TW201905147A - Adhesive composition and adhesive film - Google Patents
Adhesive composition and adhesive filmInfo
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- TW201905147A TW201905147A TW106141144A TW106141144A TW201905147A TW 201905147 A TW201905147 A TW 201905147A TW 106141144 A TW106141144 A TW 106141144A TW 106141144 A TW106141144 A TW 106141144A TW 201905147 A TW201905147 A TW 201905147A
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- adhesive composition
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- 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
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- 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
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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
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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- 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
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- C—CHEMISTRY; METALLURGY
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- 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
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
- C09J2301/314—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 layer and/or the carrier being conductive
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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
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—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
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- C09J2433/00—Presence of (meth)acrylic polymer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Polarising Elements (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本發明涉及一種黏著劑組合物及黏著膜，該黏著劑組合物及黏著膜例如能夠使用於在被黏物為液晶面板的、具有觸控面板的功能的內嵌式(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 used, for example, on an in-cell panel having a touch panel function as a liquid crystal panel as an adherend. Use for bonding.
特別涉及一種具有黏著劑層的表面電阻率為9.0×10+10Ω/□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 of 9.0 × 10 +10 Ω / □ or less and extremely excellent antistatic performance, and an adhesive film using the adhesive composition.
有人提出了用於將偏光板、相位差板等光學構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(例如參考專利文獻1~2)。 Various adhesive films have been proposed for bonding optical members such as a polarizing plate and a retardation plate to an adherend such as a liquid crystal cell via an adhesive layer (for example, refer to Patent Documents 1 to 2).
專利文獻1中記載了一種含有丙烯酸類聚合物的光學用黏著劑組合物，其中該丙烯酸類聚合物以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而成。 Patent Document 1 describes an optical adhesive composition containing an acrylic polymer in which acrylamine compounds and the like are copolymerized 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類聚合物的光學用黏著劑組合物，其中該丙烯酸類聚合物以具有碳原子數為4~8的烷基的(甲基)丙烯酸酯作為主成分的單體，使含羧基單體及含氮乙烯基單體共聚而成。 Patent Document 2 describes an optical adhesive composition containing an acrylic polymer, wherein the acrylic polymer contains a (meth) acrylic acid ester having an alkyl group having 4 to 8 carbon atoms as a main component. Body by copolymerizing a carboxyl-containing monomer and a nitrogen-containing vinyl monomer.
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
然而，對於用於貼合偏光板與液晶面板的黏著劑層，在液晶面板為具有觸控面板的功能的內嵌式(In-cell)面板的情況下，要求將該黏著劑層的表面電阻率設為低於以往的表面電阻率的值。 However, for an adhesive layer for bonding a polarizing plate and a liquid crystal panel, when the liquid crystal panel is an in-cell panel having a function of a touch panel, the surface resistance of the adhesive layer is required. The ratio is set to a value lower than the conventional surface resistivity.
因此，對於用於將偏光板貼合於液晶面板上的黏著劑層，要求將該黏著劑層的表面電阻率設為9.0×10+10Ω/□以下，但在現有技術中，表現出如此高度的抗靜電性能是非常困難的。 Therefore, for an adhesive layer for bonding a polarizing plate to a liquid crystal panel, the surface resistivity of the adhesive layer is required to be 9.0 × 10 +10 Ω / □ or less, but it has been shown in the prior art High antistatic performance is very difficult.
此外，即使在能夠表現出如此高度的抗靜電性能的情況下，也難以同時維持黏著劑層的耐久性。 In addition, even in a case where such a high degree of antistatic performance can be exhibited, it is difficult to simultaneously maintain the durability of the adhesive layer.
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9.0×10+10Ω/□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 9.0 × 10 +10 Ω / □ or less, which has extremely excellent antistatic performance and does not impair durability, and uses the adhesive. Adhesive film of the composition.
本申請的發明人為了解決難以同時達到如此高度的抗靜電性能與耐久性這兩者的技術問題，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類聚合物的(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 聚物形成的丙烯酸類聚合物，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。 The inventors of the present application have conducted intensive research in order to solve the technical problem that it is difficult to achieve both such high antistatic performance and durability at the same time. 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 formed by copolymerizing an alkyl (meth) acrylate can further solve this technical problem by forming an adhesive composition containing a specific antistatic agent.
本申請的發明人發現，藉由含有所述丙烯酸類聚合物、及相對於100重量份的所述丙烯酸類聚合物以2.5~15重量份的比例含有具有含氟基陰離子的銨類抗靜電劑，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 inventors of the present application have found that by including the acrylic polymer and an ammonium antistatic agent having a fluorine-containing anion in a proportion of 2.5 to 15 parts by weight relative to 100 parts by weight of the acrylic polymer. The present invention has been achieved by obtaining an adhesive composition that has extremely excellent antistatic performance compared with conventional adhesive compositions, and that the antistatic agent does not precipitate and has excellent durability that 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9.0×10+10Ω/□以下的極其優異的抗靜電性能，相對於100重量份的丙烯酸類聚合物，以2.5~15重量份的比例含有具有含氟基陰離子的銨類抗靜電劑。像這樣，在本發明中，為了得到極其優異的抗靜電性能，增大了抗靜電劑的含量。 The adhesive composition according to the present invention has a surface resistivity of the adhesive layer of 9.0 × 10 +10 Ω / □ or less, and has extremely excellent antistatic performance. The content is 2.5 to 100 parts by weight of the acrylic polymer. 15 parts by weight contains an ammonium-based antistatic agent having a fluorine-containing anion. As such, in the present invention, in order to obtain extremely excellent antistatic performance, the content of the antistatic agent is increased.
