TWI811372B - Adhesive composition, and adhesive film, surface-protective film using the same - Google Patents

Adhesive composition, and adhesive film, surface-protective film using the same Download PDF

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TWI811372B
TWI811372B TW108118505A TW108118505A TWI811372B TW I811372 B TWI811372 B TW I811372B TW 108118505 A TW108118505 A TW 108118505A TW 108118505 A TW108118505 A TW 108118505A TW I811372 B TWI811372 B TW I811372B
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meth
weight
adhesive
adhesive composition
parts
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TW108118505A
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TW202024276A (en
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長倉毅
鈴木史恵
塚田高士
大津賀健太郎
吉田弘幸
菱沼昌世
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日商藤森工業股份有限公司
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    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0075—Antistatics
    • 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
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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
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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
    • 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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    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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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    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides an adhesive composition, and an adhesive film and a surface protecting film using the same. The adhesive composition has an excellent adhesion property, and can achieve both an antistatic property and an anti-contamination property at the same time. The adhesive composition contains an acrylic polymer having a alkyl (meth)acrylic acid ester as the main component, an antistatic agent, a cross-linker, and a polyether modified siloxane, wherein the polyether modified siloxane has been purified to deodorize. The polyether modified siloxane is contained in a ratio of 0.01 to 1.0 parts by weight based on 100 parts by weight of an acrylic polymer.

Description

黏著劑組合物及使用此之黏著膜、表面保護膜Adhesive composition and adhesive film and surface protective film using the same

本發明係關於一種含有抗靜電劑的黏著劑組合物以及使用了該黏著劑組合物的黏著膜、表面保護膜。 更詳細而言，提供一種能夠謀求優異的黏著性能、同時能夠謀求兼顧抗靜電性能與抗污染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、表面保護膜。The present invention relates to an adhesive composition containing an antistatic agent and an adhesive film and surface protective film using the adhesive composition. More specifically, the present invention provides an adhesive composition that can achieve excellent adhesive performance while achieving both antistatic performance and anti-pollution performance, as well as an adhesive film and a surface protective film using the adhesive composition.

一直以來，在使用具備抗靜電性能的黏著劑組合物而形成的黏著劑層以及使用了該黏著劑層的表面保護膜中，抗靜電性能與對被黏物的抗污染性能處於權衡(trade-off)的關係，在維持抗靜電性能的同時改善抗污染性能是困難的。 進一步，近年來，表面保護膜所貼合的被黏物的材質的種類不斷增加。此外，表面保護膜所貼合的被黏物的表面的表面狀態的性狀也因對被黏物實施的多種表面處理而變得多種多樣。因此，同時對所有被黏物滿足抗污染性能與抗靜電性能變得更加困難。Conventionally, in the adhesive layer formed using an adhesive composition having antistatic properties and the surface protective film using the adhesive layer, there has been a trade-off between the antistatic properties and the anti-contamination properties of the adherend. off), it is difficult to improve anti-pollution performance while maintaining antistatic properties. Furthermore, in recent years, the types of adherend materials to which surface protective films are bonded have been increasing. In addition, the surface state of the surface of the adherend to which the surface protective film is bonded also becomes diverse due to the various surface treatments performed on the adherend. Therefore, it becomes more difficult to simultaneously satisfy anti-pollution performance and antistatic performance for all adherends.

為了解決這樣的技術問題，例如提出了一種表面保護膜，該表面保護膜使用含有下述成分的黏著劑組合物作為形成表面保護膜的黏著劑層的黏著劑組合物：以特定的比率共聚特定單體而成的丙烯酸類共聚物、抗靜電劑以及在其結構中含有氟或矽的化合物(專利文獻1)。專利文獻1中的「在其結構中含有氟或矽的化合物」為選自聚醚改質聚有機矽氧烷、含有含氟烷基的氟類表面活性劑、在其結構中含有氟或矽的丙烯酸類聚合物中的任一種。此外，即使專利文獻1中專載的表面保護膜所貼合的被黏物的表面為進行使用了含氟化合物或含矽化合物的硬塗處理、或使用了這些化合物的低反射處理或防污處理而形成的功能性層，從該被黏物上剝離表面保護膜時，也能夠抑制靜電本身的產生，抑制由剝離靜電造成的被黏物污染及由起因於剝離靜電的火花等造成的電路的破壞等損害的產生。In order to solve such a technical problem, for example, a surface protective film has been proposed that uses an adhesive composition containing the following components as an adhesive composition forming an adhesive layer of the surface protective film: copolymerizing a specific substance at a specific ratio Acrylic copolymers made of monomers, antistatic agents, and compounds containing fluorine or silicon in their structures (Patent Document 1). The "compound containing fluorine or silicon in its structure" in Patent Document 1 is selected from the group consisting of polyether-modified polyorganosiloxane, fluorine-based surfactants containing fluorine-containing alkyl groups, and compounds containing fluorine or silicon in its structure. Any of the acrylic polymers. In addition, even if the surface of the adherend to which the surface protection film specifically described in Patent Document 1 is bonded is subjected to hard coating treatment using a fluorine-containing compound or a silicon-containing compound, or low-reflection treatment or antifouling treatment using these compounds, The functional layer formed by the treatment can also suppress the generation of static electricity itself when the surface protective film is peeled off from the adherend, and can suppress the contamination of the adherend caused by the peeled static electricity and the circuit damage caused by sparks caused by the peeled static electricity. damage or other damage.

此外，提出了使用含有下述成分的黏著劑組合物來形成表面保護膜的黏著劑層：第一(甲基)丙烯酸共聚物，其包含具有羧基的特定結構的第一結構單元及來自具有羥基的單體的第二結構單元；在聚醚末端具有羥基的聚醚改質聚矽氧；鹼金屬鹽(專利文獻2)。專利文獻2中記載的表面保護膜能夠以較高水準兼顧抗靜電性能及對被黏物的低污染性。 現有技術文獻 專利文獻In addition, it is proposed to use an adhesive composition containing the following components to form an adhesive layer of the surface protection film: a first (meth)acrylic acid copolymer, which contains a first structural unit with a specific structure having a carboxyl group and a first structural unit having a hydroxyl group. The second structural unit of the monomer; a polyether-modified polysiloxane having a hydroxyl group at the polyether terminal; an alkali metal salt (Patent Document 2). The surface protective film described in Patent Document 2 can achieve both antistatic performance and low contamination of adherends at a high level. existing technical documents patent documents

專利文獻1：日本專利第5544800號公報 專利文獻2：日本專利第6058390號公報Patent Document 1: Japanese Patent No. 5544800 Patent Document 2: Japanese Patent No. 6058390

本發明要解決的問題Problems to be solved by this invention

此外，專利文獻1中記載的表面保護膜利用下述方法評價被黏物污染的試驗：「用2kgf輥往復一次，將之前得到的各表面保護膜分別壓接並貼附在上述AG偏振片及HC偏振片的功能性層側的表面上。然後，將這些試樣在70℃的環境下放置3天。然後，取出試樣，在23℃、50%RH中放置24小時後，從被黏物上剝離試樣，以目視觀察污染的程度，並以下述標準進行評價」(專利文獻1的第[0049]段)。 然而，對於將表面保護膜保管在為更嚴苛的試驗條件的高溫·高濕度的環境下(例如，溫度60℃、濕度90%RH的氣氛下)並進行評價時的抗污染性能，專利文獻1中沒有任何公開，是不明確的。 此外，專利文獻1中雖然有針對聚醚改質聚有機矽氧烷的記載，但對於該化合物所含有的雜質以及由該雜質帶來的對被黏物的污染性的不良影響沒有任何記載，也沒有任何暗示。 進一步，專利文獻1中記載的表面保護膜存在以下問題：由於使具有伸烷氧基(alkylene oxide)的(甲基)丙烯酸酯共聚而作為黏著劑的基礎聚合物的丙烯酸類共聚物，因此即使能夠得到需要的抗靜電性能或黏著性能，也難以獲得包括抗污染性能的特性平衡優異的表面保護膜。 並且，專利文獻2中記載的表面保護膜藉由使用具有羧基的特定結構的第一結構單元等特定結構的單體成分作為形成黏著劑層的黏著劑組合物的(甲基)丙烯酸類共聚物，由此兼顧抗靜電性能與抗污染性能。 然而，由於黏著劑組合物中所含有的聚醚改質聚矽氧與第一(甲基)丙烯酸類共聚物的相容性的不良或第一(甲基)丙烯酸類共聚物本身的黏著性能，因此存在難以得到具有充分的特性平衡的黏著劑層的問題。 此外，專利文獻2中雖然有針對聚醚改質聚有機矽氧烷的記載，但對於該化合物所含有的雜質以及由該雜質帶來的對被黏物的污染性的不良影響沒有任何記載，也沒有任何暗示。In addition, the surface protective film described in Patent Document 1 uses the following method to evaluate contamination by adherent substances: "Use a 2kgf roller to reciprocate once, press-bond each surface protective film obtained previously and attach it to the above-mentioned AG polarizing plate and on the surface of the functional layer side of the HC polarizing plate. Then, these samples were placed in an environment of 70°C for 3 days. Then, the samples were taken out and left at 23°C and 50% RH for 24 hours, and then removed from the adhered Peel off the sample from the object, visually observe the degree of contamination, and evaluate according to the following standards" (paragraph [0049] of Patent Document 1). However, patent documents describe the anti-fouling performance of the surface protective film when it is stored and evaluated in a high-temperature and high-humidity environment with more severe test conditions (for example, an atmosphere of 60° C. and 90% RH). Nothing is disclosed in 1 and is unclear. In addition, although there is a description of polyether-modified polyorganosiloxane in Patent Document 1, there is no description of the impurities contained in the compound and the adverse effects of the impurities on the contamination of adherends. There's no hint of that either. Furthermore, the surface protective film described in Patent Document 1 has the following problem: since it is an acrylic copolymer that is a base polymer of an adhesive by copolymerizing a (meth)acrylate having an alkylene oxide group, even if It is difficult to obtain the required antistatic properties or adhesive properties, but it is also difficult to obtain a surface protective film with an excellent balance of properties including anti-pollution properties. Furthermore, the surface protective film described in Patent Document 2 uses a (meth)acrylic copolymer of a specific structure such as a first structural unit having a specific structure such as a carboxyl group as an adhesive composition that forms an adhesive layer. , thus taking into account both antistatic performance and anti-pollution performance. However, due to poor compatibility between the polyether-modified polysiloxane contained in the adhesive composition and the first (meth)acrylic copolymer or the adhesive properties of the first (meth)acrylic copolymer itself , so there is a problem that it is difficult to obtain an adhesive layer with a sufficient balance of properties. In addition, although there is a description of polyether-modified polyorganosiloxane in Patent Document 2, there is no description of the impurities contained in the compound and the adverse effects of the impurities on the contamination of adherends. There's no hint of that either.

本發明是鑒於上述情況而進行的，其技術問題在於提供一種能夠謀求優異的黏著性能、同時能夠謀求兼顧抗靜電性能與抗污染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、表面保護膜。 解決技術問題的技術手段The present invention was made in view of the above situation, and its technical problem is to provide an adhesive composition that can achieve excellent adhesive performance while achieving both antistatic performance and anti-fouling performance, and an adhesive film using the same. , surface protective film. Technical means to solve technical problems

本申請的發明人發現，使用含有丙烯酸類聚合物、抗靜電劑及作為聚醚改質矽氧烷化合物的經過無臭化純化的聚醚改質矽氧烷化合物的黏著劑組合物而形成的黏著劑層，具有防止對被黏物表面的污染的優異的抗污染性能。 即，本申請的發明人發現，不含雜質的經過純化的聚醚改質矽氧烷化合物與含有雜質的聚醚改質矽氧烷化合物在黏著劑層的性能上、在抗靜電性能及抗污染性能的優劣上存在差異，從而完成了本發明。 本發明的技術構思在於，製成一種含有丙烯酸類聚合物、抗靜電劑及經過無臭化純化的聚醚改質矽氧烷化合物的黏著劑組合物。The inventors of the present application have discovered that an adhesive composition containing an acrylic polymer, an antistatic agent, and an odorless and purified polyether-modified siloxane compound as a polyether-modified siloxane compound forms an adhesive. The agent layer has excellent anti-pollution properties to prevent contamination of the adherend surface. That is, the inventors of the present application have found that a purified polyether-modified siloxane compound that does not contain impurities and a polyether-modified siloxane compound that contains impurities improve the adhesive layer performance, antistatic performance, and anti-static properties. There is a difference in the quality of pollution performance, and the present invention was completed. The technical concept of the present invention is to prepare an adhesive composition containing an acrylic polymer, an antistatic agent and an odorless and purified polyether modified siloxane compound.

