and from the viewpoint of heavy workability, a hydroxyl group-containing monomer is preferable.

含羧基單體的前述重量比率宜為2重量%以下，且宜為0.01~2重量%，0.05~1.5重量%更佳，又以0.1~1重量%更佳，最佳為0.1~0.5重量%。將含羧基單體的重量比率設為0.01重量%以上由耐久性之觀點來看為佳。另一方面，超過2重量%時以重工性之觀點來看不宜。The aforementioned weight ratio of the carboxyl group-containing monomer is preferably 2% by weight or less, and preferably 0.01 to 2% by weight, more preferably 0.05 to 1.5% by weight, more preferably 0.1 to 1% by weight, and most preferably 0.1 to 0.5% by weight . The weight ratio of the carboxyl group-containing monomer is preferably 0.01% by weight or more from the viewpoint of durability. On the other hand, if it exceeds 2% by weight, it is not suitable from the viewpoint of heavy workability.

含羥基單體的前述重量比率宜為3重量%以下，且宜為0.01~3重量%，0.1~2重量%更佳，且更佳為0.2~2重量%。由交聯黏著劑層之觀點、耐久性或黏著特性之觀點來看，含羥基單體的重量比率設為0.01重量%以上為佳。另一方面，超過3重量%時，以耐久性觀點來看不宜。The aforementioned weight ratio of the hydroxyl-containing monomer is preferably 3% by weight or less, and is preferably 0.01 to 3% by weight, more preferably 0.1 to 2% by weight, and more preferably 0.2 to 2% by weight. From the viewpoint of the cross-linked adhesive layer, durability, or adhesion characteristics, the weight ratio of the hydroxyl-containing monomer is preferably 0.01% by weight or more. On the other hand, when it exceeds 3% by weight, it is not suitable from the viewpoint of durability.

又，共聚單體例如可使用含芳香環(甲基)丙烯酸酯。含芳香環(甲基)丙烯酸酯係一於其結構中含有芳香環結構且含有(甲基)丙烯醯基之化合物。作為芳香環，可舉如苯環、萘環或聯苯環。In addition, as a comonomer, for example, aromatic ring-containing (meth)acrylate can be used. Aromatic ring-containing (meth)acrylate is a compound containing an aromatic ring structure and a (meth)acryloyl group in its structure. Examples of the aromatic ring include a benzene ring, a naphthalene ring, or a biphenyl ring.

含芳香環(甲基)丙烯酸酯的具體例可舉例如(甲基)丙烯酸苄酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸鄰苯基苯酚酯、(甲基)丙烯酸苯氧酯、(甲基)丙烯酸苯氧乙酯、(甲基)丙烯酸苯氧丙酯、苯氧基二乙二醇(甲基)丙烯酸酯、環氧乙烷改質壬苯酚(甲基)丙烯酸酯、環氧乙烷改質甲酚(甲基)丙烯酸酯、苯酚環氧乙烷改質(甲基)丙烯酸酯、2-羥-3-苯氧丙基(甲基)丙烯酸酯、甲氧基苄基(甲基)丙烯酸酯、氯苄基(甲基)丙烯酸酯、(甲基)丙烯酸甲苯酚酯、(甲基)丙烯酸聚苯乙烯酯等具有苯環之物；羥乙基化β-萘酚丙烯酸酯、(甲基)丙烯酸2-萘酚乙酯、丙烯酸2-萘氧乙酯、2-(4-甲氧基-1-萘氧基)乙基(甲基)丙烯酸酯等具有萘環之物；(甲基)丙烯酸聯苯酯等具有聯苯環者。Specific examples of aromatic ring-containing (meth)acrylates include benzyl (meth)acrylate, phenyl (meth)acrylate, o-phenylphenol (meth)acrylate, and phenoxy (meth)acrylate , Phenoxyethyl (meth)acrylate, phenoxypropyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, ethylene oxide modified nonphenol (meth)acrylate, Ethylene oxide modified cresol (meth)acrylate, phenol ethylene oxide modified (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, methoxybenzyl (Meth)acrylate, chlorobenzyl (meth)acrylate, cresol (meth)acrylate, polystyrene (meth)acrylate, etc., which have a benzene ring; hydroxyethylated β-naphthalene Phenol acrylate, 2-naphtholethyl (meth)acrylate, 2-naphthoxyethyl acrylate, 2-(4-methoxy-1-naphthoxy)ethyl (meth)acrylate, etc. have naphthalene Rings; (meth) acrylate and other biphenyls having a biphenyl ring.

由黏著特性及耐久性之觀點，前述含芳香環(甲基)丙烯酸酯宜為(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧乙酯，且尤為(甲基)丙烯酸苯氧乙酯。From the viewpoint of adhesion properties and durability, the aforementioned aromatic ring-containing (meth)acrylates are preferably benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and especially phenoxyethyl (meth)acrylate .

含芳香環(甲基)丙烯酸酯的前述重量比率宜為25重量%以下，且宜為3~25重量%，以10~22重量%為佳，14~20重量%更佳。含芳香環(甲基)丙烯酸酯的重量比率為3重量%以上時，由抑制顯示不均來看為佳。另一方面，若超過25重量%，顯示不均的抑制反而不夠充分，有耐久性降低之傾向。The aforementioned weight ratio of the aromatic ring-containing (meth)acrylate is preferably 25% by weight or less, and preferably 3 to 25% by weight, preferably 10 to 22% by weight, and more preferably 14 to 20% by weight. When the weight ratio of the aromatic ring-containing (meth)acrylate is 3% by weight or more, it is preferable to suppress display unevenness. On the other hand, if it exceeds 25% by weight, the suppression of display unevenness is insufficient, and durability tends to decrease.

上述以外之其他共聚單體之具體例可舉馬來酸酐、伊康酸酐等含酸酐基單體；丙烯酸的己內酯加成物；烯丙基磺酸、2-(甲基)丙烯醯胺基-2-甲基丙磺酸、(甲基)丙烯醯胺基丙磺酸、磺丙基(甲基)丙烯酸酯等含磺酸基單體；2-羥乙基丙烯醯基磷酸酯等含磷酸基單體等。Specific examples of other comonomers other than the above include acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; caprolactone adducts of acrylic acid; allyl sulfonic acid, 2-(meth)acrylamide Sulfonic acid group-containing monomers such as methyl-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid, sulfopropyl(meth)acrylate; 2-hydroxyethylacryloyl phosphate, etc. Phosphoric acid group-containing monomers, etc.

又，以改質為目的的單體之例還可列舉(甲基)丙烯酸胺乙酯、N,N-二甲基胺乙基(甲基)丙烯酸酯、三級丁基胺乙基(甲基)丙烯酸酯等(甲基)丙烯酸烷基胺基烷基酯；(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等(甲基)丙烯酸烷氧基烷基酯；N-(甲基)丙烯醯氧基亞甲基琥珀醯亞胺或N-(甲基)丙烯醯基-6-氧基六亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-8-氧基八亞甲基琥珀醯亞胺等琥珀醯亞胺系單體；N-環己基馬來醯亞胺或N-異丙基馬來醯亞胺、N-月桂基馬來醯亞胺或N-苯基馬來醯亞胺等馬來醯亞胺系單體；N-甲基伊康醯亞胺、N-乙基伊康醯亞胺、N-丁基伊康醯亞胺、N-辛基伊康醯亞胺、N-2-乙基己基伊康醯亞胺、N-環己基伊康醯亞胺、N-月桂基伊康醯亞胺等伊康醯亞胺系單體等。In addition, examples of monomers for the purpose of modification include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, tertiary butylaminoethyl (meth) (Meth)acrylic acid esters and other (meth)acrylic acid alkylamino alkyl esters; (meth)acrylic acid methoxyethyl, (meth)acrylic acid ethoxyethyl, and (meth)acrylic acid alkoxyalkyl groups Esters; N-(meth)acryloyloxymethylenesuccinimide or N-(meth)acryloyl-6-oxyhexamethylenesuccinimide, N-(meth)propylene Succinimidyl monomers such as octamethylene succinimidine such as octamethylene; N-cyclohexylmaleimide or N-isopropylmaleimide, N-laurylima Maleimines such as lyimines or N-phenylmaleimines; N-methylikonimines, N-ethylikonimines, N-butylikon Ikonimines, N-octyl Ikonimines, N-2-ethylhexyl Ikonimines, N-cyclohexyl Ikonimines, N-Lauryl Ikonimines, etc. Imine monomers, etc.

並且，改質單體也可使用乙酸乙烯酯、丙酸乙烯酯等乙烯基系單體；丙烯腈、甲基丙烯腈等氰基丙烯酸酯系單體；(甲基)丙烯酸環氧丙酯等含環氧基(甲基)丙烯酸酯；(甲基)丙烯酸聚乙二醇酯、(甲基)丙烯酸聚丙二醇酯、(甲基)丙烯酸甲氧基乙二醇酯、(甲基)丙烯酸甲氧基聚丙二醇酯等二醇系(甲基)丙烯酸酯；(甲基)丙烯酸四氫糠酯、氟(甲基)丙烯酸酯、聚矽氧(甲基)丙烯酸酯或2-甲氧基乙基丙烯酸酯等(甲基)丙烯酸酯單體等。更可列舉異戊二烯、丁二烯、異丁烯、乙烯基醚等。In addition, as the modified monomer, vinyl monomers such as vinyl acetate and vinyl propionate; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; and glycidyl (meth)acrylate can also be used. Epoxy group-containing (meth)acrylate; polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethylene glycol (meth)acrylate, methyl (meth)acrylate Glycol (meth)acrylate such as oxypolypropylene glycol ester; tetrahydrofurfuryl (meth)acrylate, fluoro(meth)acrylate, polysiloxane (meth)acrylate or 2-methoxyethyl (Meth)acrylate monomers such as methacrylate. More examples include isoprene, butadiene, isobutylene, vinyl ether, and the like.

並且，上述以外之可共聚單體可舉如含有矽原子之矽烷系單體等。作為矽烷系單體，可列舉例如3-丙烯醯氧丙基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、4-乙烯基丁基三甲氧基矽烷、4-乙烯基丁基三乙氧基矽烷、8-乙烯基辛基三甲氧基矽烷、8-乙烯基辛基三乙氧基矽烷、10-甲基丙烯醯氧癸基三甲氧基矽烷、10-丙烯醯氧癸基三甲氧基矽烷、10-甲基丙烯醯氧癸基三乙氧基矽烷、10-丙烯醯氧癸基三乙氧基矽烷等。In addition, the copolymerizable monomers other than the above can be exemplified by silane-based monomers containing silicon atoms. As the silane-based monomer, for example, 3-propylene oxypropyl triethoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, 4-vinyl butyl trimethoxy silane, 4- Vinylbutyltriethoxysilane, 8-vinyloctyltrimethoxysilane, 8-vinyloctyltriethoxysilane, 10-methacryloxydecyltrimethoxysilane, 10-propylene Oxydecyl trimethoxysilane, 10-methacryloxydecyl triethoxysilane, 10-acryloxydecyl triethoxysilane, etc.

又，作為共聚單體，也可使用三丙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、雙酚A二環氧丙基醚二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三羥甲丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、己內酯改質二新戊四醇六(甲基)丙烯酸酯等(甲基)丙烯酸與多元醇之酯化物等的具有2個以上(甲基)丙烯醯基、乙烯基等不飽和雙鍵之多官能性單體，或在聚酯、環氧、胺甲酸乙酯等的骨架上附加2個以上(甲基)丙烯醯基、乙烯基等不飽和雙鍵作為與單體成分相同的官能基的聚酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、胺甲酸乙酯(甲基)丙烯酸酯等。In addition, as a comonomer, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and bisphenol A can also be used. Diglycidyl ether di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, Neopentyl erythritol tetra (meth) acrylate, dineopentaerythritol penta (meth) acrylate, dineopentaerythritol hexa (meth) acrylate, caprolactone modified dineopentaerythritol hexa ( Polyfunctional monomers such as esters of (meth)acrylic acid and polyols such as meth)acrylates, etc., have two or more (meth)acrylic acid groups, vinyl groups and other unsaturated double bonds, or in polyester, Polyester (meth)acrylates and cyclics in which two or more (meth)acrylic groups, vinyl groups, and other unsaturated double bonds are added to the backbone of epoxy and urethane as the same functional groups as the monomer components Oxygen (meth)acrylate, urethane (meth)acrylate, etc.

在前述(甲基)丙烯酸系聚合物(A)之總構成單體(100重量%)的重量比率中，(甲基)丙烯酸系聚合物(A)中前述其他共聚單體的比率宜為0~10%左右，且宜為0~7%左右，更宜為0~5%左右。In the weight ratio of the total constituent monomers (100% by weight) of the (meth)acrylic polymer (A), the ratio of the other comonomers in the (meth)acrylic polymer (A) is preferably 0 ~10%, preferably 0~7%, more preferably 0~5%.

本發明之(甲基)丙烯酸系聚合物(A)通常重量平均分子量宜為100萬~250萬。若考慮耐久性、尤其是耐熱性，重量平均分子量宜為120萬~200萬。以耐熱性觀點來看，重量平均分子量如果在100萬以上為宜。又，重量平均分子量若大於250萬，有黏著劑容易變硬的傾向，而易發生剝落。另，顯示分子量分布之重量平均分子量(Mw)/數量平均分子量(Mn)宜為1.8以上且10以下，較宜為1.8~7，更宜為1.8~5。分子量分布(Mw/Mn)若大於10，由耐久性觀點來看不宜。此外，重量平均分子量、分子量分布(Mw/Mn)是依照GPC(凝膠滲透層析法)來測定且從以聚苯乙烯換算所算出之值而求得。The (meth)acrylic polymer (A) of the present invention usually has a weight average molecular weight of 1 million to 2.5 million. Considering durability, especially heat resistance, the weight average molecular weight should be 1.2 million to 2 million. From the viewpoint of heat resistance, the weight average molecular weight is preferably 1 million or more. In addition, if the weight average molecular weight is more than 2.5 million, the adhesive tends to become hard and peel off easily. In addition, the weight average molecular weight (Mw)/number average molecular weight (Mn) showing the molecular weight distribution is preferably 1.8 or more and 10 or less, more preferably 1.8-7, and more preferably 1.8-5. If the molecular weight distribution (Mw/Mn) is greater than 10, it is not suitable from the viewpoint of durability. In addition, the weight average molecular weight and the molecular weight distribution (Mw/Mn) are measured in accordance with GPC (Gel Permeation Chromatography), and are obtained from the values calculated in terms of polystyrene.