本發明涉及的黏著劑組合物的技術構思在於，為了使黏著劑層中大量包含的具有含氟基陰離子的銨類抗靜電劑不在黏著劑層的高溫及高濕度環境下的耐久性試驗後析出至黏著劑層的表面，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有的丙烯酸類聚合物以丙烯酸正丁酯(BA)為主體，並選擇與BA的共聚性良好的單體進行共聚而成。 The technical idea of the adhesive composition according to the present invention is to prevent the ammonium antistatic agent having a fluorine-containing anion contained in a large amount in the adhesive layer from precipitating after a durability test under high temperature and high humidity conditions of the adhesive layer. To 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 to be 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，其含有丙烯酸類聚合物、抗靜電劑及交聯劑，其特徵在於，所述丙烯酸類聚合物為使下列成分共聚而成的共聚物的重量平均分子量為100~300萬的丙烯酸類聚合物：(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、丙烯酸甲酯組成的群組中的至少一種，(C)含有羥基和/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類聚合物，以2.5~15重量份的比例含有具有含氟基陰離子的銨類抗靜電劑作為所述(E)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團的單體型或低聚物型的矽烷偶聯劑；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9.0×10+10Ω/□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，在所述黏著劑層的表面上未析出所述抗靜電劑。 In addition, in order to solve the above technical problems, the present invention provides an adhesive composition containing an acrylic polymer, an antistatic agent, and a crosslinking agent, wherein the acrylic polymer is obtained by copolymerizing the following components: Copolymer acrylic polymer with weight average molecular weight of 1 to 3 million: (A) n-butyl acrylate, (B) selected from tert-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, and methyl acrylate At least one of the group consisting of (C) at least one of a copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group, and (D) at least one of copolymerizable vinyl monomers containing an aromatic group; The adhesive composition contains, as the (E) antistatic agent, an ammonium antistatic agent having a fluorine-containing anion in a proportion of 2.5 to 15 parts by weight relative to 100 parts by weight of the acrylic polymer; The adhesive composition contains, as the (F) crosslinking agent, 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 composition further contains (G) a monomer-type or oligomer-type silane coupling agent containing at least one or more functional groups selected from the group consisting of epoxy groups, mercapto groups, and acid anhydride groups; the adhesive composition is crosslinked to The surface resistivity of the formed adhesive layer is 9.0 × 10 +10 Ω / □ or less; after the adhesive layer is subjected to a durability test under a test environment of 85 ° C. × 750 hr, or 60 ° C. × 90% After the durability test under the test environment of RH × 750hr, the antistatic agent was not precipitated 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；優選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群組中的一種。 In addition, the antistatic agent is preferably an ionic compound having a melting point of 25 ° C. or higher formed from a fluorine-containing anion and an ammonium cation; preferably, the fluorine-containing anion is selected from the group consisting of pentafluorobenzenesulfonate, hexafluorophosphate, and bis (Trifluoromethanesulfonyl) imine, bis (fluorosulfonyl) imine, and trifluoromethanesulfonate.
優選相對於100重量份的所述丙烯酸類聚合物，所述丙烯酸類聚合物以40~89重量份的比例含有所述(A)丙烯酸正丁酯，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、丙烯酸甲酯組成的群組中的至少一種以上，且(A)與(B)的比(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 the total amount is 5 to 40 parts by weight. The (B) is at least one selected from the group consisting of tert-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, and methyl acrylate, and the ratio (A) to (B) (A) / (B) is 1.0 ~ 17.8.
優選將總厚度為80μm的偏光板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，所述黏著劑層對無鹼玻璃的黏著力為1.0~6.0N/25mm；優選將10cm見方的總厚度為80μm的偏光板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 cross-linking the adhesive composition, the adhesive layer adheres to the alkali-free glass. The force is 1.0 to 6.0 N / 25 mm; it is preferable that a polarizing plate with a total thickness of 80 μm in a 10 cm square and a thickness of 20 μm cross-linked with the adhesive composition is bonded to an alkali-free glass, The finished test piece was free from blistering and peeling after being subjected to a durability test under a test environment at 85 ° C x 750hr or after being subjected to a durability test under a test environment at 60 ° C x 90% RH x 750hr.
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及含有羧基的可共聚單體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；優選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組成的化合物群組中的至少一種以上。 The (C) 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 of a hydroxyl group is selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and (meth) acrylic acid. In the compound group consisting of 2-hydroxyethyl ester, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide At least one or more; preferably the carboxyl-containing copolymerizable monomer is selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) propylene 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) acrylic acid Oxyethyl tetrahydrophthalic acid Into a compound of at least one or more of the group.
優選所述黏著劑層的初期的表面電阻率、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 9.0×10+10Ω/□以下。 It is preferable that 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 9.0 × 10 +10 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層疊使上述黏著劑組合物交聯而成的黏著劑層而成。 Moreover, this invention provides the adhesive film characterized by laminating | stacking the adhesive layer which crosslinked the said adhesive composition on the one side of the resin film, It is characterized by the above-mentioned.
此外，本發明提供一種偏光板用黏著膜，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，本發明提供一種上述的偏光板用黏著膜，其特徵在於，用於偏光板與內嵌式(In-cell)面板的貼合。 In addition, the present invention provides the above-mentioned adhesive film for a polarizing plate, which is characterized in that it is used for bonding a polarizing plate and an in-cell panel.
此外，本發明提供一種黏著膜，其特徵在於，其係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 it is a release film formed on one side of a release film with a thickness of 1 μm to 25 μm by cross-linking the above-mentioned adhesive composition. / Adhesive layer / Release film structure.