本發明的含有抗靜電劑及經過無臭化純化的聚醚改質矽氧烷化合物的黏著劑組合物、以及使用了該黏著劑組合物的黏著膜、表面保護膜，能夠謀求優異的黏著性能、同時能夠謀求兼顧抗靜電性能與抗污染性能。 本發明的黏著劑組合物及使用了該黏著劑組合物的黏著膜、表面保護膜解決了現有技術的技術問題。The adhesive composition containing an antistatic agent and an odorless purified polyether-modified siloxane compound of the present invention, as well as the adhesive film and surface protective film using the adhesive composition, can achieve excellent adhesive properties, At the same time, it can achieve both antistatic performance and anti-pollution performance. The adhesive composition and the adhesive film and surface protective film using the adhesive composition of the present invention solve the technical problems of the prior art.

為了解決上述技術問題，本發明提供一種黏著劑組合物，其為含有以(甲基)丙烯酸烷基酯為主要成分的丙烯酸類聚合物、抗靜電劑、交聯劑及聚醚改質矽氧烷化合物的組合物，其特徵在於，所述聚醚改質矽氧烷化合物為經過無臭化純化的聚醚改質矽氧烷化合物，相對於100重量份的所述丙烯酸類聚合物，以0.01~1.0重量份的比例含有所述經過無臭化純化的聚醚改質矽氧烷化合物。In order to solve the above technical problems, the present invention provides an adhesive composition, which contains an acrylic polymer with alkyl (meth)acrylate as the main component, an antistatic agent, a cross-linking agent and a polyether modified silicone. The composition of an alkane compound is characterized in that the polyether-modified siloxane compound is a polyether-modified siloxane compound that has been deodorized and purified, and is 0.01 relative to 100 parts by weight of the acrylic polymer. The proportion of ~1.0 parts by weight contains the odorless and purified polyether modified siloxane compound.

優選：所述經過無臭化純化的聚醚改質矽氧烷化合物為去除了作為副產物的丙烯基醚化聚氧化烯及/或醛縮合物的、HLB值為4~15且重均分子量為10000以下的聚醚改質矽氧烷化合物。Preferably: the odorless and purified polyether-modified siloxane compound has removed propylene etherified polyoxyalkylene and/or aldehyde condensates as by-products, has an HLB value of 4 to 15, and a weight average molecular weight of Polyether modified siloxane compounds below 10,000.

優選：所述丙烯酸類聚合物為由酸值為0.1~1.0、重均分子量超過30萬且為100萬以下的共聚物所形成的丙烯酸類聚合物，所述共聚物藉由使相對於合計為100重量份的(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體的至少一種以上，與合計為0.1~10重量份的(B)含有羥基的可共聚單體的至少一種以上與合計為0.01~0.5重量份的(C)含有羧基的可共聚單體的至少一種以上進行共聚而成，在合計為100重量份的所述(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體的至少一種以上中，以60重量份以上的比例含有丙烯酸2-乙基己酯，所述丙烯酸類聚合物的玻璃轉變溫度為0℃以下，所述交聯劑為(D)三官能度以上的異氰酸酯化合物，所述抗靜電劑為熔點為25~50℃的離子化合物，所述黏著劑組合物進一步含有(E)交聯延遲劑與作為(F)交聯催化劑的錫化合物以外的交聯催化劑。Preferably: the acrylic polymer is an acrylic polymer formed from a copolymer with an acid value of 0.1 to 1.0 and a weight average molecular weight of more than 300,000 and less than 1 million, and the copolymer is obtained by making 100 parts by weight of (A) at least one (meth)acrylate monomer with an alkyl group having carbon atoms of C1 to C18, and a total of 0.1 to 10 parts by weight of (B) a copolymerizable monomer containing a hydroxyl group It is formed by copolymerizing at least one or more of (C) carboxyl group-containing copolymerizable monomers in a total of 0.01 to 0.5 parts by weight, and the number of carbon atoms of the (A) alkyl group in a total of 100 parts by weight At least one of C1 to C18 (meth)acrylate monomers contains 2-ethylhexyl acrylate in a proportion of more than 60 parts by weight, and the glass transition temperature of the acrylic polymer is 0°C or less, The cross-linking agent is (D) an isocyanate compound with three or more functionalities, the antistatic agent is an ionic compound with a melting point of 25 to 50°C, and the adhesive composition further contains (E) a cross-linking retardant and as (F) Cross-linking catalyst other than a tin compound of the cross-linking catalyst.

優選：所述抗靜電劑為離子化合物，所述離子化合物的陽離子為選自由吡啶鎓、咪唑鎓、鏻、鋶、吡咯啶鎓、胍鎓(guanidinium)、銨、異脲鎓(isouronium)、硫脲鎓(thiouronium)、呱啶鎓、吡唑鎓(pyrazolium)、甲基碳正離子(methylium)、鋰、嗎啉鎓(morpholinium)組成的群組中的一種，相對於100重量份的所述丙烯酸類聚合物，以0.01~10重量份的比例含有所述離子化合物作為必需成分。Preferably: the antistatic agent is an ionic compound, and the cation of the ionic compound is selected from pyridinium, imidazolium, phosphonium, sulfonium, pyrrolidinium, guanidinium, ammonium, isouronium, sulfur One of the group consisting of thiouronium, pyridinium, pyrazolium, methylium, lithium and morpholinium, relative to 100 parts by weight of the The acrylic polymer contains the ionic compound as an essential component in a proportion of 0.01 to 10 parts by weight.

優選：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1.0×10＋ 12 Ω/□以下， 所述黏著劑層對使用含有氟化合物的低折射率層形成用的組合物而形成的低折射率層的剝離靜電電壓在+0.3~-0.3kV的範圍內， 使所述黏著劑組合物交聯而成的黏著劑層對在表面基材上施加有所述低折射率層的偏振片的、在低速的剝離速度0.3m/min下的黏著力為0.04~0.2N/25mm，在高速的剝離速度30m/min下的黏著力為2.0N/25mm以下， 將使所述黏著劑組合物交聯而成的黏著劑層貼合於在表面基材上施加有所述低折射率層的偏振片後，在溫度60℃、濕度90%RH的氣氛下放置2天，從所述氣氛下取出並經過1天後，將所述黏著劑層從所述偏振片上剝離時無污染性。Preferably, the surface resistivity of the adhesive layer formed by cross-linking the adhesive composition is 1.0 × 10 + 12 Ω/□ or less, and the adhesive layer is formed using a low refractive index layer containing a fluorine compound. The peeling electrostatic voltage of the low refractive index layer formed by the composition is in the range of +0.3~-0.3kV, and the adhesive layer formed by cross-linking the adhesive composition is suitable for applying the low refractive index layer on the surface substrate. The refractive index layer of the polarizer has an adhesive force of 0.04~0.2N/25mm at a low peeling speed of 0.3m/min, and an adhesive force of 2.0N/25mm or less at a high peeling speed of 30m/min, which will make After the adhesive layer cross-linked by the adhesive composition is attached to the polarizing plate with the low refractive index layer applied to the surface base material, it is left for 2 days in an atmosphere with a temperature of 60°C and a humidity of 90% RH. , after taking it out from the atmosphere for 1 day, there is no contamination when the adhesive layer is peeled off from the polarizing plate.

優選：所述(B)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， 所述(C)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 (B) hydroxyl-containing copolymerizable monomer is selected from 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, A compound composed of 2-hydroxyethyl (meth)acrylate, N-hydroxy(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, and N-hydroxyethyl(meth)acrylamide At least one or more of the groups, The (C) carboxyl-containing copolymerizable monomer is selected from (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, 2-(meth)acryloxy Ethylhexahydrophthalic acid, 2-(meth)acryloxypropylhexahydrophthalic acid, 2-(meth)acryloxyethylphthalic acid, 2-(meth)acryloxyethylphthalic acid acrylic acid, 2-(meth)acryloxyethyl maleic acid, carboxypolycaprolactone mono(meth)acrylate, 2-(meth)acryloxy At least one of the compound group consisting of ethyl tetrahydrophthalic acid.

優選：所述黏著劑組合物含有(E)交聯延遲劑與作為(F)交聯催化劑的除錫化合物以外的交聯催化劑，所述(E)交聯延遲劑為酮-烯醇互變異構體的化合物，相對於100重量份的所述丙烯酸類聚合物，以0.1~300重量份的比例含有所述(E)交聯延遲劑， 所述(F)交聯催化劑為選自由鋁螯合化合物、鈦螯合化合物、鐵螯合化合物組成的群組中的至少一種以上的金屬螯合化合物， 相對於100重量份的所述丙烯酸類聚合物，以0.001~0.5重量份的比例含有所述(F)交聯催化劑，所述(E)/所述(F)的重量份比為80~1000。Preferably: the adhesive composition contains (E) a cross-linking retarder and a cross-linking catalyst other than a tin compound as (F) a cross-linking catalyst, and the (E) cross-linking retarder is a ketone-enol tautomer. The compound of the structure contains the (E) cross-linking retardant in a ratio of 0.1 to 300 parts by weight relative to 100 parts by weight of the acrylic polymer, The (F) crosslinking catalyst is at least one metal chelate compound selected from the group consisting of aluminum chelate compounds, titanium chelate compounds, and iron chelate compounds, The cross-linking catalyst (F) is contained in a proportion of 0.001 to 0.5 parts by weight relative to 100 parts by weight of the acrylic polymer, and the weight part ratio of (E)/(F) is 80 to 1000 .

此外，本發明提供一種黏著膜，其特徵在於，在樹脂膜的單面上積層有使上述黏著劑組合物交聯而成的黏著劑層。Furthermore, the present invention provides an adhesive film characterized in that an adhesive layer obtained by cross-linking the adhesive composition is laminated on one side of the resin film.

此外，本發明提供一種表面保護膜，其使用了上述黏著膜。Furthermore, the present invention provides a surface protective film using the above-mentioned adhesive film.

此外，本發明提供一種偏振片用的表面保護膜，其使用了上述黏著膜。Furthermore, the present invention provides a surface protective film for polarizing plates using the above-mentioned adhesive film.

此外，本發明提供一種帶黏著劑層的光學膜，其中，在光學膜的至少一側的面上積層有使上述黏著劑組合物交聯而成的黏著劑層。Furthermore, the present invention provides an optical film with an adhesive layer in which an adhesive layer obtained by crosslinking the adhesive composition is laminated on at least one surface of the optical film.

此外，本發明提供一種黏著膜，其中，對所述樹脂膜的、與形成有所述黏著劑層的一側為相反面的單面進行了抗靜電處理及防污處理。 發明效果Furthermore, the present invention provides an adhesive film in which one side of the resin film opposite to the side on which the adhesive layer is formed is subjected to antistatic treatment and antifouling treatment. Invention effect

關於本發明的表面保護膜的用途，可適用於光學膜的表面，該光學膜具有選自由三醋酸纖維素(TAC)、聚對苯二甲酸乙二醇酯(PET)、聚甲基丙烯酸甲酯(PMMA)組成的基材群組中的表面基材(例如，表面保護層)作為被黏物。 本發明的表面保護膜對這些被黏物具有優異的黏著性能、抗污染性能，且具有優異的抗剝離靜電性能。 進一步，即使在於上述被黏物的表面上形成含有氟化合物的防污層或使用含有氟化合物的樹脂組合物形成低折射率層的情況下，本發明的表面保護膜也具有優異的黏著性能、抗污染性能，且具有優異的抗剝離靜電性能。 根據本發明，能夠提供一種可謀求優異的黏著性能、同時可謀求兼顧抗靜電性能與抗污染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、表面保護膜。因此，本發明在產業上的利用價值極大。 此外，本發明的表面保護膜對被黏物具有優異的黏著性能、抗污染性能，且具有優異的抗剝離靜電性能。 此外，本發明的含有丙烯酸類聚合物、抗靜電劑及經過無臭化純化的聚醚改質矽氧烷化合物的黏著劑組合物以及使用了該黏著劑組合物的黏著膜、表面保護膜可謀求優異的黏著性能、同時可謀求兼顧抗靜電性能與抗污染性能。 在本發明中，使用含有丙烯酸類聚合物、抗靜電劑及作為聚醚改質矽氧烷化合物的經過無臭化純化的聚醚改質矽氧烷化合物的黏著劑組合物而形成的黏著劑層，其能夠謀求優異的黏著性能、同時能夠謀求兼顧抗靜電性能與抗污染性能的理由尚不明確。作為推測的理由，例如可考慮下述理由：藉由對聚醚改質矽氧烷化合物進行無臭化純化，成為聚醚改質矽氧烷化合物所含有的副產物極少的狀態，與丙烯酸類聚合物的相容性得以提高，由此分散性得到改善，不產生聚醚改質矽氧烷化合物的滲出。Regarding the use of the surface protective film of the present invention, it can be applied to the surface of an optical film having a material selected from the group consisting of triacetylcellulose (TAC), polyethylene terephthalate (PET), and polymethyl methacrylate. The surface substrate (for example, surface protective layer) in the substrate group composed of ester (PMMA) serves as the adherend. The surface protective film of the present invention has excellent adhesion properties and anti-pollution properties to these adherends, and has excellent anti-peeling electrostatic properties. Furthermore, even when an antifouling layer containing a fluorine compound is formed on the surface of the adherend or a low refractive index layer is formed using a resin composition containing a fluorine compound, the surface protective film of the present invention has excellent adhesive properties. Anti-pollution properties and excellent anti-stripping static properties. According to the present invention, it is possible to provide an adhesive composition that can achieve excellent adhesive performance while achieving both antistatic performance and anti-pollution performance, as well as an adhesive film and a surface protective film using the adhesive composition. Therefore, the present invention has great industrial application value. In addition, the surface protective film of the present invention has excellent adhesion properties and anti-pollution properties to adherends, and has excellent anti-peeling electrostatic properties. In addition, the adhesive composition of the present invention containing an acrylic polymer, an antistatic agent and an odorless and purified polyether-modified siloxane compound, as well as an adhesive film and a surface protective film using the adhesive composition, can achieve Excellent adhesion performance, while achieving both antistatic and anti-pollution properties. In the present invention, an adhesive layer is formed using an adhesive composition containing an acrylic polymer, an antistatic agent, and an odorless and purified polyether-modified siloxane compound as a polyether-modified siloxane compound. , the reason why it can achieve excellent adhesion performance while achieving both antistatic performance and anti-pollution performance is not yet clear. As a reason for speculation, for example, the following reason can be considered: by deodorizing and purifying the polyether-modified siloxane compound, the polyether-modified siloxane compound is in a state in which the by-products are extremely small, and the polyether-modified siloxane compound is polymerized with acrylic. The compatibility of the product is improved, thereby improving the dispersion and preventing the polyether-modified siloxane compound from exuding.

