TW201945500A - Adhesive composition and adhesive film - Google Patents

Adhesive composition and adhesive film Download PDF

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Publication number
TW201945500A
TW201945500A TW108113024A TW108113024A TW201945500A TW 201945500 A TW201945500 A TW 201945500A TW 108113024 A TW108113024 A TW 108113024A TW 108113024 A TW108113024 A TW 108113024A TW 201945500 A TW201945500 A TW 201945500A
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meth
adhesive composition
adhesive
acrylate
group
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TW108113024A
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Chinese (zh)
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長倉毅
大津賀健太郎
鈴木史恵
吉田弘幸
菱沼昌世
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日商藤森工業股份有限公司
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Publication of TW201945500A publication Critical patent/TW201945500A/en

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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
    • C09J7/10—Adhesives in the form of films or foils without 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
    • 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
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • 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
    • 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
    • G02B5/3041—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 comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—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 comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • 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
    • 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
    • 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
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer

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

Abstract

The present invention provides an adhesive composition and an adhesive film using the same. The adhesive composition and an adhesive film have an excellent reoperability and durability, and have no uneven brightness. The adhesive composition and an adhesive film do not cause a liquid display panel to curl when an optical film is bonded to a thin liquid crystal cell serving as an adherend via the adhesive film, thus having good anti-crimp ability. Moreover, the adhesive film also provides excellence with anti-dent during loading. The acrylic polymer in the composition is copolymerized by (A) an alkyl (meth)acrylic acid ester monomer having a C8 to C18 alkyl group, and (B) an alkyl (meth) acrylic acid ester monomer having a C1 to C5 alkyl group, (C) a copolymerizable vinyl monomer containing a hydroxyl group, and (D) a copolymerizable vinyl monomer containing an aromatic group in a way that has no copolymerizable vinyl group having a carboxyl group. The acrylic polymer has a weight average molecular weight of 1,500,000 to 3,000,000. A cross-linker agent in the composition is a trifunctional or multifunctional isocyanate compound.

Description

黏著劑組合物及黏著膜Adhesive composition and adhesive film

本發明涉及黏著劑組合物及黏著膜。進一步詳細而言，涉及用於安裝於顯示面板的光學膜的貼合的黏著劑組合物以及使用了該組合物的黏著膜。
此外，本發明提供具有優異的再操作性、耐久性，不產生作為產生顏色的明暗等亮度不均的原因的顯示面板的捲曲，具有良好的抗捲曲（彎曲）性的黏著劑組合物及使用了該組合物的黏著膜。
進一步，使用了本發明的黏著劑組合物的黏著劑層在負載時的耐凹陷性也優異。The present invention relates to an adhesive composition and an adhesive film. More specifically, the present invention relates to an adhesive composition for bonding an optical film mounted on a display panel, and an adhesive film using the composition.
In addition, the present invention provides an adhesive composition having excellent re-operability and durability, without causing curl of a display panel as a cause of uneven brightness, such as color shading, and excellent curl resistance (bending) resistance, and use thereof The adhesive film of the composition.
Furthermore, the adhesive layer using the adhesive composition of the present invention is also excellent in dent resistance during loading.

近年來，作為顯示圖像的顯示器（圖像顯示裝置），液晶顯示器及有機EL顯示器等各種顯示方式的顯示器正在廣泛地普及。構成這些顯示器的顯示面板中，使用黏著劑層而貼合、安裝有具有各種各樣的功能的光學膜。以下，作為代表例，對液晶顯示器中使用的液晶顯示面板進行說明。
例如，一般的液晶顯示面板為在2片玻璃基板之間封入有液晶、並使用黏著劑層將偏振片貼合在該玻璃基板的表面上的結構。In recent years, as a display (image display device) that displays an image, a variety of display methods such as a liquid crystal display and an organic EL display have been widely spread. In the display panels constituting these displays, an optical film having various functions is bonded and attached using an adhesive layer. Hereinafter, as a representative example, a liquid crystal display panel used in a liquid crystal display will be described.
For example, a general liquid crystal display panel has a structure in which liquid crystal is sealed between two glass substrates, and a polarizing plate is bonded to the surface of the glass substrate using an adhesive layer.

此外，液晶顯示面板中，除了偏振片以外，例如安裝有相位差板、亮度提高膜、顯示器用的鏡片膜、防反射膜、硬塗層膜、觸摸面板用透明導電性膜等光學膜。
通常，安裝於液晶顯示面板的光學膜的縱向及橫向的熱收縮率不均勻，此外，層疊有多個光學膜時，各個光學膜的熱收縮率不同。因此，根據顯示器的使用環境（溫度、濕度）的變化，安裝於液晶顯示面板的光學膜會發生尺寸變化。因此，液晶顯示面板上會發生捲曲、變形。此時，液晶顯示面板中，在使用於光學膜的貼合的黏著劑層中，因伴隨光學膜的尺寸變化的變形而產生應力。例如，液晶顯示面板發生捲曲時，存在在顯示圖像上產生顏色的明暗等亮度不均的問題。In addition, in the liquid crystal display panel, in addition to the polarizer, optical films such as a retardation plate, a brightness enhancement film, a lens film for a display, an anti-reflection film, a hard coat film, and a transparent conductive film for a touch panel are mounted.
Generally, the thermal shrinkage of the optical film mounted on the liquid crystal display panel is not uniform in the vertical and horizontal directions. When a plurality of optical films are laminated, the thermal shrinkage of each optical film is different. Therefore, the size of the optical film mounted on the liquid crystal display panel changes depending on the use environment (temperature, humidity) of the display. Therefore, the liquid crystal display panel is curled and deformed. At this time, in the liquid crystal display panel, stress is generated in the adhesive layer used for bonding of the optical film due to the deformation caused by the dimensional change of the optical film. For example, when the liquid crystal display panel is curled, there is a problem that brightness unevenness such as light and dark colors occurs on a display image.

此外，用於各種用途的液晶顯示面板中，特別是車載用的液晶顯示面板（適合於車載監控、汽車導航等）中，與電視及電腦用的液晶顯示面板相比，由於所實施的耐久性的試驗條件（高溫：例如，105℃，高溫及高濕條件：例如，85℃、85%RH、反覆高溫低溫等）更加嚴格，因此安裝於液晶顯示面板的光學膜的尺寸變化及應力更容易產生。In addition, liquid crystal display panels used in various applications, particularly in-vehicle liquid crystal display panels (suitable for in-vehicle monitoring, car navigation, etc.) are more durable than liquid crystal display panels for televisions and computers. Test conditions (high temperature: for example, 105 ° C, high temperature and high humidity conditions: for example, 85 ° C, 85% RH, repeated high temperature and low temperature, etc.) are more stringent, so the dimensional change and stress of the optical film mounted on the liquid crystal display panel are easier produce.

此外，近年來，為了使液晶顯示面板變得更輕，一直在推進薄型化，因此液晶顯示面板無法承受所貼合的光學膜的尺寸變化及應力，發生捲曲的問題也越來越顯著。因此，要求顯示器在更嚴格條件下抑制捲曲等不良情況、防止捲曲等不良情況的發生（抗捲曲性）。In addition, in recent years, in order to make the liquid crystal display panel lighter, thinning has been promoted, so the liquid crystal display panel cannot withstand the dimensional change and stress of the bonded optical film, and the problem of curling has become more and more significant. Therefore, the display is required to suppress undesirable conditions such as curling and prevent the occurrence of undesirable conditions such as curling (curling resistance) under stricter conditions.

作為改善顯示圖像的顏色的明暗等不均的現有技術，例如，公開了使用高分子量的丙烯酸類聚合物，使用基於交聯的凝膠分率得以減小的黏著劑層（專利文獻1）。
認為若使用該黏著劑層，則不僅能滿足耐熱性及耐濕熱性，而且能夠緩和由偏振膜等構件的尺寸變化導致的應力，從而大幅度地抑制漏光或顏色不均。As a conventional technique for improving unevenness of the color of a displayed image, for example, it is disclosed that an adhesive layer using a high molecular weight acrylic polymer and a reduced gel fraction by cross-linking is used (Patent Document 1) .
The use of this adhesive layer is considered to not only satisfy heat resistance and humidity and heat resistance, but also reduce stress caused by dimensional changes of members such as a polarizing film, thereby significantly suppressing light leakage and color unevenness.

此外，作為改善顯示圖像的顏色的明暗等不均的現有技術的其他方法，公開了使用由具有芳香環的丙烯酸類單體共聚而成的高分子量的聚合物，應用具有特定範圍的黏度係數的黏著劑層（專利文獻2）。認為若使用該黏著劑層，則能夠得到不在液晶元件上發生顏色不均及白斑現象的光學用黏著劑組合物。In addition, as another method of the prior art for improving unevenness of lightness and darkness of a displayed image, a high molecular weight polymer obtained by copolymerizing an acrylic monomer having an aromatic ring is disclosed, and a viscosity coefficient having a specific range is applied. Adhesive layer (Patent Document 2). By using this adhesive layer, it is thought that the optical adhesive composition which does not generate color unevenness and a white spot phenomenon on a liquid crystal element can be obtained.

進一步，作為改善顯示圖像的顏色的明暗等不均的現有技術的其他方法，公開了使用具有特定範圍的分支度(branching degree)的丙烯酸類聚合物，應用凝膠分率低的黏著劑層（專利文獻3）。
認為若為使用了該黏著劑組合物的黏著劑層，則經由黏著劑層而將構成液晶顯示面板的玻璃基板與偏振片貼合時，能夠抑制玻璃基板的翹曲。Furthermore, as another method of the prior art for improving unevenness such as lightness and darkness of a displayed image, it is disclosed to use an acrylic polymer having a specific range of branching degree and apply an adhesive layer having a low gel fraction. (Patent Document 3).
If it is an adhesive layer using this adhesive composition, it is thought that when the glass substrate which comprises a liquid crystal display panel and a polarizing plate are bonded via an adhesive layer, the curvature of a glass substrate can be suppressed.

然而，專利文獻1中記載的發明以藉由調節重均分子量來解決顯示圖像的不均為技術構思，規定了形成黏著劑層的黏著劑組合物中的丙烯酸類聚合物的重均分子量為50萬以上200萬以下。
然而，專利文獻1的實施例1~6中使用的丙烯酸類聚合物的重均分子量在70萬~140萬的範圍內，關於重均分子量超過140萬的丙烯酸類聚合物，發明的效果尚未得到證實。
此外，對於專利文獻1中記載的發明的黏著劑層而言，優選將凝膠分率設為1~50%，專利文獻1的實施例1、2、4、5中，凝膠分率小於40%。
為了確認專利文獻1中記載的發明的效果，進行了追加試驗，結果確認到專利文獻1中記載的發明的黏著劑層在耐久性或耐熱性方面尚不充分。However, the invention described in Patent Document 1 is based on the technical idea of solving the non-uniformity of the displayed image by adjusting the weight average molecular weight, and specifies the weight average molecular weight of the acrylic polymer in the adhesive composition forming the adhesive layer as 500,000 to 2 million.
However, the weight average molecular weight of the acrylic polymer used in Examples 1 to 6 of Patent Document 1 is in the range of 700,000 to 1.4 million, and the effect of the invention on the acrylic polymer having a weight average molecular weight exceeding 1.4 million has not yet been obtained. Confirmed.
In addition, for the adhesive layer of the invention described in Patent Document 1, the gel fraction is preferably 1 to 50%. In Examples 1, 2, 4, and 5 of Patent Document 1, the gel fraction is less than 40%.
In order to confirm the effect of the invention described in Patent Document 1, an additional test was performed. As a result, it was confirmed that the adhesive layer of the invention described in Patent Document 1 was insufficient in terms of durability or heat resistance.

此外，專利文獻2中記載的發明的技術構思為：藉由使具有特定範圍的黏度係數的黏著劑層錯位從而緩和變形，解決液晶元件的顏色不均及白斑現象。
此外，專利文獻2中記載的發明的黏著劑層中，將丙烯酸類聚合物的共聚物的重均分子量設為100萬~200萬，但實施例1~11中使用的共聚物的重均分子量為120萬~127萬，關於重均分子量超過127萬的情況，發明的效果尚未得到證實。
如此，專利文獻2中記載的發明的黏著劑層與專利文獻1中記載的發明的黏著劑層同樣，具有在耐熱性或耐久性的方面不充分的可能。In addition, the technical idea of the invention described in Patent Document 2 is to displace the adhesive layer having a viscosity coefficient in a specific range to ease the deformation, and solve the color unevenness and white spot phenomenon of the liquid crystal element.
In addition, in the adhesive layer of the invention described in Patent Document 2, the weight average molecular weight of the copolymer of the acrylic polymer is 1 to 2 million, but the weight average molecular weight of the copolymer used in Examples 1 to 11 It is 1.2 million to 1.27 million, and the effect of the invention has not yet been confirmed for a case where the weight average molecular weight exceeds 1.27 million.
As described above, similarly to the adhesive layer of the invention described in Patent Document 1, the adhesive layer of the invention described in Patent Document 2 may have insufficient heat resistance or durability.

此外，專利文獻3中記載的發明的技術構思為：藉由使用含有具有特定範圍的分支度的丙烯酸類聚合物的黏著劑組合物，形成低凝膠分率的黏著劑層，由此藉由支鏈的纏結，一邊維持耐久性一邊實現應力的緩和。
此外，在專利文獻3的實施例1~14中，使用的（甲基）丙烯酸類共聚物的重均分子量為40萬~130萬，黏著劑層的凝膠分率為30質量%以下。
如此，即使專利文獻3中記載的發明的黏著劑層因凝膠分率低而應力緩和性優異，但也有耐久性不充分的可能。In addition, the technical idea of the invention described in Patent Document 3 is to form an adhesive layer with a low gel fraction by using an adhesive composition containing an acrylic polymer having a specific range of branching degree. The entanglement of the branches achieves relaxation of stress while maintaining durability.
In addition, in Examples 1 to 14 of Patent Document 3, the (meth) acrylic copolymer used had a weight average molecular weight of 400,000 to 1.3 million, and the gel fraction of the adhesive layer was 30% by mass or less.
As described above, even if the adhesive layer of the invention described in Patent Document 3 has a low gel fraction and excellent stress relaxation properties, there is a possibility that the durability is insufficient.