此外，本發明提供一種帶黏著劑層的光學膜，其特徵在於，其係使上述的黏著劑組合物交聯而成的黏著劑層在光學膜的至少一個面上層疊而成的、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 characterized in that the adhesive layer formed by cross-linking the above-mentioned adhesive composition is laminated on at least one side of the optical film and is released. Structure of film / adhesive layer / optical film.
此外，本發明提供一種帶黏著劑層的偏光板，其特徵在於，其係使上述的黏著劑組合物交聯而成的黏著劑層在偏光板的單面上層疊而成的、離型膜/黏著劑層/偏光板的結構。 In addition, the present invention provides a polarizing plate with an adhesive layer, characterized in that it is a release film in which an adhesive layer obtained by cross-linking the above-mentioned adhesive composition is laminated on one side of the polarizing plate. / Adhesive layer / Polarizer structure.
此外，本發明提供一種液晶面板，其特徵在於，使用了上述的帶黏著劑層的偏光板。 In addition, the present invention provides a liquid crystal panel using the above-mentioned polarizing plate with an adhesive layer.
此外，本發明提供一種內嵌(In-cell)型液晶面板，其特徵在於，使用了上述的帶黏著劑層的偏光板。 In addition, the present invention provides an in-cell liquid crystal panel, which is characterized by using the above-mentioned polarizing plate with an adhesive layer.
根據本發明，能夠提供一種具有黏著劑層的表面電阻率為9.0×10+10Ω/□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 of 9.0 × 10 +10 Ω / □ or less, which has extremely excellent antistatic performance and does not impair durability, and uses the same. Film.
以下，基於適宜的實施方式，對本發明進行說明。 Hereinafter, the present invention will be described based on suitable embodiments.
本實施方式的黏著劑組合物含有丙烯酸類聚合物、抗靜電劑及交聯劑，其特徵在於，所述丙烯酸類聚合物為使下列成分共聚而成的共聚物的重量平均分子量為100~300萬的丙烯酸類聚合物：(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、丙烯酸甲酯組成的群組中的至少一種，(C)含有羥基和/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類聚合物，以2.5~15重量份的比例含有具有含氟基陰離子的銨類抗靜電劑作為所述(E)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團的單體型或低聚物型的矽烷偶聯劑；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9.0×10+10Ω/□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，在所述黏著劑層的表面上未析出所述抗靜電劑。 The adhesive composition according to the present embodiment contains an acrylic polymer, an antistatic agent, and a crosslinking agent, wherein the acrylic polymer is a copolymer having the following components having 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 antistatic agent having a fluorine-containing anion as the (E) antistatic agent in an amount of 2.5 to 15 parts by weight; the adhesive composition contains The (F) cross-linking agent is at least one or more cross-linking agents in a group consisting of an isocyanate compound or more and an epoxy compound having more than two functions; the adhesive composition further contains (G) Epoxy, Group, at least a monomeric or oligomeric silane-coupling agent is an acid anhydride group in one or more functional groups; said adhesive composition is crosslinked with a surface resistivity of the adhesive layer is 9.0 × 10 + 10 Ω / □ or less; after the adhesive layer is subjected to a durability test in a test environment at 85 ° C × 750hr, or after a durability test in a test environment at 60 ° C × 90% RH × 750hr, The antistatic agent was not precipitated on the surface of the adhesive layer.
(A)丙烯酸正丁酯及(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優選將構成丙烯酸類聚合物的(甲基)丙烯酸烷基酯的單體設為特定的兩種以上的(A)及(B)的組合。 (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 (meth) acrylic acid Alkyl ester monomer. In the adhesive composition of the present embodiment, it is preferable that the monomer of the (meth) acrylic acid alkyl ester constituting the acrylic polymer is a combination of two or more specific types (A) and (B).
本實施方式的丙烯酸類聚合物，以(A)丙烯酸正丁酯為主體，例如，相對於100重量份的丙烯酸類聚合物，優選以40~89重量份的比例含有(A)丙烯酸正丁酯。進一步，丙烯酸類聚合物優選以總計為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(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, the acrylic polymer preferably contains (A) n-butyl acrylate in an amount of 40 to 89 parts by weight based on 100 parts by weight of the acrylic polymer. . Further, the acrylic polymer 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 a weight ratio of 1.0 to 17.8.
作為(C)含有羥基和/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)及含有羧基的可共聚單體(含羧基單體)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，也可以使含羥基單體及含羧基單體這兩者共聚。相對於(A)、(B)及(D)的總量100重量份，(C)含有羥基和/或羧基的共聚性乙烯基單體的比例優選為0.1~5重量份的比例。另外，(A)、(B)及(D)均為不含羥基及羧基的乙烯基單體。 (C) The copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group includes a copolymer selected from a copolymerizable monomer (hydroxyl-containing monomer) containing a hydroxyl group and a copolymerizable monomer (carboxyl-containing monomer) containing a carboxyl group. At least one 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. The ratio of (C) the copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total amount of (A), (B), and (D). In addition, (A), (B), and (D) are all vinyl monomers which do not contain a hydroxyl group and a carboxyl group.
