TWI575045B - Adhesive composition for optical member, Adhesive for optical member, Optical member with adhesive layer, and image display device - Google Patents

Adhesive composition for optical member, Adhesive for optical member, Optical member with adhesive layer, and image display device Download PDF

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Publication number
TWI575045B
TWI575045B TW100136681A TW100136681A TWI575045B TW I575045 B TWI575045 B TW I575045B TW 100136681 A TW100136681 A TW 100136681A TW 100136681 A TW100136681 A TW 100136681A TW I575045 B TWI575045 B TW I575045B
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optical member
adhesive
meth
monomer
acrylate
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TW100136681A
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Chinese (zh)
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TW201300480A (en
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池端晃
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日本合成化學工業股份有限公司
住友化學股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • 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
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polarising Elements (AREA)
  • Adhesive Tapes (AREA)
  • Liquid Crystal (AREA)

Description

光學構件用黏著劑組成物，光學構件用黏著劑，附有黏著劑層之光學構件及影像顯示裝置Adhesive composition for optical member, adhesive for optical member, optical member with adhesive layer, and image display device

本發明係關於一種光學構件用黏著劑組成物、光學構件用黏著劑、附有黏著劑層之光學構件及影像顯示裝置。詳細而言，本發明係關於如下之光學構件用黏著劑組成物、使該黏著劑組成物交聯而成之光學構件用黏著劑、形成有含有該光學構件用黏著劑之黏著劑層的附有黏著劑層之光學構件，尤其是附有黏著劑層之偏光板、進而含有該附有黏著劑層之光學構件之影像顯示裝置；該光學構件用黏著劑組成物係用於接著液晶顯示裝置、有機EL(Electro Luminescence，電致發光)顯示裝置、PDP(Plasma Display Panel，電漿顯示器)等影像顯示裝置中適宜使用之光學膜(偏光膜、相位差膜、光學補償膜、亮度提高膜)等光學構件，尤其具體而言為以三乙酸纖維素系膜等保護膜被覆偏光膜而成之光學積層體、與液晶單元之玻璃基板。The present invention relates to an adhesive composition for an optical member, an adhesive for an optical member, an optical member to which an adhesive layer is attached, and an image display device. In particular, the present invention relates to an adhesive composition for an optical member, an adhesive for an optical member obtained by crosslinking the adhesive composition, and an adhesive layer formed with an adhesive for the optical member. An optical member having an adhesive layer, in particular, a polarizing plate with an adhesive layer and an image display device including the optical member with the adhesive layer; the adhesive composition for the optical member is used for a liquid crystal display device An optical film (a polarizing film, a retardation film, an optical compensation film, a brightness enhancement film) suitable for use in an image display device such as an organic EL (Electro Luminescence) display device or a PDP (Plasma Display Panel) In particular, the optical member is an optical laminate in which a polarizing film is coated with a protective film such as a cellulose triacetate film, and a glass substrate of a liquid crystal cell.

先前，係將經賦予偏光性之聚乙烯醇系膜等偏光片之兩面以纖維素系膜等保護膜被覆，將所得之偏光板積層於具有配向於2片玻璃板間之液晶成分的液晶單元之表面，而製成液晶顯示板，通常，該對液晶單元面之積層係藉由使設置於偏光板表面上之黏著劑層與上述液晶單元抵接並推壓而進行。In the prior art, both sides of a polarizer such as a polarizing polyvinyl alcohol-based film are coated with a protective film such as a cellulose film, and the obtained polarizing plate is laminated on a liquid crystal cell having a liquid crystal component disposed between two glass plates. The surface of the liquid crystal display panel is usually formed by laminating and pressing the adhesive layer provided on the surface of the polarizing plate against the liquid crystal cell.

對於形成該黏著劑層之黏著劑，係要求於因加工時之失誤或異物之捲入而將偏光板等光學構件自液晶單元剝離時，可容易地剝離而無糊劑殘留之再加工性(再剝離性)。又，若長時間曝露於高溫或高濕度等嚴酷之環境下，則有時產生由黏著劑引起之剝離或發泡，對形成該黏著劑層之黏著劑亦要求耐久性。進而，於產生偏光板之經時之尺寸變化時，該黏著劑層隨著偏光板之尺寸變化，故而產生應變，使黏著劑層中之聚合物局部配向，因此而發生雙折射，產生液晶顯示板之周緣部亮於或暗於中央等色彩不均、漏光現象。因此，對於形成該黏著劑層之黏著劑，亦要求可抑制因伴隨偏光板等光學構件之尺寸變化之應力而產生之色彩不均、漏光現象。The adhesive for forming the pressure-sensitive adhesive layer is required to be easily peeled off from the liquid crystal cell when the optical member such as a polarizing plate is peeled off from the liquid crystal cell due to a mistake in processing or a foreign matter, and the reworkability without the residue remains ( Re-peelability). Further, if it is exposed to a severe environment such as high temperature or high humidity for a long period of time, peeling or foaming due to the adhesive may occur, and durability of the adhesive forming the adhesive layer is also required. Further, when the dimensional change of the polarizing plate occurs, the adhesive layer changes with the size of the polarizing plate, so that strain occurs, and the polymer in the adhesive layer is partially aligned, thereby causing birefringence to generate a liquid crystal display. The peripheral portion of the plate is brighter or darker than the central color and light leakage. Therefore, it is also required to suppress the color unevenness and light leakage caused by the stress accompanying the dimensional change of the optical member such as the polarizing plate for the adhesive forming the adhesive layer.

為了解決上述問題，於專利文獻1中揭示含有使含三級胺基之單體(參照該文獻之段落[0036]所記載之丙烯酸酯或丙烯醯胺)共聚合而成之(甲基)丙烯酸系聚合物之光學膜用黏著劑組成物，於專利文獻2中則揭示積層含有特定之矽烷偶合劑之丙烯酸系黏著劑層而成之黏著型偏光板。In order to solve the above problem, Patent Document 1 discloses (meth)acrylic acid containing a monomer containing a tertiary amino group (refer to the acrylate or acrylamide described in paragraph [0036] of the document). In the adhesive film composition for an optical film of a polymer, Patent Document 2 discloses an adhesive polarizing plate in which an acrylic pressure-sensitive adhesive layer containing a specific decane coupling agent is laminated.

[先前技術文獻][Previous Technical Literature]

[專利文獻][Patent Literature]

專利文獻1：日本專利特開2009-215528號公報Patent Document 1: Japanese Patent Laid-Open Publication No. 2009-215528

專利文獻2：日本專利特開平9-288214號公報Patent Document 2: Japanese Patent Laid-Open No. Hei 9-288214

然而，於專利文獻1、2等先前技術中，存在如下問題：難以達成使再加工性與於長時間曝露於高溫、高濕度下時之耐久性並存，若提高再加工性，則耐久性惡化，相反地，若提高耐久性，則再加工性惡化，故具有進一步改善之餘地。However, in the prior art such as Patent Documents 1 and 2, there is a problem that it is difficult to achieve the durability of the reworkability and the long-term exposure to high temperature and high humidity, and the durability is deteriorated when the reworkability is improved. On the contrary, if the durability is improved, the reworkability is deteriorated, so that there is room for further improvement.

本發明係有鑑於上述情況而成者，其目的在於提供一種可達成使再加工性與耐久性並存，且在應用於液晶顯示板等影像顯示裝置時可抑制色彩不均、漏光現象的光學構件用黏著劑組成物、使該黏著劑組成物交聯而成之光學構件用黏著劑、形成有含有該光學構件用黏著劑之黏著劑層的附有黏著劑層之光學構件、含有該附有黏著劑層之光學構件之影像顯示裝置。In view of the above, an object of the present invention is to provide an optical member capable of suppressing color unevenness and light leakage when applied to an image display device such as a liquid crystal display panel, in order to achieve reworkability and durability. An adhesive member for an optical member obtained by crosslinking an adhesive composition, an adhesive member for forming an adhesive layer containing the adhesive for the optical member, and an adhesive member having an adhesive layer formed thereon An image display device for an optical member of an adhesive layer.

本發明者有鑑於上述實情進行努力研究，結果發現，藉由使用以N-(烷氧基烷基)(甲基)丙烯醯胺系單體(即，(甲基)丙烯醯胺系單體，且鍵結於醯胺鍵之氮上之烷基鏈經烷氧基取代之單體)作為共聚合成分之丙烯酸系樹脂，可達成使再加工性與耐久性並存，且在應用於影像顯示裝置時可抑制色彩不均、漏光現象，從而完成本發明。The present inventors conducted intensive studies in view of the above circumstances, and as a result, found that by using an N-(alkoxyalkyl)(meth)acrylamide-based monomer (i.e., (meth)acrylamide monomer) And an acrylic resin which is a copolymerization component of a monomer which is bonded to an alkyl group of a nitrogen bond of a hydrazine bond, which is substituted with an alkoxy group, can achieve reworkability and durability, and is applied to image display. The present invention can be completed by suppressing color unevenness and light leakage.

即，本發明之主旨係關於一種光學構件用黏著劑組成物，其係含有使以(甲基)丙烯酸烷基酯系單體(a1)作為主成分之共聚合成分[1]進行共聚合而獲得之丙烯酸系樹脂(A)而成者，其中係含有N-(烷氧基烷基)(甲基)丙烯醯胺系單體(a2)作為共聚合成分[1]而成。In other words, the present invention relates to an adhesive composition for an optical member which comprises copolymerizing a copolymerized component [1] having a (meth)acrylic acid alkyl ester monomer (a1) as a main component. The obtained acrylic resin (A) is obtained by containing an N-(alkoxyalkyl)(meth)acrylamide-based monomer (a2) as a copolymerization component [1].

進而，本發明係關於一種使上述光學構件用黏著劑組成物交聯而成之光學構件用黏著劑、形成有含有該光學構件用黏著劑之黏著劑層的附有黏著劑層之光學構件、含有該附有黏著劑層之光學構件之影像顯示裝置。Furthermore, the present invention relates to an optical member adhesive agent obtained by crosslinking an adhesive composition for an optical member, and an optical member having an adhesive layer formed with an adhesive layer containing the optical member adhesive, An image display device comprising the optical member with the adhesive layer.

本發明包含以下態樣。The present invention encompasses the following aspects.

[1]一種光學構件用黏著劑組成物，其係含有使以(甲基)丙烯酸烷基酯系單體(a1)作為主成分之共聚合成分[1]進行共聚合而獲得之丙烯酸系樹脂(A)而成者，其中係含有N-(烷氧基烷基)(甲基)丙烯醯胺系單體(a2)作為共聚合成分[1]而成。[1] An adhesive composition for an optical member, which comprises an acrylic resin obtained by copolymerizing a copolymerized component [1] having a (meth)acrylic acid alkyl ester monomer (a1) as a main component. (A) In general, the N-(alkoxyalkyl)(meth)acrylamide-based monomer (a2) is contained as a copolymerization component [1].

[2]如上述[1]之光學構件用黏著劑組成物，其中含有選自含芳香環之單體(a3)及含羧基之單體(a4)中之至少一種，作為共聚合成分[1]。[2] The adhesive composition for an optical member according to the above [1], which contains at least one selected from the group consisting of an aromatic ring-containing monomer (a3) and a carboxyl group-containing monomer (a4) as a copolymer component [1] ].

[3]如上述[1]或[2]之光學構件用黏著劑組成物，其中係含有交聯劑(B)而成。[3] The adhesive composition for an optical member according to the above [1] or [2], which comprises a crosslinking agent (B).