所述(甲基)丙烯酸系聚合物(A)的製造，可適當選擇溶液聚合、塊狀聚合、乳化聚合、各種自由基聚合等公知的製造方法。又，所得(甲基)丙烯酸系聚合物(A)可為無規共聚物、嵌段共聚物、接枝共聚物等任一者。For the production of the (meth)acrylic polymer (A), known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations can be appropriately selected. In addition, the obtained (meth)acrylic polymer (A) may be any of random copolymers, block copolymers, and graft copolymers.

此外，溶液聚合中，聚合溶劑可使用例如乙酸乙酯、甲苯等。作為具體之溶液聚合例，反應可於氮等非活性氣體氣流下添加聚合引發劑，且一般係於50~70℃左右、5~30小時左右之反應條件下進行。In addition, in solution polymerization, the polymerization solvent can be, for example, ethyl acetate, toluene, etc. As a specific example of solution polymerization, the reaction can be carried out under reaction conditions of about 50 to 70°C for about 5 to 30 hours by adding a polymerization initiator under an inert gas stream such as nitrogen.

自由基聚合所使用之聚合引發劑、鏈轉移劑、乳化劑等無特別限定可適當選擇並使用。此外，(甲基)丙烯酸系聚合物(A)之重量平均分子量可藉由聚合引發劑、鏈轉移劑的使用量及反應條件來控制，並可因應其等之種類來適當調整其使用量。The polymerization initiator, chain transfer agent, emulsifier, etc. used for radical polymerization are not particularly limited and can be appropriately selected and used. In addition, the weight average molecular weight of the (meth)acrylic polymer (A) can be controlled by the usage amount of the polymerization initiator and the chain transfer agent and the reaction conditions, and the usage amount can be appropriately adjusted according to the types of these.

本發明之黏著劑組成物可含有離子性化合物(B)。離子性化合物(B)可適宜使用鹼金屬鹽及/或有機陽離子-陰離子鹽。鹼金屬鹽可使用鹼金屬之有機鹽及無機鹽。又，本發明所謂「有機陽離子-陰離子鹽」係表示其為有機鹽且其陽離子部由有機物所構成者，而陰離子部可為有機物亦可為無機物。「有機陽離子-陰離子鹽」亦稱為離子性液體、離子性固體。藉由使前述黏著劑層含有離子性化合物(B)，可使黏著劑層之表面電阻值降低而抑制靜電產生，從而可抑制靜電打亂液晶層之定向而發生漏光(帶電不均)。The adhesive composition of the present invention may contain an ionic compound (B). As the ionic compound (B), alkali metal salts and/or organic cation-anion salts can be suitably used. As the alkali metal salt, organic and inorganic salts of alkali metals can be used. In addition, the "organic cation-anion salt" in the present invention means that it is an organic salt and the cation part is composed of an organic substance, and the anion part may be an organic substance or an inorganic substance. "Organic cation-anion salt" is also called ionic liquid and ionic solid. By containing the ionic compound (B) in the adhesive layer, the surface resistance of the adhesive layer can be reduced and the generation of static electricity can be suppressed, thereby preventing the static electricity from disrupting the orientation of the liquid crystal layer and causing light leakage (uneven charging).

>鹼金屬鹽> 構成鹼金屬鹽之陽離子部的鹼金屬離子可舉如鋰、鈉、鉀之各離子。該等鹼金屬離子之中以鋰離子為佳。>Alkali metal salt> The alkali metal ions constituting the cation part of the alkali metal salt can be exemplified by the respective ions of lithium, sodium, and potassium. Among the alkali metal ions, lithium ion is preferred.

鹼金屬鹽之陰離子部可以有機物構成，亦可以無機物構成。構成有機鹽之陰離子部例如可使用CH3 COO- 、CF3 COO- 、CH3 SO3 - 、CF3 SO3 - 、(CF3 SO2 )3 C- 、C4 F9 SO3 - 、C3 F7 COO- 、(CF3 SO2 )(CF3 CO)N- 、- O3 S(CF2 )3 SO3 - 、PF6 - 、CO3 2- 或下述通式(A)至(D)所示者等： (A)：(Cn F2n ＋1 SO2 )2 N- (惟，n為0~10之整數)、 (B)：CF2 (Cm F2m SO2 )2 N- (惟，m為1~10之整數)、 (C)：- O3 S(CF2 )l SO3 - (惟，l為1~10之整數)、 (D)：(Cp F2p ＋1 SO2 )N- (Cq F2q ＋1 SO2 )(惟，p、q為1~10之整數)。 特別是含氟原子之陰離子部由於可獲得離子解離性佳的離子化合物故適於使用。構成無機鹽之陰離子部可使用Cl- 、Br- 、I- 、AlCl4 - 、Al2 Cl7 - 、BF4 - 、PF6 - 、ClO4 - 、NO3 - 、AsF6 - 、SbF6 - 、NbF6 - 、TaF6 - 、(CN)2 N- 等。陰離子部宜為(CF3 SO2 )2 N－ 、(C2 F5 SO2 )2 N－ 等前述通式(A)所示(全氟烷基磺醯基)醯亞胺，尤以(CF3 SO2 )2 N－ 所示(三氟甲磺醯基)醯亞胺為宜。The anion part of the alkali metal salt may be composed of an organic substance or an inorganic substance. Constituting the anion of the organic salt of example, using CH 3 COO -, CF 3 COO -, CH 3 SO 3 -, CF 3 SO 3 -, (CF 3 SO 2) 3 C -, C 4 F 9 SO 3 -, C 3 F 7 COO -, (CF 3 SO 2) (CF 3 CO) N -, - O 3 S (CF 2) 3 SO 3 -, PF 6 -, CO 3 2- or the following formula (A) to (D), and the like by: (A) :( C n F 2n +1 SO 2) 2 N - ( but, n is an integer of 0 to 10), (B): CF 2 (C m F 2m SO 2) 2 N - (but, m is an integer of 1 to 10), (C): - O 3 S (CF 2) l SO 3 - ( but, l is an integer of 1 to 10), (D) :( C p F 2p +1 SO 2) N - (C q F 2q +1 SO 2) ( but, p, q is an integer of 1 to 10). In particular, the anion part containing a fluorine atom is suitable for use because an ionic compound with good ion dissociation can be obtained. Anion portion constituting the inorganic salt may be used Cl -, Br -, I - , AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, AsF 6 -, SbF 6 - , NbF 6 -, TaF 6 - , (CN) 2 N - and the like. The anion part is preferably (CF 3 SO 2 ) 2 N － , (C 2 F 5 SO 2 ) 2 N －, etc. (perfluoroalkylsulfonyl) imide represented by the general formula (A), especially ( 2 N CF 3 SO 2) - shown in (trifluoromethane sulfonic acyl) (PEI) is appropriate.

鹼金屬之有機鹽具體上可舉如醋酸鈉、海藻酸鈉、木質磺酸鈉、甲苯磺酸鈉、LiCF3 SO3 、Li(CF3 SO2 )2 N、Li(CF3 SO2 )2 N、Li(C2 F5 SO2 )2 N、Li(C4 F9 SO2 )2 N、Li(CF3 SO2 )3 C、KO3 S(CF2 )3 SO3 K、LiO3 S(CF2 )3 SO3 K等，其等之中以LiCF3 SO3 、Li(CF3 SO2 )2 N、Li(C2 F5 SO2 )2 N、Li(C4 F9 SO2 )2 N、Li(CF3 SO2 )3 C等為佳，Li(CF3 SO2 )2 N、Li(C2 F5 SO2 )2 N、Li(C4 F9 SO2 )2 N等屬雙(氟磺醯基)醯亞胺鋰鹽之含氟鋰醯亞胺鹽較佳，(全氟烷基磺醯基)醯亞胺鋰鹽尤佳。其他還可舉4,4,5,5-四氟-1,3,2-二四氫噻唑-1,1,3,3-四氧化鋰鹽等。Specific examples of organic salts of alkali metals include sodium acetate, sodium alginate, sodium lignosulfonate, sodium toluenesulfonate, LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N, Li(CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N, Li(C 4 F 9 SO 2 ) 2 N, Li(CF 3 SO 2 ) 3 C, KO 3 S(CF 2 ) 3 SO 3 K, LiO 3 S(CF 2 ) 3 SO 3 K, etc. Among them, LiCF 3 SO 3 , Li(CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N, Li(C 4 F 9 SO 2 ) 2 N, Li(CF 3 SO 2 ) 3 C, etc. are better, Li(CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N, Li(C 4 F 9 SO 2 ) 2 The fluorine-containing lithium imide salt of bis(fluorosulfonyl)imide lithium salt such as N is preferred, and the (perfluoroalkylsulfonyl)imide lithium salt is particularly preferred. Other examples include 4,4,5,5-tetrafluoro-1,3,2-ditetrahydrothiazole-1,1,3,3-tetraoxide lithium salt.

而鹼金屬的無機鹽可列舉如過氯酸鋰、碘化鋰。Examples of inorganic salts of alkali metals include lithium perchlorate and lithium iodide.

>有機陽離子-陰離子鹽> 本發明所用之有機陽離子-陰離子鹽係由陽離子成分與陰離子成分構成，且前述陽離子成分為有機物所構成之物。作為陽離子成分，具體而言可舉如吡啶陽離子、哌啶陽離子、吡咯啶陽離子、具二氫吡咯骨架的陽離子、具吡咯骨架的陽離子、咪唑陽離子、四氫嘧啶陽離子、二氫嘧啶陽離子、吡唑陽離子、吡唑啉陽離子、四烷基銨陽離子、三烷基鋶陽離子、四烷基鏻陽離子等。>Organic Cation-Anion Salt> The organic cation-anion salt used in the present invention is composed of a cation component and an anion component, and the aforementioned cation component is composed of an organic substance. Specific examples of the cationic component include pyridine cation, piperidine cation, pyrrolidine cation, dihydropyrrole skeleton cation, pyrrole skeleton cation, imidazole cation, tetrahydropyrimidine cation, dihydropyrimidine cation, pyrazole Cations, pyrazoline cations, tetraalkylammonium cations, trialkylsulfonium cations, tetraalkylphosphonium cations, etc.

陰離子成分例如可使用例如Cl- 、Br- 、I- 、AlCl4 - 、Al2 Cl7 - 、BF4 - 、PF6 - 、ClO4 - 、NO3 - 、CH3 COO- 、CF3 COO- 、CH3 SO3 - 、CF3 SO3 - 、(CF3 SO2 )3 C- 、AsF6 - 、SbF6 - 、NbF6 - 、TaF6 - 、(CN)2 N- 、C4 F9 SO3 - 、C3 F7 COO- 、((CF3 SO2 )(CF3 CO)N- 、- O3 S(CF2 )3 SO3 - 及下述通式(A)至(D)所示者等： (A)：(Cn F2n+1 SO2 )2 N- (惟，n為0~10之整數)、 (B)：CF2 (Cm F2m SO2 )2 N- (惟，m為1~10之整數)、 (C)：- O3 S(CF2 )l SO3 - (惟，l為1~10之整數)、 (D)：(Cp F2p+1 SO2 )N- (Cq F2q+1 SO2 )(惟，p、q為1~10之整數)。 其中特別是含氟原子之陰離子成分因可獲得離子解離性良好的離子化合物故適於使用。Anionic component, for example, may be used, for example, Cl -, Br -, I - , AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, CH 3 COO -, CF 3 COO - , CH 3 SO 3 -, CF 3 SO 3 -, (CF 3 SO 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, (CN) 2 N -, C 4 F 9 SO 3 -, C 3 F 7 COO -, ((CF 3 SO 2) (CF 3 CO) N -, - O 3 S (CF 2) 3 SO 3 - and the following general formula (A) to (D) like that shown: (A) :( C n F 2n + 1 SO 2) 2 N - ( but, n is an integer of 0 to 10), (B): CF 2 (C m F 2m SO 2) 2 N - (However, m is an integer of 1 to 10), (C): - O 3 S (CF 2) l SO 3 - ( but, l is an integer of 1 to 10), (D) :( C p F 2p +1 SO 2) N - (C q F 2q + 1 SO 2) ( but, p, q is an integer of 1 to 10) wherein the anion component containing a fluorine atom is particularly due to the ionic dissociation is obtained having good ionic compound. It is suitable for use.

有機陽離子-陰離子鹽可適當選擇由上述陽離子成分與陰離子成分組合構成之化合物來使用。有機陽離子-陰離子鹽之較佳具體例可舉例如甲基三辛基銨雙(三氟甲磺醯基)醯亞胺、1-甲基-1-丙基吡咯啶鎓雙(三氟甲磺醯基)醯亞胺、乙基甲基咪唑鎓雙(氟磺醯基醯亞胺)。其中更宜為1-甲基-1-丙基吡咯啶鎓雙(三氟甲磺醯基)醯亞胺、乙基甲基咪唑鎓雙(氟磺醯基醯亞胺)。The organic cation-anion salt can be used by appropriately selecting a compound composed of the above-mentioned cation component and anion component in combination. Preferred specific examples of organic cation-anion salts include, for example, methyl trioctyl ammonium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfon) (Acetyl) imide, ethyl methyl imidazolium bis (fluorosulfonyl imide). Among them, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide and ethylmethylimidazolium bis(fluorosulfonylimide) are more preferred.