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-羥甲基(甲基)丙烯醯胺、N-羥乙基(甲基)丙烯醯胺等含羥基的(甲基)丙烯醯胺類等中的至少一種以上。 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含有的含羥基單體，可用作用於減少含羧基單體的含量的共聚性單體，認為所述含羧基單體對所得到的黏著劑層對透明導電性膜的ITO表面等易腐蝕的被黏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、且降低腐蝕性的作用。相對於(A)、(B)及(D)的總量100重量份，本實施方式的黏著劑組合物中含有的含羥基單體的比例優選為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, and it is considered that the adhesive layer pair obtained by the carboxyl group-containing monomer pair The ITO surface of the transparent conductive film is affected by the corrosivity of adherends that are easily corroded. Therefore, the hydroxyl-containing monomer can improve the adhesion of the adhesive layer and reduce the corrosiveness. The ratio of the hydroxyl-containing monomer contained in the adhesive composition of this embodiment is preferably 0.1 to 5.0 parts by weight, and more preferably 100 parts by weight of the total amount of (A), (B), and (D). The ratio of 0.1 to 4.4 parts by weight 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含有的含羧基單體，能夠對所得到的黏著劑層賦予必要的凝聚力。相對於(A)、(B)及(D)的總量100重量份，本實施方式涉及的黏著劑組合物中的含羧基單體的比例優選為0~5.0重量份。另外，使含羥基單體共聚於丙烯酸類聚合物中時，也可允 許不使含羧基單體共聚的情況。此外，在使含羧基單體進行共聚時，更優選0.01~5.0重量份的比例，特別優選0.01~3.3重量份的比例，最優選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 with respect to 100 parts by weight of the total amount of (A), (B), and (D). In addition, when copolymerizing a hydroxyl group-containing monomer in an acrylic polymer, the case where the carboxyl group-containing monomer is not copolymerized may be allowed. When 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。在包含含有芳香族基團的(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時，由於其與由(A)及(B)的組合組成的(甲基)丙烯酸烷基酯單體的共聚性優異，故而優選。 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. When a (meth) acrylic acid ester monomer containing an aromatic group is included as (D) a copolymerizable vinyl monomer containing an aromatic group, since it is composed of a combination of (A) and (B) ( An alkyl (meth) acrylate monomer is preferable because it has excellent copolymerizability.
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混合含有芳香族基團的(甲基)丙烯酸酯單體中的至少一種以上。藉由使這些含有芳香族基團的(甲基)丙烯酸酯單體共聚於丙烯酸類聚合物中，能夠提高並調節所得到的黏著劑層的折射率，降低光學構件間的折射率差，藉由降低全反射能夠提高總透光率。本實施方式涉及的黏著劑組合物中，相對於100重量份的丙烯酸類聚合物，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重量份的比例包含含有芳香族基團的(甲基)丙烯酸酯單體。 In order to obtain an adhesive layer having a high refractive index, it is preferable to mix at least one or more kinds of (meth) acrylate monomers containing an aromatic group into the adhesive composition according to the present embodiment. By copolymerizing these (meth) acrylate monomers containing an aromatic group in an acrylic polymer, the refractive index of the obtained adhesive layer can be increased and adjusted, and the refractive index difference between optical members can be reduced. The total transmittance can be increased by reducing total reflection. In the adhesive composition according to this 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 of parts includes a (meth) acrylate monomer containing an aromatic group.
本實施方式涉及的黏著劑組合物中含有的丙烯酸類聚合物的製備方法沒有特別限定，可使用溶液聚合法、乳液 聚合法等適宜、習知的聚合方法。丙烯酸類聚合物的共聚物的重量平均分子量優選為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 suitable and known polymerization methods such as a solution polymerization method and 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.
為了得到抗靜電性能，本實施方式涉及的黏著劑組合物含有(E)抗靜電劑。相對於100重量份的丙烯酸類聚合物，優選以2.5~15重量份的比例、更優選以3~15重量份的比例、特別優選以4~15重量份的比例含有具有含氟基陰離子的銨類抗靜電劑作為(E)抗靜電劑。該抗靜電劑為由含氟基陰離子與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℃下為固體的、熔點為25℃~80℃的離子化合物。 In order to obtain antistatic performance, the adhesive composition which concerns on this embodiment contains (E) an antistatic agent. The ammonium having a fluorine-containing anion is contained in an amount of 2.5 to 15 parts by weight, more preferably 3 to 15 parts by weight, and particularly preferably 4 to 15 parts by weight with respect to 100 parts by weight of the acrylic polymer. Antistatic agents are used as (E) antistatic agents. The antistatic agent is an ionic compound formed by 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)抗靜電劑中含有的含氟基陰離子，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他原子鍵結的氟原子。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-)、含氟基的醇鹽或酚鹽陰離子(RO-)、含氟基的有機亞胺陰離子(R2N-)、含氟基的甲基化物(R3C-)陰離子、含氟基的有機硼酸根(R4B-)陰離子等中，具有含氟基有機基團作為R的至少1個以上的陰離子。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。在陰離子具有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群組中的一種。 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 include fluorinated sulfonate anion group (RSO 3 -), a fluorine-containing carboxylate anion group (RCOO -), an alkoxide or phenoxide anion of a fluorine-containing group (RO -) , imide anion fluorinated organic group (R 2 N -), fluorinated methide group (R 3 C -) an anionic, fluorine-containing organic borate (R 4 B -) anion having containing The fluorine-based organic group is at least one anion of R. Examples of the organic group include alkyl groups, alkoxy groups, aromatic groups (aryl groups, aralkyl groups, etc.), alkylcarbonyl groups, aromatic carbonyl groups, alkylsulfonyl groups, and aromatic sulfonyl groups. 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 them, one selected from the group consisting of pentafluorobenzenesulfonate, hexafluorophosphate, bis (trifluoromethanesulfonyl) imine, bis (fluorosulfonyl) imine, and trifluoromethanesulfonate is preferred. .
