TWI741082B - Adhesive composition and adhesive film - Google Patents
Adhesive composition and adhesive film Download PDFInfo
- Publication number
- TWI741082B TWI741082B TW106141144A TW106141144A TWI741082B TW I741082 B TWI741082 B TW I741082B TW 106141144 A TW106141144 A TW 106141144A TW 106141144 A TW106141144 A TW 106141144A TW I741082 B TWI741082 B TW I741082B
- Authority
- TW
- Taiwan
- Prior art keywords
- adhesive layer
- adhesive
- meth
- group
- adhesive composition
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- 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
- 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
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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, for example, can be used on an in-cell panel with a touch panel function where the adherend is a liquid crystal panel The purpose of lamination.
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, it relates to an adhesive composition having an extremely excellent antistatic performance with an adhesive layer having a surface resistivity of 9.0×10 +10 Ω/□ or less, 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 for bonding optical members such as polarizing plates and retardation plates to adherends such as liquid crystal cells via an adhesive layer have been proposed (for example, refer to Patent Documents 1 and 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 the acrylic polymer is made by copolymerizing acrylamide compounds and the like with monomers such as butyl acrylate as the 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 has a (meth)acrylate having an alkyl group with 4 to 8 carbon atoms as a main component of the monomer composition. It is formed by copolymerization of carboxyl-containing monomer and nitrogen-containing vinyl monomer.
專利文獻1：日本特開2012-177022號公報 Patent Document 1: JP 2012-177022 A
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 the adhesive layer used to bond the polarizing plate and the liquid crystal panel, when the liquid crystal panel is an in-cell panel with the function of a touch panel, the surface resistance of the adhesive layer is required The rate 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 the adhesive layer used to attach the polarizing plate to the liquid crystal panel, the surface resistivity of the adhesive layer is required to be 9.0×10 +10 Ω/□ or less, but in the prior art, this is shown A high degree of 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 when 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 an adhesive layer with a surface resistivity of 9.0×10 +10 Ω/□ or less, extremely excellent antistatic performance, and without impairing durability, and using the adhesive The 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。 In order to solve the technical problem that it is difficult to achieve both antistatic performance and durability of such a high degree at the same time, the inventor of the present application has conducted in-depth research. As a result, by limiting the number of carbon atoms of the alkyl group of the alkyl (meth)acrylate of the acrylic polymer constituting the adhesive composition to a specific range, two or more types of ( The acrylic polymer formed by the copolymer formed by copolymerization of alkyl meth)acrylate can 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 discovered that by containing the acrylic polymer and an ammonium antistatic agent having a fluorine-containing anion in a ratio of 2.5 to 15 parts by weight relative to 100 parts by weight of the acrylic polymer It is possible to obtain an adhesive composition having extremely excellent antistatic performance compared with conventional adhesive compositions, no precipitation of the antistatic agent, and excellent durability that does not degrade over time, thereby completing the present invention.