又，離子性化合物(B)除了前述鹼金屬鹽、有機陽離子-陰離子鹽之外，尚可列舉如氯化銨、氯化鋁、氯化銅、氯化亞鐵、氯化鐵、硫酸銨等之無機鹽。In addition to the aforementioned alkali metal salts and organic cation-anion salts, the ionic compound (B) includes ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, ammonium sulfate, etc. The inorganic salt.

為了獲得所期望的電阻值，前述離子性化合物(B)可單獨使用或可將多種併用。特別當目的是將黏著劑層之表面電阻值控制在1×1010 ~1×1012 Ω/□之範圍內時，就前述離子性化合物(B)來說，在可提高抗靜電性能之觀點上以鹼金屬鹽為佳，藉由使用鹼金屬鹽，即使只有少量的摻混份數也可獲得抗靜電性能高的黏著劑。另一方面，當目的是將黏著劑層之表面電阻值控制在1×108 ~1×1010 Ω/□之範圍內時，就前述離子性化合物(B)來說，在可提高抗靜電性能之觀點上以有機陽離子-陰離子鹽為佳，藉由使用有機陽離子-陰離子鹽，就算是較少的摻混份數也可獲得抗靜電性能高的黏著劑。In order to obtain a desired resistance value, the aforementioned ionic compound (B) may be used singly or plural kinds may be used in combination. Especially when the purpose is to control the surface resistance of the adhesive layer within the range of 1×10 10 ~1×10 12 Ω/□, in terms of the aforementioned ionic compound (B), it can improve the antistatic performance. Above all, alkali metal salts are preferred. By using alkali metal salts, an adhesive with high antistatic properties can be obtained even with a small amount of blending. On the other hand, when the purpose is to control the surface resistance of the adhesive layer within the range of 1×10 8 to 1×10 10 Ω/□, the aforementioned ionic compound (B) can improve antistatic properties. From the viewpoint of performance, organic cation-anion salts are preferred. By using organic cation-anion salts, an adhesive with high antistatic properties can be obtained even with a small amount of blending.

本發明之黏著劑組成物的離子性化合物(B)比率宜適當調整成可滿足黏著劑層之抗靜電特性與觸控面板的感度。例如，為使黏著劑層的表面電阻值成為1.0×108 ~1.0×1012 Ω/□之範圍，宜一邊考慮導入於(甲基)丙烯酸系聚合物(A)中之含醯胺基單體(a2)的重量比率、偏光薄膜之透明保護薄膜的種類等，一邊因應內嵌觸控感測機能之液晶面板的種類來調整離子性化合物(B)之比率。例如，圖2所示之內置型內嵌觸控感測機能之液晶面板中，黏著劑層之初始的表面電阻值宜控制在1×108 ~1×1010 Ω/□之範圍。又，圖3所示之半內置型或圖4所示之上置型內嵌觸控感測機能之液晶面板中，黏著劑層之初始的表面電阻值宜控制在1×1010 ~1×1012 Ω/□之範圍。The ratio of the ionic compound (B) of the adhesive composition of the present invention is suitably adjusted to satisfy the antistatic properties of the adhesive layer and the sensitivity of the touch panel. For example, in order to make the surface resistance of the adhesive layer in the range of 1.0×10 8 to 1.0×10 12 Ω/□, it is advisable to consider the amino group-containing monomer introduced into the (meth)acrylic polymer (A) The weight ratio of the body (a2), the type of the transparent protective film of the polarizing film, etc., are adjusted according to the type of the liquid crystal panel with the built-in touch sensing function to adjust the ratio of the ionic compound (B). For example, in the liquid crystal panel with built-in in-cell touch sensing function shown in Figure 2, the initial surface resistance of the adhesive layer should be controlled within the range of 1×10 8 to 1×10 10 Ω/□. In addition, in the semi-built-in type shown in Figure 3 or the top-mounted type in-cell touch-sensing liquid crystal panel shown in Figure 4, the initial surface resistance of the adhesive layer should be controlled within 1×10 10 ~1×10 The range of 12 Ω/□.

前述離子性化合物(B)若變多，離子性化合物(B)可能會析出，進而易發生加濕剝落。前述離子性化合物(B)之比率，例如相對於(甲基)丙烯酸系聚合物(A)100重量份，一般宜為40重量份以下，且30重量份以下更佳，並以20重量份以下為佳，10重量份以下最佳。另一方面，以使抗靜電性能提升來看，宜使用0.01重量份以上之前述離子性化合物(B)。基於此觀點，前述離子性化合物(B)宜為0.1重量份以上，更宜為0.5重量份以上。另一方面，前述離子性化合物(B)若變多，會有表面電阻值變得過低而發生基線變動(因表面電阻值過低造成觸控時之誤動作)，使觸控面板的感度降低之虞。If the aforementioned ionic compound (B) increases, the ionic compound (B) may be precipitated, and humidification peeling is likely to occur. The ratio of the aforementioned ionic compound (B), for example, relative to 100 parts by weight of the (meth)acrylic polymer (A), generally preferably 40 parts by weight or less, and more preferably 30 parts by weight or less, and 20 parts by weight or less Preferably, 10 parts by weight or less is best. On the other hand, in order to improve the antistatic performance, it is preferable to use 0.01 parts by weight or more of the aforementioned ionic compound (B). From this viewpoint, the aforementioned ionic compound (B) is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more. On the other hand, if the aforementioned ionic compound (B) increases, the surface resistance value will become too low and the baseline will fluctuate (the surface resistance value will be too low and cause malfunction during touch), which will reduce the sensitivity of the touch panel. The fear.

本發明之黏著劑組成物可含有交聯劑(C)。作為交聯劑(C)，可使用有機系交聯劑或多官能性金屬螯合物。有機系交聯劑可舉出如異氰酸酯系交聯劑、過氧化物系交聯劑、環氧系交聯劑、亞胺系交聯劑等。多官能性金屬螯合物是多價金屬與有機化合物共價鍵結或配位鍵結之物。多價金屬原子可列舉Al、Cr、Zr、Co、Cu、Fe、Ni、V、Zn、In、Ca、Mg、Mn、Y、Ce、Sr、Ba、Mo、La、Sn、Ti等。有機化合物中可共價鍵結或配位鍵結之原子可舉如氧原子等，有機化合物可舉如烷基酯、醇化合物、羧酸化合物、醚化合物、酮化合物等。The adhesive composition of the present invention may contain a crosslinking agent (C). As the crosslinking agent (C), an organic crosslinking agent or a polyfunctional metal chelate can be used. Examples of the organic crosslinking agent include isocyanate-based crosslinking agents, peroxide-based crosslinking agents, epoxy-based crosslinking agents, and imine-based crosslinking agents. Multifunctional metal chelate is a covalent bond or coordination bond between a multivalent metal and an organic compound. Examples of polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like. Examples of the atoms that can be covalently bonded or coordinately bonded in the organic compounds include oxygen atoms, and the organic compounds include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, and ketone compounds.

交聯劑(C)宜為異氰酸酯系交聯劑及/或過氧化系交聯劑。The crosslinking agent (C) is preferably an isocyanate-based crosslinking agent and/or a peroxide-based crosslinking agent.

異氰酸酯系交聯劑(C)可使用具有至少2個異氰酸酯基之化合物。例如，一般會使用胺甲酸乙酯化反應所用之公知的脂肪族聚異氰酸酯、脂環族聚異氰酸酯、芳香族聚異氰酸酯等。As the isocyanate-based crosslinking agent (C), a compound having at least two isocyanate groups can be used. For example, generally known aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, etc. used in the urethane reaction are generally used.

過氧化物只要是經加熱或光照射會產生自由基活性種而使黏著劑組成物之基底聚合物進行交聯者即可適當使用，但考慮到作業性及穩定性，宜使用1分鐘半衰期溫度在80℃~160℃之過氧化物，且較宜使用在90℃~140℃之過氧化物。As long as the peroxide is heated or irradiated with free radicals to generate free radical active species to crosslink the base polymer of the adhesive composition, it can be used appropriately. However, considering the workability and stability, a 1-minute half-life temperature should be used. The peroxide temperature is between 80°C and 160°C, and the peroxide temperature between 90°C and 140°C is more suitable.

可使用之過氧化物可舉如二(2-乙基己基)過氧二碳酸酯(1分鐘半衰期溫度：90.6℃)、二(4-三級丁基環己基)過氧二碳酸酯(1分鐘半衰期溫度：92.1℃)、過氧二碳酸二-二級丁酯(1分鐘半衰期溫度：92.4℃)、過氧新癸酸三級丁酯(1分鐘半衰期溫度：103.5℃)、過氧化三甲基乙酸三級己酯(1分鐘半衰期溫度：109.1℃)、過氧化三甲基乙酸三級丁酯(1分鐘半衰期溫度：110.3℃)、二月桂醯基過氧化物(1分鐘半衰期溫度：116.4℃)、二正辛醯基過氧化物(1分鐘半衰期溫度：117.4℃)、1,1,3,3-四甲基丁基過氧基-2-乙基己酸酯(1分鐘半衰期溫度：124.3℃)、二(4-甲基苯甲醯基)過氧化物(1分鐘半衰期溫度：128.2℃)、二苯甲醯基過氧化物(1分鐘半衰期溫度：130.0℃)、過異丁酸三級丁酯(1分鐘半衰期溫度：136.1℃)、1,1-二(三級己基過氧基)環己烷(1分鐘半衰期溫度：149.2℃)等。其中，尤從交聯反應效率佳之觀點來看，以二(4-三級丁基環己基)過氧二碳酸酯(1分鐘半衰期溫度：92.1℃)、二月桂醯基過氧化物(1分鐘半衰期溫度：116.4℃)、二苯甲醯基過氧化物(1分鐘半衰期溫度：130.0℃)等適於使用。The peroxides that can be used include bis(2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: 90.6℃), bis(4-tertiarybutylcyclohexyl)peroxydicarbonate (1 One-minute half-life temperature: 92.1℃), di-secondary butyl peroxydicarbonate (1 minute half-life temperature: 92.4℃), tertiary butyl peroxyneodecanoate (1 minute half-life temperature: 103.5℃), tri-peroxide Tertiary hexyl methyl acetate (1 minute half-life temperature: 109.1°C), trimethyl peroxide tertiary butyl acetate (1 minute half-life temperature: 110.3°C), dilauryl peroxide (1 minute half-life temperature: 116.4℃), di-n-octyl peroxide (1 minute half-life temperature: 117.4℃), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (1 minute half-life temperature: 124.3°C), bis(4-methylbenzyl) peroxide (1 minute half-life temperature: 128.2°C), dibenzyl peroxide (1 minute half-life temperature: 130.0°C), perisobutyric acid Tertiary butyl ester (1 minute half-life temperature: 136.1°C), 1,1-di(tertiary hexylperoxy) cyclohexane (1 minute half-life temperature: 149.2°C), etc. Among them, especially from the viewpoint of good crosslinking reaction efficiency, bis(4-tertiarybutylcyclohexyl)peroxydicarbonate (1 minute half-life temperature: 92.1℃), dilaurinyl peroxide (1 minute Half-life temperature: 116.4°C), dibenzoyl peroxide (1 minute half-life temperature: 130.0°C), etc. are suitable for use.

相對於(甲基)丙烯酸系聚合物(A)100重量份，交聯劑(C)之使用量宜為3重量份以下，且較宜為0.01~3重量份，更宜為0.02~2重量份，又更宜為0.03~1重量份。另，交聯劑(C)低於0.01重量份時，黏著劑層恐交聯不足而無法滿足耐久性或黏著特性；另一方面，若多過3重量份，黏著劑層會變得太硬而有耐久性降低之傾向。Relative to 100 parts by weight of the (meth)acrylic polymer (A), the amount of crosslinking agent (C) used is preferably 3 parts by weight or less, more preferably 0.01 to 3 parts by weight, more preferably 0.02 to 2 parts by weight Parts, and more preferably 0.03 to 1 parts by weight. On the other hand, when the crosslinking agent (C) is less than 0.01 parts by weight, the adhesive layer may not be sufficiently crosslinked to satisfy durability or adhesion characteristics; on the other hand, if it exceeds 3 parts by weight, the adhesive layer may become too hard And there is a tendency to decrease durability.

本發明之黏著劑組成物中可含有矽烷耦合劑(D)。藉由使用矽烷耦合劑(D)可提高耐久性。作為矽烷耦合劑，具體上可舉例如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乙氧基矽烷、2-(3-4-環氧環己基)乙基三甲氧基矽烷等含環氧基之矽烷耦合劑；3-胺丙基三甲氧基矽烷、N-2-(胺乙基)-3-胺丙基甲基二甲氧基矽烷、3-三乙氧基矽基-N-(1,3-二甲基亞丁基)丙胺、N-苯基-γ-胺丙基三甲氧基矽烷等含胺基之矽烷耦合劑；3-丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧丙基三乙氧基矽烷等含(甲基)丙烯醯基之矽烷耦合劑；3-異氰酸酯丙基三乙氧基矽烷等含異氰酸酯基之矽烷耦合劑等。前述例示之矽烷耦合劑宜為含環氧基之矽烷耦合劑。The adhesive composition of the present invention may contain a silane coupling agent (D). The durability can be improved by using silane coupling agent (D). Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyl Diethoxysilane, 2-(3-4-epoxycyclohexyl)ethyltrimethoxysilane and other epoxy-containing silane coupling agents; 3-aminopropyltrimethoxysilane, N-2-(amine Ethyl)-3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, N-phenyl-γ-aminopropyl Amino-containing silane coupling agents such as trimethoxysilane; 3-propenyloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. containing (meth)acrylic acid groups The silane coupling agent; 3-isocyanate propyl triethoxy silane and other isocyanate group-containing silane coupling agents. The silane coupling agent exemplified above is preferably an epoxy-containing silane coupling agent.

