TW202248245A - Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, optical laminate, image display device, and method for producing pressure-sensitive adhesive sheet - Google Patents

Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, optical laminate, image display device, and method for producing pressure-sensitive adhesive sheet Download PDF

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TW202248245A
TW202248245A TW111114459A TW111114459A TW202248245A TW 202248245 A TW202248245 A TW 202248245A TW 111114459 A TW111114459 A TW 111114459A TW 111114459 A TW111114459 A TW 111114459A TW 202248245 A TW202248245 A TW 202248245A
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meth
weight
adhesive sheet
film
adhesive composition
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山本悟士
久世雅大
長田潤枝
外山雄祐
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日商日東電工股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • 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
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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]
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

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

Abstract

The present invention provides a pressure-sensitive adhesive composition which contains a sufficient amount of an isocyanate-based crosslinking agent and is suitable for producing pressure-sensitive adhesive sheets that are less apt to cause a depression and that have improved durability. This pressure-sensitive adhesive composition comprises a (meth)acrylic polymer (A), an isocyanate-based crosslinking agent, the amount of which is at least 2 parts by weight per 100 parts by weight of the (meth)acrylic polymer (A), and a peroxide-based crosslinking agent. The amount of the peroxide-based crosslinking agent is, for example, 0.01-5 parts by weight per 100 parts by weight of the (meth)acrylic polymer (A).

Description

黏著劑組成物、黏著片、光學積層體、影像顯示裝置及黏著片之製造方法Adhesive composition, adhesive sheet, optical laminate, image display device, and method for producing adhesive sheet

本發明涉及黏著劑組成物、黏著片、光學積層體、影像顯示裝置及黏著片之製造方法。The present invention relates to an adhesive composition, an adhesive sheet, an optical laminate, an image display device and a method for producing the adhesive sheet.

近年來，以液晶顯示裝置及電致發光(EL)顯示裝置(例如有機EL顯示裝置、無機EL顯示裝置)為代表之影像顯示裝置急速普及。該等各種影像顯示裝置通常具有液晶層、EL發光層等之影像形成層與光學積層體之積層結構，且該光學積層體包含光學薄膜及黏著片。黏著片主要用於接合光學積層體所含之薄膜間或接合影像形成層與光學積層體。光學薄膜之例為偏光板、相位差薄膜、及偏光板與相位差薄膜一體化而成之附相位差薄膜之偏光板。 先前技術文獻 專利文獻 In recent years, image display devices represented by liquid crystal display devices and electroluminescent (EL) display devices (such as organic EL display devices and inorganic EL display devices) have been rapidly popularized. These various image display devices generally have a laminated structure of an image forming layer such as a liquid crystal layer, an EL light-emitting layer, and an optical layered body, and the optical layered body includes an optical film and an adhesive sheet. Adhesive sheets are mainly used to join the films contained in the optical laminate or to join the image forming layer and the optical laminate. Examples of optical films are polarizing plates, retardation films, and polarizing plates with retardation films in which a polarizing plate and a retardation film are integrated. prior art literature patent documents

專利文獻1：日本專利特開2008-096734號公報Patent Document 1: Japanese Patent Laid-Open No. 2008-096734

發明欲解決之課題 光學薄膜之尺寸隨溫度變化而過度變化會成為影像顯示裝置之漏光或顏色不均之原因。漏光或顏色不均尤其容易發生於使用附相位差薄膜之偏光板的具有較大尺寸之影像顯示裝置中。又，邊框(bezel)經設計成較窄(經窄邊框化)之影像顯示裝置持續普及，從而抑制尺寸變化愈來愈重要。 The problem to be solved by the invention Excessive changes in the size of the optical film as the temperature changes will cause light leakage or color unevenness in the image display device. Light leakage or color unevenness is especially likely to occur in a relatively large-sized image display device using a polarizing plate with a retardation film. In addition, image display devices whose bezels are designed to be narrower (bezel narrowed) continue to be popularized, so it is becoming more and more important to suppress dimensional changes.

為了抑制尺寸變化，考慮提高光學積層體所含之黏著片的彈性模數。使黏著片之彈性模數增加的方法，可舉增加用以製作黏著片之黏著劑組成物中之交聯劑的摻混量。例如，在專利文獻1中揭示了使用有充分量之異氰酸酯系交聯劑的黏著劑組成物。In order to suppress dimensional changes, it is conceivable to increase the modulus of elasticity of the adhesive sheet contained in the optical layered body. The method of increasing the modulus of elasticity of the adhesive sheet may be to increase the blending amount of the cross-linking agent in the adhesive composition used to make the adhesive sheet. For example, Patent Document 1 discloses an adhesive composition using a sufficient amount of an isocyanate-based crosslinking agent.

但，根據本發明人等之研討，發現在使用包含充分量之異氰酸酯系交聯劑的黏著劑組成物來製作黏著片時，容易於該黏著片發生微小的凹陷。該凹陷可能會成為光學上之缺陷。並且，以僅提高黏著片之彈性模數來說，還有黏著片之耐久性降低而無法追隨尺寸變化之情形。However, according to the study of the inventors of the present invention, it has been found that when an adhesive sheet is produced using an adhesive composition containing a sufficient amount of an isocyanate-based crosslinking agent, minute dents tend to occur on the adhesive sheet. The depression may become an optical defect. In addition, simply increasing the modulus of elasticity of the adhesive sheet may reduce the durability of the adhesive sheet and may not be able to follow dimensional changes.

爰此，本發明目的在於提供一種黏著劑組成物，其包含充分量之異氰酸酯系交聯劑，且適於製作不易發生凹陷且耐久性經改善之黏著片。Therefore, an object of the present invention is to provide an adhesive composition, which contains a sufficient amount of isocyanate-based crosslinking agent, and is suitable for producing an adhesive sheet that is less prone to dents and has improved durability.

用以解決課題之手段 本發明人等努力研討，結果發現在使用包含充分量之異氰酸酯系交聯劑的黏著劑組成物來製作黏著片時，黏著片在剛製作後之凝膠分率(初始凝膠分率)低。本發明人等基於該見解進一步進行研討，發現初始凝膠分率會影響凹陷之易發生度、及若適當組合交聯劑便可使初始凝膠分率上升，遂而完成本發明。 means to solve problems The inventors of the present invention have studied hard and found that when an adhesive sheet is produced using an adhesive composition containing a sufficient amount of an isocyanate-based crosslinking agent, the gel fraction (initial gel fraction) of the adhesive sheet immediately after production is low. . Based on this knowledge, the present inventors conducted further research and found that the initial gel fraction affects the susceptibility of sags, and that the initial gel fraction can be increased by appropriately combining a crosslinking agent, and thus completed the present invention.

本發明提供一種黏著劑組成物，包含： (甲基)丙烯酸系聚合物(A)； 異氰酸酯系交聯劑，其相對於前述(甲基)丙烯酸系聚合物(A)100重量部，其摻混量為2重量份以上；及 過氧化物系交聯劑。 The present invention provides an adhesive composition, comprising: (meth)acrylic polymer (A); An isocyanate-based crosslinking agent in an amount of 2 parts by weight or more relative to 100 parts by weight of the aforementioned (meth)acrylic polymer (A); and Peroxide-based crosslinking agent.

並且，本發明提供一種黏著片，其係由上述黏著劑組成物形成者。Furthermore, the present invention provides an adhesive sheet formed of the above-mentioned adhesive composition.

並且，本發明提供一種光學積層體，其包含上述黏著片與光學薄膜。Furthermore, the present invention provides an optical laminate including the above-mentioned adhesive sheet and an optical film.

並且，本發明提供一種影像顯示裝置，其具備上述光學積層體。Furthermore, the present invention provides an image display device including the above-mentioned optical layered body.

並且，本發明提供一種黏著片之製造方法，包含以下步驟： 將上述黏著劑組成物塗佈於基材上，形成塗佈膜；及 使前述塗佈膜乾燥。 Moreover, the present invention provides a method for manufacturing an adhesive sheet, comprising the following steps: coating the adhesive composition above on a substrate to form a coating film; and The aforementioned coating film was dried.

發明效果 根據本發明可提供一種黏著劑組成物，其包含充分量之異氰酸酯系交聯劑，且適合製作不易發生凹陷且耐久性經改善之黏著片。 Invention effect According to the present invention, there can be provided an adhesive composition which contains a sufficient amount of isocyanate-based crosslinking agent and is suitable for producing an adhesive sheet which is less prone to dents and has improved durability.

以下詳細說明本發明，惟本發明不受以下實施形態限定，可在不脫離本發明要旨之範圍內任意變更並實施。The present invention will be described in detail below, but the present invention is not limited by the following embodiments, and can be arbitrarily changed and implemented without departing from the gist of the present invention.

(黏著劑組成物之實施形態) 本實施形態之黏著劑組成物，包含：(甲基)丙烯酸系聚合物(A)；異氰酸酯系交聯劑，其相對於(甲基)丙烯酸系聚合物(A)100重量部，其摻混量為2重量份以上；及過氧化物系交聯劑。由黏著劑組成物可製作黏著片。 (Example of Adhesive Composition) The adhesive composition of the present embodiment includes: (meth)acrylic polymer (A); isocyanate crosslinking agent, which is blended with respect to 100 parts by weight of (meth)acrylic polymer (A) The amount is more than 2 parts by weight; and a peroxide-based crosslinking agent. Adhesive sheets can be produced from the adhesive composition.

[(甲基)丙烯酸系聚合物(A)] (甲基)丙烯酸系聚合物(A)可作為丙烯酸系黏著劑之基底聚合物發揮功能。丙烯酸系黏著劑具有優異之光學透明性、適當之濡濕性、凝集性、接著性等黏著特性，且有優異之耐候性、耐熱性等傾向。(甲基)丙烯酸系聚合物(A)例如含有源自(甲基)丙烯酸烷基酯之構成單元作為主成分。本說明書中，「(甲基)丙烯酸酯」意指丙烯酸酯及/或甲基丙烯酸酯。「主成分」係指構成聚合物之總構成單元中，以重量基準計包含最多的構成單元。 [(Meth)acrylic polymer (A)] The (meth)acrylic polymer (A) can function as a base polymer of an acrylic adhesive. Acrylic adhesives have excellent optical transparency, appropriate wettability, cohesiveness, adhesion and other adhesive properties, and have excellent weather resistance, heat resistance and other tendencies. The (meth)acrylic polymer (A) contains, for example, a structural unit derived from an alkyl (meth)acrylate as a main component. In this specification, "(meth)acrylate" means acrylate and/or methacrylate. "Main component" refers to the structural unit that contains the most on a weight basis among the total structural units constituting the polymer.

用以形成(甲基)丙烯酸系聚合物(A)之主骨架的(甲基)丙烯酸烷基酯中所含之烷基之碳數無特別限定，例如為1~30。該烷基可為直鏈狀亦可為支鏈狀，亦可為環狀。烷基可列舉例如：甲基、乙基、丙基、異丙基、丁基、異丁基、戊基、己基、環己基、庚基、2-乙基己基、異辛基、壬基、癸基、異癸基、十二基、異肉豆蔻基、月桂基、十三基、十五基、十六基、十七基、十八基等。(甲基)丙烯酸烷基酯可單獨或組合來使用。烷基的平均碳數宜為3~9。(甲基)丙烯酸烷基酯宜為丙烯酸丁酯。The number of carbon atoms of the alkyl group contained in the alkyl (meth)acrylate used to form the main skeleton of the (meth)acrylic polymer (A) is not particularly limited, and is, for example, 1-30. This alkyl group may be linear, branched, or cyclic. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl, isooctyl, nonyl, Decyl, isodecyl, dodecyl, isomyristyl, lauryl, tridecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, etc. Alkyl (meth)acrylates can be used alone or in combination. The average carbon number of the alkyl group is preferably 3-9. The alkyl (meth)acrylate is preferably butyl acrylate.

(甲基)丙烯酸系聚合物(A)中，由提升黏著片之接著性之觀點來看，源自(甲基)丙烯酸烷基酯之構成單元之含有率例如為50重量%以上，宜為60重量%以上，較宜為70重量%以上，更宜為80重量%以上。In the (meth)acrylic polymer (A), from the viewpoint of improving the adhesiveness of the adhesive sheet, the content of the structural unit derived from the alkyl (meth)acrylate is, for example, 50% by weight or more, preferably 50% by weight or more. 60% by weight or more, more preferably 70% by weight or more, more preferably 80% by weight or more.

構成(甲基)丙烯酸系聚合物(A)之單體，除了(甲基)丙烯酸烷基酯外，還可舉選自於由含芳香環單體、含醯胺基單體、含羧基單體、含羥基單體所構成群組中之1種共聚單體。共聚單體可單獨或組合來使用。The monomers constituting the (meth)acrylic polymer (A) can be selected from monomers containing aromatic rings, monomers containing amide groups, monomers containing carboxyl groups in addition to alkyl (meth)acrylates. A comonomer in the group consisting of monomers and hydroxyl-containing monomers. Comonomers may be used alone or in combination.

(甲基)丙烯酸系聚合物(A)宜包含源自含芳香環單體之構成單元。含芳香環單體係一於其結構中包含芳香環結構且含有(甲基)丙烯醯基、乙烯基等聚合性不飽和雙鍵之化合物。芳香環可舉例如苯環、萘環或聯苯環等。含芳香環單體宜為含芳香環(甲基)丙烯酸酯。The (meth)acrylic polymer (A) preferably contains a structural unit derived from an aromatic ring-containing monomer. Aromatic ring-containing monomer system is a compound containing an aromatic ring structure in its structure and polymerizable unsaturated double bonds such as (meth)acryl and vinyl groups. The aromatic ring may, for example, be a benzene ring, a naphthalene ring or a biphenyl ring. The aromatic ring-containing monomer is preferably an aromatic ring-containing (meth)acrylate.

含芳香環(甲基)丙烯酸酯可列舉例如：(甲基)丙烯酸苄酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸鄰苯基苯酚酯、(甲基)丙烯酸苯氧酯、(甲基)丙烯酸苯氧乙酯、(甲基)丙烯酸苯氧丙酯、苯氧基二乙二醇(甲基)丙烯酸酯、氧化乙烯改質壬苯酚(甲基)丙烯酸酯、氧化乙烯改質甲酚(甲基)丙烯酸酯、苯酚氧化乙烯改質(甲基)丙烯酸酯、2-羥-3-苯氧丙基(甲基)丙烯酸酯、甲氧基苄基(甲基)丙烯酸酯、氯苄基(甲基)丙烯酸酯、(甲基)丙烯酸甲苯酚酯、(甲基)丙烯酸聚苯乙烯酯等具有苯環者；羥乙基化β-萘酚丙烯酸酯、(甲基)丙烯酸2-萘酚乙酯、丙烯酸2-萘氧乙酯、2-(4-甲氧基-1-萘氧基)乙基(甲基)丙烯酸酯等具有萘環者；(甲基)丙烯酸聯苯酯等具有聯苯環者等。該等之中，由提升黏著片之黏著特性或耐久性之觀點來看，又宜為(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧乙酯，較宜為丙烯酸苄酯。Examples of aromatic ring-containing (meth)acrylates include benzyl (meth)acrylate, phenyl (meth)acrylate, o-phenylphenol (meth)acrylate, phenoxy (meth)acrylate, ( Phenoxyethyl methacrylate, phenoxypropyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, ethylene oxide modified nonylphenol (meth)acrylate, ethylene oxide modified Cresol (meth)acrylate, phenol ethylene oxide modified (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, methoxybenzyl (meth)acrylate, Chlorobenzyl (meth)acrylate, cresol (meth)acrylate, polystyrene (meth)acrylate, etc. with a benzene ring; hydroxyethylated β-naphthol acrylate, (meth)acrylic acid 2-Naphthol ethyl ester, 2-naphthyloxyethyl acrylate, 2-(4-methoxy-1-naphthyloxy)ethyl (meth)acrylate, etc. have a naphthalene ring; (meth)acrylic acid Phenyl esters and the like have a biphenyl ring, and the like. Among them, benzyl (meth)acrylate and phenoxyethyl (meth)acrylate are more preferable from the viewpoint of improving the adhesive properties and durability of the adhesive sheet, and benzyl acrylate is more preferable.

(甲基)丙烯酸系聚合物(A)亦可包含有源自含醯胺基單體之構成單元。含醯胺基單體係一於其結構中包含醯胺基且含有(甲基)丙烯醯基、乙烯基等聚合性不飽和雙鍵之化合物。含醯胺基單體可列舉例如：(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-異丙基丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-己基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥甲基-N-丙烷(甲基)丙烯醯胺、胺甲基(甲基)丙烯醯胺、胺乙基(甲基)丙烯醯胺、巰甲基(甲基)丙烯醯胺、巰乙基(甲基)丙烯醯胺等丙烯醯胺系單體；N-(甲基)丙烯醯基嗎福林、N-(甲基)丙烯醯基哌啶、N-(甲基)丙烯醯基吡咯啶等N-丙烯醯基雜環單體；N-乙烯吡咯啶酮、N-乙烯基-ε-己內醯胺等含N-乙烯基內醯胺系單體等。該等之中，由提升黏著片之耐久性之觀點來看，又宜為含N-乙烯基內醯胺系單體。The (meth)acrylic polymer (A) may also contain a structural unit derived from an amide group-containing monomer. Amide group-containing monomer system is a compound containing an amide group in its structure and a polymerizable unsaturated double bond such as a (meth)acryl group or a vinyl group. Amide-containing monomers include, for example: (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N- Isopropylacrylamide, N-methyl(meth)acrylamide, N-butyl(meth)acrylamide, N-hexyl(meth)acrylamide, N-methylol(methyl)acrylamide ) acrylamide, N-methylol-N-propane(meth)acrylamide, aminomethyl(meth)acrylamide, aminoethyl(meth)acrylamide, mercaptomethyl(methyl)acrylamide ) acrylamide, mercaptoethyl (meth)acrylamide and other acrylamide-based monomers; N-acryl heterocyclic monomers such as (meth)acrylpyrrolidine; N-vinyl lactam-containing monomers such as N-vinylpyrrolidone and N-vinyl-ε-caprolactam Wait. Among them, from the viewpoint of improving the durability of the adhesive sheet, N-vinyllactamide-based monomers are more preferable.

