TW201837146A - Adhesive composition and adhesive film - Google Patents

Adhesive composition and adhesive film Download PDF

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TW201837146A
TW201837146A TW106137357A TW106137357A TW201837146A TW 201837146 A TW201837146 A TW 201837146A TW 106137357 A TW106137357 A TW 106137357A TW 106137357 A TW106137357 A TW 106137357A TW 201837146 A TW201837146 A TW 201837146A
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adhesive layer
adhesive
meth
adhesive composition
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TW106137357A
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TWI761383B (en
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長倉毅
吉田弘幸
鈴木史恵
大津賀健太郎
菱沼昌世
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日商藤森工業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • 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

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (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 has an extremely superior antistatic property with surface resistivity of 2.0*10<SP>+9</SP>[Omega]/□ or less as an adhesive layer and does not impair the durability. The adhesive composition contains an acrylic polymer, and further contains (E) an ammonium based antistatic agent having a fluorine-containing anion, (F) a cross-linker formed by a trifunctional or higher functional isocyanate compound or a bifunctional or higher functional epoxy compound, and (G) a silane coupling agent having one or more functional group selected from the group consisting of epoxy, mercapto, and anhydride groups. The acrylic polymer is copolymerized by (A) n-butyl acrylate, (B) at least one selected from the group consisting of t-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, and methyl acrylate, (C) a copolymerizable vinyl monomer containing a hydroxyl group and/or a carboxy group and (D) a copolymerizable vinyl monomer having an aromatic group.

Description

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

本發明係有關於一種黏著劑組合物以及黏著膜，該黏著劑組合物以及黏著膜例如能夠使用於在被黏物為液晶面板的、結合有觸控面板的功能的In-cell面板上進行貼合的用途。 The present invention relates to an adhesive composition and an adhesive film. The adhesive composition and the adhesive film can be applied to, for example, an In-cell panel with a touch panel function and a liquid crystal panel as an adherend. Suitable use.

特別涉及一種具有黏著劑層的表面電阻率為現有技術中無法達到的2.0×10+9Ω/□以下的極其優異的抗靜電性能的黏著劑組合物、以及使用了該黏著劑組合物的黏著膜。 In particular, the present invention relates to an adhesive composition having a surface resistivity of an adhesive layer having an extremely excellent antistatic performance of 2.0 × 10 +9 Ω / □ or less, which cannot be achieved in the prior art, and an adhesive using the adhesive composition. membrane.

有用於將偏振片、相位差板等光學部件經由黏著劑層而貼合於液晶單元等被黏物上的各種黏著膜的提案(例如參照專利文獻1~2)。 There are proposals for bonding various optical films such as a polarizer and a retardation film to an adherend such as a liquid crystal cell via an adhesive layer (see, for example, Patent Documents 1 to 2).

專利文獻1中記載了一種含有丙烯酸系聚合物的光學用黏著劑組合物，其中該丙烯酸系聚合物藉由將丙烯酸丁酯等作為主成分的單體，使丙烯醯胺化合物等共聚合而成。 Patent Document 1 describes an acrylic adhesive composition containing an acrylic polymer, wherein the acrylic polymer is obtained by copolymerizing an acrylamide compound or the like with a monomer containing butyl acrylate or the like as a main component. .

專利文獻2中記載了一種含有丙烯酸系聚合物的光學用黏著劑組合物，其中該丙烯酸系聚合物藉由以具有碳原子數為4~8的烷基的(甲基)丙烯酸酯作為主成分的單體，使含羧基單體、以及含氮乙烯基單體共聚合而成。 Patent Document 2 describes an acrylic adhesive composition containing an acrylic polymer, wherein the acrylic polymer contains a (meth) acrylate having an alkyl group having 4 to 8 carbon atoms as a main component. The monomer is obtained by copolymerizing a carboxyl-containing monomer and a nitrogen-containing vinyl monomer.

[現有技術文獻]     [Prior Art Literature]     [專利文獻]     [Patent Literature]    

專利文獻1：日本特開2012-177022號公報 Patent Document 1: Japanese Patent Application Publication No. 2012-177022

專利文獻2：日本特開2012-201734號公報 Patent Document 2: Japanese Patent Application Publication No. 2012-201734

但是，在用於貼合偏振片和液晶面板的黏著劑層中，在液晶面板為具有觸控面板的功能的In-cell面板的情況下，要求該黏著劑層的表面電阻率為比以往的表面電阻率低的值。 However, in an adhesive layer for bonding a polarizer and a liquid crystal panel, when the liquid crystal panel is an In-cell panel having a function of a touch panel, the surface resistivity of the adhesive layer is required to be higher than conventional Low surface resistivity.

因此，對於用於將偏振片貼合於液晶面板上的黏著劑層，要求使該黏著劑層的表面電阻率為2.0×10+9Ω/□以下。但是，在現有技術中，表現這樣的高度的抗靜電性能是非常難的。 Therefore, an adhesive layer for bonding a polarizing plate to a liquid crystal panel is required to have a surface resistivity of the adhesive layer of 2.0 × 10 +9 Ω / □ or less. However, it is very difficult to express such a high antistatic performance in the prior art.

此外，即使能表現出這樣的高度的抗靜電性能，也難以同時維持黏著劑層的耐久性。 In addition, even if such a high degree of antistatic performance can be exhibited, it is difficult to maintain the durability of the adhesive layer at the same time.

本發明的技術問題在於提供一種具有黏著劑層的表面電阻率為2.0×10+9Ω/□以下的極其優異的抗靜電性能、並且不損害耐久性的黏著劑組合物、以及使用了該黏著劑組合物的黏著膜。 The technical problem of the present invention is to provide an adhesive composition having a surface resistivity of an adhesive layer of 2.0 × 10 +9 Ω / □ or less, which has extremely excellent antistatic performance and does not impair durability, and uses the adhesive. Film of the agent composition.

為了解決難以同時達到這樣的高度的抗靜電性能和耐久性這兩者的技術問題，本發明的發明人進行了深入研究。其結果，藉由將構成黏著劑組合物的丙烯酸系聚合物的(甲基)丙烯酸烷基酯的烷基的碳原子數限定在特定的範圍，形成 由使特定的組合的兩種以上的(甲基)丙烯酸烷基酯共聚而成的共聚物組成的丙烯酸系聚合物，進一步，藉由形成含有特定的抗靜電劑的黏著劑組合物，能夠解決該技術問題。 In order to solve the technical problem that it is difficult to achieve both such high antistatic performance and durability at the same time, the inventors of the present invention have conducted intensive studies. As a result, by limiting the number of carbon atoms in the alkyl group of the (meth) acrylic acid alkyl ester of the acrylic polymer constituting the adhesive composition to a specific range, two or more ( An acrylic polymer composed of a copolymer of alkyl (meth) acrylate copolymers can further solve this technical problem by forming an adhesive composition containing a specific antistatic agent.

本發明人們發現，藉由含有所述丙烯酸系聚合物、以及相對於100重量份的所述丙烯酸系聚合物以超過15重量份的比例含有具有含氟基陰離子的銨系抗靜電劑，能夠得到與以往的黏著劑組合物相比，具有極其優異的抗靜電性能、且抗靜電劑不析出、具有不經時劣化的優異的耐久性的黏著劑組合物，從而完成了本發明。 The present inventors have found that by containing the acrylic polymer and containing an ammonium antistatic agent having a fluorine-containing anion in an amount exceeding 15 parts by weight based on 100 parts by weight of the acrylic polymer, it is possible to obtain Compared with the conventional adhesive composition, this invention is an adhesive composition which has extremely excellent antistatic performance, does not precipitate an antistatic agent, and has excellent durability which does not deteriorate over time.

本發明涉及的黏著劑組合物，為了使黏著劑層的表面電阻率為2.0×10+9Ω/□以下的極其優異的抗靜電性能，相對於100重量份的丙烯酸系聚合物，以超過15重量份的比例含有具有含氟基陰離子的銨系抗靜電劑。像這樣，在本發明中，為了得到在現有技術中無法達到的極其優異的抗靜電性能，而提高抗靜電劑的含量。 The adhesive composition according to the present invention has a surface resistivity of the adhesive layer of 2.0 × 10 +9 Ω / □ or less, and has an extremely excellent antistatic performance. The proportion by weight includes an ammonium-based antistatic agent having a fluorine-containing anion. As described above, in the present invention, the content of the antistatic agent is increased in order to obtain extremely excellent antistatic performance that cannot be achieved in the prior art.

本發明涉及的黏著劑組合物的技術構思在於，為了使在黏著劑層的高溫、高濕度環境下的耐久性試驗後，黏著劑層中大量含有的具有含氟基陰離子的銨系抗靜電劑不從黏著劑層的表面析出，成為能夠維持耐久性的黏著劑層，而使黏著劑組合物中所含的丙烯酸系聚合物以丙烯酸正丁酯(BA)為主體、選擇與BA的共聚性良好的單體而進行共聚合而成。 The technical idea of the adhesive composition according to the present invention is to make ammonium antistatic agents with fluorine-containing anions contained in a large amount in the adhesive layer after the durability test under the high temperature and high humidity environment of the adhesive layer. Instead of precipitating from the surface of the adhesive layer, it becomes an adhesive layer capable of maintaining durability, and the acrylic polymer contained in the adhesive composition is mainly composed of n-butyl acrylate (BA), and the copolymerizability with BA is selected. Good monomers are copolymerized.