又，矽烷耦合劑(D)亦可使用於分子內具有多個烷氧矽基者。具體上可列舉如信越化學公司製X-41-1053、X-41-1059A、X-41-1056、X-41-1805、X-41-1818、X-41-1810、X-40-2651等。該等於分子內具有多個烷氧矽基之矽烷耦合劑由於不易揮發且具有多個烷氧矽基，因此可有效提升耐久性而較為理想。尤其是在附黏著劑層之光學薄膜的被黏著體為較玻璃更不易與烷氧矽基反應的透明導電層(例如ITO等)時，耐久性仍佳。又，於分子內具有多個烷氧矽基之矽烷耦合劑宜為於分子內具有環氧基者，且環氧基於分子內具有多個更佳。於分子內具有多個烷氧矽基且具有環氧基之矽烷耦合劑在被黏著體為透明導電層(例如ITO等)時耐久性仍有良好之傾向。於分子內具有多個烷氧矽基且具有環氧基之矽烷耦合劑的具體例可舉信越化學公司製X-41-1053、X-41-1059A、X-41-1056，尤以環氧基含量多的信越化學公司製X-41-1056為佳。In addition, the silane coupling agent (D) can also be used for those having multiple alkoxysilyl groups in the molecule. Specifically, X-41-1053, X-41-1059A, X-41-1056, X-41-1805, X-41-1818, X-41-1810, X-40-2651 manufactured by Shin-Etsu Chemical Co., Ltd. Wait. The silane coupling agent having multiple alkoxysilyl groups in the molecule is ideal because it is not volatile and has multiple alkoxysilyl groups, so it can effectively improve durability. Especially when the adherend of the optical film with the adhesive layer is a transparent conductive layer (such as ITO) that is less likely to react with alkoxysilyl than glass, the durability is still good. In addition, the silane coupling agent having a plurality of alkoxysilyl groups in the molecule preferably has an epoxy group in the molecule, and it is more preferable that the epoxy group has a plurality of epoxy groups in the molecule. Silane coupling agents with multiple alkoxysilyl groups in the molecule and epoxy groups have a tendency to have good durability when the adherend is a transparent conductive layer (such as ITO). Specific examples of the silane coupling agent having multiple alkoxysilyl groups and epoxy groups in the molecule include X-41-1053, X-41-1059A, X-41-1056 manufactured by Shin-Etsu Chemical Co., Ltd., especially epoxy X-41-1056 manufactured by Shin-Etsu Chemical Co., Ltd. having a large base content is preferable.

前述矽烷耦合劑(D)可單獨使用，亦可將2種以上混合來使用，但整體含量相對於前述(甲基)丙烯酸系聚合物(A)100重量份，宜為5重量份以下，且0.001~5重量份為佳，較宜為0.01~1重量份，更宜為0.02~1重量份，並且以0.05~0.6重量份為佳。是可提升耐久性之量。The aforementioned silane coupling agent (D) may be used alone or in a mixture of two or more, but the total content is preferably 5 parts by weight or less with respect to 100 parts by weight of the (meth)acrylic polymer (A), and It is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight, more preferably 0.02 to 1 part by weight, and preferably 0.05 to 0.6 part by weight. It is the amount that can improve durability.

本發明之黏著劑組成物中可摻合具有反應性矽基之聚醚化合物(E)。聚醚化合物(E)以可使重工性提升之觀點來看為宜。聚醚化合物(E)可使用例如日本特開第2010-275522號公報中所揭示者。The adhesive composition of the present invention can be blended with a polyether compound (E) having a reactive silicon group. The polyether compound (E) is suitable from the viewpoint of improving heavy workability. As the polyether compound (E), for example, those disclosed in JP 2010-275522 A can be used.

本發明黏著劑組成物中聚醚化合物(E)之比率，例如相對於(甲基)丙烯酸系聚合物(A)100重量份，宜為10重量份以下，且0.001~10重量份更佳。前述聚醚化合物(E)若低於0.001重量份，則有重工性提升之效果不充分的情形。前述聚醚化合物(E)在0.01重量份以上為宜，更宜為0.1重量份以上。另一方面，前述聚醚化合物(E)如果多過10重量份，在耐久性之觀點上不宜。前述聚醚化合物(E)在5重量份以下為宜，更宜為2重量份以下。前述聚醚化合物(E)之比率可採用前述上限值或下限值來設定適當範圍。The ratio of the polyether compound (E) in the adhesive composition of the present invention, for example, relative to 100 parts by weight of the (meth)acrylic polymer (A), is preferably 10 parts by weight or less, and more preferably 0.001-10 parts by weight. If the aforementioned polyether compound (E) is less than 0.001 parts by weight, the effect of improving reworkability may be insufficient. The aforementioned polyether compound (E) is preferably 0.01 part by weight or more, more preferably 0.1 part by weight or more. On the other hand, if the aforementioned polyether compound (E) exceeds 10 parts by weight, it is not suitable from the viewpoint of durability. The aforementioned polyether compound (E) is preferably 5 parts by weight or less, and more preferably 2 parts by weight or less. The ratio of the aforementioned polyether compound (E) can be set in an appropriate range using the aforementioned upper limit or lower limit.

並且，本發明黏著劑組成物中亦可含有其他公知添加劑，例如可視使用用途適當添加聚丙二醇等聚伸烷基二醇的聚醚化合物、著色劑、顏料等粉體、染料、界面活性劑、塑化劑、增黏劑、表面潤滑劑、調平劑、軟化劑、抗氧化劑、抗老化劑、光穩定劑、紫外線吸收劑、聚合抑制劑、無機或有機的充填劑、金屬粉、粒子狀、箔狀物等。又，亦可在可控制的範圍內採用添加還原劑的氧化還原系。該等添加劑相對於(甲基)丙烯酸系聚合物(A)100重量份宜在5重量份以下、較宜在3重量份以下且更宜在1重量份以下的範圍使用。In addition, the adhesive composition of the present invention may also contain other well-known additives, such as polyether compounds of polyalkylene glycol such as polypropylene glycol, powders such as colorants and pigments, dyes, surfactants, etc., depending on the application. Plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, particles , Foil, etc. In addition, an oxidation-reduction system with a reducing agent can also be used within a controllable range. These additives are preferably used in the range of 5 parts by weight or less, more preferably 3 parts by weight or less, and more preferably 1 part by weight or less relative to 100 parts by weight of the (meth)acrylic polymer (A).

形成黏著劑層的方法可藉由例如以下方法來製作：將前述黏著劑組成物塗佈於經剝離處理過的分離件等，並乾燥去除聚合溶劑等形成黏著劑層後轉印到光學薄膜(偏光薄膜)之方法；或者將前述黏著劑組成物塗佈於光學薄膜(偏光薄膜)後，乾燥去除聚合溶劑等以在光學薄膜形成黏著劑層的方法。另，於塗佈黏著劑時可適當另外添加聚合溶劑以外之一種以上溶劑。The method of forming the adhesive layer can be produced by, for example, the following method: applying the aforementioned adhesive composition to a release-treated separator, etc., and drying to remove the polymerization solvent, etc., to form an adhesive layer, and then transferring it to an optical film ( Polarizing film); or applying the aforementioned adhesive composition to an optical film (polarizing film), and then drying and removing the polymerization solvent to form an adhesive layer on the optical film. In addition, one or more solvents other than the polymerization solvent may be added appropriately when applying the adhesive.

黏著劑層的厚度無特別限制，例如為1~100μm左右。宜為2~50μm，較宜為2~40μm，更宜為5~35μm。The thickness of the adhesive layer is not particularly limited, and is, for example, about 1 to 100 μm. It is preferably 2~50μm, more preferably 2~40μm, more preferably 5~35μm.

>影像顯示面板、影像顯示裝置> 本發明附黏著劑層之偏光薄膜可應用於各種影像顯示面板，且該影像顯示面板可應用於以往之影像顯示裝置。影像顯示裝置之其他構成與以往之影像顯示裝置相同。可應用影像顯示面板的影像顯示裝置之具體例可舉液晶顯示裝置、電致發光(EL)顯示器、電漿顯示器(PD)、場發射顯示器(FED：Field Emission Display)等。>Image display panel, image display device> The polarizing film with adhesive layer of the present invention can be applied to various image display panels, and the image display panel can be applied to conventional image display devices. The other structure of the image display device is the same as that of the conventional image display device. Specific examples of the image display device to which the image display panel can be applied include a liquid crystal display device, an electroluminescence (EL) display, a plasma display (PD), a field emission display (FED: Field Emission Display), etc.

本發明附黏著劑層之偏光薄膜的表面電阻值之變動比小，適宜應用於內嵌觸控感測機能之液晶面板。The surface resistance of the polarizing film with the adhesive layer of the present invention has a small variation ratio, and is suitable for use in liquid crystal panels with embedded touch sensing functions.

並且，除了上述構成以外，液晶面板中還可適當設置相位差薄膜、視角補償薄膜、增亮薄膜等光學薄膜。In addition to the above-mentioned configuration, optical films such as retardation films, viewing angle compensation films, and brightness enhancement films can also be appropriately provided in the liquid crystal panel.

液晶層並無特別限定，可使用例如TN型或STN型、π型、VA型、IPS型等任意類型等之任意類型者。透明基板9(光源側)只要為透明的基板即可，並無特別限定其素材，例如可舉玻璃、透明樹脂薄膜基材。透明樹脂薄膜基材可舉前述物。The liquid crystal layer is not particularly limited, and any type such as TN type, STN type, π type, VA type, and IPS type can be used. The transparent substrate 9 (light source side) may be a transparent substrate, and its material is not particularly limited, and examples thereof include glass and transparent resin film substrates. Examples of the transparent resin film substrate include the foregoing.

另外，在相對於液晶層的光源側，可使用本領域中以往使用的附黏著劑層之偏光薄膜，且，本說明書中記載者亦可適宜使用。In addition, on the light source side with respect to the liquid crystal layer, a polarizing film with an adhesive layer conventionally used in this field can be used, and those described in this specification can also be suitably used.

上述內嵌觸控感測機能之液晶面板之具體例例如示於圖2至圖4。圖2至圖4中係例示作為本發明之附黏著劑層之偏光薄膜，將圖1所示附黏著劑層之偏光薄膜1用於液晶單元之視辨側的情況。亦即，圖1之單面保護偏光薄膜11、黏著劑21在圖2至圖4中係以第1偏光薄膜11、第1黏著劑層21顯示。Specific examples of the above-mentioned liquid crystal panel with embedded touch sensing function are shown in FIGS. 2 to 4, for example. FIGS. 2 to 4 illustrate the case where the polarizing film with an adhesive layer of the present invention is used for the viewing side of a liquid crystal cell. That is, the single-sided protective polarizing film 11 and the adhesive 21 in FIG. 1 are shown as the first polarizing film 11 and the first adhesive layer 21 in FIGS. 2 to 4.

圖2係所謂內置型內嵌觸控感測機能之液晶面板，從視辨側起具有第1偏光薄膜11/第1黏著劑層21/第1透明基板41/觸控感測器部5/液晶層3/驅動電極兼感測器部6/第2透明基板42/第2黏著劑層22/第2偏光薄膜12之構成。圖2之內置型內嵌觸控感測機能之液晶面板中，例如液晶單元C於包夾液晶層3之第1、2玻璃基板41、42內(液晶單元內)具有觸控感測器部5及驅動電極兼感測器部6。Figure 2 is a liquid crystal panel with a so-called built-in in-cell touch sensing function. It has a first polarizing film 11/first adhesive layer 21/first transparent substrate 41/touch sensor section 5/ from the viewing side Composition of liquid crystal layer 3 / driving electrode and sensor part 6 / second transparent substrate 42 / second adhesive layer 22 / second polarizing film 12. In the liquid crystal panel with built-in touch sensing function in Figure 2, for example, the liquid crystal cell C has a touch sensor part in the first and second glass substrates 41, 42 (in the liquid crystal cell) sandwiching the liquid crystal layer 3 5 and the driving electrode and sensor part 6.

又，圖3係所謂內置型(半內置型)內嵌觸控感測機能之液晶面板之變形例，從視辨側起具有第1偏光薄膜11/第1黏著劑層21/觸控感測器部5/第1透明基板41/液晶層3/驅動電極兼感測器部6/第2透明基板42/第2黏著劑層22/第2偏光薄膜12之構成。圖3之內置型內嵌觸控感測機能之液晶面板中，例如液晶單元C於第1透明基板41之外側，觸控感測器部5係直接接觸第1黏著劑層21，且液晶單元C於包夾液晶層3之第1、2玻璃基板41、42內(液晶單元內)之第2透明基板42之側具有驅動電極兼感測器部6。In addition, FIG. 3 is a modification of the so-called built-in (semi-built-in type) LCD panel with built-in touch sensing function, with the first polarizing film 11/first adhesive layer 21/touch sensing from the viewing side The structure of the device portion 5/first transparent substrate 41/liquid crystal layer3/drive electrode and sensor portion 6/second transparent substrate 42/second adhesive layer 22/second polarizing film 12 In the liquid crystal panel with built-in in-cell touch sensing function of FIG. 3, for example, the liquid crystal cell C is on the outer side of the first transparent substrate 41, the touch sensor part 5 directly contacts the first adhesive layer 21, and the liquid crystal cell C has the driving electrode and sensor part 6 on the side of the second transparent substrate 42 in the first and second glass substrates 41 and 42 (in the liquid crystal cell) sandwiching the liquid crystal layer 3.