(甲基)丙烯酸系聚合物(A)亦可包含有源自含羧基單體之構成單元。含羧基單體係一於其結構中包含羧基且含有(甲基)丙烯醯基、乙烯基等聚合性不飽和雙鍵之化合物。含羧基單體可舉例如(甲基)丙烯酸、(甲基)丙烯酸羧乙酯、(甲基)丙烯酸羧戊酯、伊康酸、馬來酸、延胡索酸、巴豆酸等。該等之中，由改善共聚性、價格及黏著片之黏著特性之觀點來看，宜為丙烯酸。藉由(甲基)丙烯酸系聚合物(A)具有源自含羧基單體、尤其是丙烯酸之構成單元，例如可提高異氰酸酯系交聯劑之自聚合性。交聯劑之異氰酸酯系交聯劑之自聚合性的提升尤其可有助於抑制黏著片在加濕環境下之剝落、或異氰酸酯系交聯劑之含有率高之系統之黏著片的物性穩定化。The (meth)acrylic polymer (A) may contain a structural unit derived from a carboxyl group-containing monomer. The carboxyl group-containing monomer is a compound containing a carboxyl group in its structure and a polymerizable unsaturated double bond such as a (meth)acryl group or a vinyl group. Examples of carboxyl group-containing monomers include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like. Among them, acrylic acid is preferable from the viewpoint of improving copolymerizability, price, and adhesive properties of the adhesive sheet. When the (meth)acrylic polymer (A) has a structural unit derived from a carboxyl group-containing monomer, especially acrylic acid, for example, the self-polymerization property of an isocyanate-based crosslinking agent can be improved. The improvement of the self-polymerization of the isocyanate-based cross-linking agent in the cross-linking agent can especially contribute to the suppression of peeling of the adhesive sheet in a humid environment, or the stabilization of the physical properties of the adhesive sheet in a system with a high content of the isocyanate-based cross-linking agent .

(甲基)丙烯酸系聚合物(A)亦可包含有源自含羥基單體之構成單元。含羥基單體係一於其結構中包含羥基且含有(甲基)丙烯醯基、乙烯基等聚合性不飽和雙鍵之化合物。含羥基單體可列舉例如：(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸6-羥己酯、(甲基)丙烯酸8-羥辛酯、(甲基)丙烯酸10-羥癸酯、(甲基)丙烯酸12-羥月桂酯等含羥基之(甲基)丙烯酸烷基酯；(4-羥甲基環己基)-甲基丙烯酸酯等含羥基之(甲基)丙烯酸環烷基酯。該等中，又宜為(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸4-羥丁酯。The (meth)acrylic polymer (A) may contain a structural unit derived from a hydroxyl group-containing monomer. Hydroxyl-containing monomer system is a compound that contains a hydroxyl group in its structure and contains a polymerizable unsaturated double bond such as a (meth)acryl group or a vinyl group. Examples of hydroxyl-containing monomers include: 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate and other hydroxyl-containing alkyl (meth)acrylates; (4- Cycloalkyl (meth)acrylates containing hydroxyl groups such as hydroxymethylcyclohexyl)-methacrylate. Among these, 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are more preferable.

共聚單體中，由接著性、耐久性等觀點來看，又宜使用含芳香環單體及含羧基單體，尤宜使用含芳香環單體。包含源自含羧基單體之結構單元的(甲基)丙烯酸系聚合物(A)會擷取周圍氣體環境中之水分，從而有促進異氰酸酯系交聯劑彼此之反應的傾向。含芳香環單體可提升(甲基)丙烯酸系聚合物(A)與包含源自後述異氰酸酯系交聯劑之構成單元作為主成分之聚合物(B)的相溶性，而適於維持黏著片之透明性。並且，含芳香環單體亦適於調整黏著片之重工性或黏著性。Among the comonomers, aromatic ring-containing monomers and carboxyl group-containing monomers are preferably used from the viewpoint of adhesiveness, durability, and the like, and aromatic ring-containing monomers are particularly preferably used. The (meth)acrylic polymer (A) comprising a structural unit derived from a carboxyl group-containing monomer tends to absorb moisture in the surrounding air environment, thereby tending to promote the reaction between isocyanate-based crosslinking agents. The aromatic ring-containing monomer improves the compatibility between the (meth)acrylic polymer (A) and the polymer (B) mainly composed of a structural unit derived from an isocyanate crosslinking agent described later, and is suitable for maintaining an adhesive sheet of transparency. Moreover, aromatic ring-containing monomers are also suitable for adjusting the reworkability or adhesiveness of the adhesive sheet.

(甲基)丙烯酸系聚合物(A)中，源自共聚單體之構成單元之含有率無特別限定，例如為0~40重量%，可為0.1~30重量%，亦可為0.1~20重量%。In the (meth)acrylic polymer (A), the content rate of the constituent unit derived from the comonomer is not particularly limited, for example, it may be 0 to 40% by weight, may be 0.1 to 30% by weight, or may be 0.1 to 20% by weight. weight%.

(甲基)丙烯酸系聚合物(A)中，源自含芳香環單體之構成單元之含有率無特別限定，例如為3~25重量%，較宜為22重量%以下，更宜為20重量%以下。該含有率較宜為8重量%以上，更宜為12重量%以上。In the (meth)acrylic polymer (A), the content rate of the structural unit derived from the aromatic ring-containing monomer is not particularly limited, for example, it is 3 to 25% by weight, preferably 22% by weight or less, and more preferably 20% by weight. Weight% or less. The content is preferably at least 8% by weight, more preferably at least 12% by weight.

(甲基)丙烯酸系聚合物(A)中，源自含醯胺基單體之構成單元之含有率無特別限定，例如為0.1~10重量%，較宜為0.2~8重量%，更宜為0.6~6重量%。In the (meth)acrylic polymer (A), the content of the structural unit derived from the amide group-containing monomer is not particularly limited, for example, it is 0.1 to 10% by weight, preferably 0.2 to 8% by weight, more preferably 0.6 to 6% by weight.

(甲基)丙烯酸系聚合物(A)中，源自含羧基單體之構成單元之含有率無特別限定，例如為0.1~25重量%，較宜為3重量%以上，更宜為8重量%以上。該含有率較宜為20重量%以下。In the (meth)acrylic polymer (A), the content of the structural unit derived from the carboxyl group-containing monomer is not particularly limited, for example, it is 0.1 to 25% by weight, preferably 3% by weight or more, more preferably 8% by weight %above. The content is preferably 20% by weight or less.

此外，(甲基)丙烯酸系聚合物(A)中，源自與異氰酸酯系交聯劑之反應性高之具活性氫之共聚單體、例如源自含羥基單體之構成單元之含有率宜低。(甲基)丙烯酸系聚合物(A)中，源自含羥基單體之構成單元之含有率例如為1重量%以下，較宜為0.5重量%以下，更宜為0.1重量%以下。(甲基)丙烯酸系聚合物(A)亦可實質上不含源自含羥基單體之構成單元。In addition, in the (meth)acrylic polymer (A), the content rate of a comonomer having active hydrogen having high reactivity with an isocyanate-based crosslinking agent, such as a constituent unit derived from a hydroxyl group-containing monomer, is preferably Low. In the (meth)acrylic polymer (A), the content of the structural unit derived from the hydroxyl group-containing monomer is, for example, 1% by weight or less, preferably 0.5% by weight or less, more preferably 0.1% by weight or less. The (meth)acrylic polymer (A) may not substantially contain a structural unit derived from a hydroxyl group-containing monomer.

就單體成分而言，除了(甲基)丙烯酸烷基酯及上述共聚單體外，為了改善黏著片之接著性、耐熱性，還可使用具有包含(甲基)丙烯醯基或乙烯基等不飽和雙鍵之聚合性官能基的其他共聚單體。其他共聚單體可單獨或組合來使用。In terms of monomer components, in addition to alkyl (meth)acrylates and the above-mentioned comonomers, in order to improve the adhesiveness and heat resistance of the adhesive sheet, it is also possible to use compounds containing (meth)acryl or vinyl groups, etc. Other comonomers with polymerizable functional groups of unsaturated double bonds. Other comonomers may be used alone or in combination.

其他共聚單體可列舉例如：馬來酸酐、伊康酸酐等含酸酐基單體；丙烯酸之己內酯加成物；烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯等含磺酸基單體；2-羥乙基丙烯醯基磷酸酯等含磷酸基單體；(甲基)丙烯酸胺乙酯、(甲基)丙烯酸N,N-二甲胺乙酯、(甲基)丙烯酸三級丁基胺乙酯等(甲基)丙烯酸烷基胺基烷基酯；(甲基)丙烯酸甲氧乙酯、(甲基)丙烯酸乙氧乙酯等(甲基)丙烯酸烷氧烷基酯；N-(甲基)丙烯醯基氧基亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-6-氧基六亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-8-氧基八亞甲基琥珀醯亞胺等琥珀醯亞胺系單體；N-環己基馬來醯亞胺、N-異丙基馬來醯亞胺、N-月桂基馬來醯亞胺、N-苯基馬來醯亞胺等馬來醯亞胺系單體；N-甲基伊康醯亞胺、N-乙基伊康醯亞胺、N-丁基伊康醯亞胺、N-辛基伊康醯亞胺、N-2-乙基己基伊康醯亞胺、N-環己基伊康醯亞胺、N-月桂基伊康醯亞胺等伊康醯亞胺系單體；乙酸乙烯酯、丙酸乙烯酯等乙烯基系單體；丙烯腈、甲基丙烯腈等氰基丙烯酸酯系單體；(甲基)丙烯酸環氧丙酯等含環氧基(甲基)丙烯酸酯；聚乙二醇(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、甲氧基乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯等二醇系(甲基)丙烯酸酯；(甲基)丙烯酸四氫糠酯、氟(甲基)丙烯酸酯、聚矽氧(甲基)丙烯酸酯、丙烯酸2-甲氧乙酯等(甲基)丙烯酸酯單體；3-丙烯醯氧基丙基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、4-乙烯基丁基三甲氧基矽烷、4-乙烯基丁基三乙氧基矽烷、8-乙烯基辛基三甲氧基矽烷、8-乙烯基辛基三乙氧基矽烷、10-甲基丙烯醯基氧基癸基三甲氧基矽烷、10-丙烯醯基氧基癸基三甲氧基矽烷、10-甲基丙烯醯基氧基癸基三乙氧基矽烷、10-丙烯醯基氧基癸基三乙氧基矽烷等含有矽原子之矽烷系單體等。Other comonomers include, for example, anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; caprolactone adducts of acrylic acid; allylsulfonic acid, 2-(meth)acrylamide-2-form Monomers containing sulfonic acid groups such as propanesulfonic acid, (meth)acrylamidopropanesulfonic acid, sulfopropyl (meth)acrylate; monomers containing phosphoric acid groups such as 2-hydroxyethylacryloyl phosphate; ( Aminoethyl methacrylate, N,N-dimethylaminoethyl (meth)acrylate, tertiary butylamine ethyl (meth)acrylate, etc., alkylaminoalkyl (meth)acrylates; ( Alkoxyalkyl (meth)acrylates such as methoxyethyl methacrylate and ethoxyethyl (meth)acrylate; N-(meth)acryloxymethylene succinimide, N -(Meth)acryl-6-oxyhexamethylene succinimide, N-(meth)acryl-8-oxyoctamethylene succinimide and other succinimide series Monomer; N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide and other maleimide series Monomer; N-methyl iconimide, N-ethyl iconimide, N-butyl iconimide, N-octyl iconimide, N-2-ethylhexyl Iconimide monomers such as Iconimide, N-cyclohexyl Iconimide, N-Lauryl Iconimide, etc.; Vinyl monomers such as vinyl acetate and vinyl propionate; Cyanoacrylate-based monomers such as acrylonitrile and methacrylonitrile; (meth)acrylates containing epoxy groups such as glycidyl (meth)acrylate; polyethylene glycol (meth)acrylate, polypropylene glycol Diol-based (meth)acrylates such as (meth)acrylates, methoxyethylene glycol (meth)acrylates, and methoxypolypropylene glycol (meth)acrylates; tetrahydrofurfuryl (meth)acrylates (meth)acrylate monomers such as ester, fluoro(meth)acrylate, polysiloxane (meth)acrylate, 2-methoxyethyl acrylate; 3-acryloxypropyltriethoxysilane , Vinyltrimethoxysilane, Vinyltriethoxysilane, 4-Vinylbutyltrimethoxysilane, 4-Vinylbutyltriethoxysilane, 8-Vinyloctyltrimethoxysilane, 8-Vinyloctyltriethoxysilane, 10-Methacryloxydecyltrimethoxysilane, 10-Acryloxydecyltrimethoxysilane, 10-Methacryloxydecyltrimethoxysilane Silane-based monomers containing silicon atoms, such as decyltriethoxysilane and 10-acryloxydecyltriethoxysilane.

並且，其他共聚單體可列舉例如：三丙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、雙酚A二環氧丙基醚二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三羥甲丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、己內酯改質二新戊四醇六(甲基)丙烯酸酯等具有2個以上不飽和雙鍵之多官能性單體等。In addition, other comonomers include, for example, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A Diglycidyl ether di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentylthritol tri(meth)acrylate, Neopentylthritol tetra(meth)acrylate, diperythritol penta(meth)acrylate, diperythritol hexa(meth)acrylate, caprolactone modified diperythritol hexa( Polyfunctional monomers such as meth)acrylates having two or more unsaturated double bonds, etc.

使用其他共聚單體作為單體成分時，(甲基)丙烯酸系聚合物(A)中源自其他共聚單體之構成單元之含有率宜為10重量%以下，較宜為7重量%以下，更宜為5重量%以下。When other comonomers are used as monomer components, the content of the constituent units derived from other comonomers in the (meth)acrylic polymer (A) is preferably 10% by weight or less, more preferably 7% by weight or less, More preferably, it is 5% by weight or less.

(甲基)丙烯酸系聚合物(A)之重量平均分子量通常為30萬~400萬。由耐久性之觀點來看，(甲基)丙烯酸系聚合物(A)之重量平均分子量宜為30萬~300萬，更宜為40萬~200萬。以耐熱性方面來看，重量平均分子量宜為30萬以上。重量平均分子量若為400萬以下，有黏著片不易變硬而不易發生剝落之傾向。意指分子量分布之重量平均分子量(Mw)/數量平均分子量(Mn)宜為1.8~10，較宜為1.8~7，更宜為1.8~5。以耐熱性方面來看，分子量分布(Mw/Mn)宜為10以下。重量平均分子量、分子量分布(Mw/Mn)係藉由GPC(凝膠滲透層析法)來測定且從以聚苯乙烯換算所算出之值而求得。The weight average molecular weight of a (meth)acryl-type polymer (A) is 300,000-4 million normally. From the viewpoint of durability, the weight average molecular weight of the (meth)acrylic polymer (A) is preferably 300,000 to 3 million, more preferably 400,000 to 2 million. From the viewpoint of heat resistance, the weight average molecular weight is preferably 300,000 or more. When the weight average molecular weight is 4 million or less, the adhesive sheet tends to harden and peel off less easily. It means that the weight average molecular weight (Mw)/number average molecular weight (Mn) of the molecular weight distribution is preferably 1.8~10, more preferably 1.8~7, more preferably 1.8~5. From the viewpoint of heat resistance, the molecular weight distribution (Mw/Mn) is preferably 10 or less. The weight average molecular weight and molecular weight distribution (Mw/Mn) are measured by GPC (gel permeation chromatography), and are calculated|required from the value calculated by polystyrene conversion.

(甲基)丙烯酸系聚合物(A)可藉由溶液聚合、電子束或UV等放射線聚合、塊狀聚合、乳化聚合等各種自由基聚合等之公知聚合方法來製作。所得之(甲基)丙烯酸系聚合物(A)可為無規共聚物、嵌段共聚物、接枝共聚物等之任一者。The (meth)acrylic polymer (A) can be produced by known polymerization methods such as solution polymerization, radiation polymerization such as electron beam or UV, bulk polymerization, emulsion polymerization, and various radical polymerizations. The obtained (meth)acrylic polymer (A) may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.

溶液聚合中，聚合溶劑可使用例如乙酸乙酯、甲苯等。溶液聚合例如可在氮等非活性氣體氣流下添加聚合引發劑，且通常在50~70℃左右、5~30小時左右之反應條件下進行。In solution polymerization, ethyl acetate, toluene, etc. can be used as a polymerization solvent, for example. For solution polymerization, for example, a polymerization initiator can be added under an inert gas flow such as nitrogen, and it is usually carried out under reaction conditions of about 50 to 70° C. and about 5 to 30 hours.

用於自由基聚合之聚合引發劑、鏈轉移劑、乳化劑等無特別限定，可適當選擇來使用。(甲基)丙烯酸系聚合物(A)之重量平均分子量可藉由聚合引發劑、鏈轉移劑之使用量、反應條件等來控制。因此，針對聚合引發劑及鏈轉移劑，係因應其組成適當調整其使用量。A polymerization initiator, a chain transfer agent, an emulsifier, and the like used in radical polymerization are not particularly limited, and can be appropriately selected for use. The weight average molecular weight of the (meth)acrylic polymer (A) can be controlled by the usage-amount of a polymerization initiator, a chain transfer agent, reaction conditions, etc. Therefore, for the polymerization initiator and the chain transfer agent, the usage amount thereof is appropriately adjusted according to the composition thereof.

聚合引發劑可列舉例如：2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2-脒基丙烷)二鹽酸鹽、2,2’-偶氮雙[2-(5-甲基-2-咪唑啉-2-基)丙烷]二鹽酸鹽、2,2’-偶氮雙(2-甲基丙脒)二硫酸鹽、2,2’-偶氮雙(N,N’-二亞甲基異丁基脒)、2,2’-偶氮雙[N-(2-羧乙基)-2-甲基丙脒]水合物(和光純藥公司製，VA-057)等偶氮系引發劑；過硫酸鉀、過硫酸銨等過硫酸鹽；二(2-乙基己基)過氧化二碳酸酯、二(4-三級丁基環己基)過氧化二碳酸酯、二-二級丁基過氧化二碳酸酯、過氧化新癸酸三級丁酯、過氧化三甲基乙酸三級己酯、過氧化三甲基乙酸三級丁酯、二月桂醯基過氧化物、二正辛醯基過氧化物、1,1,3,3-四甲基丁基過氧基-2-乙基己酸酯、二(4-甲基苯甲醯基)過氧化物、二苯甲醯基過氧化物、過異丁酸三級丁酯、1,1-二(三級己基過氧基)環己烷、三級丁基過氧化氫、過氧化氫等過氧化物系引發劑；過硫酸鹽與亞硫酸氫鈉之組合、過氧化物與抗壞血酸鈉之組合等過氧化物與還原劑組合而成之氧化還原系引發劑等，但不受該等所限。Examples of polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis[2- (5-Methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-Azobis(2-methylpropionamidine)disulfate, 2,2'-Azobis (N,N'-dimethyleneisobutylamidine), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate (manufactured by Wako Pure Chemical Industries, Ltd. , VA-057) and other azo initiators; persulfates such as potassium persulfate and ammonium persulfate; bis(2-ethylhexyl) peroxydicarbonate, bis(4-tertiary butylcyclohexyl) persulfate Oxidized dicarbonate, di-secondary butyl peroxydicarbonate, tertiary butyl peroxyneodecanoate, tertiary hexyl peroxytrimethylacetate, tertiary butyl peroxytrimethylacetate, di Lauryl peroxide, di-n-octyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, bis(4-methylbenzoyl) Peroxide, dibenzoyl peroxide, tertiary butyl perisobutyrate, 1,1-di(tertiary hexylperoxy)cyclohexane, tertiary butyl hydroperoxide, hydrogen peroxide Peroxide-based initiators such as peroxide-based initiators; combinations of persulfate and sodium bisulfite, combinations of peroxide and sodium ascorbate, etc. Limited.