如上所述，現有技術中，降低圖像顯示裝置的顏色的明暗等亮度不均時，難以同時解決用於貼合安裝於液晶顯示面板的光學膜的黏著劑層的再操作性、耐久性及抗捲曲性。
現有技術文獻As described above, in the prior art, when the brightness unevenness of the color of the image display device is reduced, it is difficult to simultaneously solve the reworkability, durability, and durability of the adhesive layer for bonding the optical film mounted on the liquid crystal display panel. Curl resistance.
Prior art literature

專利文獻
專利文獻1：日本特開2004-091500號公報
專利文獻2：日本特開2007-169329號公報
專利文獻3：國際公開第2015/141382號Patent Literature Patent Literature 1: Japanese Patent Laid-Open No. 2004-091500 Patent Literature 2: Japanese Patent Laid-Open No. 2007-169329 Patent Literature 3: International Publication No. 2015/141382

[本發明要解決的技術問題][Technical problem to be solved by the present invention]

鑒於上述問題，本發明的技術問題在於提供具有優異的再操作性、耐久性，不產生作為發生顏色的明暗等亮度不均的原因的顯示面板的捲曲，具有良好的抗捲曲（彎曲）性的黏著劑組合物及使用了該組合物的黏著膜。
此外，本發明的另一個技術問題在於提供一種施加負荷時的耐凹陷性優異的黏著劑層。
[解決技術問題的技術手段]In view of the above-mentioned problems, the technical problem of the present invention is to provide a display panel that has excellent re-operability and durability, does not cause curl of the display panel as a cause of uneven brightness, and the like, and has good curl resistance. Adhesive composition and adhesive film using the same.
Another technical problem of the present invention is to provide an adhesive layer having excellent dent resistance when a load is applied.
[Technical means to solve technical problems]

為了解決這樣的技術問題，本發明提供了一種黏著劑組合物，其含有丙烯酸類聚合物、交聯劑及矽烷偶聯劑，
所述丙烯酸類聚合物為使下述成分以不含帶羧基的共聚性乙烯基單體的方式共聚而成的、重均分子量為150萬~300萬的丙烯酸類聚合物：
（A）烷基的碳原子數為C8~C18的（甲基）丙烯酸烷基酯單體的至少一種；
（B）烷基的碳原子數為C1~C5的（甲基）丙烯酸烷基酯單體的至少一種；
（C）含有羥基的共聚性乙烯基單體的至少一種；及
（D）含有芳香族基團的共聚性乙烯基單體的至少一種，
所述交聯劑為3官能度以上的異氰酸酯化合物。In order to solve such a technical problem, the present invention provides an adhesive composition containing an acrylic polymer, a crosslinking agent, and a silane coupling agent.
The acrylic polymer is an acrylic polymer having a weight average molecular weight of 1.5 to 3 million, which is obtained by copolymerizing the following components in a manner that does not contain a copolymerizable vinyl monomer having a carboxyl group:
(A) at least one of alkyl (meth) acrylate monomers having a carbon number of C8 to C18;
(B) at least one type of an alkyl (meth) acrylate monomer having a carbon number of C1 to C5;
(C) at least one copolymerizable vinyl monomer containing a hydroxyl group; and (D) at least one copolymerizable vinyl monomer containing an aromatic group,
The crosslinking agent is an isocyanate compound having a trifunctional or higher functionality.

就本發明的黏著劑組合物而言，藉由將由該黏著劑組合物交聯而成的黏著劑層用於液晶顯示面板與光學膜的貼合，由此黏著劑層緩和伴隨光學膜的尺寸變化而產生的收縮應力、減弱液晶顯示面板產生的捲曲，同時可形成具有優異的再操作性、高耐久性及施加負荷時的耐凹陷性的黏著劑層。In the adhesive composition of the present invention, the adhesive layer formed by cross-linking the adhesive composition is used for bonding a liquid crystal display panel and an optical film, so that the adhesive layer reduces the size of the optical film. The shrinkage stress caused by the change reduces the curl caused by the liquid crystal display panel, and at the same time, it can form an adhesive layer having excellent re-operability, high durability, and dent resistance when a load is applied.

由本發明的黏著劑組合物交聯而成的黏著劑層緩和產生於貼合的光學膜的收縮應力、減弱液晶顯示面板產生的捲曲，同時表現優異的再操作性、高耐久性及耐凹陷性的理由的詳細情況尚未解明。作為可能的理由，推測基於構成黏著劑組合物的丙烯酸類聚合物的（A）烷基的碳原子數為C8~C18的（甲基）丙烯酸烷基酯單體的側鏈的柔軟性、而緩和應力，基於與丙烯酸類聚合物中的其他共聚成分的組合的硬度的表現，以及基於交聯性成分的凝聚力的提高，而使上述特性的顯現成為可能。The adhesive layer formed by cross-linking the adhesive composition of the present invention relieves the shrinkage stress generated in the bonded optical film, weakens the curl caused by the liquid crystal display panel, and exhibits excellent re-operability, high durability and dent resistance Details of the reasons have not been elucidated. As a possible reason, it is presumed that the flexibility of the side chain of the (A) alkyl (meth) acrylic acid alkyl ester monomer having C8 to C18 in the acrylic polymer constituting the adhesive composition is The relaxation of the stress, the expression of the hardness based on the combination with other copolymerization components in the acrylic polymer, and the improvement of the cohesiveness based on the crosslinkable component make it possible to develop the above characteristics.

優選：相對於所述（A）、所述（B）及所述（D）的合計100重量份，所述丙烯酸類聚合物藉由使下述成分共聚而得到：
20重量份以上69重量份以下的所述（A）烷基的碳原子數為C8~C18的（甲基）丙烯酸烷基酯單體的至少一種；
30重量份以上79重量份以下的所述（B）烷基的碳原子數為C1~C5的（甲基）丙烯酸烷基酯單體的至少一種；
超過0重量份且為5重量份以下的所述（C）含有羥基的共聚性乙烯基單體的至少一種；及
1~50重量份的所述（D）含有芳香族基團的共聚性乙烯基單體的至少一種，
相對於所述（A）、所述（B）及所述（D）的合計100重量份，所述黏著劑組合物以0.001重量份以上0.05重量份以下的比例含有所述3官能度以上的異氰酸酯化合物。Preferably, the acrylic polymer is obtained by copolymerizing the following components with respect to 100 parts by weight of the total of (A), (B), and (D):
At least one of (A) alkyl (meth) acrylic acid alkyl ester monomers having a carbon number of C8 to C18 of 20 parts by weight to 69 parts by weight;
30 parts by weight to 79 parts by weight of the (B) alkyl group having at least one type of (meth) acrylic acid alkyl ester monomer having C1 to C5;
More than 0 parts by weight and 5 parts by weight or less of at least one of the (C) hydroxyl-containing copolymerizable vinyl monomers; and
1 to 50 parts by weight of at least one of the (D) copolymerizable vinyl monomer containing an aromatic group,
The adhesive composition contains the trifunctional or more functional compound in a proportion of 0.001 part by weight or more and 0.05 part by weight or less with respect to 100 parts by weight of the total of (A), (B), and (D). Isocyanate compounds.

優選所述（C）含有羥基的共聚性乙烯基單體的至少一種為選自由（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2-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）丙烯醯胺組成的化合物群組中的至少一種以上。Preferably, at least one of the (C) hydroxyl-containing copolymerizable vinyl monomers is selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4- Hydroxybutyl, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamine At least one or more members of the compound group composed of amines.

優選：所述（A）烷基的碳原子數為C8~C18的（甲基）丙烯酸烷基酯單體的至少一種為選自丙烯酸2-乙基己酯、丙烯酸異辛酯、丙烯酸異壬酯、丙烯酸異癸酯中的至少一種；所述（B）烷基的碳原子數為C1~C5的（甲基）丙烯酸烷基酯單體的至少一種為選自由丙烯酸正丁酯、丙烯酸三級丁酯、丙烯酸異丁酯、甲基丙烯酸正丁酯、丙烯酸甲酯組成的組中的至少一種以上。Preferably, at least one of the (A) alkyl (meth) acrylic acid alkyl ester monomers having a carbon number of C8 to C18 is selected from 2-ethylhexyl acrylate, isooctyl acrylate, and isonon acrylate. At least one of an ester and isodecyl acrylate; at least one of the (B) alkyl (meth) acrylic acid alkyl monomers having a carbon number of C1 to C5 is selected from the group consisting of n-butyl acrylate, and triacrylate At least one or more selected from the group consisting of grade butyl, isobutyl acrylate, n-butyl methacrylate, and methyl acrylate.

優選所述（D）含有芳香族基團的共聚性乙烯基單體的至少一種為選自（甲基）丙烯酸苄酯、（甲基）丙烯酸苯氧基乙酯中的至少一種以上。It is preferable that at least one type of the (D) copolymerizable vinyl monomer containing an aromatic group is at least one type selected from benzyl (meth) acrylate and phenoxyethyl (meth) acrylate.

此外，優選所述矽烷偶聯劑為具有選自環氧基、巰基、酸酐基中的至少一種官能基的矽烷偶聯劑。In addition, the silane coupling agent is preferably a silane coupling agent having at least one functional group selected from an epoxy group, a mercapto group, and an acid anhydride group.

優選所述丙烯酸類聚合物的分子量的分散度（Mw[重均分子量]/Mn[數均分子量]）為6.0以下。The molecular weight dispersion (Mw [weight average molecular weight] / Mn [number average molecular weight]) of the acrylic polymer is preferably 6.0 or less.

經由由所述黏著劑組合物交聯而成的黏著劑層貼合作為偏光素膜（polarizing raw film）的保護膜的以PET（聚對苯二甲酸乙二酯膜：厚度20μm）為表面基材且厚度為140μm的偏振片與厚度為0.4mm的無鹼玻璃，按照JIS-Z0237、沿180°方向以300mm/分鐘的剝離速度，將以PET為表面基材的偏振片從玻璃面上剝離時的黏著力優選為4N/25mm以下。該黏著力進一步優選為1~4N/25mm。PET (polyethylene terephthalate film: thickness 20 μm) is used as a surface layer to adhere to a protective film of a polarizing raw film through an adhesive layer cross-linked from the adhesive composition. The polarizing plate with a thickness of 140 μm and the alkali-free glass with a thickness of 0.4 mm are peeled from the glass surface with a PET-based polarizing plate at a peeling speed of 300 mm / min in the 180 ° direction in accordance with JIS-Z0237 The adhesive force at the time is preferably 4 N / 25 mm or less. The adhesive force is more preferably 1 to 4 N / 25 mm.

並且，將所述黏著劑組合物溶解於溶劑而成的黏著劑組合物溶液的觸變指數（TI值）優選為1.25以下。The thixotropic index (TI value) of the adhesive composition solution obtained by dissolving the adhesive composition in a solvent is preferably 1.25 or less.

此外，本發明提供一種黏著劑層，其由所述黏著劑組合物交聯而成，厚度為20μm，耐凹陷性為10g以上。In addition, the present invention provides an adhesive layer, which is formed by crosslinking the adhesive composition, has a thickness of 20 μm, and has a dent resistance of 10 g or more.

此外，本發明提供一種黏著膜，其藉由將由所述黏著劑組合物交聯而成的黏著劑層層疊於樹脂膜的單面而成。In addition, the present invention provides an adhesive film formed by laminating an adhesive layer obtained by crosslinking the adhesive composition on one side of a resin film.

優選所述黏著膜為用於將偏振片貼合於被黏物的黏著膜。The adhesive film is preferably an adhesive film for attaching a polarizing plate to an adherend.

此外，本發明提供一種黏著膜，其中，在離型膜的單面形成有由所述黏著劑組合物交聯而成的黏著劑層，為離型膜/黏著劑層/離型膜的結構。In addition, the present invention provides an adhesive film in which an adhesive layer formed by crosslinking the adhesive composition is formed on one side of a release film, and has a structure of a release film / adhesive layer / release film. .

此外，本發明提供一種帶黏著劑層的光學膜，其藉由在光學膜的至少一側的面上層疊由所述黏著劑組合物交聯而成的黏著劑層而成，為離型膜/黏著劑層/光學膜的結構。In addition, the present invention provides an optical film with an adhesive layer, which is formed by laminating an adhesive layer crosslinked by the adhesive composition on at least one side of the optical film, and is a release film. / Adhesive layer / structure of optical film.

此外，本發明提供一種帶黏著劑層的偏振片，其藉由在偏振片的單面上層疊由所述黏著劑組合物交聯而成的黏著劑層而成，為離型膜/黏著劑層/偏振片的結構。In addition, the present invention provides a polarizing plate with an adhesive layer, which is formed by laminating an adhesive layer crosslinked by the adhesive composition on one side of the polarizing plate, and is a release film / adhesive. Layer / polarizer structure.