[4]如上述[1]至[3]中任一項之光學構件用黏著劑組成物，其中係含有矽烷偶合劑(C)而成。[4] The adhesive composition for an optical member according to any one of the above [1] to [3] wherein the decane coupling agent (C) is contained.

[5]一種光學構件用黏著劑，其特徵在於使上述[1]至[4]中任一項之光學構件用黏著劑組成物交聯而成。[5] An adhesive for an optical member, which is characterized in that the optical member for an optical member according to any one of the above [1] to [4] is crosslinked.

[6]如上述[5]之光學構件用黏著劑，其中光學構件為偏光板。[6] The adhesive for optical members according to the above [5], wherein the optical member is a polarizing plate.

[7]一種附有黏著劑層之光學構件，其特徵在於含有包含上述[5]或[6]之光學構件用黏著劑之黏著劑層及光學構件之積層結構。[7] An optical member with an adhesive layer, characterized by comprising a laminate structure comprising an adhesive layer for an optical member according to the above [5] or [6] and an optical member.

[8]一種影像顯示裝置，其特徵在於含有上述[7]之附有黏著劑層之光學構件。[8] An image display device comprising the optical member with the adhesive layer of the above [7].

[9]如上述[7]之附有黏著劑層之光學構件，其中光學構件為偏光板。[9] The optical member with an adhesive layer as described in [7] above, wherein the optical member is a polarizing plate.

由於將本發明之光學構件用黏著劑組成物交聯而獲得之光學構件用黏著劑之再加工性優異，故而，於因加工時之失誤或異物之捲入而將偏光板等光學構件自液晶單元等剝離時，可容易地剝離而無糊劑殘留。又，由於本發明之黏著劑於長時間曝露於高溫、高濕度下時之耐久性優異，故而可獲得如下影像顯示裝置，其即便於高溫、高濕之環境下、及重複低溫～高溫之環境變化中，光學積層體、尤其是偏光板與玻璃基板之接著性仍優異，黏著劑層與玻璃基板之間不易產生發泡或剝離。進而，形成有含本發明黏著劑之黏著劑層的附有黏著劑層之光學構件，即便於產生光學構件之經時之尺寸變化時，亦可使黏著劑層之雙折射接近於零，故於含有該附有黏著劑層之光學構件之影像顯示裝置中，可抑制色彩不均、漏光現象。Since the adhesive for an optical member obtained by crosslinking the optical member adhesive composition of the present invention is excellent in reworkability, an optical member such as a polarizing plate is self-crystallized due to a mistake during processing or a foreign matter. When the unit or the like is peeled off, it can be easily peeled off without sticking. Further, since the adhesive of the present invention is excellent in durability when exposed to high temperature and high humidity for a long period of time, the following image display device can be obtained, even in a high-temperature, high-humidity environment, and in a low-temperature to high-temperature environment. In the change, the optical laminate, in particular, the adhesion between the polarizing plate and the glass substrate is still excellent, and foaming or peeling is less likely to occur between the adhesive layer and the glass substrate. Further, the optical member with the adhesive layer containing the adhesive layer of the adhesive of the present invention can make the birefringence of the adhesive layer close to zero even when the dimensional change of the optical member occurs over time. In the image display device including the optical member with the adhesive layer, color unevenness and light leakage can be suppressed.

以下詳細說明本發明，但該等僅為表示理想之實施態樣之一例者。再者，於本發明中，(甲基)丙烯酸意指丙烯酸或甲基丙烯酸，(甲基)丙烯醯基意指丙烯醯基或甲基丙烯醯基，(甲基)丙烯酸酯意指丙烯酸酯或甲基丙烯酸酯。The present invention will be described in detail below, but these are merely examples showing ideal embodiments. Further, in the present invention, (meth)acrylic means acrylic acid or methacrylic acid, (meth)acrylonitrile group means acrylonitrile group or methacryl fluorenyl group, and (meth) acrylate means acrylate Or methacrylate.

[光學構件用黏著劑組成物][Adhesive Composition for Optical Member]

首先，對於本發明之光學構件用黏著劑組成物(以下亦簡稱為「黏著劑組成物」)進行說明。First, the adhesive composition for an optical member of the present invention (hereinafter also simply referred to as "adhesive composition") will be described.

本發明之黏著劑組成物係含有丙烯酸系樹脂(A)而成者。The adhesive composition of the present invention contains an acrylic resin (A).

本發明所使用之丙烯酸系樹脂(A)含有(甲基)丙烯酸烷基酯系單體(a1)作為主成分，進而含有N-(烷氧基烷基)(甲基)丙烯醯胺系單體(a2)作為必需成分，較佳為將含有含芳香環之單體(a3)及/或含羧基之單體(a4)之共聚合成分[1]予以共聚合而成。The acrylic resin (A) used in the present invention contains a (meth)acrylic acid alkyl ester monomer (a1) as a main component, and further contains an N-(alkoxyalkyl)(meth)acrylamide series. The body (a2) is an essential component, and it is preferred to copolymerize a copolymerized component [1] containing a monomer (a3) containing an aromatic ring and/or a monomer (a4) containing a carboxyl group.

作為該(甲基)丙烯酸烷基酯系單體(a1)，烷基之碳數通常較佳為1～20，尤佳為1～12，進而較佳為1～8，特佳為4～8，具體而言，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異酯等。該等可單獨使用一種，或併用兩種以上。The alkyl (meth) acrylate monomer (a1) preferably has 1 to 20 carbon atoms, more preferably 1 to 12, still more preferably 1 to 8, and particularly preferably 4 to 4 carbon atoms. 8. Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, n-propyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isodecyl (meth)acrylate , lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid Ester and the like. These may be used alone or in combination of two or more.

於該(甲基)丙烯酸烷基酯系單體(a1)之中，就共聚合性、黏著物性、操作容易性及原料獲取容易性之方面而言，較佳為使用(甲基)丙烯酸正丁酯、(甲基)丙烯酸-2-乙基己酯，就耐久性優異之方面而言，更佳為使用(甲基)丙烯酸正丁酯。Among the alkyl (meth)acrylate monomers (a1), it is preferred to use (meth)acrylic acid in terms of copolymerizability, adhesiveness, ease of handling, and ease of obtaining raw materials. Butyl ester and 2-ethylhexyl (meth)acrylate are more preferably n-butyl (meth)acrylate from the viewpoint of excellent durability.

將(甲基)丙烯酸烷基酯系單體(a1)「作為主成分」意指相對於共聚合成分[1]整體，含有(甲基)丙烯酸烷基酯系單體(a1)50重量%以上。該(甲基)丙烯酸烷基酯系單體(a1)相對於共聚合成分[1]整體之含有比例較佳為50～97重量%，尤佳為60～95重量%，進而較佳為80～93重量%。The "alkyl methacrylate" monomer (a1) "as a main component" means that the alkyl (meth) acrylate monomer (a1) is 50% by weight based on the total of the copolymerized component [1]. the above. The content ratio of the alkyl (meth) acrylate monomer (a1) to the entire copolymerization component [1] is preferably 50 to 97% by weight, particularly preferably 60 to 95% by weight, and still more preferably 80. ～93% by weight.

若該(甲基)丙烯酸烷基酯系單體(a1)之含有比例過少，則於使黏著劑組成物交聯而使用作為黏著劑之情形時，有黏著力不足之傾向。When the content ratio of the alkyl (meth)acrylate monomer (a1) is too small, when the adhesive composition is crosslinked and used as an adhesive, the adhesive strength tends to be insufficient.

作為N-(烷氧基烷基)(甲基)丙烯醯胺系單體(a2)，烷氧基之碳數通常較佳為1～10，尤佳為1～8，進而較佳為1～6，特佳為1～4，烷基之碳數通常較佳為1～6，尤佳為1～4，進而較佳為1～2，特佳為1，具體而言，例如可列舉：N-(甲氧基甲基)(甲基)丙烯醯胺、N-(正丁氧基甲基)(甲基)丙烯醯胺、N-(異丁氧基甲基)(甲基)丙烯醯胺、N-(正丁氧基乙基)(甲基)丙烯醯胺等，其中，就耐久性、再加工性平衡良好地優異之方面而言，較佳為使用N-(正丁氧基甲基)丙烯醯胺、N-(甲氧基甲基)丙烯醯胺、N-(異丁氧基甲基)丙烯醯胺。該等可單獨使用一種，或併用兩種以上。The N-(alkoxyalkyl)(meth)acrylamide monomer (a2) has a carbon number of usually 1 to 10, particularly preferably 1 to 8, more preferably 1 ～6, particularly preferably from 1 to 4, the carbon number of the alkyl group is usually preferably from 1 to 6, more preferably from 1 to 4, still more preferably from 1 to 2, particularly preferably 1, and specifically, for example, :N-(methoxymethyl)(meth)acrylamide, N-(n-butoxymethyl)(meth)acrylamide, N-(isobutoxymethyl)(methyl) In the case of acrylamide, N-(n-butoxyethyl)(meth) acrylamide, etc., it is preferred to use N-(n-butyl) in terms of excellent balance between durability and reworkability. Oxymethyl) acrylamide, N-(methoxymethyl) acrylamide, N-(isobutoxymethyl) acrylamide. These may be used alone or in combination of two or more.

該N-(烷氧基烷基)(甲基)丙烯醯胺系單體(a2)相對於共聚合成分[1]整體之含有比例較佳為0.1～3重量%，尤佳為0.3～2重量%，進而較佳為0.3～1重量%。The content ratio of the N-(alkoxyalkyl)(meth)acrylamide monomer (a2) to the entire copolymerization component [1] is preferably from 0.1 to 3% by weight, particularly preferably from 0.3 to 2. The weight % is further preferably 0.3 to 1% by weight.

若該N-(烷氧基烷基)(甲基)丙烯醯胺系單體(a2)之含有比例過少，則具有因凝集力不足而耐久性及再加工性降低之傾向，若過多，則有黏度變高或樹脂之穩定性降低之傾向。When the content ratio of the N-(alkoxyalkyl)(meth)acrylamide monomer (a2) is too small, durability and reworkability tend to be lowered due to insufficient cohesive force, and if too large, There is a tendency that the viscosity becomes high or the stability of the resin is lowered.

作為含芳香環之單體(a3)，例如可列舉：(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸乙氧基化鄰苯基苯酯、苯基二乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸-2-羥基-3-苯氧基丙酯、苯乙烯、α-甲基苯乙烯等，其中就耐漏光性優異之方面而言，較佳為使用苯基二乙二醇丙烯酸酯、丙烯酸苯氧基乙酯。該等可單獨使用一種，或併用兩種以上。Examples of the aromatic ring-containing monomer (a3) include phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and ethoxylated (meth)acrylate. O-phenylphenyl ester, phenyl diethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, styrene, α-methyl styrene, etc. In terms of excellent light leakage resistance, phenyl diethylene glycol acrylate and phenoxyethyl acrylate are preferably used. These may be used alone or in combination of two or more.

含芳香環之單體(a3)相對於共聚合成分[1]整體之含有比例較佳為3～20重量%，尤佳為3～15重量%，進而較佳為5～15重量%。The content ratio of the aromatic ring-containing monomer (a3) to the copolymerizable component [1] as a whole is preferably from 3 to 20% by weight, particularly preferably from 3 to 15% by weight, still more preferably from 5 to 15% by weight.