聚合引發劑可單獨或可組合來使用，但整體使用量相對於單體成分100重量份，宜為0.005~1重量份左右，較宜為0.02~0.5重量份左右。The polymerization initiator can be used alone or in combination, but the overall usage amount is preferably about 0.005-1 part by weight, more preferably about 0.02-0.5 part by weight, relative to 100 parts by weight of monomer components.

鏈轉移劑可列舉例如月桂基硫醇、環氧丙基硫醇、巰乙酸、2-巰基乙醇、氫硫乙酸、氫硫乙酸2-乙基己酯、2,3-二巰基-1-丙醇等。鏈轉移劑可單獨使用，亦可混合2種以上來使用，但整體使用量相對於單體成分100重量份，為0.1重量份左右以下。Chain transfer agents include, for example, lauryl mercaptan, epoxypropyl mercaptan, thioglycolic acid, 2-mercaptoethanol, hydrogen thioacetic acid, 2-ethylhexyl hydrogen thioacetate, 2,3-dimercapto-1-propane Alcohol etc. The chain transfer agent may be used alone or in combination of two or more, but the total amount used is about 0.1 part by weight or less with respect to 100 parts by weight of the monomer components.

作為用於進行乳化聚合時的乳化劑，可列舉例如月桂基硫酸鈉、月桂基硫酸銨、十二基苯磺酸鈉、聚氧伸乙基烷基醚硫酸銨、聚氧伸乙基烷基苯基醚硫酸鈉等陰離子系乳化劑；聚氧伸乙基烷基醚、聚氧伸乙基烷基苯基醚、聚氧伸乙基脂肪酸酯、聚氧伸乙基-聚氧伸丙基嵌段聚合物等非離子系乳化劑等。乳化劑可單獨或組合來使用。Examples of emulsifiers used for emulsion polymerization include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, polyoxyethylene alkyl ether ammonium sulfate, polyoxyethylene alkyl Anionic emulsifiers such as phenyl ether sodium sulfate; polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene Non-ionic emulsifiers such as base block polymers, etc. Emulsifiers can be used alone or in combination.

具有反應性之乳化劑可舉導入有丙烯基、烯丙基醚基等自由基聚合性官能基之乳化劑。該乳化劑之具體例可舉Aqualon HS-10、HS-20、KH-10、BC-05、BC-10、BC-20(以上皆為第一工業製藥公司製)、ADEKA REASOAP SE10N(ADEKA公司製)等。具有反應性之乳化劑於聚合後會被組入聚合物鏈，從而耐水性會提升，故理想。相對於單體成分之總量100重量份，乳化劑之使用量宜為0.3~5重量份，由聚合穩定性或機械穩定性來看較宜為0.5~1重量份。Examples of reactive emulsifiers include emulsifiers introduced with radically polymerizable functional groups such as acryl groups and allyl ether groups. Specific examples of the emulsifier include Aqualon HS-10, HS-20, KH-10, BC-05, BC-10, BC-20 (the above are manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.), ADEKA REASOAP SE10N (ADEKA company system) etc. Reactive emulsifiers will be incorporated into polymer chains after polymerization, so water resistance will be improved, so it is ideal. Relative to 100 parts by weight of the total amount of monomer components, the amount of the emulsifier used is preferably 0.3-5 parts by weight, more preferably 0.5-1 part by weight in terms of polymerization stability or mechanical stability.

放射線聚合時，係藉由對單體成分照射電子束、UV等放射線進行聚合，來製造(甲基)丙烯酸系聚合物(A)。以電子束進行放射線聚合時，無須特別使單體成分含有光聚合引發劑。以UV進行放射線聚合時，由可縮短聚合時間之優點等來看，亦可使單體成分含有光聚合引發劑。光聚合引發劑可單獨或組合來使用。In radiation polymerization, the (meth)acrylic polymer (A) is manufactured by irradiating a monomer component with radiation, such as an electron beam and UV, and polymerizing. When performing radiation polymerization with an electron beam, it is not particularly necessary to make the monomer component contain a photopolymerization initiator. In the case of UV radiation polymerization, the monomer component may contain a photopolymerization initiator from the advantage of shortening the polymerization time. A photopolymerization initiator can be used individually or in combination.

光聚合引發劑若為能引發光聚合者即無特別限制，可使用一般使用之光聚合引發劑。光聚合引發劑可使用例如苯偶姻醚系、苯乙酮系、α-酮醇系、光活性肟系、苯偶姻系、苯甲基系、二苯基酮系、縮酮系、9-氧硫𠮿

Figure 111114459-A0304-1
系等。相對於單體成分100重量份，光聚合引發劑之使用量為0.05~1.5重量份，宜為0.1~1重量份。光聚合引發劑可單獨或組合來使用。The photopolymerization initiator is not particularly limited as long as it can initiate photopolymerization, and generally used photopolymerization initiators can be used. As photopolymerization initiators, for example, benzoin ether series, acetophenone series, α-ketol series, photoactive oxime series, benzoin series, benzyl series, benzophenone series, ketal series, 9 -Oxysulfur 𠮿
Figure 111114459-A0304-1
department etc. The photopolymerization initiator is used in an amount of 0.05 to 1.5 parts by weight, preferably 0.1 to 1 part by weight, relative to 100 parts by weight of monomer components. A photopolymerization initiator can be used individually or in combination.

[異氰酸酯系交聯劑] 異氰酸酯系交聯劑可使用具有至少2個異氰酸酯基的化合物(異氰酸酯化合物)。異氰酸酯化合物中所含之異氰酸酯基之數量宜為3以上。異氰酸酯基之數量的上限值無特別限定，例如為5。異氰酸酯化合物可舉芳香族異氰酸酯化合物、脂環族異氰酸酯化合物、脂肪族異氰酸酯化合物等。異氰酸酯系交聯劑宜可藉由與水進行反應而自行聚合。 [Isocyanate crosslinking agent] As the isocyanate crosslinking agent, a compound (isocyanate compound) having at least two isocyanate groups can be used. The number of isocyanate groups contained in the isocyanate compound is preferably 3 or more. Although the upper limit of the number of isocyanate groups is not specifically limited, For example, it is 5. Examples of the isocyanate compound include aromatic isocyanate compounds, alicyclic isocyanate compounds, and aliphatic isocyanate compounds. The isocyanate-based crosslinking agent is preferably self-polymerizable by reacting with water.

芳香族異氰酸酯化合物可列舉例如：二異氰酸伸苯酯、2,4-二異氰酸甲苯酯、2,6-二異氰酸甲苯酯、2,2’-二苯甲烷二異氰酸酯、4,4’-二苯甲烷二異氰酸酯、4,4’-甲苯胺二異氰酸酯、4,4’-二苯基醚二異氰酸酯、4,4’-二苯基二異氰酸酯、1,5-萘二異氰酸酯、伸茬基二異氰酸酯等。Aromatic isocyanate compounds include, for example: phenylene diisocyanate, 2,4-cresyl diisocyanate, 2,6-cresyl diisocyanate, 2,2'-diphenylmethane diisocyanate, 4 ,4'-Diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate , Extended stubble diisocyanate, etc.

脂環族異氰酸酯化合物可列舉例如：1,3-環戊烯二異氰酸酯、1,3-環己烷二異氰酸酯、1,4-環己烷二異氰酸酯、異佛酮二異氰酸酯、加氫二苯甲烷二異氰酸酯、加氫伸茬基二異氰酸酯、加氫二異氰酸甲苯酯、加氫四甲基伸茬基二異氰酸酯等。Examples of alicyclic isocyanate compounds include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane Diisocyanate, hydrogenated diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethyl diisocyanate, etc.

脂肪族異氰酸酯化合物可列舉：三亞甲基二異氰酸酯、四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、五亞甲基二異氰酸酯、1,2-伸丙基二異氰酸酯、1,3-伸丁基二異氰酸酯、十二亞甲基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯等。Aliphatic isocyanate compounds include: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc.

異氰酸酯系交聯劑還可列舉：上述異氰酸酯化合物的多聚物(二聚物、三聚物、五聚物等)、加成至三羥甲丙烷等多元醇而得之加成物、脲改質物、縮二脲改質物、脲甲酸酯改質物、三聚異氰酸酯改質物、碳二亞胺改質物、加成至聚醚多元醇、聚酯多元醇、丙烯酸多元醇、聚丁二烯多元醇、聚異戊二烯多元醇等而得之胺甲酸酯預聚物等。Isocyanate-based crosslinking agents also include: multipolymers (dimers, trimers, pentamers, etc.) of the above-mentioned isocyanate compounds, adducts obtained by adding trimethylolpropane and other polyols, modified biuret, modified allophanate, modified isocyanate, modified carbodiimide, added to polyether polyol, polyester polyol, acrylic polyol, polybutadiene polyol Urethane prepolymers obtained from alcohols, polyisoprene polyols, etc.

異氰酸酯系交聯劑宜為芳香族異氰酸酯化合物及其衍生物，較宜為二異氰酸甲苯酯及其衍生物，換言之為二異氰酸甲苯酯系(TDI系)交聯劑。由反應性之觀點來看，相較於伸茬基二異氰酸酯及其衍生物、換言之相較於伸茬基二異氰酸酯系(XDI系)交聯劑，TDI系交聯劑更適於本實施形態之黏著劑組成物。尤其，異氰酸酯系交聯劑宜包含多元醇及二異氰酸甲苯酯之加成物作為TDI系交聯劑。該加成物之具體例可舉三羥甲丙烷/二異氰酸甲苯酯三聚物加成物。The isocyanate-based cross-linking agent is preferably an aromatic isocyanate compound and its derivatives, more preferably toluene diisocyanate and its derivatives, in other words, a toluene diisocyanate-based (TDI-based) cross-linking agent. From the viewpoint of reactivity, TDI-based cross-linking agents are more suitable for this embodiment than extended-diisocyanate and its derivatives, in other words, compared to extended-diisocyanate-based (XDI-based) cross-linking agents. Adhesive composition. In particular, the isocyanate-based crosslinking agent preferably includes an adduct of polyol and toluene diisocyanate as a TDI-based crosslinking agent. Specific examples of the adduct include a trimethylolpropane/cresyl diisocyanate trimer adduct.

異氰酸酯系交聯劑之市售物可列舉例如：Tosoh公司製之商品名「Millionate MT」、「Millionate MTL」、「Millionate MR-200」、「Millionate MR-400」、「CORONATE L」、「CORONATE HL」「CORONATE HX」；三井化學公司製之商品名「Takenate D-110N」、「Takenate D-120N」、「Takenate D-140N」、「Takenate D-160N」、「Takenate D-165N」、「Takenate D-170HN」、「Takenate D-178N」、「Takenate 500」、「Takenate 600」等，宜為CORONATE L。Commercially available isocyanate-based crosslinking agents include, for example, trade names "Millionate MT", "Millionate MTL", "Millionate MR-200", "Millionate MR-400", "CORONATE L", "CORONATE HL" "CORONATE HX"; trade names "Takenate D-110N", "Takenate D-120N", "Takenate D-140N", "Takenate D-160N", "Takenate D-165N", "Takenate D-165N" manufactured by Mitsui Chemicals Takenate D-170HN", "Takenate D-178N", "Takenate 500", "Takenate 600", etc., preferably CORONATE L.

異氰酸酯系交聯劑可將上述之物單獨使用1種，亦可混合2種以上來使用。相對於(甲基)丙烯酸系聚合物(A)100重量份，異氰酸酯系交聯劑之摻混量為2重量份以上，宜為3重量份以上，較宜為5重量份以上，更宜為8重量份以上，尤宜為10重量份以上，亦可為11重量份以上。相對於(甲基)丙烯酸系聚合物(A)100重量份，異氰酸酯系交聯劑之摻混量例如為30重量份以下，宜為20重量份以下，較宜小於15重量份，更宜為13重量份以下。相對於(甲基)丙烯酸系聚合物(A)100重量份，異氰酸酯系交聯劑之摻混量宜為2~30重量份。The isocyanate-based crosslinking agent may be used alone or in combination of two or more of the above-mentioned ones. With respect to 100 parts by weight of the (meth)acrylic polymer (A), the blending amount of the isocyanate-based crosslinking agent is 2 parts by weight or more, preferably 3 parts by weight or more, more preferably 5 parts by weight or more, more preferably 8 parts by weight or more, particularly preferably 10 parts by weight or more, and may be 11 parts by weight or more. With respect to 100 parts by weight of the (meth)acrylic polymer (A), the blending amount of the isocyanate-based crosslinking agent is, for example, not more than 30 parts by weight, preferably not more than 20 parts by weight, more preferably less than 15 parts by weight, more preferably 13 parts by weight or less. The blending amount of the isocyanate-based crosslinking agent is preferably 2 to 30 parts by weight relative to 100 parts by weight of the (meth)acrylic polymer (A).

黏著劑組成物中，相對於(甲基)丙烯酸系聚合物(A)100重量份，異氰酸酯系交聯劑之摻混量多至2重量份以上之程度時，在製作黏著片時，異氰酸酯系交聯劑會彼此反應，而有形成包含源自異氰酸酯系交聯劑之構成單元作為主成分的聚合物(B)之情形。聚合物(B)藉由賦予黏著片充分之凝集力，而適於抑制黏著片之尺寸變化。即，聚合物(B)適於抑制影像顯示裝置中之顯示不均或漏光。並且，(甲基)丙烯酸系聚合物(A)及聚合物(B)之組合適於提升黏著片在高溫多濕環境下等之耐久性。In the adhesive composition, when the compounding amount of the isocyanate-based crosslinking agent is as large as 2 parts by weight or more with respect to 100 parts by weight of the (meth)acrylic polymer (A), when producing an adhesive sheet, the isocyanate-based Crosslinking agents may react with each other to form a polymer (B) containing, as a main component, a structural unit derived from an isocyanate-based crosslinking agent. The polymer (B) is suitable for suppressing dimensional changes of the adhesive sheet by imparting sufficient cohesive force to the adhesive sheet. That is, the polymer (B) is suitable for suppressing display unevenness and light leakage in an image display device. In addition, the combination of the (meth)acrylic polymer (A) and the polymer (B) is suitable for improving the durability of the adhesive sheet under high-temperature and high-humidity environments.

[過氧化物系交聯劑] 過氧化物系交聯劑若為藉由加熱或光照射會產生自由基活性種而使(甲基)丙烯酸系聚合物(A)進行交聯之過氧化物，便可適當使用，惟考慮到作業性或穩定性，宜使用1分鐘半衰期溫度在80℃~160℃之過氧化物，較宜使用1分鐘半衰期溫度在90℃~140℃之過氧化物。 [Peroxide crosslinking agent] The peroxide-based cross-linking agent can be used appropriately if it is a peroxide that cross-links the (meth)acrylic polymer (A) by generating free radical active species by heating or light irradiation. For workability or stability, it is preferable to use a peroxide with a half-life temperature of 1 minute at 80°C to 160°C, and a peroxide with a half-life temperature of 90°C to 140°C is more suitable.

過氧化物之半衰期係表示過氧化物之分解速度的指標，意指過氧化物之殘存量變成一半時的時間。關於用以於任意時間達半衰期所需的分解溫度、或於任意溫度下之半衰期時間，係記載於製造商型錄等，例如係記載於日本油脂公司之「有機過氧化物型錄第9版(2003年5月)」等。The half-life of peroxide is an index showing the decomposition rate of peroxide, and means the time until the remaining amount of peroxide becomes half. Regarding the decomposition temperature required to reach the half-life at any time, or the half-life time at any temperature, it is recorded in the manufacturer's catalog, etc., for example, it is recorded in "Organic Peroxide Catalog 9th Edition" of NOF Corporation (May 2003)", etc.

過氧化物可列舉例如：二(2-乙基己基)過氧二碳酸酯(1分鐘半衰期溫度：90.6℃)、二(4-三級丁基環己基)過氧二碳酸酯(1分鐘半衰期溫度：92.1℃)、過氧二碳酸二-二級丁酯(1分鐘半衰期溫度：92.4℃)、過氧新癸酸三級丁酯(1分鐘半衰期溫度：103.5℃)、過氧化三甲基乙酸三級己酯(1分鐘半衰期溫度：109.1℃)、過氧化三甲基乙酸三級丁酯(1分鐘半衰期溫度：110.3℃)、二月桂醯基過氧化物(1分鐘半衰期溫度：116.4℃)、二正辛醯基過氧化物(1分鐘半衰期溫度：117.4℃)、1,1,3,3-四甲基丁基過氧基-2-乙基己酸酯(1分鐘半衰期溫度：124.3℃)、二(4-甲基苯甲醯基)過氧化物(1分鐘半衰期溫度：128.2℃)、苯甲醯基過氧化物(1分鐘半衰期溫度：130.0℃)、過異丁酸三級丁酯(1分鐘半衰期溫度：136.1℃)、1,1-二(三級己基過氧基)環己烷(1分鐘半衰期溫度：149.2℃)等，由交聯反應效率優異來看，宜為二(4-三級丁基環己基)過氧二碳酸酯、二月桂醯基過氧化物、苯甲醯基過氧化物，尤宜為苯甲醯基過氧化物。Examples of peroxides include: bis(2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: 90.6°C), bis(4-tertiary butylcyclohexyl) peroxydicarbonate (1 minute half-life Temperature: 92.1°C), di-secondary butyl peroxydicarbonate (1-minute half-life temperature: 92.4°C), tertiary butyl peroxyneodecanoate (1-minute half-life temperature: 103.5°C), trimethyl peroxide Tertiary hexyl acetate (1-minute half-life temperature: 109.1°C), tertiary butyl peroxytrimethylacetate (1-minute half-life temperature: 110.3°C), dilauroyl peroxide (1-minute half-life temperature: 116.4°C ), di-n-octyl peroxide (1-minute half-life temperature: 117.4°C), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (1-minute half-life temperature: 124.3°C ), bis(4-methylbenzoyl) peroxide (1-minute half-life temperature: 128.2°C), benzoyl peroxide (1-minute half-life temperature: 130.0°C), tertiary butyl perisobutyrate Esters (1-minute half-life temperature: 136.1°C), 1,1-bis(tertiary hexylperoxy)cyclohexane (1-minute half-life temperature: 149.2°C), etc., in view of the excellent cross-linking reaction efficiency, two (4-tertiary butylcyclohexyl) peroxydicarbonate, dilauroyl peroxide, benzoyl peroxide, especially benzoyl peroxide.