具體實施方式Detailed implementation

以下，根據優選的實施方式對本發明進行說明。 本發明的黏著劑組合物含有以(甲基)丙烯酸烷基酯為主要成分的丙烯酸類聚合物、抗靜電劑、交聯劑及聚醚改質矽氧烷化合物，其特徵在於，所述聚醚改質矽氧烷化合物為經過無臭化純化的聚醚改質矽氧烷化合物，相對於100重量份的所述丙烯酸類聚合物，以0.01~1.0重量份的比例含有所述經過無臭化純化的聚醚改質矽氧烷化合物。Hereinafter, the present invention will be described based on preferred embodiments. The adhesive composition of the present invention contains an acrylic polymer with alkyl (meth)acrylate as the main component, an antistatic agent, a cross-linking agent and a polyether-modified siloxane compound, and is characterized in that the polyether-modified siloxane compound is The ether-modified siloxane compound is an odorless-purified polyether-modified siloxane compound, which is contained in a ratio of 0.01 to 1.0 parts by weight relative to 100 parts by weight of the acrylic polymer. Polyether modified siloxane compounds.

用於本實施方式的黏著劑組合物的丙烯酸類聚合物為黏著劑組合物的主要成分聚合物，其為玻璃轉變溫度為0℃以下的丙烯酸類聚合物。此外，丙烯酸類聚合物優選為以(甲基)丙烯酸烷基酯中的(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體為主要成分的共聚物。此處，例如將丙烯酸類聚合物的整體設為100重量份時，主要成分的比例優選為50重量份以上，更優選為80重量份以上，特別優選為90重量份以上。The acrylic polymer used in the adhesive composition of this embodiment is a main component polymer of the adhesive composition, and is an acrylic polymer having a glass transition temperature of 0° C. or lower. Furthermore, the acrylic polymer is preferably a copolymer whose main component is a (meth)acrylate monomer in which the (A) alkyl group in the (meth)acrylic acid alkyl ester has a carbon number of C1 to C18. Here, for example, when the total acrylic polymer is 100 parts by weight, the proportion of the main component is preferably 50 parts by weight or more, more preferably 80 parts by weight or more, and particularly preferably 90 parts by weight or more.

作為(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體，可列舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯等。(甲基)丙烯酸烷基酯單體的烷基可以是直鏈、支鏈狀、環狀中的任一種。Examples of the (A) (meth)acrylate monomer in which the alkyl group has C1 to C18 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. , butyl (meth)acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, Isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, (meth) Undecyl acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate , Cetyl (meth)acrylate, Heptadecyl (meth)acrylate, Octadecyl (meth)acrylate, Cyclopentyl (meth)acrylate, Cyclohexyl (meth)acrylate Ester etc. The alkyl group of the (meth)acrylic acid alkyl ester monomer may be linear, branched, or cyclic.

本實施方式的黏著劑組合物所使用的丙烯酸類聚合物在合計為100重量份的(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體的至少一種以上中，優選以60重量份以上的比例、更優選以70重量份以上的比例、特別優選以80重量份以上的比例含有丙烯酸2-乙基己酯。The acrylic polymer used in the adhesive composition of this embodiment contains a total of 100 parts by weight of at least one (meth)acrylate monomer with a carbon number of C1 to C18 in the (A) alkyl group, 2-ethylhexyl acrylate is preferably contained in a proportion of 60 parts by weight or more, more preferably 70 parts by weight or more, particularly preferably 80 parts by weight or more.

本實施方式的黏著劑組合物所使用的丙烯酸類聚合物中，作為與(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體共聚的單體，可列舉出(B)含有羥基的可共聚單體及(C)含有羧基的可共聚單體。In the acrylic polymer used in the adhesive composition of this embodiment, examples of monomers copolymerized with (A) a (meth)acrylate monomer in which the carbon number of the alkyl group is C1 to C18 include (A) B) hydroxyl group-containing copolymerizable monomer and (C) carboxyl group-containing copolymerizable monomer.

作為(B)含有羥基的可共聚單體，可列舉出選自由(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。(B) The copolymerizable monomer containing a hydroxyl group may be selected from the group consisting of 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, A compound composed of 2-hydroxyethyl (meth)acrylate, N-hydroxy(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, and N-hydroxyethyl(meth)acrylamide At least one of the groups.

本實施方式的黏著劑組合物所使用的丙烯酸類聚合物，相對於合計為100重量份的(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體的至少一種以上，優選以合計為0.1~10重量份的比例、更優選以1.0~6.0重量份的比例、進一步優選以2.0~5.0重量份的比例、特別優選以2.5~4.5重量份的比例含有(B)含有羥基的可共聚單體的至少一種以上。The acrylic polymer used in the adhesive composition of this embodiment contains at least one (meth)acrylate monomer with a carbon number of C1 to C18 in the (A) alkyl group relative to a total of 100 parts by weight. (B) is preferably contained in a total proportion of 0.1 to 10 parts by weight, more preferably in a proportion of 1.0 to 6.0 parts by weight, still more preferably in a proportion of 2.0 to 5.0 parts by weight, and particularly preferably in a proportion of 2.5 to 4.5 parts by weight. at least one copolymerizable monomer of hydroxyl group.

作為(C)含有羧基的可共聚單體，可列舉出選自由(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。(C) The carboxyl group-containing copolymerizable monomer may be selected from (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, and 2-(meth)propylene. Cyloxyethylhexahydrophthalic acid, 2-(meth)acryloxypropylhexahydrophthalic acid, 2-(meth)acryloxyethylphthalic acid, 2-(meth)acryloxyethylhexahydrophthalic acid (Meth)acryloxyethylsuccinic acid, 2-(meth)acryloxyethylmaleic acid, carboxypolycaprolactone mono(meth)acrylate, 2-(meth)acrylyl At least one of the compound group consisting of oxyethyl tetrahydrophthalic acid.

本實施方式的黏著劑組合物所使用的丙烯酸類聚合物，相對於合計為100重量份的(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體的至少一種以上，優選以合計為0.01~0.5重量份的比例、更優選以0.01~0.4重量份的比例、特別優選以0.01~0.3重量份的比例含有(C)含有羧基的可共聚單體的至少一種以上。The acrylic polymer used in the adhesive composition of this embodiment contains at least one (meth)acrylate monomer with a carbon number of C1 to C18 in the (A) alkyl group relative to a total of 100 parts by weight. , preferably contains (C) at least one or more carboxyl group-containing copolymerizable monomers in a proportion of 0.01 to 0.5 parts by weight in total, more preferably in a proportion of 0.01 to 0.4 parts by weight, particularly preferably in a proportion of 0.01 to 0.3 parts by weight.

本實施方式的黏著劑組合物所使用的丙烯酸類聚合物優選為酸值為0.1~1.0、重均分子量(Mw)超過30萬且為100萬以下的共聚物。Mw更優選為80萬以下，進一步優選為60萬以下。由此，可有助於改善抗污染性能。此處，「酸值」是表示酸含量的指標之一，以中和1g含有羧基的聚合物所需要的氫氧化鉀的mg數來表示。The acrylic polymer used in the adhesive composition of this embodiment is preferably a copolymer with an acid value of 0.1 to 1.0 and a weight average molecular weight (Mw) of more than 300,000 and not more than 1 million. Mw is more preferably 800,000 or less, still more preferably 600,000 or less. This can help improve the anti-pollution performance. Here, the "acid value" is one of the indicators indicating acid content, and is expressed as the number of mg of potassium hydroxide required to neutralize 1 g of a carboxyl group-containing polymer.

本實施方式的黏著劑組合物所使用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、公知的聚合方法。丙烯酸類聚合物的製備所使用的單體優選至少分別含有上述(A)~(C)中的一種以上。在不損害本發明的效果的範圍內，可共聚其他單體。The preparation method of the acrylic polymer used in the adhesive composition of this embodiment is not particularly limited, and suitable and well-known polymerization methods such as solution polymerization and emulsion polymerization can be used. The monomer used in the preparation of the acrylic polymer preferably contains at least one or more of the above-mentioned (A) to (C). Other monomers may be copolymerized within the scope that does not impair the effects of the present invention.

為了容易得到包括黏著性能的特性平衡優異的黏著劑組合物，本實施方式的黏著劑組合物所使用的丙烯酸類聚合物優選為不含具有伸烷氧基的(甲基)丙烯酸酯的共聚物。此處，作為具有伸烷氧(alkylene oxide)基的(甲基)丙烯酸酯，可列舉出聚伸烷基二醇單(甲基)丙烯酸酯、聚伸烷基二醇二(甲基)丙烯酸酯、烷氧基聚伸烷基二醇單(甲基)丙烯酸酯等。此外，作為伸烷氧基，可列舉出環氧乙烷基、環氧丙烷基、環氧丁烷基等。In order to easily obtain an adhesive composition with an excellent balance of characteristics including adhesive properties, the acrylic polymer used in the adhesive composition of the present embodiment is preferably a copolymer that does not contain (meth)acrylate having an alkyloxy group. . Here, examples of the (meth)acrylate having an alkylene oxide group include polyalkylene glycol mono(meth)acrylate and polyalkylene glycol di(meth)acrylate. ester, alkoxy polyalkylene glycol mono(meth)acrylate, etc. Examples of the alkyleneoxy group include an oxirane group, an oxypropanyl group, an oxybutanyl group, and the like.

本實施方式的黏著劑組合物含有抗靜電劑。本實施方式的抗靜電劑優選為離子化合物，特別優選為在溫度25℃下為固體、熔點為25~50℃的離子化合物。推測由於這樣的離子化合物的熔點低且具有長鏈的烷基，因此其與丙烯酸類聚合物的親和性高。相對於100重量份的丙烯酸類聚合物，優選以合計為0.01~10重量份的比例含有所述離子化合物的至少一種以上作為必需成分。The adhesive composition of this embodiment contains an antistatic agent. The antistatic agent of this embodiment is preferably an ionic compound, and particularly preferably an ionic compound that is solid at a temperature of 25°C and has a melting point of 25 to 50°C. It is presumed that such ionic compounds have high affinity with acrylic polymers because they have a low melting point and a long-chain alkyl group. It is preferable that at least one of the ionic compounds is contained as an essential component in a total proportion of 0.01 to 10 parts by weight relative to 100 parts by weight of the acrylic polymer.

作為所述離子化合物的陰離子，可列舉出六氟磷酸鹽(PF6 - )、硫氰酸鹽(SCN- )、過氯酸鹽(ClO4 - )、四氟硼酸鹽(BF4 - )等無機陰離子，羧酸鹽(RCOO- )、磺酸鹽(RSO3 - )、醇鹽或酚鹽(RO- )、有機醯亞胺鹽(R2 N- )、甲基化物鹽(R3 C- )、有機硼酸鹽(R4 B- )等有機陰離子等。有機陰離子的各通式中所含的R為可具有氟取代的有機基團。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)、脂肪族或芳香族的羰基、脂肪族或芳香族的磺醯基等中的至少一種以上。這些有機基團的氫原子的一部分或全部可被氟原子取代。Examples of the anion of the ionic compound include hexafluorophosphate (PF 6 - ), thiocyanate (SCN - ), perchlorate (ClO 4 - ), tetrafluoroborate (BF 4 - ), and the like. Inorganic anions, carboxylate (RCOO - ), sulfonate (RSO 3 - ), alkoxide or phenoxide (RO - ), organoimide salt (R 2 N - ), methide salt (R 3 C - ), organic borate (R 4 B - ) and other organic anions. R included in each general formula of the organic anion is an organic group that may have fluorine substitution. Examples of the organic group include at least one of an alkyl group, an alkoxy group, an aromatic group (aryl group, aralkyl group, etc.), an aliphatic or aromatic carbonyl group, an aliphatic or aromatic sulfonyl group, etc. More than one kind. Some or all of the hydrogen atoms of these organic groups may be substituted with fluorine atoms.