作為(E)抗靜電劑中含有的銨陽離子，可列舉出具有1~4個有機基團的有機銨陽離子，特別優選季銨陽離子(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。在陽離子具有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 the 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重量份的丙烯酸類聚合物，可列舉出0.01~5重量份的比例。 The adhesive composition according to the present embodiment further contains, as the (F) crosslinking agent, at least one or more crosslinking agents selected from the group consisting of a trifunctional or higher isocyanate compound and a bifunctional or higher epoxy compound. 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、苯二亞甲基二異氰酸酯等的二異氰酸酯類的縮二脲改性體或異氰脲酸酯改性體；與三羥甲基丙烷或甘油等三元以上的多元醇的加成物等。 Examples of the trifunctional or higher isocyanate compound include diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, xylylene diisocyanate, and the like. Modified biuret or isocyanurate; adducts with trihydric or higher polyhydric alcohols such as trimethylolpropane or glycerol.
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)矽烷偶聯劑。作為(G)矽烷偶聯劑，可列舉出在一分子中具有至少一個有機官能團及至少一個水解性基團的、所述水解性 基團為與矽原子鍵結的烷氧基等的化合物。(G)矽烷偶聯劑含有選自環氧基、巰基、酸酐基中的至少一種以上的官能團。(G)矽烷偶聯劑可使用單體型或低聚物型的一者或兩者中的至少一種以上。矽烷偶聯劑的比例，例如相對於100重量份的丙烯酸類聚合物，可列舉出0.01~0.5重量份。 The adhesive composition according to this embodiment further contains (G) a silane coupling agent. Examples of the (G) silane coupling agent include compounds having at least one organic functional group and at least one hydrolyzable group in one molecule, and the hydrolyzable group is 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 of one or both of a monomer type and an oligomer type can be used. The proportion 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聯劑，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聯劑，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聯劑，例如可列舉出3-三甲氧基甲矽烷基丙基琥珀酸酐、3-三乙氧基甲矽烷基丙基琥珀酸酐等。此外，低聚物化的烷氧基低聚物(有機矽烷氧基低聚物)等也可以用作矽烷偶聯劑。 Examples of the silane coupling agent having an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxy Propylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) 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 so on. Examples of the silane coupling agent having a mercapto group 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. In addition, oligomerized alkoxy oligomers (organosiloxy oligomers) and the like can also be used as the silane coupling agent.
本實施方式的黏著劑組合物，可適當混合抗氧化劑、表面活性劑、固化促進劑、增塑劑、填充劑、交聯催化劑、交聯延遲劑、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使用，或者也可以同時使用兩種以上。 The adhesive composition of this embodiment may be appropriately mixed 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 an anti-aging agent. And other conventional additives as arbitrary components. These arbitrary components may be used alone or in combination of two or more kinds.
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9.0×10+10Ω/□以下，更優選5.0×10+10Ω/□以下，特別優選2.0×10+10Ω/□以下。優選該黏著劑層的初期的表面電阻率及耐久性試驗後的表面電阻率均為9.0×10+10Ω/□以下，更優選均為5.0×10+10Ω/□以下，特別優選均為2.0×10+10Ω/□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之前的表面電阻率。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 9.0 × 10 +10 Ω / □ or less, more preferably 5.0 × 10 +10 Ω / □ or less, and particularly preferably 2.0 × 10 +10 Ω / □ or less. The initial surface resistivity of the adhesive layer and the surface resistivity after the durability test are both preferably 9.0 × 10 +10 Ω / □ or less, more preferably 5.0 × 10 +10 Ω / □ or less, and particularly preferably both 2.0 × 10 +10 Ω / □ or less. Here, the initial surface resistivity refers to the surface resistivity before the adhesive layer is subjected 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、以及在供於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 pressure-sensitive adhesive layer obtained by cross-linking the pressure-sensitive adhesive composition of the present embodiment under a test environment of 85 ° C × 750hr and a test environment of 60 ° C × 90% RH × 750hr After the endurance 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.
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是以下性能：製造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)抗靜電劑未析出。 The (E) antistatic agent precipitation prevention performance in the adhesive composition of the present embodiment may be the following performance: two or more samples of the adhesive layer obtained by cross-linking the same adhesive composition are produced, and one After the sample was subjected to a durability test under a test environment at 85 ° C x 750hr, (E) the antistatic agent was not precipitated, and another sample was subjected to a durability test under a test environment at 60 ° C x 90% RH x 750hr. (E) Antistatic agent is not precipitated.
對於使本實施方式的黏著劑組合物交聯而成的黏著劑層而言，優選：將總厚度為80μm的偏光板經由厚度為20μm的黏著劑層而貼合於無鹼玻璃上時，黏著劑層對無鹼玻璃的黏著力為1.0~6.0N/25mm。 For the adhesive layer obtained by crosslinking the adhesive composition of the present embodiment, it is preferable that 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, the adhesive layer is adhered. The adhesive force of the agent layer on the alkali-free glass is 1.0 ~ 6.0N / 25mm.
此外，優選：將10cm見方的總厚度為80μm的偏光板經由厚度為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、及供於60℃×90%RH×750hr的試驗環境下的耐久性試驗後，無起泡及脫落。 In addition, it is preferable that a test piece obtained by bonding a polarizing plate having a total thickness of 80 μm with a size of 10 cm square to an alkali-free glass through an adhesive layer having a thickness of 20 μm is subjected to a durability test in a test environment of 85 ° C. × 750 hr After that, and after the durability test in a test environment of 60 ° C × 90% RH × 750hr, there was no blistering or falling off.
本實施方式的黏著劑組合物的無起泡及脫落的性能可以是以下性能：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，無起泡及脫落。 The non-foaming and peeling performance of the adhesive composition of this embodiment may be the following performance: two or more test pieces manufactured using the same adhesive composition are manufactured, and one test piece is supplied at 85 ° C. for 750 hr. After the durability test in the test environment, there was no foaming and peeling, and after the other test piece was subjected to the durability test in the test environment at 60 ° C × 90% RH × 750hr, there was no foaming or peeling.