此外，本發明提供一種液晶顯示面板，其使用所述帶黏著劑層的偏振片。
[發明效果]In addition, the present invention provides a liquid crystal display panel using the polarizer with an adhesive layer.
[Inventive effect]

根據本發明，能夠提供一種可形成具有優異的再操作性或耐久性，不發生顏色的明暗等亮度不均，具有良好的抗捲曲（彎曲）性的黏著劑層的黏著劑組合物。
此外，提供一種黏著劑組合物，其可形成當經由由本發明的黏著劑組合物交聯而成的黏著劑層而對薄型的液晶單元貼合光學膜時，液晶顯示面板不發生捲曲，具有良好的抗捲曲（彎曲）性，同時在黏著劑層上施加負荷時的耐凹陷性優異的黏著劑層。
此外，能夠提供一種塗布性也良好的黏著劑組合物。According to the present invention, it is possible to provide an adhesive composition that can form an adhesive layer that has excellent reworkability or durability, does not cause uneven brightness, such as color shading, and has excellent curling resistance.
In addition, an adhesive composition is provided, which can form a liquid crystal display panel without curling when an optical film is bonded to a thin liquid crystal cell through an adhesive layer cross-linked from the adhesive composition of the present invention, and has good properties. An adhesive layer having excellent curl resistance (bending) resistance and excellent dent resistance when a load is applied to the adhesive layer.
In addition, it is possible to provide an adhesive composition that is also excellent in coatability.

以下，基於優選的實施方式對本發明進行說明。Hereinafter, the present invention will be described based on preferred embodiments.

本實施方式的黏著劑組合物為含有丙烯酸類聚合物、交聯劑及矽烷偶聯劑的黏著劑組合物，所述丙烯酸類聚合物為使（A）烷基的碳原子數為C8~C18的（甲基）丙烯酸烷基酯單體的至少一種、（B）烷基的碳原子數為C1~C5的（甲基）丙烯酸烷基酯單體的至少一種、（C）含有羥基的共聚性乙烯基單體的至少一種及（D）含有芳香族基團的共聚性乙烯基單體的至少一種，以不含帶羧基的共聚性乙烯基單體的方式共聚而成的、重均分子量為150萬~300萬的丙烯酸類聚合物，所述交聯劑為3官能度以上的異氰酸酯化合物。The adhesive composition of this embodiment is an adhesive composition containing an acrylic polymer, a cross-linking agent, and a silane coupling agent, and the acrylic polymer is such that the number of carbon atoms in the (A) alkyl group is C8 to C18 At least one kind of (meth) acrylic acid alkyl ester monomer, (B) at least one kind of (meth) acrylic acid alkyl ester monomer having C1 to C5 alkyl group, (C) hydroxyl-containing copolymerization Weight average molecular weight of at least one polymerizable vinyl monomer and (D) at least one copolymerizable vinyl monomer containing an aromatic group, copolymerized so as not to contain a copolymerizable vinyl monomer having a carboxyl group It is an acrylic polymer of 1.5 million to 3 million, and the cross-linking agent is an isocyanate compound having 3 or more functionalities.

本實施方式的黏著劑組合物中的丙烯酸類聚合物為使（A）烷基的碳原子數為C8~C18的（甲基）丙烯酸烷基酯單體的至少一種、（B）烷基的碳原子數為C1~C5的（甲基）丙烯酸烷基酯單體的至少一種、（C）含有羥基的共聚性乙烯基單體的至少一種及（D）含有芳香族基團的共聚性乙烯基單體的至少一種，以不含帶羧基的共聚性乙烯基單體的方式共聚而得到的共聚物。本說明書中，（甲基）丙烯酸酯為丙烯酸酯及甲基丙烯酸酯的總稱。The acrylic polymer in the adhesive composition of the present embodiment is (A) an alkyl (meth) acrylic acid alkyl ester monomer having at least one carbon atom number of C8 to C18, and (B) an alkyl group. At least one type of (meth) acrylic acid alkyl ester monomer having C1 to C5, (C) at least one type of copolymerizable vinyl monomer containing a hydroxyl group, and (D) copolymerizable ethylene containing an aromatic group A copolymer obtained by copolymerizing at least one of the base monomers without containing a copolymerizable vinyl monomer having a carboxyl group. In this specification, (meth) acrylate is a general term for acrylate and methacrylate.

作為構成本實施方式的黏著劑組合物中的丙烯酸類聚合物的（A）烷基的碳原子數為C8~C18的（甲基）丙烯酸烷基酯單體，可列舉出選自由（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）丙烯酸異癸酯、（甲基）丙烯酸十一烷基酯、（甲基）丙烯酸異十一烷基酯、（甲基）丙烯酸十二烷基酯、（甲基）丙烯酸異十二烷基酯、（甲基）丙烯酸十三烷基酯、（甲基）丙烯酸異十三烷基酯、（甲基）丙烯酸十四烷基酯、（甲基）丙烯酸異十四烷基酯、（甲基）丙烯酸十五烷基酯、（甲基）丙烯酸十六烷基酯、（甲基）丙烯酸十七烷基酯、（甲基）丙烯酸十八烷基酯、（甲基）丙烯酸肉豆蔻酯、（甲基）丙烯酸異肉豆蔻酯、（甲基）丙烯酸鯨蠟酯、（甲基）丙烯酸異鯨蠟酯、（甲基）丙烯酸十八烷基酯、（甲基）丙烯酸異十八烷基酯組成的化合物群組中的至少一種以上。（甲基）丙烯酸烷基酯單體的烷基可以為直鏈，可以為支鏈，也可以為環狀（脂環族）。Examples of the (A) alkyl (meth) acrylic acid alkyl monomer having C8 to C18 in the (A) alkyl group constituting the acrylic polymer in the adhesive composition of the present embodiment include a group selected from (methyl) ) Octyl acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate , Isodecyl (meth) acrylate, undecyl (meth) acrylate, isoundecyl (meth) acrylate, dodecyl (meth) acrylate, isodecyl (meth) acrylate Dodecyl ester, tridecyl (meth) acrylate, isotridecyl (meth) acrylate, tetradecyl (meth) acrylate, isotetradecyl (meth) acrylate Ester, pentadecyl (meth) acrylate, cetyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, (meth) Myristyl acrylate, isomyristyl (meth) acrylate, cetyl (meth) acrylate, (formyl ) Acrylate, cetyl (meth) acrylate, stearyl acrylate, isostearyl group compound (meth) acrylate consisting of at least one or more. The alkyl group of the (meth) acrylic acid alkyl ester monomer may be linear, branched, or cyclic (alicyclic).

丙烯酸類聚合物中包含的（甲基）丙烯酸烷基酯單體的烷基的碳原子數為7以下時，例如，含有下述（B）、但是不含所述（A）的丙烯酸類聚合物中，作為側鏈的烷基的柔軟性不充分，由黏著劑組合物交聯而成的黏著劑層所帶來的抗捲曲性的效果變得難以發揮，故而不優選。另一方面，所述烷基的碳原子數多時，存在柔性過度，黏著劑層容易因荷載而凹陷，且容易引起烷基的結晶化、黏著劑層的透明性降低的情況，故而不優選。When the number of carbon atoms in the alkyl group of the (meth) acrylic acid alkyl ester monomer contained in the acrylic polymer is 7 or less, for example, acrylic polymerization containing the following (B) but not including the above (A) Among them, the flexibility of the alkyl group as a side chain is insufficient, and the effect of curl resistance by an adhesive layer formed by crosslinking the adhesive composition becomes difficult to exhibit, which is not preferable. On the other hand, when the number of carbon atoms of the alkyl group is large, there is a case where the flexibility is excessive, the adhesive layer is likely to sag due to a load, and crystallization of the alkyl group is easily caused, and the transparency of the adhesive layer may be reduced, which is not preferable. .

作為（A）烷基的碳原子數為C8~C18的（甲基）丙烯酸烷基酯單體，其中，優選烷基的碳原子數為C8~C10的（甲基）丙烯酸烷基酯單體的至少一種，其中，優選選自丙烯酸2-乙基己酯、丙烯酸異辛酯、丙烯酸異壬酯、丙烯酸異癸酯中的至少一種。The (A) alkyl (meth) acrylic acid alkyl ester monomer having C8 to C18 alkyl groups, of which the alkyl (meth) acrylic acid alkyl ester monomer having C8 to C10 alkyl groups is preferred. Among them, at least one is preferably selected from the group consisting of 2-ethylhexyl acrylate, isooctyl acrylate, isononyl acrylate, and isodecyl acrylate.

相對於（A）烷基的碳原子數為C8~C18的（甲基）丙烯酸烷基酯單體的至少一種、（B）烷基的碳原子數為C1~C5的（甲基）丙烯酸烷基酯單體的至少一種及（D）含有芳香族基團的共聚性乙烯基單體的至少一種的合計100重量份，本實施方式的黏著劑組合物中的丙烯酸類聚合物能夠使（A）烷基的碳原子數為C8~C18的（甲基）丙烯酸烷基酯單體以20重量份以上69重量份以下的比例共聚。
作為所述（A）的共聚比例的下限值，優選設為25重量份以上的比例，特別優選設為35重量份以上的比例。作為所述（A）的共聚比例的上限值，優選65重量份以下的比例，特別優選55重量份以下的比例。(A) Alkyl (meth) acrylic acid having C8 to C18 alkyl (meth) acrylate monomers and (B) Alkyl (meth) acrylic acid having C1 to C5 alkyls A total of 100 parts by weight of at least one of the ester monomers and (D) at least one of the copolymerizable vinyl monomers containing an aromatic group, the acrylic polymer in the adhesive composition of the present embodiment can make (A The alkyl (meth) acrylic acid alkyl ester monomer having a carbon number of C8 to C18 is copolymerized in a proportion of 20 parts by weight to 69 parts by weight.
The lower limit of the copolymerization ratio of (A) is preferably a ratio of 25 parts by weight or more, and particularly preferably a ratio of 35 parts by weight or more. The upper limit of the copolymerization ratio of (A) is preferably a ratio of 65 parts by weight or less, and particularly preferably a ratio of 55 parts by weight or less.

作為構成本實施方式的黏著劑組合物中的丙烯酸類聚合物的（B）烷基的碳原子數為C1~C5的（甲基）丙烯酸烷基酯單體，可列舉出選自由（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）丙烯酸三級丁酯、（甲基）丙烯酸戊酯、（甲基）丙烯酸異戊酯組成的化合物群組中的至少一種以上。（甲基）丙烯酸烷基酯單體的烷基可以為直鏈，可以為支鏈，也可以為環狀（脂環族）。
作為（B）烷基的碳原子數為C1~C5的（甲基）丙烯酸烷基酯單體，優選選自由丙烯酸正丁酯、丙烯酸三級丁酯、丙烯酸異丁酯、甲基丙烯酸正丁酯、丙烯酸甲酯組成的組中的至少一種以上。
作為（B）烷基的碳原子數為C1~C5的（甲基）丙烯酸烷基酯單體，也優選組合使用兩種以上，例如，優選將丙烯酸丁酯、尤其是丙烯酸正丁酯與丙烯酸甲酯組合。Examples of the (B) alkyl (meth) acrylic acid alkyl ester monomer having C1 to C5 in the (B) alkyl group constituting the acrylic polymer in the adhesive composition of the present embodiment include those selected from (Methyl) ) Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) ) At least one or more compounds selected from the group consisting of tertiary butyl acrylate, amyl (meth) acrylate, and isoamyl (meth) acrylate. The alkyl group of the (meth) acrylic acid alkyl ester monomer may be linear, branched, or cyclic (alicyclic).
The (B) alkyl (meth) acrylic acid alkyl ester monomer having C1 to C5 as the alkyl group is preferably selected from n-butyl acrylate, tertiary butyl acrylate, isobutyl acrylate, and n-butyl methacrylate At least one or more of the group consisting of an ester and methyl acrylate.
As the (B) alkyl (meth) acrylic acid alkyl ester monomer having a carbon number of C1 to C5, it is also preferable to use two or more kinds in combination. For example, butyl acrylate, especially n-butyl acrylate and acrylic acid are preferably used. Methyl ester combination.

相對於（A）烷基的碳原子數為C8~C18的（甲基）丙烯酸烷基酯單體的至少一種、（B）烷基的碳原子數為C1~C5的（甲基）丙烯酸烷基酯單體的至少一種及（D）含有芳香族基團的共聚性乙烯基單體的至少一種的合計100重量份，本實施方式的黏著劑組合物中的丙烯酸類聚合物能夠使（B）烷基的碳原子數為C1~C5的（甲基）丙烯酸烷基酯單體以30重量份以上79重量份以下的比例共聚。
作為所述（B）的共聚比例的下限值，優選設為40重量份以上的比例，特別優選設為50重量份以上的比例。作為所述（B）的共聚比例的上限值，優選75重量份以下的比例，特別優選65重量份以下的比例。(A) Alkyl (meth) acrylic acid having C8 to C18 alkyl (meth) acrylate monomers and (B) Alkyl (meth) acrylic acid having C1 to C5 alkyls A total of 100 parts by weight of at least one of the alkyl ester monomer and (D) at least one of the copolymerizable vinyl monomer containing an aromatic group, the acrylic polymer in the adhesive composition of the present embodiment can make (B ) Alkyl (meth) acrylic acid alkyl ester monomers having a carbon number of C1 to C5 are copolymerized at a ratio of 30 parts by weight to 79 parts by weight.
The lower limit of the copolymerization ratio of (B) is preferably a ratio of 40 parts by weight or more, and particularly preferably a ratio of 50 parts by weight or more. The upper limit of the copolymerization ratio of (B) is preferably a ratio of 75 parts by weight or less, and particularly preferably a ratio of 65 parts by weight or less.

作為構成本實施方式的黏著劑組合物的丙烯酸類聚合物的（C）含有羥基的共聚性乙烯基單體，可列舉出（甲基）丙烯酸2-羥基乙酯、（甲基）丙烯酸2-羥基丙酯、（甲基）丙烯酸3-羥基丙酯、（甲基）丙烯酸4-羥基丁酯、（甲基）丙烯酸6-羥基己酯、（甲基）丙烯酸8-羥基辛酯等含羥基的（甲基）丙烯酸酯類；或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，優選選自這些化合物群組中的至少一種以上。其中，作為（C）含有羥基的共聚性乙烯基單體，優選選自由（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2-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）丙烯醯胺組成的化合物群組中的至少一種以上。Examples of the (C) hydroxyl-containing copolymerizable vinyl monomer of the acrylic polymer constituting the adhesive composition of the present embodiment include 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate. Hydroxyl groups such as hydroxypropyl, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, etc. (Meth) acrylic acid esters; or hydroxyl-containing compounds such as N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide The (meth) acrylamide is preferably at least one or more kinds selected from the group of these compounds. Among them, as the copolymerizable vinyl monomer containing (C) a hydroxyl group, it is preferably selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Ester, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide At least one of the compound group.