作為所述離子化合物的陽離子，可列舉出選自由吡啶鎓、咪唑鎓、鏻、鋶、吡咯啶鎓、胍鎓、銨、異脲鎓、硫脲鎓、呱啶鎓、吡唑鎓、甲基碳正離子、鋰、嗎啉鎓組成的群組中的一種。 當離子化合物的陰離子及/或陽離子含有烷基等有機基團時，藉由烷基的鏈長或取代基的位置、個數等的選擇，能夠得到熔點為25~50℃的離子化合物。Examples of the cation of the ionic compound include pyridinium, imidazolium, phosphonium, sulfonium, pyrrolidinium, guanidium, ammonium, isouronium, thiouronium, pyridinium, pyrazolium, and methyl One of the group consisting of carbocation, lithium, and morpholinium. When the anion and/or cation of an ionic compound contains an organic group such as an alkyl group, an ionic compound with a melting point of 25 to 50°C can be obtained by selecting the chain length of the alkyl group or the position and number of substituents.

本實施方式的黏著劑組合物進一步含有交聯劑。作為交聯劑，優選(D)三官能度以上的異氰酸酯化合物。作為(D)三官能度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、二苯甲烷二異氰酸酯、甲伸苯二異氰酸酯、二甲苯撐基(xylylene)二異氰酸酯等二異氰酸酯類的縮二脲改質體或異氰脲酸酯改質體、與三羥甲基丙烷或甘油等三價以上的多元醇的加成物等。相對於100重量份的丙烯酸類聚合物，優選以合計為0.1~10重量份的比例、進一步優選以0.5~5重量份的比例、特別優選以1~3重量份的比例含有(D)三官能度以上的異氰酸酯化合物的至少一種以上。The adhesive composition of this embodiment further contains a crosslinking agent. As the cross-linking agent, (D) an isocyanate compound having a trifunctionality or higher is preferred. Examples of the isocyanate compound having (D) trifunctionality or higher include hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, and xylylene diisocyanate. Biuret-modified bodies or isocyanurate-modified bodies of diisocyanates such as isocyanate, adducts with polyhydric alcohols having a trivalent or higher value such as trimethylolpropane or glycerol, etc. The (D) trifunctionality is preferably contained in a proportion of 0.1 to 10 parts by weight in total, more preferably in a proportion of 0.5 to 5 parts by weight, and particularly preferably in a proportion of 1 to 3 parts by weight relative to 100 parts by weight of the acrylic polymer. At least one type of isocyanate compound having a degree of or higher.

本實施方式的黏著劑組合物也可含有(E)交聯延遲劑。作為(E)交聯延遲劑，優選酮-烯醇互變異構體的化合物，作為具體例，可列舉出乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯乙酸辛酯、乙醯乙酸油醇酯(oleyl acetoacetate)、乙醯乙酸月桂酯、乙醯乙酸硬脂醯酯等β-酮酯，或者乙醯丙酮、2,4-己二酮、苯甲醯丙酮等β-二酮。在以聚異氰酸酯化合物為交聯劑的黏著劑組合物中，這些交聯延遲劑對交聯劑所具有的異氰酸酯基進行封端(block)，由此能夠抑制黏著劑組合物在摻合交聯劑後的過度的黏度上升或凝膠化，能夠延長黏著劑組合物的貯存期。相對於100重量份的所述丙烯酸類聚合物，優選以0.1~300重量份的比例含有(E)交聯延遲劑。The adhesive composition of this embodiment may contain (E) a crosslinking retardant. (E) The crosslinking retardant is preferably a compound of a keto-enol tautomer, and specific examples include methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, and oil acetoacetate. β-ketoesters such as oleyl acetoacetate, lauryl acetoacetate, stearyl acetoacetate, or β-diketones such as acetoacetone, 2,4-hexanedione, and benzoylacetone. In adhesive compositions using polyisocyanate compounds as cross-linking agents, these cross-linking retarder blocks the isocyanate groups of the cross-linking agent, thereby inhibiting the mixing and cross-linking of the adhesive composition. Excessive viscosity rise or gelation after application can extend the storage life of the adhesive composition. The crosslinking retardant (E) is preferably contained in a proportion of 0.1 to 300 parts by weight relative to 100 parts by weight of the acrylic polymer.

本實施方式的黏著劑組合物也可含有錫化合物以外的交聯催化劑作為(F)交聯催化劑。作為錫化合物以外的交聯催化劑，可列舉出第三級胺等胺類化合物、錫螯合物以外的金屬螯合化合物。 作為第三級胺，可列舉出三烷基胺、N,N,N’,N’-四烷基二胺、N,N-二烷基胺基醇、三乙烯二胺、嗎啉衍生物、呱嗪衍生物等。 (F)交聯催化劑優選為選自由鋁螯合化合物、鈦螯合化合物、鐵螯合化合物組成的群組中的至少一種以上的金屬螯合化合物。作為金屬螯合化合物的具體例，可列舉出三(2,4-戊二酮)鐵(III)、三乙醯丙酮鐵、三乙醯丙酮鈦、三乙醯丙酮鋁、三(2,4-己二酮)鐵(III)、三(2,4-己二酮)鈦、三(2,4-己二酮)鋁等。 相對於100重量份的所述丙烯酸類聚合物，優選以0.001~0.5重量份的比例含有所述(F)交聯催化劑。The adhesive composition of this embodiment may contain a crosslinking catalyst other than a tin compound as (F) a crosslinking catalyst. Examples of crosslinking catalysts other than tin compounds include amine compounds such as tertiary amines and metal chelate compounds other than tin chelates. Examples of the tertiary amine include trialkylamine, N,N,N',N'-tetraalkyldiamine, N,N-dialkylaminoalcohol, triethylenediamine, and morpholine derivatives. , guazine derivatives, etc. (F) The crosslinking catalyst is preferably at least one metal chelate compound selected from the group consisting of aluminum chelate compounds, titanium chelate compounds, and iron chelate compounds. Specific examples of the metal chelate compound include tris(2,4-pentanedione)iron(III), iron triacetylacetonate, titanium triacetylacetonate, aluminum triacetylacetonate, and tris(2,4-pentanedione). -Hexanedione) iron(III), tris(2,4-hexanedione)titanium, tris(2,4-hexanedione)aluminum, etc. The (F) crosslinking catalyst is preferably contained in a proportion of 0.001 to 0.5 parts by weight relative to 100 parts by weight of the acrylic polymer.

由於(E)交聯延遲劑與(F)交聯催化劑相反，具有抑制交聯的效果，因此優選適當地設定(E)交聯延遲劑與(F)交聯催化劑的比例。為了延長黏著劑組合物的貯存期，提高貯存穩定性，(E)/(F)的重量份比優選為80~1000，更優選為80~700，特別優選為80~300。此處，(E)/(F)的重量份比為用(E)的重量份除以(F)的重量份而計算得到的商的值。Since the (E) cross-linking retarder has the effect of inhibiting cross-linking opposite to the (F) cross-linking catalyst, it is preferable to appropriately set the ratio of the (E) cross-linking retardant to the (F) cross-linking catalyst. In order to extend the storage period of the adhesive composition and improve the storage stability, the weight part ratio of (E)/(F) is preferably 80 to 1000, more preferably 80 to 700, and particularly preferably 80 to 300. Here, the weight part ratio of (E)/(F) is the value of the quotient calculated by dividing the weight part of (E) by the weight part of (F).

本實施方式的黏著劑組合物含有經過無臭化純化的聚醚改質矽氧烷化合物作為聚醚改質矽氧烷化合物。相對於100重量份的所述丙烯酸類聚合物，優選以0.01~1.0重量份的比例、更優選以0.01~0.8重量份的比例含有經過無臭化純化的聚醚改質矽氧烷化合物。藉由在黏著劑組合物中摻合經過無臭化純化的聚醚改質矽氧烷化合物，能夠改善黏著劑層的黏著力及抗污染性能。 進一步，本實施方式的、使用含有經過無臭化純化的聚醚改質矽氧烷化合物的黏著劑組合物而形成的黏著劑層，具有防止對被黏物表面的污染的優異的抗污染性能。The adhesive composition of this embodiment contains an odorless and purified polyether-modified siloxane compound as a polyether-modified siloxane compound. The polyether-modified siloxane compound that has been deodorized and purified is preferably contained in a proportion of 0.01 to 1.0 parts by weight, more preferably in a proportion of 0.01 to 0.8 parts by weight relative to 100 parts by weight of the acrylic polymer. By blending an odorless and purified polyether-modified siloxane compound into the adhesive composition, the adhesive force and anti-pollution performance of the adhesive layer can be improved. Furthermore, in this embodiment, the adhesive layer formed using an adhesive composition containing an odorless and purified polyether-modified siloxane compound has excellent anti-pollution properties to prevent contamination of the adherend surface.

聚醚改質矽氧烷化合物為具有聚醚基的矽氧烷化合物，除了具有通常的矽氧烷單元[-SiR1 2 -O-]以外，還具有含有聚醚基的矽氧烷單元[-SiR1 (R2 O(R3 O)n R4 )-O-]。此處，R1 表示一種或兩種以上的烷基或芳基，R2 及R3 表示一種或兩種以上的伸烷基，R4 表示一種或兩種以上的烷基或醯基等(末端基團)。作為聚醚基，可列舉出聚氧伸乙基[(C2 H4 O)n ]、聚氧伸丙基[(C3 H6 O)n ]等聚氧伸烷基。在具有聚醚基的矽氧烷單元中，聚醚基的末端也可以是OH基(上述通式中R4 =H)。The polyether modified siloxane compound is a siloxane compound having a polyether group. In addition to the usual siloxane unit [-SiR 1 2 -O-], it also has a siloxane unit containing a polyether group [ -SiR 1 (R 2 O(R 3 O) n R 4 )-O-]. Here, R 1 represents one or more alkyl groups or aryl groups, R 2 and R 3 represent one or more alkylene groups, R 4 represents one or more alkyl groups or acyl groups, etc. ( terminal group). Examples of polyether groups include polyoxyalkylene groups such as polyoxyethylene groups [(C 2 H 4 O) n ] and polyoxypropylene groups [(C 3 H 6 O) n ]. In the siloxane unit having a polyether group, the end of the polyether group may also be an OH group (R 4 =H in the above general formula).

聚醚改質矽氧烷化合物例如能夠藉由以下方式得到：藉由氫化矽烷化反應使具有不飽和鍵及聚氧伸烷基的有機化合物接枝於具有氫化矽基的聚有機矽氧烷的主鏈。具體而言，可列舉出二甲基矽氧烷-甲基(聚氧伸乙基)矽氧烷共聚物、二甲基矽氧烷-甲基(聚氧伸乙基)矽氧烷-甲基(聚氧伸丙基)矽氧烷共聚物、二甲基矽氧烷-甲基(聚氧伸丙基)矽氧烷聚合物等。The polyether-modified siloxane compound can be obtained, for example, by grafting an organic compound having an unsaturated bond and a polyoxyalkylene group onto a polyorganosiloxane having a hydrogenated siloxane group through a hydrosilylation reaction. main chain. Specific examples include dimethylsiloxane-methyl(polyoxyethylidene)siloxane copolymer, dimethylsiloxane-methyl(polyoxyethylidene)siloxane-methane (polyoxypropylene) siloxane copolymer, dimethylsiloxane-methyl (polyoxypropylene) siloxane polymer, etc.

本發明的特徵在於，使用去除副產物而成的經過無臭化純化的聚醚改質矽氧烷化合物。 作為該副產物，例如在氫化矽烷化反應中，使用烯丙基醚化聚氧化烯作為具有不飽和鍵及聚氧伸烷基的有機化合物時，有時因烯丙基的異構化而生成丙烯基醚化聚氧化烯。進一步，有時因丙烯基醚基的水解而生成丙醛或其縮合物(縮醛等)。因此，優選所述經過無臭化純化的聚醚改質矽氧烷化合物為去除作為副產物的丙烯基醚化聚氧化烯及/或醛縮合物而成的聚醚改質矽氧烷化合物。這些副產物可藉由酸分解、氫化等去除。藉由使用去除上述副產物而成的經過無臭化純化的聚醚改質矽氧烷化合物，能夠改善抗污染性能。本實施方式的黏著劑組合物藉由不含未經過無臭化純化的聚醚改質矽氧烷化合物，能夠製成不含上述副產物的黏著劑組合物。The present invention is characterized by using an odorless and purified polyether-modified siloxane compound obtained by removing by-products. As this by-product, for example, when allyl etherified polyoxyalkylene is used as an organic compound having an unsaturated bond and a polyoxyalkylene group in a hydrosilylation reaction, it may be produced due to isomerization of the allyl group. Propylene etherified polyoxyalkylene. Furthermore, propionaldehyde or its condensate (acetal, etc.) may be produced by hydrolysis of the allyl ether group. Therefore, it is preferable that the odorless-purified polyether-modified siloxane compound is a polyether-modified siloxane compound obtained by removing propenyl etherified polyoxyalkylene and/or aldehyde condensate as by-products. These by-products can be removed by acid decomposition, hydrogenation, etc. By using an odorless and purified polyether-modified siloxane compound obtained by removing the above-mentioned by-products, the anti-pollution performance can be improved. The adhesive composition of this embodiment does not contain a polyether-modified siloxane compound that has not been deodorized and purified, so that it can be made into an adhesive composition that does not contain the above-mentioned by-products.

