TW201538659A - Adhesive layer and adhesive film - Google Patents

Adhesive layer and adhesive film Download PDF

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TW201538659A
TW201538659A TW104122869A TW104122869A TW201538659A TW 201538659 A TW201538659 A TW 201538659A TW 104122869 A TW104122869 A TW 104122869A TW 104122869 A TW104122869 A TW 104122869A TW 201538659 A TW201538659 A TW 201538659A
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meth
adhesive
adhesive layer
film
acrylate
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TW104122869A
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TWI568814B (en
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Takeshi Nagakura
Ryuusuke Shimaguchi
Ryo Hasegawa
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Fujimori Kogyo Co
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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 
    • G02F1/165—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 translational movement of particles in a fluid under the influence of an applied field
    • G02F1/166—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 translational movement of particles in a fluid under the influence of an applied field characterised by the electro-optical or magneto-optical effect
    • G02F1/167—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 translational movement of particles in a fluid under the influence of an applied field characterised by the electro-optical or magneto-optical effect by electrophoresis
    • 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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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Theoretical Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • Health & Medical Sciences (AREA)
  • Human Computer Interaction (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polarising Elements (AREA)

Abstract

The present invention provides an adhesive layer having high adhesive strength and high adherence perfomances irrespective of being a thin film having a thickness of 1 to 20 [mu]m, and an adhesive film using the same. In accordance with the present invention, an adhesive layer in which an adhesive composition comprising an acrylic-based polymer is cross-linked, wherein the adhesive composition contains at least one or more alkyl (meth)acrylate monomers having a C1 to C14 alkyl group as the main component meth(acrylate) monomer and, as other copolymerizable monomers, at least one or more nitrogen-containing vinyl monomers and at least one or more carboxyl group-containing copolymerizable vinyl monomers and/or hydroxyl group-containing copolymerizable vinyl monomers; the thickness of the adhesive layer is 1 to 20 [mu]m; and the adhesive strength when the thickness is 5 [mu]m is 4.0 (N/25 mm) or more, is provided.

Description

黏著劑層及黏著膜 Adhesive layer and adhesive film

本發明涉及一種用於光學構件的層間貼合等的黏著劑層及使用該黏著劑層的黏著膜，該黏著劑層雖然是厚度只有1μm~20μm的薄膜，但具有高黏著力和高附著性。 The present invention relates to an adhesive layer for interlayer bonding or the like of an optical member, and an adhesive film using the adhesive layer, which is a film having a thickness of only 1 μm to 20 μm, but has high adhesion and high adhesion. .

為了藉由黏著劑層將偏光板、相位差板等光學構件貼合在液晶單元等被黏附體上，提出了各種黏著膜(例如，參照專利文獻1~2)。 In order to bond an optical member such as a polarizing plate or a retardation film to an adherend such as a liquid crystal cell by an adhesive layer, various adhesive films have been proposed (for example, refer to Patent Documents 1 and 2).

為了藉由黏著劑層將偏光板、相位差板等光學構件貼合在液晶單元等被黏附體上，提出了各種黏著膜(例如，參照專利文獻1~2)。 In order to bond an optical member such as a polarizing plate or a retardation film to an adherend such as a liquid crystal cell by an adhesive layer, various adhesive films have been proposed (for example, refer to Patent Documents 1 and 2).

專利文獻1中記載了一種將丙烯酸丁酯等作為主要成分的單體，並含有丙烯醯胺化合物等的光學用黏著劑組合物。 Patent Document 1 describes an optical adhesive composition containing a butyl acrylate or the like as a main component and containing an acrylamide compound or the like.

專利文獻2中記載了一種將具有碳原子數為4~8的烷基的(甲基)丙烯酸酯作為主要成分單體，並含有含羧基的單體及含氮的乙烯基單體的光學用黏著劑組合物。 Patent Document 2 describes an optical device in which a (meth) acrylate having an alkyl group having 4 to 8 carbon atoms is used as a main component monomer, and a carboxyl group-containing monomer and a nitrogen-containing vinyl monomer are contained. Adhesive composition.

另外，為了提高黏著劑層的折射率，經過反復研究提出了多種黏著膜(例如，參照專利文獻3~8)。 Further, in order to increase the refractive index of the adhesive layer, various adhesive films have been proposed through repeated studies (for example, refer to Patent Documents 3 to 8).

專利文獻3中記載了一種具有芳環並含有折射率為1.51~1.75的增黏劑的光學用黏著劑組合物。 Patent Document 3 describes an optical adhesive composition having an aromatic ring and containing a tackifier having a refractive index of 1.51 to 1.75.

專利文獻4中記載了一種使用了含共聚性聚合物的黏著劑組合物的黏著片，該共聚性聚合物是含芳環的丙烯酸改性單體的共聚性聚合物。 Patent Document 4 describes an adhesive sheet using an adhesive composition containing a copolymerizable polymer which is a copolymerizable polymer of an aromatic ring-containing acrylic modified monomer.

專利文獻5中記載了一種含有具有芳環的增黏樹脂和芳香族磷酸酯類增塑劑的光學用黏著劑組合物。 Patent Document 5 describes an optical adhesive composition containing a tackifier resin having an aromatic ring and an aromatic phosphate plasticizer.

專利文獻6中記載了一種由黏著劑組合物固化而成的黏著劑，該黏著劑組合物包括：丙烯酸類樹脂；以及含一個乙烯性不飽和基團的芳香族化合物。 Patent Document 6 describes an adhesive formed by curing an adhesive composition comprising: an acrylic resin; and an aromatic compound containing one ethylenically unsaturated group.

專利文獻7中記載了一種通過含芳香族單體的丙烯酸類黏著劑將相位差膜和雙折射板相互固定而成的光學元件。 Patent Document 7 describes an optical element in which a retardation film and a birefringent plate are fixed to each other by an acrylic adhesive containing an aromatic monomer.

專利文獻8中記載了一種含有聚胺酯樹脂的黏著劑組合物，該聚胺酯樹脂是使芳香族二異氰酸酯和芳香族聚酯二醇反應而成。 Patent Document 8 describes an adhesive composition containing a polyurethane resin obtained by reacting an aromatic diisocyanate with an aromatic polyester diol.

近年來，為了實現光學構件的薄膜化，要求用於 光學構件的層間貼合的黏著膜是黏著劑層為厚度20μm以下薄層的黏著膜。 In recent years, in order to realize thin film formation of optical members, it is required to be used for The adhesive film to which the layers of the optical member are bonded is an adhesive film in which the adhesive layer is a thin layer having a thickness of 20 μm or less.

通常，黏著劑層的黏著力與黏著劑層的厚度大致成比例，因此，如果將黏著劑層的厚度變薄，隨之會降低黏著力。 Generally, the adhesive force of the adhesive layer is approximately proportional to the thickness of the adhesive layer. Therefore, if the thickness of the adhesive layer is made thinner, the adhesive force is lowered.

但是，近年來要求黏著膜具有如下性能：即使將 黏著劑層的厚度變薄，也具有與以往的黏著膜(黏著劑層是厚度約為30μm的厚層)同等的黏著力，並且對於高溫、高濕環境下長時間放置後的耐久性，也具有與以往的黏著膜同等以上的性能。 However, in recent years, adhesive films have been required to have the following properties: The thickness of the adhesive layer is also reduced, and it has the same adhesive force as the conventional adhesive film (the adhesive layer is a thick layer having a thickness of about 30 μm), and the durability after long-term placement in a high-temperature and high-humidity environment is also It has the same performance as the conventional adhesive film.

另外，從能夠將黏著劑層的厚度變薄並能夠形成無需實施 時效處理(在恆溫下實施熟化)的黏著劑層的觀點出發，要求形成為NCF(Non Carrier Film，非承載膜)的形態，其具有包括去掉了黏著膜的基材後的黏著劑層的、“脫模膜/黏著劑層/脫模膜”的構件構成。 In addition, the thickness of the adhesive layer can be reduced and can be formed without implementation From the viewpoint of the aging treatment (curing at a constant temperature), it is required to be formed into an NCF (Non Carrier Film) having an adhesive layer including a base material from which an adhesive film has been removed. The component structure of the "release film/adhesive layer/release film".