過氧化物系交聯劑之摻混量無特別限定，相對於(甲基)丙烯酸系聚合物(A)100重量份，例如為0.01~5重量份，宜為2重量份以下，較宜為1重量份以下，更宜為0.5重量份以下。過氧化物系交聯劑之摻混量為上述範圍時，可容易調整黏著片之加工性、交聯穩定性等。The blending amount of the peroxide-based crosslinking agent is not particularly limited, but it is, for example, 0.01 to 5 parts by weight, preferably 2 parts by weight or less, with respect to 100 parts by weight of the (meth)acrylic polymer (A). 1 part by weight or less, more preferably 0.5 part by weight or less. When the blending amount of the peroxide-based crosslinking agent is within the above range, the processability, crosslinking stability, etc. of the adhesive sheet can be easily adjusted.

[其他成分] 黏著劑組成物亦可包含有異氰酸酯系交聯劑及過氧化物系交聯劑以外之其他交聯劑。其他交聯劑可舉環氧系交聯劑、亞胺系交聯劑、多官能性金屬螯合物等。相對於(甲基)丙烯酸系聚合物(A)100重量份，其他交聯劑之摻混量宜為2重量份以下，較宜為1重量份以下。由黏著片之耐久性之觀點來看，黏著劑組成物亦可實質上不含其他交聯劑、尤其不含環氧系交聯劑。 [other ingredients] The adhesive composition may also contain other cross-linking agents other than the isocyanate-based cross-linking agent and the peroxide-based cross-linking agent. Other cross-linking agents include epoxy-based cross-linking agents, imine-based cross-linking agents, polyfunctional metal chelate compounds, and the like. The blending amount of other crosslinking agents is preferably 2 parts by weight or less, more preferably 1 part by weight or less, based on 100 parts by weight of the (meth)acrylic polymer (A). From the viewpoint of the durability of the adhesive sheet, the adhesive composition may not substantially contain other crosslinking agents, especially epoxy-based crosslinking agents.

黏著劑組成物亦可更包含有(甲基)丙烯酸系寡聚物。The adhesive composition may further include a (meth)acrylic oligomer.

(甲基)丙烯酸系寡聚物除了重量平均分子量(Mw)不同外，可具有與上述(甲基)丙烯酸系聚合物(A)相同之組成。(甲基)丙烯酸系寡聚物之重量平均分子量(Mw)例如為1000以上，亦可為2000以上、3000以上，更可為4000以上。(甲基)丙烯酸系寡聚物之重量平均分子量(Mw)的上限例如為30000以下，亦可為15000以下、10000以下，更可為7000以下。The (meth)acrylic oligomer may have the same composition as that of the above-mentioned (meth)acrylic polymer (A) except that the weight average molecular weight (Mw) is different. The weight average molecular weight (Mw) of a (meth)acryl-type oligomer is 1000 or more, for example, 2000 or more, 3000 or more, and 4000 or more. The upper limit of the weight average molecular weight (Mw) of a (meth)acrylic oligomer is 30000 or less, for example, 15000 or less, 10000 or less, and 7000 or less.

(甲基)丙烯酸系寡聚物例如具有1種或2種以上源自以下各單體之構成單元：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一酯及(甲基)丙烯酸十二酯等之(甲基)丙烯酸烷基酯；(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯及(甲基)丙烯酸二環戊酯等之(甲基)丙烯酸與脂環族醇之酯；(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯等之含芳香環(甲基)丙烯酸酯；以及由萜化合物衍生物醇所得之(甲基)丙烯酸酯。(Meth)acrylic oligomers have, for example, one or more constituent units derived from the following monomers: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate , Isopropyl (meth)acrylate, Butyl (meth)acrylate, Isobutyl (meth)acrylate, Secondary butyl (meth)acrylate, Tertiary butyl (meth)acrylate, (Meth) ) pentyl acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, Isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate Alkyl (meth)acrylates such as lauryl (meth)acrylate and lauryl (meth)acrylate; Esters of (meth)acrylic acid and alicyclic alcohols; (meth)acrylates containing aromatic rings such as phenyl (meth)acrylate and benzyl (meth)acrylate; meth)acrylate.

(甲基)丙烯酸系寡聚物宜具有源自具有體積較大之結構的(甲基)丙烯酸系單體之構成單元。此時，可更提高黏著片之接著性。該丙烯酸系單體之例為：(甲基)丙烯酸異丁酯及(甲基)丙烯酸三級丁酯等具有具支鏈結構之烷基之(甲基)丙烯酸烷基酯；(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯及(甲基)丙烯酸二環戊酯等(甲基)丙烯酸與脂環族醇之酯；(甲基)丙烯酸苯酯及(甲基)丙烯酸苄酯等含芳香環(甲基)丙烯酸酯。該單體宜具有環狀結構，較宜具有2個以上環狀結構。又，於(甲基)丙烯酸系寡聚物聚合時、及/或在形成黏著劑片時實施紫外線照射之情況下，由不易阻礙聚合及/或形成之進行來看，上述單體宜不具不飽和鍵，例如可使用具有具支鏈結構之烷基之(甲基)丙烯酸烷基酯、(甲基)丙烯酸與脂環族醇之酯。The (meth)acrylic oligomer preferably has a constituent unit derived from a (meth)acrylic monomer having a bulky structure. In this case, the adhesion of the adhesive sheet can be further improved. Examples of the acrylic monomers are: (meth)acrylic acid alkyl esters with branched alkyl groups such as isobutyl (meth)acrylate and tertiary butyl (meth)acrylate; Esters of (meth)acrylic acid and cycloaliphatic alcohols such as cyclohexyl acrylate, isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate; phenyl (meth)acrylate and (meth)acrylic acid Aromatic ring-containing (meth)acrylate such as benzyl ester. The monomer preferably has a cyclic structure, and preferably has two or more cyclic structures. In addition, when the (meth)acrylic oligomer is polymerized and/or in the case of ultraviolet irradiation when forming an adhesive sheet, the above-mentioned monomer is preferably free from the viewpoint that it is difficult to hinder the progress of polymerization and/or formation. As the saturated bond, for example, an alkyl (meth)acrylate having an alkyl group having a branched chain structure, an ester of (meth)acrylic acid and an alicyclic alcohol can be used.

(甲基)丙烯酸系寡聚物之具體例為：丙烯酸丁酯與丙烯酸甲酯與丙烯酸之共聚物、甲基丙烯酸環己酯與甲基丙烯酸異丁酯之共聚物、甲基丙烯酸環己酯與甲基丙烯酸異莰酯之共聚物、甲基丙烯酸環己酯與丙烯醯嗎福林之共聚物、甲基丙烯酸環己酯與二乙基丙烯醯胺之共聚物、丙烯酸1-金剛烷基酯與甲基丙烯酸甲酯之共聚物、甲基丙烯酸二環戊酯與甲基丙烯酸異莰酯之共聚物、選自甲基丙烯酸二環戊酯、甲基丙烯酸環己酯、甲基丙烯酸異莰酯、丙烯酸異莰酯、甲基丙烯酸環戊酯中之至少1種與甲基丙烯酸甲酯之共聚物、丙烯酸二環戊酯之均聚物、甲基丙烯酸1-金剛烷基酯之均聚物及丙烯酸1-金剛烷基酯之均聚物。Specific examples of (meth)acrylic oligomers are: copolymers of butyl acrylate, methyl acrylate and acrylic acid, copolymers of cyclohexyl methacrylate and isobutyl methacrylate, cyclohexyl methacrylate Copolymer with isocamphoryl methacrylate, copolymer of cyclohexyl methacrylate and acrylmorphin, copolymer of cyclohexyl methacrylate and diethylacrylamide, 1-adamantyl acrylate Copolymer of ester and methyl methacrylate, copolymer of dicyclopentyl methacrylate and isobornyl methacrylate, selected from dicyclopentanyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate Copolymer of camphenyl, isocamphoryl acrylate, and cyclopentyl methacrylate with methyl methacrylate, homopolymer of dicyclopentyl acrylate, homopolymer of 1-adamantyl methacrylate Polymer and homopolymer of 1-adamantyl acrylate.

(甲基)丙烯酸系寡聚物之聚合可採用上述(甲基)丙烯酸系聚合物(A)之聚合方法。The polymerization method of the said (meth)acrylic-type polymer (A) can be used for the polymerization of a (meth)acrylic-type oligomer.

黏著劑組成物包含(甲基)丙烯酸系寡聚物時，相對於(甲基)丙烯酸系聚合物(A)100重量份，其摻混量例如為70重量份以下，亦可為50重量份以下，更可為40重量份以下。相對於(甲基)丙烯酸系聚合物(A)100重量份，摻混量的下限例如為1重量份以上，亦可為2重量份以上，更可為3重量份以上。黏著劑組成物亦可不含(甲基)丙烯酸系寡聚物。When the adhesive composition contains a (meth)acrylic oligomer, the blending amount thereof is, for example, 70 parts by weight or less, or 50 parts by weight relative to 100 parts by weight of the (meth)acrylic polymer (A). Below, it may be 40 weight part or less. The lower limit of the compounding quantity is 1 weight part or more with respect to 100 weight part of (meth)acryl-type polymers (A), For example, 2 weight part or more may be sufficient as 3 weight part or more. The adhesive composition may not contain a (meth)acrylic oligomer.

黏著劑組成物亦可更含有公知之添加劑。添加劑可列舉例如：矽烷耦合劑、溶劑、著色劑、顏料等粉體、染料、界面活性劑、塑化劑、增黏劑(賦黏劑)、表面潤滑劑、調平劑、重工提升劑、軟化劑、抗氧化劑、抗老化劑、光穩定劑、紫外線吸收劑、聚合抑制劑、無機或有機充填劑、金屬粉、粒子、箔狀物等。並且，亦可在可控制之範圍內採用添加有還原劑的氧化還原系。相對於(甲基)丙烯酸系聚合物(A)100重量份，該等添加劑可在例如10重量份以下、宜在5重量份以下、較宜在1重量份以下之範圍下使用。The adhesive composition may further contain known additives. Additives include, for example: silane coupling agents, solvents, colorants, pigments and other powders, dyes, surfactants, plasticizers, tackifiers (tackifiers), surface lubricants, leveling agents, heavy industry enhancers, Softeners, antioxidants, antiaging agents, light stabilizers, UV absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, particles, foils, etc. In addition, a redox system in which a reducing agent is added can also be used within a controllable range. These additives can be used in an amount of, for example, 10 parts by weight or less, preferably 5 parts by weight or less, more preferably 1 part by weight or less, based on 100 parts by weight of the (meth)acrylic polymer (A).

矽烷耦合劑之具體例可列舉例如：3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、2-(3-4-環氧環己基)乙基三甲氧基矽烷等含環氧基之矽烷耦合劑；3-胺丙基三甲氧基矽烷、N-2-(胺乙基)-3-胺丙基甲基二甲氧基矽烷、3-三乙氧基矽基-N-(1,3-二甲基亞丁基)丙胺、N-苯基-γ-胺丙基三甲氧基矽烷等含胺基之矽烷耦合劑；3-丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧丙基三乙氧基矽烷等含(甲基)丙烯醯基之矽烷耦合劑；3-異氰酸酯丙基三乙氧基矽烷等含異氰酸酯基之矽烷耦合劑等。Specific examples of silane coupling agents include, for example: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyl Diethoxysilane, 2-(3-4-epoxycyclohexyl)ethyltrimethoxysilane and other epoxy-containing silane coupling agents; 3-aminopropyltrimethoxysilane, N-2-(amine Ethyl)-3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, N-phenyl-γ-aminopropyl Amino-containing silane coupling agents such as trimethoxysilane; 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. silane coupling agent; 3-isocyanate propyltriethoxysilane and other silane coupling agents containing isocyanate groups.

黏著劑組成物包含矽烷耦合劑時，相對於(甲基)丙烯酸系聚合物(A)100重量份，其摻混量例如為5重量份以下，亦可為3重量份以下、1重量份以下、0.5重量份以下、0.2重量份以下、0.1重量份以下，更可為0.05重量份以下。黏著劑組成物亦可不含矽烷耦合劑。When the adhesive composition contains a silane coupling agent, the blending amount thereof is, for example, 5 parts by weight or less, or 3 parts by weight or less, or 1 part by weight or less with respect to 100 parts by weight of the (meth)acrylic polymer (A). , 0.5 parts by weight or less, 0.2 parts by weight or less, 0.1 parts by weight or less, more preferably 0.05 parts by weight or less. The adhesive composition may also not contain silane coupling agent.

黏著劑組成物之類型例如為乳膠型、溶劑型(溶液型)、活性能量線(光硬化型)、熱熔融型(熱熔型)等。由可形成耐久性優異之黏著片之觀點來看，黏著劑組成物亦可為溶劑型。溶劑型黏著劑組成物亦可實質上不含紫外線硬化劑等光硬化劑。The types of the adhesive composition are, for example, latex type, solvent type (solution type), active energy ray (photohardening type), hot-melt type (hot-melt type), and the like. From the viewpoint of being able to form an adhesive sheet excellent in durability, the adhesive composition may be a solvent type. The solvent-based adhesive composition may not substantially contain photocuring agents such as ultraviolet curing agents.

[黏著劑組成物之特性] 如上述，本實施形態之黏著劑組成物中，相對於(甲基)丙烯酸系聚合物(A)100重量份，異氰酸酯系交聯劑之摻混量為2重量份以上。異氰酸酯系交聯劑相對於(甲基)丙烯酸系聚合物(A)之摻混量如該程度般多時，有由黏著劑組成物製成之黏著片之初始凝膠分率低之傾向。但，根據本實施形態之黏著劑組成物，藉由進一步包含過氧化物系交聯劑，可使黏著片之初始凝膠分率上升。吾等認為黏著片之初始凝膠分率的上升係因利用過氧化物系交聯劑之自由基的(甲基)丙烯酸系聚合物(A)之交聯反應所致。根據本發明人等之研討，黏著片之初始凝膠分率高時，有可抑制於黏著片發生凹陷之傾向。並且，根據本發明人等之研討，以由本實施形態之黏著劑組成物形成之黏著片來說，亦有耐久性被改善之傾向。 [Characteristics of Adhesive Composition] As mentioned above, in the adhesive composition of this embodiment, the compounding quantity of an isocyanate crosslinking agent is 2 weight part or more with respect to 100 weight part of (meth)acrylic-type polymers (A). When the compounding quantity of an isocyanate crosslinking agent with respect to a (meth)acrylic-type polymer (A) is as large as this, the initial gel fraction of the adhesive sheet which consists of an adhesive composition will tend to be low. However, according to the adhesive composition of the present embodiment, the initial gel fraction of the adhesive sheet can be increased by further including a peroxide-based crosslinking agent. We believe that the increase in the initial gel fraction of the adhesive sheet is due to the cross-linking reaction of the (meth)acrylic polymer (A) using free radicals of the peroxide-based cross-linking agent. According to the study of the inventors of the present invention, when the initial gel fraction of the adhesive sheet is high, it tends to suppress the occurrence of dents in the adhesive sheet. Furthermore, according to the study of the inventors of the present invention, the durability of the adhesive sheet formed of the adhesive composition of the present embodiment tends to be improved.

舉一例而言，藉由將黏著劑組成物塗佈於基材上以形成塗佈膜，並對塗佈膜在120℃下進行300秒鐘乾燥處理而獲得黏著片，所得黏著片之初始凝膠分率為40%以上，宜為50%以上。黏著片之初始凝膠分率的上限值無特別限定，例如為70%。For example, an adhesive sheet is obtained by applying an adhesive composition on a substrate to form a coating film, and drying the coating film at 120° C. for 300 seconds. The initial coagulation of the obtained adhesive sheet The glue fraction is more than 40%, preferably more than 50%. The upper limit of the initial gel fraction of the adhesive sheet is not particularly limited, and is, for example, 70%.