聚醚改質矽氧烷化合物的HLB值優選為4~15的範圍。HLB值是指例如JIS K3211(界面活性劑術語)等中規定的親水親油平衡值(親油親水比)。此外，聚醚改質矽氧烷化合物的分子量，例如以重均分子量(Mw)計，優選為10000以下。從與丙烯酸類聚合物的相容性的角度出發，雖然HLB值低且分子量低時相容性更良好，但為分子量較低的聚醚改質矽氧烷化合物時，即使HLB值較高且與聚合物的相容性稍低，也能夠得到優異的抗靜電性能。The HLB value of the polyether-modified siloxane compound is preferably in the range of 4 to 15. The HLB value refers to the hydrophilic-lipophilic balance value (lipophilic to hydrophilic ratio) specified in, for example, JIS K3211 (surfactant terminology). In addition, the molecular weight of the polyether-modified siloxane compound is preferably 10,000 or less in terms of weight average molecular weight (Mw), for example. From the perspective of compatibility with acrylic polymers, although the compatibility is better when the HLB value is low and the molecular weight is low, when it is a polyether-modified siloxane compound with a low molecular weight, even if the HLB value is high and Even with slightly lower compatibility with polymers, excellent antistatic properties can be obtained.

不限於上述添加劑，本實施方式的黏著劑組合物中還可適當地摻合有界面活性劑、固化促進劑、增塑劑、填充劑、固化延遲劑、加工助劑、抗老化劑、抗氧化劑等公知的添加劑。這些添加劑可單獨使用或者同時使用兩種以上。Not limited to the above-mentioned additives, the adhesive composition of this embodiment may also be appropriately blended with surfactants, curing accelerators, plasticizers, fillers, curing retardants, processing aids, anti-aging agents, and antioxidants. well-known additives. These additives may be used alone or two or more types may be used in combination.

本實施方式的黏著劑組合物適合作為貼合於偏振片的表面基材(例如，偏光鏡的保護層)的表面保護膜用的黏著劑組合物。此處，作為偏振片的偏光鏡的保護層，可列舉出選自由TAC類膜、PMMA類膜、PET類膜組成的群組中的一種。此處，TAC為三醋酸纖維素的簡稱，PMMA為聚甲基丙烯酸甲酯的簡稱，PET為聚對苯二甲酸乙二醇酯的簡稱。 此外，對偏振片的偏光鏡的保護層的表面實施的表面處理可以為選自由未處理、AG處理、LR處理、AR處理、AG-LR處理、AG-AR處理組成的群組中的一種。此處，AG是指防眩(Anti Glare)，LR是指低反射(Low Reflection)，AR是指抗反射(Anti Reflection)。The adhesive composition of this embodiment is suitable as an adhesive composition for a surface protective film bonded to a surface base material of a polarizing plate (for example, a protective layer of a polarizer). Here, the protective layer of the polarizer of the polarizing plate may be one selected from the group consisting of TAC-based films, PMMA-based films, and PET-based films. Here, TAC is the abbreviation of cellulose triacetate, PMMA is the abbreviation of polymethyl methacrylate, and PET is the abbreviation of polyethylene terephthalate. In addition, the surface treatment performed on the surface of the protective layer of the polarizer of the polarizer may be one selected from the group consisting of untreated, AG treated, LR treated, AR treated, AG-LR treated, and AG-AR treated. Here, AG refers to anti-glare (Anti Glare), LR refers to low reflection (Low Reflection), and AR refers to anti-reflection (Anti Reflection).

將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1.0×10＋ 12 Ω/□以下，更優選為5.0×10＋ 11 Ω/□以下，特別優選為1.0×10＋ 11 Ω/□以下。若表面電阻率大，則釋放從被黏物上剝離黏著劑層時所產生的靜電的性能差。因此，藉由充分地減小表面電阻率，能夠降低伴隨從被黏物上剝離黏著劑層時所產生的靜電而產生的剝離靜電電壓，抑制對被黏物的影響。The surface resistivity of the adhesive layer obtained by cross-linking the adhesive composition of the present embodiment is preferably 1.0×10 + 12 Ω/□ or less, more preferably 5.0×10 + 11 Ω/□ or less, and particularly preferably 1.0 ×10 + 11 Ω/□ or less. If the surface resistivity is high, the performance of releasing static electricity generated when peeling off the adhesive layer from the adherend is poor. Therefore, by sufficiently reducing the surface resistivity, the peeling electrostatic voltage caused by the static electricity generated when peeling off the adhesive layer from the adherend can be reduced, thereby suppressing the influence on the adherend.

將本實施方式的黏著劑組合物交聯而成的黏著劑層，優選黏著劑層對使用含有氟化合物的低折射率層形成用的組合物而形成的低折射率層的剝離靜電電壓在+0.3~-0.3kV的範圍內。作為用於低折射率層形成用的組合物的氟化合物，可列舉出作為氟化烯烴類、氟化乙烯基醚類、(甲基)丙烯酸氟化烷基酯等中的一種或兩種以上的聚合物的含氟共聚物、含氟化烷基的矽烷化合物等縮合物。含氟共聚物除了經過氟化的單體以外，還可以共聚有烯烴類、乙烯基醚類、(甲基)丙烯酸酯等未被氟化的單體。低折射率層也可與高折射率層等進行組合而構成抗反射層。形成低折射率層的基材例如可列舉出選自三醋酸纖維素(TAC)、聚甲基丙烯酸甲酯(PMMA)、聚對苯二甲酸乙二醇酯(PET)等中的至少一種以上。黏著劑層對以PMMA為基材的低折射率層的剝離靜電電壓優選在+0.3~-0.3kV的範圍內。The adhesive layer formed by cross-linking the adhesive composition of the present embodiment preferably has a peeling electrostatic voltage of + Within the range of 0.3~-0.3kV. Examples of the fluorine compound used in the composition for forming a low refractive index layer include one or more of fluorinated olefins, fluorinated vinyl ethers, fluorinated alkyl (meth)acrylate, and the like. Condensates of polymers such as fluorinated copolymers and silane compounds containing fluorinated alkyl groups. In addition to fluorinated monomers, the fluorinated copolymer can also be copolymerized with unfluorinated monomers such as olefins, vinyl ethers, and (meth)acrylates. The low refractive index layer can also be combined with a high refractive index layer to form an anti-reflective layer. Examples of the base material forming the low refractive index layer include at least one selected from the group consisting of triacetylcellulose (TAC), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), and the like. . The peeling electrostatic voltage of the adhesive layer to the low refractive index layer based on PMMA is preferably in the range of +0.3~-0.3kV.

優選：將由本實施方式的黏著劑組合物交聯而成的黏著劑層貼合於被黏物後，在溫度60℃、濕度90%RH的氣氛下放置2天(48hr)，在從所述氣氛下取出並經過1天後，將所述黏著劑層從所述被黏物上剝離時無污染性。作為被黏物，可列舉出PMMA基材、TAC基材等表面基材，或者使用含有氟化合物的低折射率層形成用的組合物在其表面上形成的低折射率層，或者具有這些表面基材或低折射率層的偏振片等。Preferably: after the adhesive layer cross-linked by the adhesive composition of this embodiment is attached to the adherend, it is left for 2 days (48 hours) in an atmosphere with a temperature of 60°C and a humidity of 90% RH. After taking it out in the atmosphere for 1 day, the adhesive layer has no contamination when peeled off from the adherend. Examples of adherends include surface substrates such as PMMA substrates and TAC substrates, or low refractive index layers formed on their surfaces using a low refractive index layer-forming composition containing a fluorine compound, or having these surfaces. Polarizer of base material or low refractive index layer, etc.

將本實施方式的黏著劑組合物交聯而成的黏著劑層對被黏物的黏著力，優選在低速的剝離速度0.3m/min下的黏著力為0.04~0.2N/25mm，在高速的剝離速度30m/min下的黏著力為2.0N/25mm以下，更優選後者的黏著力為0.2~1.6N/25mm。由此，可得到黏著力起因於剝離速度的變化為小的性能，即使藉由高速剝離也能夠快速地進行剝離。此外，即使為了重新貼合而暫時將表面保護膜從被黏物上剝離時，也不需要過大的力，易於從被黏物上剝離。作為被黏物，可列舉出PMMA基材、TAC基材等表面基材，或者使用含有氟化合物的低折射率層形成用的組合物在其表面上形成的低折射率層，或者具有這些表面基材或低折射率層的偏振片，例如實施了低反射(LR)表面處理的偏振片、實施了AG-LR處理的偏振片等。The adhesive force of the adhesive layer formed by cross-linking the adhesive composition of this embodiment to the adherend is preferably 0.04~0.2N/25mm at a low peeling speed of 0.3m/min. The adhesive force at a peeling speed of 30m/min is 2.0N/25mm or less, and the latter is more preferably 0.2~1.6N/25mm. Thus, it is possible to obtain a performance in which the change in the adhesive force caused by the peeling speed is small, and the peeling can be performed quickly even by high-speed peeling. In addition, even when the surface protective film is temporarily peeled off from the adherend for re-adhesion, it does not require excessive force and is easily peeled off from the adherend. Examples of adherends include surface substrates such as PMMA substrates and TAC substrates, or low refractive index layers formed on their surfaces using a low refractive index layer-forming composition containing a fluorine compound, or having these surfaces. The polarizing plate of the base material or low refractive index layer may be, for example, a polarizing plate subjected to low reflection (LR) surface treatment, a polarizing plate subjected to AG-LR treatment, or the like.

將本實施方式的黏著劑組合物交聯而成的黏著劑層的凝膠分率優選為95~100%，更優選為97~100%。由於黏著劑層的凝膠分率如此地高，因此在低速的剝離速度下，黏著力不會變得過大。此外，能夠有助於降低未聚合單體或低聚物從黏著劑組合物所含有的共聚物中的溶出量，改善高溫·高濕度下的耐久性，抑制被黏物的污染。The gel fraction of the adhesive layer formed by cross-linking the adhesive composition of this embodiment is preferably 95 to 100%, and more preferably 97 to 100%. Since the gel fraction of the adhesive layer is so high, the adhesive force will not become too large at low peeling speeds. In addition, it can help reduce the amount of unpolymerized monomers or oligomers eluted from the copolymer contained in the adhesive composition, improve durability under high temperature and high humidity, and suppress contamination of adherends.

本實施方式的黏著膜為在樹脂膜的單面或兩面上形成將本實施方式的黏著劑組合物交聯而成的黏著劑層而成。此外，本實施方式的表面保護膜為在樹脂膜的單面上形成所述黏著劑層而成的表面保護膜。本實施方式的黏著劑組合物具備優異的抗靜電性能，在低速的剝離速度及高速的剝離速度下，黏著力的平衡優異，進一步具有優異的抗污染性能。因此，能夠適宜地用於偏振片的表面保護膜的用途。The adhesive film of this embodiment is formed by forming an adhesive layer obtained by cross-linking the adhesive composition of this embodiment on one side or both sides of a resin film. In addition, the surface protective film of this embodiment is a surface protective film in which the adhesive layer is formed on one side of a resin film. The adhesive composition of this embodiment has excellent antistatic properties, has an excellent balance of adhesive force at low peeling speeds and high peeling speeds, and further has excellent anti-pollution properties. Therefore, it can be suitably used as a surface protective film of a polarizing plate.

作為黏著劑層的基材膜或保護黏著面的離型膜(隔離膜)，能夠使用聚酯膜等的樹脂膜等。 可對樹脂膜的、與形成有所述黏著劑層側為相反面的單面進行抗靜電處理及防污處理。作為抗靜電處理，可列舉出抗靜電劑的塗布或捏合等。作為防污處理，可列舉出利用聚矽氧類、氟類的離型劑或塗布劑、二氧化矽微粒等的處理。也可利用聚矽氧類、氟類、長鏈烷基類的離型劑等，對離型膜的、與黏著劑層的黏著面貼合的一側的面實施離型處理。As the base film of the adhesive layer or the release film (isolation film) that protects the adhesive surface, a resin film such as a polyester film or the like can be used. The single side of the resin film opposite to the side on which the adhesive layer is formed may be subjected to antistatic treatment and antifouling treatment. Examples of the antistatic treatment include application of an antistatic agent, kneading, and the like. Examples of the antifouling treatment include treatment using silicone-based, fluorine-based release agents or coating agents, silica fine particles, and the like. You can also use polysilicone-based, fluorine-based, long-chain alkyl-based release agents, etc. to perform release treatment on the side of the release film that is in contact with the adhesive surface of the adhesive layer.