本實施方式涉及的黏著劑層可藉由將本實施方式的黏著劑組合物塗佈於樹脂膜或離型膜等基材後，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構件的層間的貼合等時，為了減少在黏著劑層與光學構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 member or the like, in order to reduce reflection of light on the interface between the adhesive layer and the optical member, 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藉由在樹脂膜或離型膜等基材的單面上形成本實施方式涉及的黏著劑層而製造。作為成為基材的樹脂膜或離型膜(隔離膜)，可使用聚酯膜等樹脂膜等。對於離型膜，也可以利用矽酮類、氟類的離型劑等對與黏著劑層的黏著面貼合的一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一側相反的面上，實施基於矽酮類、氟類的離型劑或塗佈劑、二氧化矽微粒等的防汙處理，基於抗靜電劑的塗佈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 this embodiment can be produced by forming an adhesive layer according to this embodiment on one side 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 base material, 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 surface on the side to be bonded to the adhesive surface of the adhesive layer using a silicone-based, fluorine-based release agent, or the like. For the resin film used as a base material, a silicone-based, fluorine-based release agent or coating agent, or a silica particle can be applied to the surface of the resin film opposite to the side on which the adhesive layer is formed. Antifouling treatment, antistatic treatment based on application or kneading of antistatic agents. Examples of the thickness of the adhesive layer include a thickness of 1 μm to 25 μm.
也可以藉由在一個黏著劑層的兩面上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。在該情況下，藉由將兩側的離型膜依次或同時剝離而露出黏著面，由此能夠與光學膜等光學構件貼合。作為光學膜，可列舉出偏光膜、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、亮度提高膜等。作為光學構件所適用的儀器，可列舉出液晶面板、有機EL面板、觸控面板、內嵌(In-cell)型液晶面板等。 It is also possible to form a "release film / adhesive layer / release film" structure by laminating the release film-treated surface on both sides of an adhesive layer, respectively. In this case, by releasing the release films on both sides sequentially or simultaneously to expose the adhesive surface, it is possible to attach the release film 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, and a brightness enhancement film. As an apparatus applicable to an optical member, a liquid crystal panel, an organic EL panel, a touch panel, an in-cell type liquid crystal panel, etc. are mentioned.
本實施方式的黏著膜適合作為偏光板用黏著膜。特別是也可用於偏光板與內嵌(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層疊所述黏著劑層而成的帶黏著劑層的光學膜。藉由在偏光板的單面上使用上述的黏著膜，能夠提供帶黏著劑層的偏光板。可使用上述的帶黏著劑層的偏光板，而提供內嵌(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 polarizing plate and an in-cell panel. Further, 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. By using the above-mentioned adhesive film on one side of the polarizing plate, a polarizing plate with an adhesive layer can be provided. The above-mentioned polarizing plate with an adhesive layer can be used to provide a liquid crystal panel such as an in-cell liquid crystal panel.
作為帶黏著劑層的光學膜的層疊結構的具體例，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光板的層疊結構的具體例，可列舉出“離型膜/黏著劑層/偏光板”、“離型膜/黏著劑層/偏光板/黏著劑層/離型膜”、“偏光板/黏著劑層”、“黏著劑層/偏光板/黏著劑層”等。作為液晶面板等的部分構造，也可以包含這些層疊結構。 Specific examples of the laminated structure of the optical film with an adhesive layer include "release film / adhesive layer / optical film", "release film / adhesive layer / optical film / adhesive layer / release 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 polarizing plate with an adhesive layer include "release film / adhesive layer / polarizing plate", "release film / adhesive layer / polarizing plate / adhesive layer / release film" "," Polarizing plate / adhesive layer "," adhesive layer / polarizing plate / adhesive layer ", etc. These laminated structures may be included as a partial structure of a liquid crystal panel or the like.
以下，根據實施例對本發明進行具體說明。 Hereinafter, the present invention will be specifically described based on examples.
<丙烯酸類聚合物的製備> <Preparation of acrylic polymer>
[實施例1] [Example 1]
向帶有攪拌機、溫度計、回流冷卻器及氮氣導入管的反應裝置中導入氮氣，用氮氣置換了反應裝置內的空氣。然後，向反應裝置中加入了70重量份的丙烯酸正丁酯、15重量份的甲基丙烯酸正丁酯、2.0重量份的丙烯酸-8-羥基辛酯、15重量份的丙烯酸苄基酯，同時加入了溶劑(乙酸乙酯)。然後，以2小時滴加0.1重量份的作為聚合引發劑的偶氮二異丁腈，在65℃下反應6小時，得到了用於實施例1的丙烯酸類聚合物的溶液。 Nitrogen was introduced into a reaction device equipped with a stirrer, a thermometer, a reflux cooler, and a nitrogen introduction tube, and the air in the reaction device was replaced with nitrogen. Then, 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, and 15 parts by weight of benzyl acrylate were added to the reaction device, and A solvent (ethyl acetate) was added. 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 a solution of an acrylic polymer used in Example 1.
[實施例2~7及比較例1~3] [Examples 2 to 7 and Comparative Examples 1 to 3]
除了將單體的組成分別設為如表1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2~7及比較例1~3的丙烯酸類聚合物溶液。 Except that the compositions of the monomers were set as described in Tables (A) to (D), respectively, the same procedures as those in Example 1 were used to obtain the monomers used in Examples 2 to 7 and Comparative Examples 1 to 3. Acrylic polymer solution.