此外，在以往的黏著膜中，由於在被黏附體上貼 合黏著膜後實施時效處理，因此，能夠提高被黏附體和黏著劑層之間的附著性。 In addition, in the past adhesive film, due to sticking on the adhered body The aging treatment is carried out after the film is adhered, so that the adhesion between the adherend and the adhesive layer can be improved.

但是，採用NCF形態的黏著膜在將黏著膜貼合在被黏附體之前，已經完成了黏著劑層的時效處理，因此被黏附體與黏著劑層之間的附著性不足。基於此，存在需要對被黏附體的表面進行電暈處理等表面處理的問題。 However, the adhesive film using the NCF form has completed the aging treatment of the adhesive layer before the adhesive film is attached to the adherend, and thus the adhesion between the adhered body and the adhesive layer is insufficient. Based on this, there is a problem that it is necessary to perform surface treatment such as corona treatment on the surface of the adherend.

因此需要一種滿足這些要求和克服這些問題的黏著膜。 There is therefore a need for an adhesive film that meets these requirements and overcomes these problems.

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

【專利文獻1】日本特開2012-177022號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-177022

【專利文獻2】日本特開2012-201734號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-201734

【專利文獻3】日本特開2007-084762號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-084762

【專利文獻4】日本特開2011-153169號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2011-153169

【專利文獻5】日本特開2012-167188號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2012-167188

【專利文獻6】日本特開2012-021148號公報 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2012-021148

【專利文獻7】日本特開2006-293281號公報 [Patent Document 7] Japanese Patent Laid-Open Publication No. 2006-293281

【專利文獻8】日本特開2009-091522號公報 [Patent Document 8] Japanese Patent Laid-Open Publication No. 2009-091522

本發明是鑒於上述事情而完成的發明，其課題在於，提供一種雖然是厚度為1μm~20μm的薄膜，但具有高黏著力和高附著性的黏著劑層及使用該黏著劑層的黏著膜。 The present invention has been made in view of the above circumstances, and an object of the invention is to provide an adhesive layer having high adhesion and high adhesion, and an adhesive film using the adhesive layer, although the film has a thickness of 1 μm to 20 μm.

為了解決上述課題，本發明將以下作為技術思想：在使包括丙烯酸類聚合物的黏著劑組合物交聯而成的黏著劑層中，將烷基碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體中的至少一種作為主要成分的單體，並含有作為其他共聚合性單體之可共聚的含氮乙烯基單體中的至少一種以上，藉由共聚和交聯形成具有堅韌的黏著力和高附著性的黏著劑層。 In order to solve the above problems, the present invention has a technical idea of (meth) having an alkyl group having a carbon number of C1 to C14 in an adhesive layer obtained by crosslinking an adhesive composition comprising an acrylic polymer. a monomer having at least one of an alkyl acrylate monomer as a main component and containing at least one of a copolymerizable nitrogen-containing vinyl monomer as another copolymerizable monomer, formed by copolymerization and crosslinking Tough adhesion and high adhesion adhesive layer.

此外，為瞭解決上述課題，本發明提供一種黏著劑層，其是使包括丙烯酸類聚合物的黏著劑組合物交聯而成，其中，該黏著劑組合物含有作為主要成分的(甲基)丙烯酸酯單體之烷基碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體中的至少一種以上，並含有作為其他共聚合性單體之含氮的乙烯基單體中的至少一種以上、含羧基的共聚合性乙烯基單體和/或含羥基的共聚合性乙烯基單體中的至少一種以上，而且，該黏著劑層的厚度為1μm~20μm，厚度5μm時的黏著力為4.0(N/25mm)以上。 Further, in order to solve the above problems, the present invention provides an adhesive layer obtained by crosslinking an adhesive composition comprising an acrylic polymer containing (meth) as a main component. The acrylate monomer has at least one of an alkyl (meth) acrylate monomer having an alkyl group having a C1 to C14 alkyl group, and contains a nitrogen-containing vinyl monomer as another copolymerizable monomer. At least one or more of at least one of a carboxyl group-containing copolymerizable vinyl monomer and/or a hydroxyl group-containing copolymerizable vinyl monomer, and the thickness of the adhesive layer is from 1 μm to 20 μm and a thickness of 5 μm The adhesion is 4.0 (N/25mm) or more.

此外，較佳為該黏著劑組合物包括：相對於含有(A)烷基碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體中的至少一種以上的作為主要成分的(甲基)丙烯酸酯單體100重量份，含有5~50重量份的(B)含氮的乙烯基單體中的一種以上和0.1~5重量份的(C)含羧基的共聚合性乙烯基單 體和/或含羥基的共聚合性乙烯基單體中的至少一種以上的重均分子量為20萬~200萬的共聚物；以及0.01~5重量份的(D)交聯劑。 Further, it is preferable that the adhesive composition comprises at least one or more of the (meth)acrylic acid alkyl ester monomers having a CA to C14 alkyl group (A) as a main component (A) 100 parts by weight of the acrylate monomer, containing 5 to 50 parts by weight of one or more of (B) nitrogen-containing vinyl monomers and 0.1 to 5 parts by weight of (C) carboxyl group-containing copolymerized vinyl monomer A copolymer having at least one of a bulk and/or a hydroxyl group-containing copolymerizable vinyl monomer having a weight average molecular weight of 200,000 to 2,000,000; and 0.01 to 5 parts by weight of a (D) crosslinking agent.

此外，該黏著劑組合物在該主要成分的(甲基)丙烯酸酯單體100重量份內，較佳為含有20重量份以上的丙烯酸甲酯單體。 Further, the adhesive composition preferably contains 20 parts by weight or more of a methyl acrylate monomer in 100 parts by weight of the (meth) acrylate monomer of the main component.

此外，在該黏著劑組合物中，相對於該作為主要成分的(甲基)丙烯酸酯單體100重量份，較佳為含羧基的共聚合性乙烯基單體中的一種以上的含量為2.0重量份以下和/或含羥基的共聚合性乙烯基單體中的一種以上的含量為5.0重量份以下。 In the adhesive composition, it is preferred that the content of one or more of the carboxyl group-containing copolymerizable vinyl monomers is 2.0 based on 100 parts by weight of the (meth) acrylate monomer as the main component. The content of one or more of the parts by weight or less and/or the hydroxyl group-containing copolymerizable vinyl monomer is 5.0 parts by weight or less.

此外，該黏著劑層的折射率較佳為1.47~1.50。 Further, the adhesive layer preferably has a refractive index of 1.47 to 1.50.

此外，本發明提供一種在脫模膜的單面形成有該黏著劑層並具有脫模膜/黏著劑層/脫模膜的構成的黏著膜。 Further, the present invention provides an adhesive film having a structure in which the adhesive layer is formed on one surface of a release film and has a release film/adhesive layer/release film.

此外，本發明提供一種在基材的單面層疊上述黏著劑層而成的黏著膜。 Further, the present invention provides an adhesive film in which the above-mentioned adhesive layer is laminated on one surface of a substrate.

此外，本發明提供一種使用了上述黏著膜的偏光板週邊構件用膜。 Moreover, the present invention provides a film for a peripheral member of a polarizing plate using the above adhesive film.

此外，本發明提供一種使用了上述黏著膜的觸控面板用膜。 Further, the present invention provides a film for a touch panel using the above adhesive film.

此外，本發明提供一種使用了上述黏著膜的電子紙用膜。 Further, the present invention provides a film for an electronic paper using the above adhesive film.

此外，本發明提供一種使用了上述黏著膜的有機EL(Electro-Luminescence)用膜。 Further, the present invention provides a film for organic EL (Electro-Luminescence) using the above adhesive film.

此外，本發明提供一種在光學膜的至少一個面上層疊上述黏著劑層而成的帶有黏著劑層的光學膜。 Further, the present invention provides an optical film with an adhesive layer formed by laminating the above-mentioned adhesive layer on at least one surface of an optical film.