此外，為了解決上述技術問題，本發明提供一種黏著劑組合物，其含有丙烯酸系聚合物、抗靜電劑、以及交聯劑，其特徵在於，所述丙烯酸系聚合物為使下列單體共聚而成 的共聚物的重均分子量為100~300萬的丙烯酸系聚合物：(A)丙烯酸正丁酯，(B)選自由丙烯酸叔丁酯、丙烯酸異丁酯、甲基丙烯酸正丁酯、丙烯酸甲酯所組成的群組中的至少一種，(C)含有羥基及/或羧基的共聚性乙烯基單體中的至少一種，以及(D)含有芳香族基團的共聚性乙烯基單體中的至少一種；所述黏著劑組合物，相對於100重量份的所述丙烯酸系聚合物，以超過15重量份且為40重量份以下的比例含有作為所述(E)抗靜電劑的具有含氟基陰離子的銨系抗靜電劑；所述黏著劑組合物含有選自由三官能以上的異氰酸酯化合物、雙官能以上的環氧化合物所組成的群組中的至少一種以上的交聯劑，作為所述(F)交聯劑；所述黏著劑組合物進一步含有(G)含有選自環氧基、巰基、酸酐基中的至少一種以上的官能基的單體型或低聚物型的矽烷偶合劑；使所述黏著劑組合物交聯而成的黏著劑層的表面電阻率為2.0×10+9Ω/□以下；將所述黏著劑層供於85℃×750hr的試驗環境下的耐久性試驗後、或供於60℃×90%RH×750hr的試驗環境下的耐久性試驗後，所述抗靜電劑未在所述黏著劑層的表面上析出。 In addition, in order to solve the above-mentioned technical problems, the present invention provides an adhesive composition containing an acrylic polymer, an antistatic agent, and a cross-linking agent, wherein the acrylic polymer copolymerizes the following monomers: The resulting copolymer has an acrylic polymer having a weight average molecular weight of 1 to 3 million: (A) n-butyl acrylate, and (B) selected from t-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, and acrylic acid. At least one of the group consisting of methyl esters, (C) at least one of copolymerizable vinyl monomers containing a hydroxyl group and / or a carboxyl group, and (D) of copolymerizable vinyl monomers containing an aromatic group The (E) antistatic agent contains at least one of the adhesive composition in an amount of more than 15 parts by weight and 40 parts by weight or less with respect to 100 parts by weight of the acrylic polymer. A fluorine-based anionic ammonium-based antistatic agent; the adhesive composition contains at least one or more crosslinking agents selected from the group consisting of a trifunctional or higher isocyanate compound and a difunctional or higher epoxy compound; The (F) crosslinking agent; the adhesive composition further contains (G) a monomer-type or oligomer-type silane containing at least one functional group selected from an epoxy group, a mercapto group, and an acid anhydride group. Coupling agent; the surface resistivity of the adhesive layer formed by cross-linking the adhesive composition is 2.0 × 10 +9 Ω / □ or less; the adhesive layer is supplied in a test environment at 85 ° C. × 750 hr After the durability test, or after a durability test in a test environment of 60 ° C. × 90% RH × 750 hr, the antistatic agent did not precipitate on the surface of the adhesive layer.

此外，優選所述抗靜電劑為由含氟基陰離子與銨陽離子形成的、熔點為25℃以上的離子化合物；所述含氟基陰離子為選自由五氟苯磺酸根、六氟磷酸根、雙(三氟甲烷磺醯基)亞胺、雙(氟磺醯基)亞胺、三氟甲磺酸根組成的組中的一種。 In addition, the antistatic agent is preferably an ionic compound formed by a fluorine-containing anion and an ammonium cation and having a melting point of 25 ° C or higher; and the fluorine-containing anion is selected from the group consisting of pentafluorobenzenesulfonate, hexafluorophosphate, and (Trifluoromethanesulfonyl) imine, bis (fluorosulfonyl) imine, and trifluoromethanesulfonate.

優選所述丙烯酸系聚合物，相對於100重量份的所述丙烯酸系聚合物，以40~89重量份的比例含有所述(A)丙烯酸正丁酯、以及以總計為5~40重量份的比例含有所述(B) 選自由丙烯酸叔丁酯、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，並且，(A)與(B)的比例(A)/(B)為1.0~17.8。 Preferably, the acrylic polymer contains the (A) n-butyl acrylate in an amount of 40 to 89 parts by weight relative to 100 parts by weight of the acrylic polymer, and 5 to 40 parts by weight in total. The ratio (B) contains at least one or more selected from the group consisting of tert-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, and methyl acrylate, and the ratio of (A) to (B) ( A) / (B) is 1.0 ~ 17.8.

優選將總厚度為80μm的偏振片經由使所述黏著劑組合物交聯而成的厚度為20μm的黏著劑層而貼合於無鹼玻璃上時，所述黏著劑層對於無鹼玻璃的黏著力為1.0~6.0N/25mm；將10cm見方的總厚度為80μm的偏振片經由使所述黏著劑組合物交聯而成的厚度為20μm的黏著劑層而貼合於無鹼玻璃上而成的試驗片，供於85℃×750hr的試驗環境下的耐久性試驗後、或供於60℃×90%RH×750hr的試驗環境下的耐久性試驗後，無起泡以及脫落。 Preferably, when a polarizing plate having a total thickness of 80 μm is bonded to an alkali-free glass through an adhesive layer having a thickness of 20 μm, which is obtained by crosslinking the adhesive composition, the adhesive layer adheres to the alkali-free glass. The force is 1.0 ~ 6.0N / 25mm; a polarizing plate with a total thickness of 80 μm and a thickness of 10 cm square is bonded to an alkali-free glass through an adhesive layer having a thickness of 20 μm obtained by crosslinking the adhesive composition. After being subjected to a durability test in a test environment at 85 ° C. × 750 hr or a durability test in a test environment at 60 ° C. × 90% RH × 750 hr, the test piece was free of blistering and peeling.

優選所述(C)含有羥基和/或羧基的共聚性乙烯基單體，為選自由含有羥基的可共聚單體、以及含有羧基的可共聚單體組成的組中的至少一種以上；所述含有羥基的可共聚單體為選自由(甲基)丙烯酸-8-羥基辛酯、(甲基)丙烯酸-6-羥基己酯、(甲基)丙烯酸-4-羥基丁酯、(甲基)丙烯酸-2-羥基乙酯、N-羥基(甲基)丙烯醯胺、N-羥基甲基(甲基)丙烯醯胺、N-羥基乙基(甲基)丙烯醯胺所組成的化合物群組中的至少一種以上；所述含有羧基的可共聚單體為選自由(甲基)丙烯酸、羧乙基(甲基)丙烯酸酯、羧戊基(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基馬來酸、羧基聚己內酯單(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基四氫鄰苯二甲酸 所組成的化合物群組中的至少一種以上。 (C) The copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group is preferably at least one or more selected from the group consisting of a copolymerizable monomer containing a hydroxyl group and a copolymerizable monomer containing a carboxyl group; The copolymerizable monomer containing a hydroxyl group is selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and (meth) Compound group consisting of 2-hydroxyethyl acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide At least one of the above; the carboxyl-containing copolymerizable monomer is selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) Acrylic ethoxyethyl hexahydrophthalic acid, 2- (meth) acrylic ethoxypropyl hexahydrophthalic acid, 2- (meth) acrylic ethoxyethyl phthalic acid, 2 -(Meth) acryloxyethyl succinic acid, 2- (meth) acryloxyethyl maleic acid, carboxy polycaprolactone mono (meth) acrylate, 2- (meth) propylene Ethoxyethyltetrahydro-o-benzene Carboxylic acid group of compounds consisting of at least one or more.

優選所述黏著劑層的初期的表面電阻率、以及供於85℃×750hr的試驗環境下的耐久性試驗後的表面電阻率，均為2.0×10+9Ω/□以下。 Preferably, the initial surface resistivity of the adhesive layer and the surface resistivity after a durability test in a test environment of 85 ° C. × 750 hr are both 2.0 × 10 +9 Ω / □ or less.

此外，本發明提供一種黏著膜，其特徵在於，藉由在樹脂膜的單面上積層使上述的黏著劑組合物交聯而成的黏著劑層而成。 The present invention also provides an adhesive film, which is formed by laminating an adhesive layer obtained by crosslinking the above-mentioned adhesive composition on one surface of a resin film.

此外，本發明提供一種偏振片用黏著膜，其使用了上述的黏著膜。 The present invention also provides an adhesive film for a polarizing plate using the above-mentioned adhesive film.

此外，本發明提供上述的偏振片用黏著膜，其特徵在於，用於偏振片與In-cell面板的貼合。 In addition, the present invention provides the above-mentioned adhesive film for a polarizing plate, which is used for bonding a polarizing plate to an In-cell panel.

此外，本發明提供一種黏著膜，其特徵在於，為使上述的黏著劑組合物交聯而成的黏著劑層以1μm~25μm的厚度在離型膜的單面上形成的、離型膜/黏著劑層/離型膜的結構。 In addition, the present invention provides an adhesive film, characterized in that a release film formed on one side of a release film with a thickness of 1 μm to 25 μm in order to cross-link the above-mentioned adhesive composition Structure of the adhesive layer / release film.

此外，本發明提供一種帶黏著劑層的光學膜，其特徵在於，其藉由將使上述的黏著劑組合物交聯而成的黏著劑層積層於光學膜的至少一個面上而成。 In addition, the present invention provides an optical film with an adhesive layer, which is formed by laminating an adhesive layer formed by crosslinking the above-mentioned adhesive composition on at least one surface of the optical film.

此外，本發明提供一種帶黏著劑層的偏振片，其特徵在於，其藉由將使上述的黏著劑組合物交聯而成的黏著劑層積層於偏振片的單面上而成。 In addition, the present invention provides a polarizing plate with an adhesive layer, which is characterized in that an adhesive layer obtained by cross-linking the above-mentioned adhesive composition is laminated on one surface of the polarizing plate.

此外，本發明提供一種液晶面板，其特徵在於，使用上述的帶黏著劑層的偏振片。 In addition, the present invention provides a liquid crystal panel using the above-mentioned polarizing plate with an adhesive layer.

此外，本發明提供一種In-cell型液晶面板，其特徵 在於，使用上述的帶黏著劑層的偏振片。 In addition, the present invention provides an In-cell type liquid crystal panel, characterized in that the polarizing plate with an adhesive layer described above is used.

根據本發明，能夠提供一種具有黏著劑層的表面電阻率為現有技術中無法達到的2.0×10+9Ω/□以下的極其優異的抗靜電性能、且不損害耐久性的黏著劑組合物、以及使用了該黏著劑組合物的黏著膜。 According to the present invention, it is possible to provide an adhesive composition having a surface resistivity of an adhesive layer that is extremely excellent in antistatic performance of 2.0 × 10 +9 Ω / □ or less that cannot be achieved in the prior art, and does not impair durability, And an adhesive film using the adhesive composition.

以下，基於適宜的實施方式來說明本發明。 Hereinafter, the present invention will be described based on suitable embodiments.