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 of the present invention, in order to make the surface resistivity of the adhesive layer 9.0×10 +10 Ω/□ or less extremely excellent antistatic performance, relative to 100 parts by weight of acrylic polymer, 2.5~ The ratio of 15 parts by weight contains an ammonium-based antistatic agent having a fluorine-containing group anion. In this way, 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 of 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 being precipitated after the durability test under the high temperature and high humidity environment of the adhesive layer To the surface of the adhesive layer, it becomes an adhesive layer that can maintain durability. The acrylic polymer contained in the adhesive composition is mainly composed of n-butyl acrylate (BA), and the copolymerization with BA is good. The 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, which contains an acrylic polymer, an antistatic agent and a crosslinking agent, characterized in that the acrylic polymer is copolymerized with the following components The copolymer has an acrylic polymer with a weight average molecular weight of 1 to 3 million: (A) n-butyl acrylate, (B) selected from t-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, methyl acrylate At least one of the group consisting of (C) at least one of copolymerizable vinyl monomers containing hydroxyl and/or carboxyl groups and (D) at least one of copolymerizable vinyl monomers containing aromatic groups; The adhesive composition contains an ammonium antistatic agent having a fluorine-containing anion as the (E) antistatic agent in a ratio of 2.5 to 15 parts by weight relative to 100 parts by weight of the acrylic polymer; The adhesive composition contains at least one crosslinking agent selected from the group consisting of isocyanate compounds having trifunctional or higher functionalities and epoxy compounds having higher functionalities as the (F) crosslinking agent; the adhesive The composition further contains (G) a monomeric or oligomeric silane coupling agent containing at least one functional group selected from epoxy groups, mercapto groups, and acid anhydride groups; crosslinking the adhesive composition The resulting adhesive layer has a surface resistivity of 9.0×10 +10 Ω/□ or less; the adhesive layer is subjected to a durability test under a test environment of 85℃×750hr, or 60℃×90% After the durability test under the test environment of RH×750hr, 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；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, it is preferable that the antistatic agent is an ionic compound formed of a fluorine-containing anion and an ammonium cation with a melting point of 25°C or higher; One of the group consisting of (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, relative to 100 parts by weight of the acrylic polymer, the acrylic polymer contains the (A) n-butyl acrylate in a ratio of 40 to 89 parts by weight, and contains a total of 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 of (A) to (B) is (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 with a total thickness of 80 μm is bonded to an alkali-free glass through an adhesive layer with a thickness of 20 μm formed by cross-linking the adhesive composition, the adhesion of the adhesive layer to the alkali-free glass The force is 1.0~6.0N/25mm; preferably a 10cm square polarizing plate with a total thickness of 80μm is pasted on the alkali-free glass through an adhesive layer with a thickness of 20μm formed by crosslinking the adhesive composition The finished test piece was subjected to a durability test under a test environment of 85°C×750hr or after a durability test under a test environment of 60°C×90%RH×750hr, and there was no blistering or falling off.
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。 Preferably, the (C) copolymerizable vinyl monomer containing a hydroxyl group and/or a carboxyl group is 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 the 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 -2-hydroxyethyl, N-hydroxy(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide At least one or more; preferably the copolymerizable monomer containing a carboxyl group is selected from (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, 2-(meth)propylene Acetyloxyethylhexahydrophthalic acid, 2-(meth)acryloxypropylhexahydrophthalic acid, 2-(meth)acryloxyethyl phthalic acid, 2- (Meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethylmaleic acid, carboxypolycaprolactone mono(meth)acrylate, 2-(meth)acrylic acid At least one or more of the compound group consisting of oxyethyltetrahydrophthalic acid.
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 the 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。 In addition, the present invention provides an adhesive film characterized by laminating an adhesive layer formed by crosslinking the adhesive composition on one side of a resin film.
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。 In addition, the present invention provides an adhesive film for a polarizing plate, which uses 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 polarizing plate, which is characterized by being 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 the adhesive layer formed by crosslinking the above-mentioned adhesive composition is formed on one side of the release film with a thickness of 1 μm to 25 μm. /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 it is formed by laminating an adhesive layer formed by crosslinking the above-mentioned adhesive composition on at least one surface of the optical film. The structure of the 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 formed by laminating an adhesive layer formed by crosslinking the above-mentioned adhesive composition on a single side of the polarizing plate /Adhesive layer/The structure of the polarizing plate.
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 characterized by 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 type 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 an adhesive layer with a surface resistivity of 9.0×10 +10 Ω/□ or less, extremely excellent antistatic performance, and without impairing durability, and using the adhesive composition The adhesive film of the object.