根據本發明，能夠滿足以往技術中的要求事項以及克服以往技術中存在的問題，能夠提供一種雖然厚度只有1μm~20μm薄膜，但具有高黏著力、高附著性的黏著劑層及使用該黏著劑層的黏著膜。 According to the present invention, it is possible to satisfy the requirements in the prior art and overcome the problems in the prior art, and it is possible to provide an adhesive layer having high adhesion and high adhesion even though a film having a thickness of only 1 μm to 20 μm, and the use of the adhesive. Adhesive film of the layer.

下面，根據較佳的實施方式對本發明進行說明。 Hereinafter, the present invention will be described based on preferred embodiments.

本發明的黏著劑層是使包括丙烯酸類聚合物的黏著劑組合物交聯而成，其中，該黏著劑組合物含有作為主要成分的(甲基)丙烯酸酯單體之烷基碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體中的至少一種以上，並含有作為其他共聚合性單體之含氮的乙烯基單體中的至少一種以上、含羧基的共聚合性乙烯基單體和/或含羥基的共聚合性乙烯基單體中的至少一種以上，而且，該黏著劑層的厚度為1μm~20μm，厚度5μm時的黏著力為4.0(N/25mm)以上。 The adhesive layer of the present invention is obtained by crosslinking an adhesive composition comprising an acrylic polymer, wherein the adhesive composition contains, as a main component, a (meth) acrylate monomer having an alkyl carbon number of At least one or more of the alkyl (meth) acrylate monomers of C1 to C14, and at least one or more of the nitrogen-containing vinyl monomers as the other copolymerizable monomer, the carboxyl group-containing copolymerized ethylene At least one of the base monomer and/or the hydroxyl group-containing copolymerizable vinyl monomer, and the adhesive layer has a thickness of 1 μm to 20 μm and an adhesive force of 4.0 (N/25 mm) or more at a thickness of 5 μm.

作為烷基碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體，可以舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲 基)丙烯酸2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯等中的至少一種以上。(甲基)丙烯酸烷基酯單體中的烷基可以是直鏈、支鏈、環狀中的任意一種。相對於黏合劑組合物的丙烯酸類聚合物(共聚物)100重量份，烷基碳原子數為C1~C14的(甲基)丙烯酸酯單體的比例較佳為50~95重量份。 Examples of the (meth)acrylic acid alkyl ester monomer having an alkyl group having C1 to C14 include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. Isopropyl methacrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, ( Octyl methacrylate, isooctyl (meth)acrylate, (A) 2-ethylhexyl acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, (methyl) At least one of lauryl acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like More than one. The alkyl group in the alkyl (meth) acrylate monomer may be any of a straight chain, a branched chain, and a cyclic group. The proportion of the (meth) acrylate monomer having an alkyl group having a C1 to C14 alkyl group is preferably 50 to 95 parts by weight based on 100 parts by weight of the acrylic polymer (copolymer) of the binder composition.

此外，在本發明的黏著劑層中，對黏著劑組合物而言，在由烷基碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體中的一種以上組成的主要成分即(甲基)丙烯酸酯單體100重量份內，含有20重量份以上的丙烯酸甲酯的單體，由此，能夠將黏著劑層的折射率提高為1.47以上。 Further, in the adhesive layer of the present invention, the main component of the adhesive composition is one or more of alkyl (meth) acrylate monomers having an alkyl group having C1 to C14. The monomer having 20 parts by weight or more of methyl acrylate monomer in 100 parts by weight of the (meth) acrylate monomer can increase the refractive index of the pressure-sensitive adhesive layer to 1.47 or more.

本發明的黏著劑組合物中，作為主要成分的(甲基) 丙烯酸酯單體，還可以含有含芳基的(甲基)丙烯酸酯單體中的一種以上。作為含芳基的(甲基)丙烯酸酯單體，可以舉出(甲基)丙烯酸苄酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苯氧乙酯、(甲基)丙烯酸苯氧丁酯、(甲基)丙烯酸2-(1-萘氧基)乙酯、(甲基)丙烯酸2-(2-萘氧基)乙酯、(甲基)丙烯酸6-(1-萘氧基)己酯、(甲基)丙烯酸6-(2-萘氧基)己酯、(甲基)丙烯酸8-(1-萘氧基)辛酯、(甲基)丙烯酸8-(2-萘氧基)辛酯等。為了得到折射率高的黏著劑層，較佳為配合至少一種以上的含芳基的(甲基)丙烯酸酯單體。 (meth) as a main component in the adhesive composition of the present invention The acrylate monomer may further contain one or more of aryl group-containing (meth) acrylate monomers. Examples of the aryl group-containing (meth) acrylate monomer include benzyl (meth) acrylate, naphthyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxy (meth) acrylate. Butyl ester, 2-(1-naphthalenyloxy)ethyl (meth)acrylate, 2-(2-naphthalenyloxy)ethyl (meth)acrylate, 6-(1-naphthyloxy)(meth)acrylate Hexyl ester, 6-(2-naphthyloxy)hexyl (meth)acrylate, 8-(1-naphthalenyloxy)octyl (meth)acrylate, 8-(2-naphthyloxy)(meth)acrylate Base) octyl ester and the like. In order to obtain an adhesive layer having a high refractive index, at least one or more aryl group-containing (meth) acrylate monomers are preferably blended.

藉由將這些含芳基的(甲基)丙烯酸酯單體與作為 主要成分的單體即烷基碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體加以混合，能夠使所得到的黏著劑層的折射率提高而進行調整，減小光學構件間的折射率差，降低全反射，由此能夠提高全光線透過率。在本發明的黏著劑層中，當黏著劑組合物含有含芳基的(甲基)丙烯酸酯單體的情況下，其含量相對於作為主要成分的(甲基)丙烯酸酯單體100重量份，較佳為5~30重量份。 By using these aryl-containing (meth) acrylate monomers as The monomer of the main component, that is, the alkyl (meth) acrylate monomer having an alkyl group having C1 to C14, can be adjusted to increase the refractive index of the obtained adhesive layer, and the optical member can be reduced. The difference in refractive index reduces total reflection, thereby increasing the total light transmittance. In the adhesive layer of the present invention, when the adhesive composition contains an aryl group-containing (meth) acrylate monomer, the content thereof is 100 parts by weight based on the (meth) acrylate monomer as a main component. Preferably, it is 5 to 30 parts by weight.

此外，藉由使含芳基的(甲基)丙烯酸酯單體共聚，具有比在上述主要成分的(甲基)丙烯酸酯單體100重量份內含有20重量份以上的丙烯酸甲酯單體來提高黏著劑層的折射率，能夠進一步提高黏著劑層的折射率的效果。 Further, by copolymerizing the aryl group-containing (meth) acrylate monomer, it has 20 parts by weight or more of methyl acrylate monomer in 100 parts by weight of the (meth) acrylate monomer of the above main component. Increasing the refractive index of the adhesive layer can further increase the refractive index of the adhesive layer.

此外，如上所述，作為提高黏著劑層的折射率的方法有兩種方法，即，在作為主要成分的(甲基)丙烯酸酯單體100重量份內含有20重量份以上的丙烯酸甲酯單體的方法和使含芳基的(甲基)丙烯酸酯單體共聚的方法，可以單獨地採用每個方法，但更較佳為並用這兩種方法。 Further, as described above, as a method of increasing the refractive index of the adhesive layer, there are two methods of containing 20 parts by weight or more of methyl acrylate alone in 100 parts by weight of the (meth) acrylate monomer as a main component. The method of the bulk and the method of copolymerizing the aryl group-containing (meth) acrylate monomer may be carried out by using each method individually, but it is more preferred to use both methods in combination.