此外，藉由將使本實施方式的黏著劑組合物交聯而成的黏著劑層積層於光學膜的至少一側的面上，能夠得到附黏著劑層的光學膜。作為光學膜，可列舉出偏振膜、相位差膜、抗反射膜、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設備，可列舉出液晶面板、有機EL面板、觸控面板等。 在為偏振片用的表面保護膜等光學用的表面保護膜及黏著膜的情況下，優選基材膜及黏著劑層具有充分的透明性。 實施例Furthermore, by laminating an adhesive layer obtained by crosslinking the adhesive composition of the present embodiment on at least one surface of the optical film, an optical film with an adhesive layer can be obtained. Examples of optical films include polarizing films, retardation films, anti-reflection films, anti-glare films, ultraviolet absorbing films, infrared absorbing films, optical compensation films, brightness improvement films, and the like. Examples of equipment to which optical members are applied include liquid crystal panels, organic EL panels, touch panels, and the like. In the case of an optical surface protective film and an adhesive film such as a surface protective film for polarizing plates, it is preferable that the base film and the adhesive layer have sufficient transparency. Example

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

＜丙烯酸類聚合物的製備＞ [實施例1] 向具備攪拌機、溫度計、回流冷凝器及氮氣導入管的反應裝置中導入氮氣，用氮氣對反應裝置內的空氣進行置換。然後，向反應裝置中添加100重量份的丙烯酸2-乙基己酯、4.0重量份的丙烯酸8-羥基辛酯、0.1重量份的丙烯酸，同時添加溶劑(乙酸乙酯)。然後，經2小時滴加0.1重量份的作為聚合起始劑的偶氮二異丁腈，以65℃反應6小時，得到用於實施例1的丙烯酸類聚合物。 [實施例2~6及比較例1~3] 除了將單體的組成分別調整為如表1的(A)~(C)所記載的以外，以與上述的用於實施例1的丙烯酸類聚合物溶液相同的方式，得到用於實施例2~6及比較例1~3的丙烯酸類聚合物溶液。 將實施例1~6及比較例1~3的丙烯酸類聚合物的重均分子量(Mw)記載於表2。＜Preparation of acrylic polymer＞ [Example 1] Nitrogen gas was introduced into a reaction device equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction pipe, and the air in the reaction device was replaced with nitrogen gas. Then, 100 parts by weight of 2-ethylhexyl acrylate, 4.0 parts by weight of 8-hydroxyoctyl acrylate, and 0.1 parts by weight of acrylic acid were added to the reaction device, and a solvent (ethyl acetate) was added at the same time. Then, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours, and the reaction was carried out at 65° C. for 6 hours, thereby obtaining the acrylic polymer used in Example 1. [Examples 2 to 6 and Comparative Examples 1 to 3] The acrylic polymer solution used in Example 2 was obtained in the same manner as the above-mentioned acrylic polymer solution used in Example 1, except that the compositions of the monomers were adjusted to those described in (A) to (C) of Table 1. ~6 and the acrylic polymer solutions of Comparative Examples 1 to 3. The weight average molecular weight (Mw) of the acrylic polymers of Examples 1 to 6 and Comparative Examples 1 to 3 is shown in Table 2.

＜黏著劑組合物及表面保護膜的製備＞ [實施例1] 向如上所述製備的實施例1的丙烯酸類聚合物溶液中添加2.0重量份的交聯劑(CORONATE HX)、9.0重量份的交聯延遲劑(乙醯丙酮)、0.1重量份的交聯催化劑(三乙醯丙酮鈦)、0.9重量份的抗靜電劑(4-甲基-1-辛基吡啶鎓 六氟磷酸鹽)、0.05重量份的經過無臭化純化的聚醚改質矽氧烷化合物(KF-6017P(無臭化型)、HLB值=5)，進行攪拌混合，得到實施例1的黏著劑組合物。將該黏著劑組合物塗布在離型膜(塗布有聚矽氧樹脂的PET膜)上後，藉由以90℃進行乾燥從而去除溶劑，得到厚度為20μm的黏著劑層。然後，將帶離型膜的黏著劑層轉印至基材膜(一側的面經過抗靜電及防污處理的PET膜)的、與經過抗靜電及防污處理的面為相反的面上，得到具有「基材膜/黏著劑層/離型膜」的積層結構的實施例1的表面保護膜。 [實施例2~6及比較例1~3] 除了將添加劑的組成分別調整為如表1的(D)~(H)所記載的以外，以與上述實施例1的表面保護膜相同的方式，得到實施例2~6及比較例1~3的表面保護膜。＜Preparation of adhesive composition and surface protective film＞ [Example 1] To the acrylic polymer solution of Example 1 prepared as described above, 2.0 parts by weight of the cross-linking agent (CORONATE HX), 9.0 parts by weight of the cross-linking retardant (acetyl acetone), and 0.1 parts by weight of the cross-linking catalyst were added. (Titanium triacetyl acetonate), 0.9 parts by weight of antistatic agent (4-methyl-1-octylpyridinium hexafluorophosphate), 0.05 parts by weight of odorless and purified polyether modified siloxane compound (KF-6017P (odorless type), HLB value = 5), stir and mix to obtain the adhesive composition of Example 1. After the adhesive composition was coated on a release film (PET film coated with polysiloxane resin), the solvent was removed by drying at 90° C. to obtain an adhesive layer with a thickness of 20 μm. Then, transfer the adhesive layer with the release film to the surface of the base film (a PET film with antistatic and antifouling treatment on one side) opposite to the antistatic and antifouling surface. , the surface protective film of Example 1 having a laminated structure of "base film/adhesive layer/release film" was obtained. [Examples 2 to 6 and Comparative Examples 1 to 3] Examples 2 to 6 and Comparative Examples 1 to 3 were obtained in the same manner as the surface protective film of Example 1, except that the compositions of the additives were adjusted to be as described in (D) to (H) of Table 1. surface protective film.

[表1]   (A) (B) (C) (D) (E) (F) (G) (H) 實施例1 2EHA 100 8HOA 4.0 AAc 0.1 HX 2.0 (1.92) AA 9 (8.65) TI 0.1 (0.10) G-1 0.9 (0.86) H-1 0.05 (0.05) 實施例2 2EHA 90 IOA 10 6HHA 3.5 CEA 0.1 HL 2.5 (2.41) AA 8.5 (8.20) FE 0.05 (0.05) G-2 1.0 (0.97) H-2 0.1 (0.10) 實施例3 2EHA 90 BA 10 4HBA 2.0 HEAA 0.5 CPA 0.2 D-140N 1.8 (1.75) AA 6.0 (5.84) TI 0.03 (0.03) G-3 1.0 (0.97) H-3 0.09 (0.09) 實施例4 2EHA 100 4HBA 1.5 HEA 2.5 C-1 0.3 HX 2.0 (1.92) AA 5.0 (4.79) TI 0.04 (0.04) G-4 0.9 (0.86) H-4 0.12 (0.12) 實施例5 2EHA 90 MA 10 6HHA 3.0 C-2 0.3 HL 2.0 (1.94) AA 6.5 (6.29) FE 0.05 (0.05) G-1 0.2 (0.19) G-4 0.5 (0.48) H-1 0.1 (0.10) 實施例6 2EHA 100 6HHA 0.5 4HBA 3.0 C-2 0.3 HX 2.5 (2.41) ETAC 5.5 (5.30) FE 0.05 (0.05) AL 0.01 (0.01) G-5 1.2 (1.16) H-2 0.08 (0.08) 比較例1 2EHA 100 8HOA 4.0 AAc 0.1 HX 2.0 (1.92) AA 9 (8.65) TI 0.1 (0.10) G-1 0.9 (0.86) H-5 0.05 (0.05) 比較例2 2EHA 90 BA 10 4HBA 2.0 HEAA 0.5 CPA 0.2 D-140N 1.8 (1.75) AA 6.0 (5.84) TI 0.03 (0.03) G-3 1.0 (0.97) H-6 0.1 (0.10) 比較例3 2EHA 60 MA 40 4HBA 0.3 AAc 2.0 L 0.2 (0.20) AA 3.0 (2.93) AL 0.1 (0.10) G-6 0.8 (0.78) H-6 0.1 (0.10) [Table 1] (A) (B) (C) (D) (E) (F) (G) (H) Example 1 2EHA 100 8HOA 4.0 AAc 0.1 HX 2.0 (1.92) AA 9 (8.65) TI 0.1 (0.10) G-1 0.9 (0.86) H-1 0.05 (0.05) Example 2 2EHA 90 IOA 10 6HHA 3.5 CEA 0.1 HL 2.5 (2.41) AA 8.5 (8.20) FE 0.05 (0.05) G-2 1.0 (0.97) H-2 0.1 (0.10) Example 3 2EHA 90 BA 10 4HBA 2.0 HEAA 0.5 CPA 0.2 D-140N 1.8 (1.75) AA 6.0 (5.84) TI 0.03 (0.03) G-3 1.0 (0.97) H-3 0.09 (0.09) Example 4 2EHA 100 4HBA 1.5 HEA 2.5 C-1 0.3 HX 2.0 (1.92) AA 5.0 (4.79) TI 0.04 (0.04) G-4 0.9 (0.86) H-4 0.12 (0.12) Example 5 2EHA 90 MA 10 6HHA 3.0 C-2 0.3 HL 2.0 (1.94) AA 6.5 (6.29) FE 0.05 (0.05) G-1 0.2 (0.19) G-4 0.5 (0.48) H-1 0.1 (0.10) Example 6 2EHA 100 6HHA 0.5 4HBA 3.0 C-2 0.3 HX 2.5 (2.41) ETAC 5.5 (5.30) FE 0.05 (0.05) AL 0.01 (0.01) G-5 1.2 (1.16) H-2 0.08 (0.08) Comparative example 1 2EHA 100 8HOA 4.0 AAc 0.1 HX 2.0 (1.92) AA 9 (8.65) TI 0.1 (0.10) G-1 0.9 (0.86) H-5 0.05 (0.05) Comparative example 2 2EHA 90 BA 10 4HBA 2.0 HEAA 0.5 CPA 0.2 D-140N 1.8 (1.75) AA 6.0 (5.84) TI 0.03 (0.03) G-3 1.0 (0.97) H-6 0.1 (0.10) Comparative example 3 2EHA 60 MA 40 4HBA 0.3 AAC 2.0 L 0.2 (0.20) AA 3.0 (2.93) AL 0.1 (0.10) G-6 0.8 (0.78) H-6 0.1 (0.10)

[表2]   丙烯酸類聚合物的Mw 實施例1 40萬 實施例2 50萬 實施例3 45萬 實施例4 48萬 實施例5 60萬 實施例6 40萬 比較例1 25萬 比較例2 20萬 比較例3 120萬 [Table 2] Mw of acrylic polymer Example 1 400,000 Example 2 500,000 Example 3 450,000 Example 4 480,000 Example 5 600,000 Example 6 400,000 Comparative example 1 250,000 Comparative example 2 200,000 Comparative example 3 1.2 million

在表1中，將(A)的合計設為100重量份來求出各成分的重量份。此外，在(D)~(H)各欄中，以括弧( )內的數值表示將丙烯酸類聚合物設為100重量份而求得的各成分的重量份。 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3。另外，CORONATE(註冊商標) HX、CORONATE HL及CORONATE L為TOSOH CORPORATION的商品名稱，TAKENATE(註冊商標) D-140N為Mitsui Chemicals, Inc.的商品名稱。 表3的G-1~G-5是熔點為25~50℃的離子化合物(常溫下為固體)，G-6為熔點超過50℃的離子化合物(常溫下為固體)。 在表3的(H)欄中同時記載了HLB值與商品名稱。H-1及H-3~H-6為Shin-Etsu Chemical Co., Ltd.的商品名稱，H-2為Dow Corning Toray Co., Ltd.的商品名稱。H-1~H-4的重均分子量(Mw)均為1萬以下，H-5的Mw為2萬，H-6的Mw為3萬。In Table 1, the weight part of each component was calculated|required, assuming that the total of (A) was 100 weight part. In addition, in each column (D) to (H), the numerical value in parentheses ( ) represents the weight part of each component obtained by assuming that the acrylic polymer is 100 parts by weight. In addition, the compound names of the abbreviations of each component used in Table 1 are shown in Table 3. In addition, CORONATE (registered trademark) HX, CORONATE HL and CORONATE L are trade names of TOSOH CORPORATION, and TAKENATE (registered trademark) D-140N is a trade name of Mitsui Chemicals, Inc. G-1 to G-5 in Table 3 are ionic compounds with a melting point of 25 to 50°C (solid at room temperature), and G-6 is an ionic compound with a melting point exceeding 50°C (solid at room temperature). In column (H) of Table 3, the HLB value and the product name are both described. H-1 and H-3~H-6 are the trade names of Shin-Etsu Chemical Co., Ltd., and H-2 is the trade name of Dow Corning Toray Co., Ltd. The weight average molecular weights (Mw) of H-1 to H-4 are all below 10,000, the Mw of H-5 is 20,000, and the Mw of H-6 is 30,000.