黏著片之初始凝膠分率例如可藉由以下方法來評估。首先，針對藉由上述方法製出之黏著片，在製作後2小時以內刮取一部分而獲得小片。接著，將獲得之小片以聚四氟乙烯之延伸多孔質膜包覆並用風箏線綑綁。藉此，可獲得試驗片。接著，測定黏著片之小片、延伸多孔質膜及風箏線之重量的合計(重量A)。此外，將所使用之延伸多孔質膜及風箏線的合計定義為重量B。接著，將試驗片浸漬於裝滿乙酸乙酯之容器後，在23℃下靜置1星期。靜置後，從容器取出試驗片，使其在設定成130℃之乾燥機中乾燥2小時後，測定試驗片之重量C。根據下述式，可從重量A、重量B及重量C算出黏著片之初始凝膠分率。 凝膠分率(重量%)=(C-B)/(A-B)×100 The initial gel fraction of the adhesive sheet can be evaluated by the following method, for example. First, a small piece was obtained by scraping a part of the adhesive sheet produced by the above method within 2 hours after production. Next, the obtained small pieces were covered with stretched porous polytetrafluoroethylene films and bound with kite strings. Thereby, a test piece can be obtained. Next, the total weight (weight A) of the small piece of the adhesive sheet, the stretched porous film, and the kite string was measured. In addition, the total of the stretched porous film and the kite string used is defined as weight B. Next, after immersing the test piece in the container filled with ethyl acetate, it left still at 23 degreeC for 1 week. After standing still, the test piece was taken out from the container and dried for 2 hours in a dryer set at 130° C., and then the weight C of the test piece was measured. The initial gel fraction of the adhesive sheet can be calculated from the weight A, the weight B, and the weight C according to the following formula. Gel fraction (weight%)=(C-B)/(A-B)×100

(黏著片之實施形態) 於圖1顯示本實施形態之黏著片之一例。本實施形態之黏著片1係由上述黏著劑組成物形成者。黏著片1例如包含(甲基)丙烯酸系聚合物(A)之交聯物、與包含源自異氰酸酯系交聯劑之構成單元作為主成分之聚合物(B)。聚合物(B)中，源自異氰酸酯系交聯劑之構成單元之含有率例如為70重量%以上，宜為90重量%以上。聚合物(B)例如實質上僅由源自異氰酸酯系交聯劑之構成單元構成。在黏著片1中，(甲基)丙烯酸系聚合物(A)之交聯物與聚合物(B)亦可構成互穿網(IPN)結構。該IPN結構適於使黏著片1之彈性模數增加的同時提升耐久性。 (Example of Adhesive Sheet) An example of the adhesive sheet of this embodiment is shown in FIG. 1. The adhesive sheet 1 of the present embodiment is formed of the above-mentioned adhesive composition. The adhesive sheet 1 contains, for example, a cross-linked product of a (meth)acrylic polymer (A), and a polymer (B) containing a structural unit derived from an isocyanate-based cross-linking agent as a main component. In the polymer (B), the content of the structural unit derived from the isocyanate-based crosslinking agent is, for example, 70% by weight or more, preferably 90% by weight or more. The polymer (B) is substantially composed of, for example, only structural units derived from an isocyanate-based crosslinking agent. In the adhesive sheet 1, the cross-linked product of the (meth)acrylic polymer (A) and the polymer (B) can also form an interpenetrating network (IPN) structure. The IPN structure is suitable for increasing the elastic modulus of the adhesive sheet 1 while improving durability.

黏著片1之厚度無特別限制，例如為1~100µm左右，宜為2~50µm，較宜為2~40µm，更宜為5~35µm。The thickness of the adhesive sheet 1 is not particularly limited, for example, it is about 1-100 µm, preferably 2-50 µm, more preferably 2-40 µm, more preferably 5-35 µm.

黏著片1之製造方法例如包含以下步驟：將上述黏著劑組成物塗佈於基材上，形成塗佈膜；與，使所得之塗佈膜乾燥。The method for producing the adhesive sheet 1 includes, for example, the following steps: coating the above-mentioned adhesive composition on a substrate to form a coating film; and drying the obtained coating film.

基材可使用例如脫模薄膜。形成於脫模薄膜之黏著片1例如可轉印至光學薄膜等。基材亦可為光學薄膜。此時，可藉由形成黏著片1來獲得光學積層體。As the substrate, for example, a release film can be used. The adhesive sheet 1 formed on the release film can be transferred to an optical film or the like, for example. The substrate can also be an optical film. At this time, an optical layered body can be obtained by forming the adhesive sheet 1 .

在將黏著片1轉印至光學薄膜後，脫模薄膜可至黏著片1供於實際使用為止前作為剝離襯材來使用，從而可在製程方面簡略化。After the adhesive sheet 1 is transferred to the optical film, the release film can be used as a release liner until the adhesive sheet 1 is actually used, thereby simplifying the manufacturing process.

脫模薄膜之構成材料可列舉例如：塑膠薄膜；紙、布、不織布等多孔質材料；網狀物、發泡片、金屬箔及該等之層合體等適當的薄片體等等，由表面平滑性優異方面來看，可適宜使用塑膠薄膜。The constituent materials of the release film include, for example: plastic films; porous materials such as paper, cloth, and non-woven fabrics; suitable thin sheets such as meshes, foam sheets, metal foils, and their laminates; In terms of excellent performance, plastic film can be used suitably.

塑膠薄膜無特別限定，可列舉例如：聚乙烯薄膜、聚丙烯薄膜、聚丁烯薄膜、聚丁二烯薄膜、聚甲基戊烯薄膜、聚氯乙烯薄膜、氯乙烯共聚物薄膜、聚對苯二甲酸乙二酯薄膜、聚對苯二甲酸丁二酯薄膜、聚胺甲酸酯薄膜、乙烯-乙酸乙烯酯共聚物薄膜等。The plastic film is not particularly limited, and examples thereof include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyparaphenylene Ethylene diformate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, etc.

脫模薄膜之厚度通常為5~200µm，宜為5~100µm左右。對於脫模薄膜施有例如聚矽氧系、氟系、長鏈烷基系等脫模處理。亦可對於脫模薄膜施行有使用脂肪醯胺系脫模劑、矽粉等進行的脫模及防污處理、塗佈型、捏合型、蒸鍍型等抗靜電處理。The thickness of the release film is usually 5~200µm, preferably about 5~100µm. For the release film, release treatment such as silicone-based, fluorine-based, long-chain alkyl-based, etc. is applied. The release film can also be subjected to release and antifouling treatment using aliphatic amide release agents, silicon powder, etc., antistatic treatment such as coating type, kneading type, and vapor deposition type.

對於基材亦可塗佈包含黏著劑組成物之溶液(黏著劑溶液)。黏著劑溶液之固體成分濃度例如為5~50重量%，宜為10~40重量%。此外，黏著劑溶液可因應(甲基)丙烯酸系聚合物(A)之聚合形態，將與聚合溶劑相同之溶劑或不同溶劑適當添加於黏著劑組成物中藉此來調製。A solution containing an adhesive composition (adhesive solution) may also be applied to the substrate. The solid content concentration of the adhesive solution is, for example, 5 to 50% by weight, preferably 10 to 40% by weight. In addition, the adhesive solution can be prepared by appropriately adding the same solvent as the polymerization solvent or a different solvent to the adhesive composition according to the polymerization form of the (meth)acrylic polymer (A).

將黏著劑組成物塗佈於基材上之方法可使用各種方法，可列舉例如：輥塗佈、接觸輥塗佈、凹版塗佈、逆塗佈、輥刷、噴塗佈、浸漬輥塗佈、棒塗佈、刮刀塗佈、氣刀塗佈、簾式塗佈、唇塗佈、利用模塗機等的擠壓式塗佈法等方法。黏著劑組成物之塗佈量可因應目標之黏著片1之厚度來適當調整。Various methods can be used to coat the adhesive composition on the substrate, for example: roll coating, touch roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating , rod coating, knife coating, air knife coating, curtain coating, lip coating, extrusion coating using a die coater or the like. The coating amount of the adhesive composition can be appropriately adjusted according to the thickness of the target adhesive sheet 1 .

藉由使塗佈膜乾燥，塗佈膜會硬化，而形成黏著片1。塗佈膜之乾燥溫度無特別限定，例如為130℃以下，宜為125℃以下，較宜為120℃以下。塗佈膜之乾燥溫度可為60℃以上，亦可為100℃以上。乾燥溫度在60℃以上時，異氰酸酯系交聯劑之反應會順利進行，而可提升黏著片1之凝集力，從而有可減少影像顯示裝置之顯示不均的傾向。乾燥溫度在130℃以下時，可適當調整異氰酸酯系交聯劑的反應速度，而有可良好地維持(甲基)丙烯酸系聚合物(A)與聚合物(B)之相溶性，確保透明性之傾向。塗佈膜亦可在90℃以下之溫度下預加熱後，以高於90℃之溫度(例如120℃)進行加熱使其乾燥。By drying the coating film, the coating film hardens, and the adhesive sheet 1 is formed. The drying temperature of the coating film is not particularly limited, for example, it is below 130°C, preferably below 125°C, more preferably below 120°C. The drying temperature of the coating film may be 60°C or higher, or may be 100°C or higher. When the drying temperature is above 60°C, the reaction of the isocyanate-based crosslinking agent proceeds smoothly, and the cohesive force of the adhesive sheet 1 can be improved, thereby reducing the display unevenness of the image display device. When the drying temperature is below 130°C, the reaction rate of the isocyanate-based crosslinking agent can be adjusted appropriately, and the compatibility between the (meth)acrylic polymer (A) and the polymer (B) can be maintained well, ensuring transparency tendency. The coating film may also be dried by heating at a temperature higher than 90°C (for example, 120°C) after preheating at a temperature below 90°C.

由包含過氧化物系交聯劑之以往的黏著劑組成物形成黏著片時，必須將塗佈膜的乾燥溫度設定成較高溫(例如155℃左右)，以使過氧化物系交聯劑之熱分解發生。但，以本實施形態之黏著劑組成物來說，由異氰酸酯系交聯劑之反應而產生之胺基可促進過氧化物系交聯劑之熱分解。因此，本實施形態之黏著劑組成物有即便在130℃以下之較低溫的乾燥溫度下，仍能利用過氧化物系交聯劑充分進行交聯反應之傾向。When forming an adhesive sheet from a conventional adhesive composition containing a peroxide-based crosslinking agent, it is necessary to set the drying temperature of the coating film to a relatively high temperature (for example, about 155°C) so that the peroxide-based crosslinking agent Thermal decomposition occurs. However, in the adhesive composition of this embodiment, the amine group generated by the reaction of the isocyanate-based crosslinking agent can accelerate the thermal decomposition of the peroxide-based crosslinking agent. Therefore, the adhesive composition of this embodiment tends to be able to sufficiently carry out the cross-linking reaction by the peroxide-based cross-linking agent even at a relatively low drying temperature of 130° C. or lower.

塗佈膜之乾燥時間可因應黏著劑組成物之組成適當調節，宜為30秒~300秒，更宜為40秒~240秒，尤宜為60秒~180秒。The drying time of the coating film can be appropriately adjusted according to the composition of the adhesive composition, preferably 30 seconds to 300 seconds, more preferably 40 seconds to 240 seconds, and especially preferably 60 seconds to 180 seconds.

[黏著片之特性] 黏著片1宜具有高透明性。黏著片1之厚度為15µm時，黏著片1之霧度例如為1%以下，宜為0.8%以下，更宜為0.5%以下。 [Characteristics of Adhesive Sheet] The adhesive sheet 1 preferably has high transparency. When the thickness of the adhesive sheet 1 is 15 µm, the haze of the adhesive sheet 1 is, for example, 1% or less, preferably 0.8% or less, more preferably 0.5% or less.

黏著片1在25℃下之儲存彈性模數G'無特別限定，例如為0.5MPa以上，宜為0.8MPa以上，較宜為1.0MPa以上。黏著片1在25℃下之儲存彈性模數G'的上限值無特別限定，例如為2.0MPa。儲存彈性模數G'在上述範圍內之高彈性係數之黏著片1適於抑制光學薄膜之尺寸變化。The storage elastic modulus G' of the adhesive sheet 1 at 25° C. is not particularly limited, for example, it is not less than 0.5 MPa, preferably not less than 0.8 MPa, more preferably not less than 1.0 MPa. The upper limit of the storage elastic modulus G' of the adhesive sheet 1 at 25° C. is not particularly limited, and is, for example, 2.0 MPa. The adhesive sheet 1 with a high elastic coefficient and a storage elastic modulus G' within the above range is suitable for suppressing the dimensional change of the optical film.

黏著片1在25℃下之儲存彈性模數G'可藉由以下方法特定。首先，準備以構成黏著片1之材料構成之測定用試樣。測定用試樣之形狀為圓盤狀。測定用試樣之底面直徑為8mm，厚度為2mm。測定用試樣亦可為將複數片黏著片1積層而成之積層體沖裁成圓盤狀者。接著，對測定用試樣進行動態黏彈性測定。動態黏彈性測定例如可使用TA Instruments公司製「ARES-G2」。由動態黏彈性測定之結果可特定黏著片1在25℃下之儲存彈性模數G'。此外，動態黏彈性測定之條件如下。 ・測定條件 頻率：1Hz 變形模式：扭轉 測定溫度：-70℃~150℃ 升溫速度：5℃/分鐘 The storage elastic modulus G' of the adhesive sheet 1 at 25° C. can be specified by the following method. First, a measurement sample made of the material constituting the adhesive sheet 1 is prepared. The shape of the sample for measurement is disc-shaped. The diameter of the bottom surface of the sample for measurement is 8mm, and the thickness is 2mm. The sample for measurement may be a laminate obtained by laminating a plurality of adhesive sheets 1 and punched out into a disc shape. Next, dynamic viscoelasticity measurement was performed on the sample for measurement. For the measurement of dynamic viscoelasticity, "ARES-G2" manufactured by TA Instruments can be used, for example. The storage elastic modulus G' of the adhesive sheet 1 at 25°C can be determined from the results of the dynamic viscoelasticity measurement. In addition, the conditions of dynamic viscoelasticity measurement are as follows. ・Measurement conditions Frequency: 1Hz Deformation Mode: Twist Measuring temperature: -70℃~150℃ Heating rate: 5°C/min

(光學積層體之實施形態) 於圖2顯示本實施形態之光學積層體之一例。圖2之光學積層體10A包含黏著片1與光學薄膜2。黏著片1與光學薄膜2係相互積層。光學積層體10A可作為附黏著片之光學薄膜使用。 (Embodiment of Optical Laminated Body) An example of the optical layered body of this embodiment is shown in FIG. 2 . The optical laminate 10A in FIG. 2 includes an adhesive sheet 1 and an optical film 2 . The adhesive sheet 1 and the optical film 2 are laminated together. The optical layered body 10A can be used as an optical film with an adhesive sheet attached.

光學薄膜2之例為偏光板、相位差薄膜、以及包含偏光板及/或相位差薄膜之積層薄膜。惟，光學薄膜2不受上述例限定。光學薄膜2亦可包含有玻璃製薄膜。Examples of the optical film 2 are a polarizing plate, a retardation film, and a laminated film including a polarizing plate and/or a retardation film. However, the optical film 2 is not limited to the above examples. The optical film 2 may also include a glass film.

偏光板例如為包含偏光件及透明保護薄膜之積層體。透明保護薄膜例如係配置成與層狀偏光件之主面(具有最寬廣面積之表面)相接。偏光件亦可配置於2個透明保護薄膜之間。The polarizing plate is, for example, a laminate including a polarizer and a transparent protective film. The transparent protective film is arranged, for example, so as to be in contact with the principal surface (the surface having the widest area) of the layered polarizer. The polarizer can also be arranged between two transparent protective films.

偏光件無特別限定，可使用各種之物。作為偏光件，可舉例如使聚乙烯醇系薄膜、部分縮甲醛化聚乙烯醇系薄膜、乙烯-乙酸乙烯酯共聚物系部分皂化薄膜等親水性高分子薄膜吸附碘或二色性染料之二色性物質並進行單軸延伸者；聚乙烯醇之脫水處理物、聚氯乙烯之脫鹽酸處理物等多烯系定向薄膜等。該等之中，又宜為由聚乙烯醇系薄膜與碘等二色性物質構成之偏光件，較宜為含有碘及/或碘離子之碘系偏光件。偏光件之厚度無特別限制，一般為5~80µm左右。The polarizer is not particularly limited, and various kinds can be used. As a polarizer, for example, a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or an ethylene-vinyl acetate copolymer partially saponified film can absorb iodine or a dichroic dye. Colored substances and uniaxial stretching; polyene-based oriented films such as dehydrated polyvinyl alcohol and polyvinyl chloride dehydrochloridized. Among them, a polarizer composed of a polyvinyl alcohol-based film and a dichroic substance such as iodine is preferable, and an iodine-based polarizer containing iodine and/or iodine ions is more preferable. The thickness of the polarizer is not particularly limited, and is generally about 5-80 µm.

將聚乙烯醇系薄膜用碘染色並單軸延伸所得之偏光件可藉由例如將聚乙烯醇浸漬於碘水溶液中染色，並延伸成原長的3~7倍來製作。亦可視需要，將聚乙烯醇浸漬於包含硼酸、硫酸鋅、氯化鋅等之碘化鉀等的水溶液中。更可視需要在染色前將聚乙烯醇系薄膜浸漬於水中進行水洗。藉由水洗聚乙烯醇系薄膜，可洗淨聚乙烯醇系薄膜表面的污垢或抗黏結劑，除此之外藉由使聚乙烯醇系薄膜膨潤還有抑制發生染色參差等之效果。聚乙烯醇系薄膜之延伸可在使用碘染色後進行，可一邊染色一邊進行，亦可在以碘染色前進行。延伸亦可在硼酸、碘化鉀等之水溶液中或水浴中進行。A polarizer obtained by dyeing a polyvinyl alcohol-based film with iodine and uniaxially stretching it can be fabricated by, for example, dipping polyvinyl alcohol in an aqueous solution of iodine, dyeing it, and stretching it to 3 to 7 times its original length. Alternatively, polyvinyl alcohol may be immersed in an aqueous solution of boric acid, zinc sulfate, zinc chloride, and potassium iodide, etc., as needed. If necessary, the polyvinyl alcohol-based film may be dipped in water and washed with water before dyeing. By washing the polyvinyl alcohol-based film with water, dirt and anti-adhesive agents on the surface of the polyvinyl alcohol-based film can be washed away. In addition, the swelling of the polyvinyl alcohol-based film also has the effect of suppressing uneven dyeing. Stretching of polyvinyl alcohol-based film can be performed after dyeing with iodine, while dyeing, or before dyeing with iodine. The extension can also be carried out in an aqueous solution of boric acid, potassium iodide, etc. or in a water bath.

偏光件亦可使用厚度為10µm以下之薄型偏光件。由薄型化觀點來說，偏光件之厚度宜為1~7µm。這種薄型偏光件因厚度參差少，視辨性佳，且尺寸變化少故耐久性優異，並且能圖謀偏光板之薄型化，由這方面來看理想。Thin polarizers with a thickness of 10µm or less can also be used as polarizers. From the viewpoint of thinning, the thickness of the polarizer should be 1~7µm. This kind of thin polarizer is ideal in terms of less variation in thickness, better visibility and less dimensional change, excellent durability, and the ability to reduce the thickness of the polarizer.

薄型偏光件代表上可舉日本專利特開昭51-069644號公報、日本專利特開2000-338329號公報、國際公開第2010/100917號、日本專利第4751481號公報、日本專利特開2012-073563號公報所記載之薄型偏光件。該等薄型偏光件可藉由包含以下步驟之製法而獲得：將聚乙烯醇系樹脂(以下，亦稱PVA系樹脂)層與延伸用樹脂基材在積層體之狀態下進行延伸之步驟與進行染色之步驟。若為該製法，因PVA系樹脂層被延伸用樹脂基材支持著，故即使PVA系樹脂層很薄，仍可抑制因延伸造成斷裂等不良情況。Examples of thin polarizers include Japanese Patent Laid-Open No. 51-069644, Japanese Patent Laid-Open No. 2000-338329, International Publication No. 2010/100917, Japanese Patent No. 4751481, and Japanese Patent Laid-Open No. 2012-073563 The thin polarizer described in the Publication No. These thin polarizers can be obtained by a manufacturing method including the steps of stretching a polyvinyl alcohol-based resin (hereinafter, also referred to as PVA-based resin) layer and a resin substrate for stretching in the state of a laminate and carrying out The steps of dyeing. According to this manufacturing method, since the PVA-based resin layer is supported by the resin substrate for stretching, even if the PVA-based resin layer is thin, defects such as breakage due to stretching can be suppressed.