作為含氮的乙烯基單體，例如可以舉出N-乙烯基 吡咯烷酮、N-乙烯基己內醯胺、(甲基)丙烯醯16啉等環狀氮乙烯基化合物；N-乙基-N-甲基(甲基)丙烯醯胺、N-甲基-N-丙基(甲基)丙烯醯胺、N-甲基-N-異丙基(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,N-二丙基(甲基)丙烯醯胺、N,N-二異丙基(甲基)丙烯醯胺、N,N-二丁基(甲基)丙烯醯胺等二烷基取代(甲基)丙烯醯胺；(甲基)丙烯酸N-乙基-N-甲基胺乙酯、(甲基)丙烯酸N-甲基-N-丙基胺乙酯、 (甲基)丙烯酸N-甲基-N-異丙基胺乙酯、(甲基)丙烯酸N,N-二甲基胺甲酯、(甲基)丙烯酸N,N-二甲基胺乙酯、(甲基)丙烯酸N,N-二甲基胺丙酯、(甲基)丙烯酸N,N-二甲基胺丁酯、(甲基)丙烯酸N,N-二丙基胺乙酯、(甲基)丙烯酸N,N-二丁基胺乙酯等(甲基)丙烯酸二烷基胺酯；N-乙基-N-甲基胺丙基(甲基)丙烯醯胺、N-甲基-N-丙基胺丙基(甲基)丙烯醯胺、N-甲基-N-異丙基胺丙基(甲基)丙烯醯胺、N,N-二甲基胺丙基(甲基)丙烯醯胺、N,N-二乙基胺丙基(甲基)丙烯醯胺、N,N-二丙基胺丙基(甲基)丙烯醯胺、N,N-二甲基胺乙基(甲基)丙烯醯胺、N,N-二乙基胺乙基(甲基)丙烯醯胺等二烷基取代胺基烷基(甲基)丙烯醯胺等中的至少一種以上。 As the nitrogen-containing vinyl monomer, for example, N-vinyl may be mentioned. a cyclic nitrogen vinyl compound such as pyrrolidone, N-vinyl caprolactam, (meth) propylene sulfonium 16 or the like; N-ethyl-N-methyl (meth) acrylamide, N-methyl-N -propyl (meth) acrylamide, N-methyl-N-isopropyl (meth) acrylamide, N,N-dimethyl(meth) acrylamide, N,N-diethyl (meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-dibutyl (methyl a dialkyl-substituted (meth)acrylamide such as acrylamide; N-ethyl-N-methylamine ethyl (meth)acrylate; N-methyl-N-propylamine (meth)acrylate Ethyl ester, N-methyl-N-isopropylamine ethyl (meth)acrylate, N,N-dimethylamine methyl (meth)acrylate, N,N-dimethylamine ethyl (meth)acrylate , N,N-dimethylaminopropyl (meth)acrylate, N,N-dimethylamine (meth)acrylate, N,N-dipropylamine ethyl (meth)acrylate, ( Dialkylamine (meth)acrylate such as N,N-dibutylamine ethyl methacrylate; N-ethyl-N-methylaminopropyl (meth) acrylamide, N-methyl -N-propylaminopropyl (meth) acrylamide, N-methyl-N-isopropylamine propyl (meth) acrylamide, N,N-dimethylaminopropyl (methyl Acrylamide, N,N-diethylaminopropyl (meth) acrylamide, N,N-dipropylaminopropyl (meth) acrylamide, N,N-dimethylamine At least one of a dialkyl-substituted aminoalkyl (meth) acrylamide such as a (meth)acrylamide or an N,N-diethylamineethyl(meth)acrylamide or the like.

為了能夠與後述(C)的化合物區別，作為上述含氮 的乙烯基單體，較佳為不含有羥基，更較佳為不含有羥基和羧基。作為這種單體，較佳為上述例示的單體，例如，含有N,N-二烷基取代胺基或N,N-二烷基取代醯胺基的丙烯酸類單體；N-乙烯基吡咯烷酮、N-乙烯基己內醯胺等N-乙烯基取代內醯胺類；N-(甲基)丙烯醯16啉等N-(甲基)丙烯醯基取代環狀胺類。 In order to be able to distinguish from the compound (C) described later, as the above nitrogen-containing compound The vinyl monomer preferably does not contain a hydroxyl group, and more preferably does not contain a hydroxyl group or a carboxyl group. As such a monomer, preferred are the above-exemplified monomers, for example, an acrylic monomer containing an N,N-dialkyl substituted amine group or an N,N-dialkyl substituted decylamino group; N-vinyl group N-vinyl substituted indoleamines such as pyrrolidone and N-vinyl caprolactam; and N-(methyl)acrylinyl substituted cyclic amines such as N-(meth)acrylofluorene 16-phenyl.

此外，在本發明的黏著劑層中，黏著劑組合物所 含有的含氮的乙烯基單體，能夠賦予黏著劑層必要的黏著力和耐久性。在本發明的黏著劑層中，黏著劑組合物中含有的含氮乙烯基單體的含量相對於主要成分的(甲基)丙烯酸酯單體100重量份較佳為5~50重量份。 Further, in the adhesive layer of the present invention, an adhesive composition body Containing a nitrogen-containing vinyl monomer, it imparts the necessary adhesion and durability to the adhesive layer. In the adhesive layer of the present invention, the content of the nitrogen-containing vinyl monomer contained in the adhesive composition is preferably 5 to 50 parts by weight based on 100 parts by weight of the (meth) acrylate monomer of the main component.

此外，在本發明的黏著劑層中，作為黏著劑組合物含有的含氮的乙烯基單體，特別較佳為使用N-乙烯基吡咯烷酮、N,N- 二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N,N-二丙基(甲基)丙烯醯胺、N,N-二異丙基(甲基)丙烯醯胺、N,N-二丁基(甲基)丙烯醯胺、N,N-二甲基胺丙基(甲基)丙烯醯胺、N,N-二乙基胺丙基(甲基)丙烯醯胺、N,N-二甲基胺乙基(甲基)丙烯醯胺、N-乙烯基己內醯胺等。 Further, in the adhesive layer of the present invention, as the nitrogen-containing vinyl monomer contained in the adhesive composition, it is particularly preferred to use N-vinylpyrrolidone, N, N- Dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N, N-diisopropyl ( Methyl) acrylamide, N,N-dibutyl(meth) acrylamide, N,N-dimethylaminopropyl (meth) acrylamide, N,N-diethylaminopropyl (Meth) acrylamide, N,N-dimethylamine ethyl (meth) acrylamide, N-vinyl caprolactam, and the like.

作為含有羧基的共聚合性乙烯基單體(含有羧基的 單體)，例如可以舉出(甲基)丙烯酸、(甲基)丙烯酸羧乙酯、(甲基)丙烯酸羧戊酯、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基馬來酸、羧基聚己酸內酯單(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基四氫鄰苯二甲酸等中的至少一種以上。 As a carboxyl group-containing copolymerizable vinyl monomer (containing a carboxyl group) Examples of the monomer) include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, and 2-(methyl)acryloxyethyl hexahydrophthalic acid. , 2-(Methyl)acryloxypropylhexahydrophthalic acid, 2-(meth)acryloxyethyl phthalate, 2-(meth)acryloxyethyl amber Acid, 2-(meth) propylene oxiranyl ethyl maleic acid, carboxy polycaprolactone mono(meth) acrylate, 2-(methyl) propylene oxiranyl ethyl tetrahydrophthalic acid At least one of the above.

此外，在本發明的黏著劑層中，黏著劑組合物所含有的含羧基的單體能夠賦予黏著劑層必要的凝聚力。在本發明的黏著劑層中，黏著劑組合物中含有的含羧基的單體的含量相對於主要成分的(甲基)丙烯酸酯單體100重量份較佳為0.1~5重量份。 Further, in the adhesive layer of the present invention, the carboxyl group-containing monomer contained in the adhesive composition can impart the necessary cohesive force to the adhesive layer. In the adhesive layer of the present invention, the content of the carboxyl group-containing monomer contained in the adhesive composition is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the (meth) acrylate monomer of the main component.