又，圖4係所謂上置型內嵌觸控感測機能之液晶面板，從視辨側起具有第1偏光薄膜11/第1黏著劑層21/觸控感測器部5/驅動電極兼感測器部6/第1透明基板41/液晶層3/驅動電極7/第2透明基板42/第2黏著劑層22/第2偏光薄膜12之構成。圖4之上置型內嵌觸控感測機能之液晶面板中，例如液晶單元C於第1透明基板41之外側具有觸控感測器部5及驅動電極兼感測器部6，觸控感測器部5係直接接觸第1黏著劑層21，且液晶單元C於包夾液晶層3之第1、2玻璃基板41、42內(液晶單元內)之第2透明基板42之側具有驅動電極7。In addition, FIG. 4 is a liquid crystal panel with a so-called top-mounted in-cell touch sensing function. It has a first polarizing film 11/first adhesive layer 21/touch sensor part 5/driving electrode and sensor from the viewing side The structure of the sensor part 6/first transparent substrate 41/liquid crystal layer 3/drive electrode 7/second transparent substrate 42/second adhesive layer 22/second polarizing film 12 In the liquid crystal panel with a top-mounted in-cell touch sensing function in FIG. 4, for example, the liquid crystal cell C has a touch sensor part 5 and a driving electrode and sensor part 6 on the outer side of the first transparent substrate 41, and the touch sensor The sensor part 5 is in direct contact with the first adhesive layer 21, and the liquid crystal cell C is driven on the side of the second transparent substrate 42 in the first and second glass substrates 41, 42 (in the liquid crystal cell) sandwiching the liquid crystal layer 3 Electrode 7.

在內嵌觸控感測機能之液晶面板中，前述液晶單元C之觸控感測器部5與第1黏著劑層21直接接觸時，第1黏著劑層21(含有離子性化合物)之抗靜電機能容易降低，尤其在加濕環境下容易降低。因此，本發明內嵌觸控感測機能之液晶面板適宜應用於前述例示中圖3所示內置型(變形例)或圖4所示上置型內嵌觸控感測機能之液晶面板。In a liquid crystal panel with embedded touch sensing function, when the touch sensor part 5 of the aforementioned liquid crystal cell C is in direct contact with the first adhesive layer 21, the resistance of the first adhesive layer 21 (containing ionic compound) The electrostatic function is easy to decrease, especially in a humidified environment. Therefore, the liquid crystal panel with in-cell touch sensing function of the present invention is suitable for application to the liquid crystal panel with the built-in type (modified) shown in FIG. 3 or the top-mounted type in-cell touch sensing function shown in FIG.

此外，配置在液晶單元C之視辨側的第1偏光薄膜11及配置在前述視辨側之相反側的第2偏光薄膜12，可分就各配置位置的適性與其他光學薄膜積層來使用。前述其他光學薄膜可舉例如可為反射板或反透射板、相位差薄膜(包含1/2或1/4等的波長板)、視角補償薄膜、增亮薄膜等可用於形成液晶顯示裝置等之光學層者。該等可使用1層或2層以上。使用該等其他光學薄膜時，也宜將最靠近液晶層3側之黏著劑層作為前述第1黏著劑層21。In addition, the first polarizing film 11 arranged on the viewing side of the liquid crystal cell C and the second polarizing film 12 arranged on the side opposite to the aforementioned viewing side can be laminated and used with other optical films according to the suitability of each arrangement position. The aforementioned other optical films can be, for example, reflective plates or anti-transmission plates, retardation films (including 1/2 or 1/4 wavelength plates), viewing angle compensation films, brightness enhancement films, etc., which can be used to form liquid crystal display devices, etc. Optical layer. These can use 1 layer or 2 or more layers. When using these other optical films, it is also preferable to use the adhesive layer closest to the liquid crystal layer 3 as the first adhesive layer 21.

液晶單元C具有之液晶層3可使用可應用於內嵌觸控感測機能之液晶面板之包含在電場不存在之狀態下平行定向之液晶分子的液晶層。就液晶層3來說，適宜使用譬如IPS方式之液晶層。除此之外，液晶層3譬如可使用TN型或STN型、π型、VA型等任意類型之液晶層。前述液晶層之厚度例如為1.5μm~4μm左右。The liquid crystal layer 3 of the liquid crystal cell C can be a liquid crystal layer containing liquid crystal molecules aligned in parallel in the absence of an electric field, which can be applied to a liquid crystal panel with an embedded touch sensing function. For the liquid crystal layer 3, it is suitable to use, for example, an IPS type liquid crystal layer. In addition, the liquid crystal layer 3 may use any type of liquid crystal layer such as TN type, STN type, π type, VA type, etc., for example. The thickness of the aforementioned liquid crystal layer is, for example, about 1.5 μm to 4 μm.

在液晶單元C中，第1透明基板41及第2透明基板42可包夾前述液晶層3而形成液晶單元。於液晶單元之內或外因應內嵌觸控感測機能之液晶面板的形態形成觸控感測器部5、驅動電極兼感測器部6、驅動電極7等。又，可於液晶單元上(第1透明基板41)設置彩色濾光片基板。In the liquid crystal cell C, the first transparent substrate 41 and the second transparent substrate 42 may sandwich the liquid crystal layer 3 to form a liquid crystal cell. The touch sensor part 5, the driving electrode and sensor part 6, the driving electrode 7 and the like are formed inside or outside the liquid crystal cell according to the shape of the liquid crystal panel with the built-in touch sensing function. In addition, a color filter substrate may be provided on the liquid crystal cell (the first transparent substrate 41).

形成前述透明基板之材料可列舉如玻璃或聚合物薄膜。前述聚合物薄膜可舉如聚對苯二甲酸乙二酯、聚環烯烴、聚碳酸酯等。前述透明基板係由玻璃形成時，其厚度例如為0.3mm~1mm左右。前述透明基板係由聚合物薄膜形成時，其厚度例如為10μm~200μm左右。上述透明基板可於其表面具有易接著層或硬塗層。The material forming the aforementioned transparent substrate can be, for example, glass or polymer film. Examples of the aforementioned polymer film include polyethylene terephthalate, polycyclic olefin, and polycarbonate. When the aforementioned transparent substrate is formed of glass, its thickness is, for example, about 0.3 mm to 1 mm. When the aforementioned transparent substrate is formed of a polymer film, its thickness is, for example, about 10 μm to 200 μm. The above-mentioned transparent substrate may have an easy-adhesion layer or a hard coat layer on its surface.

觸控感測器部5(電容感測器)、驅動電極兼感測器部6、驅動電極7係形成為透明導電層。前述透明導電層之構成材料無特別限定，可列舉如金、銀、銅、鉑、鈀、鋁、鎳、鉻、鈦、鐵、鈷、錫、鎂、鎢等金屬及該等金屬之合金等。又，前述透明導電層之構成材料可列舉銦、錫、鋅、鎵、銻、鋯、鎘之金屬氧化物，具體上可列舉氧化銦、氧化錫、氧化鈦、氧化鎘及由該等之混合物等所構成的金屬氧化物。其他可使用由碘化銅等所構成之其他金屬化合物等。前述金屬氧化物中可視需求進一步含有上述群組所示金屬原子之氧化物。宜使用譬如含氧化錫之氧化銦(ITO)、含銻之氧化錫等，尤宜使用ITO。ITO宜含有80~99重量%之氧化銦及1~20重量%之氧化錫。The touch sensor part 5 (capacitance sensor), the driving electrode and sensor part 6, and the driving electrode 7 are formed as a transparent conductive layer. The constituent materials of the transparent conductive layer are not particularly limited, and examples include metals such as gold, silver, copper, platinum, palladium, aluminum, nickel, chromium, titanium, iron, cobalt, tin, magnesium, tungsten, and alloys of these metals. . In addition, the constituent material of the transparent conductive layer may include metal oxides of indium, tin, zinc, gallium, antimony, zirconium, and cadmium, and specifically include indium oxide, tin oxide, titanium oxide, cadmium oxide, and mixtures thereof. And other metal oxides. Other metal compounds composed of copper iodide can be used. The aforementioned metal oxides may further contain oxides of metal atoms in the above group if necessary. It is suitable to use tin oxide-containing indium oxide (ITO), antimony-containing tin oxide, etc., especially ITO. ITO preferably contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide.

液晶單元C中形成觸控感測器層5之處無限制，可因應內嵌觸控感測機能之液晶面板的形態形成觸控感測器層5。例如，在圖2至圖4中係例示觸控感測器層5配置在第1偏光薄膜11與液晶層3之間的情況。觸控感測器層5譬如可以透明電極圖案形成於第1透明基板41上。關於驅動電極兼感測器部6、驅動電極7，亦可因應內嵌觸控感測機能之液晶面板的形態依循一般方法形成透明電極圖案。上述透明電極圖案通常係與形成於透明基板端部之繞線(未圖示)電連接，上述繞線則與控制器IC(未圖示)連接。透明電極圖案之形狀除了櫛形以外，可視用途採用任意形狀如條紋狀或菱形形狀等。透明電極圖案之高度例如為10nm~100nm，寬為0.1mm~5mm。There is no limitation on the place where the touch sensor layer 5 is formed in the liquid crystal cell C, and the touch sensor layer 5 can be formed in accordance with the shape of the liquid crystal panel with embedded touch sensing function. For example, in FIGS. 2 to 4, a case where the touch sensor layer 5 is arranged between the first polarizing film 11 and the liquid crystal layer 3 is illustrated. The touch sensor layer 5 may be formed on the first transparent substrate 41 with a transparent electrode pattern, for example. Regarding the driving electrode and the sensor part 6 and the driving electrode 7, a transparent electrode pattern can also be formed according to the general method according to the form of the liquid crystal panel with the built-in touch sensing function. The transparent electrode pattern is usually electrically connected to a winding wire (not shown) formed at the end of the transparent substrate, and the winding wire is connected to a controller IC (not shown). In addition to the shape of the transparent electrode pattern, any shapes such as stripes or rhombuses can be used for visual purposes. The height of the transparent electrode pattern is, for example, 10 nm to 100 nm, and the width is 0.1 mm to 5 mm.

又，內嵌觸控感測機能之液晶顯示面板可適當使用如在照明系統使用背光或反射板等用以形成液晶顯示裝置的構件。 實施例In addition, the liquid crystal display panel with built-in touch sensing function can appropriately use the components used to form the liquid crystal display device such as the backlight or the reflective plate in the lighting system. Example

以下，以實施例來具體說明本發明，惟本發明不受該等實施例限定。此外，各例中之份及%皆為重量基準。以下，未特別規定之室溫放置條件皆為23℃且65%RH。Hereinafter, the present invention will be specifically described with examples, but the present invention is not limited by these examples. In addition, the parts and% in each example are based on weight. Below, the room temperature storage conditions not specifically specified are 23°C and 65%RH.

>測定(甲基)丙烯酸系聚合物(A)之重量平均分子量> (甲基)丙烯酸系聚合物(A)之重量平均分子量(Mw)是利用GPC(凝膠滲透層析法)來測定。針對Mw/Mn亦同樣進行測定。且，聚合物(a)等之重量平均分子量的測定亦同樣應用(溶劑以外)。 ・分析裝置：Tosoh(東曹)公司製，HLC-8120GPC ・管柱：Tosoh公司製，G7000HXL +GMHXL +GMHXL ・管柱尺寸：各7.8mmφ×30cm 計90cm ・管柱溫度：40℃ ・流量：0.8mL/min ・注入量：100μL ・溶析液：四氫呋喃 ・檢測器：示差折射計(RI) ・標準試料：聚苯乙烯>Measure the weight average molecular weight of the (meth)acrylic polymer (A)> The weight average molecular weight (Mw) of the (meth)acrylic polymer (A) is measured by GPC (gel permeation chromatography). Mw/Mn is also measured in the same way. In addition, the measurement of the weight average molecular weight of the polymer (a) etc. is also applied in the same way (except for the solvent).・Analyzing device: Tosoh (Tosoh) Corporation, HLC-8120GPC ・Column: Tosoh Corporation, G7000H XL +GMH XL +GMH XL・Column size: 7.8mmφ×30cm each, total 90cm ・Column temperature: 40℃・Flow rate: 0.8mL/min ・Injection volume: 100μL ・Eluent: Tetrahydrofuran ・Detector: Differential Refractometer (RI) ・Standard sample: Polystyrene

>製作單面保護偏光薄膜(1)> (製作薄型偏光件A) 對吸水率0.75%、Tg75℃之非晶質間苯二甲酸共聚聚對苯二甲酸乙二酯(IPA共聚PET)薄膜(厚度：100μm)基材的單面施行電暈處理，並在該電暈處理面上於25℃下塗佈以9：1之比含有聚乙烯醇(聚合度4200，皂化度99.2莫耳%)及乙醯乙醯基改質PVA(聚合度1200，乙醯乙醯基改質度4.6%，皂化度99.0莫耳%以上，日本合成化學工業公司製，商品名「Gohsefimer Z200」)的水溶液並乾燥，形成厚度11μm的PVA系樹脂層，而製作出積層體。 將所得積層體在120℃之烘箱內於周速相異的輥件間沿縱方向(長邊方向)進行自由端單軸延伸2.0倍(空中輔助延伸處理)。 接著，使積層體浸漬於液溫30℃的不溶解浴(相對於水100重量份摻混4重量份之硼酸而得的硼酸水溶液)中30秒(不溶解處理)。 接著，一邊使其浸漬於液溫30℃的染色浴中一邊調整碘濃度、浸漬時間以使偏光板成為預定之透射率。本實施例係使其浸漬於相對於100重量份的水摻混0.2重量份的碘、1.0重量份的碘化鉀所得之碘水溶液中60秒(染色處理)。 接著，使其浸漬於液溫30℃的交聯浴(相對於水100重量份摻混3重量份的碘化鉀並摻混3重量份的硼酸而得之硼酸水溶液)中30秒(交聯處理)。 其後，一邊使積層體浸漬於液溫70℃之硼酸水溶液(相對於100重量份的水摻混4重量份硼酸並摻混5重量份碘化鉀所得之水溶液)，一邊於不同周速之輥件間沿縱方向(長邊方向)進行單軸延伸以使總延伸倍率達5.5倍(水中延伸)。 之後，使積層體浸漬於液溫30℃的洗淨浴(相對於水100重量份摻混4重量份的碘化鉀而得之水溶液)中(洗淨處理)。 以上述方式獲得了包含厚度5μm之偏光件的光學薄膜積層體。>Making a single-sided protective polarizing film (1)> (Making thin polarizer A) Perform corona treatment on one side of the amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA copolymerized PET) film (thickness: 100μm) with a water absorption rate of 0.75% and a Tg of 75°C. The halo-treated surface was coated at 25°C with a ratio of 9:1 containing polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mol%) and acetyl acetyl modified PVA (polymerization degree 1200, acetyl acetate) The base modification degree is 4.6%, the saponification degree is 99.0 mol% or more, an aqueous solution manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "Gohsefimer Z200") and dried to form a PVA-based resin layer with a thickness of 11 μm to produce a laminate. The resulting laminate was subjected to uniaxial extension of the free end 2.0 times in the longitudinal direction (long side direction) between rollers with different peripheral speeds in an oven at 120° C. (air-assisted extension treatment). Next, the layered body was immersed in an insoluble bath (a boric acid aqueous solution obtained by mixing 4 parts by weight of boric acid with respect to 100 parts by weight of water) at a liquid temperature of 30°C for 30 seconds (insoluble treatment). Next, while immersing in a dyeing bath at a liquid temperature of 30°C, the iodine concentration and immersion time were adjusted so that the polarizing plate had a predetermined transmittance. In this example, it was immersed in an iodine aqueous solution obtained by mixing 0.2 parts by weight of iodine and 1.0 parts by weight of potassium iodide with respect to 100 parts by weight of water for 60 seconds (dyeing treatment). Then, it was immersed in a cross-linking bath (a boric acid aqueous solution obtained by mixing 3 parts by weight of potassium iodide and 3 parts by weight of boric acid with respect to 100 parts by weight of water with a liquid temperature of 30°C) for 30 seconds (cross-linking treatment) . Thereafter, while immersing the layered body in an aqueous solution of boric acid at a liquid temperature of 70°C (an aqueous solution obtained by mixing 4 parts by weight of boric acid and 5 parts by weight of potassium iodide with respect to 100 parts by weight of water), it was placed on rolls of different peripheral speeds The space is stretched uniaxially in the longitudinal direction (long side direction) to make the total stretch magnification up to 5.5 times (underwater stretch). After that, the layered body was immersed in a washing bath (an aqueous solution obtained by mixing 4 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 30°C (washing treatment). In the above manner, an optical thin film laminate including a polarizer having a thickness of 5 μm was obtained.