[表3] 組 縮寫符號 化合物名稱 (A)組 MA 丙烯酸甲酯 2EHA 丙烯酸2-乙基己酯 IOA 丙烯酸異辛酯 BA 丙烯酸丁酯 (B)組 8HOA 丙烯酸8-羥基辛酯 6HHA 丙烯酸6-羥基己酯 4HBA 丙烯酸4-羥基丁酯 HEA 丙烯酸2-羥基乙酯 HEAA N-羥乙基丙烯醯胺 (C)組 AAc 丙烯酸 CEA 羧乙基丙烯酸酯 CPA 羧戊基丙烯酸酯 C-1 2-甲基丙烯醯氧基乙基馬來酸 C-2 丙烯醯氧基乙基琥珀酸 (D)組 HX CORONATE HX：HDI異氰脲酸酯體 HL CORONATE HL：HDI加成物 D-140N TAKENATE D-140N：IPDI加成物 L CORONATE L：TDI加成物 (E)組 AA 乙醯丙酮 ETAC 乙醯乙酸乙酯 (F)組 TI 鈦螯合物：三乙醯丙酮鈦 FE 鐵螯合物：三(2,4-戊二酮)鐵(III) AL 鋁螯合物 (G)組 G-1 4-甲基-1-辛基吡啶鎓 六氟磷酸鹽 G-2 1-甲基-3-丙基咪唑鎓 六氟磷酸鹽 G-3 4-甲基-1-辛基吡啶鎓 五氟苯磺酸鹽 G-4 3-甲基-1-辛基吡啶鎓 九氟丁烷磺酸鹽 G-5 N,N,N-三辛基-N-苄基溴化銨 G-6 乙基吡啶鎓 六氟磷酸鹽 (H)組 H-1 HLB=5 KF-6017P(無臭化型) H-2 HLB=12 SS2804(無臭化型) H-3 HLB=7 KF-6012P(無臭化型) H-4 HLB=12 KF-6011P(無臭化型) H-5 HLB=16 KF-354L(通常型) H-6 HLB=7 KF-352A(通常型) [table 3] group abbreviation symbol Compound name (A)Group MA Methyl acrylate 2EHA 2-ethylhexyl acrylate IOA Isooctyl acrylate BA Butyl acrylate (B)Group 8HOA 8-hydroxyoctyl acrylate 6HHA 6-hydroxyhexyl acrylate 4HBA 4-hydroxybutyl acrylate HEA 2-hydroxyethyl acrylate HEAA N-Hydroxyethylacrylamide (C)Group AAC acrylic acid CEA Carboxyethyl acrylate CPA carboxypentyl acrylate C-1 2-Methacrylyloxyethylmaleic acid C-2 Acryloxyethylsuccinic acid (D)Group HX CORONATE HX: HDI isocyanurate body HL CORONATE HL: HDI adduct D-140N TAKENATE D-140N: IPDI adduct L CORONATE L: TDI adduct (E)Group AA Acetyl acetone ETAC Acetoethyl acetate (F)Group TI Titanium chelate: titanium triacetyl acetonate FE Iron Chelate: Tris(2,4-pentanedione)iron(III) AL Aluminum chelate (G)Group G-1 4-Methyl-1-octylpyridinium hexafluorophosphate G-2 1-Methyl-3-propylimidazolium hexafluorophosphate G-3 4-Methyl-1-octylpyridinium pentafluorobenzenesulfonate G-4 3-Methyl-1-octylpyridinium nonafluorobutanesulfonate G-5 N,N,N-Trioctyl-N-benzylammonium bromide G-6 Ethylpyridinium hexafluorophosphate (H)Group H-1 HLB=5 KF-6017P (odorless type) H-2 HLB=12 SS2804 (odorless type) H-3 HLB=7 KF-6012P (odorless type) H-4 HLB=12 KF-6011P (odorless type) H-5 HLB=16 KF-354L (normal type) H-6 HLB=7 KF-352A (normal type)

＜試驗方法及評價＞ 在溫度23℃、濕度50%RH的氣氛下分別對實施例1~6及比較例1~3中的表面保護膜進行7天熟化，然後藉由以下的試驗方法進行評價。＜Test methods and evaluation＞ The surface protective films in Examples 1 to 6 and Comparative Examples 1 to 3 were aged for 7 days in an atmosphere of 23°C and 50% RH, respectively, and then evaluated by the following test method.

＜黏著力的試驗方法＞ 剝離離型膜，將露出了黏著劑層的表面保護膜經由黏著劑層貼合在偏振片的表面上，放置1天後，以50℃、5個大氣壓進行20分鐘壓熱處理，進一步在室溫下放置12小時，然後將其作為黏著力的測定試樣。使用拉伸試驗機，在低速度(0.3m/min)或高速度(30m/min)下沿180°方向剝離得到的測定試樣，將測定的剝離強度作為黏著力。＜Test method for adhesion＞ Peel off the release film, and stick the surface protective film with the adhesive layer exposed on the surface of the polarizer through the adhesive layer. After leaving it for 1 day, perform autoclave treatment at 50°C and 5 atmospheres for 20 minutes, and further heat it at room temperature. Leave it for 12 hours, and then use it as a sample for measuring adhesion. Use a tensile testing machine to peel the test sample in the 180° direction at low speed (0.3m/min) or high speed (30m/min), and use the measured peel strength as the adhesive force.

＜表面電阻率的試驗方法＞ 在對表面保護膜進行熟化後、貼合於偏振片之前，剝離離型膜，露出黏著劑層，使用電阻率儀HIRESTA UP-HT450(Mitsubishi Chemical Analytech Co., Ltd.製造)，測定黏著劑層的表面電阻率。＜Test method for surface resistivity＞ After curing the surface protective film and before laminating it to the polarizing plate, peel off the release film to expose the adhesive layer, and measure the adhesive layer using a resistivity meter HIRESTA UP-HT450 (manufactured by Mitsubishi Chemical Analytech Co., Ltd.). surface resistivity.

＜剝離靜電電壓的試驗方法＞ 剝離離型膜，將露出了黏著劑層的表面保護膜貼合在偏振片上，該偏振片在被黏面上具有使用含有氟化合物的低折射率層形成用的組合物而形成的低折射率層。在以30m/min的拉伸速度對表面保護膜進行180°剝離時，使用高精度靜電感測器SK-035、SK-200(KEYENCE CORPORATION製造)，測定被黏物帶電而產生的電壓(靜電電壓)，將測定值的最大值作為剝離靜電電壓。<Test method for peeling electrostatic voltage> The release film is peeled off, and the surface protective film with the adhesive layer exposed is bonded to a polarizing plate having a low refractive index on the adhered surface using a composition for forming a low refractive index layer containing a fluorine compound. layer. When the surface protective film is peeled off 180° at a stretching speed of 30m/min, high-precision electrostatic sensors SK-035 and SK-200 (manufactured by KEYENCE CORPORATION) are used to measure the voltage (static electricity) generated by charging the adherend. voltage), and the maximum value of the measured value is regarded as the peeling electrostatic voltage.

＜抗污染性能的試驗方法＞ 使用貼合機，將實施了低反射(LR)表面處理的偏振片經由黏著劑層(雙面黏著膠帶)貼合在玻璃板的單面上。然後，使用貼合機，將表面保護膜貼合在所述偏振片的表面上。貼合於被黏物後，在溫度60℃、濕度90%RH的氣氛下放置2天(48hr)，從所述氣氛下取出並經過1天後，從被黏物上剝離表面保護膜，以目視觀察偏振片的表面的污染狀態。關於抗污染性能的判斷標準，將對所述偏振片的表面無污染的情況評價為「○」，將有輕微污染的情況評價為「△」，將有污染的情況評價為「×」。＜Test method for anti-pollution performance＞ Using a laminating machine, the polarizing plate that has been subjected to low-reflection (LR) surface treatment is bonded to one side of the glass plate through an adhesive layer (double-sided adhesive tape). Then, a surface protection film is bonded to the surface of the polarizing plate using a bonding machine. After being attached to the adherend, place it in an atmosphere with a temperature of 60°C and a humidity of 90% RH for 2 days (48 hours). After taking it out of the atmosphere for 1 day, peel off the surface protective film from the adherend. The contamination state of the surface of the polarizing plate was visually observed. Regarding the judgment criteria for the anti-pollution performance, the case where the surface of the polarizing plate is free of contamination is evaluated as "○", the case where there is slight contamination is evaluated as "△", and the case where there is contamination is evaluated as "×".

＜無臭性的試驗方法＞ 在抗污染性能的試驗中，在從被黏物上剝離表面保護膜時，嗅聞剝離的表面保護膜的黏著劑層的表面及偏振片的表面的氣味，評價臭味的程度。將剝離時沒有特殊臭味的情況評價為「○」，將有少許臭味的情況評價為「△」，將有特殊臭味的情況評價為「×」。 另外，關於作為聚醚改質矽氧烷化合物中所含有的雜質的、副產物的丙烯基醚化聚氧化烯及醛縮合物的含量，僅含有機器分析無法進行測定的程度的極微量。因此，作為判定是否為經過無臭化純化的聚醚改質矽氧烷化合物的方法，採用無臭性的試驗。＜Test method for odorless property＞ In the anti-fouling performance test, when the surface protective film is peeled off from the adherend, the odor of the surface of the adhesive layer of the peeled surface protective film and the surface of the polarizing plate is smelled to evaluate the degree of odor. The case where there was no special odor during peeling was evaluated as "○", the case where there was a slight odor was evaluated as "△", and the case where there was a special odor was evaluated as "×". In addition, the content of propenyl etherified polyoxyalkylene and aldehyde condensates, which are impurities contained in the polyether-modified siloxane compound and are by-products, are only extremely trace amounts that cannot be measured by mechanical analysis. Therefore, as a method to determine whether it is a polyether-modified siloxane compound that has been deodorized and purified, an odorless test is used.

針對實施例1~6及比較例1~3的表面保護膜，在表4中示出各種試驗的評價結果。「表面電阻率」藉由將「m×10＋ n 」記作「mE＋n」的方式 (其中，m為任意的實數值，n為正整數)進行記載。 在「抗污染性能」一欄中，顯示出在實施例1~6及比較例1~3的表面保護膜的性能試驗中使用的偏振片的表面基材的材質(PMMA)及表面處理(AG-LR)。Table 4 shows the evaluation results of various tests for the surface protective films of Examples 1 to 6 and Comparative Examples 1 to 3. "Surface resistivity" is described by writing "m×10 + n " as "mE + n" (where m is an arbitrary real value and n is a positive integer). In the "anti-pollution performance" column, the material (PMMA) and surface treatment (AG) of the surface substrate of the polarizer used in the performance tests of the surface protective films of Examples 1 to 6 and Comparative Examples 1 to 3 are shown. -LR).

[表4]   黏著力(N/25mm) 表面電阻率 (Ω/□) 剝離靜電電壓 (kV) 抗污染性能 無臭性   0.3m/min 30m/min PMMA AG-LR 實施例1 0.05 0.8 4.26E+10 0.2 ○ ○ 實施例2 0.05 0.5 5.34E+10 0.2 ○ ○ 實施例3 0.07 0.8 4.32E+10 0.1 ○ ○ 實施例4 0.05 0.5 6.12E+10 0.2 ○ ○ 實施例5 0.04 0.5 6.45E+10 0.1 ○ ○ 實施例6 0.05 0.7 6.52E+10 0.1 ○ ○ 比較例1 0.04 0.5 4.85E+11 0.4 × × 比較例2 0.06 0.6 2.46E+11 0.5 △ × 比較例3 6.8 18 6.82E+11 0.6 × × [Table 4] Adhesion (N/25mm) Surface resistivity (Ω/□) Stripping electrostatic voltage (kV) Anti-pollution properties Odorless 0.3m/min 30m/min PMMA AG-LR Example 1 0.05 0.8 4.26E+10 0.2 ○ ○ Example 2 0.05 0.5 5.34E+10 0.2 ○ ○ Example 3 0.07 0.8 4.32E+10 0.1 ○ ○ Example 4 0.05 0.5 6.12E+10 0.2 ○ ○ Example 5 0.04 0.5 6.45E+10 0.1 ○ ○ Example 6 0.05 0.7 6.52E+10 0.1 ○ ○ Comparative example 1 0.04 0.5 4.85E+11 0.4 × × Comparative example 2 0.06 0.6 2.46E+11 0.5 △ × Comparative example 3 6.8 18 6.82E+11 0.6 × ×

實施例1~6的表面保護膜對為被黏物的偏振片的、在低速的剝離速度0.3m/min下的黏著力為0.04~0.2N/25mm，在高速的剝離速度30m/min下的黏著力為2.0N/25mm以下，黏著性能優異。 此外，實施例1~6的表面保護膜的黏著劑層的表面電阻率為1.0×10＋ 12 Ω/□以下，黏著劑層對使用含有氟化合物的低折射率層形成用的組合物而形成的低折射率層的被黏物的剝離靜電電壓在+0.3~-0.3kV的範圍內，抗靜電性能優異。 進一步，將實施例1~6的表面保護膜貼合於被黏物後，在溫度60℃、濕度90%RH的氣氛下放置2天，從所述氣氛下取出並經過1天後，將表面保護膜從被黏物上剝離時無污染性，抗污染性能也優異。 即，表4所示的評價結果證明了實施例1~6的表面保護膜能夠解決本發明的問題。The adhesion force of the surface protection films of Examples 1 to 6 to the polarizing plate as the adherend at a low peeling speed of 0.3m/min is 0.04~0.2N/25mm, and at a high peeling speed of 30m/min The adhesion force is below 2.0N/25mm, and the adhesion performance is excellent. In addition, the surface resistivity of the adhesive layer of the surface protective film of Examples 1 to 6 is 1.0×10 + 12 Ω/□ or less, and the adhesive layer is formed using a composition for forming a low refractive index layer containing a fluorine compound. The peeling electrostatic voltage of the adherend of the low refractive index layer is in the range of +0.3~-0.3kV, and the antistatic performance is excellent. Furthermore, after the surface protective films of Examples 1 to 6 were attached to the adherend, they were placed in an atmosphere with a temperature of 60° C. and a humidity of 90% RH for 2 days. After being taken out of the atmosphere for 1 day, the surface was removed. There is no contamination when the protective film is peeled off from the adherend, and the anti-contamination performance is also excellent. That is, the evaluation results shown in Table 4 prove that the surface protective films of Examples 1 to 6 can solve the problems of the present invention.