作為含羥基的共聚合性乙烯基單體(含羥基的單 體)，例如可以舉出(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸羥基乙酯等(甲基)丙烯酸羥基烷基酯類，N-羥基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥乙基(甲基)丙烯醯胺等含羥基的(甲基)丙烯醯胺類等中的至少一種以上。 As a hydroxyl group-containing copolymerizable vinyl monomer (hydroxyl-containing single Examples of the compound include 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and hydroxyethyl (meth)acrylate. Hydroxyalkyl methacrylates, hydroxyl groups such as N-hydroxy(methyl) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide At least one of (meth) acrylamide and the like.

此外，在本發明的黏著劑層中，黏著劑組合物含有的含羥 基的單體是作為用於減少含羧基的單體含量的共聚合性單體來使用，該含羧基的單體使所得到的黏著劑層對透明導電性膜的ITO表面等易腐蝕的被黏附體的腐蝕性產生影響。因此，含羥基的單體能夠有助於提高黏著劑層的黏著力，並且有助於減少腐蝕性。在本發明的黏著劑層中，黏著劑組合物中含有的含羥基的單體的含量相對於主要成分的(甲基)丙烯酸酯單體100重量份較佳為0.1~5重量份。 Further, in the adhesive layer of the present invention, the adhesive composition contains a hydroxyl group The monomer of the group is used as a copolymerizable monomer for reducing the content of a carboxyl group-containing monomer which causes the obtained adhesive layer to be corroded to the surface of the ITO of the transparent conductive film. The corrosive nature of the adherent has an effect. Therefore, the hydroxyl group-containing monomer can contribute to the adhesion of the adhesive layer and contribute to the reduction of corrosion. In the adhesive layer of the present invention, the content of the hydroxyl group-containing monomer contained in the adhesive composition is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the (meth) acrylate monomer of the main component.

對用於本發明黏著劑層的黏著劑組合物的共聚物 而言，相對於100重量份的(A)作為主要成分的(甲基)丙烯酸酯單體、即烷基碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體中的至少一種以上，較佳為含有5~50重量份的(B)含氮的乙烯基單體中的一種以上和0.1~5重量份的(C)含羧基的共聚合性乙烯基單體和/或含羥基的共聚合性乙烯基單體中的至少一種以上。 Copolymer of an adhesive composition for use in the adhesive layer of the present invention In terms of at least one of 100 parts by weight of (A) a (meth) acrylate monomer as a main component, that is, an alkyl (meth) acrylate monomer having an alkyl group having C1 to C14; The above is preferably one or more of (B) a nitrogen-containing vinyl monomer and 0.1 to 5 parts by weight of (C) a carboxyl group-containing copolymerizable vinyl monomer and/or a content of 5 to 50 parts by weight. At least one or more of the hydroxyl group-containing copolymerizable vinyl monomers.

此外，相對於主要成分的(甲基)丙烯酸酯單體100重量份，較佳為含有一種以上的含羧基的共聚合性乙烯基單體2.0重量份以下和/或一種以上的含羥基的共聚合性乙烯基單體5.0重量份以下。 Further, it is preferably contained in an amount of 2.0 parts by weight or less and/or one or more kinds of hydroxyl groups containing one or more kinds of carboxyl group-containing copolymerizable vinyl monomers, based on 100 parts by weight of the (meth) acrylate monomer of the main component. The polymerizable vinyl monomer is 5.0 parts by weight or less.

對共聚物的聚合方法沒有特別的限定，可以使用 溶液聚合法、乳液聚合法等適宜的公知的聚合方法。共聚物的重均分子量較佳為20萬~200萬。 The polymerization method of the copolymer is not particularly limited and can be used. A suitable known polymerization method such as a solution polymerization method or an emulsion polymerization method. The weight average molecular weight of the copolymer is preferably from 200,000 to 2,000,000.

上述共聚物較佳為丙烯酸類聚合物，較佳為含有(甲基)丙烯酸酯單體或(甲基)丙烯酸、(甲基)丙烯醯胺類等丙烯酸類單體50~100重量%。 The copolymer is preferably an acrylic polymer, and preferably contains 50 to 100% by weight of an acrylic monomer such as a (meth) acrylate monomer or a (meth)acrylic acid or a (meth) acrylamide.

在上述黏著劑組合物中，藉由對上述共聚物配合交聯劑、適宜的任意添加劑，能夠調整所需的物理性質等特性。 In the above adhesive composition, characteristics such as desired physical properties can be adjusted by blending the above-mentioned copolymer with a crosslinking agent and a suitable optional additive.

作為交聯劑，例如可以舉出六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、二苯甲烷二異氰酸酯、甲苯二異氰酸酯、苯二甲基二異氰酸酯等二異氰酸酯類的縮二脲改性體或異氰脲酸酯改性體；與三羥甲基丙烷或甘油等三價以上的多元醇的加成物等的聚異氰酸酯化合物；金屬類螯合物；環氧化合物等中的至少一種以上。此外，也可以藉由紫外線等光交聯來使黏著劑進行交聯。 Examples of the crosslinking agent include biuret modified diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, and benzodimethyl diisocyanate. Or an isocyanurate-modified product; at least one of a polyisocyanate compound such as an adduct of a trivalent or higher polyhydric alcohol such as trimethylolpropane or glycerin; a metal chelate compound; an epoxy compound; . Further, the adhesive may be crosslinked by photocrosslinking such as ultraviolet rays.

在使用交聯劑來使共聚物交聯的情況下，較佳為共聚物具有能夠與交聯劑進行交聯反應的官能團(根據交聯劑的種類可以選擇羥基或羧基等)，而且較佳為含有在側鏈具有這些官能團的單體。此外，較佳為黏著劑組合物含有0.01~5重量份的(D)交聯劑。此外，重量份的基準與上述共聚物中的(A)至(C)相同。 In the case where a crosslinking agent is used to crosslink the copolymer, it is preferred that the copolymer has a functional group capable of crosslinking reaction with a crosslinking agent (a hydroxyl group or a carboxyl group may be selected depending on the kind of the crosslinking agent), and preferably. It is a monomer having these functional groups in a side chain. Further, it is preferred that the adhesive composition contains 0.01 to 5 parts by weight of the (D) crosslinking agent. Further, the basis of the parts by weight is the same as (A) to (C) in the above copolymer.

作為其他任意成分，可以適宜地配合矽烷偶聯劑、抗氧化劑、表面活性劑、固化促進劑、增塑劑、填充劑、交聯催化劑、交聯抑制劑、固化抑制劑、加工助劑、防老化劑等公知的添加劑。這些添加劑可以單獨使用或並用兩種以上使用。 As other optional components, a decane coupling agent, an antioxidant, a surfactant, a curing accelerator, a plasticizer, a filler, a crosslinking catalyst, a crosslinking inhibitor, a curing inhibitor, a processing aid, and an anti-proof agent can be suitably blended. A well-known additive such as an aging agent. These additives may be used singly or in combination of two or more.

本發明的黏著劑層可以藉由在基材或脫模膜上塗布上述黏著劑組合物後，使黏著劑組合物交聯而得到。 The pressure-sensitive adhesive layer of the present invention can be obtained by coating the above-mentioned pressure-sensitive adhesive composition on a substrate or a release film, and then crosslinking the pressure-sensitive adhesive composition.

希望用於光學構件的層間貼合的黏著劑層是薄的黏著劑層，較佳為上述黏著劑層的厚度為1μm~20μm。而且，通常黏著劑層的黏著力與黏著劑層的厚度大致成比例，但較佳為厚度 5μm時的黏著力為4.0(N/25mm)以上。此外，當黏著劑層的厚度不為5μm的情況下，“厚度5μm時的黏著力”(N/25mm)，可將黏著劑層的厚度記為T(μm)、將黏著劑層的黏著力記為F(N/25mm)，並藉由算式“(厚度5μm時的黏著力)=5F/T”來推算。 It is desirable that the adhesive layer for interlayer bonding of the optical member is a thin adhesive layer, and it is preferable that the thickness of the above adhesive layer is from 1 μm to 20 μm. Moreover, usually the adhesion of the adhesive layer is approximately proportional to the thickness of the adhesive layer, but preferably the thickness The adhesion at 5 μm was 4.0 (N/25 mm) or more. Further, when the thickness of the adhesive layer is not 5 μm, the "adhesion at a thickness of 5 μm" (N/25 mm), the thickness of the adhesive layer can be referred to as T (μm), and the adhesive force of the adhesive layer. It is denoted as F (N/25 mm) and is estimated by the formula "(adhesion at a thickness of 5 μm) = 5 F/T".