本實施方式的黏著劑組合物為含有丙烯酸系聚合物、抗靜電劑、以及交聯劑的黏著劑組合物，其特徵在於，所述丙烯酸系聚合物為使(A)、(B)、(C)以及(D)共聚合而成的共聚物的重均分子量為100~300萬的丙烯酸系聚合物，其中所述(A)為丙烯酸正丁酯，所述(B)為選自由丙烯酸叔丁酯、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，所述(C)為含有羥基及/或羧基的共聚性乙烯基單體中的至少一種，所述(D)為含有芳香族基團的共聚性乙烯基單體中的至少一種；所述黏著劑組合物，相對於100重量份的所述丙烯酸系聚合物，以超過15重量份且為40重量份以下的比例含有作為所述(E)抗靜電劑的具有含氟基陰離子的銨系抗靜電劑；所述黏著劑組合物含有選自由三官能以上的異氰酸酯化合物、雙官能以上的環氧化合物所組成的組中的至少一種以上的交聯劑，作為所述(F)交聯劑；所述黏著劑組 合物進一步含有(G)含有選自環氧基、巰基、酸酐基中的至少一種以上的官能基的單體型或低聚物型的矽烷偶合劑；使所述黏著劑組合物交聯而成的黏著劑層的表面電阻率為2.0×10+9Ω/□以下；將所述黏著劑層供於85℃×750hr的試驗環境下的耐久性試驗後、或供於60℃×90%RH×750hr的試驗環境下的耐久性試驗後，所述抗靜電劑未在所述黏著劑層的表面上析出。 The adhesive composition according to this embodiment is an adhesive composition containing an acrylic polymer, an antistatic agent, and a crosslinking agent, wherein the acrylic polymer is (A), (B), ( C) and (D) are copolymers of acrylic polymers having a weight average molecular weight of 1 to 3 million, wherein (A) is n-butyl acrylate and (B) is selected from tertiary acrylic acid At least one of the group consisting of butyl ester, isobutyl acrylate, n-butyl methacrylate, and methyl acrylate, (C) is at least one of copolymerizable vinyl monomers containing a hydroxyl group and / or a carboxyl group, The (D) is at least one of copolymerizable vinyl monomers containing an aromatic group; the adhesive composition is more than 15 parts by weight of 100 parts by weight of the acrylic polymer and is 40 parts by weight or less contains an ammonium antistatic agent having a fluorine-containing anion as the (E) antistatic agent; the adhesive composition contains a trifunctional or higher isocyanate compound and a bifunctional or higher ring At least one or more of the group consisting of oxygen compounds A cross-linking agent, as the (F) cross-linking agent; the adhesive composition further contains (G) a monomer type or oligomer containing at least one functional group selected from an epoxy group, a mercapto group, and an acid anhydride group. Type of silane coupling agent; the surface resistivity of the adhesive layer obtained by cross-linking the adhesive composition is 2.0 × 10 +9 Ω / □ or less; the adhesive layer is supplied at 85 ° C. × 750 hr. After the durability test in the test environment or the durability test in the test environment at 60 ° C. × 90% RH × 750 hr, the antistatic agent did not precipitate on the surface of the adhesive layer.

(A)丙烯酸正丁酯、以及(B)選自由丙烯酸叔丁酯、丙烯酸異丁酯、甲基丙烯酸正丁酯、丙烯酸甲酯所組成的群組中的至少一種，均相當於(甲基)丙烯酸烷基酯單體。本實施方式的黏著劑組合物，構成丙烯酸系聚合物的(甲基)丙烯酸烷基酯的單體設作特定的兩種以上、以(A)以及(B)的組合為佳。 (A) n-butyl acrylate, and (B) at least one selected from the group consisting of tert-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, and methyl acrylate, all of which are equivalent to (methyl ) Alkyl acrylate monomer. In the adhesive composition of the present embodiment, the monomer of the (meth) acrylic acid alkyl ester constituting the acrylic polymer is specifically two or more kinds, and a combination of (A) and (B) is preferable.

本實施方式的丙烯酸系聚合物，以(A)丙烯酸正丁酯為主體，例如，相對於100重量份的丙烯酸系聚合物，優選以40~89重量份的比例含有(A)丙烯酸正丁酯。丙烯酸系聚合物進一步優選以總計為5~40重量份的比例含有(B)選自由丙烯酸叔丁酯、丙烯酸異丁酯、甲基丙烯酸正丁酯、丙烯酸甲酯所組成的群組中的至少一種以上，作為除(A)丙烯酸正丁酯以外的(甲基)丙烯酸烷基酯單體。並且，(A)與(B)的比例(A)/(B)，以重量比計，優選為1.0~17.8。 The acrylic polymer of the present embodiment is mainly composed of (A) n-butyl acrylate. For example, it is preferable to contain (A) n-butyl acrylate in an amount of 40 to 89 parts by weight based on 100 parts by weight of the acrylic polymer. . The acrylic polymer further preferably contains (B) at least a total of 5 to 40 parts by weight selected from the group consisting of tert-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, and methyl acrylate. One or more kinds are used as (meth) acrylic acid alkyl ester monomers other than (A) n-butyl acrylate. The ratio (A) / (B) of (A) to (B) is preferably 1.0 to 17.8 in terms of weight ratio.

作為(C)含有羥基及/或羧基的共聚性乙烯基單體，可列舉出選自由含有羥基的可共聚單體(含羥基單體)、以及含有羧基的可共聚單體(含羧基單體)所組成的群組中的至少一種以上。即，可以僅選擇含羥基單體、或含羧基單體中 的任意一者進行共聚合，也可以使含羥基單體、以及含羧基單體這兩者進行共聚合。 Examples of the copolymerizable vinyl monomer containing (C) a hydroxyl group and / or a carboxyl group include a copolymerizable monomer (hydroxyl-containing monomer) containing a hydroxyl group and a copolymerizable monomer (carboxyl-containing monomer) containing a carboxyl group. ) At least one or more of the groups. That is, only one of a hydroxyl-containing monomer or a carboxyl-containing monomer may be selected for copolymerization, or both a hydroxyl-containing monomer and a carboxyl-containing monomer may be copolymerized.

作為含羥基單體，例如可列舉出(甲基)丙烯酸-8-羥基辛酯、(甲基)丙烯酸-6-羥基己酯、(甲基)丙烯酸-4-羥基丁酯、(甲基)丙烯酸-2-羥基乙酯等(甲基)丙烯酸羥基烷基酯類；或N-羥基(甲基)丙烯醯胺、N-羥基甲基(甲基)丙烯醯胺、N-羥基乙基(甲基)丙烯醯胺等含羥基的(甲基)丙烯醯胺類等中的至少一種以上。 Examples of the hydroxyl-containing monomer include 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and (meth) Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl acrylate; or N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl ( At least one or more of hydroxyl-containing (meth) acrylamides such as (meth) acrylamide.

此外，本實施方式涉及的黏著劑組合物中所含的含羥基單體，可以作為用於減少含羧基單體的含量的共聚性單體而使用，其中所述含羧基單體，對所得到的黏著劑層對於透明導電性膜的ITO表面等易腐蝕的被黏物的腐蝕性造成影響。因此，含羥基單體能夠起到提高黏著劑層的黏著力、且減低腐蝕性的作用。本實施方式的黏著劑組合物中所含的含羥基單體的比例，相對於100重量份的丙烯酸系聚合物，優選為0.1~5.0重量份的比例，更優選為0.1~4.4重量份的比例，特別優選為0.1~3.8重量份的比例。 In addition, the hydroxyl group-containing monomer contained in the adhesive composition according to this embodiment can be used as a copolymerizable monomer for reducing the content of a carboxyl group-containing monomer. The adhesive layer affects the corrosiveness of adherends that are easily corroded, such as the ITO surface of the transparent conductive film. Therefore, the hydroxyl-containing monomer can improve the adhesion of the adhesive layer and reduce the corrosiveness. The ratio of the hydroxyl group-containing monomer contained in the adhesive composition of this embodiment is preferably 0.1 to 5.0 parts by weight, and more preferably 0.1 to 4.4 parts by weight with respect to 100 parts by weight of the acrylic polymer. It is particularly preferably a ratio of 0.1 to 3.8 parts by weight.

作為含羧基單體，例如可列舉出(甲基)丙烯酸、羧乙基(甲基)丙烯酸酯、羧戊基(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基馬來酸、羧基聚己內酯單(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基四氫鄰苯二甲酸等中的至少一種以上。 Examples of the carboxyl group-containing monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, and 2- (meth) acryloxyethylhexahydro Phthalic acid, 2- (meth) acryloxypropylhexahydrophthalic acid, 2- (meth) acryloxyethyl phthalate, 2- (meth) acryloxy Ethyl ethyl succinic acid, 2- (meth) acryloxyethylmaleic acid, carboxy polycaprolactone mono (meth) acrylate, 2- (meth) acryloxyethyl tetrahydro-ortho At least one or more of phthalic acid and the like.

此外，本實施方式涉及的黏著劑組合物中所含的含羧基單體，能夠對所得到的黏著劑層賦予必要的凝聚力。本實施方式涉及的黏著劑組合物中的含羧基單體的比例，相對於100重量份的丙烯酸系聚合物，優選為0~5.0重量份(也允許不使含羧基單體共聚合的情況)，在使含羧基單體共聚合的情況下，更優選為0.01~5.0重量份的比例，特別優選為0.01~3.3重量份的比例，最優選為0.01~2.8重量份的比例。 In addition, the carboxyl group-containing monomer contained in the adhesive composition according to the present embodiment can impart the necessary cohesive force to the obtained adhesive layer. The ratio of the carboxyl group-containing monomer in the adhesive composition according to the present embodiment is preferably 0 to 5.0 parts by weight relative to 100 parts by weight of the acrylic polymer (the case where the carboxyl group-containing monomer is not copolymerized is also allowed) In the case of copolymerizing a carboxyl group-containing monomer, a ratio of 0.01 to 5.0 parts by weight is more preferable, a ratio of 0.01 to 3.3 parts by weight is particularly preferable, and a ratio of 0.01 to 2.8 parts by weight is most preferable.

作為(D)含有芳香族基團的共聚性乙烯基單體，例如可列舉出(甲基)丙烯酸苄基酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸苯氧基丁酯、(甲基)丙烯酸-2-(1-萘氧基)乙酯、(甲基)丙烯酸-2-(2-萘氧基)乙酯、(甲基)丙烯酸-6-(1-萘氧基)己酯、(甲基)丙烯酸-6-(2-萘氧基)己酯、(甲基)丙烯酸-8-(1-萘氧基)辛酯、(甲基)丙烯酸-8-(2-萘氧基)辛酯等中的至少一種以上。在含有含芳香族基團的(甲基)丙烯酸酯單體作為(D)含有芳香族基團的共聚性乙烯基單體的情況下，由於與由(A)以及(B)的組合組成的(甲基)丙烯酸烷基酯單體的共聚性優異，因此優選。 Examples of the (D) copolymerizable vinyl monomer containing an aromatic group include benzyl (meth) acrylate, naphthyl (meth) acrylate, phenoxyethyl (meth) acrylate, ( Phenoxybutyl meth) acrylate, 2- (1-naphthyloxy) ethyl (meth) acrylate, 2- (2-naphthyloxy) ethyl (meth) acrylate, (meth) 6- (1-naphthyloxy) hexyl acrylate, 6- (2-naphthyloxy) hexyl (meth) acrylate, 8- (1-naphthyloxy) octyl (meth) acrylate, At least one or more of (meth) acrylic acid 8- (2-naphthyloxy) octyl ester and the like. In the case where the aromatic group-containing (meth) acrylate monomer is contained as (D) the aromatic vinyl group-containing copolymerizable vinyl monomer, since it is composed of a combination of (A) and (B) The alkyl (meth) acrylate monomer is excellent in copolymerizability, and is therefore preferable.