(製作應用於透明保護薄膜之接著劑) 將丙烯醯基嗎福林45重量份、1,9-壬二醇二丙烯酸酯45份、(甲基)丙烯酸單體聚合而成的丙烯酸系寡聚物(ARUFON UP1190，東亞合成公司製)10份、光聚合引發劑(IRGACURE 907，BASF公司製)3份、聚合引發劑(KAYACURE DETX-S，日本化藥公司製)1.5份混合，而調製出紫外線硬化型接著劑。(Manufacture of adhesives for transparent protective films) Acrylic oligomer (ARUFON UP1190, manufactured by Toagosei Co., Ltd.) obtained by polymerizing 45 parts by weight of acrylophrine, 45 parts of 1,9-nonanediol diacrylate, and (meth)acrylic monomers. 10 Parts, 3 parts of a photopolymerization initiator (IRGACURE 907, manufactured by BASF Corporation), and 1.5 parts of a polymerization initiator (KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.) were mixed to prepare an ultraviolet curable adhesive.

(製作附硬塗層之厚25μm之TAC薄膜) 於將胺甲酸乙酯丙烯酸酯作為主成分之紫外線硬化型樹脂單體或寡聚物溶解於乙酸丁酯之樹脂溶液(DIC(股)製，商品名：UNIDIC 17-806，固體成分濃度：80%)中，相對於該溶液中之固體成分每100份，添加光聚合引發劑(BASF(股)製，商品名：IRGACURE 907)5份及調平劑(DIC(股)製，商品名：GRANDIC PC4100)0.1份。並且，於前述溶液中以45：55之比率加入環戊酮與丙二醇單甲基醚以使前述溶液中之固體成分濃度成為36%，而製作出硬塗層形成材料。將所製作出之硬塗層形成材料以使硬化後之硬塗層厚度成為7μm之方式塗佈至TJ25UL(富士軟片(Fujifilm)製，原料：三醋酸纖維素系聚合物，厚度：25μm)上而形成塗膜。之後，於90℃下將塗膜乾燥1分鐘，並以高壓水銀燈對塗膜照射累積光量300mJ/cm2 之紫外線，使前述塗膜硬化形成硬塗層而製作出附HC之25μmTAC(三醋酸纖維素)薄膜。(Making a 25μm thick TAC film with a hard coat layer) Dissolve a UV-curable resin monomer or oligomer with urethane acrylate as the main component in a resin solution of butyl acetate (made by DIC, Trade name: UNIDIC 17-806, solid content concentration: 80%), for every 100 parts of solid content in the solution, add 5 parts of a photopolymerization initiator (made by BASF (Stock), trade name: IRGACURE 907) and Leveling agent (made by DIC (Stock), trade name: GRANDIC PC4100) 0.1 part. In addition, cyclopentanone and propylene glycol monomethyl ether were added to the aforementioned solution at a ratio of 45:55 so that the solid content concentration in the aforementioned solution became 36% to produce a hard coat layer forming material. Coat the prepared hard coat forming material on TJ25UL (manufactured by Fujifilm, raw material: cellulose triacetate polymer, thickness: 25 μm) so that the thickness of the hard coat after hardening becomes 7 μm To form a coating film. After that, the coating film was dried at 90°C for 1 minute, and a high-pressure mercury lamp was used to irradiate the coating film with a cumulative light intensity of 300mJ/cm 2 of ultraviolet rays to harden the coating film to form a hard coat layer to produce 25μm TAC with HC. Vegetarian) film.

(製作單面保護偏光薄膜(1)) 在上述光學薄膜積層體之偏光件A的表面一邊將上述紫外線硬化型接著劑a以使硬化後接著劑層厚度達1μm的方式進行塗佈，一邊貼合上述透明保護薄膜(附HC之25μmTAC薄膜：三醋酸纖維素薄膜側)，然後照射作為活性能量線的紫外線使接著劑硬化。紫外線照射是使用充有鎵之金屬鹵素燈，照射裝置：Fusion UV Systems, Inc公司製的Light HAMMER10，燈泡：V燈泡，峰值照度：1600mW/cm2 ，累積照射量1000/mJ/cm2 (波長380~440nm)，紫外線照度則使用Solatell公司製的Sola-Check系統來測定。接著，將非晶性PET基材剝離，而製作出使用有薄型偏光件的單面保護偏光薄膜(1)。所得單面保護偏光薄膜之光學特性為單體透射率42.8%、偏光度99.99%。(Preparation of single-sided protective polarizing film (1)) The ultraviolet curable adhesive a is applied to the surface of the polarizer A of the optical film laminate so that the thickness of the adhesive layer after curing becomes 1 μm, and the Combine the above transparent protective film (25μm TAC film with HC: triacetate cellulose film side), and then irradiate ultraviolet rays as active energy rays to harden the adhesive. Ultraviolet rays are irradiated using a gallium-filled metal halide lamp, irradiation device: Light HAMMER10 manufactured by Fusion UV Systems, Inc., bulb: V bulb, peak illuminance: 1600mW/cm 2 , cumulative irradiation amount 1000/mJ/cm 2 (wavelength 380~440nm), and the ultraviolet illuminance is measured using the Sola-Check system manufactured by Solarell. Next, the amorphous PET substrate was peeled off to produce a single-sided protective polarizing film (1) using a thin polarizer. The optical properties of the obtained single-sided protective polarizing film were 42.8% monomer transmittance and 99.99% polarization degree.

>製作雙面保護偏光薄膜(2)> 一邊於單面保護偏光薄膜(1)的偏光件之面(偏光件之未設有透明保護薄膜之面)以使硬化後之接著劑層之厚度成為1μm之方式塗佈前述紫外線硬化型接著劑a，一邊貼合TJ25UL(富士薄膜製，原料：三醋酸纖維素系聚合物，厚度：25μm)後，照射紫外線作為活性能量線使接著劑硬化而製作出雙面保護偏光薄膜(2)。>Making double-sided protective polarizing film(2)> Coating the aforementioned ultraviolet-curing adhesive on the side of the polarizer that protects the polarizing film (1) on one side (the side of the polarizer without a transparent protective film) so that the thickness of the adhesive layer after curing becomes 1 μm a. After laminating TJ25UL (manufactured by Fuji Film, raw material: cellulose triacetate polymer, thickness: 25 μm), irradiating ultraviolet rays as active energy rays to cure the adhesive to produce a double-sided protective polarizing film (2).

>透明層之形成材> 形成材A：：胺甲酸乙酯預聚物(a)的溶液係使用由二異氰酸甲苯酯(TDI)與三羥甲丙烷(TMP)構成的胺甲酸乙酯預聚物之75%乙酸乙酯溶液(Tosoh(東曹)公司製，商品名「CORONATE L」)。 另一方面，將三羥甲丙烷溶解於環戊酮中並使固體成分濃度成為10%，而調製出三羥甲丙烷溶液。 於上述胺甲酸乙酯預聚物之75%乙酸乙酯溶液(Tosoh(東曹)公司製，商品名「Coronate L」)100份中添加上述三羥甲丙烷溶液，使胺甲酸乙酯預聚物：三羥甲丙烷之固體成分比率為90：10，再加入二月桂酸二辛錫系觸媒(Tokyo Fine Chemical CO.,LTD.製，商品名「EMBILIZER OL-1」)0.1份，並以甲基異丁基酮為溶劑，而調製出固體成分濃度調製為10%的形成材(塗敷液)。>Transparent layer forming material> Forming material A:: The solution of urethane prepolymer (a) uses 75% acetic acid of urethane prepolymer composed of toluene diisocyanate (TDI) and trimethylolpropane (TMP) Ethyl ester solution (manufactured by Tosoh Corporation, trade name "CORONATE L"). On the other hand, trimethylolpropane was dissolved in cyclopentanone so that the solid content concentration was 10%, to prepare a trimethylolpropane solution. Add the above trimethylolpropane solution to 100 parts of the 75% ethyl acetate solution of the above urethane prepolymer (manufactured by Tosoh Corporation, trade name "Coronate L") to prepolymerize the urethane Substance: The solid content ratio of trimethylolpropane is 90:10, and 0.1 part of dioctyl tin dilaurate catalyst (manufactured by Tokyo Fine Chemical CO., LTD., trade name "EMBILIZER OL-1") is added, and Using methyl isobutyl ketone as a solvent, a forming material (coating liquid) with a solid content concentration of 10% was prepared.

形成材B：在由二異氰酸甲苯酯與三羥甲丙烷構成的胺甲酸乙酯預聚物之75%乙酸乙酯溶液(Tosoh(東曹)公司製，商品名「CORONATE L」)100份中，加入二月桂酸二辛錫系觸媒(東京FINE CHIMICAL公司製，商品名「Embilizer OL-1」0.1份，並以甲基異丁基酮為溶劑使固體成分濃度為10%而調製出胺甲酸乙酯預聚物塗敷液。Forming material B: 75% ethyl acetate solution of urethane prepolymer composed of toluene diisocyanate and trimethylolpropane (manufactured by Tosoh Corporation, trade name "CORONATE L") 100 Add 0.1 part of dioctyl tin dilaurate catalyst (manufactured by Tokyo Fine Chemical Co., Ltd., trade name "Embilizer OL-1",” and use methyl isobutyl ketone as a solvent to make the solid content concentration 10%. Out the urethane prepolymer coating solution.

形成材C：將甲基丙烯酸甲酯97.0份、通式(1)：所示單體(通式(1e)之單體)3.0份、聚合引發劑(2,2'-偶氮雙(異丁腈))0.2份溶解於甲苯200份中。接著，於氮氣環境下一邊加熱至70℃一邊進行聚合反應5小時，而獲得聚合物(a)(固體成分濃度：33重量%)。所得聚合物(a)之重量平均分子量為85,000。 混合前述聚合物(a)15份與環氧樹脂(Mitsubishi Chemical Co.製，商品名：jER(註冊商標) YX7200B35)85份，調製出丙烯酸-環氧樹脂之形成材(塗敷液)。Forming material C: 97.0 parts of methyl methacrylate, general formula (1): 3.0 parts of the monomer (monomer of general formula (1e)), polymerization initiator (2,2'-azobis(iso Nitrile)) 0.2 part was dissolved in 200 parts of toluene. Next, the polymerization reaction was performed for 5 hours while heating to 70° C. in a nitrogen atmosphere to obtain a polymer (a) (solid content concentration: 33% by weight). The weight average molecular weight of the obtained polymer (a) was 85,000. 15 parts of the aforementioned polymer (a) and 85 parts of epoxy resin (manufactured by Mitsubishi Chemical Co., trade name: jER (registered trademark) YX7200B35) were mixed to prepare an acrylic-epoxy resin forming material (coating liquid).

>調製導電層之形成材> 以固體成分計，將含有10~50重量%之噻吩系聚合物的溶液(商品名：Denatron P-580W、Nagase ChemteX Co.製)8.6份、含有含

Figure 108143758-A0304-12-0059-1
唑啉基之丙烯酸聚合物的溶液(商品名：Epocros WS-700、(股)日本觸媒製)1份及水90.4份混合，調製出固體成分濃度為0.5重量%之導電層形成用塗佈液。所得導電層形成用塗佈液中含有0.04重量%之聚噻吩系聚合物、0.25重量%之含
Figure 108143758-A0304-12-0059-1
唑啉基丙烯酸聚合物。>Preparation of the conductive layer forming material> 8.6 parts of a solution (trade name: Denatron P-580W, manufactured by Nagase ChemteX Co.) containing 10-50% by weight of a thiophene-based polymer based on solid content, containing
Figure 108143758-A0304-12-0059-1
Mix 1 part of oxazoline-based acrylic polymer solution (trade name: Epocros WS-700, manufactured by Nippon Shokubai Co., Ltd.) and 90.4 parts of water to prepare a coating for forming a conductive layer with a solid content of 0.5% by weight liquid. The resulting coating solution for forming a conductive layer contained 0.04% by weight of polythiophene polymer and 0.25% by weight of
Figure 108143758-A0304-12-0059-1
Oxazoline acrylic polymer.