當將本發明的黏著劑層用於光學構件的層間貼合 等的情況下，為了減少黏著劑層與光學構件的介面上的光線的反射，希望折射率差儘可能小。因此，上述黏著劑層的折射率較佳為1.47~1.50。 When the adhesive layer of the present invention is used for interlayer bonding of optical members In the case of the like, in order to reduce the reflection of light on the interface between the adhesive layer and the optical member, it is desirable that the refractive index difference be as small as possible. Therefore, the refractive index of the above adhesive layer is preferably from 1.47 to 1.50.

本發明的黏著膜可藉由在基材或脫模膜的單面形 成本發明的黏著劑層來製備。 The adhesive film of the present invention can be formed by a single surface on a substrate or a release film The adhesive layer of the invention is prepared.

作為用於形成黏著劑層的基材膜或保護黏著面的脫模膜(隔膜)，可以使用聚酯膜等樹脂膜等。 A resin film such as a polyester film or the like can be used as the release film (separator) for forming the base film of the pressure-sensitive adhesive layer or the protective adhesive surface.

對基材膜而言，可在樹脂膜的與形成有黏著劑層一側相反的面上，實施藉由矽酮類、氟類的脫模劑或塗層劑、二氧化矽微粒等進行的防污處理，可實施藉由抗靜電劑的塗布或混入等進行的抗靜電處理。 The base film can be formed on the surface of the resin film opposite to the side on which the adhesive layer is formed by an anthrone or a fluorine-based release agent, a coating agent, cerium oxide particles or the like. The antifouling treatment can be carried out by an antistatic treatment by application or mixing of an antistatic agent.

對剝離膜而言，在與黏著劑層的黏著面進行貼合 一側的面上，實施藉由矽酮類、氟類的脫模劑等進行的脫模處理。 For the release film, it is bonded to the adhesive surface of the adhesive layer. On one surface, a release treatment by an anthrone or a fluorine-based release agent is carried out.

藉由在一個黏著劑層的兩面分別貼合脫模膜的實施了脫模處理的面，能夠形成“脫模膜/黏著劑層/脫模膜”的構成。在此情況下，藉由將兩側的脫模膜依次或同時剝離而露出黏著面，從而能夠與光學膜等光學構件貼合。作為光學膜，可以舉 出偏光膜、相位差膜、防反射膜、防眩(防閃光)膜、紫外線吸收膜、紅外線吸收膜、光學補償膜、亮度提高膜等。 The "release film/adhesive layer/release film" can be formed by bonding the surface of the release film to the mold release film on both surfaces of one adhesive layer. In this case, the release film on both sides can be peeled off sequentially or simultaneously to expose the adhesive surface, and can be bonded to an optical member such as an optical film. As an optical film, it can be mentioned A polarizing film, a retardation film, an antireflection film, an antiglare (antiglare) film, an ultraviolet absorbing film, an infrared absorbing film, an optical compensation film, a brightness enhancement film, and the like.

本發明的黏著膜可用於以偏光板為主的液晶顯示 器的週邊構件用各種光學膜、觸控面板用各種光學膜、電子紙用各種光學膜、有機EL用各種光學膜等的貼合中。 The adhesive film of the invention can be used for liquid crystal display mainly based on polarizing plate The peripheral member of the device is used for bonding various optical films, various optical films for touch panels, various optical films for electronic paper, various optical films for organic EL, and the like.

另外，可在這些光學膜的至少單面上層疊上述黏著劑層而製備帶有黏著劑層的光學膜。具體地，可以舉出“光學膜/黏著劑層/光學膜”、“光學膜/黏著劑層/脫模膜”、“光學膜/黏著劑層”、“光學膜/黏著劑層/光學膜/黏著劑層/光學膜”、“光學膜/黏著劑層/光學膜/黏著劑層/脫模膜”、“脫模膜/黏著劑層/光學膜/黏著劑層/脫模膜”等構成。 Further, the above-mentioned adhesive layer may be laminated on at least one side of these optical films to prepare an optical film with an adhesive layer. Specifically, “optical film/adhesive layer/optical film”, “optical film/adhesive layer/release film”, “optical film/adhesive layer”, “optical film/adhesive layer/optical film” /Adhesive layer / optical film", "optical film / adhesive layer / optical film / adhesive layer / release film", "release film / adhesive layer / optical film / adhesive layer / release film", etc. Composition.

例如，如“光學膜/黏著劑層/脫模膜”，具有由脫模膜保護的黏著劑層的情況下，藉由剝掉脫模膜而露出像“光學膜/黏著劑層”那樣的黏著劑層，並與其他光學膜進行貼合，能夠得到將黏著劑層用於層間貼合的如“光學膜/黏著劑層/光學膜”的構成。 For example, in the case of an "optical film/adhesive layer/release film" having an adhesive layer protected by a release film, a release film such as an "optical film/adhesive layer" is exposed by peeling off the release film. The adhesive layer is bonded to other optical films to obtain a structure in which an adhesive layer is used for interlayer bonding such as "optical film/adhesive layer/optical film".

【實施例】 [Examples]

下面藉由實施例具體說明本發明。 The invention will be specifically described below by way of examples.

<丙烯酸共聚物的製備> <Preparation of acrylic acid copolymer> [實施例1] [Example 1]

向具有攪拌機、溫度計、回流冷凝器及氮導入管的反應裝置中導入氮氣，從而將反應器內的空氣置換為氮氣。之後，向反應裝置內加入丙烯酸丁酯70重量份、丙烯酸甲酯30重量份、N-甲基吡咯烷酮10重量份、丙烯酸1.5重量份、丙烯酸 6-羥基己酯0.5重量份及溶劑(乙酸乙酯)60重量份。之後，經過2小時滴入0.1重量份的作為聚合引發劑的偶氮二異丁腈，在65℃下使其反應6小時，得到了重均分子量為50萬的、用於實施例1的丙烯酸共聚物溶液1。取丙烯酸共聚物的一部分，用作後述的酸值測定試樣。 Nitrogen gas was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube to replace the air in the reactor with nitrogen. Thereafter, 70 parts by weight of butyl acrylate, 30 parts by weight of methyl acrylate, 10 parts by weight of N-methylpyrrolidone, 1.5 parts by weight of acrylic acid, and acrylic acid were added to the reaction apparatus. 0.5 parts by weight of 6-hydroxyhexyl ester and 60 parts by weight of a solvent (ethyl acetate). Thereafter, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise thereto over 2 hours, and the mixture was reacted at 65 ° C for 6 hours to obtain an acrylic acid used in Example 1 having a weight average molecular weight of 500,000. Copolymer solution 1. A part of the acrylic copolymer was taken and used as an acid value measurement sample described later.

[實施例2~6及比較例1~3] [Examples 2 to 6 and Comparative Examples 1 to 3]

除了如表1的(A)、(B)、(C-1)、(C-2)中所述分別調整了各單體的組成以外，與上述用於實施例1的丙烯酸共聚物溶液1同樣地進行操作，得到了用於實施例2~6及比較例1~3的丙烯酸共聚物溶液。在此，雖沒有特別示出測定結果，但實施例2~6及比較例1~3的丙烯酸共聚物溶液中含有的共聚物的重均分子量在20萬~200萬的範圍內。 The acrylic copolymer solution 1 used in the above Example 1 was prepared except that the composition of each monomer was adjusted as described in (A), (B), (C-1), and (C-2) of Table 1. The acrylic copolymer solution used in Examples 2 to 6 and Comparative Examples 1 to 3 was obtained in the same manner. Here, the measurement results are not particularly shown, but the copolymers contained in the acrylic copolymer solutions of Examples 2 to 6 and Comparative Examples 1 to 3 have a weight average molecular weight of 200,000 to 2,000,000.