相對於（A）烷基的碳原子數為C8~C18的（甲基）丙烯酸烷基酯單體的至少一種、（B）烷基的碳原子數為C1~C5的（甲基）丙烯酸烷基酯單體的至少一種及（D）含有芳香族基團的共聚性乙烯基單體的至少一種的合計100重量份，本實施方式的黏著劑組合物中的丙烯酸類聚合物能夠以超過0重量份且為5重量份以下、優選為0.05~2.5重量份、特別優選為0.1~2.0重量份、進一步優選為0.5~1.5重量份的比例含有（C）含有羥基的共聚性乙烯基單體的至少一種。(A) Alkyl (meth) acrylic acid having C8 to C18 alkyl (meth) acrylate monomers and (B) Alkyl (meth) acrylic acid having C1 to C5 alkyls A total of 100 parts by weight of at least one of the acrylic ester monomers and (D) at least one of the copolymerizable vinyl monomers containing an aromatic group, the acrylic polymer in the adhesive composition of the present embodiment may exceed 0 5 parts by weight or less, preferably 0.05 to 2.5 parts by weight, particularly preferably 0.1 to 2.0 parts by weight, and more preferably 0.5 to 1.5 parts by weight, containing (C) a copolymerizable vinyl monomer containing a hydroxyl group At least one.

作為構成本實施方式的黏著劑組合物中的丙烯酸類聚合物的（D）含有芳香族基團的共聚性乙烯基單體（以下有時簡稱為“含芳香族基團的單體”），能夠使用具有（甲基）丙烯醯基或乙烯基等不飽和雙鍵之聚合性的官能基、且具有芳香族基團或雜環者。作為含芳香族基團的單體，例如可列舉出苯乙烯、α-甲基苯乙烯等苯乙烯類單體；乙烯基甲苯、α-乙烯基甲苯等乙烯基甲苯類單體；乙烯基吡啶、乙烯基哌啶酮、乙烯基嘧啶、乙烯基哌、乙烯基吡、乙烯基吡咯、乙烯基咪唑、乙烯基㗁唑、乙烯基嗎啉等具有雜環的乙烯基類單體；（甲基）丙烯酸苯氧基乙酯、（甲基）丙烯酸苄酯這樣的含有芳香族環的（甲基）丙烯酸烷基酯；N-丙烯醯嗎啉、N-丙烯醯哌啶、N-甲基丙烯醯哌啶、N-丙烯醯基吡咯啶等含有雜環的（甲基）丙烯酸類單體等，優選選自這些化合物群組中的至少一種以上。另外，例示於上述化合物中的雜環中，哌啶酮、哌、嗎啉、哌啶、吡咯啶為不在環內具有不飽和鍵的飽和雜環，吡啶、嘧啶、吡、吡咯、咪唑、㗁唑為在環內具有不飽和鍵的不飽和雜環（雜芳環）。上述含芳香族基團的單體可以為不含羥基及羧基的單體。
其中，作為（D）含有芳香族基團的共聚性乙烯基單體，優選選自（甲基）丙烯酸苄酯、（甲基）丙烯酸苯氧基乙酯中的至少一種以上。(D) an aromatic group-containing copolymerizable vinyl monomer (hereinafter sometimes simply referred to as an "aromatic group-containing monomer") as the acrylic polymer constituting the acrylic polymer in the adhesive composition of the present embodiment, A polymerizable functional group having an unsaturated double bond such as a (meth) acrylfluorenyl group or a vinyl group, and an aromatic group or a heterocyclic ring can be used. Examples of the aromatic group-containing monomer include styrene-based monomers such as styrene and α-methylstyrene; vinyl toluene-based monomers such as vinyl toluene and α-vinyl toluene; and vinylpyridine , Vinyl piperidone, vinyl pyrimidine, vinyl piperidine, vinyl pyridine, vinyl pyrrole, vinyl imidazole, vinyl oxazole, vinyl morpholine and other vinyl monomers with heterocyclic rings; ( Aromatic ring-containing alkyl (meth) acrylates such as phenoxyethyl methacrylate and benzyl (meth) acrylate; N-acrylic acid morpholine, N-acrylic acid piperidine, N-formyl Heterocyclic-containing (meth) acrylic monomers such as methacrylic acid piperidine and N-propenylpyrrolidine are preferably selected from at least one or more of these compound groups. Among the heterocycles exemplified in the above compounds, piperidone, piperidine, morpholine, piperidine, and pyrrolidine are saturated heterocyclic rings having no unsaturated bond in the ring, and pyridine, pyrimidine, pyridine, pyrrole, and imidazole The oxazole is an unsaturated heterocyclic ring (heteroaromatic ring) having an unsaturated bond in the ring. The aromatic group-containing monomer may be a monomer not containing a hydroxyl group and a carboxyl group.
Among these, as the (D) copolymerizable vinyl monomer containing an aromatic group, at least one or more kinds selected from benzyl (meth) acrylate and phenoxyethyl (meth) acrylate are preferred.

為了得到折射率高的黏著劑層，優選使用（D）含有芳香族基團的共聚性乙烯基單體。此外，本實施方式的黏著劑組合物中，藉由使（D）含有芳香族基團的共聚性乙烯基單體與構成丙烯酸類聚合物的其他成分一同共聚，從而對由黏著劑組合物交聯而成的黏著劑層賦予一定程度的硬度，表現出耐凹陷性。In order to obtain an adhesive layer having a high refractive index, it is preferable to use (D) a copolymerizable vinyl monomer containing an aromatic group. In addition, in the adhesive composition of the present embodiment, the copolymerizable vinyl monomer (D) containing an aromatic group is copolymerized with other components constituting the acrylic polymer, so that the adhesive composition is transferred to the adhesive composition. The combined adhesive layer imparts a certain degree of hardness and exhibits dent resistance.

（A）烷基的碳原子數為C8~C18的（甲基）丙烯酸烷基酯單體的至少一種、（B）烷基的碳原子數為C1~C5的（甲基）丙烯酸烷基酯單體的至少一種及（D）含有芳香族基團的共聚性乙烯基單體的至少一種的合計100重量份中，本實施方式的黏著劑組合物中的丙烯酸類聚合物能夠以1~50重量份、優選以3~40重量份、特別優選以5~20重量份、作為共聚比例的上限值進一步優選以15重量份以下的比例含有（D）含有芳香族基團的共聚性乙烯基單體的至少一種。(A) At least one kind of (meth) acrylic acid alkyl ester monomer having C8 to C18 alkyl groups, (B) (meth) acrylic acid alkyl ester having C1 to C5 alkyl groups The acrylic polymer in the adhesive composition of the present embodiment may be present in an amount of 1 to 50 parts by weight based on 100 parts by weight of the total of at least one of the monomers and (D) at least one of the copolymerizable vinyl monomers containing an aromatic group. The upper limit of the copolymerization ratio is preferably 3 to 40 parts by weight, particularly preferably 5 to 20 parts by weight, and more preferably 15 parts by weight or less. (D) Copolymerizable vinyl group containing an aromatic group At least one monomer.

本實施方式的黏著劑組合物中的丙烯酸類聚合物為以不含帶羧基的共聚性乙烯基單體的方式共聚得到的共聚物。
本實施方式的黏著劑組合物中，用作丙烯酸類聚合物的共聚物的聚合方法沒有特別限定，可使用溶液聚合法、乳液聚合法等適宜、公知的聚合方法。The acrylic polymer in the adhesive composition of the present embodiment is a copolymer obtained by copolymerization so as not to contain a copolymerizable vinyl monomer having a carboxyl group.
In the adhesive composition of this embodiment, the polymerization method used as a copolymer of an acrylic polymer is not specifically limited, A suitable and well-known polymerization method, such as a solution polymerization method and an emulsion polymerization method, can be used.

本實施方式中，用作丙烯酸類聚合物的共聚物的玻璃化轉變溫度（以下，記作Tg）優選為-70℃以上-20℃以下。若Tg小於-70℃，則耐起泡性（耐久性）與耐凹陷性降低，若Tg大於-20℃，則抗捲曲性降低，而且容易發生亮度不均，故而不優選。另外，用作本實施方式的黏著劑組合物中的丙烯酸類聚合物的共聚物的Tg更優選為-65℃~-30℃。In this embodiment, the glass transition temperature (hereinafter, referred to as Tg) of the copolymer used as the acrylic polymer is preferably -70 ° C or higher and -20 ° C or lower. If Tg is lower than -70 ° C, foam resistance (durability) and dent resistance are reduced. If Tg is higher than -20 ° C, curl resistance is reduced, and uneven brightness is liable to occur, which is not preferable. The Tg of the copolymer of the acrylic polymer used in the adhesive composition of the present embodiment is more preferably -65 ° C to -30 ° C.

此外，本實施方式的黏著劑組合物中，用作丙烯酸類聚合物的共聚物的重均分子量能夠設為150萬~300萬。優選為175萬~275萬的範圍，特別優選為200萬~250萬的範圍。
用作丙烯酸類聚合物的共聚物的重均分子量若小於上述下限值，則耐久性不充分，故而不優選。Moreover, in the adhesive composition of this embodiment, the weight average molecular weight of the copolymer used as an acrylic polymer can be set to 1.5 to 3 million. A range of 1.75 million to 2.75 million is preferable, and a range of 2 million to 2.5 million is particularly preferable.
If the weight-average molecular weight of the copolymer used as the acrylic polymer is less than the above-mentioned lower limit, the durability is insufficient, which is not preferable.

此外，本實施方式的黏著劑組合物中，用作丙烯酸類聚合物的共聚物的分子量的分散度（Mw[重均分子量]/Mn[數均分子量]）優選為6.0以下。
藉由使用作丙烯酸類聚合物的共聚物的重均分子量為150萬~300萬，且使共聚物的分子量的分散度為6.0以下，例如能夠提高在超過100℃的高溫下放置後的剝離耐久性，可抑制黏著劑層的剝落或起泡的發生。
作為共聚物的分子量的分散度，更優選為5.2以下，進一步優選為4.5以下。In the adhesive composition of the present embodiment, the molecular weight dispersion (Mw [weight average molecular weight] / Mn [number average molecular weight]) used as the copolymer of the acrylic polymer is preferably 6.0 or less.
When the copolymer used as an acrylic polymer has a weight average molecular weight of 1.5 million to 3 million, and the molecular weight dispersion of the copolymer is 6.0 or less, for example, the peeling durability after being left at a high temperature exceeding 100 ° C can be improved. It can suppress the peeling or foaming of the adhesive layer.
The degree of dispersion of the molecular weight of the copolymer is more preferably 5.2 or less, and still more preferably 4.5 or less.

本實施方式的黏著劑組合物中，作為交聯劑，使用3官能度以上的異氰酸酯化合物。作為3官能度以上的異氰酸酯化合物，為在1分子中具有至少3個以上的異氰酸酯（NCO）基的聚異氰酸酯化合物即可，可列舉出六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、二苯基甲烷二異氰酸酯、甲伸苯二異氰酸酯、二甲苯撐基二異氰酸酯等二異氰酸酯類（1分子中具有2個NCO基的化合物）的縮二脲改質體或異氰脲酸酯改質體、與三羥甲基丙烷或甘油等3價以上的多元醇（1分子中具有至少3個以上OH基的化合物）的加合物（多元醇改質體）等。
其中，3官能度以上的異氰酸酯化合物為在1分子中具有至少3個以上異氰酸酯（NCO）基的聚異氰酸酯化合物，特別優選為選自由六亞甲基二異氰酸酯化合物的異氰脲酸酯體、異佛爾酮二異氰酸酯化合物的異氰脲酸酯體、六亞甲基二異氰酸酯化合物的加合物、異佛爾酮二異氰酸酯化合物的加合物、六亞甲基二異氰酸酯化合物的縮二脲體、異佛爾酮二異氰酸酯化合物的縮二脲體組成的化合物群組中的至少一種以上。
相對於所述（A）、所述（B）及所述（D）的合計100重量份，能夠以0.001~0.05重量份的比例含有交聯劑的3官能度以上的異氰酸酯化合物。In the adhesive composition of the present embodiment, as the crosslinking agent, an isocyanate compound having a trifunctionality or higher is used. The isocyanate compound having three or more functionalities may be a polyisocyanate compound having at least three or more isocyanate (NCO) groups in one molecule, and examples include hexamethylene diisocyanate, isophorone diisocyanate, and diisocyanate. Biuret modifiers or isocyanurate modifiers of diisocyanates (compounds with two NCO groups in one molecule) such as phenylmethane diisocyanate, methylene diisocyanate, and xylylene diisocyanate And adducts (polyol modifiers) with trivalent or higher polyhydric alcohols (compounds having at least 3 or more OH groups in one molecule) such as trimethylolpropane or glycerol.
Among them, the isocyanate compound having three or more functionalities is a polyisocyanate compound having at least three or more isocyanate (NCO) groups in one molecule, and is particularly preferably an isocyanurate or an isocyanurate compound selected from a hexamethylene diisocyanate compound. Isocyanurate body of phorone diisocyanate compound, adduct of hexamethylene diisocyanate compound, adduct of isophorone diisocyanate compound, biuret body of hexamethylene diisocyanate compound And at least one or more compounds of the biuret body of the isophorone diisocyanate compound.
The isocyanate compound having a trifunctional or higher functionality of the crosslinking agent may be contained in a proportion of 0.001 to 0.05 parts by weight based on 100 parts by weight of the total of the components (A), (B), and (D).