實施例1 (調製丙烯酸系聚合物(A)) 將含有丙烯酸丁酯99份及丙烯酸4-羥丁酯1份之單體混合物饋入具備攪拌葉片、溫度計、氮氣導入管、冷卻器的4口燒瓶中。並相對於前述單體混合物(固體成分)100份，將作為聚合引發劑之2,2’-偶氮雙異丁腈0.1份與乙酸乙酯100份一起饋入，一邊緩慢攪拌一邊導入氮氣進行氮取代後，將燒瓶內的液溫保持在55℃附近，進行8小時聚合反應，調製出重量平均分子量(Mw)160萬且Mw/Mn=3.7之丙烯酸系聚合物溶液。Example 1 (Preparation of acrylic polymer (A)) A monomer mixture containing 99 parts of butyl acrylate and 1 part of 4-hydroxybutyl acrylate was fed into a 4-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a cooler. With respect to 100 parts of the aforementioned monomer mixture (solid content), 0.1 part of 2,2'-azobisisobutyronitrile as a polymerization initiator and 100 parts of ethyl acetate were fed together, and nitrogen was introduced while slowly stirring. After the nitrogen substitution, the liquid temperature in the flask was maintained at around 55°C, and the polymerization reaction was performed for 8 hours to prepare an acrylic polymer solution with a weight average molecular weight (Mw) of 1.6 million and Mw/Mn=3.7.

(調製黏著劑組成物) 相對於上述所得丙烯酸系聚合物溶液之固體成分100份，摻混異氰酸酯交聯劑(三井化學公司製之Takenate D160N，三羥甲丙烷六亞甲基二異氰酸酯)0.1份、過氧化苯甲醯(日本油脂公司製之NYPER BMT)0.3份及含環氧基之矽烷耦合劑(信越化學工業公司製：X-41-1056)0.3份，而調製出丙烯酸系黏著劑組成物之溶液。(Preparation of adhesive composition) With respect to 100 parts of the solid content of the acrylic polymer solution obtained above, 0.1 part of isocyanate crosslinking agent (Takenate D160N manufactured by Mitsui Chemicals Co., Ltd., trimethylolpropane hexamethylene diisocyanate), and benzyl peroxide ( 0.3 parts of NYPER BMT manufactured by Nippon Oil & Fat Co., Ltd. and 0.3 parts of epoxy-containing silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.: X-41-1056) to prepare a solution of acrylic adhesive composition.

(製作黏著劑層) 接著，以使乾燥後的黏著劑層的厚度成為20μm，將上述丙烯酸系黏著劑組成物之溶液塗佈於經聚矽氧系剝離劑處理過之聚對苯二甲酸乙二酯薄膜(分離薄膜：三菱化學聚酯薄膜(股)製，MRF38)的單面上，並以155℃乾燥1分鐘，而於分離薄膜表面形成黏著劑層。(Making the adhesive layer) Next, so that the thickness of the dried adhesive layer becomes 20 μm, the solution of the acrylic adhesive composition is applied to a polyethylene terephthalate film (separation film) treated with a silicone release agent : Mitsubishi Chemical Polyester Film Co., Ltd., MRF38) on one side, and dried at 155°C for 1 minute to form an adhesive layer on the surface of the separation film.

>製作附透明層之單面保護偏光薄膜(1)> 以棒塗機將上述透明層之形成材A塗佈於上述單面保護偏光薄膜(1)的偏光件之面(偏光件之未設置透明保護薄膜的面)後，在60℃下施行12小時熱處理來進行，而形成了厚度3μm之胺甲酸乙酯樹脂層。>Making a single-sided protective polarizing film with a transparent layer (1)> After coating the transparent layer forming material A with a bar coater on the surface of the polarizer of the single-sided protective polarizing film (1) (the side of the polarizer without the transparent protective film), it was performed at 60°C for 12 hours The heat treatment was performed to form a urethane resin layer with a thickness of 3 μm.

>形成導電層> 將前述導電層形成用塗佈液以使乾燥後之厚度成為0.06μm之方式塗佈於前述附透明層之單面保護偏光薄膜(1)的透明層上，並於80℃下乾燥2分鐘後形成了導電層。所得導電層中分別含有8重量%之噻吩系聚合物、50重量%之含

Figure 108143758-A0304-12-0059-1
唑啉基丙烯酸聚合物。>Formation of conductive layer> The coating solution for forming a conductive layer is applied to the transparent layer of the single-sided protective polarizing film (1) with a transparent layer so that the thickness after drying becomes 0.06μm, and the temperature is 80°C After drying for 2 minutes, a conductive layer was formed. The resulting conductive layer contains 8% by weight of thiophene polymer and 50% by weight of
Figure 108143758-A0304-12-0059-1
Oxazoline acrylic polymer.

>製作附黏著劑層之單面保護偏光薄膜(1)> 接著，將形成於分離薄膜上的黏著劑層轉印至形成於前述附透明層之單面保護偏光薄膜(1)的導電層上，而製作出了附黏著劑層之單面保護偏光薄膜(1)。>Making a single-sided protective polarizing film with adhesive layer(1)> Next, the adhesive layer formed on the separation film was transferred to the conductive layer formed on the single-sided protective polarizing film with transparent layer (1), and the adhesive layer-attached single-sided protective polarizing film ( 1).

實施例2~9、比較例1~3、參考例 將實施例1中，如表1所示，將偏光薄膜之種類、調製丙烯酸系聚合物(A)所用單體混合物之組成、調製黏著劑組成物所用離子性化合物(B)之種類(EMI-FSI或Li-TFSI)或其摻混比率、黏著劑層之厚度、有無形成導電層、有無透明層之形成材、種類或其厚度變更成如表1所示，除此之外依與實施例1相同方式而製出附黏著劑層之單面保護(或雙面保護)偏光薄膜。 又，實施例9之透明層係以棒塗機將上述透明層之形成材C塗佈於上述單面保護偏光薄膜的偏光件之面(偏光件之未設置透明保護薄膜的面)後，在60℃下施行2分鐘熱處理來進行，而形成了厚度0.5μm之透明層。 比較例及參考例中並未形成透明層。 比較例1、比較例1、3中並未形成導電層。 參考例係於雙面保護偏光薄膜(2)之不具硬塗層之側依與實施例1相同方式形成導電層後，再於形成有導電層之面轉印黏著劑層。 離子性化合物(B)之摻混量係相對於丙烯酸系聚合物溶液之固體成分100份之值。Examples 2~9, Comparative Examples 1~3, Reference Examples In Example 1, as shown in Table 1, the type of polarizing film, the composition of the monomer mixture used to prepare the acrylic polymer (A), and the type of ionic compound (B) used to prepare the adhesive composition (EMI- FSI or Li-TFSI) or its blending ratio, the thickness of the adhesive layer, whether the conductive layer is formed, whether the transparent layer is formed, the type or its thickness are changed as shown in Table 1, except that it is in accordance with the embodiment 1 In the same way, a single-sided protective (or double-sided protective) polarizing film with an adhesive layer is prepared. In addition, the transparent layer of Example 9 was formed by coating the transparent layer forming material C on the surface of the polarizing member of the single-sided protective polarizing film (the side of the polarizing member on which the transparent protective film was not provided) with a bar coater. The heat treatment was performed at 60°C for 2 minutes to form a transparent layer with a thickness of 0.5 μm. In the comparative example and the reference example, no transparent layer was formed. In Comparative Examples 1, Comparative Examples 1, and 3, no conductive layer was formed. The reference example is to form a conductive layer on the side without a hard coat layer of the double-sided protective polarizing film (2) in the same manner as in Example 1, and then transfer the adhesive layer on the surface where the conductive layer is formed. The blending amount of the ionic compound (B) is relative to 100 parts of the solid content of the acrylic polymer solution.

針對上述實施例、比較例及參考性所得附黏著劑層之單面保護(或雙面保護)偏光薄膜進行以下的評估。將評估結果列於表1。The following evaluations were performed for the single-sided protective (or double-sided protective) polarizing film with the adhesive layer obtained in the above-mentioned examples, comparative examples and reference. The evaluation results are listed in Table 1.

>表面電阻值(Ω/□)：導電性> 導電層之表面電阻值係針對形成黏著劑層前之附導電層之單面保護(或雙面保護)偏光薄膜的導電層側表面進行測定。黏著劑層之表面電阻值係針對形成在分離薄膜上的黏著劑層表面進行測定。並從附黏著劑層之單面保護(或雙面保護)偏光薄膜剝離分離薄膜後，測定黏著劑層表面之表面電阻值，作為附黏著劑層之單面保護(或雙面保護)偏光薄膜之表面電阻值。測定是使用三菱化學ANALYTECH公司製MCP-HT450來進行。>Surface resistance (Ω/□): conductivity> The surface resistance of the conductive layer is measured on the conductive layer side surface of the single-sided protection (or double-sided protection) polarizing film with a conductive layer before forming the adhesive layer. The surface resistance of the adhesive layer is measured on the surface of the adhesive layer formed on the separation film. After peeling off the separation film from the single-sided protection (or double-sided protection) polarizing film with the adhesive layer, measure the surface resistance of the adhesive layer as a single-sided protection (or double-sided protection) polarizing film with the adhesive layer The surface resistance value. The measurement was performed using MCP-HT450 manufactured by Mitsubishi Chemical Analytech.

>評估端部褪色> 將在實施例及比較例中所得附黏著劑層之單面保護(或雙面保護)偏光薄膜裁切成50mm×50mm，並剝離分離薄膜後，透過黏著劑層將其貼合於1.2~1.5mm厚之鹼玻璃(松波硝子公司製，載玻片)，而製作出試樣。在將該試樣保持於60℃90%RH之高溫高濕環境下500小時之後，在下述條件下以微分干涉顯微鏡(Olympus製，製品名「MX-61L」)測定端部褪色量。端部褪色量係於試樣之四個角的對角線上，將連接顏色變得較中央部更淡的部分中最靠近中央部之處與角的直線距離定為端部褪色量(μm)，並將四個角之平均值定為該試樣的端部褪色量。 裝置：Olympus公司製，MX-61L 測定條件 透鏡倍率：5倍 ISO：200 快門速度：1/100 反射光量：刻度0 白平衡：自動 透射光控制器：LG-PS2 透射光量：刻度5 透射光偏光方向：對偏光薄膜透射軸呈正交偏光之方向>Assess end fading> The single-sided protection (or double-sided protection) polarizing film with the adhesive layer obtained in the examples and comparative examples was cut into 50mm×50mm, and the separation film was peeled off, and the adhesive layer was pasted to 1.2~1.5 mm thick alkali glass (manufactured by Matsuba Glass Co., Ltd., glass slide), and prepared a sample. After the sample was kept in a high temperature and high humidity environment of 60° C. and 90% RH for 500 hours, the amount of end discoloration was measured with a differential interference microscope (manufactured by Olympus, product name "MX-61L") under the following conditions. The amount of end fading is on the diagonal of the four corners of the sample, and the linear distance between the closest part and the corner of the part where the color becomes lighter than the center is defined as the amount of end fading (μm) , And set the average value of the four corners as the amount of fading at the end of the sample. Device: Olympus company system, MX-61L Measurement conditions Lens magnification: 5 times ISO: 200 Shutter speed: 1/100 The amount of reflected light: scale 0 White balance: automatic Transmitted light controller: LG-PS2 The amount of transmitted light: scale 5 Transmitted light polarization direction: the direction of orthogonal polarization to the transmission axis of the polarizing film

>ESD試驗> 從附黏著劑層之單面保護(或雙面保護)偏光薄膜剝除分離薄膜後，依表1所示貼合於內置型液晶單元或上置型液晶單元之視辨側，而作出內嵌觸控感測機能之液晶面板。即，實施例2~8、比較例3所得附黏著劑層之偏光薄膜係貼合於圖2所示之內置型液晶單元的第1透明基板，而形成第1黏著劑層及第1偏光薄膜。實施例1、比較例1、2及參考例所得附黏著劑層之偏光薄膜係貼合於圖4所示之上置型液晶單元之感測器層(觸控感測器部)，而形成第1黏著劑層及第1偏光薄膜。對前述液晶面板之偏光薄膜面發射ESD(靜電放電)槍(10kV)，測定因電氣而出現泛白之部分消失的時間，並以下述基準進行判斷。將其作為初始評估。 (評估基準) A：0.5秒以內。 B：大於0.5秒且在1秒以內。 C：大於1秒且在10秒以內。 D：大於10秒。 並針對所得內嵌觸控感測機能之液晶面板，於60℃/95%RH之加濕環境下投入250小時並於40℃下使其乾燥1小時後，進行與上述相同之評估。>ESD Test> After peeling off the separation film from the single-sided protection (or double-sided protection) polarizing film with the adhesive layer, attach it to the visible side of the built-in liquid crystal cell or the top-mounted liquid crystal cell as shown in Table 1, and make an in-line touch The LCD panel that controls the sensing function. That is, the polarizing film with the adhesive layer obtained in Examples 2 to 8 and Comparative Example 3 was bonded to the first transparent substrate of the built-in liquid crystal cell shown in FIG. 2 to form the first adhesive layer and the first polarizing film . The polarizing film with the adhesive layer obtained in Example 1, Comparative Examples 1, 2 and the Reference Example was attached to the sensor layer (touch sensor portion) of the over-mounted liquid crystal cell shown in FIG. 4 to form the first 1 Adhesive layer and first polarizing film. For the polarizing film surface-emitting ESD (electrostatic discharge) gun (10kV) of the aforementioned liquid crystal panel, the time for the electric whitening part to disappear was measured, and the judgment was made based on the following criteria. Use this as the initial assessment. (Assessment criteria) A: Within 0.5 seconds. B: More than 0.5 second and within 1 second. C: More than 1 second and within 10 seconds. D: More than 10 seconds. And for the obtained liquid crystal panel with embedded touch sensing function, put it in a humidified environment of 60°C/95%RH for 250 hours and dry it at 40°C for 1 hour, then perform the same evaluation as above.