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 of this embodiment contains an acrylic polymer, an antistatic agent, and a crosslinking agent, and is characterized in that the acrylic polymer is a copolymer obtained by copolymerizing the following components. The weight average molecular weight of the copolymer is 100 to 300 Wan’s acrylic polymer: (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) at least one of the copolymerizable vinyl monomers containing hydroxyl and/or carboxyl groups and (D) at least one of the copolymerizable vinyl monomers containing aromatic groups; the adhesive composition is relative to 100 Parts by weight of the acrylic polymer contains an ammonium-based antistatic agent having a fluorine-containing anion as the (E) antistatic agent in a ratio of 2.5 to 15 parts by weight; the adhesive composition contains three selected from At least one crosslinking agent selected from the group consisting of a functional isocyanate compound and a bifunctional epoxy compound is used as the (F) crosslinking agent; the adhesive composition further contains (G) A monomer-type or oligomer-type silane coupling agent with at least one or more functional groups among epoxy groups, mercapto groups, and acid anhydride groups; the surface resistivity of the adhesive layer formed by crosslinking the adhesive composition 9.0×10 +10 Ω/□ or less; after the adhesive layer is subjected to a durability test under a test environment of 85℃×750hr, or a durability test under a test environment of 60℃×90%RH×750hr After the test, the antistatic agent did not precipitate 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 t-butyl acrylate, isobutyl acrylate, n-butyl methacrylate and methyl acrylate, both of which are equivalent to (meth)acrylic acid Alkyl ester monomers. In the adhesive composition of the present embodiment, it is preferable that the monomer constituting the alkyl (meth)acrylate of the acrylic polymer is a combination of two or more specific (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 this embodiment is mainly composed of (A) n-butyl acrylate. For example, it is preferable to contain (A) n-butyl acrylate in a ratio of 40 to 89 parts by weight relative to 100 parts by weight of the acrylic polymer. . Furthermore, the acrylic polymer preferably contains at least (B) selected from the group consisting of t-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, and methyl acrylate in a total ratio of 5 to 40 parts by weight. One or more types are used as alkyl (meth)acrylate monomers other than (A) n-butyl acrylate. In addition, 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 may be selected from a copolymerizable monomer containing a hydroxyl group (a hydroxyl group-containing monomer) and a copolymerizable monomer containing a carboxyl group (a carboxyl group-containing monomer) At least one of the group consisting of. That is, only one of the hydroxyl group-containing monomer and the carboxyl group-containing monomer may be selected for copolymerization, or both of the hydroxyl group-containing monomer and the carboxyl group-containing monomer may be copolymerized. The ratio of (C) the copolymerizable vinyl monomer containing a hydroxyl group and/or a carboxyl group is preferably a ratio of 0.1 to 5 parts by weight relative to 100 parts by weight of the total amount of (A), (B), and (D). In addition, (A), (B), and (D) are all vinyl monomers that 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 hydroxyl-containing monomers 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 of the present embodiment can be used as a copolymerizable monomer for reducing the content of the carboxyl group-containing monomer. The ITO surface of the transparent conductive film is affected by the corrosiveness of easily corrosive adherends. 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 the present embodiment is preferably 0.1 to 5.0 parts by weight relative to 100 parts by weight of the total amount of (A), (B) and (D), more preferably The ratio of 0.1 to 4.4 parts by weight is particularly preferably the 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 carboxyl group-containing monomers include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, and 2-(meth)acryloyloxyethylhexahydro Phthalic acid, 2-(meth)acryloyloxypropylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxy Ethyl ethyl succinic acid, 2-(meth)acryloyloxyethyl maleic acid, carboxypolycaprolactone mono(meth)acrylate, 2-(meth)acryloyloxyethyl tetrahydroo At least one 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 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 the hydroxyl group-containing monomer is copolymerized in the acrylic polymer, the case where the carboxyl group-containing monomer is not copolymerized can also be allowed. In addition, when the carboxyl group-containing monomer is copolymerized, 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。 (D) The copolymerizable vinyl monomer containing an aromatic group includes, for example, benzyl (meth)acrylate, naphthyl (meth)acrylate, phenoxyethyl (meth)acrylate, ( Phenoxybutyl meth)acrylate, 2-(1-naphthyloxy)ethyl (meth)acrylate, 2-(2-naphthoxy)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 an aromatic group-containing (meth)acrylate monomer is included as (D) an aromatic group-containing copolymerizable vinyl monomer, it is due to the combination of (A) and (B) ( The alkyl meth)acrylate monomer is excellent in copolymerizability, so it is preferred.