另外，雖然沒有特別示出測定結果，但實施例1~7及比較例1~3的丙烯酸類聚合物溶液中所含的共聚物的重量平均分子量在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 7 and Comparative Examples 1 to 3 is in the range of 1 to 3 million.
<黏著膜的製備> <Preparation of Adhesive Film>
[實施例1] [Example 1]
向如上所述而製備的實施例1的丙烯酸類聚合物溶液中，以10重量份的比例添加環己基三甲銨雙(三氟甲烷磺醯基)亞胺、以0.1重量份的比例添加交聯劑(D-110N)、以0.05重量份的比例添加矽烷偶聯劑(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 10 parts by weight, and crosslinking was added in a proportion of 0.1 part by weight. Agent (D-110N), and a silane coupling agent (X-12-967C) was 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佈在由已塗佈矽酮樹脂的聚對苯二甲酸乙二醇酯(PET)膜形成的離型膜上，然後，藉由在90℃下進行乾燥而去除了溶劑。然後，藉由在23℃、50%RH的氣氛下熟化7天，由此得到了在離型膜的單面上具有使黏著劑組合物交聯而成黏著劑層的、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. Then, the solvent was removed by drying at 90 ° C. Then, by curing for 7 days in an atmosphere of 23 ° C. and 50% RH, a release film having a pressure-sensitive adhesive layer formed by cross-linking the pressure-sensitive adhesive composition on one side of the release film was obtained. Structure of Adhesive Layer / Release Film The adhesive film of Example 1.
[實施例2~7及比較例1~3] [Examples 2 to 7 and Comparative Examples 1 to 3]
除了將添加劑的組成分別設為如表1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得到了實施例2~7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) of Table 1, respectively, Examples 2 to 7 and Comparative Examples 1 to 3 were obtained in the same manner as the adhesive film of Example 1 described above. Adhesive film.
表1中，在各成分的縮寫符號後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，將表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包含於(B)中。在(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 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為TOSOH CORPORATION的商品名稱，D-110N為Mitsui Chemicals,Inc.的商品名稱，TETRAD(註冊商標)-X為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是指苯二亞甲基二異氰酸酯。此外，KBM-403、X-12-967C、X-41-1805、KBM-503均為Shin-Etsu Chemical Co.,Ltd.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, Inc., 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.
<試驗方法及評價> <Test method and evaluation>
從實施例1~7及比較例1~3的黏著膜上剝離離型膜(已塗佈矽酮樹脂的PET膜)，露出所述黏著膜的黏著劑層的單面。然後，經由所述黏著劑層在厚度為80μm的偏光板(樹脂膜)的單面上貼合所述黏著膜，得到了為離型膜/黏著劑層/偏光板的結構的帶黏著劑層的偏光板。 A release film (a silicone resin-coated PET film) was peeled from the adhesive films of Examples 1 to 7 and Comparative Examples 1 to 3 to expose one side of the adhesive layer of the adhesive film. Then, the adhesive film was laminated on one side of a polarizing plate (resin film) having a thickness of 80 μm through the adhesive layer to obtain an adhesive layer with a structure of a release film / adhesive layer / polarizing plate. Polarizer.
<黏著力的測定方法> <Method for measuring adhesive force>
將上述所得到的帶黏著劑層的偏光板的離型膜剝離，利用壓輥將帶有黏著劑層的偏光板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))的經丙酮清洗過的面上，從而製造了試驗片。然後，在50℃、0.5MPa×20分鐘的條件下對該試驗片進行了壓熱處理。然後，返回到23℃×50%RH的氣氛下，利用拉伸試驗機，以JIS Z0237“黏著膠帶‧黏著片試驗方法”為基準測定經過1小時後的帶黏著劑層的偏光板的剝離強度，將沿180°方向以0.3m/分鐘的速度進行剝離時的剝離強度作為了黏著劑層對無鹼玻璃的黏著力。 The release film of the polarizing plate with an adhesive layer obtained as described above was peeled off, and the polarizing plate with an adhesive layer was bonded to an alkali-free glass (Eagle XG manufactured by Corning Incorporated) via a pressure roller using a pressure roller. (Registered trademark)), the test piece was produced by washing the surface with acetone. Then, this test piece was autoclaved under the conditions of 50 ° C. and 0.5 MPa × 20 minutes. Then, return to an atmosphere of 23 ° C. × 50% RH and use a tensile tester to measure the peeling strength of the polarizing plate with an adhesive layer after 1 hour based on JIS Z0237 “Adhesive Tape · Adhesive Sheet Test Method” The peeling strength when peeling at a speed of 0.3 m / min in the 180 ° direction 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>
對於上述所得到的帶黏著劑層的偏光板，使用電阻率計HIRESTA(註冊商標)UP-HT450(Mitsubishi Chemical Analytech Co.,Ltd.製造)在23℃×50%RH的氣氛下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光板進行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。 With respect to the polarizing plate with an adhesive layer obtained above, the resistivity meter HIRSTA (registered trademark) UP-HT450 (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) was used to measure the adhesive layer in an atmosphere of 23 ° C. 50% RH. The surface resistivity (Ω / □) was calculated, and the initial surface resistivity was obtained. The same polarizing plate with an adhesive layer was subjected to a durability test in a test environment at 85 ° C. × 750 hr. Then, the surface resistivity was measured in the same manner, and the surface resistivity after the durability test was obtained.