若含芳香環之單體(a3)之含有比例過少，則具有耐漏光性(抑制漏光之性能)容易降低之傾向，若過多，則有使耐漏光性降低，丙烯酸系樹脂之黏著性能較差，或聚合之穩定性降低之傾向。When the content ratio of the aromatic ring-containing monomer (a3) is too small, the light leakage resistance (performance of suppressing light leakage) tends to be lowered, and if it is too large, the light leakage resistance is lowered, and the adhesion property of the acrylic resin is poor. Or the tendency of the stability of the polymerization to decrease.

作為含羧基之單體(a4)，例如可列舉：(甲基)丙烯酸、丙烯酸二聚物、丁烯酸、順丁烯二酸、順丁烯二酸酐、反丁烯二酸、甲基順丁烯二酸、戊烯二酸、衣康酸、丙烯醯胺N-乙醇酸、肉桂酸等，其中較佳為使用(甲基)丙烯酸。該等可單獨使用一種，或併用兩種以上。 Examples of the carboxyl group-containing monomer (a4) include (meth)acrylic acid, acrylic acid dimer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, and methyl cis. Butenic acid, glutaconic acid, itaconic acid, acrylamide N-glycolic acid, cinnamic acid, etc., among which (meth)acrylic acid is preferably used. These may be used alone or in combination of two or more.

含羧基之單體(a4)相對於共聚合成分[1]整體之含有比例較佳為1.5重量%以下，尤佳為0.05~1重量%，進而較佳為0.05~0.6重量%。 The content ratio of the carboxyl group-containing monomer (a4) to the copolymerizable component [1] as a whole is preferably 1.5% by weight or less, more preferably 0.05 to 1% by weight, still more preferably 0.05 to 0.6% by weight.

若含羧基之單體(a4)之含有比例過少，則有因凝集力不足而耐久性能降低之傾向，若過多，則有黏度變高或樹脂之穩定性變差之傾向。 When the content ratio of the carboxyl group-containing monomer (a4) is too small, the durability may be lowered due to insufficient cohesive force, and if it is too large, the viscosity tends to be high or the stability of the resin tends to be deteriorated.

本發明所使用之丙烯酸系樹脂(A)除上述(a1)~(a4)之單體，亦可將其他共聚合性單體(a5)作為共聚合成分[1]。作為該其他共聚合性單體(a5)，例如可列舉：含羥基之單體、含胺基之單體、含乙醯基之單體、含異氰酸酯基之單體、含環氧丙基之單體等，該等之中，就可有效地進行交聯反應之方面而言，較佳為使用含羥基之單體。 In the acrylic resin (A) used in the present invention, in addition to the monomers (a1) to (a4) described above, another copolymerizable monomer (a5) may be used as a copolymerization component [1]. Examples of the other copolymerizable monomer (a5) include a hydroxyl group-containing monomer, an amine group-containing monomer, an ethylidene group-containing monomer, an isocyanate group-containing monomer, and an epoxy group-containing monomer. Among the monomers and the like, among these, a hydroxyl group-containing monomer is preferably used in terms of an effective crosslinking reaction.

作為含羥基之單體，例如可列舉：(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-4-羥基丁酯、(甲基)丙烯酸-5-羥基戊酯、(甲基)丙烯酸-6-羥基己酯、(甲基)丙烯酸-8-羥基辛酯等丙烯酸羥基烷基酯，己內酯改性(甲基)丙烯酸-2-羥基乙酯等己內酯改性單體，二乙二醇(甲基)丙烯酸酯、聚乙二醇(甲基)丙烯酸酯等氧基伸烷基改性單體，此外2-丙烯醯氧基乙基-2-羥基乙基鄰苯二甲酸、N-羥甲基(甲基)丙烯醯胺等含一級羥基之單體；(甲基)丙烯酸-2-羥基丙酯、(甲基)丙烯酸-2-羥基 丁酯、(甲基)丙烯酸-3-氯-2-羥基丙酯、(甲基)丙烯酸-2-羥基3-苯氧基丙酯等含二級羥基之單體；(甲基)丙烯酸-2,2-二甲基-2-羥基乙酯等含三級羥基之單體。 Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 5-hydroxypentyl (meth)acrylate. a hydroxyalkyl acrylate such as 6-hydroxyhexyl acrylate or -8-hydroxyoctyl (meth)acrylate, and a caprolactone modified single modified by caprolactone such as 2-hydroxyethyl (meth)acrylate An alkylene-modified monomer such as diethylene glycol (meth) acrylate or polyethylene glycol (meth) acrylate, in addition to 2-propenyloxyethyl-2-hydroxyethyl phthalate Monocarboxylic acid-containing monomer such as dicarboxylic acid or N-methylol (meth) acrylamide; 2-hydroxypropyl (meth)acrylate, 2-hydroxyl (meth)acrylate a monomer containing a secondary hydroxyl group such as butyl ester, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate; (meth)acrylic acid- A monomer having a tertiary hydroxyl group such as 2,2-dimethyl-2-hydroxyethyl ester.

於含羥基之單體中，就與交聯劑之反應性優異之方面而言，較佳為含1級羥基之單體。進而，就二(甲基)丙烯酸酯等雜質較少、容易製造之方面而言，尤佳為使用丙烯酸-2-羥基乙酯、丙烯酸-4-羥基丁酯。 Among the hydroxyl group-containing monomers, a monomer having a hydroxyl group of a first order is preferred in terms of excellent reactivity with a crosslinking agent. Further, in view of the fact that impurities such as di(meth)acrylate are small and easy to manufacture, it is particularly preferable to use 2-hydroxyethyl acrylate or 4-hydroxybutyl acrylate.

再者，作為本發明所使用之含羥基之單體，較佳為使用作為雜質之二(甲基)丙烯酸酯之含有比例為0.5重量%以下者，進而較佳為0.2重量%以下，特佳為0.1重量%以下，具體而言，較佳為使用丙烯酸-2-羥基乙酯、丙烯酸-2-羥基丙酯、丙烯酸-4-羥基丁酯。 Further, as the hydroxyl group-containing monomer used in the present invention, the content of the di(meth)acrylate as the impurity is preferably 0.5% by weight or less, more preferably 0.2% by weight or less, particularly preferably It is 0.1% by weight or less, and specifically, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate are preferably used.

作為含胺基之單體，例如可列舉：(甲基)丙烯酸第三丁基胺基乙酯、(甲基)丙烯酸乙基胺基乙酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸二乙基胺基乙酯等。 Examples of the amino group-containing monomer include, for example, tert-butylaminoethyl (meth)acrylate, ethylaminoethyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate. And diethylaminoethyl (meth)acrylate.

作為含乙醯基之單體，例如可列舉：(甲基)丙烯酸-2-(乙醯乙醯氧基)乙酯、乙醯乙酸烯丙酯等。 Examples of the ethylidene group-containing monomer include 2-(ethionethoxy)ethyl (meth)acrylate and allyl acetate.

作為含異氰酸酯基之單體，例如可列舉：異氰酸-2-丙烯醯氧基乙酯、異氰酸-2-甲基丙烯醯氧基乙酯或該等之環氧烷加成物等。 Examples of the isocyanate group-containing monomer include isocyanate-2-propenyloxyethyl ester, isocyanate-2-methylpropenyloxyethyl ester, and the like, such as an alkylene oxide adduct. .

作為含環氧丙基之單體，例如可列舉：(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸烯丙基環氧丙酯等。Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate and allyl propyl propyl (meth)acrylate.

作為其他共聚合性單體(a5)之其他之例，可列舉：(甲基)丙烯酸-2-甲氧基乙酯、(甲基)丙烯酸-2-乙氧基乙酯、(甲基)丙烯酸-3-甲氧基丁酯、(甲基)丙烯酸-2-丁氧基乙酯、2-丁氧基二乙二醇(甲基)丙烯酸酯、甲氧基二乙二醇(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯、乙氧基二乙二醇(甲基)丙烯酸酯、甲氧基二丙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、辛氧基聚乙二醇-聚丙二醇-單(甲基)丙烯酸酯、月桂氧基聚乙二醇單(甲基)丙烯酸酯、硬脂氧基聚乙二醇單(甲基)丙烯酸酯等含有烷氧基及氧基伸烷基之單體；丙烯腈、甲基丙烯腈、乙酸乙烯酯、丙酸乙烯酯、硬酯酸乙烯酯、氯乙烯、偏二氯乙烯、烷基乙烯醚、乙烯基甲苯、乙烯基吡啶、乙烯基吡咯啶酮、衣康酸二烷基酯、反丁烯二酸二烷基酯、烯丙醇、丙烯醯氯、甲基乙烯基酮、N-丙烯醯胺甲基三甲基氯化銨、烯丙基三甲基氯化銨、二甲基烯丙基乙烯基酮等。Other examples of the other copolymerizable monomer (a5) include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and (methyl). 3-methoxybutyl acrylate, 2-butoxyethyl (meth)acrylate, 2-butoxy diethylene glycol (meth) acrylate, methoxy diethylene glycol (methyl Acrylate, methoxytriethylene glycol (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, methoxy dipropylene glycol (meth) acrylate, methoxy polyethylene Alcohol (meth) acrylate, octyloxy polyethylene glycol-polypropylene glycol mono(meth) acrylate, lauryl oxy polyethylene glycol mono (meth) acrylate, stearoxy polyethylene glycol a monomer containing an alkoxy group and an alkyloxy group such as a mono(meth)acrylate; acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, and dichlorochloride. Ethylene, alkyl vinyl ether, vinyl toluene, vinyl pyridine, vinyl pyrrolidone, dialkyl itaconate, dialkyl fumarate, allyl alcohol, propylene chloride, methyl ethylene Ketone, N-acrylamide Trimethyl ammonium chloride, allyl trimethyl ammonium chloride, dimethyl allyl vinyl ketone.

其他共聚合性單體(a5)相對於共聚合成分[1]整體之含有比例較佳為5重量%以下，尤佳為0.5～3重量%，進而較佳為0.4～1.6重量%。The content ratio of the other copolymerizable monomer (a5) to the entire copolymerization component [1] is preferably 5% by weight or less, more preferably 0.5 to 3% by weight, still more preferably 0.4 to 1.6% by weight.

若其他共聚合性單體(a5)之含有比例過多，則有變得難以獲得本發明之效果之傾向。When the content ratio of the other copolymerizable monomer (a5) is too large, it tends to be difficult to obtain the effects of the present invention.

於本發明中，亦可將N-(烷氧基烷基)(甲基)丙烯醯胺系單體(a2)以外之醯胺系單體(即不具有烷氧基烷基之醯胺系單體，例如(甲基)丙烯醯基啉、二甲基(甲基)丙烯醯胺、二乙基(甲基)丙烯醯胺、二甲基胺基(甲基)丙烯醯胺、二甲基胺基丙基(甲基)丙烯醯胺等)作為其他共聚合性單體(a5)，而於不損害本發明之效果之範圍中併用為共聚合成分[1]。In the present invention, a guanamine-based monomer other than the N-(alkoxyalkyl)(meth)acrylamide-based monomer (a2) (that is, an amide group having no alkoxyalkyl group) may be used. Monomer, such as (meth) acrylonitrile Porphyrin, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, dimethyl amino (meth) acrylamide, dimethyl amino propyl (meth) propylene oxime The amine or the like is used as the other copolymerizable monomer (a5), and is used as a copolymerization component [1] in the range which does not impair the effects of the present invention.