為了得到折射率高的黏著劑層，優選向本實施方式涉及的黏著劑組合物中摻合含芳香族基團的(甲基)丙烯酸酯單體中的至少一種以上。藉由使這些含芳香族基團的(甲基)丙烯酸酯單體共聚於丙烯酸系聚合物，能夠提高並調節所得到的黏著劑層的折射率，減少光學部件間的折射率差，藉由減少全反射，能夠提高總透光率。在本實施方式涉及的黏著劑組合物中，相對於100重量份的丙烯酸系聚合物，優選以5~30重量份 的比例、更優選以6~28重量份的比例、特別優選以6~24重量份的比例含有含芳香族基團的(甲基)丙烯酸酯單體。 In order to obtain an adhesive layer having a high refractive index, it is preferable that at least one or more of the aromatic group-containing (meth) acrylate monomers are blended into the adhesive composition according to the present embodiment. By copolymerizing these aromatic group-containing (meth) acrylate monomers to an acrylic polymer, the refractive index of the obtained adhesive layer can be increased and adjusted, and the refractive index difference between optical components can be reduced. Reducing total reflection can increase total light transmittance. In the adhesive composition according to the present embodiment, it is preferably 5 to 30 parts by weight, more preferably 6 to 28 parts by weight, and particularly preferably 6 to 24 parts by weight relative to 100 parts by weight of the acrylic polymer. The proportion by weight contains an aromatic group-containing (meth) acrylate monomer.

本實施方式涉及的黏著劑組合物中所含的丙烯酸系聚合物的製備方法，沒有特別的限定，可使用溶液聚合法、乳液聚合法等適宜的習知的聚合方法。丙烯酸系聚合物的共聚物的重均分子量優選為100~300萬。 The method for producing the acrylic polymer contained in the adhesive composition according to the present embodiment is not particularly limited, and an appropriate known polymerization method such as a solution polymerization method or an emulsion polymerization method can be used. The weight average molecular weight of the copolymer of the acrylic polymer is preferably 1 to 3 million.

本實施方式涉及的黏著劑組合物，為了得到抗靜電性能而含有(E)抗靜電劑。相對於100重量份的丙烯酸系聚合物，優選以超過15重量份且為40重量份以下的比例、更優選以16~40重量份的比例、特別優選以16~38重量份的比例含有具有含氟基陰離子的銨系抗靜電劑作為(E)抗靜電劑。該抗靜電劑為由含氟基陰離子和銨陽離子形成的離子化合物。優選該離子化合物為熔點為25℃以上的離子化合物，在常溫(例如25℃)下為固體。此外，該離子化合物更優選為在溫度25℃為固體的、熔點為25℃~80℃的離子化合物。 The adhesive composition according to the present embodiment contains (E) an antistatic agent in order to obtain antistatic performance. With respect to 100 parts by weight of the acrylic polymer, it is preferably contained in a proportion of more than 15 parts by weight and 40 parts by weight or less, more preferably in a proportion of 16 to 40 parts by weight, and particularly preferably in a proportion of 16 to 38 parts by weight. A fluorine-based anion ammonium-based antistatic agent is used as the (E) antistatic agent. The antistatic agent is an ionic compound formed from a fluorine-containing anion and an ammonium cation. The ionic compound is preferably an ionic compound having a melting point of 25 ° C or higher, and is solid at normal temperature (for example, 25 ° C). The ionic compound is more preferably an ionic compound which is solid at a temperature of 25 ° C and has a melting point of 25 ° C to 80 ° C.

作為(E)抗靜電劑中所含的含氟基陰離子，可列舉出無機或有機的含氟基陰離子。在此，氟基是指與構成陰離子的其它原子鍵結的氟原子。作為無機的含氟基陰離子，可列舉出PF6 -、AsF6 -、SbF6 -、BF4 -、AlF4 -、(FSO2)2N-、FSO3 -等。作為有機的含氟基陰離子，可列舉出在含氟基的磺酸根陰離子(RSO3 -)、含氟基的羧酸根陰離子(RCOO-)、含氟基的烷氧化物(alkoxide)或苯氧化物(phenoxide)陰離子(RO-)、含氟基的有機醯亞胺陰離子(R2N-)、含氟基的甲基化合物(methide)(R3C-)陰離子、含氟基的有機硼酸根(R4B-)陰離子等，R 中的至少1個以上為具有含氟基的有機基團的陰離子。作為有機基團，可列舉出烷基、烷氧基、芳香族基團(芳基、芳烷基等)、烷基羰基、芳香族羰基、烷基磺醯基、芳香族磺醯基等中的一種以上。陰離子具有2個以上的R時，也可以在2個以上的R之間具有鍵結而形成環狀。其中，優選選自由五氟苯磺酸根、六氟磷酸根、雙(三氟甲烷磺醯基)亞胺、雙(氟磺醯基)亞胺、三氟甲磺酸根組成的組中的一種。 Examples of the fluorine-containing anion contained in the (E) antistatic agent include inorganic or organic fluorine-containing anions. Here, the fluorine group means a fluorine atom bonded to another atom constituting an anion. As the fluorine-containing inorganic anion include PF 6 -, AsF 6 -, SbF 6 -, BF 4 -, AlF 4 -, (FSO 2) 2 N -, FSO 3 - and the like. Examples of the organic fluorine-containing anion, sulfonic acid anion include fluorinated group (RSO 3 -), a fluorine-containing carboxylate anion group (RCOO -), a fluorine-containing alkoxide (alkoxide) or benzene oxidation was (phenoxide) anion (RO -), a fluorine-containing organic anion (PEI) (R 2 N -), methyl group, fluorine-containing compounds (methide) (R 3 C - ) an anionic, fluorine-containing organic acid root (R 4 B -) anion, at least one or more anionic organic group having a fluorine-containing group in R. Examples of the organic group include an alkyl group, an alkoxy group, an aromatic group (aryl group, aralkyl group, etc.), an alkylcarbonyl group, an aromatic carbonyl group, an alkylsulfonyl group, and an aromatic sulfonyl group. More than one. When the anion has two or more Rs, it may have a bond between two or more Rs to form a ring. Among these, one selected from the group consisting of pentafluorobenzenesulfonate, hexafluorophosphate, bis (trifluoromethanesulfonyl) imide, bis (fluorosulfonyl) imine, and trifluoromethanesulfonate is preferred.

作為(E)抗靜電劑中所含的銨陽離子，可列舉出具有1~4個有機基團的有機銨陽離子，特別優選四級銨陽離子(R4N+)。作為R，可列舉出非環狀或環狀的烷基、芳香族基團(芳基、芳烷基等)等烴基。陽離子具有2個以上的R時，也可以在2個以上的R之間具有鍵結而形成環狀。 Examples of the ammonium cation contained in the (E) antistatic agent include organic ammonium cations having 1 to 4 organic groups, and a quaternary ammonium cation (R 4 N + ) is particularly preferred. Examples of R include a hydrocarbon group such as an acyclic or cyclic alkyl group and an aromatic group (such as an aryl group or an aralkyl group). When a cation has two or more Rs, it may have a bond between two or more Rs to form a ring.

本實施方式涉及的黏著劑組合物，進一步含有選自由三官能以上的異氰酸酯化合物、雙官能以上的環氧化合物所組成的群組中的至少一種以上的交聯劑，作為(F)交聯劑。作為(F)交聯劑的比例，例如，相對於100重量份的丙烯酸系聚合物，可列舉出0.01~5重量份的比例。 The adhesive composition according to the present embodiment further contains at least one or more crosslinking agents selected from the group consisting of a trifunctional or higher isocyanate compound and a difunctional or higher epoxy compound, as the (F) crosslinking agent. . As a ratio of (F) crosslinking agent, for example, the ratio of 0.01-5 weight part with respect to 100 weight part of acrylic polymers is mentioned.

作為三官能以上的異氰酸酯化合物，例如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、甲苯二異氰酸酯、二甲苯撐基(xylylene)二異氰酸酯等二異氰酸酯類的縮二脲改性體或三聚異氰酸改性體；三羥甲基丙烷或甘油等三元以上的多元醇的加合物等。 Examples of the trifunctional or higher isocyanate compound include diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, and xylylene diisocyanate. Biuret modified product or trimeric isocyanate modified product; trimethylolpropane or adduct of trivalent or higher polyhydric alcohol, etc.

作為雙官能以上的環氧化合物，可列舉出二元醇類的二縮水甘油醚、雙酚類的二縮水甘油醚、三元醇類的三縮水甘油 醚、二羧酸的二縮水甘油酯、二縮水甘油基取代的胺類、四縮水甘油基取代的二胺類等。 Examples of the difunctional or higher epoxy compounds include diglycidyl ethers of diols, diglycidyl ethers of bisphenols, triglycidyl ethers of triols, diglycidyl esters of dicarboxylic acids, Diglycidyl substituted amines, tetraglycidyl substituted diamines, and the like.

本實施方式涉及的黏著劑組合物進一步含有(G)矽烷偶合劑。作為(G)矽烷偶合劑，在1分子中具有至少一個有機官能基、以及至少一個水解性基團，所述水解性基團可列舉出為與矽原子鍵結的烷氧基等的化合物。(G)矽烷偶合劑含有選自環氧基、巰基、酸酐基中的至少一種以上的官能基。(G)矽烷偶合劑可以使用單體型或低聚物型的一者或兩者中的至少一種以上。矽烷偶合劑的比例，例如，相對於100重量份的丙烯酸系聚合物，可列舉出0.01~0.5重量份。 The adhesive composition according to the present embodiment further contains (G) a silane coupling agent. The (G) silane coupling agent has at least one organic functional group and at least one hydrolyzable group in one molecule. Examples of the hydrolyzable group include compounds such as an alkoxy group bonded to a silicon atom. (G) The silane coupling agent contains at least one type or more of functional groups selected from an epoxy group, a mercapto group, and an acid anhydride group. (G) As the silane coupling agent, at least one or both of a monomer type and an oligomer type can be used. The ratio of the silane coupling agent is, for example, 0.01 to 0.5 parts by weight based on 100 parts by weight of the acrylic polymer.