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 with a high refractive index, it is preferable to mix at least one type of (meth)acrylate monomer containing an aromatic group in the adhesive composition according to this embodiment. By copolymerizing these aromatic group-containing (meth)acrylate monomers in acrylic polymers, the refractive index of the resulting adhesive layer can be increased and adjusted, and the refractive index difference between optical components can be reduced. The total light transmittance can be increased by reducing the total reflection. In the adhesive composition according to the present embodiment, relative to 100 parts by weight of the acrylic polymer, 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. The proportion of parts contains aromatic group-containing (meth)acrylate monomers.
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 preparation method of the acrylic polymer contained in the adhesive composition according to the present embodiment is not particularly limited, and a suitable and conventional polymerization method 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 according to this embodiment contains (E) an antistatic agent. Relative to 100 parts by weight of the acrylic polymer, preferably 2.5-15 parts by weight, more preferably 3-15 parts by weight, particularly preferably 4-15 parts by weight, containing ammonium having a fluorine-containing group anion Class antistatic agent is used as (E) antistatic agent. The antistatic agent is an ionic compound formed by a fluorine-containing group anion and an ammonium cation. Preferably, the ionic compound is an ionic compound having a melting point of 25°C or higher, and is a solid at normal temperature (for example, 25°C). In addition, the ionic compound is more preferably an ionic compound that 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。 (E) The fluorine-containing group anion contained in the antistatic agent includes inorganic or organic fluorine-containing group anions. Here, the fluorine group refers to a fluorine atom bonded to other atoms constituting the 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 serves as at least one anion of R. Examples of organic groups include alkyl groups, alkoxy groups, aromatic groups (aryl groups, aralkyl groups, etc.), alkylcarbonyl groups, aromatic carbonyl groups, alkylsulfonyl groups, aromatic sulfonyl groups, etc. More than one kind. When the anion has two or more Rs, it may have a bond between two or more Rs to form a ring. Among them, preferably one selected from the group consisting of pentafluorobenzenesulfonate, hexafluorophosphate, bis(trifluoromethanesulfonyl)imine, bis(fluorosulfonyl)imine, and trifluoromethanesulfonate .
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。 (E) The ammonium cation contained in the antistatic agent includes organic ammonium cations having 1 to 4 organic groups, and quaternary ammonium cations (R 4 N + ) are particularly preferred. Examples of R include hydrocarbon groups such as acyclic or cyclic alkyl groups and aromatic groups (aryl groups, aralkyl groups, etc.). 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 this embodiment further contains at least one crosslinking agent selected from the group consisting of trifunctional or higher isocyanate compounds and bifunctional or higher epoxy compounds as the (F) crosslinking agent. As a ratio of (F) crosslinking agent, the ratio of 0.01-5 weight part with respect to 100 weight part of acrylic polymers is mentioned, for example.
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。 As trifunctional or higher isocyanate compounds, for example, diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, xylylene diisocyanate, etc. Biuret modified body or isocyanurate modified body; adducts with trimethylolpropane or glycerin and other trivalent or higher polyhydric alcohols, 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 epoxy compounds with more than bifunctionality include diglycidyl ethers of diols, diglycidyl ethers of bisphenols, triglycidyl ethers of triols, and diglycidyl esters of dicarboxylic acids, Diglycidyl substituted amines, tetraglycidyl substituted diamines, etc.
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. (G) Silane coupling agents 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 or the like. (G) The silane coupling agent contains at least one functional group selected from an epoxy group, a mercapto group, and an acid anhydride group. (G) The silane coupling agent can use at least one of a monomer type or an oligomer type, or at least one of both. The ratio of the silane coupling agent is, for example, 0.01 to 0.5 parts by weight relative to 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。 As the silane coupling agent having an epoxy group, for example, 3-glycidoxypropyl trimethoxy silane, 3-glycidoxy propyl methyl diethoxy silane, 3-glycidoxy propylene Propylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4- Epoxycyclohexyl) ethyl methyl dimethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl methyl diethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl Triethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 5,6-epoxyhexylmethyldimethoxysilane, 5,6-epoxyhexylmethyldiethoxysilane, 5 ,6-Epoxyhexyltriethoxysilane, etc. As the silane coupling agent having a mercapto group, for example, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3 -Mercaptopropyl triethoxysilane, etc. Examples of the silane coupling agent having an acid anhydride group include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, and the like. In addition, oligomerized alkoxy oligomers (organosiloxane alkoxy oligomers) and the like can also be used as silane coupling agents.