<耐久性的試驗方法> <Durability test method>
利用與黏著力的測定相同的方法，剝離10cm見方的帶黏著劑層的偏光板的離型膜，將其貼合於無鹼玻璃的經丙酮清洗過的面上，製造了試驗片。然後，對該試驗片進行85℃×750hr的試驗環境下的耐久性試驗、及60℃×90%RH×750hr的試驗環境下的耐久性試驗後，取出至23℃×50%RH氣氛下，1小時後藉由目視觀察黏著劑層的狀態，判斷了耐久性。 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 this was bonded to the acetone-washed surface of an alkali-free glass to produce a test piece. Then, the test piece was subjected to a durability test in a test environment of 85 ° C × 750hr and a durability test in a test environment of 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.
○：無黏著劑層的起泡及脫落。 ○: No foaming or peeling of the adhesive layer.
△：在黏著劑層的一部分發生起泡、脫落。 Δ: Foaming and peeling occurred in a part of the adhesive layer.
×：在黏著劑層的整體發生起泡、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相同的方法，剝離10cm見方的帶黏著劑層的偏光板的離型膜，將其貼合於無鹼玻璃的經丙酮清洗過的面上，製造了試驗片。然後，對該試驗片進行85℃×750hr的試驗環境下的耐久性試驗、及60℃×90%RH×750hr的試驗環境下的耐久性試驗後，取出至23℃×50%RH氣氛下， 1小時後藉由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 this was bonded to the acetone-washed surface of an alkali-free glass to produce a test piece. Then, the test piece was subjected to a durability test in a test environment of 85 ° C × 750hr and a durability test in a test environment of 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 the state of precipitation 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.
×：在黏著劑層的表面的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.
評價結果示於表3。 The evaluation results are shown in Table 3.
實施例1~7的黏著膜對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、及85℃×750hr的試驗環境下的耐久性試驗後的表面電阻率均為9.0×10+10Ω/□以下，在85℃×750hr的試驗環境下的耐久性試驗、及60℃×90%RH×750hr的試驗環境下的耐久性試驗後無起泡及脫落，具有耐久性，且在黏著劑層的表面上也沒有抗靜電劑的析出。即，關於實施例1~7的黏著膜的評價結果證實了能夠解決本發明的技術問題。 The adhesive force of the adhesive films of Examples 1 to 7 on the alkali-free glass was 1.0 to 6.0 N / 25 mm, the initial surface resistivity of the adhesive layer, and the surface resistance after the durability test in a test environment at 85 ° C × 750hr. The rate is 9.0 × 10 +10 Ω / □ or less. After the durability test under the test environment of 85 ° C × 750hr and the durability test under the test environment of 60 ° C × 90% RH × 750hr, there is no blistering or falling 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 7 confirmed that the technical problems of the present invention can be solved.
關於比較例1的黏著膜，丙烯酸類聚合物中所共 聚的(甲基)丙烯酸烷基酯單體不是TBA、IBA、BMA、MA中的任一者，且沒有使(D)含有芳香族基團的共聚性乙烯基單體共聚。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，關於比較例1的黏著膜，由於(E)抗靜電劑的含有比例大，因此雖然黏著劑層的表面電阻率變低，但在耐久性試驗後，抗靜電劑在黏著劑層的表面的整個面上析出。 Regarding the adhesive film of Comparative Example 1, the alkyl (meth) acrylate monomer copolymerized in the acrylic polymer was not any of TBA, IBA, BMA, and MA, and (D) did not contain an aromatic group. Copolymerizable vinyl monomers are 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, regarding the adhesive film of Comparative Example 1, the content of the antistatic agent (E) was large. Although the surface resistivity of the adhesive layer was low, the antistatic agent was on the surface of the adhesive layer after the durability test. Precipitated on the entire surface.
比較例2的黏著膜雖然含有(G)矽烷偶聯劑，但並不含有選自環氧基、巰基、酸酐基中的至少一種以上的官能團。因此，比較例2的黏著膜的黏著劑層的耐久性差，在耐久性試驗後，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 contained a (G) silane coupling agent, it did 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. After the durability test, the antistatic agent was analyzed on the upper surface of the adhesive layer.
關於比較例3的黏著膜，丙烯酸類聚合物中所共聚的(甲基)丙烯酸烷基酯單體不是TBA、IBA、BMA、MA中的任一者，且沒有使(D)含有芳香族基團的共聚性乙烯基單體共聚。因此，比較例3的黏著膜即使不含有(G)矽烷偶聯劑，耐久性試驗前的黏著劑層的黏著力也過大，耐久性差。此外，關於比較例3的黏著膜，由於(E)抗靜電劑的含有比例小，因此雖然沒有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增高。 Regarding 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 an aromatic group. Copolymerizable vinyl monomers are 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 a durability test is too large, and durability is inferior. In addition, regarding the adhesive film of Comparative Example 3, the content of the antistatic agent (E) was small. Therefore, although there was no precipitation of the antistatic agent on the surface of the adhesive layer after the durability test, the surface resistivity of the adhesive layer Increase.
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9.0×10+10Ω/□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及使用了該黏著劑組合物的黏著膜，作為用於貼合偏光板與液晶面板的黏著劑組合物及使用了該該黏著劑組合物的黏著膜，具有極其優異的抗靜電性能，且具有耐久性，因此在工業上的利用價值大。 According to the present invention, it is possible to provide an adhesive composition having a surface resistivity of an adhesive layer of 9.0 × 10 +10 Ω / □ or less, which has extremely excellent antistatic performance and does not impair durability, and uses the same. Film. Therefore, the adhesive composition according to the present invention and an adhesive film using the same are used 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 application value.
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| KR101177685B1 (en) * | 2005-09-20 | 2012-08-27 | 소켄 케미칼 앤드 엔지니어링 캄파니, 리미티드 | Pressure-sensitive adhesive composition for polarizing plate and polarizing plate with pressure-sensitive adhesive layer |
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