比較例1~3的表面保護膜可能由於在黏著劑組合物中摻合了未經過無臭化純化的聚醚改質矽氧烷化合物，因此抗靜電性能及對上述的被黏物的抗污染性能差。特別是實施例1與比較例1的丙烯酸類聚合物的組成比例相同，但含有經過無臭化純化的聚醚改質矽氧烷化合物的實施例1與含有未經過無臭化純化的聚醚改質矽氧烷化合物的比較例1在抗污染性能上產生了差異。進一步，比較例3的表面保護膜在低速的剝離速度0.3m/min下的黏著力及在高速的剝離速度30m/min下的黏著力均過高，因此黏著劑層的黏著性能也差。 如上所述，比較例1~3的表面保護膜未能解決本發明的問題。The surface protective films of Comparative Examples 1 to 3 may have poor antistatic properties and anti-pollution properties for the adherends mentioned above because the adhesive composition contains a polyether-modified siloxane compound that has not been deodorized and purified. Difference. In particular, the composition ratio of the acrylic polymer in Example 1 and Comparative Example 1 is the same, but Example 1 containing a polyether-modified siloxane compound that has been deodorized and purified is different from Example 1 containing a modified polyether compound that has not been deodorized. Comparative Example 1 of the siloxane compound produced a difference in anti-fouling performance. Furthermore, the adhesive force of the surface protective film of Comparative Example 3 was too high at a low peeling speed of 0.3 m/min and at a high peeling speed of 30 m/min, so the adhesive performance of the adhesive layer was also poor. As described above, the surface protective films of Comparative Examples 1 to 3 failed to solve the problems of the present invention.

無。without.

無。without.

無。without.

Claims (11)

一種黏著劑組合物，其含有以(甲基)丙烯酸烷基酯為主要成分的丙烯酸類聚合物、抗靜電劑、交聯劑及聚醚改質矽氧烷化合物，其特徵在於，所述丙烯酸類聚合物為由酸值為0.1~1.0、重均分子量超過30萬且為100萬以下的共聚物形成的丙烯酸類聚合物，所述共聚物為相對於合計為100重量份的(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體的至少一種以上，與合計為0.1~10重量份的(B)含有羥基的可共聚單體的至少一種以上與合計為0.01~0.5重量份的(C)含有羧基的可共聚單體的至少一種以上進行共聚而成，在合計為100重量份的所述(A)烷基的碳原子數為C1~C18的(甲基)丙烯酸酯單體的至少一種以上中，以60重量份以上的比例含有丙烯酸2-乙基己酯，所述丙烯酸類聚合物的玻璃轉變溫度為0℃以下，所述抗靜電劑為熔點為25~50℃的離子化合物，所述交聯劑為(D)三官能度以上的異氰酸酯化合物，所述聚醚改質矽氧烷化合物為去除了作為副產物的丙烯基醚化聚氧化烯和/或醛縮合物的、HLB值為4~15且重均分子量為10000以下的經過無臭化純化的聚醚改質矽氧烷化合物，相對於100重量份的所述丙烯酸類聚合物，以0.01~10重量份的比例含有所述抗靜電劑，以0.1~10重量份的比例含有所述交聯劑，以0.01~1.0重量份的比例含有所述經過無臭化純化的聚醚改質矽氧烷化合物。 An adhesive composition, which contains an acrylic polymer with (meth)acrylic acid alkyl ester as the main component, an antistatic agent, a cross-linking agent and a polyether modified siloxane compound, characterized in that the acrylic acid The polymer is an acrylic polymer formed from a copolymer with an acid value of 0.1 to 1.0 and a weight average molecular weight of more than 300,000 and less than 1,000,000, and the copolymer is an alkane (A) based on a total of 100 parts by weight. At least one or more (meth)acrylate monomers whose carbon atoms in the group are C1 to C18, and at least one or more (B) hydroxyl-containing copolymerizable monomers with a total of 0.1 to 10 parts by weight, and a total of 0.01 ~0.5 parts by weight of (C) at least one or more carboxyl group-containing copolymerizable monomers are copolymerized, and a total of 100 parts by weight of the (A) alkyl group has a carbon number of C1~C18 (methyl ) At least one acrylate monomer contains 2-ethylhexyl acrylate in a proportion of 60 parts by weight or more, the glass transition temperature of the acrylic polymer is 0°C or lower, and the antistatic agent has a melting point of Ionic compound at 25~50°C, the cross-linking agent is (D) an isocyanate compound with three or more functionalities, and the polyether-modified siloxane compound is a by-product of propylene etherified polyoxyalkylene and / Or an odorless and purified polyether-modified siloxane compound of an aldehyde condensate with an HLB value of 4 to 15 and a weight average molecular weight of less than 10,000, relative to 100 parts by weight of the acrylic polymer, 0.01 The antistatic agent is contained in a proportion of ~10 parts by weight, the cross-linking agent is contained in a proportion of 0.1-10 parts by weight, and the odorless and purified polyether modified silicone is contained in a proportion of 0.01-1.0 parts by weight. Alkane compounds. 如申請專利範圍第1項所述的黏著劑組合物，其中，所述黏著劑組合物進一步含有(E)交聯延遲劑與作為(F)交聯催化劑的錫化合物以外的交聯催化劑。 The adhesive composition according to claim 1, wherein the adhesive composition further contains (E) a cross-linking retardant and a cross-linking catalyst other than the tin compound as (F) the cross-linking catalyst. 如申請專利範圍第1或2項所述的黏著劑組合物，其中，所述離子化合物的陽離子為選自由吡啶鎓、咪唑鎓、鏻、鋶、吡咯啶鎓、 胍鎓、銨、異脲鎓、硫脲鎓、呱啶鎓、吡唑鎓、甲基碳正離子、鋰、嗎啉鎓組成的群組中的一種。 The adhesive composition as described in item 1 or 2 of the patent application, wherein the cation of the ionic compound is selected from the group consisting of pyridinium, imidazolium, phosphonium, sulfonium, pyrrolidinium, One of the group consisting of guanidium, ammonium, isouronium, thiouronium, pyridinium, pyrazolium, methylcarbocation, lithium, and morpholinium. 如申請專利範圍第1或2項所述的黏著劑組合物，其中，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1.0×10+12Ω/□以下，所述黏著劑層對使用含有氟化合物的低折射率層形成用的組合物而形成的低折射率層的剝離靜電電壓在+0.3~-0.3kV的範圍內，使所述黏著劑組合物交聯而成的黏著劑層對在表面基材上施加有所述低折射率層的偏振片的、在低速的剝離速度0.3m/min下的黏著力為0.04~0.2N/25mm，在高速的剝離速度30m/min下的黏著力為2.0N/25mm以下，將使所述黏著劑組合物交聯而成的黏著劑層貼合於在表面基材上施加有所述低折射率層的偏振片後，在溫度60℃、濕度90%RH的氣氛下放置2天，從所述氣氛下取出並經過1天後，將所述黏著劑層從所述偏振片上剝離時無污染性。 The adhesive composition according to claim 1 or 2, wherein the adhesive layer formed by cross-linking the adhesive composition has a surface resistivity of 1.0×10 +12 Ω/□ or less, so The peeling electrostatic voltage of the adhesive layer to the low refractive index layer formed using a low refractive index layer-forming composition containing a fluorine compound is in the range of +0.3 to -0.3 kV, and the adhesive composition is cross-linked The adhesive force of the resulting adhesive layer to the polarizing plate with the low refractive index layer applied to the surface base material at a low peeling speed of 0.3m/min is 0.04~0.2N/25mm, and at a high speed peeling The adhesive force at a speed of 30m/min is 2.0N/25mm or less, and the adhesive layer formed by cross-linking the adhesive composition is bonded to the polarizing plate with the low refractive index layer applied to the surface base material. Then, it was placed in an atmosphere with a temperature of 60° C. and a humidity of 90% RH for 2 days. After being taken out of the atmosphere for 1 day, the adhesive layer was peeled off from the polarizing plate without contamination. 如申請專利範圍第1或2項所述的黏著劑組合物，其中，所述(B)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，所述(C)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 adhesive composition as described in item 1 or 2 of the patent application, wherein the (B) hydroxyl-containing copolymerizable monomer is selected from the group consisting of 8-hydroxyoctyl (meth)acrylate, (meth)acrylic acid 6-hydroxyhexyl ester, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-hydroxy(meth)acrylamide, N-hydroxymethyl(meth)acrylamide At least one or more of the compound group consisting of amine and N-hydroxyethyl (meth)acrylamide, the (C) carboxyl-containing copolymerizable monomer is selected from (meth)acrylic acid, carboxyethyl ( Meth)acrylate, carboxypentyl(meth)acrylate, 2-(meth)acryloxyethylhexahydrophthalic acid, 2-(meth)acryloxypropylhexahydrophthalate Phthalic acid, 2-(meth)acryloxyethyl phthalic acid, 2-(meth)acryloxyethyl succinic acid, 2-(meth)acryloxyethylmale At least one of the compound group consisting of acid, carboxyl polycaprolactone mono(meth)acrylate, and 2-(meth)acryloxyethyltetrahydrophthalic acid. 如申請專利範圍第2項所述的黏著劑組合物，其中，所述(E)交聯延遲劑為酮-烯醇互變異構體的化合物，相對於100重量份的所述丙烯酸類聚合物，以0.1~300重量份的比例含有所述(E)交聯延遲劑，所述(F)交聯催化劑為選自由鋁螯合化合物、鈦螯合化合物、鐵螯合化合物組成的群組中的至少一種以上的金屬螯合化合物，相對於100重量份的所述丙烯酸類聚合物，以0.001~0.5重量份的比例含有所述(F)交聯催化劑，所述(E)/所述(F)的重量份比為80~1000。 The adhesive composition as described in item 2 of the patent application, wherein the (E) cross-linking retardant is a compound of keto-enol tautomer, relative to 100 parts by weight of the acrylic polymer , containing the (E) cross-linking retarder in a proportion of 0.1 to 300 parts by weight, and the (F) cross-linking catalyst is selected from the group consisting of aluminum chelate compounds, titanium chelate compounds, and iron chelate compounds At least one or more metal chelate compounds, containing the (F) cross-linking catalyst in a ratio of 0.001 to 0.5 parts by weight relative to 100 parts by weight of the acrylic polymer, the (E)/the ( The weight ratio of F) is 80~1000. 一種黏著膜，其特徵在於，在樹脂膜的單面上積層有使如申請專利範圍第1~6項中任一項所述的黏著劑組合物交聯而成的黏著劑層。 An adhesive film characterized in that an adhesive layer formed by cross-linking the adhesive composition described in any one of items 1 to 6 of the patent application is laminated on one side of a resin film. 一種表面保護膜，其使用了如申請專利範圍第7項所述的黏著膜。 A surface protection film using the adhesive film described in Item 7 of the patent application. 一種偏振片用的表面保護膜，其使用了如申請專利範圍第7項所述的黏著膜。 A surface protective film for polarizers using the adhesive film described in Item 7 of the patent application. 一種附黏著劑層的光學膜，其中，在光學膜的至少一側的面上積層有使如申請專利範圍第1~6項中任一項所述的黏著劑組合物交聯而成的黏著劑層。 An optical film with an adhesive layer, wherein an adhesive formed by cross-linking the adhesive composition described in any one of items 1 to 6 of the patent application is laminated on at least one side of the optical film. agent layer. 如申請專利範圍第7項所述的黏著膜，其中，對所述樹脂膜的、與形成有所述黏著劑層的一側為相反面的單面進行了抗靜電處理及防污處理。 The adhesive film described in claim 7, wherein an antistatic treatment and an antifouling treatment are performed on one side of the resin film opposite to the side on which the adhesive layer is formed.
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