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 can be appropriately mixed with antioxidants, surfactants, curing accelerators, plasticizers, fillers, crosslinking catalysts, crosslinking retarders, curing retarders, processing aids, and anti-aging agents. Such as conventional additives as optional components. These arbitrary components may be used alone, or two or more of them may be used at the same time.
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 formed 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. Preferably, the initial surface resistivity of the adhesive layer and the surface resistivity after the durability test are both 9.0×10 +10 Ω/□ or less, more preferably both 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. In addition, the surface resistivity after the durability test refers to the surface resistivity after the durability test in which the adhesive layer is subjected to a test environment of 85° C.×750 hr. Here, the test environment of 85°C×750hr may also 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 adhesive layer formed by cross-linking the adhesive composition of the present embodiment is subjected to a durability test under a test environment of 85°C×750hr and a test environment of 60°C×90%RH×750hr After the durability test, (E) the antistatic agent did not precipitate on the surface of the adhesive layer. Here, the test environment of 85°C×750hr may also 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 performance of preventing precipitation of (E) antistatic agent in the adhesive composition of the present embodiment may be the following performance: two or more samples of the adhesive layer formed by crosslinking the same adhesive composition are produced, and one After the sample was subjected to the durability test under the test environment of 85℃×750hr, (E) the antistatic agent was not precipitated, and another sample was subjected to the durability test under the test environment of 60℃×90%RH×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 formed by crosslinking the adhesive composition of the present embodiment, it is preferable that when a polarizing plate with a total thickness of 80 μm is bonded to an alkali-free glass through an adhesive layer with a thickness of 20 μm, the adhesive The adhesive force of the agent layer to 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 made by bonding a 10 cm square polarizing plate with a total thickness of 80 μm to an alkali-free glass via an adhesive layer with a thickness of 20 μm is subjected to a durability test under a test environment of 85° C. × 750 hr. After the endurance 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 performance of the adhesive composition of the present embodiment without blistering and shedding may be the following performance: two or more test pieces manufactured using the same adhesive composition are produced, and one test piece is provided at 85°C×750hr After the durability test under the test environment, there was no blistering or falling off, and after another test piece was subjected to the durability test under the test environment of 60°C × 90%RH × 750hr, there was no blistering or falling off.
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 optical members, etc., in order to reduce the 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 manufactured by forming the adhesive layer according to this embodiment on one side of a base material such as a resin film or a release film. As a resin film or a release film (separation film) used as a base material, resin films, such as a polyester film, etc. can be used. With regard to the release film, it is also possible to perform a release treatment on the surface of the adhesive layer that is bonded to the adhesive surface of the adhesive layer with a silicone-based or fluorine-based release agent. For the resin film used as the base material, the surface of the resin film opposite to the side on which the adhesive layer is formed can be applied with silicone-based, fluorine-based release agents or coating agents, silica particles, etc. Antifouling treatment, antistatic treatment based on coating or kneading of an antistatic agent. As the thickness of the adhesive layer, for example, a thickness of 1 μm to 25 μm can be cited.
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 attaching the release film on both sides of an adhesive layer, respectively. In this case, by peeling the release films on both sides sequentially or at the same time to expose the adhesive surface, it is possible to bond with optical members such as optical films. As an optical film, a polarizing film, a retardation film, an anti-reflection film, an anti-glare film, an ultraviolet absorption film, an infrared absorption film, an optical compensation film, a brightness improvement film, etc. are mentioned. Examples of equipment to which the optical member is applied include liquid crystal panels, organic EL panels, touch panels, and in-cell liquid crystal panels.