<黏著劑組合物、黏著劑層及黏著膜的製備> <Preparation of Adhesive Composition, Adhesive Layer and Adhesive Film> [實施例1] [Example 1]

在如上述製備的實施例1的丙烯酸共聚物溶液1中加入Coronate L-45(甲苯二異氰酸酯(TDI)化合物的加成物)0.3重量份並進行攪拌混合，得到了實施例1的黏著劑組合物。將該黏著劑組合物塗布於由塗有矽酮樹脂的聚對苯二甲酸乙二醇酯(PET)膜構成的剝離膜上，然後在90℃下進行乾燥而去除溶劑。之後，藉由在23℃、50%RH的環境下實施7天的時效處理，獲得了在剝離膜的單面具有黏著劑層的實施例1的黏著膜，該黏著劑層是使黏著劑組合物交聯而成。 To the acrylic copolymer solution 1 of Example 1 prepared as described above, 0.3 parts by weight of Coronate L-45 (adduct of toluene diisocyanate (TDI) compound) was added and stirred and mixed to obtain an adhesive composition of Example 1. Things. This adhesive composition was applied onto a release film composed of a polyethylene terephthalate (PET) film coated with an anthrone resin, and then dried at 90 ° C to remove the solvent. Thereafter, an adhesive film of Example 1 having an adhesive layer on one side of the release film was obtained by performing an aging treatment for 7 days in an environment of 23 ° C and 50% RH, and the adhesive layer was an adhesive combination. The matter is cross-linked.

[實施例2~6及比較例1~3] [Examples 2 to 6 and Comparative Examples 1 to 3]

除了如表1的(D)所述分別調整了添加劑的組成以外，與 上述實施例1的黏著膜同樣地進行操作，得到了實施例2~6及比較例1~3的黏著膜。 In addition to the composition of the additive adjusted as described in (D) of Table 1, The adhesive film of the above Example 1 was similarly operated, and the adhesive films of Examples 2 to 6 and Comparative Examples 1 to 3 were obtained.

表1中，括弧內的數值表示以(A)組的合計重量設 為100重量份而求出的(B)~(D)組的重量份的數值。 In Table 1, the numerical values in parentheses indicate the total weight of the group (A). The value of the parts by weight of the (B) to (D) group determined for 100 parts by weight.

另外，將與表1中使用的各成分的簡稱對應的化合物名稱示於表2中。在此，Coronate(註冊商標)L-45為日本聚胺酯工業(股)公司的商品名稱，D-110N為三井化學(股)公司的商品名稱。TDI指甲苯二異氰酸酯，XDI指苯二甲基二異氰酸酯。 Further, the names of the compounds corresponding to the abbreviations of the respective components used in Table 1 are shown in Table 2. Here, Coronate (registered trademark) L-45 is the trade name of Japan Polyurethane Industry Co., Ltd., and D-110N is the trade name of Mitsui Chemicals Co., Ltd. TDI refers to toluene diisocyanate and XDI refers to benzenedimethyl diisocyanate.

<試驗方法及評價> <Test method and evaluation>

從實施例1~6和比較例1~3的黏著膜剝掉剝離膜(塗有矽酮樹脂的PET膜)而露出黏著劑層，並將黏著劑層轉移至偏光板(膜)的單面上。 The release film (PET film coated with an oxime resin) was peeled off from the adhesive films of Examples 1 to 6 and Comparative Examples 1 to 3 to expose the adhesive layer, and the adhesive layer was transferred to one side of the polarizing plate (film). on.

<黏著力的測定方法> <Method for measuring adhesion>

將黏著劑層轉移至厚度180μm的偏光板(膜)的單面，從而得到了作為試樣的黏著膜(帶有黏著劑層的光學膜)。 The adhesive layer was transferred to one side of a polarizing plate (film) having a thickness of 180 μm to obtain an adhesive film (an optical film with an adhesive layer) as a sample.

用壓緊輥將該黏著膜貼合在用丙酮清洗過的鈉鈣玻璃的 非錫面上。之後，在50℃、0.5MPa×20分鐘的條件下進行高壓鍋處理後，回到23℃×50%RH的環境，藉由拉伸試驗機測定經過1小時後的黏著膜的剝離強度。根據JIS Z0237《黏著帶、黏著片試驗方法》進行測定，將以300mm/min的速度向180°方向剝離時的剝離強度作為黏著膜的黏著劑層的黏著力。 The adhesive film is attached to the soda lime glass washed with acetone by a pinch roller Non-tin surface. Thereafter, the autoclave treatment was carried out under the conditions of 50 ° C and 0.5 MPa × 20 minutes, and then returned to an environment of 23 ° C × 50% RH, and the peeling strength of the adhesive film after one hour passed was measured by a tensile tester. According to JIS Z0237 "Adhesive tape and adhesive sheet test method", the peel strength at the time of peeling at 180 mm/min in the 180° direction was used as the adhesive force of the adhesive layer of the adhesive film.

<附著性的試驗方法> <Test method for adhesion>

用目視確認測定黏著力後的試樣的黏著膜的黏著劑層，並以從基材層的偏光板(膜)脫落的狀態，判斷其附著性。 The adhesive layer of the adhesive film of the sample after the measurement of the adhesive force was visually confirmed, and the adhesion was judged in a state of being peeled off from the polarizing plate (film) of the base material layer.

○．．黏著劑層完全没有從基材層脫落。 ○. . The adhesive layer did not fall off from the substrate layer at all.

△．．黏著劑層的一部分從基材層分離而脫落。 △. . A part of the adhesive layer separates from the substrate layer and falls off.

×．．黏著劑層從基材層脫落而附著在被黏附體的玻璃上。 ×. . The adhesive layer is detached from the substrate layer and adheres to the glass of the adherend.

<耐久性的試驗方法> <Test method for durability>

將藉由與黏著力的測定同樣的方法製備的10cm見方的黏著膜，用同樣的方法貼合在鈉鈣玻璃的非錫面上，從而獲得了試樣。將該試樣放置在60℃×90%RH的環境下250小時後，取出至23℃×50%RH的環境，用目視觀察1小時後的黏著膜的狀態，從而判斷耐久性。 A 10 cm square adhesive film prepared by the same method as the measurement of the adhesive force was applied to the non-tin surface of the soda lime glass in the same manner to obtain a sample. The sample was placed in an environment of 60° C.×90% RH for 250 hours, and then taken out to an environment of 23° C.×50% RH, and the state of the adhesive film after 1 hour was visually observed to determine the durability.

○．．黏著膜完全没有產生剝離及發泡。 ○. . The adhesive film did not cause peeling and foaming at all.

△．．黏著膜的一部分產生了剝離及發泡。 △. . A part of the adhesive film is peeled off and foamed.

×．．黏著膜的整體產生了剝離及發泡。 ×. . The entire adhesive film is peeled and foamed.

<折射率的測定方法> <Method for Measuring Refractive Index>

用阿貝折射儀(製造商：ERMA，型號：ER-2S)測定23℃下的黏著劑層的折射率。 The refractive index of the adhesive layer at 23 ° C was measured using an Abbe refractometer (manufacturer: ERMA, model: ER-2S).

表3中示出了評價結果。 The evaluation results are shown in Table 3.

在實施例1~6的黏著膜中，厚度5μm的黏著劑層 的黏著力為4.0N/25mm以上、黏著劑層的折射率在1.47~1.50的範圍內、並且附著性及耐久性也優異。即，實施例1~6的黏著膜能夠滿足所需要求及克服問題。 In the adhesive films of Examples 1 to 6, an adhesive layer having a thickness of 5 μm The adhesive force is 4.0 N/25 mm or more, and the refractive index of the adhesive layer is in the range of 1.47 to 1.50, and the adhesion and durability are also excellent. That is, the adhesive films of Examples 1 to 6 can satisfy the required requirements and overcome the problems.