作為具有環氧基的矽烷偶合劑，例如可列舉出3-環氧丙氧丙基三甲氧基矽烷、3-環氧丙氧丙基甲基二乙氧基矽烷、3-環氧丙氧丙基甲基二甲氧基矽烷、3-環氧丙氧丙基三乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基甲基二乙氧基矽烷、2-(3,4-環氧環己基)乙基三乙氧基矽烷、5,6-環氧己基三甲氧基矽烷、5,6-環氧己基甲基二甲氧基矽烷、5,6-環氧己基甲基二乙氧基矽烷、5,6-環氧己基三乙氧基矽烷等。作為具有巰基的矽烷偶合劑，例如可列舉出3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基甲基二乙氧基矽烷、3-巰基丙基三乙氧基矽烷等。作為具有酸酐基的矽烷偶合劑，例如可列舉出3-三甲氧基矽烷基丙基琥珀酸酐、3-三乙氧基矽烷基丙基琥珀酸酐等。此外，低聚物化的烷氧基低聚物(矽氧烷烷氧基低聚物)等也可以用作矽烷偶合劑。 Examples of the silane coupling agent having an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyl Methyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-cyclo Oxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Triethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 5,6-epoxyhexylmethyldimethoxysilane, 5,6-epoxyhexylmethyldiethoxysilane, 5, 6-epoxyhexyltriethoxysilane and the like. Examples of the thiol-containing silane coupling agent include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, and 3- Mercaptopropyltriethoxysilane and the like. Examples of the silane coupling agent having an acid anhydride group include 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, and the like. Moreover, oligomerized alkoxy oligomers (siloxy alkoxy oligomers) etc. can also be used as a silane coupling agent.

本實施方式的黏著劑組合物，可以適當摻合抗氧化劑、界面活性劑、固化促進劑、增塑劑、填充劑、交聯催化劑、交聯延遲劑、固化延遲劑、加工助劑、抗老化劑等習知的添加劑，作為任意的成分。這些任意的成分可以單獨、或組合使用兩種以上。 The adhesive composition according to this embodiment may be appropriately blended with an antioxidant, a surfactant, a curing accelerator, a plasticizer, a filler, a crosslinking catalyst, a crosslinking delaying agent, a curing delaying agent, a processing aid, and anti-aging. A conventional additive such as an agent is used as an arbitrary component. These arbitrary components can be used individually or in combination of 2 or more types.

使本實施方式的黏著劑組合物交聯而成的黏著劑層的表面電阻率，優選為2.0×10+9Ω/□以下，更優選為1.0×10+9Ω/□以下，特別優選為8.0×10+8Ω/□以下。優選該黏著劑層的初期的表面電阻率、以及耐久性試驗後的表面電阻率均為2.0×10+9Ω/□以下，更優選為1.0×10+9Ω/□以下，特別優選為8.0×10+8Ω/□以下。在此，初期的表面電阻率是指將黏著劑層供於耐久性試驗前的表面電阻率。此外，耐久性試驗後的表面電阻率是指將黏著劑層供於85℃×750hr的試驗環境下的耐久性試驗後的表面電阻率。在此，85℃×750hr的試驗環境也可以為乾燥條件。 The surface resistivity of the adhesive layer obtained by crosslinking the adhesive composition of the present embodiment is preferably 2.0 × 10 +9 Ω / □ or less, more preferably 1.0 × 10 +9 Ω / □ or less, and particularly preferably 8.0 × 10 +8 Ω / □ or less. The initial surface resistivity of the adhesive layer and the surface resistivity after the durability test are both preferably 2.0 × 10 +9 Ω / □ or less, more preferably 1.0 × 10 +9 Ω / □ or less, and particularly preferably 8.0. × 10 +8 Ω / □ or less. Here, the initial surface resistivity refers to the surface resistivity before the adhesive layer is applied to the durability test. The surface resistivity after the durability test refers to the surface resistivity after the durability test in which the adhesive layer was subjected to a test environment at 85 ° C. × 750 hr. Here, the test environment at 85 ° C. × 750 hr may be a dry condition.

使本實施方式的黏著劑組合物交聯而成的黏著劑層，在供於85℃×750hr的試驗環境下的耐久性試驗、以及60℃×90%RH×750hr的試驗環境下的耐久性試驗後，(E)抗靜電劑未在黏著劑層的表面上析出。在此，85℃×750hr的試驗環境也可以為乾燥條件。 The durability of the adhesive layer obtained by cross-linking the adhesive composition of the present embodiment in a test environment at 85 ° C × 750hr and in a test environment at 60 ° C × 90% RH × 750hr After the test, (E) the antistatic agent did not precipitate on the surface of the adhesive layer. Here, the test environment at 85 ° C. × 750 hr may be a dry condition.

關於本實施方式的黏著劑組合物中的(E)抗靜電劑的析出防止性能，可以製作兩個以上的使相同的黏著劑組合物交聯而成的黏著劑層的樣品，將一個樣品供於85℃×750hr的試驗環境下的耐久性試驗後，(E)抗靜電劑未析出，並且，將另一個 樣品供於60℃×90%RH×750hr的試驗環境下的耐久性試驗後，(E)抗靜電劑也未析出。 Regarding the (E) antistatic agent precipitation prevention performance in the adhesive composition of the present embodiment, two or more samples of the adhesive layer obtained by cross-linking the same adhesive composition can be prepared, and one sample can be supplied. After the durability test under the test environment at 85 ° C × 750hr, (E) the antistatic agent did not precipitate, and after another sample was subjected to the durability test under the test environment at 60 ° C × 90% RH × 750hr, (E) No antistatic agent was precipitated.

本實施方式的黏著劑組合物交聯而成的黏著劑層優選經由厚度為20μm的黏著劑層，將總厚度為80μm的偏振片貼合於無鹼玻璃上時，黏著劑層對於無鹼玻璃的黏著力為1.0~6.0N/25mm。 The adhesive layer formed by crosslinking the adhesive composition of the present embodiment is preferably a 20 μm thick adhesive layer, and when a polarizing plate having a total thickness of 80 μm is bonded to the alkali-free glass, the adhesive layer is suitable for the alkali-free glass. The adhesive force is 1.0 ~ 6.0N / 25mm.

此外，優選將經由厚度為20μm的黏著劑層將10cm見方的總厚度為80μm的偏振片貼合於無鹼玻璃上而成的試驗片，供於85℃×750hr的試驗環境下的耐久性試驗、以及供於60℃×90%RH×750hr的試驗環境下的耐久性試驗後，無起泡以及脫落。 In addition, a test piece obtained by bonding a polarizing plate having a total thickness of 80 μm with a thickness of 10 cm square to an alkali-free glass through an adhesive layer with a thickness of 20 μm is preferably used for a durability test under a test environment of 85 ° C. × 750 hr. After the durability test in a test environment of 60 ° C × 90% RH × 750hr, there was no foaming or falling off.

關於本實施方式的黏著劑組合物的無起泡以及脫落的性能，可以製造兩個以上的使用相同的黏著劑組合物而製造的試驗片，將一個試驗片供於85℃×750hr的試驗環境下的耐久性試驗後，無起泡以及脫落，並且，將另一個試驗片供於60℃×90%RH×750hr的試驗環境下的耐久性試驗後，也無起泡以及脫落。 Regarding the non-foaming and peeling properties of the adhesive composition of the present embodiment, two or more test pieces manufactured using the same adhesive composition can be produced, and one test piece can be subjected to a test environment of 85 ° C. × 750 hr. After the durability test under test, there was no blistering and peeling, and after the other test piece was subjected to a durability test under a test environment of 60 ° C. × 90% RH × 750 hr, there was no blistering or peeling.

本實施方式涉及的黏著劑層，可以藉由在將本實施方式的黏著劑組合物塗布於樹脂膜或離型膜等基材上後，將黏著劑組合物交聯而得到。 The adhesive layer according to this embodiment can be obtained by applying the adhesive composition of this embodiment to a substrate such as a resin film or a release film, and then crosslinking the adhesive composition.

在將本實施方式涉及的黏著劑層用於光學部件的層間的貼合等的情況下，為了減少黏著劑層與光學部件的介面上的光線的反射，希望折射率的差盡可能小。因此，黏著劑層的折射率優選為1.47~1.50。 When the adhesive layer according to the present embodiment is used for bonding between layers of an optical component or the like, in order to reduce reflection of light on the interface between the adhesive layer and the optical component, it is desirable that the difference in refractive index is as small as possible. Therefore, the refractive index of the adhesive layer is preferably 1.47 to 1.50.

本實施方式涉及的黏著膜，可以藉由將本實施方式涉及的黏著劑層形成在樹脂膜或離型膜等基材的單面上而製造。作為成為基材的樹脂膜或離型膜(隔離膜)，可以使用聚酯膜等樹脂膜等。對於離型膜，也可以利用矽氧系、氟系的離型劑等對與黏著劑層的黏著面貼合的側的面實施離型處理。對於成為基材的樹脂膜，可以對樹脂膜的與形成有黏著劑層的側相反的面，實施基於矽氧系、氟系的離型劑或塗布劑、二氧化矽微粒等的防汙處理、基於抗靜電劑的塗布或捏合等的抗靜電處理。作為黏著劑層的厚度，例如可列舉出1μm~25μm的厚度。 The adhesive film according to the present embodiment can be produced by forming the adhesive layer according to the present embodiment on one surface of a substrate such as a resin film or a release film. As a resin film or a release film (separator film) serving as a substrate, a resin film such as a polyester film or the like can be used. For the release film, a release treatment may be performed on the side surface that is in contact with the adhesive surface of the adhesive layer using a silicone-based or fluorine-based release agent. For the resin film used as a base material, 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. Antistatic treatment based on coating or kneading of antistatic agents. Examples of the thickness of the adhesive layer include a thickness of 1 μm to 25 μm.

也可以藉由對一個黏著劑層的兩面分別貼合離型膜的實施了離型處理的面，從而形成“離型膜/黏著劑層/離型膜”的結構。該情況下，藉由使兩側的離型膜依次、或者同時剝離而露出黏著面，能夠與光學膜等光學部件貼合。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、亮度增強膜等。作為光學部件所適用的儀器，可列舉出液晶面板、有機EL面板、觸控面板、In-cell型液晶面板等。 It is also possible to form a "release film / adhesive layer / release film" structure by attaching the release film-treated surface to both sides of one adhesive layer, respectively. In this case, by releasing the release films on both sides sequentially or at the same time 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 absorbing film, an infrared absorbing film, an optical compensation film, and a brightness enhancement film. Examples of the device applicable to the optical component include a liquid crystal panel, an organic EL panel, a touch panel, and an In-cell liquid crystal panel.