在包含在積層體之狀態下進行延伸之步驟與進行染色之步驟的製法中，由可高倍率延伸而可提升偏光性能之方面來看，宜為國際公開第2010/100917號、日本專利第4751481號、日本專利特開2012-073563號公報所記載之包含在硼酸水溶液中進行延伸之步驟的製法，尤宜為日本專利第4751481號公報或日本專利特開2012-073563號公報所記載之包含在硼酸水溶液中進行延伸前輔助性地進行空中延伸之步驟的製法。In the production method including the step of stretching in the state of the laminate and the step of dyeing, it is preferable to use International Publication No. 2010/100917 and Japanese Patent No. 4751481 in terms of high-magnification stretching and polarization performance improvement. No., Japanese Patent Application Laid-Open No. 2012-073563 includes the method of extending in an aqueous solution of boric acid, especially Japanese Patent No. 4751481 or Japanese Patent Application No. 2012-073563. A method of supplementarily carrying out a step of in-flight stretching before carrying out stretching in aqueous boric acid solution.

用以形成設於偏光件之單面或兩面的透明保護薄膜之材料，例如可使用透明性、機械強度、熱穩定性、水分阻斷性、各向同性等優異的熱塑性樹脂。所述熱塑性樹脂之具體例可列舉：三醋酸纖維素等之纖維素樹脂、聚酯樹脂、聚醚碸樹脂、聚碸樹脂、聚碳酸酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚烯烴樹脂、(甲基)丙烯酸樹脂、環狀聚烯烴樹脂(降𦯉烯系樹脂)、聚芳酯樹脂、聚苯乙烯樹脂、聚乙烯醇樹脂及該等之混合物。透明保護薄膜之材料亦可為(甲基)丙烯酸系、胺甲酸酯系、丙烯酸胺甲酸酯系、環氧系、聚矽氧系等熱硬化性樹脂或紫外線硬化型樹脂。偏光板具有2個透明保護薄膜時，2個透明保護薄膜之材料可互同亦可互異。例如，亦可對偏光件之一主面透過接著劑貼合有以熱塑性樹脂構成之透明保護薄膜，且於偏光件之另一主面貼合有以熱硬化性樹脂或紫外線硬化型樹脂構成之透明保護薄膜。透明保護薄膜亦可包含有1種以上任意之添加劑。添加劑可舉例如紫外線吸收劑、抗氧化劑、滑劑、塑化劑、脫模劑、抗著色劑、阻燃劑、成核劑、抗靜電劑、顏料、著色劑等。透明保護薄膜中之熱塑性樹脂之含有率宜為50~100重量%，較宜為50~99重量%，更宜為60~98重量%，尤宜為70~97重量%。當透明保護薄膜中之熱塑性樹脂之含有率為50重量%以上時，有可充分展現熱塑性樹脂原本具有之高透明性等之傾向。As a material for forming the transparent protective film on one or both sides of the polarizer, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture blocking property, and isotropy can be used. Specific examples of the thermoplastic resin include cellulose resins such as cellulose triacetate, polyester resins, polyether resins, polyresins, polycarbonate resins, polyamide resins, polyimide resins, polyester resins, Olefin resins, (meth)acrylic resins, cyclic polyolefin resins (northylene-based resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof. The material of the transparent protective film can also be thermosetting resins such as (meth)acrylic, urethane, acrylic urethane, epoxy, polysiloxane or ultraviolet curable resins. When the polarizing plate has two transparent protective films, the materials of the two transparent protective films may be the same as or different from each other. For example, a transparent protective film made of thermoplastic resin may be attached to one main surface of the polarizer through an adhesive, and a thermosetting resin or ultraviolet curable resin may be attached to the other main surface of the polarizer. Transparent protective film. The transparent protective film may also contain one or more optional additives. Examples of additives include ultraviolet absorbers, antioxidants, slip agents, plasticizers, release agents, anti-coloring agents, flame retardants, nucleating agents, antistatic agents, pigments, and colorants. The thermoplastic resin content in the transparent protective film is preferably 50-100% by weight, more preferably 50-99% by weight, more preferably 60-98% by weight, and especially preferably 70-97% by weight. When the content rate of the thermoplastic resin in a transparent protective film is 50 weight% or more, it exists in the tendency which fully exhibits high transparency etc. which a thermoplastic resin originally has.

保護薄膜之厚度可適當決定，惟一般由強度或操作性等作業性、薄膜性等方面來看，為10~200μm左右。The thickness of the protective film can be determined appropriately, but generally it is about 10~200μm in terms of workability such as strength and operability, and film properties.

偏光件與透明保護薄膜通常係透過水系接著劑等密著。就水系接著劑而言，可例示異氰酸酯系接著劑、聚乙烯醇系接著劑、明膠系接著劑、乙烯基系乳膠、水系聚胺甲酸酯、水系聚酯等。上述接著劑以外之其他接著劑可舉紫外線硬化型接著劑、電子束硬化型接著劑等。電子束硬化型偏光板用接著劑係對各種透明保護薄膜展現適宜之接著性。接著劑亦可包含有金屬化合物填料。The polarizer and the transparent protective film are usually adhered through water-based adhesives or the like. Examples of the water-based adhesive include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, vinyl-based latex, water-based polyurethane, and water-based polyester. Adhesives other than the above adhesives include ultraviolet curable adhesives, electron beam curable adhesives, and the like. Adhesives for electron beam hardening type polarizing plates exhibit suitable adhesiveness to various transparent protective films. The adhesive may also contain metallic compound fillers.

偏光板中，亦可於偏光件上形成相位差薄膜等來取代透明保護薄膜。透明保護薄膜上亦可進一步設置其他透明保護薄膜、設置相位差薄膜等。In the polarizing plate, a retardation film or the like may be formed on the polarizer instead of the transparent protective film. On the transparent protective film, another transparent protective film, a retardation film, etc. may be further provided.

關於透明保護薄膜，可於與偏光件接著之表面相對向之表面設置有硬塗層，亦可施行為了抗反射、抗黏、擴散、防眩等之處理。Regarding the transparent protective film, a hard coat layer may be provided on the surface opposite to the surface of the polarizer, or it may be treated for anti-reflection, anti-sticking, diffusion, and anti-glare.

相位差膜薄膜可使用使高分子薄膜延伸而得者或已使液晶材料定向、固定化者。相位差薄膜例如於面內及/或厚度方向上具有雙折射。As the retardation film, one obtained by stretching a polymer film or one in which a liquid crystal material is oriented and fixed can be used. The retardation film has birefringence, for example, in-plane and/or in the thickness direction.

相位差薄膜可舉抗反射用相位差薄膜(參照日本專利特開2012-133303號公報[0221]、[0222]、[0228])、視角補償用相位差薄膜(參照日本專利特開2012-133303號公報[0225]、[0226])、視角補償用傾斜定向相位差薄膜(參照日本專利特開2012-133303號公報[0227])等。The retardation film can be anti-reflection retardation film (refer to Japanese Patent Laid-Open No. 2012-133303 communique [0221], [0222], [0228]), viewing angle compensation retardation film (refer to Japanese Patent Laid-Open No. 2012-133303 Publication No. [0225], [0226]), oblique orientation retardation film for viewing angle compensation (refer to Japanese Patent Application Laid-Open No. 2012-133303 [0227]), etc.

相位差薄膜若為實質上具有上述功能者，則例如相位差值、配置角度、3維雙折射率、單層或多層等無特別限制，可使用公知之相位差薄膜。As long as the retardation film substantially has the above-mentioned functions, such as retardation value, arrangement angle, three-dimensional birefringence, single-layer or multi-layer, etc., there are no special restrictions, and known retardation films can be used.

相位差薄膜之厚度宜為20µm以下，較宜為10µm以下，更宜為1~9µm，尤宜為3~8µm。The thickness of the retardation film is preferably less than 20 µm, more preferably less than 10 µm, more preferably 1-9 µm, especially 3-8 µm.

相位差薄膜例如係由液晶材料經定向、固定化之1/4波長板、1/2波長板這2層構成。The retardation film is composed of, for example, two layers of a 1/4 wavelength plate and a 1/2 wavelength plate in which a liquid crystal material is oriented and immobilized.

於圖3顯示本實施形態之光學積層體之另一例。圖3之光學積層體10B具有以下積層結構：依序積層有剝離襯材3、黏著片1及光學薄膜2。光學積層體10B可藉由剝離剝離襯材3而作為附黏著片之光學薄膜使用。Another example of the optical layered body of this embodiment is shown in FIG. 3 . The optical laminate 10B in FIG. 3 has the following laminated structure: a release liner 3 , an adhesive sheet 1 and an optical film 2 are laminated in this order. The optical layered body 10B can be used as an optical film with an adhesive sheet by peeling off the release liner 3 .

剝離襯材3之構成材料可列舉例如：聚乙烯、聚丙烯、聚對苯二甲酸乙二酯、聚酯薄膜等之塑膠薄膜；紙、布、不織布等之多孔質材料；網狀物、發泡片、金屬箔及該等之層合體等適當的薄片體等等，由表面平滑性優異方面來看，可適宜使用塑膠薄膜。The constituent materials of the release liner 3 include, for example: plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester film; porous materials such as paper, cloth, and non-woven fabric; Suitable thin sheets such as blister sheets, metal foils, and their laminates can be suitably used for plastic films because of their excellent surface smoothness.

塑膠薄膜若為可保護黏著劑片1之薄膜即無特別限定，可列舉例如：聚乙烯薄膜、聚丙烯薄膜、聚丁烯薄膜、聚丁二烯薄膜、聚甲基戊烯薄膜、聚氯乙烯薄膜、氯乙烯共聚物薄膜、聚對苯二甲酸乙二酯薄膜、聚對苯二甲酸丁二酯薄膜、聚胺甲酸酯薄膜、乙烯-乙酸乙酯共聚物薄膜等。The plastic film is not particularly limited if it is a film that can protect the adhesive sheet 1, for example: polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film Film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-ethyl acetate copolymer film, etc.

剝離襯材3之厚度通常為5~200µm，宜為5~100µm左右。對於剝離襯材3，可視需要利用聚矽氧系、氟系、長鏈烷基系或脂肪醯胺系脫模劑、矽粉等進行的脫模及防污處理、或者塗佈型、捏合型、蒸鍍型等抗靜電處理。尤其，藉由對於剝離襯材3之表面適當實施聚矽氧處理、長鏈烷基處理、氟處理等剝離處理，可更提高從黏著片1剝離之剝離性。The thickness of the release liner 3 is usually 5-200 µm, preferably about 5-100 µm. For the release liner 3, if necessary, use silicone-based, fluorine-based, long-chain alkyl-based or aliphatic amide-based release agents, silicon powder, etc. for mold release and antifouling treatment, or coating type, kneading type , Evaporation type and other antistatic treatment. In particular, by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the release liner 3, the releasability from the adhesive sheet 1 can be further improved.

此外，如上述，亦可將製作黏著片1時利用之脫模薄膜作為剝離襯材3來使用。In addition, as mentioned above, the release film used when producing the adhesive sheet 1 can also be used as the release liner 3 .

於圖4顯示本實施形態之光學積層體之另一例。圖4之光學積層體10C具有以下積層結構：依序積層有剝離襯材3、黏著片1、相位差薄膜2A、層間黏著劑4及偏光板2B。光學積層體10C可在剝離剝離襯材3後，例如貼附於影像形成層來使用。Another example of the optical layered body of this embodiment is shown in FIG. 4 . The optical laminate 10C in FIG. 4 has the following laminate structure: a release liner 3 , an adhesive sheet 1 , a retardation film 2A, an interlayer adhesive 4 and a polarizing plate 2B are laminated in sequence. The optical layered body 10C can be used after peeling off the release liner 3, for example, by sticking to an image forming layer.

層間黏著劑4可使用公知之黏著劑。亦可將黏著片1使用於層間黏著劑4。A well-known adhesive can be used for the interlayer adhesive 4. The adhesive sheet 1 can also be used for the interlayer adhesive 4 .

於圖5顯示本實施形態之光學積層體之另一例。圖5之光學積層體10D具有以下積層結構：依序積層有剝離襯材3、黏著片1、相位差薄膜2A、層間黏著劑4、偏光板2B及保護薄膜5。光學積層體10D可在剝離剝離襯材3後，例如貼附於影像形成層來使用。Another example of the optical layered body of this embodiment is shown in FIG. 5 . The optical laminate 10D in FIG. 5 has the following laminate structure: a release liner 3 , an adhesive sheet 1 , a retardation film 2A, an interlayer adhesive 4 , a polarizing plate 2B and a protective film 5 are laminated in sequence. The optical layered body 10D can be used after peeling off the release liner 3, for example, by sticking to the image forming layer.

保護薄膜5在光學積層體10D之流通及保管時、以及在光學積層體10D已組入影像顯示裝置之狀態下，具有保護作為最外層之光學薄膜2(偏光板2B)的功能。又，在已組入影像顯示裝置之狀態下，亦可為作為對外部空間之視窗發揮功能的保護薄膜5。保護薄膜5典型上為樹脂薄膜。構成保護薄膜5之樹脂例如為PET等聚酯、聚乙烯及聚丙烯等聚烯烴、丙烯酸、環烯烴、聚醯亞胺以及聚醯胺，宜為聚酯。惟，保護薄膜5不受上述例限定。保護薄膜5亦可為玻璃製薄膜、或包含玻璃製薄膜之積層薄膜。於保護薄膜5亦可施有防眩、抗反射、抗靜電等之表面處理。The protective film 5 has the function of protecting the outermost optical film 2 (polarizing plate 2B) during distribution and storage of the optical layered body 10D and when the optical layered body 10D is incorporated into an image display device. In addition, in a state where an image display device is incorporated, the protective film 5 functioning as a window to the external space may also be used. The protective film 5 is typically a resin film. The resin constituting the protective film 5 is, for example, polyester such as PET, polyolefin such as polyethylene and polypropylene, acrylic, cycloolefin, polyimide, and polyamide, preferably polyester. However, the protective film 5 is not limited to the above examples. The protective film 5 may be a glass film or a laminated film including a glass film. Surface treatments such as anti-glare, anti-reflection, and anti-static can also be applied to the protective film 5 .

保護薄膜5亦可藉由任意之黏著劑接合於光學薄膜2。亦可藉由黏著片1來接合。The protective film 5 can also be bonded to the optical film 2 by any adhesive. It can also be joined by the adhesive sheet 1 .

本實施形態之光學積層體例如可以將帶狀之光學積層體捲繞成之捲繞體之形態、或單片狀之光學積層體之形態進行流通及保管。The optical layered body of this embodiment can be distributed and stored, for example, in the form of a winding body in which a tape-shaped optical layered body is wound, or in the form of a single sheet-shaped optical layered body.

本實施形態之光學積層體典型上可用於影像顯示裝置。影像顯示裝置例如為液晶顯示器、有機EL顯示器及無機EL顯示器等EL顯示器。Typically, the optical layered body of this embodiment can be used for an image display device. The image display device is, for example, an EL display such as a liquid crystal display, an organic EL display, or an inorganic EL display.

(影像顯示裝置之實施形態) 於圖6顯示本實施形態之影像顯示裝置一例。圖6之影像顯示裝置11具有以下積層結構：依序積層有基板7、影像形成層(例如為有機EL層或液晶層)6、黏著片1、相位差薄膜2A、層間黏著劑4、偏光板2B及保護薄膜5。影像顯示裝置11具有圖3~5之光學積層體10B、10C、10D(惟，剝離襯材3除外)。基板7及影像形成層6若各自具有與公知之影像顯示裝置具備之基板及影像形成層相同之構成即可。 (Embodiment of Image Display Device) An example of the image display device of this embodiment is shown in FIG. 6 . The image display device 11 of FIG. 6 has the following laminated structure: a substrate 7, an image forming layer (such as an organic EL layer or a liquid crystal layer) 6, an adhesive sheet 1, a retardation film 2A, an interlayer adhesive 4, and a polarizing plate are laminated in sequence. 2B and protective film 5. The image display device 11 has the optical laminates 10B, 10C, and 10D shown in FIGS. 3 to 5 (except for the release liner 3 ). The substrate 7 and the image forming layer 6 may each have the same configuration as the substrate and image forming layer of a known image display device.

圖6之影像顯示裝置11可為有機EL顯示器，亦可為液晶顯示器。惟，影像顯示裝置11不受該例限定。影像顯示裝置11亦可為電致發光(EL)顯示器、電漿顯示器(PD)、場發射顯示器(FED：Field Emission Display)等。影像顯示裝置11可用於家電用途、車載用途、公共資訊顯示器(PID)用途等。The image display device 11 in FIG. 6 can be an organic EL display or a liquid crystal display. However, the image display device 11 is not limited to this example. The image display device 11 can also be an electroluminescence (EL) display, a plasma display (PD), a field emission display (FED: Field Emission Display) and the like. The image display device 11 can be used in home appliances, in-vehicle applications, public information display (PID) applications, and the like.

本實施形態之影像顯示裝置只要具備本實施形態之光學積層體，便可具有任意構成。The image display device of this embodiment may have any configuration as long as it includes the optical layered body of this embodiment.

實施例 以下藉由實施例更詳細說明本發明。本發明不受以下所示實施例所限。 Example The present invention will be described in detail below by means of examples. The present invention is not limited by the Examples shown below.