本實施方式的黏著劑組合物中，能夠在黏著劑組合物中含有矽烷偶聯劑。
作為矽烷偶聯劑，可列舉出乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基參（2-甲氧基乙氧基）矽烷等含乙烯基的矽烷偶聯劑；3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-甲基丙烯醯氧丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧丙基甲基二乙氧基矽烷等含甲基丙烯醯氧基的矽烷偶聯劑；乙烯基三乙醯氧基矽烷等含乙醯氧基的矽烷偶聯劑；3-丙烯醯氧基丙基三甲氧基矽烷、3-丙烯醯氧基丙基三乙氧基矽烷等含丙烯醯氧基的矽烷偶聯劑；3-縮水甘油醚氧基丙基三甲氧基矽烷、3-縮水甘油醚氧基丙基三乙氧基矽烷、3-縮水甘油醚氧基丙基甲基二甲氧基矽烷、3-縮水甘油醚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的矽烷偶聯劑；乙烯基三氯矽烷等含氯基的矽烷偶聯劑；3-巰丙基三甲氧基矽烷;、3-巰丙基三乙氧基矽烷、3-巰丙基甲基二甲氧基矽烷、3-巰基丙基甲基二乙氧基矽烷等含巰基的矽烷偶聯劑；3-三甲氧基矽基丙基琥珀酸酐等含酸酐基的矽烷偶聯劑；3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷等含胺基的矽烷偶聯劑；3-異氰酸酯基丙基三甲氧基矽烷、3-異氰酸酯基丙基三乙氧基矽烷等含異氰酸酯基的矽烷偶聯劑等。這些矽烷偶聯劑能夠使用一種或混合使用兩種以上，作為添加量，相對於100重量份的黏著劑組合物，通常優選添加0.001~5重量份。
作為矽烷偶聯劑，優選使用具有選自環氧基、巰基、酸酐基中的至少一種官能基的矽烷偶聯劑。
相對於所述（A）、所述（B）及所述（D）的合計100重量份，能夠含有0.01~0.1重量份的矽烷偶聯劑。The adhesive composition of this embodiment can contain a silane coupling agent in an adhesive composition.
Examples of the silane coupling agent include vinyl-containing silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyl ginseng (2-methoxyethoxy) silane; 3- Methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methyl Methacryloxysilane-containing silane coupling agents such as propylene-oxypropylmethyldiethoxysilane; Acetyloxysilane-containing silane coupling agents such as vinyltriethoxysilane; 3-propylene Acrylic alkoxy-containing silane coupling agents such as oxypropyltrimethoxysilane, 3-propenyloxypropyltriethoxysilane; 3-glycidyl etheroxypropyltrimethoxysilane, 3- Glycidyletheroxypropyltriethoxysilane, 3-glycidyletheroxypropylmethyldimethoxysilane, 3-glycidyletheroxypropylmethyldiethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane-containing silane coupling agents; vinyltrichlorosilane-containing silane coupling agents; 3-mercaptopropyltrimethoxysilane ;, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane and other mercapto-containing silane coupling agents; 3-trimethyl Silyl coupling agents containing acid anhydride groups such as oxysilylpropylsuccinic anhydride; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl ) Amine-containing silane coupling agents such as 3-aminopropyltrimethoxysilane; isocyanate-containing silanes such as 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane Coupling agent, etc. These silane coupling agents can be used singly or in combination of two or more kinds. It is generally preferable to add 0.001 to 5 parts by weight based on 100 parts by weight of the adhesive composition.
As the silane coupling agent, a silane coupling agent having at least one functional group selected from an epoxy group, a mercapto group, and an acid anhydride group is preferably used.
The silane coupling agent can be contained in an amount of 0.01 to 0.1 parts by weight based on 100 parts by weight of the total of (A), (B), and (D).

作為本實施方式的黏著劑組合物，能夠使用觸變指數（TI值）為1.25以下的黏著劑組合物溶液，所述觸變指數為使用BH型黏度計（TOKI SANGYO CO.,LTD.製造），在25℃下、使轉子轉速變化為2rpm及20rpm而測定的黏度的比，觸變指數（TI值）=[2rpm下的黏度]/[20rpm下的黏度]。
上述TI值為評價將黏著劑組合物溶解於溶劑而成的黏著劑組合物溶液的黏度特性中的、黏度的剪切速度依賴性的值，為成為所謂的“觸變性黏度”的尺度的值。使用BH型黏度計，測定黏著劑組合物溶液的黏度時，使轉子的轉速變化為2rpm及20rpm並進行測定，能夠以其值的比率算出TI值。
TI值高時，伴隨剪切速度的上升，由黏著劑組合物形成的塗布材料的黏度大幅降低。例如，在將由黏著劑組合物形成的塗布材料塗布於樹脂膜的工序中，由該塗布材料的剪切變形導致的黏度下降變得顯著，作為其結果，塗布性變差。As the adhesive composition of the present embodiment, an adhesive composition solution having a thixotropic index (TI value) of 1.25 or less can be used, and the thixotropic index is a BH-type viscometer (manufactured by TOKI SANGYO CO., LTD.) , The ratio of the viscosity measured at 25 ° C with the rotor speed changed to 2 rpm and 20 rpm, the thixotropic index (TI value) = [viscosity at 2 rpm] / [viscosity at 20 rpm].
The TI value is a value that evaluates the shear rate dependence of the viscosity among the viscosity characteristics of an adhesive composition solution obtained by dissolving the adhesive composition in a solvent, and is a value that is a measure of the so-called "thixotropic viscosity". . When the viscosity of the adhesive composition solution is measured using a BH-type viscometer, the rotation speed of the rotor is changed to 2 rpm and 20 rpm, and the measurement is performed. The TI value can be calculated as a ratio of the values.
When the TI value is high, the viscosity of the coating material formed from the adhesive composition is significantly reduced with an increase in the shear rate. For example, in the step of applying a coating material made of an adhesive composition to a resin film, a decrease in viscosity due to shear deformation of the coating material becomes significant, and as a result, applicability is deteriorated.

作為本實施方式的黏著劑組合物，能夠使用TI值為1.25以下的黏著劑組合物溶液。TI值超過1.25時，黏著劑組合物的塗布性變差，不能進行穩定的塗布。
通常在使用烷基的碳原子數為C8以上的（甲基）丙烯酸烷基酯單體作為單體成分、並進行聚合而得到的分子量為100萬以上的丙烯酸聚合物中，藉由基於碳原子數為C8以上的長鏈烷基的聚合物鏈的纏結，表現出觸變性黏度，上述TI值有變高的傾向，作為黏著劑組合物塗料而使用時，塗布性變差。
本實施方式的黏著劑組合物中，上述TI值範圍的黏著劑組合物溶液可藉由進行構成黏著劑組合物的丙烯酸類聚合物的單體成分的種類或含量比的調節、共聚物的聚合方法的調節、溶解於乙酸乙酯等溶劑時的丙烯酸類聚合物的濃度的調節而得到。
就本實施方式的黏著劑組合物溶液而言，即使用作丙烯酸類聚合物的共聚物的重均分子量為150萬以上，但由於TI值為1.25以下，因此可得到穩定的塗布性。As the adhesive composition of the present embodiment, an adhesive composition solution having a TI value of 1.25 or less can be used. When the TI value exceeds 1.25, the coatability of the adhesive composition is deteriorated, and stable coating cannot be performed.
Generally, an acrylic polymer having a molecular weight of 1 million or more obtained by polymerizing an alkyl (meth) acrylic acid alkyl ester monomer having an alkyl group of C8 or more as a monomer component and using a carbon atom is The entanglement of polymer chains of a long-chain alkyl group having a number of C8 or more exhibits thixotropic viscosity, and the above-mentioned TI value tends to be high. When used as a coating material for an adhesive composition, the coatability is poor.
In the adhesive composition of the present embodiment, the adhesive composition solution in the TI value range can be adjusted by the type or content ratio of the monomer components of the acrylic polymer constituting the adhesive composition, and the polymerization of the copolymer. It can be obtained by adjusting the method and adjusting the concentration of the acrylic polymer when dissolved in a solvent such as ethyl acetate.
In the adhesive composition solution of the present embodiment, even if the weight average molecular weight of the copolymer used as the acrylic polymer is 1.5 million or more, since the TI value is 1.25 or less, stable coatability can be obtained.

作為除了上述以外的任意成分，本實施方式的黏著劑組合物能夠適當地摻合抗氧化劑、抗靜電劑、表面活性劑、固化促進劑、增塑劑、增黏劑、填充劑、交聯催化劑、交聯延遲劑、固化延遲劑、加工助劑、抗老化劑、紫外線吸收劑等公知的添加劑。這些添加劑可以單獨使用或同時使用2種以上。As an arbitrary component other than the above, the adhesive composition of the present embodiment can be appropriately blended with an antioxidant, an antistatic agent, a surfactant, a curing accelerator, a plasticizer, a tackifier, a filler, and a crosslinking catalyst. , Well-known additives such as crosslinking delaying agents, curing delaying agents, processing aids, anti-aging agents, and ultraviolet absorbers. These additives can be used alone or in combination of two or more.

由本實施方式的黏著劑組合物交聯而成的黏著劑層能夠藉由將所述黏著劑組合物塗布於基材或離型膜後、使黏著劑組合物交聯而形成。交聯後的黏著劑層的凝膠分率優選為40~70%，進一步，更優選為42~68%，最優選為45~65%。若黏著劑層的凝膠分率為該範圍外，則耐熱性或耐久性降低，故而不優選。The adhesive layer formed by cross-linking the adhesive composition of the present embodiment can be formed by applying the adhesive composition to a substrate or a release film, and then crosslinking the adhesive composition. The gel fraction of the cross-linked adhesive layer is preferably 40 to 70%, more preferably 42 to 68%, and most preferably 45 to 65%. When the gel fraction of the adhesive layer is outside this range, heat resistance and durability are reduced, which is not preferable.

將由本實施方式的黏著劑組合物交聯而成的黏著劑層用於光學構件的層間的貼合等時，理想的是為薄黏著劑層。黏著劑層的厚度優選為1~25μm，更優選為5~25μm，進一步優選為5~20μm。
此外，為了減少黏著劑層與光學構件的界面的光線的反射，希望光學構件與黏著劑層之間的折射率差盡可能小。When the adhesive layer obtained by crosslinking the adhesive composition of the present embodiment is used for bonding between layers of an optical member or the like, a thin adhesive layer is desirable. The thickness of the adhesive layer is preferably 1 to 25 μm, more preferably 5 to 25 μm, and even more preferably 5 to 20 μm.
In addition, in order to reduce reflection of light at the interface between the adhesive layer and the optical member, it is desirable that the refractive index difference between the optical member and the adhesive layer be as small as possible.

此外，優選由本實施方式的黏著劑組合物交聯而成的、20μm厚的黏著劑層的耐凹陷性為10g以上。
此外，經由由所述黏著劑組合物交聯而成的黏著劑層而將作為偏光素膜的保護膜的以PET（聚對苯二甲酸乙二酯；厚度20μm）為表面基材的厚度為140μm的偏振片與厚度為0.4mm的無鹼玻璃貼合，並按照JIS-Z0237、沿180°方向以300mm/分鐘的剝離速度，將以PET為表面基材的偏振片從玻璃面上剝離時的黏著力優選為4N/25mm以下。該黏著力進一步優選為1~4N/25mm，特別優選為1.2~3.8N/25mm。In addition, it is preferable that the 20 μm-thick adhesive layer formed by crosslinking the adhesive composition of the present embodiment has a dent resistance of 10 g or more.
In addition, a thickness of PET (polyethylene terephthalate; 20 μm) as a surface substrate was obtained as a protective film of a polarizer film through an adhesive layer cross-linked from the adhesive composition. When a 140 μm polarizer is bonded to an alkali-free glass with a thickness of 0.4 mm, and a polarizer with PET as the surface substrate is peeled from the glass surface in accordance with JIS-Z0237 at a peeling speed of 300 mm / min along the 180 ° direction The adhesive force is preferably 4 N / 25 mm or less. The adhesive force is more preferably 1 to 4 N / 25 mm, and particularly preferably 1.2 to 3.8 N / 25 mm.

此外，由本實施方式的黏著劑組合物交聯而成的黏著劑層層疊而成的黏著膜能夠藉由在基材、光學膜、離型膜的單面上形成黏著劑層而製造。作為用於黏著劑層的形成的基材膜或保護黏著面的離型膜（隔離膜），能夠使用聚酯膜等樹脂膜等。就基材膜而言，能夠對樹脂膜的與形成有黏著劑層的一側為相反的面進行利用矽酮類、氟類的離型劑或塗布劑、二氧化矽微粒等的防汙處理，利用抗靜電劑的塗布或捏合等的抗靜電處理。Moreover, the adhesive film which laminated | stacked the adhesive layer which cross-linked the adhesive composition of this embodiment can be manufactured by forming the adhesive layer on one surface of a base material, an optical film, and a release film. As a base film for forming an adhesive layer or a release film (release film) for protecting an adhesive surface, a resin film such as a polyester film can be used. For the base film, antifouling treatment with a silicone-based, fluorine-based release agent or coating agent, or silicon dioxide particles can be performed on the surface of the resin film opposite to the side on which the adhesive layer is formed. , Using antistatic agents such as coating or kneading antistatic treatment.