再者，於將N-(烷氧基烷基)(甲基)丙烯醯胺系單體(a2)以外之醯胺系單體作為上述共聚合性單體(a5)而併用之情形時，其含量相對於共聚合成分[1]整體通常為0.1～2重量%，較佳為0.3～1重量%以下即可，或相對於N-(烷氧基烷基)(甲基)丙烯醯胺系單體(a2)為0～100重量%，較佳為0～50重量%，尤佳為0～20重量%即可。In the case where the amide-based monomer other than the N-(alkoxyalkyl)(meth)acrylamide-based monomer (a2) is used in combination as the copolymerizable monomer (a5), The content thereof is usually 0.1 to 2% by weight, preferably 0.3 to 1% by weight or less based on the total of the copolymerized component [1], or relative to N-(alkoxyalkyl)(meth)acrylamide. The monomer (a2) is 0 to 100% by weight, preferably 0 to 50% by weight, particularly preferably 0 to 20% by weight.

又，N-(烷氧基烷基)(甲基)丙烯醯胺系單體(a2)與含羧基之單體(a4)之合計之含有比例，相對於共聚合成分[1]整體，較佳為4重量%以下，尤佳為0.3～2重量%，進而較佳為0.4～1.6重量%。Further, the total content ratio of the N-(alkoxyalkyl)(meth)acrylamide monomer (a2) to the carboxyl group-containing monomer (a4) is higher than that of the copolymerized component [1] as a whole. It is preferably 4% by weight or less, more preferably 0.3 to 2% by weight, still more preferably 0.4 to 1.6% by weight.

若該(a2)與(a4)之合計之含有比例過多，則有黏度變高或樹脂之穩定性降低之傾向。When the total content ratio of (a2) and (a4) is too large, the viscosity tends to be high or the stability of the resin tends to be lowered.

於為了使本發明所使用之丙烯酸系樹脂(A)高分子量化之情形時，亦可併用乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、二乙烯基苯等具有兩個以上之乙烯性不飽和基之化合物等。In order to polymerize the acrylic resin (A) used in the present invention, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol may be used in combination. A compound having two or more ethylenically unsaturated groups such as an alcohol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate or divinylbenzene.

於本發明中，藉由將至少含有上述(a1)及(a2)之單體，較佳為進而含有(a3)、(a4)之單體及視需要進而含有(a5)之單體的共聚合成分[1]予以共聚合，從而製造丙烯酸系樹脂(A)，該共聚合可藉由溶液自由基聚合、懸浮聚合、塊狀聚合、乳化聚合等先前公知之方法而進行。例如，於有機溶劑中混合或滴加(甲基)丙烯酸烷基酯系單體(a1)、N-(烷氧基烷基)(甲基)丙烯醯胺系單體(a2)、含芳香環之單體(a3)、含羧基之單體(a4)、其他共聚合性單體(a5)等聚合性單體、聚合起始劑，於回流狀態或50～90℃下聚合2～20小時。In the present invention, by including at least the monomers of the above (a1) and (a2), it is preferred to further contain a monomer of (a3), (a4) and, if necessary, a monomer of (a5). The polymerization component [1] is copolymerized to produce an acrylic resin (A) which can be carried out by a conventionally known method such as solution radical polymerization, suspension polymerization, bulk polymerization, or emulsion polymerization. For example, an alkyl (meth) acrylate monomer (a1), an N-(alkoxyalkyl) (meth) acrylamide monomer (a2), or a fragrance is mixed or added in an organic solvent. Polymerizable monomer such as monomer (a3), carboxyl group-containing monomer (a4), and other copolymerizable monomer (a5), polymerization initiator, polymerized under reflux or 50 to 90 ° C 2 to 20 hour.

作為該聚合所使用之有機溶劑，可列舉：甲苯、二甲苯等芳香族烴類；乙酸乙酯、乙酸丁酯等酯類；正丙醇、異丙醇等脂肪族醇類；丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮類等。Examples of the organic solvent used in the polymerization include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; and aliphatic alcohols such as n-propanol and isopropanol; acetone and methyl groups; A ketone such as ethyl ketone, methyl isobutyl ketone or cyclohexanone.

作為該自由基共聚合所使用之聚合起始劑，可列舉如下作為具體例：作為通常之自由基聚合起始劑之偶氮雙異丁腈、偶氮雙二甲基戊腈等偶氮系聚合起始劑，過氧化苯甲醯、過氧化月桂醯、過氧化二第三丁基、過氧化氫異丙苯等過氧化物系聚合起始劑等。The polymerization initiator used for the radical copolymerization is exemplified by the following examples: azobisisobutyronitrile, azobisdimethylvaleronitrile, etc., which are ordinary radical polymerization initiators. A polymerization initiator, a peroxide-based polymerization initiator such as benzamidine peroxide, lauric acid peroxide, dibutyl butyl peroxide or cumene hydroperoxide.

關於丙烯酸系樹脂(A)之重量平均分子量(Mw)，通常為40萬～200萬，較佳為45萬～190萬，尤佳為50萬～180萬。若重量平均分子量過小，則有耐久性能降低之傾向，若過大，則必需大量之稀釋溶劑，成為就塗佈性或成本之方面而言不佳之傾向。The weight average molecular weight (Mw) of the acrylic resin (A) is usually 400,000 to 2,000,000, preferably 450,000 to 1.9 million, and particularly preferably 500,000 to 1.8,000,000. When the weight average molecular weight is too small, the durability may be lowered. If the weight average molecular weight is too large, a large amount of the solvent is required to be diluted, which tends to be unfavorable in terms of coatability and cost.

又，丙烯酸系樹脂(A)之分散度(重量平均分子量(Mw)/數平均分子量(Mn))較佳為20以下，尤佳為15以下，進而較佳為10以下，特佳為7以下。若該分散度過高，則有黏著劑層之耐久性能降低，變得容易產生發泡等之傾向。再者，分散度之下限就製造之極限之方面而言，通常為2。Further, the degree of dispersion (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the acrylic resin (A) is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, particularly preferably 7 or less. . When the degree of dispersion is too high, the durability of the pressure-sensitive adhesive layer is lowered, and foaming or the like tends to occur. Further, the lower limit of the dispersion is usually 2 in terms of the limit of manufacture.

進而，丙烯酸系樹脂(A)之玻璃轉移溫度較佳為-80～-20℃，尤佳為-75～-30℃，進而較佳為-60～-40℃，若玻璃轉移溫度過高，則有黏性不足之傾向，若過低，則有耐熱性降低之傾向。Further, the glass transition temperature of the acrylic resin (A) is preferably -80 to -20 ° C, more preferably -75 to -30 ° C, still more preferably -60 to -40 ° C, and if the glass transition temperature is too high, There is a tendency that the viscosity is insufficient, and if it is too low, the heat resistance tends to decrease.

再者，上述重量平均分子量(Mw)為利用標準聚苯乙烯分子量換算而算出之重量平均分子量，係藉由使用在高效液相層析儀(High performance liquid chromatography)(日本Waters公司製造，於「Waters 2695(主體)」與「Waters 2414(檢測器)」)中，串連3根之管柱：Shodex GPC KF-806L(排除極限分子量：2×107、分離範圍：100～2x107，理論段數：10,000段/根，填充劑材質：苯乙烯-二乙烯基苯共聚合體，填充劑粒徑：10 μm)而測定者，數平均分子量(Mn)亦可使用相同之方法。又，分散度係根據重量平均分子量與數平均分子量而求出。又，玻璃轉移溫度係藉由下述之Fox式而算出。Further, the weight average molecular weight (Mw) is a weight average molecular weight calculated by conversion of a standard polystyrene molecular weight, and is used in a high performance liquid chromatography (manufactured by Waters Corporation, Japan). Waters 2695 (main body) and "Waters 2414 (detector)"), three columns in series: Shodex GPC KF-806L (excluding the limit molecular weight: 2 × 10 7 , separation range: 100 ~ 2x10 7 , theory The number of segments: 10,000 segments/root, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm), and the same method can be used for the number average molecular weight (Mn). Further, the degree of dispersion is determined from the weight average molecular weight and the number average molecular weight. Further, the glass transition temperature was calculated by the following Fox equation.

[數1][Number 1]

Tg：共聚合體之玻璃轉移溫度(K)Tg: glass transition temperature of the copolymer (K)

Tga：單體A之均聚合物之玻璃轉移溫度(K)　Wa：單體A之重量分率Tga: glass transition temperature (K) of the average polymer of monomer A Wa: weight fraction of monomer A

Tgb：單體B之均聚合物之玻璃轉移溫度(K)　Wb：單體B之重量分率Tgb: glass transition temperature (K) of the average polymer of monomer B Wb: weight fraction of monomer B

Tgn：單體N之均聚合物之玻璃轉移溫度(K)　Wn：單體N之重量分率Tgn: glass transition temperature (K) of the average polymer of monomer N Wn: weight fraction of monomer N

(Wa+Wb+…+Wn=1)(Wa+Wb+...+Wn=1)

於本發明中，提供使含有上述丙烯酸系樹脂(A)作為必需成分之光學構件用黏著劑組成物交聯而成之黏著劑，但光學構件用黏著劑組成物較佳為進而含有交聯劑(B)，並利用交聯劑交聯而獲得之黏著劑。In the present invention, an adhesive agent obtained by crosslinking an adhesive composition for an optical member containing the acrylic resin (A) as an essential component is provided, but the adhesive composition for an optical member preferably further contains a crosslinking agent. (B), and an adhesive obtained by crosslinking with a crosslinking agent.

作為該交聯劑(B)，例如可列舉：異氰酸酯系交聯劑、環氧系交聯劑、氮丙啶系交聯劑、三聚氰胺系交聯劑、醛系交聯劑、胺系交聯劑、金屬螯合物系交聯劑。其中，就提高與基材之密接性之方面或就與基質聚合物之反應性之方面而言，適宜為使用異氰酸酯系交聯劑。Examples of the crosslinking agent (B) include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a melamine crosslinking agent, an aldehyde crosslinking agent, and an amine crosslinking. Agent, metal chelate crosslinking agent. Among them, an isocyanate crosslinking agent is preferably used in terms of improving the adhesion to the substrate or the reactivity with the matrix polymer.

作為上述異氰酸酯系交聯劑，例如可列舉：2,4-甲苯二異氰酸酯酯、2,6-甲苯二異氰酸酯酯、氫化甲苯二異氰酸酯、1,3-苯二甲基二異氰酸酯、1,4-苯二甲基二異氰酸酯、六亞甲基二異氰酸酯、二苯基甲烷-4,4-二異氰酸酯、異佛爾酮二異氰酸酯、1,3-雙(異氰酸基甲基)環己烷、四甲基苯二甲基二異氰酸酯、1,5-萘二異氰酸酯、三苯基甲烷三異氰酸酯、及該等聚異氰酸酯化合物與三羥甲基丙烷等多元醇化合物之加合物、該等聚異氰酸酯化合物之縮二脲體或異氰尿酸酯體等。Examples of the isocyanate crosslinking agent include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hydrogenated toluene diisocyanate, 1,3-benzenedimethyl diisocyanate, and 1,4-. Benzyl diisocyanate, hexamethylene diisocyanate, diphenylmethane-4,4-diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, Tetramethyl dimethyl diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, and adducts of the polyisocyanate compound and a polyol compound such as trimethylolpropane, and the polyisocyanate a biuret or isocyanurate body of the compound.