本實施方式的黏著膜，適合作為偏振片用黏著膜。特別是也可以用於偏振片與In-cell面板的貼合。此外，可以形成在上述的光學膜的至少一個面上積層所述黏著劑層而成的帶黏著劑層的光學膜。此外，藉由在偏振片的單面上使用上述的黏著膜，能夠提供帶黏著劑層的偏振片。能夠使用上述的帶黏著劑層的偏振片，而提供In-cell型液晶面板等液晶面 板。 The adhesive film of this embodiment is suitable as an adhesive film for polarizing plates. In particular, it can also be used for bonding a polarizer and an In-cell panel. In addition, an optical film with an adhesive layer formed by laminating the adhesive layer on at least one surface of the optical film may be formed. In addition, by using the above-mentioned adhesive film on one side of the polarizing plate, a polarizing plate with an adhesive layer can be provided. A liquid crystal panel such as an In-cell liquid crystal panel can be provided by using the above-mentioned polarizing plate with an adhesive layer.

作為這樣的帶黏著劑層的光學膜的積層結構的具體例，可列舉出“離型膜/黏著劑層/光學膜”、“離型膜/黏著劑層/光學膜/黏著劑層/離型膜”、“光學膜/黏著劑層/光學膜”、“光學膜/黏著劑層”、“黏著劑層/光學膜/黏著劑層”等。作為帶黏著劑層的偏振片的積層結構的具體例，可列舉出“離型膜/黏著劑層/偏振片”、“離型膜/黏著劑層/偏振片/黏著劑層/離型膜”、“偏振片/黏著劑層”、“黏著劑層/偏振片/黏著劑層”等。作為液晶面板等的部分結構，也可以結合有這些帶黏著劑層的光學膜、或帶黏著劑層的偏振片。 Specific examples of the laminated structure of such an optical film with an adhesive layer include "release film / adhesive layer / optical film", "release film / adhesive layer / optical film / adhesive layer / release" Type film "," optical film / adhesive layer / optical film "," optical film / adhesive layer "," adhesive layer / optical film / adhesive layer ", etc. Specific examples of the laminated structure of the polarizer with an adhesive layer include "release film / adhesive layer / polarizer", "release film / adhesive layer / polarizer / adhesive layer / release film" "," Polarizer / adhesive layer "," adhesive layer / polarizer / adhesive layer ", etc. As a partial structure of a liquid crystal panel or the like, these optical films with an adhesive layer or a polarizing plate with an adhesive layer may be combined.

另外，像“離型膜/黏著劑層/光學膜”、“離型膜/黏著劑層/偏振片”等一樣，在使離型膜包含於積層結構中的情況下，剝離離型膜後，經由黏著劑層將光學膜或偏振片貼合於被黏物上。 In addition, like "release film / adhesive layer / optical film", "release film / adhesive layer / polarizer", etc., when the release film is included in the laminated structure, the release film is peeled off An optical film or a polarizer is attached to an adherend via an adhesive layer.

[實施例]     [Example]    

以下，利用實施例對本發明進行具體說明。 Hereinafter, the present invention will be specifically described using examples.

<丙烯酸系聚合物的製備> <Preparation of acrylic polymer>

[實施例1] [Example 1]

向具有攪拌機、溫度計、回流冷卻器以及氮氣導入管的反應裝置中導入氮氣，利用氮氣置換了反應裝置內的空氣。之後，向反應裝置中加入了丙烯酸正丁酯70重量份、甲基丙烯酸正丁酯15重量份、丙烯酸-8-羥基辛酯2.0重量份、丙烯酸苄基酯15重量份、以及溶劑(乙酸乙酯)。之後，以2小時滴加作為聚合起始劑的偶氮二異丁腈0.1重量份，在65℃下反應6小時， 得到了用於實施例1的丙烯酸系聚合物的溶液。 Nitrogen was introduced into a reaction device having a stirrer, a thermometer, a reflux cooler, and a nitrogen introduction tube, and the air in the reaction device was replaced with nitrogen. Thereafter, 70 parts by weight of n-butyl acrylate, 15 parts by weight of n-butyl methacrylate, 2.0 parts by weight of 8-hydroxyoctyl acrylate, 15 parts by weight of benzyl acrylate, and a solvent (ethyl acetate) were added to the reaction device. ester). Thereafter, 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 a solution of an acrylic polymer used in Example 1.

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

除了將單體的組成分別設為如表1中的(A)~(D)所記載以外，以與上述的實施例1相同的方式得到了用於實施例2~6以及比較例1~3的丙烯酸系聚合物溶液。 Except that the compositions of the monomers were set as described in (A) to (D) in Table 1, respectively, the same procedures as those in Example 1 were used to obtain Examples 2 to 6 and Comparative Examples 1 to 3. Acrylic polymer solution.

另外，雖未特別表示測定結果，但實施例1~6以及比較例1~3的丙烯酸系聚合物溶液中所含的共聚物的重均分子量在100~300萬的範圍內。 Although the measurement results are not particularly shown, the weight average molecular weight of the copolymers contained in the acrylic polymer solutions of Examples 1 to 6 and Comparative Examples 1 to 3 is in the range of 1 to 3 million.

<黏著膜的製造> <Manufacture of Adhesive Film>

[實施例1] [Example 1]

向如上所述而製備的實施例1的丙烯酸系聚合物溶液中，以20重量份的比例加入環己基三甲基銨雙(三氟甲烷磺醯基)亞胺、以0.1重量份的比例加入交聯劑(D-110N)、以及以0.05重量份的比例加入矽烷偶合劑(X-12-967C)，進行攪拌混合，得到了實施例1的黏著劑組合物。 To the acrylic polymer solution of Example 1 prepared as described above, cyclohexyltrimethylammonium bis (trifluoromethanesulfonyl) imine was added in a proportion of 20 parts by weight, and 0.1 parts by weight was added. The cross-linking agent (D-110N) and the silane coupling agent (X-12-967C) were added in a proportion of 0.05 parts by weight, followed by stirring and mixing to obtain the adhesive composition of Example 1.

以乾燥後的黏著劑層的厚度成為20μm的方式，將該黏著劑組合物塗布在由已塗布矽氧樹脂的聚對苯二甲酸乙二醇酯(PET)膜形成的離型膜上後，藉由在90℃下乾燥而去除了溶劑。之後，藉由在23℃、50%RH的氛圍下熟化7天，從而得到了在離型膜的單面上具有使黏著劑組合物交聯而成的黏著劑層的、為離型膜/黏著劑層/離型膜的結構的實施例1的黏著膜。 This adhesive composition was coated on a release film formed of a polyethylene terephthalate (PET) film coated with a silicone resin so that the thickness of the dried adhesive layer became 20 μm. The solvent was removed by drying at 90 ° C. After that, the film was cured for 7 days in an atmosphere of 23 ° C and 50% RH to obtain a release film having a pressure-sensitive adhesive layer formed by crosslinking the pressure-sensitive adhesive composition on one side of the release film. Structure of Adhesive Layer / Release Film The adhesive film of Example 1.

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

除了將添加劑的組成分別設為如表1中的(E)~(G)所記載以外，以與上述的實施例1的黏著膜相同的方式進行、得 到了實施例2~6以及比較例1~3的黏著膜。 Except that the compositions of the additives were set as described in (E) to (G) in Table 1, respectively, the same procedures as in the adhesive film of Example 1 described above were performed, and Examples 2 to 6 and Comparative Example 1 were obtained. ~ 3 adhesive film.

在表1中，各成分的縮寫符號後面所添加的數值表示重量份。該重量份藉由將(A)、(B)及(D)的總量設為100重量份而求得。此外，表1中使用的各成分的縮寫符號的化合物名稱示於表2。為了簡便，IOA包含在(B)中。(C)中，將含有羥基的單體分類為“(C)OH”，將含有羧基的單體分類為“(C)COOH”。 In Table 1, the numerical value added after the abbreviation of each component shows a weight part. This weight part is calculated | required by making the total amount of (A), (B), and (D) into 100 weight part. In addition, the compound names of the abbreviations of the respective components used in Table 1 are shown in Table 2. For simplicity, IOA is included in (B). In (C), a monomer containing a hydroxyl group is classified as "(C) OH", and a monomer containing a carboxyl group is classified as "(C) COOH".

在表2中，CORONATE(註冊商標)L是TOSOH CORPORATION的商品名稱，D-110N是\三井化學股份公司的商品名稱，TETRAD(註冊商標)-X是MITSUBISHI GAS CHEMICAL COMPANY,INC.的商品名稱。此外，TDI是指甲苯二異氰酸酯，TMP是指三羥甲基丙烷，XDI是指二甲苯撐基二異氰酸酯。此外，KBM-403、X-12-967C、X-41-1805、KBM-503均為信越化學股份公司的商品名稱。 In Table 2, CORONATE (registered trademark) L is a trade name of TOSOH CORPORATION, D-110N is a trade name of Mitsui Chemicals Co., Ltd., and TETRAD (registered trademark)-X is a trade name of MITSUBISHI GAS CHEMICAL COMPANY, INC. In addition, TDI means toluene diisocyanate, TMP means trimethylolpropane, and XDI means xylylene diisocyanate. In addition, KBM-403, X-12-967C, X-41-1805, and KBM-503 are the trade names of Shin-Etsu Chemical Co., Ltd.

<試驗方法以及評價> <Test method and evaluation>

從實施例1~6以及比較例1~3中的黏著膜上剝離離型膜(已塗布矽氧樹脂的PET膜)，露出所述黏著膜的黏著劑層的單面。之後，經由所述黏著劑層，將所述黏著膜貼合在厚度為80μm的偏振片(樹脂膜)的單面上，得到了為離型膜/黏著劑層/偏振片的結構的帶黏著劑層的偏振片。 The release film (the silicone-coated PET film) was peeled from the adhesive films in Examples 1 to 6 and Comparative Examples 1 to 3 to expose one side of the adhesive layer of the adhesive film. Then, the adhesive film was bonded to one side of a polarizing plate (resin film) having a thickness of 80 μm through the adhesive layer, and a tape with a structure of a release film / adhesive layer / polarizing plate was obtained. Polarizer of the agent layer.

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

剝離上述所得到的帶黏著劑層的偏振片的離型膜，利用壓輥將帶黏著劑層的偏振片經由所述黏著劑層而貼合在無鹼玻璃(Corning Incorporated製造的EAGLE XG(註冊商標))的已利用丙酮清洗的面上，從而製造了試驗片。之後，將該試驗片在50℃、0.5MPa×20分鐘的條件下進行了壓熱處理。之後，返回到23℃×50%RH的氛圍下，利用拉伸試驗機，依據JIS Z0237“黏著膠帶‧黏著片試驗方法”測定經過1小時後的帶黏著劑層的偏振片的剝離強度，將沿180。方向以0.3m/分鐘的速度剝離時的剝離強度，作為黏著劑層對於無鹼玻璃的黏著力。 The release film of the polarizing plate with an adhesive layer obtained as described above was peeled, and the polarizing plate with an adhesive layer was bonded to an alkali-free glass (EAGLE XG (registered by Corning Incorporated) through a pressure roller through a pressure roller). (Trademark)), which had been washed with acetone, thereby producing a test piece. Then, this test piece was autoclaved under the conditions of 50 ° C. and 0.5 MPa × 20 minutes. After that, return to an atmosphere of 23 ° C × 50% RH, and use a tensile tester to measure the peeling strength of the polarizer with an adhesive layer after 1 hour in accordance with JIS Z0237 "Adhesive Tape · Adhesive Sheet Test Method". Along 180. The peeling strength at the time of peeling at a speed of 0.3 m / min was used as the adhesive force of the adhesive layer to the alkali-free glass.