[(甲基)丙烯酸系聚合物A1] 於具備攪拌葉片、溫度計、氮氣導入管、冷卻器之四口燒瓶中，饋入含有丙烯酸丁酯(BA)95.1重量份、丙烯酸(AA)4.8重量份及丙烯酸2-羥乙酯0.1重量份之單體混合物。並相對於單體混合物100重量份將作為聚合引發劑之2,2’-偶氮雙異丁腈(AIBN)0.1重量份與乙酸乙酯一同饋入，一邊緩慢地攪拌一邊導入氮氣進行氮取代後，將燒瓶內的液溫保持在55℃附近進行7小時聚合反應。之後，於所得之應液中添加乙酸乙酯，調整成固體成分濃度30%，而獲得(甲基)丙烯酸系聚合物A1之溶液。 [(meth)acrylic polymer A1] In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a cooler, feed 95.1 parts by weight of butyl acrylate (BA), 4.8 parts by weight of acrylic acid (AA) and 0.1 parts by weight of 2-hydroxyethyl acrylate. monomer mixture. 0.1 part by weight of 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator was fed together with ethyl acetate with respect to 100 parts by weight of the monomer mixture, and nitrogen gas was introduced while stirring slowly to carry out nitrogen substitution. Thereafter, the temperature of the liquid in the flask was maintained at around 55° C. to carry out a polymerization reaction for 7 hours. Then, ethyl acetate was added to the obtained solution to adjust to a solid content concentration of 30%, and a solution of (meth)acrylic polymer A1 was obtained.

[(甲基)丙烯酸系聚合物A2~A8] 除了將使用之單體如表1所示變更外，以與(甲基)丙烯酸系聚合物A1相同方法，分別調製出(甲基)丙烯酸系聚合物A2~A8之溶液。 [(Meth)acrylic polymers A2~A8] Except for changing the monomers used as shown in Table 1, solutions of (meth)acrylic polymers A2 to A8 were prepared in the same manner as in (meth)acrylic polymer A1.

[表1]

Figure 02_image001
[Table 1]
Figure 02_image001

表1中之簡稱如下。 BA：丙烯酸正丁酯 BzA：丙烯酸苄酯 NVP：N-乙烯吡咯啶酮 AA：丙烯酸 HEA：丙烯酸2-羥乙酯 HBA：丙烯酸4-羥丁酯 AIBN：偶氮系聚合引發劑，2,2'-偶氮雙異丁腈(KISHIDA化學公司製) The abbreviations in Table 1 are as follows. BA: n-butyl acrylate BzA: benzyl acrylate NVP: N-vinylpyrrolidone AA: Acrylic HEA: 2-Hydroxyethyl Acrylate HBA: 4-Hydroxybutyl Acrylate AIBN: Azo-based polymerization initiator, 2,2'-azobisisobutyronitrile (manufactured by KISHIDA Chemical Co., Ltd.)

[黏著片之製作] (實施例1~10及比較例1~2) 以成為以下表2所示組成之方式混合(甲基)丙烯酸系聚合物及交聯劑，而獲得溶劑型黏著劑組成物。接著，將黏著劑組成物塗佈於作為基材薄膜(剝離襯材)之PET薄膜的表面上，以使乾燥後之黏著片的厚度會成為15µm。黏著劑組成物之塗佈係使用噴泉式塗佈機。針對所得之塗佈膜，以空氣循環式恆溫烘箱在120℃下進行乾燥處理300秒鐘，藉此形成實施例1~10及比較例1~2之黏著片。 [Making of Adhesive Sheet] (Examples 1-10 and Comparative Examples 1-2) A solvent-based adhesive composition was obtained by mixing a (meth)acrylic polymer and a crosslinking agent so as to have the composition shown in Table 2 below. Next, the adhesive composition was coated on the surface of the PET film as the base film (release liner) so that the thickness of the adhesive sheet after drying would be 15 µm. The coating of the adhesive composition uses a fountain coating machine. The obtained coating film was dried in an air circulation constant temperature oven at 120°C for 300 seconds to form the adhesive sheets of Examples 1-10 and Comparative Examples 1-2.

[表2]

Figure 02_image003
[Table 2]
Figure 02_image003

表2中之簡稱如下。 C/L：三羥甲丙烷/二異氰酸甲苯酯(Tosoh公司製，商品名：CORONATE L) TETRAD-C：1,3-雙(N,N-二環氧丙基胺基甲基)環己烷(MITSUBISHI GAS CHEMICAL公司製，商品名：TETRAD C) 過氧化物：苯甲醯基過氧化物(日本油脂公司製，商品名：NYPER BMT) The abbreviations in Table 2 are as follows. C/L: trimethylolpropane/cresyl diisocyanate (manufactured by Tosoh, trade name: CORONATE L) TETRAD-C: 1,3-bis(N,N-diecidylaminomethyl)cyclohexane (manufactured by MITSUBISHI GAS CHEMICAL, trade name: TETRAD C) Peroxide: benzoyl peroxide (manufactured by NOF Corporation, trade name: NYPER BMT)

[評估] ＜(甲基)丙烯酸系聚合物之重量平均分子量(Mw)＞ 所得之(甲基)丙烯酸系聚合物之重量平均分子量(Mw)係利用GPC(凝膠滲透層析法)測定。 ・分析裝置：Tosoh(東曹)公司製，HLC-8120GPC ・管柱：Tosoh公司製，G7000H XL+GMH XL+GMH XL・管柱尺寸：各7.8mmφ×30cm 計90cm ・管柱溫度：40℃ ・流量：0.8ml/分鐘 ・注入量：100µl ・溶析液：四氫呋喃 ・檢測器：示差折射計(RI) ・標準試料：聚苯乙烯 [Evaluation] <Weight average molecular weight (Mw) of (meth)acrylic polymer> The weight average molecular weight (Mw) of the obtained (meth)acrylic polymer was measured by GPC (gel permeation chromatography).・Analyzer: HLC-8120GPC manufactured by Tosoh Corporation ・Column: G7000H XL + GMH XL + GMH XL manufactured by Tosoh Corporation ・Column size: 7.8mmφ×30cm each, 90cm in total・Flow rate: 0.8ml/min ・Injection volume: 100µl ・Eluent: THF ・Detector: Differential refractometer (RI) ・Standard sample: Polystyrene

＜厚度＞ 黏著片等之厚度係使用度盤規(Mitutoyo製)進行測定。 ＜Thickness＞ The thickness of the adhesive sheet and the like was measured using a dial gauge (manufactured by Mitutoyo).

＜初始凝膠分率＞ 針對黏著片，從製作後起算2小時以內刮取一部分而獲得小片，然後藉由上述方法來評估初始之凝膠分率。所得之小片之重量約0.2g。聚四氟乙烯之延伸多孔質膜係採用日東電工製NTF1122(平均孔徑0.2µm)。 ＜Initial Gel Fraction＞ For the adhesive sheet, a small piece is obtained by scraping a part within 2 hours after production, and then the initial gel fraction is evaluated by the above method. The weight of the obtained pellets was about 0.2 g. Nitto Denko NTF1122 (average pore size: 0.2 µm) was used as the extended porous film of polytetrafluoroethylene.

＜儲存彈性模數G'＞ 黏著片在25℃下之儲存彈性模數G'之評估係藉由上述方法實施。動態黏彈性測定係使用TA Instruments公司製「ARES-G2」來進行。 ＜Storage elastic modulus G'＞ The evaluation of the storage elastic modulus G' of the adhesive sheet at 25°C was carried out by the above-mentioned method. The dynamic viscoelasticity measurement was performed using "ARES-G2" manufactured by TA Instruments.

＜霧度＞ 黏著片(厚度15µm)之霧度例如係依循JIS K7136：1981，使用村上色彩技術研究所製之霧度計HR300，在25℃之氣體環境中進行測定。此外，測定係於松浪硝子工業製載玻片S012140(厚度1.3mm)上貼合有評估對象之黏著片(厚度15µm)之狀態下實施。 ＜Haze＞ The haze of the adhesive sheet (thickness 15 µm) is measured in a gas environment at 25°C using, for example, a haze meter HR300 manufactured by Murakami Color Technology Research Institute in accordance with JIS K7136:1981. In addition, the measurement was carried out in a state where the adhesive sheet (thickness 15 µm) of the evaluation object was attached to the glass slide S012140 (thickness 1.3 mm) manufactured by Matsunami Glass Industry.

＜加濕耐久性＞ 黏著片之加濕耐久性(相當於耐久性之加速試驗)係利用以下方法進行評估。首先，形成附黏著片之圓偏光板，其於其中一露出面具備實施例及比較例中所製作之各黏著片。接著，透過上述黏著片，將圓偏光板固定於玻璃板(康寧製，EAGLE XG)之表面。圓偏光板之固定係於23℃及50% RH之氣體環境中實施。接著，在50℃及5氣壓(絕對壓力)之高壓釜中處理15分鐘後，放置冷卻至23℃，使圓偏光板接合至玻璃板穩定後，於60℃及95%RH之加熱加濕氣體環境中放置500小時。放置後，回復至23℃及50%RH之氣體環境，以肉眼確認有無圓偏光板從玻璃板剝落或有無於玻璃板與圓偏光板之間發生發泡，並如下評估加濕耐久性。 A：未觀察到發泡或剝落等外觀上之變化。 B：於端部觀察到些微單獨之剝落或發泡，但實用上在無問題之範圍內。 C：於端部觀察到明顯的剝落或發泡，實用上有問題。 ＜Humidification Durability＞ The humidity durability of the adhesive sheet (corresponding to the accelerated test of durability) was evaluated by the following method. First, an adhesive sheet-attached circular polarizing plate was formed, which was equipped with each of the adhesive sheets produced in Examples and Comparative Examples on one exposed surface. Next, a circular polarizing plate was fixed on the surface of a glass plate (made by Corning, Eagle XG) through the above-mentioned adhesive sheet. The fixation of the circular polarizer is carried out in an air environment of 23°C and 50% RH. Then, after 15 minutes in an autoclave at 50°C and 5 atmospheres (absolute pressure), let it cool down to 23°C to stabilize the circular polarizing plate and the glass plate, then heat and humidify the gas at 60°C and 95% RH Placed in the environment for 500 hours. After standing, return to the gas environment of 23°C and 50%RH, check with the naked eye whether the circular polarizing plate is peeled off from the glass plate or whether there is foaming between the glass plate and the circular polarizing plate, and evaluate the humidity durability as follows. A: No change in appearance such as foaming or peeling was observed. B: Slight individual peeling or foaming was observed at the edge, but practically within the range of no problem. C: Significant peeling or foaming was observed at the edge, and there was a practical problem.

以下顯示用於評估加濕耐久性的附黏著片之圓偏光板之形成方法。A method of forming a circular polarizing plate with an adhesive sheet for evaluation of humidity durability is shown below.

＜偏光板P1之製作＞ (偏光件之製作) 用輥延伸機將長條狀聚乙烯醇(PVA)系樹脂薄膜(Kuraray製，製品名「PE3000」，厚度30µm)往長邊方向進行單軸延伸(總延伸倍率5.9倍)，同時對上述樹脂薄膜依序施行膨潤、染色、交聯、洗淨及乾燥之各處理，而製出厚度12µm之偏光件。膨潤處理中，係將上述樹脂薄膜一邊以20℃之純水進行處理一邊延伸2.2倍。染色處理中，一邊利用以重量比1：7含有碘及碘化鉀之30℃的水溶液進行處理，一邊將上述樹脂薄膜延伸1.4倍。水溶液中之碘濃度係調整成可使製作之偏光件的單體透射率成為45.0%。交聯處理係採用2階段處理。第一階段之交聯處理中，係一邊以溶解有硼酸及碘化鉀之40℃的水溶液進行處理，一邊將上述樹脂薄膜延伸1.2倍。第一階段之交聯處理所用之水溶液中之硼酸含有率設為5.0重量%，碘化鉀含有率設為3.0重量%。第二階段之交聯處理中，係一邊以溶解有硼酸及碘化鉀之65℃的水溶液進行處理，一邊將上述樹脂薄膜延伸1.6倍。第二階段之交聯處理所用的水溶液中，硼酸含有率設為4.3重量%，碘化鉀含有率設為5.0重量%。洗淨處理中係使用20℃之碘化鉀水溶液。洗淨處理所使用之水溶液中，碘化鉀含有率設為2.6重量%。乾燥處理係於70℃及5分鐘之乾燥條件下實施。 ＜Production of polarizing plate P1＞ (production of polarizer) A long strip of polyvinyl alcohol (PVA)-based resin film (manufactured by Kuraray, product name "PE3000", thickness 30µm) was uniaxially stretched in the longitudinal direction with a roll stretcher (total stretch ratio: 5.9 times), and the above resin Swelling, dyeing, cross-linking, washing and drying are performed on the film sequentially to produce a polarizer with a thickness of 12µm. In the swelling treatment, the above-mentioned resin film was stretched 2.2 times while being treated with pure water at 20°C. In the dyeing process, the above-mentioned resin film was stretched 1.4 times while being treated with a 30° C. aqueous solution containing iodine and potassium iodide at a weight ratio of 1:7. The concentration of iodine in the aqueous solution was adjusted so that the single transmittance of the manufactured polarizer could be 45.0%. The cross-linking treatment system adopts 2-stage treatment. In the first stage of cross-linking treatment, the above-mentioned resin film was stretched 1.2 times while treating with a 40° C. aqueous solution in which boric acid and potassium iodide were dissolved. The content of boric acid in the aqueous solution used in the first-stage crosslinking treatment was set to 5.0% by weight, and the content of potassium iodide was set to 3.0% by weight. In the second stage of cross-linking treatment, the above-mentioned resin film was stretched 1.6 times while treating with a 65° C. aqueous solution in which boric acid and potassium iodide were dissolved. In the aqueous solution used in the second-stage crosslinking treatment, the content of boric acid was 4.3% by weight, and the content of potassium iodide was 5.0% by weight. A potassium iodide aqueous solution at 20°C is used for cleaning. In the aqueous solution used for the cleaning treatment, the content of potassium iodide was 2.6% by weight. The drying treatment is carried out under the drying conditions of 70° C. and 5 minutes.

(偏光板P1之製作) 於上述製出之偏光件的各主面分別透過聚乙烯醇系接著劑貼合三醋酸纖維素(TAC)薄膜(Konica Minolta製，製品名「KC2UA」，厚度25µm)。惟，對於貼合於一主面之TAC薄膜，於與偏光件側相反側的主面形成有硬塗層(厚度7µm)。依上述方式，而獲得具有附硬塗層之保護層/偏光件/保護層(無硬塗層)之構成的偏光板P1。 (Production of Polarizer P1) A triacetyl cellulose (TAC) film (manufactured by Konica Minolta, product name "KC2UA", thickness 25 µm) was attached to each main surface of the polarizer prepared above through a polyvinyl alcohol-based adhesive. However, for the TAC film bonded to one main surface, a hard coat layer (thickness 7 µm) was formed on the main surface opposite to the polarizer side. In the above-mentioned manner, the polarizing plate P1 having the composition of protective layer with hard coat/polarizer/protective layer (no hard coat) was obtained.

＜相位差薄膜R1之製作＞ (第1相位差薄膜之製作) 將異山梨醇(ISB)26.2重量份、9,9-[4-(2-羥乙氧基)苯基]茀(BHEPF)100.5重量份、1,4-環己烷二甲醇(1,4-CHDM)10.7重量份、碳酸二苯酯(DPC)105.1重量份及作為觸媒之碳酸銫(0.2重量%水溶液)0.591重量份投入反應容器中，在氮氣環境下使其溶解(約15分鐘)。此時，反應容器之熱介質溫度設為150℃，且視需要實施了攪拌。接下來，將反應容器內之壓力減壓至13.3kPa，並在1小時內使熱介質溫度升溫至190℃。隨著熱介質溫度上升而產生的酚會排出至反應容器外(以下皆同)。接著，將反應容器內之溫度在190℃下保持15分鐘後，將反應容器內之壓力變更成6.67kPa，並在15分鐘內使熱介質溫度上升至230℃。在反應容器所具備之攪拌機其攪拌轉矩升起的時間點，在8分鐘內使熱介質溫度上升至250℃，並進一步使反應容器內之壓力在0.200kPa以下。到達預定之攪拌轉矩後，結束反應，將所生成之反應物擠出至水中使其丸粒化。依上述方式，而獲得具有BHEPF/ISB/1,4-CHDM=47.4莫耳%/37.1莫耳%/15.5莫耳%之組成的聚碳酸酯樹脂。所得之聚碳酸酯樹脂之玻璃轉移溫度為136.6℃，比濃黏度為0.395dL/g。 ＜Production of Retardation Film R1＞ (Production of the first retardation film) 26.2 parts by weight of isosorbide (ISB), 100.5 parts by weight of 9,9-[4-(2-hydroxyethoxy)phenyl] fennel (BHEPF), 1,4-cyclohexanedimethanol (1,4 -CHDM) 10.7 parts by weight, diphenyl carbonate (DPC) 105.1 parts by weight, and cesium carbonate (0.2% by weight aqueous solution) as a catalyst 0.591 parts by weight were put into the reaction vessel and dissolved under nitrogen atmosphere (about 15 minutes) . At this time, the temperature of the heat medium in the reaction container was set to 150° C., and stirring was performed as necessary. Next, the pressure in the reaction container was reduced to 13.3 kPa, and the temperature of the heat medium was raised to 190° C. within 1 hour. Phenol generated as the temperature of the heat medium rises is discharged to the outside of the reaction container (the same applies hereinafter). Next, after maintaining the temperature in the reaction container at 190° C. for 15 minutes, the pressure in the reaction container was changed to 6.67 kPa, and the temperature of the heat medium was raised to 230° C. within 15 minutes. When the stirring torque of the stirrer equipped in the reaction vessel was increased, the temperature of the heat medium was raised to 250° C. within 8 minutes, and the pressure in the reaction vessel was further reduced to 0.200 kPa or less. After the predetermined stirring torque is reached, the reaction is ended, and the generated reactant is extruded into water to pelletize it. In the above manner, a polycarbonate resin having a composition of BHEPF/ISB/1,4-CHDM=47.4 mol %/37.1 mol %/15.5 mol % was obtained. The glass transition temperature of the obtained polycarbonate resin was 136.6° C., and the reduced viscosity was 0.395 dL/g.

將製出之聚碳酸酯樹脂的丸粒在80℃下、真空乾燥5小時，之後，使用具備單軸擠製機(Isuzu Chemical Industries Co.,Ltd.製，螺桿徑25mm，缸筒設定溫度220℃)、T型模(寬200mm，設定溫度220℃)、冷卻輥(設定溫度120~130℃)及捲取機之薄膜製膜裝置，以獲得厚120µm之長條狀樹脂薄膜。接著，利用拉幅延伸機，以延伸溫度137-139℃、延伸倍率2.5倍，將所得之樹脂薄膜往寬度方向延伸，而獲得第1相位差薄膜。The prepared polycarbonate resin pellets were vacuum-dried at 80° C. for 5 hours. After that, a single-screw extruder (manufactured by Isuzu Chemical Industries Co., Ltd., screw diameter 25 mm, cylinder set temperature 220 ℃), T-die (width 200mm, set temperature 220°C), cooling roll (set temperature 120~130°C) and film-making device of coiler to obtain a long strip of resin film with a thickness of 120µm. Next, the obtained resin film was stretched in the width direction at a stretching temperature of 137-139° C. and a stretching ratio of 2.5 times using a tenter stretcher to obtain a first retardation film.