[表1]

Figure 02_image009
[Table 1]
Figure 02_image009

表1中： BA表示丙烯酸丁酯、 NVP表示N-乙烯基-2-吡咯啶酮、 HBA表示丙烯酸4-羥丁酯、 AA表示丙烯酸、 EMI-FSI表示乙基甲基咪唑鎓雙(氟磺醯基醯亞胺)、 Li‐TFSI表示雙(三氟甲磺醯基)醯亞胺鋰。in FIG. 1: BA means butyl acrylate, NVP stands for N-vinyl-2-pyrrolidone, HBA stands for 4-hydroxybutyl acrylate, AA means acrylic, EMI-FSI stands for ethyl methyl imidazolium bis (fluorosulfonyl imide), Li-TFSI stands for lithium bis(trifluoromethanesulfonyl) imide.

如表1所示可知，本發明附黏著劑層之偏光薄膜即便於單面保護偏光薄膜之前述偏光件側設有導電層之情況下，仍可於加濕環境下抑制偏光件端部褪色，且即便於黏著劑層含有離子性化合物時仍可於加濕環境下抑制黏著劑層之電阻值上升。As shown in Table 1, it can be seen that even if the polarizing film with adhesive layer of the present invention is provided with a conductive layer on the polarizer side of the single-sided protective polarizing film, it can still prevent the end of the polarizer from fading in a humidified environment. And even when the adhesive layer contains an ionic compound, the resistance value of the adhesive layer can be suppressed from increasing in a humidified environment.

1:附黏著劑層之偏光薄膜 11:單面保護偏光薄膜、第1偏光薄膜 a:偏光件 b:透明保護薄膜 c:透明層 d:導電層 21:黏著劑層 12:第2偏光薄膜 21,22:第1、第2黏著劑層 3:液晶層 41,42:第1、第2透明基板 5:觸控感測器部 6:驅動電極兼感測器部 7:驅動電極 C:液晶單元1: Polarizing film with adhesive layer 11: Single-sided protective polarizing film, first polarizing film a: Polarizing parts b: Transparent protective film c: transparent layer d: conductive layer 21: Adhesive layer 12: The second polarizing film 21, 22: The first and second adhesive layers 3: Liquid crystal layer 41, 42: The first and second transparent substrates 5: Touch sensor section 6: Drive electrode and sensor part 7: Drive electrode C: Liquid crystal cell

圖1係顯示本發明附黏著劑層之偏光薄膜之一例的截面圖。 圖2係顯示使用有本發明附黏著劑層之偏光薄膜的附觸控感測機能之液晶面板之一例的截面圖。 圖3係顯示使用有本發明附黏著劑層之偏光薄膜的附觸控感測機能之液晶面板之一例的截面圖。 圖4係顯示使用有本發明附黏著劑層之偏光薄膜的附觸控感測機能之液晶面板之一例的截面圖。Fig. 1 is a cross-sectional view showing an example of the polarizing film with an adhesive layer of the present invention. 2 is a cross-sectional view showing an example of a liquid crystal panel with touch sensing function using a polarizing film with an adhesive layer of the present invention. 3 is a cross-sectional view showing an example of a liquid crystal panel with touch sensing function using the polarizing film with the adhesive layer of the present invention. 4 is a cross-sectional view showing an example of a liquid crystal panel with touch sensing function using the polarizing film with the adhesive layer of the present invention.

1:附黏著劑層之偏光薄膜 1: Polarizing film with adhesive layer

11:單面保護偏光薄膜 11: Single-sided protection polarizing film

a:偏光件 a: Polarizing parts

b:透明保護薄膜 b: Transparent protective film

c:透明層 c: transparent layer

d:導電層 d: conductive layer

21:黏著劑層 21: Adhesive layer

Claims (21)

一種附黏著劑層之偏光薄膜，具有偏光薄膜及黏著劑層； 該附黏著劑層之偏光薄膜之特徵在於： 前述偏光薄膜具有偏光件、僅於前述偏光件之單面具有透明保護薄膜及於前述偏光件之另一面隔著透明層具有導電層，該透明層係直接形成於前述偏光件上且厚度為10μm以下，並且前述黏著劑層係隔著前述導電層設置。A polarizing film with an adhesive layer, having a polarizing film and an adhesive layer; The characteristics of the polarizing film with adhesive layer are: The polarizing film has a polarizing member, a transparent protective film is provided on only one side of the polarizing member, and a conductive layer is provided on the other side of the polarizing member via a transparent layer. The transparent layer is directly formed on the polarizing member and has a thickness of 10 μm Hereinafter, the adhesive layer is provided via the conductive layer. 如請求項1之附黏著劑層之偏光薄膜，其中前述透明層為含有胺甲酸乙酯預聚物的形成材之硬化物，該胺甲酸乙酯預聚物係異氰酸酯化合物與多元醇的反應物。The polarizing film with an adhesive layer of claim 1, wherein the transparent layer is a cured product of a forming material containing a urethane prepolymer, and the urethane prepolymer is a reaction product of an isocyanate compound and a polyol . 如請求項2之附黏著劑層之偏光薄膜，其中前述異氰酸酯化合物含有選自二異氰酸甲苯酯及二苯甲烷二異氰酸酯中之至少任一種。The polarizing film with an adhesive layer according to claim 2, wherein the aforementioned isocyanate compound contains at least any one selected from toluene diisocyanate and diphenylmethane diisocyanate. 如請求項1之附黏著劑層之偏光薄膜，其中前述透明層含有環氧樹脂。The polarizing film with an adhesive layer according to claim 1, wherein the transparent layer contains epoxy resin. 如請求項1之附黏著劑層之偏光薄膜，其中前述透明層為下述樹脂組成物，該樹脂組成物包含： (a)聚合物，其係藉由將大於50重量份之丙烯酸系單體與大於0重量份且小於50重量份之下述通式(1)所示單體聚合而得者： [化學式1]
Figure 03_image001
(式中，X表示含有選自於由乙烯基、(甲基)丙烯醯基、苯乙烯基、(甲基)丙烯醯胺基、乙烯基醚基、環氧基、氧雜環丁烷基、羥基、胺基、醛基及羧基所構成群組中之至少1種反應性基的官能基，R1 及R2 分別獨立表示氫原子、可具有取代基之脂肪族烴基、可具有取代基之芳基或可具有取代基之雜環基，R1 及R2 可相互連結形成環)；及 (b)環氧樹脂；並且 前述聚合物(a)與環氧樹脂(b)之含有比例以重量比計為95：5~60：40或40：60~1：99。The polarizing film with an adhesive layer of claim 1, wherein the transparent layer is the following resin composition, the resin composition comprising: (a) a polymer, which is obtained by adding more than 50 parts by weight of an acrylic monomer It is obtained by polymerizing more than 0 parts by weight and less than 50 parts by weight of the monomer represented by the following general formula (1): [Chemical formula 1]
Figure 03_image001
(In the formula, X represents a group selected from vinyl, (meth)acryloyl, styryl, (meth)acrylamido, vinyl ether, epoxy, oxetanyl A functional group of at least one reactive group in the group consisting of, hydroxyl, amino, aldehyde, and carboxyl groups, R 1 and R 2 each independently represent a hydrogen atom, an aliphatic hydrocarbon group that may have a substituent, and a substituent that may have a substituent The aryl group or the heterocyclic group which may have a substituent, R 1 and R 2 may be connected to each other to form a ring); and (b) epoxy resin; and the content ratio of the aforementioned polymer (a) and epoxy resin (b) In terms of weight ratio, it is 95:5~60:40 or 40:60~1:99. 如請求項5之附黏著劑層之偏光薄膜，其中前述通式(1)中X所示官能基為下述通式(2)所示官能基： 通式(2)：Z-Y-(式中，Z表示含有選自於由乙烯基、(甲基)丙烯醯基、苯乙烯基、(甲基)丙烯醯胺基、乙烯基醚基、環氧基、氧雜環丁烷基、羥基、胺基、醛基及羧基所構成群組中之至少1種反應性基的官能基，Y表示有機基)。The polarizing film with adhesive layer of claim 5, wherein the functional group represented by X in the aforementioned general formula (1) is a functional group represented by the following general formula (2): General formula (2): ZY-(In the formula, Z means containing selected from vinyl, (meth)acrylic acid group, styryl group, (meth)acrylic acid amino group, vinyl ether group, epoxy A functional group of at least one reactive group in the group consisting of a oxetanyl group, an oxetanyl group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group, and Y represents an organic group). 如請求項1至6中任一項之附黏著劑層之偏光薄膜，其中前述導電層之厚度為1μm以下。The polarizing film with an adhesive layer according to any one of claims 1 to 6, wherein the thickness of the aforementioned conductive layer is 1 μm or less. 如請求項1至7中任一項之附黏著劑層之偏光薄膜，其中前述導電層含有導電性聚合物。The polarizing film with an adhesive layer according to any one of claims 1 to 7, wherein the conductive layer contains a conductive polymer. 如請求項1至8中任一項之附黏著劑層之偏光薄膜，其中前述導電層含有選自聚噻吩、聚苯胺、奈米碳管中之至少1種。The polarizing film with an adhesive layer according to any one of claims 1 to 8, wherein the conductive layer contains at least one selected from polythiophene, polyaniline, and carbon nanotubes. 如請求項1至9中任一項之附黏著劑層之偏光薄膜，其中前述黏著劑層係由含有(甲基)丙烯酸系聚合物(A)之黏著劑組成物所形成。The polarizing film with an adhesive layer according to any one of claims 1 to 9, wherein the adhesive layer is formed of an adhesive composition containing a (meth)acrylic polymer (A). 如請求項1至10中任一項之附黏著劑層之偏光薄膜，其中前述黏著劑層係由含有(甲基)丙烯酸系聚合物(A)及離子性化合物(B)之黏著劑組成物所形成。The polarizing film with an adhesive layer according to any one of claims 1 to 10, wherein the adhesive layer is composed of an adhesive composition containing a (meth)acrylic polymer (A) and an ionic compound (B) Formed. 如請求項10或11之附黏著劑層之偏光薄膜，其中前述(甲基)丙烯酸系聚合物(A)含有(甲基)丙烯酸烷基酯(a1)及含醯胺基單體(a2)作為單體單元。The polarizing film with an adhesive layer according to claim 10 or 11, wherein the (meth)acrylic polymer (A) contains an alkyl (meth)acrylate (a1) and an amine group-containing monomer (a2) As a monomer unit. 如請求項12之附黏著劑層之偏光薄膜，其中前述含醯胺基單體(a2)為含N-乙烯基內醯胺系單體。According to claim 12, the polarizing film with an adhesive layer, wherein the aforementioned amide group-containing monomer (a2) is an N-vinyl lactam-containing monomer. 如請求項12或13之附黏著劑層之偏光薄膜，其中前述含醯胺基單體(a2)作為單體單元於前述(甲基)丙烯酸系聚合物(A)中含有0.1重量%以上。According to claim 12 or 13, the polarizing film with an adhesive layer, wherein the aforementioned amide group-containing monomer (a2) is contained as a monomer unit in the aforementioned (meth)acrylic polymer (A) by 0.1% by weight or more. 如請求項11至14中任一項之附黏著劑層之偏光薄膜，其中前述離子性化合物(B)為鹼金屬鹽，且前述黏著劑層的表面電阻值為1×1010 ~1×1012 Ω/□。An adhesive layer-attached polarizing film according to any one of claims 11 to 14, wherein the ionic compound (B) is an alkali metal salt, and the surface resistance of the adhesive layer is 1×10 10 to 1×10 12 Ω/□. 如請求項11至14中任一項之附黏著劑層之偏光薄膜，其中前述離子性化合物(B)為有機陽離子-陰離子鹽，且前述黏著劑層的表面電阻值為1×108 ~1×1010 Ω/□。The polarizing film with an adhesive layer according to any one of claims 11 to 14, wherein the aforementioned ionic compound (B) is an organic cation-anion salt, and the surface resistance of the aforementioned adhesive layer is 1×10 8 ~1 ×10 10 Ω/□. 如請求項11至16中任一項之附黏著劑層之偏光薄膜，其中前述離子性化合物(B)相對於前述(甲基)丙烯酸系聚合物(A)100重量份含有0.01重量份以上。The polarizing film with an adhesive layer according to any one of claims 11 to 16, wherein the ionic compound (B) contains 0.01 parts by weight or more relative to 100 parts by weight of the (meth)acrylic polymer (A). 如請求項1至17中任一項之附黏著劑層之偏光薄膜，其中前述透明保護薄膜為纖維素樹脂薄膜或(甲基)丙烯酸樹脂薄膜。The polarizing film with an adhesive layer according to any one of claims 1 to 17, wherein the aforementioned transparent protective film is a cellulose resin film or a (meth)acrylic resin film. 一種影像顯示面板，其特徵在於：具有如請求項1至18中任一項之附黏著劑層之偏光薄膜。An image display panel, characterized in that it has a polarizing film with an adhesive layer as claimed in any one of claims 1 to 18. 如請求項19之影像顯示面板，其中於具有液晶層及觸控感測器部之內嵌觸控感測機能之液晶單元上貼合有前述附黏著劑層之偏光薄膜的黏著劑層。Such as the image display panel of claim 19, wherein the adhesive layer of the polarizing film with the adhesive layer is attached to the liquid crystal cell with the liquid crystal layer and the touch sensor part with the built-in touch sensing function. 一種影像顯示裝置，其特徵在於：具有如請求項19或20之影像顯示面板。An image display device, characterized in that it has an image display panel as in claim 19 or 20.
TW108143758A 2018-11-29 2019-11-29 Polarizing film with adhesive layer and image display device TWI839423B (en)

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JP2018223653 2018-11-29
JP2018-223653 2018-11-29
JP2019214359A JP7372824B2 (en) 2018-11-29 2019-11-27 Polarizing film with adhesive layer and image display device
JP2019-214359 2019-11-27

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