使用實施例1、3的黏著劑組合物，並用相同的方法製備了黏著劑層厚度為3μm、5μm、10μm、15μm、20μm的黏著膜，並測定了黏著力，將其結果示於表4中。可知使用了實施例1、3的黏著劑組合物的黏著劑層的黏著力如眾所周知的那樣與黏著劑層的厚度大致成比例。 Using the adhesive compositions of Examples 1 and 3, adhesive films having adhesive layer thicknesses of 3 μm, 5 μm, 10 μm, 15 μm, and 20 μm were prepared in the same manner, and the adhesion was measured, and the results are shown in Table 4. . It is understood that the adhesive strength of the adhesive layer using the adhesive compositions of Examples 1 and 3 is substantially proportional to the thickness of the adhesive layer as is well known.

比較例1的黏著膜也許是因為黏著劑組合物中不 含有含氮的單體，其厚度5μm的黏著劑層的黏著力弱。而且，黏著劑層的折射率低、附著性及耐久性也差。 The adhesive film of Comparative Example 1 may be because the adhesive composition is not The adhesive containing a nitrogen-containing monomer having a thickness of 5 μm has a weak adhesive force. Further, the adhesive layer has a low refractive index, and also has poor adhesion and durability.

比較例2的黏著膜也許是因為黏著劑組合物中含羧基的共聚合性乙烯基單體的配合量過多，厚度5μm的黏著劑層的黏著力弱。而且，黏著劑層的折射率低、附著性及耐久性也稍差。 The adhesive film of Comparative Example 2 may be because the amount of the carboxyl group-containing copolymerizable vinyl monomer in the adhesive composition is too large, and the adhesive layer having a thickness of 5 μm has a weak adhesive force. Moreover, the adhesive layer has a low refractive index, and the adhesion and durability are also slightly inferior.

比較例3的黏著膜也許是因為黏著劑組合物中既不含有含羧基的共聚合性乙烯基單體也不含有含羥基的共聚合性乙烯基單體，厚度5μm的黏著劑層的黏著力弱。而且，黏著劑層的折射率低、附著性及耐久性也差。 The adhesive film of Comparative Example 3 may be because the adhesive composition contains neither a carboxyl group-containing copolymerizable vinyl monomer nor a hydroxyl group-containing copolymerizable vinyl monomer, and an adhesive layer having a thickness of 5 μm. weak. Further, the adhesive layer has a low refractive index, and also has poor adhesion and durability.

如此的，比較例1~3的黏著膜不能滿足以往所需要求及克服以往的問題。 Thus, the adhesive films of Comparative Examples 1 to 3 did not satisfy the conventional requirements and overcome the conventional problems.

Claims (12)

一種黏著劑層，其是使含有丙烯酸類聚合物和交聯劑的黏著劑組合物交聯而成，其中，該黏著劑組合物包含：使下列(A)~(C)共聚合而成之重均分子量為20萬~200萬的共聚物所構成的上述丙烯類聚合物、和下列(D)交聯劑：(A)烷基碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體中的至少一種以上、和含芳基的(甲基)丙烯酸酯單體中的至少一種以上，合計為100重量份；(B)5~50重量份的含氮的乙烯基單體中的至少一種以上；(C)0.1~2重量份的含羧基的共聚合性乙烯基單體中的至少一種以上，和/或0.1~5重量份的含羥基的共聚合性乙烯基單體中的至少一種以上；(D)0.01~5重量份的上述交聯劑。 An adhesive layer obtained by crosslinking an adhesive composition containing an acrylic polymer and a crosslinking agent, wherein the adhesive composition comprises: copolymerizing the following (A) to (C) The above propylene-based polymer composed of a copolymer having a weight average molecular weight of 200,000 to 2,000,000, and the following (D) crosslinking agent: (A) an alkyl (meth) acrylate having an alkyl group having a C1 to C14 carbon number At least one or more of the ester monomers and at least one of the aryl group-containing (meth) acrylate monomers are 100 parts by weight in total; (B) 5 to 50 parts by weight of the nitrogen-containing vinyl monomer At least one or more of (C) 0.1 to 2 parts by weight of at least one of carboxyl group-containing copolymerizable vinyl monomers, and/or 0.1 to 5 parts by weight of hydroxyl group-containing copolymerizable vinyl monomer At least one of the above; (D) 0.01 to 5 parts by weight of the above crosslinking agent. 如申請專利範圍第1項之黏著劑層，其中，該黏著劑組合物包含，在上述(A)烷基碳原子數為C1~C14的(甲基)丙烯酸烷基酯單體中的至少一種以上、和含芳基的(甲基)丙烯酸酯單體中的至少一種以上合計為100重量份之中，上述含芳基的(甲基)丙烯酸酯單體中的至少一種以上為5~30重量份。 The adhesive layer according to claim 1, wherein the adhesive composition comprises at least one of (A) an alkyl (meth) acrylate monomer having an alkyl group having C1 to C14; In a total of at least one or more of the aryl group-containing (meth) acrylate monomers, at least one or more of the aryl group-containing (meth) acrylate monomers are 5 to 30. Parts by weight. 如申請專利範圍第1或2項之黏著劑層，其中，該含羥基的共聚合性乙烯基單體為選自由(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸羥基乙酯、N-羥基(甲基)丙烯醯胺、N-羥甲基 (甲基)丙烯醯胺、N-羥乙基(甲基)丙烯醯胺所構成的群組中之一種以上。 The adhesive layer according to claim 1 or 2, wherein the hydroxyl group-containing copolymerizable vinyl monomer is selected from the group consisting of 8-hydroxyoctyl (meth)acrylate and 6-hydroxyhexyl (meth)acrylate. Ester, 4-hydroxybutyl (meth)acrylate, hydroxyethyl (meth)acrylate, N-hydroxy(meth)acrylamide, N-methylol One or more of the group consisting of (meth) acrylamide and N-hydroxyethyl (meth) acrylamide. 如申請專利範圍第1或2項之黏著劑層，其中，在該黏著劑層的厚度為1μm~20μm，厚度5μm時的黏著力為4.0(N/25mm)以上。 The adhesive layer according to claim 1 or 2, wherein the adhesive layer has a thickness of 1 μm to 20 μm and a thickness of 5 μm, and the adhesive force is 4.0 (N/25 mm) or more. 如申請專利範圍第1或2項之黏著劑層，其中，該黏著劑層的折射率為1.47~1.50。 The adhesive layer of claim 1 or 2, wherein the adhesive layer has a refractive index of 1.47 to 1.50. 一種黏著膜，其在脫模膜的單面形成如申請專利範圍第1至5項中任一項之黏著劑層而成，並具有脫模膜/黏著劑層/脫模膜的構成。 An adhesive film formed by forming an adhesive layer according to any one of claims 1 to 5 on one side of a release film, and having a release film/adhesive layer/release film. 一種黏著膜，其在基材的單面上層疊如申請專利範圍第1至5項中任一項之黏著劑層而成。 An adhesive film obtained by laminating an adhesive layer according to any one of claims 1 to 5 on one side of a substrate. 一種偏光板的週邊構件用膜，其使用了如申請專利範圍第6或7項之黏著膜。 A film for a peripheral member of a polarizing plate which uses an adhesive film as disclosed in claim 6 or 7. 一種觸控面板用膜，其使用了如申請專利範圍第6或7項之黏著膜。 A film for a touch panel using an adhesive film as disclosed in claim 6 or 7. 一種電子紙用膜，其使用了如申請專利範圍第6或7項之黏著膜。 A film for electronic paper using an adhesive film as disclosed in claim 6 or 7. 一種有機EL用膜，其使用了如申請專利範圍第6或7項之黏著膜。 A film for an organic EL which uses an adhesive film as disclosed in claim 6 or 7. 一種帶有黏著劑層的光學膜，其在光學膜的至少一個面上層疊如申請專利範圍第1至5項中任一項之黏著劑層而成。 An optical film having an adhesive layer formed by laminating an adhesive layer according to any one of claims 1 to 5 on at least one side of the optical film.
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