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 polarizers and in-cell panels. In addition, an optical film with an adhesive layer formed by laminating the adhesive layer on at least one surface of the above-mentioned optical film may be formed. By using the above-mentioned adhesive film on one side of the polarizing plate, it is possible to provide a polarizing plate with an adhesive layer. The above-mentioned polarizing plate with adhesive layer can be used to provide liquid crystal panels such as in-cell type liquid crystal panels.
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 ", "Polarizer/Adhesive Layer", "Adhesive Layer/Polarizer/Adhesive Layer", etc. As a partial structure of a liquid crystal panel, etc., these laminated structures may also be included.
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 pipe, 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. Solvent (ethyl acetate) was added. Then, 0.1 parts by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours and reacted at 65° C. for 6 hours to obtain the acrylic polymer solution 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 composition of the monomers was set as described in (A) to (D) of Table 1, in the same manner as in Example 1 above, the materials used in Examples 2 to 7 and Comparative Examples 1 to 3 were obtained. 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。 In addition, although the measurement result is not particularly shown, the weight average molecular weight of the copolymer contained in the acrylic polymer solution 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 at a ratio of 10 parts by weight, and crosslinking was added at a ratio of 0.1 parts by weight. (D-110N), the silane coupling agent (X-12-967C) was added at a ratio of 0.05 parts by weight, stirred and mixed, and the adhesive composition of Example 1 was obtained.
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。 The 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 adhesive layer after drying became 20 μm Then, the solvent was removed by drying at 90°C. Then, by aging for 7 days in an atmosphere of 23°C and 50% RH, a release film having an adhesive layer formed by crosslinking the adhesive composition on one side of the release film was obtained. The adhesive film of Example 1 of the structure of the adhesive layer/release film.
[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 composition of the additives was set as described in (E) to (G) of Table 1, the adhesive films of Examples 2 to 7 and Comparative Examples 1 to 3 were obtained in the same manner as the adhesive film of Example 1 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 represents part by weight. This weight part is calculated|required by making the total amount of (A), (B), and (D) 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), monomers containing hydroxyl groups are classified as "(C)OH", and monomers containing carboxyl groups are 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 the trade name of TOSOH CORPORATION, D-110N is the trade name of Mitsui Chemicals, Inc., and TETRAD (registered trademark)-X is the 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 all 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。 The release film (PET film coated with silicone resin) was peeled off 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 attached to one side of a polarizing plate (resin film) with a thickness of 80 μm via the adhesive layer, and an adhesive layer with a structure of a release film/adhesive layer/polarizing plate was obtained. Polarizing plate.
<黏著力的測定方法> <Method of Measuring Adhesion>
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 the adhesive layer obtained above was peeled off, and the polarizing plate with the adhesive layer was bonded to the alkali-free glass (Eagle XG manufactured by Corning Incorporated) via the adhesive layer using a pressing roller. (Registered trademark)) on the acetone-washed surface to produce a test piece. Then, the 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 testing machine to measure the peel strength of the polarizing plate with the adhesive layer after 1 hour based on JIS Z0237 "Adhesive Tape and Adhesive Sheet Test Method" , The peel strength when peeling in the 180° direction 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> <Measurement method of 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。 For the polarizing plate with an adhesive layer obtained above, the adhesive layer was measured using a resistivity meter HIRESTA (registered trademark) UP-HT450 (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) in an atmosphere of 23° C.×50% RH Surface resistivity (Ω/□), and the initial surface resistivity was obtained. After the same polarizing plate with an adhesive layer was subjected to a durability test in a test environment of 85° C.×750 hr, the surface resistivity was measured in the same manner, and the surface resistivity after the durability test was determined.
<耐久性的試驗方法> <Test method of durability>
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。 Using the same method as the adhesive force measurement, the release film of the polarizing plate with an adhesive layer of 10 cm square was peeled off, and it was attached to the acetone-washed surface of the 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 a 23°C×50%RH atmosphere, After 1 hour, the state of the adhesive layer was visually observed to determine the durability.
○：無黏著劑層的起泡及脫落。 ○: No blistering or peeling of the adhesive layer.