作為上述環氧系交聯劑，例如可列舉：雙酚A‧表氯醇型之環氧樹脂、乙二醇二環氧丙基醚、聚乙二醇二環氧丙基醚、丙三醇二環氧丙基醚、丙三醇三環氧丙基醚、1,6-已二醇二環氧丙基醚、三羥甲基丙烷三環氧丙基醚、山梨糖醇聚環氧丙基醚、聚甘油聚環氧丙基醚、季戊四醇聚環氧丙基赤蘚醇、二甘油聚環氧丙基醚等。Examples of the epoxy-based crosslinking agent include bisphenol A and epichlorohydrin type epoxy resins, ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, and glycerin. Diepoxypropyl ether, glycerol triepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, trimethylolpropane triepoxypropyl ether, sorbitol polyepoxypropyl Alkyl ether, polyglycerol polyepoxypropyl ether, pentaerythritol polyepoxypropyl erythritol, diglycerol polyepoxypropyl ether, and the like.

作為上述氮丙啶系交聯劑，例如可列舉：四羥甲基甲烷-三-β-氮丙啶基丙酸酯、三羥甲基丙烷-三-β-氮丙啶基丙酸酯、N,N'-二苯基甲烷-4,4'-雙(1-氮丙啶甲醯胺基)、N,N'-六亞甲基-1,6-雙(1-氮丙啶甲醯胺基)等。Examples of the aziridine-based crosslinking agent include tetramethylolmethane-tris-β-aziridine propionate and trimethylolpropane-tri-β-aziridine propionate. N,N'-diphenylmethane-4,4'-bis(1-aziridinecarbamamino), N,N'-hexamethylene-1,6-bis(1-aziridinamide Amidoxime) and the like.

作為上述三聚氰胺系交聯劑，例如可列舉六甲氧基甲基三聚氰胺、六乙氧基甲基三聚氰胺、六丙氧基甲三聚氰胺、六丁氧基甲基三聚氰胺、六戊氧基甲基三聚氰胺、六己氧基甲基三聚氰胺、三聚氰胺樹脂等。Examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl melamine, hexaethoxyoxymethyl melamine, and six. Hexyloxymethyl melamine, melamine resin, and the like.

作為上述醛系交聯劑，例如可列舉：乙二醛、丙二醛、丁二醛、順丁烯二醛、戊二醛、甲醛、乙醛、苯甲醛等。Examples of the aldehyde crosslinking agent include glyoxal, malondialdehyde, succinaldehyde, maleic aldehyde, glutaraldehyde, formaldehyde, acetaldehyde, and benzaldehyde.

作為上述胺系交聯劑，例如可列舉：六亞甲基二胺、三乙基二胺、聚乙烯亞胺、六亞甲基四胺、二伸乙基三胺、三乙基四胺、異佛爾酮二胺、胺基樹脂、聚醯胺等。Examples of the amine-based crosslinking agent include hexamethylenediamine, triethyldiamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, and triethyltetramine. Isophorone diamine, amine resin, polyamine, and the like.

作為上述金屬螯合物系交聯劑，例如可列舉：鋁、鐵、銅、鋅、錫、鈦、鎳、銻、鎂、釩、鉻、鋯等多價金屬之乙醯丙酮或乙醯乙醯酯配位化合物等。Examples of the metal chelate-based crosslinking agent include ethyl acetonide or ethyl acetonitrile of a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, ruthenium, magnesium, vanadium, chromium, or zirconium. An oxime ester coordination compound or the like.

又，該等交聯劑(B)可單獨使用，亦可併用兩種以上。Further, the crosslinking agents (B) may be used singly or in combination of two or more.

上述交聯劑(B)之含量相對於丙烯酸系樹脂(A)100重量份，較佳為0.01～10重量份，進而較佳為0.05～5重量份，尤佳為0.1～2.5重量份。若交聯劑(B)過少，則可見凝集力不足，不可獲得充分之耐久性之傾向，若過多，則由於柔軟性及黏著力降低，耐久性降低，容易產生剝離，故而可見變得難以用作光學構件之傾向。The content of the crosslinking agent (B) is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, even more preferably 0.1 to 2.5 parts by weight, per 100 parts by weight of the acrylic resin (A). When the amount of the crosslinking agent (B) is too small, the cohesive force is insufficient, and sufficient durability is not obtained. When the amount is too large, the flexibility and the adhesive force are lowered, the durability is lowered, and peeling is likely to occur, so that it becomes difficult to use. The tendency to be an optical member.

於本發明中，進而含有矽烷偶合劑(C)作為光學構件用黏著劑組成物之構成成分，就提高對光學構件之密接性之方面而言較佳。In the present invention, the decane coupling agent (C) is further contained as a constituent component of the adhesive composition for an optical member, and it is preferable in terms of improving the adhesion to the optical member.

作為該矽烷偶合劑(C)，例如可列舉：含環氧基之矽烷偶合劑、含(甲基)丙烯醯基之矽烷偶合劑、含巰基之矽烷偶合劑、含羥基之矽烷偶合劑、含羧基之矽烷偶合劑、含胺基之矽烷偶合劑、含醯胺基之矽烷偶合劑、含異氰酸酯基之矽烷偶合劑等。該等可單獨使用，亦可併用兩種以上。於該等之中，較佳為使用含環氧基之矽烷偶合劑、含巰基之矽烷偶合劑，併用含環氧基之矽烷偶合劑與含巰基之矽烷偶合劑，就提高濕熱耐久性與不過於提高黏著力之方面而言亦較佳。Examples of the decane coupling agent (C) include an epoxy group-containing decane coupling agent, a (meth)acryl fluorenyl group-containing decane coupling agent, a mercapto group-containing decane coupling agent, and a hydroxyl group-containing decane coupling agent. a decane coupling agent for a carboxyl group, a decane coupling agent containing an amine group, a decane coupling agent containing a guanamine group, a decane coupling agent containing an isocyanate group, and the like. These may be used singly or in combination of two or more. Among these, it is preferred to use an epoxy group-containing decane coupling agent, a mercapto group-containing decane coupling agent, and an epoxy group-containing decane coupling agent and a mercapto group-containing decane coupling agent to improve wet heat durability and not It is also better in terms of improving adhesion.

作為上述含環氧基之矽烷偶合劑之具體例，例如可列舉：γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基三乙氧基矽烷、γ-環氧丙氧基丙基甲基二乙氧基矽烷、γ-環氧丙氧基丙基甲基二甲氧基矽烷、甲基三(環氧丙基)矽烷、β-(3,4環氧環己基)乙基三甲氧基矽烷、β-(3,4環氧環己基)乙基三甲氧基矽烷等，其中較佳為γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基三乙氧基矽烷、γ-環氧丙氧基丙基甲基二乙氧基矽烷、β-(3,4環氧環己基)乙基三甲氧基矽烷。Specific examples of the epoxy group-containing decane coupling agent include γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, and γ-ring. Oxypropoxypropylmethyldiethoxydecane, γ-glycidoxypropylmethyldimethoxydecane, methyltris(epoxypropyl)decane, β-(3,4 epoxy Cyclohexyl)ethyltrimethoxydecane, β-(3,4 epoxycyclohexyl)ethyltrimethoxydecane, etc., among which γ-glycidoxypropyltrimethoxydecane, γ-ring is preferred. Oxypropoxypropyltriethoxydecane, γ-glycidoxypropylmethyldiethoxydecane, β-(3,4 epoxycyclohexyl)ethyltrimethoxydecane.

作為上述含巰基之矽烷偶合劑之具體例，例如可列舉：γ-巰基丙基三甲氧基矽烷、γ-巰基丙基三乙氧基矽烷、γ-巰基丙基二甲氧基甲基矽烷等。Specific examples of the mercapto group-containing decane coupling agent include γ-mercaptopropyltrimethoxydecane, γ-mercaptopropyltriethoxydecane, γ-mercaptopropyldimethoxymethylnonane, and the like. .

關於矽烷偶合劑(C)之含量，相對於丙烯酸系樹脂(A)100重量份，通常為0.001～10重量份，較佳為0.01～1重量份，尤佳為0.03～0.8重量份。若該矽烷偶合劑(C)之含量過少，則有無法獲得添加效果之傾向，若過多，則有與丙烯酸系樹脂(A)之相溶性降低，變得無法獲得接著力或凝集力之傾向。The content of the decane coupling agent (C) is usually 0.001 to 10 parts by weight, preferably 0.01 to 1 part by weight, particularly preferably 0.03 to 0.8 part by weight, per 100 parts by weight of the acrylic resin (A). When the content of the decane coupling agent (C) is too small, the effect of addition may not be obtained. If the content is too large, the compatibility with the acrylic resin (A) may be lowered, and the adhesion or cohesive force may not be obtained.

於本發明中，亦可進而含有含不飽和基之化合物(D)及聚合起始劑(E)，藉由活性能量射線及/或熱(照射活性能量射線及/或加熱)來交聯光學構件用黏著劑組成物。In the present invention, the unsaturated group-containing compound (D) and the polymerization initiator (E) may be further contained, and the optical fiber may be crosslinked by active energy ray and/or heat (irradiation active energy ray and/or heating). The component is composed of an adhesive composition.

於上述藉由活性能量射線及/或熱(照射活性能量射線及/或加熱)來交聯之情形時，使用含有含不飽和基之化合物(D)及聚合起始劑(E)之光學構件用黏著劑組成物。如此，藉由含有含不飽和基之化合物(D)，可調整交聯，並可實現適於光學構件用途之黏著物性。When the above is crosslinked by active energy ray and/or heat (irradiation active energy ray and/or heating), an optical member containing the unsaturated group-containing compound (D) and a polymerization initiator (E) is used. Use an adhesive composition. Thus, by containing the unsaturated group-containing compound (D), the crosslinking can be adjusted, and the adhesive property suitable for the use of the optical member can be achieved.

又，藉由含有上述聚合起始劑(E)，可使照射活性能量射線時及/或加熱時之反應穩定化。Further, by containing the polymerization initiator (E), the reaction at the time of irradiation of the active energy ray and/or at the time of heating can be stabilized.

於上述交聯之情形時，含不飽和基之化合物(D)藉由活性能量射線及/或熱而聚合(聚合物化)而進行與丙烯酸系樹脂(A)之交聯(物理交聯)。於丙烯酸系樹脂(A)為含不飽和基之丙烯酸系樹脂之情形時，不僅因活性能量射線及/或熱而產生含不飽和基之化合物(D)之聚合物化，亦產生伴隨含不飽和基之丙烯酸系樹脂(A)與含不飽和基之化合物(D)之聚合物化等之交聯。In the case of the above crosslinking, the unsaturated group-containing compound (D) is polymerized (polymerized) by active energy ray and/or heat to carry out crosslinking (physical crosslinking) with the acrylic resin (A). When the acrylic resin (A) is an unsaturated group-containing acrylic resin, not only the polymerization of the unsaturated group-containing compound (D) but also the accompanying unsaturated state is caused by active energy rays and/or heat. Crosslinking of the acrylic resin (A) with the polymerization of the unsaturated group-containing compound (D) or the like.