就離型膜而言，利用矽酮類、氟類的離型劑等對黏著劑層的與黏著面貼合的一側的面實施離型處理。藉由在1個光學膜用黏著劑層的兩面上分別貼合離型膜的已實施離型處理的面，還能夠製成“離型膜/黏著劑層/離型膜”的結構。此時，藉由將兩側的離型膜依次或同時剝離而露出黏著面，由此可與光學膜等光學構件貼合。作為光學膜，可列舉出偏振膜、相位差膜、防反射膜、防眩（anti-glare）膜、紫外線吸收膜、紅外線吸收膜、光學補償膜、亮度提高膜、鏡片膜、硬塗層膜、觸摸面板用透明導電性膜等。In the release film, a release treatment is performed on the side of the adhesive layer that is in contact with the adhesive surface with a silicone-based, fluorine-based release agent, or the like. A release film / adhesive layer / release film structure can also be produced by attaching the release-treated surface of the release film to both sides of one adhesive layer for an optical film. At this time, by releasing the release films on both sides sequentially or simultaneously to expose the adhesive surface, the release film can be bonded to an optical member such as an optical film. Examples of the optical film include a polarizing film, a retardation film, an anti-reflection film, an anti-glare film, an ultraviolet absorption film, an infrared absorption film, an optical compensation film, a brightness enhancement film, a lens film, and a hard coat film And transparent conductive films for touch panels.

由於由本實施方式的黏著劑組合物交聯得到的黏著劑層的耐熱性及耐久性優異，因此適用於以偏振膜/黏著劑層/液晶顯示面板的結構貼合偏振膜與液晶顯示面板的用途，進一步，適用於以偏振膜/黏著劑層/相位差膜/黏著劑層/有機EL面板的結構貼合相位差膜與偏振膜或有機EL面板的用途。Since the adhesive layer obtained by cross-linking the adhesive composition according to this embodiment is excellent in heat resistance and durability, it is suitable for use in which a polarizing film and a liquid crystal display panel are bonded with a structure of a polarizing film / adhesive layer / liquid crystal display panel. Further, it is suitable for the application of bonding a retardation film and a polarizing film or an organic EL panel with a structure of a polarizing film / adhesive layer / phase retardation film / adhesive layer / organic EL panel.

由本實施方式的黏著劑組合物交聯得到的黏著劑層及黏著膜能夠用於安裝於圖像顯示裝置的各種光學膜、觸控面板用的各種光學膜、電子紙用的各種光學膜、安裝於液晶顯示面板的各種光學膜、安裝於有機EL面板的各種光學膜的貼合。此外，能夠製成在這些光學膜的至少一側的面上層疊有所述黏著劑層的帶黏著劑層的光學膜。具有用離型膜保護的黏著劑層時，藉由剝離離型膜，從而以“光學膜/黏著劑層”的形式露出黏著劑層，並與其他光學膜貼合，由此能夠得到在層間使用黏著劑層而層疊而成的“光學膜/黏著劑層/光學膜”這樣的結構。The adhesive layer and the adhesive film obtained by crosslinking the adhesive composition of this embodiment can be used for various optical films mounted on image display devices, various optical films for touch panels, various optical films for electronic paper, and mounting. Bonding of various optical films for liquid crystal display panels and various optical films mounted on organic EL panels. Moreover, an optical film with an adhesive layer in which the said adhesive layer is laminated | stacked on the surface of at least one side of these optical films can be manufactured. When an adhesive layer protected by a release film is provided, the release film is peeled off to expose the adhesive layer in the form of an "optical film / adhesive layer" and adhere to other optical films. A structure called "optical film / adhesive layer / optical film" laminated using an adhesive layer.

由本實施方式的黏著劑組合物交聯得到的黏著劑層適用於安裝於圖像顯示裝置的各種光學膜的貼合。由本實施方式的黏著劑組合物交聯得到的黏著劑層也能夠適用於“偏振膜/黏著劑層”、“偏振膜/黏著劑層/離型膜”、“偏振膜/黏著劑層/相位差膜/黏著劑層”、“偏振膜/黏著劑層/相位差膜/黏著劑層/離型膜”等的結構。The adhesive layer obtained by crosslinking the adhesive composition of this embodiment is suitable for bonding various optical films mounted on an image display device. The adhesive layer obtained by crosslinking the adhesive composition of the present embodiment can also be applied to "polarizing film / adhesive layer", "polarizing film / adhesive layer / release film", "polarizing film / adhesive layer / phase" "Differential film / adhesive layer", "polarizing film / adhesive layer / phase difference film / adhesive layer / release film" and the like.

作為上述的圖像顯示裝置，可列舉出液晶顯示裝置（液晶顯示面板）、有機EL顯示裝置（有機EL面板）、觸摸面板、電子紙等，但是並不限定於此。以下，以有機EL面板為代表的例子進行說明，基於這些主旨的本實施方式的黏著劑層及黏著膜也可適用於液晶顯示面板等其他的圖像顯示裝置。
作為圖像顯示裝置，也可適用於特別適合於在要求高耐久性的汽車等車內使用的車載用監控、用於汽車導航等的液晶顯示面板。Examples of the image display device include a liquid crystal display device (liquid crystal display panel), an organic EL display device (organic EL panel), a touch panel, and electronic paper. However, the present invention is not limited to this. Hereinafter, an example will be described taking an organic EL panel as an example. The adhesive layer and the adhesive film of the present embodiment based on these principles can also be applied to other image display devices such as a liquid crystal display panel.
The image display device can also be applied to a liquid crystal display panel that is particularly suitable for in-vehicle monitoring used in automobiles such as automobiles requiring high durability, and used in car navigation and the like.

作為安裝於有機EL面板的相位差膜的材質，可列舉出聚碳酸酯化合物，優選具有反向波長色散特性（波長越長雙折射越大）的材料。聚碳酸酯化合物為聚合物的重複單元中含有碳酸酯鍵（-O-CO-O-）的樹脂，各碳酸酯鍵之間所含有的化學結構中，已知有芳香族類、脂肪族類等各種化學結構。重複單元可以為一種也可以為兩種以上。作為相位差膜的位相差，可列舉出1/4λ或1/2λ（波長λ的1/4倍或1/2倍）。
其中，近年來，在有機EL面板中需要用於防止反射外部光線的圓偏振片，圓偏振片為將線性偏振膜與1/4λ相位差膜進行2片重疊而成的結構，且由於將相位差膜面貼合於有機EL面板，因此有由聚碳酸酯類樹脂導致的耐久性、耐起泡性差的缺點。
由本實施方式的黏著劑組合物交聯得到的黏著劑層作為安裝有由聚碳酸酯類樹脂形成的1/4λ的相位差膜的偏振膜及有機EL面板的、光學膜的貼合用，其利用價值極高。The material of the retardation film to be mounted on the organic EL panel includes a polycarbonate compound, and a material having a reverse wavelength dispersion characteristic (birefringence is larger as the wavelength is longer) is preferable. Polycarbonate compounds are resins containing carbonate bonds (-O-CO-O-) in repeating units of polymers. Among the chemical structures contained between carbonate bonds, aromatics and aliphatics are known. And other chemical structures. The repeating unit may be one type or two or more types. Examples of the phase difference of the retardation film include 1 / 4λ or 1 / 2λ (1/4 times or 1/2 times the wavelength λ).
Among them, in recent years, a circular polarizer for preventing reflection of external light has been required in organic EL panels. The circular polarizer has a structure in which a linear polarizing film and a 1 / 4λ retardation film are overlapped with each other. The poor film surface is adhered to the organic EL panel, so there is a disadvantage that the polycarbonate resin has poor durability and foam resistance.
The adhesive layer obtained by cross-linking the adhesive composition of the present embodiment is used for bonding an optical film of a polarizing film and an organic EL panel to which a retardation film of 1 / 4λ formed of a polycarbonate resin is mounted. The use value is extremely high.

作為偏振膜，通常使用將含有碘分子（I2）的聚乙烯醇（PVA）層作為偏光鏡，作為保護層（有時也被稱作偏光鏡的保護膜）而在其兩側層疊有使用了三醋酸纖維素膜（TAC）、COP（環烯烴聚合物）、丙烯酸樹脂、聚丙烯（PP）等光學特性（透明性等）優異的材料的樹脂膜的結構。進一步，保護層的樹脂膜也有時兼具相位差膜的功能。此外，對於要求高耐久性的用途，有時也可使用染料系，而不是碘系。As a polarizing film, a polyvinyl alcohol (PVA) layer containing an iodine molecule (I2) is usually used as a polarizer, and a protective layer (sometimes referred to as a protective film of a polarizer) is used on both sides of the polarizer. Resin film structure of materials with excellent optical properties (transparency, etc.) such as cellulose triacetate film (TAC), COP (cycloolefin polymer), acrylic resin, and polypropylene (PP). Further, the resin film of the protective layer may also function as a retardation film. In addition, for applications requiring high durability, a dye system may be used instead of an iodine system.

作為有機EL面板，可列舉出具有有機發光二極體（OLED）結構，並具有在正負的電極間形成、層疊有電洞注入層、電洞傳輸層、發光層、電子傳輸層、電子注入層等多個功能層的發光元件的結構。作為電極，可列舉出具有透光性的透明電極層、不透明的金屬電極層。也可製造可撓性的有機EL面板，藉由箔、電鍍、印刷、蒸鍍、濺射等能夠在樹脂等可撓性基材上形成電極、配線、功能層等。
[實施例]Examples of the organic EL panel include an organic light emitting diode (OLED) structure, and a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer formed between positive and negative electrodes and stacked. Structure of a light-emitting element having multiple functional layers. Examples of the electrode include a transparent electrode layer having translucency and an opaque metal electrode layer. A flexible organic EL panel can also be manufactured, and electrodes, wirings, functional layers, and the like can be formed on a flexible substrate such as resin by foil, plating, printing, vapor deposition, sputtering, or the like.
[Example]

以下，藉由實施例對本發明進行具體的說明。Hereinafter, the present invention will be specifically described by way of examples.

＜丙烯酸類聚合物的製備＞
[實施例1]
向具備反應容器、攪拌機、溫度計、回流冷凝器及氮氣輸送管的反應裝置中導入氮氣，用氮氣置換反應容器內的空氣。然後，向反應容器中添加丙烯酸異壬酯50重量份、丙烯酸丁酯35重量份、丙烯酸甲酯10重量份、丙烯酸8-羥基辛酯0.2重量份、丙烯酸苄酯5重量份及溶劑（乙酸乙酯）60重量份。然後，以2小時滴加作為聚合引發劑的偶氮二異丁腈0.1重量份，於65℃反應6小時，得到實施例1的丙烯酸類聚合物溶液。
[實施例2~8及比較例1~5]
除了將構成丙烯酸類聚合物的各單體的種類、摻合比例各自設為如表1的（A）~（D）組的記載所示以外，以與上述實施例1同樣的方法，得到實施例2~8及比較例1~5的丙烯酸類聚合物溶液。<Preparation of acrylic polymer>
[Example 1]
Nitrogen was introduced into a reaction apparatus including a reaction vessel, a stirrer, a thermometer, a reflux condenser, and a nitrogen transfer pipe, and the air in the reaction vessel was replaced with nitrogen. Then, 50 parts by weight of isononyl acrylate, 35 parts by weight of butyl acrylate, 10 parts by weight of methyl acrylate, 0.2 parts by weight of 8-hydroxyoctyl acrylate, 5 parts by weight of benzyl acrylate, and a solvent (ethyl acetate) were added to the reaction vessel. Ester) 60 parts by weight. Then, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours, and the mixture was reacted at 65 ° C. for 6 hours to obtain the acrylic polymer solution of Example 1.
[Examples 2 to 8 and Comparative Examples 1 to 5]
Except that the types and blending ratios of the respective monomers constituting the acrylic polymer were as shown in the description of the groups (A) to (D) in Table 1, the same method as in Example 1 was used. The acrylic polymer solutions of Examples 2 to 8 and Comparative Examples 1 to 5.

＜黏著劑組合物、黏著劑層及黏著膜的製造＞
[實施例1]
向如上所述地製備的反應容器內的實施例1的丙烯酸類聚合物溶液中添加二甲苯撐基二異氰酸酯（XDI）的加合物（Takenate（註冊商標）D-110N；Mitsui Chemicals, Inc.製造）0.05重量份、矽烷偶聯劑（KBM-403；3-縮水甘油醚氧基丙基三甲氧基矽烷：Shin-Etsu Chemical Co., Ltd.製造）0.05重量份並進行攪拌混合，得到實施例1的黏著劑組合物。將該黏著劑組合物以乾燥後的厚度為20μm的方式塗布於離型膜（塗布有矽酮樹脂的聚對苯二甲酸乙二酯（PET）膜）上後，於90℃乾燥5分鐘從而形成黏著劑層。然後，在乾燥的黏著劑層上疊加離型處理後的離型膜，製成由離型膜/黏著劑層/離型膜構成的層結構。進一步藉由在23℃、50%RH的氣氛下進行7天熟化（curing），由此得到實施例1的黏著膜。
[實施例2~8及比較例1~5]
除了將除丙烯酸類聚合物以外的添加劑的種類、摻合比例各自設為如表1的（G）組、（H）組的記載所示以外，以與上述實施例1同樣的方法，得到實施例2~8及比較例1~5的黏著劑組合物、黏著劑層及黏著膜。<Manufacture of an adhesive composition, an adhesive layer, and an adhesive film>
[Example 1]
To the acrylic polymer solution of Example 1 in the reaction container prepared as described above, an adduct of xylylene diisocyanate (XDI) (Takenate (registered trademark) D-110N; Mitsui Chemicals, Inc. (Manufactured) 0.05 parts by weight, silane coupling agent (KBM-403; 3-glycidyl etheroxypropyltrimethoxysilane: manufactured by Shin-Etsu Chemical Co., Ltd.) 0.05 parts by weight, and mixed by stirring The adhesive composition of Example 1. This adhesive composition was applied to a release film (polyethylene terephthalate (PET) film coated with a silicone resin) so that the thickness after drying was 20 μm, and then dried at 90 ° C. for 5 minutes to thereby Form an adhesive layer. Then, the release film after the release treatment is superimposed on the dried adhesive layer to form a layer structure composed of a release film / adhesive layer / release film. Furthermore, the adhesive film of Example 1 was obtained by performing curing for 7 days in the atmosphere of 23 degreeC and 50% RH.
[Examples 2 to 8 and Comparative Examples 1 to 5]
Except that the types and blending ratios of the additives other than the acrylic polymer were set as described in Groups (G) and (H) in Table 1, the same method as in Example 1 was used. The adhesive compositions, adhesive layers, and adhesive films of Examples 2 to 8 and Comparative Examples 1 to 5.