<表面電阻率的測定方法> <Method for measuring surface resistivity>

對上述所得到的帶黏著劑層的偏振片，使用電阻率計HIRESTA(註冊商標)UP-HT450(Mitsubishi Chemical Analytech Co.,Ltd.製造)，測定黏著劑層的表面電阻率(Ω/□)，求出了初期的表面電阻率。對相同的帶黏著劑層的偏振片進行85℃×750hr的試驗環境下的耐久性試驗後，以相同的方式測定表面電阻率，求出了耐久性試驗後的表面電阻率。 About the obtained polarizing plate with an adhesive layer, the resistivity meter HIRSTA (registered trademark) UP-HT450 (made by Mitsubishi Chemical Analytech Co., Ltd.) was used to measure the surface resistivity (Ω / □) of the adhesive layer. , And obtained the initial surface resistivity. The same polarizing plate with an adhesive layer was subjected to a durability test under a test environment of 85 ° C. × 750 hr, and then the surface resistivity was measured in the same manner to obtain the surface resistivity after the durability test.

<耐久性的試驗方法> <Durability test method>

利用與黏著力的測定同樣的方法，剝離10cm見方的帶黏著劑層的偏振片的離型膜，貼合於無鹼玻璃的已利用丙酮清洗的面上，製造了試驗片。之後，對該試驗片進行85℃×750hr的試驗環境下的耐久性試驗、以及60℃×90%RH×750hr的試驗環境下的耐久性試驗後，取出至23℃×50%RH氛圍下，1小時後目視觀察黏著劑層的狀態，判斷耐久性。 A 10 cm square release film of a polarizing plate with an adhesive layer was peeled off by the same method as the measurement of the adhesive force, and a test piece was produced by bonding it to an alkali-free glass-washed surface with acetone. Then, the test piece was subjected to a durability test in a test environment at 85 ° C × 750hr and a durability test in a test environment at 60 ° C × 90% RH × 750hr, and then taken out to an atmosphere of 23 ° C × 50% RH. After 1 hour, the state of the adhesive layer was visually observed, and durability was judged.

○：無黏著劑層的起泡以及脫落。 ○: No foaming or peeling of the adhesive layer.

△：黏著劑層的一部分發生起泡、脫落。 △: Part of the adhesive layer was foamed and peeled.

×：黏著劑層整體發生起泡、脫落。 ×: Foaming and peeling occurred in the entire adhesive layer.

<抗靜電劑的析出狀態的評價方法> <Evaluation method of precipitation state of antistatic agent>

利用與黏著力的測定同樣的方法，剝離10cm見方的帶黏著劑層的偏振片的離型膜，貼合於無鹼玻璃的已利用丙酮清洗的面上，製造了試驗片。之後，對該試驗片進行85℃×750hr的試驗環境下的耐久性試驗、以及60℃×90%RH×750hr的試驗環境下的耐久性試驗後，取出至23℃×50%RH氛圍中，1小時後目視觀察黏著劑層的狀態，判斷了抗靜電劑向黏著劑層的表面的析出狀態。 A 10 cm square release film of a polarizing plate with an adhesive layer was peeled off by the same method as the measurement of the adhesive force, and a test piece was produced by bonding it to an alkali-free glass-washed surface with acetone. Then, the test piece was subjected to a durability test in a test environment at 85 ° C × 750hr and a durability test in a test environment at 60 ° C × 90% RH × 750hr, and then taken out into an atmosphere of 23 ° C × 50% RH. After 1 hour, the state of the adhesive layer was visually observed, and the precipitation state of the antistatic agent on the surface of the adhesive layer was judged.

○：在黏著劑層的表面上完全沒有抗靜電劑的析出。 ：: No antistatic agent was deposited on the surface of the adhesive layer at all.

△：在黏著劑層的表面的一部分上發生抗靜電劑的析出。 Δ: Precipitation of the antistatic agent occurred on a part of the surface of the adhesive layer.

×：在黏著劑層的表面整體上發生抗靜電劑的析出。 ×: Precipitation of the antistatic agent occurred on the entire surface of the adhesive layer.

表3中表示評價結果。 Table 3 shows the evaluation results.

關於實施例1~6的黏著膜，對於無鹼玻璃的黏著力為1.0~6.0N/25mm，黏著劑層的初期的表面電阻率、以及在85℃×750hr的試驗環境下的耐久性試驗後的表面電阻率均為2.0×10+9Ω/□以下，在85℃×750hr的試驗環境下的耐久性試驗、以及60℃×90%RH×750hr的試驗環境下的耐久性試驗後，無起泡以及脫落，具有耐久性，並且，在黏著劑層的表面上也無抗靜電劑的析出。即，實施例1~6的黏著膜的評價結果證實了能夠解決本發明的技術問題。 Regarding the adhesive films of Examples 1 to 6, the adhesive force to the alkali-free glass was 1.0 to 6.0 N / 25 mm, the initial surface resistivity of the adhesive layer, and the durability test under a test environment at 85 ° C × 750hr After the surface resistivity of 2.0 × 10 +9 Ω / □ or less, the durability test under the test environment at 85 ℃ × 750hr and the durability test under the test environment at 60 ℃ × 90% RH × 750hr, all It foams and comes off, has durability, and no antistatic agent is deposited on the surface of the adhesive layer. That is, the evaluation results of the adhesive films of Examples 1 to 6 confirmed that the technical problems of the present invention can be solved.

關於比較例1的黏著膜，丙烯酸系聚合物中所共聚合的(甲基)丙烯酸烷基酯單體不是TBA、IBA、BMA、MA中的任何一者，並且，沒有使(D)含有芳香族基團的共聚性乙烯基單體共聚合。因此，比較例1的黏著膜的耐久性試驗前的黏著劑層的黏著力過大，耐久性差。此外，比較例1的黏著膜由於(E)抗靜電劑的含有比例大，因此，黏著劑層的表面電阻率雖變低，但耐久性試驗後抗靜電劑在黏著劑層的表面整個面上析出。 Regarding the adhesive film of Comparative Example 1, the (meth) acrylic acid alkyl ester monomer copolymerized in the acrylic polymer was not any of TBA, IBA, BMA, and MA, and (D) did not contain an aromatic substance. The copolymerizable vinyl monomer of the group is copolymerized. Therefore, the adhesive force of the adhesive layer before the durability test of the adhesive film of Comparative Example 1 was too large, and the durability was poor. In addition, since the adhesive film of Comparative Example 1 has a large content of the (E) antistatic agent, the surface resistivity of the adhesive layer is low, but the antistatic agent is applied to the entire surface of the adhesive layer after the durability test. Precipitation.

比較例2的黏著膜雖含有(G)矽烷偶合劑，但不含選自環氧基、巰基、酸酐基中的至少一種以上的官能基。因此，比較例2的黏著膜的黏著劑層的耐久性差，耐久性試驗後抗靜電劑在黏著劑層的表面上部分析出。 Although the adhesive film of Comparative Example 2 contains a (G) silane coupling agent, it does not contain at least one or more functional groups selected from an epoxy group, a mercapto group, and an acid anhydride group. Therefore, the durability of the adhesive layer of the adhesive film of Comparative Example 2 was poor, and the antistatic agent was analyzed on the upper surface of the adhesive layer after the durability test.

比較例3的黏著膜，丙烯酸系聚合物中所共聚合的(甲基)丙烯酸烷基酯單體不是TBA、IBA、BMA、MA中的任何一者，並且，沒有使(D)含有芳香族基團的共聚性乙烯基單體共聚合。因此，比較例3的黏著膜即使不含有(G)矽烷偶合 劑，耐久性試驗前的黏著劑層的黏著力也過大，耐久性差。此外，由於(E)抗靜電劑的含有比例小，因此，比較例3的黏著膜雖無耐久性試驗後的抗靜電劑向黏著劑層的表面的析出，但黏著劑層的表面電阻率變高。 In the adhesive film of Comparative Example 3, the (meth) acrylic acid alkyl ester monomer copolymerized in the acrylic polymer was not any of TBA, IBA, BMA, and MA, and (D) did not contain aromatic The copolymerizable vinyl monomer of the group is copolymerized. Therefore, even if the adhesive film of Comparative Example 3 does not contain a (G) silane coupling agent, the adhesive force of the adhesive layer before the durability test is too large and the durability is poor. In addition, since the content ratio of the antistatic agent (E) is small, although the adhesive film of Comparative Example 3 did not have the antistatic agent deposited on the surface of the adhesive layer after the durability test, the surface resistivity of the adhesive layer changed. high.

像這樣，比較例1~3的黏著膜無法解決本發明的技術問題。 As such, the adhesive films of Comparative Examples 1 to 3 cannot solve the technical problems of the present invention.

根據本發明，能夠提供一種具有黏著劑層的表面電阻率為現有技術中無法達到的2.0×10+9Ω/□以下的極其優異的抗靜電性能、並且不損害耐久性的黏著劑組合物以及使用了該黏著劑組合物的黏著膜。因此，本發明涉及的黏著劑組合物以及使用了該黏著劑組合物的黏著膜，作為用於貼合偏振片和液晶面板的黏著劑組合物以及使用了該黏著劑組合物的黏著膜，具有極其優異的抗靜電性能，並且具有耐久性，因此，產業上的利用價值大。 According to the present invention, it is possible to provide an adhesive composition having a surface resistivity of an adhesive layer which is extremely excellent in antistatic performance of 2.0 × 10 +9 Ω / □ or less, which cannot be achieved in the prior art, and does not impair durability. An adhesive film using this adhesive composition. Therefore, the adhesive composition according to the present invention and an adhesive film using the same are provided as an adhesive composition for bonding a polarizing plate and a liquid crystal panel and an adhesive film using the same. It has extremely excellent antistatic performance and durability, so it has great industrial value.