作為上述含不飽和基之化合物(D)，可為於1分子中具有1個不飽和基之單官能之含不飽和基之化合物，亦可為於1分子中具有2個以上之不飽和基之多官能之含不飽和基之化合物，但就照射活性能量射線時之硬化性之方面而言，較佳為具有2個以上之不飽和基之含不飽和基之化合物，更佳為具有3個以上之不飽和基之含不飽和基之化合物。The unsaturated group-containing compound (D) may be a monofunctional unsaturated group-containing compound having one unsaturated group in one molecule, or may have two or more unsaturated groups in one molecule. a polyfunctional unsaturated group-containing compound, but it is preferably an unsaturated group-containing compound having two or more unsaturated groups, more preferably 3, in terms of hardenability upon irradiation with an active energy ray. An unsaturated group-containing compound having more than one unsaturated group.

作為上述含不飽和基之化合物(D)之結構，例如可使用(甲基)丙烯酸胺基甲酸酯系化合物、環氧(甲基)丙烯酸酯系化合物、聚酯(甲基)丙烯酸酯系化合物或於1分子中含有1個以上之乙烯性不飽和基之乙烯性不飽和單體，例如單官能單體、2官能單體、3官能以上之單體等。該等之中，就硬化速度或到達物性之穩定性優異之方面而言，較佳為使用(甲基)丙烯酸胺基甲酸酯系化合物(d1)、乙烯性不飽和單體(d2)。As the structure of the unsaturated group-containing compound (D), for example, a (meth)acrylic acid urethane-based compound, an epoxy (meth)acrylate-based compound, or a polyester (meth)acrylate-based compound can be used. The compound or an ethylenically unsaturated monomer containing one or more ethylenically unsaturated groups in one molecule, for example, a monofunctional monomer, a bifunctional monomer, a trifunctional or higher monomer, or the like. Among these, the (meth)acrylic acid urethane-based compound (d1) and the ethylenically unsaturated monomer (d2) are preferably used in terms of the curing rate or the stability of the physical properties.

上述(甲基)丙烯酸胺基甲酸酯系化合物(d1)為於分子內具有胺基甲酸酯鍵之(甲基)丙烯酸酯系化合物，使用使含有羥基之(甲基)丙烯酸系化合物與多價異氰酸酯化合物(視需要多元醇系化合物)根據公知一般之方法反應而獲得者即可，關於其重量平均分子量，通常可使用300～4000者。The (meth)acrylic acid urethane-based compound (d1) is a (meth) acrylate-based compound having a urethane bond in the molecule, and a (meth)acrylic compound containing a hydroxyl group is used. The polyvalent isocyanate compound (required polyol compound) may be obtained by a reaction according to a known general method, and the weight average molecular weight thereof may be usually from 300 to 4,000.

作為本發明所使用之乙烯性不飽和單體(d2)，可使用公知一般之單官能單體、2官能單體、3官能以上之單體等。As the ethylenically unsaturated monomer (d2) used in the present invention, a generally known monofunctional monomer, a bifunctional monomer, a trifunctional or higher monomer, or the like can be used.

關於上述含不飽和基之化合物(D)之含量，相對於丙烯酸系樹脂(A)100重量份，較佳為0.5～99重量份，更佳為1～50重量份，進而較佳為8～30重量份。若上述含不飽和基之化合物(D)之含量過多，則可見與樹脂之相溶性降低，塗膜變白之傾向，若過少，則有黏著劑之交聯密度變得不充分，耐漏光性或耐久性降低之傾向。The content of the unsaturated group-containing compound (D) is preferably 0.5 to 99 parts by weight, more preferably 1 to 50 parts by weight, still more preferably 8 to 10 parts by weight, based on 100 parts by weight of the acrylic resin (A). 30 parts by weight. When the content of the unsaturated group-containing compound (D) is too large, the compatibility with the resin is lowered, and the coating film tends to be whitened. If the amount is too small, the crosslinking density of the adhesive is insufficient, and the light leakage resistance is insufficient. Or the tendency to reduce durability.

作為上述聚合起始劑(E)，例如可使用光聚合起始劑(e1)、熱聚合起始劑(e2)等各種聚合起始劑，尤其是使用光聚合起始劑(e1)，就可藉由照射極短時間之紫外線等活性能量射線而交聯(硬化)之方面而言較佳。As the polymerization initiator (E), for example, various polymerization initiators such as a photopolymerization initiator (e1) and a thermal polymerization initiator (e2) can be used, and in particular, a photopolymerization initiator (e1) is used. It is preferable to be crosslinked (hardened) by irradiation with an active energy ray such as ultraviolet rays for a short period of time.

又，於使用上述光聚合起始劑(e1)時，藉由照射活性能量射線而使光學構件用黏著劑組成物交聯，於使用熱聚合起始劑(e2)時，藉由加熱而使光學構件用黏著劑組成物交聯，視需要，較佳為併用兩者。Moreover, when the photopolymerization initiator (e1) is used, the optical member adhesive composition is crosslinked by irradiation of an active energy ray, and when the thermal polymerization initiator (e2) is used, it is heated by heating. The optical member is crosslinked with the adhesive composition, and it is preferred to use both in combination as needed.

作為上述光聚合起始劑(e1)及上述熱聚合起始劑(e2)，並無特別限定，可使用公知一般之光聚合起始劑、熱聚合起始劑。The photopolymerization initiator (e1) and the thermal polymerization initiator (e2) are not particularly limited, and a known general photopolymerization initiator or a thermal polymerization initiator can be used.

關於上述聚合起始劑(E)之含量，相對於上述丙烯酸系樹脂(A)100重量份，較佳為0.01～10重量份，尤佳為0.1～7重量份，進而較佳為0.3～3重量份。若上述聚合起始劑(E)之含量過少，則可見缺乏硬化性，物性變得不穩定之傾向，若過多，則亦可見無法獲得更高效果之傾向。The content of the polymerization initiator (E) is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 7 parts by weight, still more preferably 0.3 to 3 parts by weight based on 100 parts by weight of the acrylic resin (A). Parts by weight. When the content of the polymerization initiator (E) is too small, the curing property tends to be unstable, and the physical properties tend to be unstable. If the content is too large, a higher effect tends to be obtained.

又，於本發明之光學構件用黏著劑組成物中，可於不損害本發明之效果之範圍中進而調配抗靜電劑、丙烯酸系樹脂(A)以外之丙烯酸系黏著劑等其他之黏著劑、胺基甲酸酯樹脂、松香、松酯、氫化松酯、酚樹脂、芳香族改性萜烯樹脂樹脂、脂肪族系石油樹脂、脂環族系石油樹脂、苯乙烯系樹脂、二甲苯系樹脂等增黏劑、著色劑、填充劑、抗熟化劑、紫外線吸收劑、功能性色素等先前公知之添加劑、或不因紫外線或放射線照射而引起顯色或變色般之化合物。Further, in the adhesive composition for an optical member of the present invention, an antistatic agent, an acrylic adhesive other than the acrylic resin (A), and the like may be further blended, and other adhesives such as an acrylic adhesive other than the acrylic resin (A) may be blended. Aurethane resin, rosin, pine ester, hydrogenated pine ester, phenol resin, aromatic modified terpene resin, aliphatic petroleum resin, alicyclic petroleum resin, styrene resin, xylene resin A conventionally known additive such as a tackifier, a colorant, a filler, an anti-curing agent, an ultraviolet absorber, a functional dye, or a compound which does not cause coloration or discoloration due to ultraviolet rays or radiation.

又，除上述添加劑以外，亦可少量含有光學構件用黏著劑組成物之構成成分之製造原料等所含有之雜質等。In addition to the above additives, impurities and the like contained in the raw material of the constituents of the constituent components of the adhesive composition for an optical member may be contained in a small amount.

作為上述抗靜電劑，例如可列舉：咪唑鎓鹽、四烷基銨磺酸鹽等4級銨鹽之陽離子型抗靜電劑；脂肪族磺酸鹽、高級醇硫酸酯鹽、高級醇環氧烷加成物硫酸酯鹽、高級醇磷酸酯鹽、高級醇環氧烷加成物磷酸酯鹽等陰離子型抗靜電劑；雙(氟磺醯基)醯亞胺鉀、雙(三氟磺醯基)醯亞胺鋰或氯化鋰等鹼金屬鹽、鹼土金屬鹽、高級醇環氧烷加成物、聚烷二醇脂肪酸酯等。Examples of the antistatic agent include cationic antistatic agents of a 4-grade ammonium salt such as an imidazolium salt or a tetraalkylammonium sulfonate; an aliphatic sulfonate, a higher alcohol sulfate, and a higher alcohol alkylene oxide; Anionic antistatic agent such as adduct sulfate salt, higher alcohol phosphate salt, higher alcohol alkylene oxide adduct phosphate salt; bis(fluorosulfonyl) quinone imide potassium, bis(trifluorosulfonyl) An alkali metal salt such as lithium sulfoxide or lithium chloride; an alkaline earth metal salt; a higher alcohol alkylene oxide adduct; or a polyalkylene glycol fatty acid ester.

再者，於本發明中，光學構件用黏著劑組成物較佳為將丙烯酸系樹脂(A)作為主成分者，此處，「作為主成分」意指相對於光學構件用黏著劑組成物總量，通常含有上述丙烯酸系樹脂(A)50重量%以上，較佳為60重量%以上，更佳為70重量%以上。再者，丙烯酸系樹脂(A)之含量之上限通常為99.9重量%。In the present invention, the adhesive composition for an optical member preferably has an acrylic resin (A) as a main component. Here, "as a main component" means a total of an adhesive composition for an optical member. The amount of the acrylic resin (A) is usually 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more. Further, the upper limit of the content of the acrylic resin (A) is usually 99.9% by weight.

如此，可獲得本發明所使用之光學構件用黏著劑組成物，並且，使該光學構件用黏著劑組成物交聯而成為本發明之光學構件用黏著劑。In this way, the adhesive composition for an optical member used in the present invention can be obtained, and the adhesive composition for the optical member can be crosslinked to form an adhesive for an optical member of the present invention.

[光學構件用黏著劑][Adhesive for optical components]

於本發明中，使上述光學構件用黏著劑組成物交聯而成之光學構件用黏著劑之膠體率，就耐久性能與耐漏光性平衡良好地優異之方面而言，較佳為60～95%，尤佳為65～90%，進而較佳為70～85%。若膠體率過低，則有因凝集力不足而容易產生耐久性不足之傾向，若膠體率過高，則有凝集力過於升高，於耐久性試驗中產生剝離之傾向。In the present invention, the colloidal ratio of the optical member adhesive agent obtained by crosslinking the optical member adhesive composition is preferably 60 to 95 in terms of excellent balance between durability and light leakage resistance. %, particularly preferably 65 to 90%, more preferably 70 to 85%. When the colloidal rate is too low, the strength tends to be insufficient due to insufficient cohesive force. If the colloidal ratio is too high, the cohesive force is too high, and peeling tends to occur in the durability test.

再者，於將黏著劑之膠體率調整為上述範圍時，例如可藉由調整交聯劑之種類與量、調整組成物中之羥基與羧基之組成比等而達成。又，由於該交聯劑與官能基量之比例藉由各自之相互作用而膠體率變化，故而必需各自取得平衡。Further, when the colloidal ratio of the adhesive is adjusted to the above range, for example, the type and amount of the crosslinking agent can be adjusted, and the composition ratio of the hydroxyl group to the carboxyl group in the composition can be adjusted. Further, since the ratio of the crosslinking agent to the amount of the functional group changes the colloidal ratio by the respective interactions, it is necessary to achieve a balance.