[表1]
[Table 1]

表1中，將（A）組的烷基的碳原子數為C8~C18的（甲基）丙烯酸烷基酯單體、（B）組的烷基的碳原子數為C1~C5的（甲基）丙烯酸烷基酯單體及（D）組的含有芳香族基團的共聚性乙烯基單體的合計設為100重量份。此外，作為（A）~（D）組、（G）組、（H）組的添加比例，將重量份的數值示於縮寫符號或名稱之後。另外，（C）組為含有羥基的共聚性乙烯基單體，但是比較例3中，包含帶羧基的共聚性乙烯基單體。此外，（G）組為3官能度以上的異氰酸酯化合物，（H）組為矽烷偶聯劑。In Table 1, the (A) alkyl group of the (A) group has C8 to C18 (meth) acrylic acid alkyl ester monomers, and the (B) group of the alkyl group has C1 to C5 (A The total amount of the alkyl group alkyl acrylate monomer and the aromatic group-containing copolymerizable vinyl monomer of the group (D) is 100 parts by weight. In addition, as the addition ratios of the groups (A) to (D), (G), and (H), the value in parts by weight is shown after the abbreviated symbol or name. The group (C) is a copolymerizable vinyl monomer containing a hydroxyl group, but in Comparative Example 3, a copolymerizable vinyl monomer having a carboxyl group was included. In addition, the group (G) is an isocyanate compound having 3 or more functionalities, and the group (H) is a silane coupling agent.

此外，將與表1所示的各成分的縮寫符號所對應的化合物名稱示於表2。另外，CORONATE（註冊商標）L為TOSOH CORPORATION的商品名稱。TDI是指甲伸苯二異氰酸酯，XDI是指二甲苯撐基二異氰酸酯。矽烷偶聯劑的KBM-403、X-12-967C（3-三甲氧基矽基丙基琥珀酸酐）、X-41-1805（含巰基的低聚物型矽烷偶聯劑）為Shin-Etsu Chemical Co., Ltd.的商品名稱。In addition, the compound names corresponding to the abbreviations of the respective components shown in Table 1 are shown in Table 2. In addition, CORONATE (registered trademark) L is a trade name of TOSOH CORPORATION. TDI is nail extension diisocyanate and XDI is xylylene diisocyanate. KBM-403, X-12-967C (3-trimethoxysilylpropylsuccinic anhydride) and X-41-1805 (mercapto-containing oligomeric silane coupling agent) for the silane coupling agent are Shin-Etsu Trade name of Chemical Co., Ltd ..

[表2]
[Table 2]

＜試驗方法及評價＞
使用得到的實施例1~8及比較例1~5的黏著膜，剝離離型膜（經矽酮樹脂塗布的PET膜），使黏著劑層露出，作為各種測定用及試驗用樣品。＜ Test method and evaluation ＞
Using the obtained adhesive films of Examples 1 to 8 and Comparative Examples 1 to 5, a release film (a PET film coated with a silicone resin) was peeled off, and the adhesive layer was exposed, and used as samples for various measurements and tests.

＜黏著力的評價＞
經由由上述實施例1~8及比較例1~5的黏著膜得到的黏著劑層將以PET（厚度20μm）為表面基材的厚度為140μm的偏振片貼合於8英寸尺寸的厚度為0.4mm的無鹼玻璃，放置1小時。然後，按照JIS-Z0237、沿180°方向以300mm/分鐘的剝離速度將以PET為表面基材的偏振片從玻璃面上剝離，將此時的剝離強度作為黏著力（N/25mm）。＜ Evaluation of adhesion ＞
A 140 μm-thick polarizer with PET (20 μm thickness) as the surface substrate was bonded to the adhesive layer obtained from the adhesive films of Examples 1 to 8 and Comparative Examples 1 to 5 above. mm of alkali-free glass, let stand for 1 hour. Then, according to JIS-Z0237, the polarizing plate with PET as the surface substrate was peeled from the glass surface at a peeling speed of 300 mm / min in the 180 ° direction, and the peeling strength at this time was used as the adhesive force (N / 25 mm).

＜耐久性‧亮度不均的評價＞
使用上述實施例1~8及比較例1~5的黏著膜，將以PET（厚度為20μm）為表面基材的厚度為140μm的偏振片貼合於8英寸尺寸的厚度為0.4mm的無鹼玻璃，然後，於105℃氣氛下保管500小時後，將有無剝落、起泡等缺點作為“耐久性”而進行評價，並評價放置於背光（back light）上時有無顏色的明暗等的“亮度不均”。耐久性評價中，將發生黏著劑層的剝落、起泡等缺點的情況記為“╳”，將完全沒有缺點的情況記為“○”。此外，亮度不均的評價中，將確認到亮度不均的情況記為“╳”，將沒有不均的情況記為“○”。<Evaluation of durability and uneven brightness>
Using the adhesive films of Examples 1 to 8 and Comparative Examples 1 to 5 above, a polarizing plate having a thickness of 140 μm using PET (thickness of 20 μm) as the surface substrate was bonded to an 8-inch-size, 0.4-mm-thick alkali-free film. The glass was then stored in a 105 ° C atmosphere for 500 hours, and evaluated for "durability" as defects such as peeling and blistering, and evaluated for "brightness" such as lightness and darkness when placed on a back light. Uneven ". In the durability evaluation, a case where defects such as peeling and foaming of the adhesive layer occurred was described as "╳", and a case where there were no defects at all was described as "○". In addition, in the evaluation of the brightness unevenness, the case where the brightness unevenness was confirmed was described as “╳”, and the case where the brightness unevenness was not recognized was described as “○”.

＜面板捲曲的評價＞
經由將黏著劑組合物交聯而形成的、厚度為20μm的黏著劑層的片，以使以PET為表面基材的厚度為140μm的偏振片成為正交尼科耳透鏡的方式將其貼合於8英寸尺寸、厚度為0.4mm的無鹼玻璃的正面與背面，製作樣品面板，並測量於80℃乾燥條件下放置120小時後的面板的捲曲。數值為將面板置於平板上時的面板端部的翹起高度。
面板的捲曲量為0.5mm以下時，視為未發生捲曲的良好的狀態。<Evaluation of panel curl>
A 20 μm-thick adhesive layer sheet formed by cross-linking the adhesive composition is bonded so that a polarizing plate with a thickness of 140 μm using PET as the surface substrate becomes a cross-Nicol lens. A sample panel was fabricated on the front and back of an 8-inch-size, 0.4 mm-thick alkali-free glass, and the curl of the panel was measured after being left to stand at 80 ° C for 120 hours. The value is the raised height of the panel end when the panel is placed on a flat plate.
When the amount of curling of the panel is 0.5 mm or less, it is considered that the curling is not in a good state.

＜黏著劑組合物溶液的TI值的評價＞
使用BH形黏度計（TOKI SANGYO CO.,LTD.製造），以2rpm及20rpm的轉子轉速測定已調節為25℃的18%黏著劑組合物溶液（溶劑：乙酸乙酯）的黏度。根據以各自的轉速測定的黏度的值算出觸變指數（TI值）=[2rpm下的黏度]/[20rpm下的黏度]。TI值為超過1.25的值時，視為觸變性黏度顯著，不具有良好的塗布性。<Evaluation of the TI value of the adhesive composition solution>
Using a BH viscometer (manufactured by TOKI SANGYO CO., LTD.), The viscosity of an 18% adhesive composition solution (solvent: ethyl acetate) adjusted to 25 ° C. was measured at 2 rpm and 20 rpm rotor speeds. The thixotropic index (TI value) was calculated from the viscosity values measured at the respective rotation speeds = [viscosity at 2 rpm] / [viscosity at 20 rpm]. When the TI value exceeds a value of 1.25, the thixotropic viscosity is considered to be significant, and the coating properties are not good.

＜丙烯酸類聚合物的平均分子量及分子量的分散度（Mw/Mn）的評價＞
使用凝膠滲透層析法（GPC），算出丙烯酸類聚合物的聚苯乙烯換算的重均分子量（Mw）及數均分子量（Mn）、分散度（Mw/Mn）。<Evaluation of the average molecular weight and the molecular weight dispersion (Mw / Mn) of the acrylic polymer>
The polystyrene-equivalent weight average molecular weight (Mw), number average molecular weight (Mn), and dispersion (Mw / Mn) of the acrylic polymer were calculated using gel permeation chromatography (GPC).

＜耐凹陷性的評價＞
針對將黏著劑組合物交聯而形成的20μm厚的黏著劑層的片，使直徑為5mm的鋼球與其表面接觸，目視觀察並評價施加負荷時的凹陷。每次增加5g荷載的品質並觀察凹陷，記錄不發生凹陷的最大荷載，作為耐凹陷性的尺度。荷載為10g且不發生凹陷時，視為耐凹陷性良好。＜ Evaluation of dent resistance ＞
Regarding a 20 μm-thick adhesive layer sheet formed by crosslinking the adhesive composition, a steel ball having a diameter of 5 mm was brought into contact with the surface thereof, and the sag when a load was applied was visually observed and evaluated. Increase the quality of the load by 5g each time and observe the depression, and record the maximum load that does not occur as a measure of the resistance to depression. When the load is 10 g and no depression occurs, it is considered that the depression resistance is good.

將評價結果示於表3。The evaluation results are shown in Table 3.

[表3]
[table 3]

滿足本申請專利範圍第1項中記載的所有發明特定事項，且為本發明的黏著劑組合物的具體例子的實施例1~8的黏著劑層具有考慮了再操作性的適當的黏著力，此外，在較高溫度下的耐久性試驗中，未發生剝落或浮起、起泡，具有良好的耐久性，進一步，也沒有發生亮度不均。即，將由本發明的黏著劑組合物形成的黏著劑層用於偏振膜等光學膜與液晶顯示面板的貼合時，可表現出優異的耐熱性及耐久性。
不僅如此，結果顯示：使用由本發明的黏著劑組合物形成的黏著劑層貼合光學膜與液晶顯示面板而成的層疊體中，即使將其放置於光學膜會發生尺寸變化的高溫下，也能夠維持面板的捲曲非常小的狀態，同時黏著劑層自身的耐凹陷性也優異。這意味著，由本發明的黏著劑組合物形成的黏著劑層具有不將因環境條件而容易產生收縮或伴隨收縮的應力的光學膜的變形或應力的影響傳遞至面板側的性能，同時黏著劑層本身具有難以變形的特性，可提供一種形成具有至今從未有過的性能的黏著劑層的黏著劑組合物的發明。The adhesive layers of Examples 1 to 8 which satisfy all the invention-specific matters described in item 1 of the patent scope of the present application and are specific examples of the adhesive composition of the present invention have an appropriate adhesive force in consideration of reworkability. In addition, in the durability test at a high temperature, no peeling, floating, or blistering occurred, it had good durability, and further, no uneven brightness occurred. That is, when the adhesive layer formed from the adhesive composition of the present invention is used for bonding an optical film such as a polarizing film to a liquid crystal display panel, excellent heat resistance and durability can be exhibited.
In addition, the results show that a laminated body in which an optical film and a liquid crystal display panel are bonded together using the adhesive layer formed of the adhesive composition of the present invention, even when the optical film is placed at a high temperature where the optical film undergoes a dimensional change. It is possible to maintain a very small curl state of the panel, and at the same time, the adhesive layer itself has excellent dent resistance. This means that the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition of the present invention has the property of not transmitting the influence of deformation or stress of the optical film which is liable to cause shrinkage or stress accompanying the shrinkage to the panel side due to environmental conditions, and at the same time the pressure-sensitive adhesive The layer itself has a characteristic of being difficult to deform, and can provide an invention of an adhesive composition that forms an adhesive layer having properties that have never been achieved before.

此外，使用了（A）烷基的碳原子數為C8~C18的（甲基）丙烯酸烷基酯單體的含量較少、不具有（D）含有芳香族基團的共聚性乙烯基單體的至少一種的丙烯酸類聚合物的、比較例1的黏著劑組合物的黏著劑層的黏著力雖然高，且在耐久性評價中的高溫處理後沒有剝落或起泡，但是發生亮度不均及面板的捲曲，不具有良好的性能。In addition, the content of the (A) alkyl (meth) acrylic acid alkyl monomer having C8 to C18 of the alkyl group is small, and the copolymerizable vinyl monomer containing no aromatic group (D) Although the adhesive force of the adhesive layer of at least one acrylic polymer of the adhesive composition of Comparative Example 1 is high, and there is no peeling or blistering after high-temperature treatment in durability evaluation, uneven brightness occurs. The curl of the panel does not have good performance.

使用了不具有（D）含有芳香族基團的共聚性乙烯基單體的至少一種、重均分子量低於本申請專利範圍第1項中規定的數值範圍的丙烯酸類聚合物，且不含有矽烷偶聯劑的、比較例2的黏著劑組合物的黏著劑層的耐久性不充分，發生亮度不均及面板的捲曲，耐凹陷性也差。此外，黏著劑組合物溶液顯示強觸變性黏度，塗布性也差。Acrylic polymer without using at least one copolymerizable vinyl monomer containing (D) aromatic group and having a weight-average molecular weight lower than the value range specified in the first patent range of the present application, and containing no silane The durability of the adhesive layer of the adhesive composition of the adhesive composition of Comparative Example 2 was insufficient, uneven brightness and curling of the panel occurred, and dent resistance was also poor. In addition, the adhesive composition solution exhibited strong thixotropic viscosity and was poor in coating properties.