△：在黏著劑層的一部分發生起泡、脫落。 △: Blistering 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。 Using the same method as the adhesive force measurement, the release film of the polarizing plate with an adhesive layer of 10 cm square was peeled off, and it was attached to the acetone-washed surface of the 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 a 23°C×50%RH atmosphere, One hour later, by visually observing the state of the adhesive layer, 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。 △: 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。 X: The 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 1-7 to the alkali-free glass is 1.0-6.0N/25mm, the initial surface resistivity of the adhesive layer, and the surface resistance after the durability test under a test environment of 85°C×750hr The rate is below 9.0×10 +10 Ω/□, and there is no blistering or peeling after the durability test under the test environment of 85℃×750hr and the durability test under the test environment of 60℃×90%RH×750hr , It is durable, and there is no antistatic agent precipitation 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 problem 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 is not any one of TBA, IBA, BMA, or MA, and (D) is not made to contain an aromatic group. Copolymerization of a group of copolymerizable vinyl monomers. 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, since the content of (E) antistatic agent was large, although the surface resistivity of the adhesive layer became low, after the durability test, the antistatic agent was on the surface of the adhesive layer. 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 contains the (G) silane coupling agent, it does not contain at least one functional group selected from epoxy groups, mercapto groups, and acid anhydride groups. Therefore, the adhesive layer of the adhesive film of Comparative Example 2 had poor durability, and 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 alkyl (meth)acrylate monomer copolymerized in the acrylic polymer is not any one of TBA, IBA, BMA, or MA, and (D) is not made to contain an aromatic group. Copolymerization of a group of copolymerizable vinyl monomers. Therefore, even if the adhesive film of Comparative Example 3 does not contain the (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, regarding the adhesive film of Comparative Example 3, since the content of (E) antistatic agent was small, 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 an adhesive layer with a surface resistivity of 9.0×10 +10 Ω/□ or less, extremely excellent antistatic performance, and without impairing durability, and using the adhesive composition The adhesive film of the object. Therefore, the adhesive composition and the adhesive film using the adhesive composition according to the present invention are used as an adhesive composition for bonding a polarizing plate and a liquid crystal panel and an adhesive film using the adhesive composition, It has extremely excellent antistatic properties and durability, so it has great industrial use value.
Claims (14)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-127545 | 2017-06-29 | ||
| JP2017127545A JP6796035B2 (en) | 2017-06-29 | 2017-06-29 | Adhesive composition and adhesive film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201905147A TW201905147A (en) | 2019-02-01 |
| TWI741082B true TWI741082B (en) | 2021-10-01 |
Family
ID=64991485
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW106141144A TWI741082B (en) | 2017-06-29 | 2017-11-27 | Adhesive composition and adhesive film |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6796035B2 (en) |
| KR (3) | KR102047663B1 (en) |
| CN (1) | CN109207101B (en) |
| TW (1) | TWI741082B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021018416A (en) * | 2019-07-17 | 2021-02-15 | 住友化学株式会社 | Polarizer having adhesive layer |
| CN111273389B (en) * | 2020-04-02 | 2022-05-06 | 佛山纬达光电材料股份有限公司 | Low-cost high weatherability's polaroid for on-vehicle display |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200940670A (en) * | 2007-12-20 | 2009-10-01 | Nitto Denko Corp | Pressure-sensitive adhesive composition for optical films, pressure-sensitive adhesive optical film and image display |