由於上述膠體率為交聯度之標準，故而可藉由例如以下方法而算出。即，利用200網目之SUS製金屬絲網包裹使黏著劑層形成於作為基材之高分子片材(例如聚對苯二甲酸乙二酯膜等)上而成之黏著片(未設置隔片者)，並於甲苯中浸漬23℃×24小時，將金屬絲網中所殘留之不溶解之黏著劑成分相對於甲苯浸漬前之黏著劑層之重量百分率設為膠體率。其中，預先減去基材之重量。Since the colloid ratio is a standard of the degree of crosslinking, it can be calculated by, for example, the following method. In other words, an adhesive sheet in which an adhesive layer is formed on a polymer sheet (for example, a polyethylene terephthalate film or the like) as a substrate by wrapping a 200 mesh SUS metal mesh (no spacer is provided) And immersed in toluene at 23 ° C for 24 hours, and the weight percentage of the insoluble adhesive component remaining in the wire mesh with respect to the adhesive layer before toluene immersion was set to the colloidal ratio. Among them, the weight of the substrate is subtracted in advance.

本發明之光學構件用黏著劑可用於概念性地包含顯示器或構成其之光學構件之光學構件。作為顯示器，可列舉文字處理機、電腦、行動電話、電視等各種顯示器，作為光學構件，可列舉偏光板或以此為基準之光學積層體等。本發明之光學構件用黏著劑除用於下述之附有黏著劑層之光學構件以外，亦可用於各種用途。尤其是本發明之光學構件用黏著劑由於再加工性與耐久性優異，故而亦可用作用以保護液晶屏幕等屏幕之保護片之黏著劑。再者，本發明之光學構件用黏著劑亦可用作電子基板等之暫時表面保護用黏著劑、雙面膠用黏著劑、醫用黏著劑、表面保護用黏著劑、一般標籤用黏著劑、玩具之密封用黏著劑、裝飾密封用黏著劑、凹凸追隨性黏著劑。The adhesive for optical members of the present invention can be used for conceptually including an optical member of a display or an optical member constituting the same. Examples of the display include various types of displays such as a word processor, a computer, a mobile phone, and a television. Examples of the optical member include a polarizing plate or an optical layered body based thereon. The adhesive for optical members of the present invention can be used for various purposes in addition to the optical members with an adhesive layer described below. In particular, the adhesive for optical members of the present invention is excellent in reworkability and durability, and can also be used as an adhesive for protecting a protective sheet such as a liquid crystal screen. Further, the adhesive for optical members of the present invention can also be used as an adhesive for temporary surface protection such as an electronic substrate, an adhesive for double-sided adhesive, a medical adhesive, an adhesive for surface protection, an adhesive for general labels, Adhesive for sealing of toys, adhesive for decorative seals, and adhesive follow-up adhesive.

[附有黏著劑層之光學構件][Optical member with adhesive layer]

於本發明中，藉由於光學構件(例如光學積層體)之單面或雙面積層形成含有上述光學構件用黏著劑之黏著劑層，可獲得附有黏著劑層之光學構件。In the present invention, an optical member having an adhesive layer can be obtained by forming an adhesive layer containing the above-mentioned optical member adhesive by a single-sided or double-area layer of an optical member (for example, an optical laminate).

於上述附有黏著劑層之光學構件中，較佳為於與黏著劑層之光學構件側之面相反之面(露出面)進而設置脫模片。In the optical member with the adhesive layer described above, it is preferable to provide a release sheet on the opposite surface (exposed surface) from the surface on the optical member side of the adhesive layer.

又，於將附有黏著劑層之光學構件供於實際使用時，可剝離上述脫模片而使用。並且，較佳為使用矽系之脫模片作為上述脫模片。Further, when the optical member with the adhesive layer is used for practical use, the release sheet can be peeled off and used. Further, it is preferable to use a release sheet of a fluorene type as the release sheet.

又，於製作附有黏著劑層之光學構件時，作為使光學構件用黏著劑組成物交聯之方法，可列舉如下方法：[1]於在光學構件上塗佈光學構件用黏著劑組成物並乾燥後，貼合脫模片，進行熟化處理；[2]於在脫模片上塗佈光學構件用黏著劑組成物並乾燥後，貼合光學構件，進行熟化處理。該等之中，[2]之方法就不損傷光學構件之方面、及操作性或穩定製造之方面而言較佳。In the case of producing an optical member having an adhesive layer, the method of crosslinking the adhesive composition for an optical member includes the following method: [1] Applying an adhesive composition for an optical member to an optical member After drying, the release sheet is bonded to the aging treatment. [2] After the adhesive composition for the optical member is applied onto the release sheet and dried, the optical member is bonded to the aging treatment. Among these, the method of [2] is preferable in terms of not impairing the optical member, and operability or stable manufacturing.

上述熟化處理係為了獲得黏著物性之平衡而進行者，作為熟化之條件，溫度通常為室溫～70℃，時間通常為1天～30天，具體而言，例如在於23℃下1天～20天、於23℃下3天～10天、於40℃下1天～7天等條件下進行即可。The aging treatment is carried out in order to obtain a balance of adhesive properties, and the temperature is usually from room temperature to 70 ° C, and the time is usually from 1 day to 30 days, specifically, for example, at 23 ° C for 1 day to 20 hours. It can be carried out under conditions of 3 days to 10 days at 23 ° C and 1 day to 7 days at 40 ° C.

於塗佈上述光學構件用黏著劑組成物時，較佳為將該光學構件用黏著劑組成物於溶劑中稀釋並塗佈，關於稀釋濃度，較佳為5～60重量%，尤佳為10～30重量%。又，作為上述溶劑，只要為使光學構件用黏著劑組成物溶解者，則並無特別限定，例如可使用乙酸甲酯、乙酸乙酯、乙醯乙酸甲酯、乙醯乙酸乙酯等酯系溶劑；丙酮、甲基乙基酮、甲基異丁基酮等酮系溶劑；甲苯、二甲苯等芳香族系溶劑；甲醇、乙醇、丙醇等醇系溶劑。該等之中，就溶解性、乾燥性、價格等方面而言，可適宜使用乙酸乙酯、甲基乙基酮。When the adhesive composition for an optical member is applied, it is preferred that the optical member adhesive composition is diluted and applied in a solvent, and the dilution concentration is preferably 5 to 60% by weight, particularly preferably 10 ～30% by weight. In addition, the solvent is not particularly limited as long as it dissolves the adhesive composition for an optical member, and for example, an ester system such as methyl acetate, ethyl acetate, methyl acetate or ethyl acetate can be used. Solvent; ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; aromatic solvent such as toluene or xylene; and alcohol solvent such as methanol, ethanol or propanol. Among these, ethyl acetate and methyl ethyl ketone can be suitably used in terms of solubility, drying property, price, and the like.

又，關於上述光學構件用黏著劑組成物之塗佈，可藉由輥塗法、模塗法(die coating)、凹版印刷塗佈法、刮刀式塗佈法、網版印刷等慣用之方法而進行。Moreover, the application of the above-mentioned adhesive composition for an optical member can be carried out by a conventional method such as a roll coating method, a die coating method, a gravure coating method, a knife coating method, or a screen printing method. get on.

又，所獲得之附有黏著劑層之光學構件中之黏著劑層厚度通常較佳為5～300 μm，尤佳為10～50 μm，進而較佳為12～30 μm。若該黏著劑層之厚度過薄，則存在黏著物性難以穩定之傾向，若過厚，則存在光學構件整體之厚度過厚之傾向。Further, the thickness of the adhesive layer in the optical member with the adhesive layer obtained is usually preferably from 5 to 300 μm, more preferably from 10 to 50 μm, still more preferably from 12 to 30 μm. If the thickness of the adhesive layer is too small, the adhesive property tends to be unstable, and if it is too thick, the thickness of the entire optical member tends to be too thick.

於本發明之附有黏著劑層之光學構件中，具有脫模片者於剝離脫模片後，將黏著劑層面例如貼合於液晶單元之玻璃基板上，並供於液晶顯示裝置。In the optical member with an adhesive layer of the present invention, after the release sheet is peeled off, the adhesive layer is bonded to, for example, a glass substrate of the liquid crystal cell, and supplied to the liquid crystal display device.

作為本發明之附有黏著劑層之光學構件中之光學構件，並無特別限定，可列舉可適宜用於液晶顯示裝置等影像顯示裝置之光學膜，例如可列舉偏光板或位相差板、橢圓偏光板、光學補償膜、亮度提高膜、進而該等積層而成之光學積層體等。其中，尤其是偏光板於本發明中有效。The optical member in the optical member with the adhesive layer of the present invention is not particularly limited, and examples thereof include an optical film which can be suitably used for a video display device such as a liquid crystal display device, and examples thereof include a polarizing plate, a phase difference plate, and an ellipse. A polarizing plate, an optical compensation film, a brightness enhancement film, and the like, and an optical laminate which is laminated. Among them, especially polarizing plates are effective in the present invention.

本發明所使用之偏光板通常係於偏光膜之雙面積層三乙酸纖維素系膜作為保護膜而成者，作為上述偏光膜，可使用包括平均聚合度為1,500～10,000、皂化度為85～100莫耳%之聚乙烯醇系樹脂之膜作為整幅膜，藉由碘-碘化鉀之水溶液或二色性染料而染色之單軸延伸膜(通常為2～10倍、較佳為3～7倍左右之延伸倍率)。The polarizing plate used in the present invention is usually a double-layered cellulose acetate-based film of a polarizing film as a protective film. As the polarizing film, an average polymerization degree of 1,500 to 10,000 and a saponification degree of 85 to 5% can be used. a film of 100 mol% of a polyvinyl alcohol-based resin as a whole film, a uniaxially stretched film dyed by an aqueous solution of iodine-potassium iodide or a dichroic dye (usually 2 to 10 times, preferably 3 to 7) The extension ratio of the magnification is about).

作為上述聚乙烯醇系樹脂，通常將使乙酸乙烯酯聚合而成之聚乙酸乙烯酯皂化而製造，但亦可含有少量之不飽和羧酸(包含其鹽、酯、醯胺、腈等)、烯烴類、乙烯醚類、不飽和磺酸鹽等可與乙酸乙烯酯共聚合之成分。又，亦可列舉使聚乙烯醇於酸之存在下與醛類反應而成之例如聚丁醛樹脂、聚乙烯甲醛樹脂等所謂之聚乙烯縮醛樹脂及聚乙烯醇衍生物。The polyvinyl alcohol-based resin is usually produced by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate, but may contain a small amount of an unsaturated carboxylic acid (including a salt, an ester, a guanamine, a nitrile, etc.), A component which can be copolymerized with vinyl acetate, such as an olefin, a vinyl ether or an unsaturated sulfonate. Further, a so-called polyvinyl acetal resin or a polyvinyl alcohol derivative such as a polybutyraldehyde resin or a polyethylene formaldehyde resin obtained by reacting polyvinyl alcohol with an aldehyde in the presence of an acid may be mentioned.