(第2相位差薄膜之製作) 將下述化學式(I)(式中，65及35係各構成單元之莫耳%)所示之側鏈型液晶聚合物(重量平均分子量5000)20重量份、顯示向列型液晶相之聚合性液晶(BASF製，商品名「PaliocolorLC242」)80重量份及光聚合引發劑(Ciba Specialty Chemicals製，商品名「IRGACURE 907」)5重量份溶解於環戊酮200重量份中，而調製出液晶塗敷液。接著，利用棒塗機將調製出的液晶塗敷液塗敷於基材薄膜之降𦯉烯系樹脂薄膜(日本ZEON製，商品名「ZEONEX」)的表面，之後，以80℃加熱及乾燥4分鐘，使塗佈膜所含之液晶定向。接著，利用紫外線照射使塗佈膜硬化，而於基材薄膜上形成作為第2相位差薄膜之液晶固化層(厚度0.58µm)。液晶固化層對波長550nm之光的面內相位差Re為0nm，厚度方向之相位差Rth為-71nm(nx=1.5326、ny=1.5326、nz=1.6550)，且液晶固化層展現nz＞nx=ny之折射率特性。 (Production of the second retardation film) 20 parts by weight of the side chain type liquid crystal polymer (weight average molecular weight 5000) shown in the following chemical formula (I) (wherein, 65 and 35 are the mole % of each constituent unit) shows the polymerization of the nematic liquid crystal phase Liquid crystal (manufactured by BASF, trade name "PaliocolorLC242") 80 parts by weight and photopolymerization initiator (manufactured by Ciba Specialty Chemicals, trade name "IRGACURE 907") 5 parts by weight were dissolved in 200 parts by weight of cyclopentanone to prepare a liquid crystal Coating solution. Next, the prepared liquid crystal coating solution was applied to the surface of a northylene-based resin film (manufactured by ZEON Japan, trade name "ZEONEX") of the substrate film using a bar coater, and then heated and dried at 80°C for 4 Minutes to align the liquid crystal contained in the coating film. Next, the coating film was cured by ultraviolet irradiation, and a liquid crystal solidified layer (thickness: 0.58 µm) was formed as a second retardation film on the base film. The in-plane retardation Re of the liquid crystal solidified layer to light with a wavelength of 550nm is 0nm, and the retardation Rth in the thickness direction is -71nm (nx=1.5326, ny=1.5326, nz=1.6550), and the liquid crystal solidified layer exhibits nz>nx=ny the refractive index properties.

[化學式1]

Figure 02_image005
[chemical formula 1]
Figure 02_image005

(相位差薄膜R1之製作) 透過接著劑貼合上述製出之第1相位差薄膜之一面與第2相位差薄膜之液晶固化層，而製出相位差薄膜R1。 (Manufacturing of Retardation Film R1) The retardation film R1 was produced by bonding one side of the above-produced first retardation film and the liquid crystal solidified layer of the second retardation film through an adhesive.

＜附黏著片之圓偏光板之製作＞ (層間黏著劑之製作) 於具備攪拌葉片、溫度計、氮氣導入管及冷卻器之四口燒瓶中，饋入含有丙烯酸丁酯79.9重量份、丙烯酸苄酯15重量份、丙烯酸5重量份及丙烯酸4-羥丁酯0.1重量份之單體混合物。接著，相對於單體混合物100重量份，一同加入作為聚合引發劑之2,2'-偶氮異丁腈0.1重量份與乙酸乙酯，一邊緩慢地攪拌一邊導入氮氣將燒瓶內進行氮取代後，將燒瓶內之液溫保持在55℃附近進行7小時聚合反應。接著，於所得之反應液中添加乙酸乙酯而調整成固體成分濃度30重量%，藉此獲得使用於層間黏著劑之(甲基)丙烯酸系聚合物之溶液。所得之聚合物之重量平均分子量為220萬。 ＜Production of circular polarizing plate with adhesive sheet＞ (Production of interlayer adhesive) In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube and a cooler, feed 79.9 parts by weight of butyl acrylate, 15 parts by weight of benzyl acrylate, 5 parts by weight of acrylic acid and 0.1 part by weight of 4-hydroxybutyl acrylate monomer mixture. Next, with respect to 100 parts by weight of the monomer mixture, 0.1 part by weight of 2,2'-azoisobutyronitrile and ethyl acetate were added together as a polymerization initiator, and nitrogen gas was introduced into the flask while stirring slowly to replace nitrogen in the flask. , The liquid temperature in the flask was kept at around 55° C. and the polymerization reaction was carried out for 7 hours. Next, ethyl acetate was added to the obtained reaction liquid to adjust to a solid content concentration of 30% by weight, thereby obtaining a solution of a (meth)acrylic polymer used as an interlayer adhesive. The weight average molecular weight of the obtained polymer was 2.2 million.

接著，於所得之(甲基)丙烯酸系聚合物之溶液中，相對於該溶液之固體成分100重量份，混合三羥甲丙烷/二異氰酸甲苯酯三聚物加成物(Tosoh製，商品名「CORONATE L」)0.5重量份、過氧化物交聯劑之苯甲醯基過氧化物0.1重量份、含環氧基之矽烷耦合劑(信越化學工業製，商品名「KBM-403」)0.2重量份及具有反應性矽基之聚醚化合物(Kaneka製，Silyl SAT10)0.5重量份，而獲得用於用以接合偏光板P1與相位差薄膜R1之層間黏著劑的黏著劑組成物PSA1。Next, in the obtained (meth)acrylic polymer solution, a trimethylolpropane/cresyl diisocyanate trimer adduct (manufactured by Tosoh, 0.5 part by weight of product name "CORONATE L", 0.1 part by weight of benzoyl peroxide as a peroxide crosslinking agent, silane coupling agent containing epoxy group (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-403") ) 0.2 parts by weight and 0.5 parts by weight of a polyether compound having a reactive silicon group (manufactured by Kaneka, Silyl SAT10) to obtain an adhesive composition PSA1 for bonding the interlayer adhesive of the polarizing plate P1 and the retardation film R1 .

(附層間黏著劑層之偏光板之製作) 將上述製出之黏著劑組成物PSA1塗佈於剝離面經施行聚矽氧處理之剝離薄膜、即塗佈於厚度38µm之聚對苯二甲酸乙二酯(PET)薄膜(Mitsubishi Polyester Film製，MRF38)的剝離面，以使乾燥後之層厚度會成為12µm，並以155℃進行1分鐘乾燥處理，而形成層間黏著劑層。接著，將所形成之層間黏著劑層轉印至偏光板P1之保護層(無硬塗層)側，而獲得附層間黏著劑層之偏光板。 (Manufacture of polarizing plate with interlayer adhesive layer) Apply the above-prepared adhesive composition PSA1 on a release film treated with silicone on the peeling surface, that is, on a polyethylene terephthalate (PET) film with a thickness of 38 µm (manufactured by Mitsubishi Polyester Film, MRF38) so that the layer thickness after drying will be 12µm, and dry at 155°C for 1 minute to form an interlayer adhesive layer. Next, the formed interlayer adhesive layer was transferred to the protective layer (no hard coat layer) side of the polarizing plate P1 to obtain a polarizing plate with an interlayer adhesive layer.

(附黏著片之圓偏光板之製作) 將實施例及比較例製出之各黏著片從剝離薄膜轉印並貼附於相位差薄膜R1之第2相位差薄膜側(製作第2相位差薄膜時，將使用作為基材薄膜之降𦯉烯系樹脂薄膜剝離)。接著，將上述製出之附層間黏著劑層的偏光板透過層間黏著劑層貼附於相位差薄膜R1之第1相位差薄膜側，而獲得附黏著片之圓偏光板。相位差薄膜R1與附層間黏著劑層之偏光板之貼附係以從第1相位差薄膜之側觀看時，第1相位差薄膜之慢軸與偏光件之吸收軸形成之角度往逆時針方向呈45度之方式實施。 (Production of circular polarizing plate with adhesive sheet) Each of the adhesive sheets produced in Examples and Comparative Examples was transferred from the release film and attached to the second retardation film side of the retardation film R1 (when making the second retardation film, the film used as the substrate film will be Vinyl resin film peeling off). Next, the above-prepared polarizer with an interlayer adhesive layer was attached to the first retardation film side of the retardation film R1 through the interlayer adhesive layer to obtain a circular polarizer with an adhesive sheet. The attachment of the retardation film R1 and the polarizing plate with the interlayer adhesive layer is based on the counterclockwise direction of the angle formed by the slow axis of the first retardation film and the absorption axis of the polarizer when viewed from the side of the first retardation film It is implemented in a 45-degree manner.

＜有無凹陷＞ 針對黏著片，以以下方法評估有無凹陷。首先，藉由上述方法製出相位差薄膜R1。於相位差薄膜R1之主面貼附剝離襯材與製作出之黏著片，而製作出附黏著片之相位差薄膜。附黏著片之相位差薄膜之長邊方向的長度為50m以上。將該附黏著片之偏光板沿長邊方向捲繞，並在捲材之狀態下在23℃下放置5天後，將捲繞狀態之附黏著片之相位差薄膜拉直，以肉眼觀察黏著片之表面，按下述基準評估有無凹陷。 A：外觀上無不良情況 B：黏著片之表面有凹凸，實用上有問題 ＜Presence or absence of dents＞ For the adhesive sheet, the presence or absence of dents was evaluated by the following method. First, the retardation film R1 is produced by the above method. A release liner and the prepared adhesive sheet were attached to the main surface of the retardation film R1 to manufacture a retardation film with an adhesive sheet. The length in the longitudinal direction of the retardation film with the adhesive sheet is 50m or more. The polarizing plate with the adhesive sheet was wound along the longitudinal direction, and after being placed in the state of the roll at 23°C for 5 days, the phase difference film with the adhesive sheet in the rolled state was straightened, and the adhesion was observed with the naked eye. The surface of the sheet was evaluated for the presence or absence of dents according to the following criteria. A: There is no defect in the appearance B: The surface of the adhesive sheet has unevenness, which is problematic for practical use

[表3]

Figure 02_image007
[table 3]
Figure 02_image007

由表3可知，相較於比較例之黏著片，實施例之黏著片係由充分量之異氰酸酯系交聯劑組合過氧化物系交聯劑之黏著劑組成物形成，從而實施例之黏著片其初始凝膠分率高，且可充分抑制住凹陷的發生。並且，相較於由包含環氧系交聯劑之黏著劑組成物形成的比較例2之黏著片，實施例之黏著片具有優異之耐久性。吾等推測：比較例2之黏著片會因環氧系交聯劑使得(甲基)丙烯酸系聚合物之交聯反應過度進行而導致其耐久性降低。It can be seen from Table 3 that, compared with the adhesive sheet of the comparative example, the adhesive sheet of the example is formed of an adhesive composition composed of a sufficient amount of isocyanate-based crosslinking agent combined with a peroxide-based crosslinking agent, so that the adhesive sheet of the example Its initial gel fraction is high, and can fully suppress the occurrence of depressions. Furthermore, compared with the adhesive sheet of Comparative Example 2 formed of an adhesive composition containing an epoxy-based crosslinking agent, the adhesive sheet of the example has excellent durability. We speculated that the durability of the adhesive sheet of Comparative Example 2 would be reduced due to the excessive progress of the crosslinking reaction of the (meth)acrylic polymer due to the epoxy-based crosslinking agent.

產業上之可利用性 本發明黏著劑組成物可適合利用於製作EL顯示器、液晶顯示器等影像顯示裝置具備之黏著片。 Industrial availability The adhesive composition of the present invention can be suitably used for producing adhesive sheets included in image display devices such as EL displays and liquid crystal displays.

1:黏著片 2:光學薄膜 2A:相位差薄膜 2B:偏光板 3:剝離襯材 4:層間黏著劑 5:保護薄膜 6:影像形成層 7:基板 10A,10B,10C,10D:光學積層體 11:影像顯示裝置 1: Adhesive sheet 2: Optical film 2A: Retardation film 2B: polarizer 3: Peel off the lining 4: interlayer adhesive 5: Protective film 6: Image forming layer 7: Substrate 10A, 10B, 10C, 10D: optical laminates 11: Image display device

圖1係示意顯示本發明黏著片之一例的截面圖。 圖2係示意顯示本發明光學積層體之一例的截面圖。 圖3係示意顯示本發明光學積層體之一例的截面圖。 圖4係示意顯示本發明光學積層體之一例的截面圖。 圖5係示意顯示本發明光學積層體之一例的截面圖。 圖6係示意顯示本發明影像顯示裝置之一例的截面圖。 Fig. 1 is a cross-sectional view schematically showing an example of the adhesive sheet of the present invention. Fig. 2 is a cross-sectional view schematically showing an example of the optical layered body of the present invention. Fig. 3 is a cross-sectional view schematically showing an example of the optical layered body of the present invention. Fig. 4 is a cross-sectional view schematically showing an example of the optical layered body of the present invention. Fig. 5 is a cross-sectional view schematically showing an example of the optical layered body of the present invention. Fig. 6 is a cross-sectional view schematically showing an example of the image display device of the present invention.

1:黏著片 1: Adhesive sheet

Claims (16)

一種黏著劑組成物，包含： (甲基)丙烯酸系聚合物(A)； 異氰酸酯系交聯劑，其相對於前述(甲基)丙烯酸系聚合物(A)100重量部，其摻混量為2重量份以上；及 過氧化物系交聯劑。 An adhesive composition comprising: (meth)acrylic polymer (A); An isocyanate-based crosslinking agent in an amount of 2 parts by weight or more relative to 100 parts by weight of the aforementioned (meth)acrylic polymer (A); and Peroxide-based crosslinking agent. 如請求項1之黏著劑組成物，其中相對於前述(甲基)丙烯酸系聚合物(A)100重量份，前述異氰酸酯系交聯劑之前述摻混量為2~30重量份。The adhesive composition according to claim 1, wherein the blending amount of the isocyanate-based crosslinking agent is 2 to 30 parts by weight relative to 100 parts by weight of the (meth)acrylic polymer (A). 如請求項1或2之黏著劑組成物，其中相對於前述(甲基)丙烯酸系聚合物(A)100重量份，前述過氧化物系交聯劑之摻混量為0.01~5重量份。The adhesive composition according to claim 1 or 2, wherein the blending amount of the peroxide-based crosslinking agent is 0.01 to 5 parts by weight relative to 100 parts by weight of the (meth)acrylic polymer (A). 如請求項1至3中任一項之黏著劑組成物，其中前述(甲基)丙烯酸系聚合物(A)包含源自含芳香環單體之構成單元。The adhesive composition according to any one of claims 1 to 3, wherein the (meth)acrylic polymer (A) contains a structural unit derived from an aromatic ring-containing monomer. 如請求項4之黏著劑組成物，其中前述(甲基)丙烯酸系聚合物(A)中，源自前述含芳香環單體之前述構成單元之含有率為3~25重量%。The adhesive composition according to claim 4, wherein in the (meth)acrylic polymer (A), the content of the structural unit derived from the aromatic ring-containing monomer is 3 to 25% by weight. 如請求項1至5中任一項之黏著劑組成物，其中前述(甲基)丙烯酸系聚合物(A)包含源自含羧基單體之構成單元。The adhesive composition according to any one of Claims 1 to 5, wherein the (meth)acrylic polymer (A) contains a structural unit derived from a carboxyl group-containing monomer. 如請求項1至6中任一項之黏著劑組成物，其中前述(甲基)丙烯酸系聚合物(A)包含源自含醯胺基單體之構成單元。The adhesive composition according to any one of Claims 1 to 6, wherein the (meth)acrylic polymer (A) contains a structural unit derived from an amide group-containing monomer. 如請求項1至7中任一項之黏著劑組成物，其中前述(甲基)丙烯酸系聚合物(A)係以1重量%以下之含有率包含源自含羥基單體之構成單元。The adhesive composition according to any one of claims 1 to 7, wherein the (meth)acrylic polymer (A) contains a constituent unit derived from a hydroxyl group-containing monomer in a content of 1% by weight or less. 如請求項1至8中任一項之黏著劑組成物，其中前述異氰酸酯系交聯劑為二異氰酸甲苯酯系交聯劑。The adhesive composition according to any one of claims 1 to 8, wherein the isocyanate-based crosslinking agent is a diisocyanate-based toluene crosslinking agent. 如請求項1至9中任一項之黏著劑組成物，藉由將前述黏著劑組成物塗佈於基材上以形成塗佈膜，並對前述塗佈膜在120℃下進行300秒鐘乾燥處理而獲得黏著片，所得黏著片之初始凝膠分率為40%以上。The adhesive composition according to any one of Claims 1 to 9, by applying the aforementioned adhesive composition on a substrate to form a coating film, and subjecting the aforementioned coating film to 120° C. for 300 seconds The adhesive sheet is obtained by drying treatment, and the initial gel fraction of the obtained adhesive sheet is above 40%. 一種黏著片，係由如請求項1至10中任一項之黏著劑組成物形成者。An adhesive sheet formed of the adhesive composition according to any one of Claims 1 to 10. 如請求項11之黏著片，其在25℃下之儲存彈性模數G'為0.5MPa以上。The adhesive sheet according to Claim 11 has a storage elastic modulus G' of 0.5 MPa or more at 25°C. 一種光學積層體，包含如請求項11或12之黏著片與光學薄膜。An optical laminate comprising the adhesive sheet and optical film according to claim 11 or 12. 一種影像顯示裝置，具備如請求項13之光學積層體。An image display device comprising the optical laminate according to claim 13. 一種黏著片之製造方法，包含以下步驟： 將如請求項1至10中任一項之黏著劑組成物塗佈於基材上，形成塗佈膜；及 使前述塗佈膜乾燥。 A method of manufacturing an adhesive sheet, comprising the following steps: Coating the adhesive composition according to any one of claims 1 to 10 on the substrate to form a coating film; and The aforementioned coating film was dried. 如請求項15之製造方法，其係在130℃以下之溫度下使前述塗佈膜乾燥。The manufacturing method according to claim 15, which is to dry the aforementioned coating film at a temperature of 130° C. or lower.
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