對於具有帶羧基的共聚性乙烯基單體來代替（C）含有羥基的共聚性乙烯基單體的丙烯酸類聚合物、且交聯劑的含量過剩的比較例3的黏著劑組合物而言，雖然黏著劑層的耐凹陷性良好，但是黏著力、亮度不均及包含面板的捲曲的耐久性差。此外，黏著劑組合物溶液的觸變性黏度也高，塗布性不良。The adhesive composition of Comparative Example 3 which has a copolymerizable vinyl monomer having a carboxyl group in place of (C) an acrylic polymer containing a copolymerizable vinyl monomer containing a hydroxyl group and has an excessive amount of a crosslinking agent, Although the adhesive layer has good dent resistance, it has poor adhesion, uneven brightness, and durability including curling of the panel. In addition, the thixotropic viscosity of the adhesive composition solution was also high, and the coating properties were poor.

此外，使用了（B）烷基的碳原子數為C1~C5的（甲基）丙烯酸烷基酯單體的含量低、不含（D）含有芳香族基團的共聚性乙烯基單體的至少一種、重均分子量低於本申請專利範圍第1項中規定的數值範圍的丙烯酸類聚合物，且使用不含矽烷偶聯劑的比較例4的黏著劑組合物的黏著劑層的亮度不均或面板的捲曲雖然良好，但是在耐久性的評價中，觀察到高溫處理後的剝落或起泡，耐凹陷性也差。塗布性也不良。In addition, the (B) alkyl (meth) acrylic acid alkyl monomer having C1 to C5 in the alkyl group has a low content and does not contain (D) an aromatic vinyl group-containing copolymerizable vinyl monomer. The brightness of the adhesive layer of at least one acrylic polymer having a weight average molecular weight lower than the numerical range specified in the first patent range of the present application and using the adhesive composition of Comparative Example 4 without a silane coupling agent is not stable. Although the average or panel curl was good, in the evaluation of durability, peeling or blistering after high-temperature treatment was observed, and dent resistance was also poor. The applicability was also poor.

此外，使用了不含（B）烷基的碳原子數為C1~C5的（甲基）丙烯酸烷基酯單體的至少一種的丙烯酸類聚合物的比較例5的黏著劑組合物的黏著劑層在耐久性的評價中，發生高溫處理後的剝落或亮度不均，不是良好的黏著劑層。Moreover, the adhesive agent of the adhesive composition of the comparative example 5 which uses the acrylic polymer which does not contain at least 1 type of (B) alkyl (meth) acrylic-acid alkyl (meth) acrylic-acid alkylester monomer of C1-C5 is used. In the evaluation of the durability of the layer, exfoliation or uneven brightness after the high-temperature treatment occurred, and the layer was not a good adhesive layer.

如上所述，使用了比較例1~5的黏著劑組合物的黏著劑層不具有充分的耐久性，此外，也不能夠兼顧面板的捲曲的抑制與耐凹陷性。As described above, the adhesive layer using the adhesive compositions of Comparative Examples 1 to 5 does not have sufficient durability, and it is not possible to achieve both suppression of curling of the panel and dent resistance.

無。no.

無。no.

Claims (16)

一種黏著劑組合物，其係含有丙烯酸類聚合物、交聯劑及矽烷偶聯劑之黏著劑組合物， 該丙烯酸類聚合物為使下述成分以不含帶羧基的共聚性乙烯基單體的方式共聚而成的、重均分子量為150萬~300萬的丙烯酸類聚合物： （A）烷基的碳原子數為C8~C18的（甲基）丙烯酸烷基酯單體的至少一種； （B）烷基的碳原子數為C1~C5的（甲基）丙烯酸烷基酯單體的至少一種； （C）含有羥基的共聚性乙烯基單體的至少一種；及 （D）含有芳香族基團的共聚性乙烯基單體的至少一種， 該交聯劑為3官能度以上的異氰酸酯化合物。An adhesive composition, which is an adhesive composition containing an acrylic polymer, a cross-linking agent, and a silane coupling agent. The acrylic polymer is an acrylic polymer having a weight average molecular weight of 1.5 to 3 million, which is obtained by copolymerizing the following components in a manner that does not contain a copolymerizable vinyl monomer having a carboxyl group: (A) at least one of alkyl (meth) acrylate monomers having a carbon number of C8 to C18; (B) at least one type of an alkyl (meth) acrylate monomer having a carbon number of C1 to C5; (C) at least one copolymerizable vinyl monomer containing a hydroxyl group; and (D) at least one copolymerizable vinyl monomer containing an aromatic group, This crosslinking agent is an isocyanate compound having a trifunctional or higher functionality. 如申請專利範圍第1項所述的黏著劑組合物，其中，相對於該（A）、該（B）及該（D）的合計100重量份，該丙烯酸類聚合物為使下述成分共聚而得到之丙烯酸類聚合物： 20重量份以上、69重量份以下的該（A）烷基的碳原子數為C8~C18的（甲基）丙烯酸烷基酯單體的至少一種； 30重量份以上、79重量份以下的該（B）烷基的碳原子數為C1~C5的（甲基）丙烯酸烷基酯單體的至少一種； 超過0重量份且為5重量份以下的該（C）含有羥基的共聚性乙烯基單體的至少一種；及 1~50重量份的該（D）含有芳香族基團的共聚性乙烯基單體的至少一種， 相對於該（A）、該（B）及該（D）的合計100重量份，該黏著劑組合物以0.001重量份以上、0.05重量份以下的比例含有該3官能度以上的異氰酸酯化合物。The adhesive composition according to item 1 of the scope of patent application, wherein the acrylic polymer copolymerizes the following components with respect to 100 parts by weight of the total of (A), (B), and (D). The obtained acrylic polymer: At least one of (A) alkyl (meth) acrylic acid alkyl ester monomers having from 20 to 69 parts by weight of carbon atoms of the (A) alkyl group; 30 parts by weight or more and 79 parts by weight or less of at least one type of the (B) alkyl (meth) acrylic acid alkyl ester monomer having a carbon number of C1 to C5; More than 0 parts by weight and 5 parts by weight or less of at least one of the (C) hydroxyl-containing copolymerizable vinyl monomers; and 1 to 50 parts by weight of at least one of the (D) copolymerizable vinyl monomer containing an aromatic group, The adhesive composition contains the trifunctional or higher isocyanate compound in a proportion of 0.001 parts by weight or more and 0.05 parts by weight or less based on 100 parts by weight of the total of (A), (B), and (D). 如申請專利範圍第1或2項所述的黏著劑組合物，其中，該（C）含有羥基的共聚性乙烯基單體的至少一種為選自由（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2-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）丙烯醯胺組成的化合物群組中的至少一種以上。The adhesive composition according to item 1 or 2 of the scope of the patent application, wherein (C) at least one of the copolymerizable vinyl monomers containing a hydroxyl group is selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, ( 6-hydroxyhexyl methacrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (methyl Group) at least one or more selected from the group consisting of acrylamide and N-hydroxyethyl (meth) acrylamide. 如申請專利範圍第1或2項所述的黏著劑組合物，其中，該（A）烷基的碳原子數為C8~C18的（甲基）丙烯酸烷基酯單體的至少一種為選自丙烯酸2-乙基己酯、丙烯酸異辛酯、丙烯酸異壬酯、丙烯酸異癸酯中的至少一種，該（B）烷基的碳原子數為C1~C5的（甲基）丙烯酸烷基酯單體的至少一種為選自由丙烯酸正丁酯、丙烯酸三級丁酯、丙烯酸異丁酯、甲基丙烯酸正丁酯、丙烯酸甲酯組成的群組中的至少一種以上。The adhesive composition according to item 1 or 2 of the scope of the patent application, wherein at least one of the (A) alkyl (meth) acrylic acid alkyl ester monomers having a carbon number of C8 to C18 is selected from the group consisting of At least one of 2-ethylhexyl acrylate, isooctyl acrylate, isononyl acrylate, and isodecyl acrylate, and the (B) alkyl (meth) acrylic acid alkyl ester having a carbon number of C1 to C5 At least one of the monomers is at least one or more selected from the group consisting of n-butyl acrylate, tertiary butyl acrylate, isobutyl acrylate, n-butyl methacrylate, and methyl acrylate. 如申請專利範圍第1或2項所述的黏著劑組合物，其中，該（D）含有芳香族基團的共聚性乙烯基單體的至少一種為選自（甲基）丙烯酸苄酯、（甲基）丙烯酸苯氧基乙酯中的至少一種以上。The adhesive composition according to item 1 or 2 of the scope of the patent application, wherein at least one of the (D) copolymerizable vinyl monomer containing an aromatic group is selected from benzyl (meth) acrylate, ( At least one or more of phenoxyethyl meth) acrylates. 如申請專利範圍第1或2項所述的黏著劑組合物，其中，該矽烷偶聯劑為具有選自環氧基、巰基、酸酐基中的至少一種官能基的矽烷偶聯劑。The adhesive composition according to item 1 or 2 of the patent application scope, wherein the silane coupling agent is a silane coupling agent having at least one functional group selected from the group consisting of an epoxy group, a mercapto group, and an acid anhydride group. 如申請專利範圍第1或2項所述的黏著劑組合物，其中，該丙烯酸類聚合物的分子量的分散度（Mw[重均分子量]/Mn[數均分子量]）為6.0以下。The adhesive composition according to item 1 or 2 of the patent application scope, wherein the molecular weight dispersion (Mw [weight average molecular weight] / Mn [number average molecular weight]) of the acrylic polymer is 6.0 or less. 如申請專利範圍第1或2項所述的黏著劑組合物，其中，經由由該黏著劑組合物交聯而成的黏著劑層貼合以PET為表面基材且厚度為140μm的偏振片與厚度為0.4mm的無鹼玻璃，按照JIS-Z0237、沿180°方向以300mm/分鐘的剝離速度，將以PET為表面基材的偏振片從玻璃面上剝離時的黏著力為4N/25mm以下。The adhesive composition according to item 1 or 2 of the scope of the patent application, wherein a polarizing plate having a thickness of 140 μm and a PET substrate as a surface substrate is bonded to the adhesive layer formed by cross-linking the adhesive composition with an adhesive layer. 0.4mm thick alkali-free glass, in accordance with JIS-Z0237, at a peeling speed of 300mm / min along the 180 ° direction, the adhesive force when peeling the polarizer with PET as the surface substrate from the glass surface is 4N / 25mm or less . 一種黏著劑組合物溶液，其特徵在於，將如申請專利範圍第1~8項中任一項所述的黏著劑組合物溶解於溶劑中而成的黏著劑組合物溶液的觸變指數（TI值）為1.25以下。An adhesive composition solution, characterized in that the thixotropic index (TI) of an adhesive composition solution obtained by dissolving the adhesive composition according to any one of claims 1 to 8 in a patent application range is dissolved in a solvent. Value) is 1.25 or less. 一種黏著劑層，其特徵在於，其由如申請專利範圍第1~8項中任一項所述的黏著劑組合物交聯而成，厚度為20μm，耐凹陷性為10g以上。An adhesive layer is characterized in that it is formed by cross-linking the adhesive composition according to any one of claims 1 to 8 in the scope of patent application, and has a thickness of 20 μm and a dent resistance of 10 g or more. 一種黏著膜，其特徵在於，其藉由將如申請專利範圍第項1~8中任一項所述的黏著劑組合物交聯而成的黏著劑層層疊於樹脂膜的單面而成。An adhesive film is characterized in that an adhesive layer obtained by cross-linking the adhesive composition according to any one of claims 1 to 8 of the scope of patent application is laminated on one side of a resin film. 如申請專利範圍第11項所述的黏著膜，其中，其用於將偏振片貼合於被黏物。The adhesive film according to item 11 of the scope of patent application, wherein the adhesive film is used to attach a polarizer to an adherend. 一種黏著膜，其特徵在於，其在離型膜的單面形成有由如申請專利範圍第1~8項中任一項所述的黏著劑組合物交聯而成的黏著劑層，為離型膜/黏著劑層/離型膜的結構。An adhesive film is characterized in that an adhesive layer formed by cross-linking the adhesive composition according to any one of claims 1 to 8 is formed on one side of a release film, and is a release film. Structure of release film / adhesive layer / release film. 一種帶黏著劑層的光學膜，其特徵在於，其藉由在光學膜的至少一側的面上層疊由如申請專利範圍第1~8項中任一項所述的黏著劑組合物交聯而成的黏著劑層而成，為離型膜/黏著劑層/光學膜的結構。An optical film with an adhesive layer is characterized in that it is crosslinked by the adhesive composition according to any one of claims 1 to 8 by laminating on at least one side of the optical film. The formed adhesive layer is a structure of a release film / adhesive layer / optical film. 一種帶黏著劑層的偏振片，其特徵在於，其藉由在偏振片的單面層疊由如申請專利範圍第1~8項中任一項所述的黏著劑組合物交聯而成的黏著劑層而成，為離型膜/黏著劑層/偏振片的結構。A polarizing plate with an adhesive layer is characterized in that it is formed by laminating on one side of a polarizing plate an adhesive formed by crosslinking the adhesive composition according to any one of claims 1 to 8 of the scope of patent application. It is made of an adhesive layer and has a structure of a release film / adhesive layer / polarizer. 一種液晶顯示面板，其特徵在於，使用如申請專利範圍第15項所述的帶黏著劑層的偏振片。A liquid crystal display panel characterized by using the polarizing plate with an adhesive layer as described in item 15 of the patent application scope.
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