| TW201336962A (en) * | 2011-12-28 | 2013-09-16 | Soken Kagaku Kk | Optical member adhesive composition as well as adhesive sheet using the same, optical component with adhesive attached and flat panel display |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI387629B (en) * | 2004-07-26 | 2013-03-01 | Nitto Denko Corp | Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheets, and surface protecting film |
| CN101268391B (en) * | 2005-09-20 | 2010-06-16 | 综研化学株式会社 | Adhesive composition for polarizing plate and polarizing plate with adhesive layer |
| JP5332315B2 (en) * | 2007-09-03 | 2013-11-06 | 住友化学株式会社 | Optical laminate |
| JP5614328B2 (en) | 2011-02-25 | 2014-10-29 | 藤倉化成株式会社 | Adhesive composition, adhesive film, and optical component |
| JP5842439B2 (en) * | 2011-03-10 | 2016-01-13 | 住友化学株式会社 | Optical film with adhesive and optical laminate using the same |
| JP5760571B2 (en) | 2011-03-24 | 2015-08-12 | Dic株式会社 | Colored adhesive tape for fixing polarizing film |
| KR20120140578A (en) * | 2011-06-21 | 2012-12-31 | 박인성 | Electronic lure |
| JP5901548B2 (en) * | 2013-01-17 | 2016-04-13 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| KR101710443B1 (en) * | 2013-09-20 | 2017-02-27 | 후지모리 고교 가부시키가이샤 | Adhesive composition and surface protection film |
| JP6002701B2 (en) * | 2014-01-27 | 2016-10-05 | 藤森工業株式会社 | Adhesive layer and adhesive film |
| JP6570266B2 (en) * | 2015-03-06 | 2019-09-04 | 綜研化学株式会社 | Optical laminate |
| JP6042036B1 (en) * | 2015-04-10 | 2016-12-14 | 日本合成化学工業株式会社 | Pressure-sensitive adhesive composition, pressure-sensitive adhesive using the same, and pressure-sensitive adhesive for polarizing plate |
| JP6721322B2 (en) * | 2015-12-01 | 2020-07-15 | 住友化学株式会社 | Adhesive composition, adhesive sheet and optical film with adhesive |
| JP6615597B2 (en) * | 2015-12-15 | 2019-12-04 | 住友化学株式会社 | Adhesive composition |
-
2017
- 2017-06-29 JP JP2017127545A patent/JP6796035B2/en active Active
- 2017-11-20 CN CN201711154599.4A patent/CN109207101B/en active Active
- 2017-11-20 KR KR1020170154893A patent/KR102047663B1/en active IP Right Grant
- 2017-11-27 TW TW106141144A patent/TWI741082B/en active
-
2019
- 2019-11-18 KR KR1020190147318A patent/KR102111342B1/en active IP Right Grant
-
2020
- 2020-05-11 KR KR1020200055629A patent/KR102174604B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200940670A (en) * | 2007-12-20 | 2009-10-01 | Nitto Denko Corp | Pressure-sensitive adhesive composition for optical films, pressure-sensitive adhesive optical film and image display |
| TW201336962A (en) * | 2011-12-28 | 2013-09-16 | Soken Kagaku Kk | Optical member adhesive composition as well as adhesive sheet using the same, optical component with adhesive attached and flat panel display |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20200054925A (en) | 2020-05-20 |
| JP6796035B2 (en) | 2020-12-02 |
| TW201905147A (en) | 2019-02-01 |
| KR20190132956A (en) | 2019-11-29 |
| CN109207101A (en) | 2019-01-15 |
| JP2019011398A (en) | 2019-01-24 |
| KR102174604B1 (en) | 2020-11-05 |
| CN109207101B (en) | 2021-10-08 |
| KR20190002266A (en) | 2019-01-08 |
| KR102111342B1 (en) | 2020-05-15 |
| KR102047663B1 (en) | 2019-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI761383B (en) | Adhesive composition and adhesive film | |
| TWI668282B (en) | Adhesive composition and adhesive film | |
| TWI704201B (en) | Adhesive layer and adhesive film | |
| TWI754363B (en) | Adhesive layer and adhesive film | |
| TWI780242B (en) | Adhesive composition and adhesive film | |
| TWI741082B (en) | Adhesive composition and adhesive film | |
| JP2024014940A (en) | Adhesive compositions, adhesive films, polarizing plates with adhesive layers, and liquid crystal panels | |
| KR20200067795A (en) | Adhesive composition and adhesive film | |
| JP7482272B2 (en) | Adhesive Film | |
| JP7227335B2 (en) | Adhesive composition and adhesive film | |
| JP2020152920A (en) | Adhesive composition and adhesive film | |
| JP2023053101A (en) | adhesive film |