Claims (14)

一種黏著劑組合物，其含有丙烯酸系聚合物、抗靜電劑、以及交聯劑，其特徵在於，所述丙烯酸系聚合物為下列單體共聚而成的共聚物的重均分子量為100~300萬的丙烯酸系聚合物：(A)丙烯酸正丁酯，(B)選自由丙烯酸叔丁酯、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，(C)含有羥基及/或羧基的共聚性乙烯基單體中的至少一種，以及(D)含有芳香族基團的共聚性乙烯基單體中的至少一種；所述黏著劑組合物，相對於100重量份的所述丙烯酸系聚合物，以超過15重量份且為40重量份以下的比例含有作為所述(E)抗靜電劑的具有含氟基陰離子的銨系抗靜電劑；所述黏著劑組合物含有選自由三官能以上的異氰酸酯化合物、雙官能以上的環氧化合物所組成的群組中的至少一種以上的交聯劑，作為所述(F)交聯劑；所述黏著劑組合物進一步含有(G)含有選自環氧基、巰基、酸酐基中的至少一種以上的官能基的單體型或低聚物型的矽烷偶合劑；使所述黏著劑組合物交聯而成的黏著劑層的表面電阻率為2.0×10 +9Ω/□以下；將所述黏著劑層供於85℃×750hr的試驗環境下的耐久性試驗後、或供於60℃×90%RH×750hr的試驗環境下的耐久性試 驗後，所述抗靜電劑未在所述黏著劑層的表面上析出。 An adhesive composition containing an acrylic polymer, an antistatic agent, and a crosslinking agent, wherein the acrylic polymer is a copolymer obtained by copolymerizing the following monomers with a weight average molecular weight of 100 to 300. 10,000 acrylic polymers: (A) n-butyl acrylate, (B) at least one selected from the group consisting of tert-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, and methyl acrylate, (C ) At least one of a copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group, and (D) at least one of a copolymerizable vinyl monomer containing an aromatic group; the adhesive composition, relative to 100 The acrylic polymer contains an ammonium-based antistatic agent having a fluorine-containing anion as the (E) antistatic agent in a proportion of more than 15 parts by weight and 40 parts by weight or less; the adhesive The composition contains at least one or more crosslinking agents selected from the group consisting of a trifunctional or higher isocyanate compound and a difunctional or higher epoxy compound, as the (F) crosslinking agent; the adhesive composition Further contains (G) Monomer type or oligomer type silane coupling agent having at least one or more functional groups selected from epoxy group, mercapto group, and acid anhydride group; the surface of the adhesive layer obtained by cross-linking the adhesive composition The resistivity is 2.0 × 10 +9 Ω / □ or less; after the adhesive layer is subjected to a durability test under a test environment of 85 ° C × 750hr, or a test environment of 60 ° C × 90% RH × 750hr After the durability test, the antistatic agent did not precipitate on the surface of the adhesive layer. 如申請專利範圍第1項所述的黏著劑組合物，其中，所述抗靜電劑為由含氟基陰離子與銨陽離子形成的、熔點為25℃以上的離子化合物；所述含氟基陰離子為選自由五氟苯磺酸根、六氟磷酸根、雙(三氟甲烷磺醯基)亞胺、雙(氟磺醯基)亞胺、三氟甲磺酸根所組成的群組中的一種。     The adhesive composition according to item 1 of the scope of patent application, wherein the antistatic agent is an ionic compound formed of a fluorine-containing anion and an ammonium cation and having a melting point of 25 ° C or higher; the fluorine-containing anion is One selected from the group consisting of pentafluorobenzenesulfonate, hexafluorophosphate, bis (trifluoromethanesulfonyl) imine, bis (fluorosulfonyl) imine, and trifluoromethanesulfonate.     如申請專利範圍第1或2項所述的黏著劑組合物，其中，所述丙烯酸系聚合物，相對於100重量份的所述丙烯酸系聚合物，以40~89重量份的比例含有所述(A)丙烯酸正丁酯、以及以總計為5~40重量份的比例含有所述(B)選自由丙烯酸叔丁酯、丙烯酸異丁酯、甲基丙烯酸正丁酯、丙烯酸甲酯所組成的群組中的至少一種以上，並且，(A)與(B)的比例(A)/(B)為1.0~17.8。     The adhesive composition according to item 1 or 2 of the scope of patent application, wherein the acrylic polymer contains the acrylic polymer in an amount of 40 to 89 parts by weight relative to 100 parts by weight of the acrylic polymer. (A) n-butyl acrylate, and containing the total of 5 to 40 parts by weight (B) selected from the group consisting of tert-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, and methyl acrylate At least one or more of the groups, and the ratio (A) / (B) of (A) to (B) is 1.0 to 17.8.     如申請專利範圍第1或2項所述的黏著劑組合物，其中，將總厚度為80μm的偏振片經由使所述黏著劑組合物交聯而成的厚度為20μm的黏著劑層而貼合於無鹼玻璃上時，所述黏著劑層對於無鹼玻璃的黏著力為1.0~6.0N/25mm；將10cm見方的總厚度為80μm的偏振片經由使所述黏著劑組合物交聯而成的厚度為20μm的黏著劑層而貼合於無鹼玻璃上而成的試驗片，供於85℃×750hr的試驗環境下的耐久性試驗後、或供於60℃×90%RH×750hr的試驗環境下的耐久性試驗後，無起泡以及脫落。     The adhesive composition according to item 1 or 2 of the scope of application for a patent, wherein a polarizing plate having a total thickness of 80 μm is bonded via an adhesive layer having a thickness of 20 μm which is obtained by cross-linking the adhesive composition. When on an alkali-free glass, the adhesive force of the adhesive layer to the alkali-free glass is 1.0 to 6.0 N / 25 mm; a 10 cm square polarizing plate having a total thickness of 80 μm is formed by crosslinking the adhesive composition The test piece made of an adhesive layer with a thickness of 20 μm and bonded to an alkali-free glass is subjected to a durability test under a test environment at 85 ° C × 750hr, or at 60 ° C × 90% RH × 750hr. After the durability test in the test environment, there was no blistering or falling off.     如申請專利範圍第1或2項所述的黏著劑組合物，其中，所 述(C)含有羥基及/或羧基的共聚性乙烯基單體，為選自由含有羥基的可共聚單體、以及含有羧基的可共聚單體所組成的群組中的至少一種以上；所述含有羥基的可共聚單體為選自由(甲基)丙烯酸-8-羥基辛酯、(甲基)丙烯酸-6-羥基己酯、(甲基)丙烯酸-4-羥基丁酯、(甲基)丙烯酸-2-羥基乙酯、N-羥基(甲基)丙烯醯胺、N-羥基甲基(甲基)丙烯醯胺、N-羥基乙基(甲基)丙烯醯胺所組成的化合物群組中的至少一種以上；所述含有羧基的可共聚單體為選自由(甲基)丙烯酸、羧乙基(甲基)丙烯酸酯、羧戊基(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基丙基六氫鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基馬來酸、羧基聚己內酯單(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基四氫鄰苯二甲酸所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 patent application, wherein (C) the copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group is selected from a copolymerizable monomer containing a hydroxyl group, and At least one or more of the group consisting of a carboxyl group-containing copolymerizable monomer; the hydroxyl group-containing copolymerizable monomer is selected from the group consisting of (meth) acrylic acid-8-hydroxyoctyl ester and (meth) acrylic acid-6- Hydroxyhexyl ester, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acryl At least one or more compounds from the group consisting of amine and N-hydroxyethyl (meth) acrylamide; the copolymerizable monomer containing a carboxyl group is selected from the group consisting of (meth) acrylic acid and carboxyethyl (methyl) ) Acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloxyethylhexahydrophthalate, 2- (meth) acryloxypropylhexahydrophthalate Formic acid, 2- (meth) acryloxyethyl phthalic acid, 2- (meth) acryloxyethyl succinic acid, 2- (meth) acryloxyethyl maleic acid, Carboxypolycaprolactone Mono (meth) acrylate, 2- (meth) oxyethyl group of compounds Bing Xixi tetrahydrophthalic acid consisting of at least one or more.     如申請專利範圍第1或2項所述的黏著劑組合物，其中，所述黏著劑層的初期的表面電阻率、以及供於85℃×750hr的試驗環境下的耐久性試驗後的表面電阻率，均為2.0×10 +9Ω/□以下。 The adhesive composition according to item 1 or 2 of the patent application scope, wherein the initial surface resistivity of the adhesive layer and the surface resistance after a durability test in a test environment at 85 ° C × 750hr The rate is less than 2.0 × 10 +9 Ω / □. 一種黏著膜，其特徵在於，藉由在樹脂膜的單面上積層如申請專利範圍第1~6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。     An adhesive film is characterized in that an adhesive layer formed by cross-linking an adhesive composition as described in any one of claims 1 to 6 of the patent application scope is laminated on one side of a resin film.     一種偏振片用黏著膜，其使用了如申請專利範圍第7項所述的黏著膜。     An adhesive film for a polarizer uses the adhesive film described in item 7 of the scope of patent application.     如申請專利範圍第8項所述的偏振片用黏著膜，其特徵在於，用於偏振片與In-cell面板的貼合。     The adhesive film for a polarizer according to item 8 of the scope of application for a patent, which is used for bonding a polarizer to an In-cell panel.     一種黏著膜，其特徵在於，為使如申請專利範圍第1~6項中任一項所述的黏著劑組合物交聯而成的黏著劑層以1μm~25μm的厚度在離型膜的單面上形成的、離型膜/黏著劑層/離型膜的結構。     A pressure-sensitive adhesive film characterized in that the pressure-sensitive adhesive layer formed by cross-linking the pressure-sensitive adhesive composition according to any one of claims 1 to 6 of the patent application range is formed in a thickness of 1 μm to 25 μm on the release film. Structure of release film / adhesive layer / release film formed on the surface.     一種帶黏著劑層的光學膜，其特徵在於，將如申請專利範圍第1~6項中任一項所述的黏著劑組合物交聯而成的黏著劑層積層於光學膜的至少一個面上而成。     An optical film with an adhesive layer, characterized in that an adhesive layer obtained by cross-linking the adhesive composition according to any one of claims 1 to 6 of the scope of patent application is laminated on at least one surface of the optical film. On.     一種帶黏著劑層的偏振片，其特徵在於，將如申請專利範圍第1~6項中任一項所述的黏著劑組合物交聯而成的黏著劑層積層於偏振片的單面上而成。     A polarizing plate with an adhesive layer is characterized in that an adhesive layer obtained by cross-linking the adhesive composition according to any one of claims 1 to 6 of the patent application scope is laminated on one side of the polarizing plate. Made.     一種液晶面板，其特徵在於，使用如申請專利範圍第12項中所述的帶黏著劑層的偏振片。     A liquid crystal panel characterized by using a polarizing plate with an adhesive layer as described in item 12 of the scope of patent application.     一種In-cell型液晶面板，其特徵在於，使用如申請專利範圍第12項中所述的帶黏著劑層的偏振片     An In-cell type liquid crystal panel characterized by using a polarizer with an adhesive layer as described in item 12 of the scope of patent application    
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