[影像顯示裝置][Image display device]

本發明之附有黏著劑層之光學構件可適宜用於液晶顯示裝置、有機EL顯示裝置、PDP、電子紙、LED(light emitting diode，發光二極體)面板等影像顯示裝置。本發明之含有附有黏著劑層之光學構件之影像顯示裝置於高溫、高濕之環境下、及重複低溫～高溫之環境變化時，於黏著劑層與影像顯示裝置之間亦難以產生發泡或剝離。又，可抑制因伴隨偏光板等光學構件之尺寸變化之應力而產生之色彩不均、漏光現象。因此，可維持影像顯示裝置之顯示品質。The optical member with an adhesive layer of the present invention can be suitably used for an image display device such as a liquid crystal display device, an organic EL display device, a PDP, an electronic paper, an LED (light emitting diode) panel, or the like. In the image display device of the present invention comprising the optical member with the adhesive layer, it is difficult to foam between the adhesive layer and the image display device in a high temperature, high humidity environment and repeated low temperature to high temperature environment changes. Or peel off. Further, it is possible to suppress color unevenness and light leakage caused by stress accompanying dimensional changes of optical members such as a polarizing plate. Therefore, the display quality of the image display device can be maintained.

[實施例][Examples]

以下，列舉實施例對本發明進而具體地進行說明，但本發明只要不超過其主旨，則並不限定於以下之實施例。再者，例中，「份」、「%」只要未特別說明，意指重量基準。Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples as long as it does not exceed the gist of the invention. In the examples, "parts" and "%" mean weight basis unless otherwise specified.

首先，以如下所述之方式製備各種丙烯酸系樹脂(A)。再者，關於丙烯酸系樹脂(A)之重量平均分子量及數平均分子量之測定係依照上述方法而測定。First, various acrylic resins (A) were prepared in the following manner. Further, the measurement of the weight average molecular weight and the number average molecular weight of the acrylic resin (A) was carried out in accordance with the above method.

[丙烯酸系樹脂(A)之製備][Preparation of Acrylic Resin (A)]

關於實施例1～13，於具備冷凝器、攪拌器、氮氣吹入口及溫度計之四口圓底燒瓶中，裝入表1所記載之量之各單體(a1)～(a5)、乙酸乙酯80份、丙酮40份，於開始加熱回流後，添加偶氮雙異丁腈0.03份作為聚合起始劑，於乙酸乙酯回流溫度下反應3小時後，藉由乙酸乙酯稀釋，獲得各丙烯酸系樹脂(A)溶液。Each of the monomers (a1) to (a5) and the acetic acid B in the amounts shown in Table 1 were placed in a four-necked round bottom flask equipped with a condenser, a stirrer, a nitrogen gas inlet, and a thermometer in each of Examples 1 to 13. 80 parts of ester and 40 parts of acetone. After heating and refluxing, 0.03 parts of azobisisobutyronitrile was added as a polymerization initiator, and the mixture was reacted at the reflux temperature of ethyl acetate for 3 hours, and then diluted with ethyl acetate to obtain each. Acrylic resin (A) solution.

關於實施例14，於具備冷凝器、攪拌器、氮氣吹入口及溫度計之四口圓底燒瓶中裝入乙酸乙酯120份，一面攪拌一面升溫，於內溫成為75℃後，以總量添加將偶氮雙異丁腈(聚合起始劑)0.05份溶解於乙酸乙酯5份中而成之溶液後，將內溫保持於74～76℃，同時將丙烯酸丁酯(a1)90.4份、苯氧基二乙二醇丙烯酸酯(a3)8份、丙烯酸2-羥基乙酯(a5)1份、N-(正丁氧基甲基)丙烯醯胺(a2)0.5份、丙烯酸(a4)0.4份之混合溶液用2小時滴加於反應系統內。其後，於內溫74～76℃下聚合5小時後，添加乙酸乙酯，獲得丙烯酸系樹脂(A)溶液。In Example 14, a four-necked round bottom flask equipped with a condenser, a stirrer, a nitrogen gas inlet, and a thermometer was charged with 120 parts of ethyl acetate, and the temperature was raised while stirring, and after the internal temperature became 75 ° C, the total amount was added. After dissolving 0.05 part of azobisisobutyronitrile (polymerization initiator) in 5 parts of ethyl acetate, the internal temperature was maintained at 74 to 76 ° C while 90.4 parts of butyl acrylate (a1) was 8 parts of phenoxy diethylene glycol acrylate (a3), 1 part of 2-hydroxyethyl acrylate (a5), 0.5 part of N-(n-butoxymethyl) acrylamide (a2), acrylic acid (a4) 0.4 parts of the mixed solution was added dropwise to the reaction system over 2 hours. Thereafter, the mixture was polymerized at an internal temperature of 74 to 76 ° C for 5 hours, and then ethyl acetate was added to obtain an acrylic resin (A) solution.

再者，關於比較例1～3，除添加表1所記載之量之其他共聚合性單體(醯胺或胺化合物)(a5)代替N-(烷氧基烷基)(甲基)丙烯醯胺系單體(a2)以外，關於比較例4，除未添加單體(a2)以外，利用與實施例1～13同樣之方式獲得各丙烯酸系樹脂(A)溶液。Further, in Comparative Examples 1 to 3, in place of N-(alkoxyalkyl)(methyl)propene, other copolymerizable monomers (amine or amine compound) (a5) in an amount described in Table 1 were added. In the same manner as in Examples 1 to 13, except for the amide-based monomer (a2), a solution of each acrylic resin (A) was obtained in the same manner as in Examples 1 to 13 except that the monomer (a2) was not added.

將上述所得之各丙烯酸系樹脂(A)溶液之重量平均分子量、數平均分子量示於表1。The weight average molecular weight and the number average molecular weight of each of the acrylic resin (A) solutions obtained above are shown in Table 1.

表1之記號所示之單體如下所述。The monomers shown in the symbols of Table 1 are as follows.

BA：丙烯酸丁酯BA: butyl acrylate

MA：丙烯酸甲酯MA: Methyl acrylate

BMAA：N-(正丁氧基甲基)丙烯醯胺BMAA: N-(n-butoxymethyl) acrylamide

MMAA：N-(甲氧基甲基)丙烯醯胺MMAA: N-(methoxymethyl) acrylamide

IBMAA：N-(異丁氧基甲基)丙烯醯胺IBMAA: N-(isobutoxymethyl) acrylamide

PEA2：苯基二乙二醇丙烯酸酯(共榮公司製造，商品名「Light Acrylate P2HA」)PEA2: phenyl diethylene glycol acrylate (manufactured by Kyoei Co., Ltd., trade name "Light Acrylate P2HA")

PEA：丙烯酸苯氧基乙酯PEA: phenoxyethyl acrylate

AAc：丙烯酸AAc: Acrylic

β-CEA：丙烯酸羧基乙酯(混合物)β-CEA: carboxyethyl acrylate (mixture)

HEA：丙烯酸-2-羥基乙酯HEA: 2-hydroxyethyl acrylate

DMAA：二甲基胺基丙烯醯胺DMAA: dimethylamino acrylamide

DMAPAA：二甲基胺基丙基丙烯醯胺DMAPAA: Dimethylaminopropyl acrylamide

DMAEA：二甲基胺基乙基丙烯酸酯DMAEA: dimethylaminoethyl acrylate

[交聯劑(B)][Crosslinking agent (B)]

準備以下者作為交聯劑(B)。The following was prepared as the crosslinking agent (B).

‧三羥甲基丙烷之甲苯二異氰酸酯酯加成物之55%乙酸乙酯溶液(日本聚胺酯公司製造，「Coronate L-55E」)(KL-55E)‧ 55% ethyl acetate solution of toluene diisocyanate adduct of trimethylolpropane (manufactured by Japan Polyurethane Co., Ltd., "Coronate L-55E") (KL-55E)

[矽烷偶合劑(C)][decane coupling agent (C)]

準備以下者作為矽烷偶合劑(C)。The following was prepared as a decane coupling agent (C).

‧γ-環氧丙氧基丙基三甲氧基矽烷多元醇(信越化學公司製造之「X-41-1805」)‧γ-glycidoxypropyltrimethoxydecane polyol (X-41-1805, manufactured by Shin-Etsu Chemical Co., Ltd.)

[抗靜電劑][antistatic agent]

準備雙(氟磺醯基)醯亞胺鉀(KFSI，potassium bis(fluorosulfonyl)imide)作為抗靜電劑。Potassium bis(fluorosulfonylimide) was prepared as an antistatic agent.

[實施例1～14、比較例1～4][Examples 1 to 14 and Comparative Examples 1 to 4]

藉由將以如上所述之方式製備、準備之各調配成分以表1所示之比例調配而製備成為光學構件用黏著劑形成材料之黏著劑組成物，將其藉由甲基乙基酮稀釋(黏度[500～1000 mPa‧s(25℃)])，製作黏著劑組成物溶液。An adhesive composition which is an adhesive forming material for an optical member is prepared by blending each of the formulated components prepared and prepared as described above in the proportions shown in Table 1, and is diluted with methyl ethyl ketone. (Viscosity [500 to 1000 mPa‧s (25 °C)]), a solution of the adhesive composition was prepared.

並且，將上述黏著劑組成物溶液以乾燥後之厚度成為25 μm之方式塗佈於聚酯系脫模片上，於90℃下乾燥3分鐘後，將形成之黏著劑組成物層側轉印於聚對苯二甲酸乙二酯(PET，polyethylene terephthalate)膜(厚度為38 μm)上，其後，於溫度23℃×相對濕度65%之條件下熟化10天，獲得附有黏著劑層之PET膜。Further, the above-mentioned adhesive composition solution was applied onto a polyester release sheet so as to have a thickness of 25 μm after drying, and dried at 90 ° C for 3 minutes, and then the formed adhesive composition layer side was transferred thereto. Polyethylene terephthalate (PET) film (thickness: 38 μm), and then aged at a temperature of 23 ° C × 65% relative humidity for 10 days to obtain PET with an adhesive layer membrane.

使用以如上所述之方式獲得之附有黏著劑層之PET膜，根據下述所示之各方法測定、評價膠體率、表面電阻率。將該等結果示於表2。The colloidal rate and the surface resistivity were measured and evaluated according to the respective methods shown below using the PET film with the adhesive layer obtained as described above. These results are shown in Table 2.

[膠體率之測定方法][Method for measuring colloidal rate]

將所獲得之附有黏著劑層之PET膜切割成40×40 mm之大小後，剝離脫模片，將黏著劑層側貼合於50×100 mm之SUS篩網片(200網目)上。根據相對於SUS篩網片之長度方向自中央部摺疊並包裹樣本後，浸漬於放入甲苯250 g之密封容器時之重量變化進行膠體率之測定。After the obtained PET film with the adhesive layer was cut into a size of 40 × 40 mm, the release sheet was peeled off, and the adhesive layer side was attached to a 50 × 100 mm SUS mesh sheet (200 mesh). The colloidal rate was measured by folding and immersing the sample from the center portion with respect to the longitudinal direction of the SUS mesh sheet, and immersing it in a sealed container containing 250 g of toluene.

[表面電阻率之測定方法][Method for measuring surface resistivity]

將所獲得之附有黏著劑層之PET膜切割成40×40 mm之大小後，將其於溫度23℃×相對濕度65%之條件下放置3小時進行濕度調控。對於剝離脫模片10～20秒後之黏著劑層，使用電阻率計(三菱化學公司製造，Hiresta UP)測定表面電阻率。再者，表面電阻率越小則意指抗靜電性能越高。The obtained PET film with the adhesive layer was cut into a size of 40 × 40 mm, and then allowed to stand at a temperature of 23 ° C × 65% relative humidity for 3 hours for humidity control. The surface resistivity of the adhesive layer after peeling off the release sheet for 10 to 20 seconds was measured using a resistivity meter (manufactured by Mitsubishi Chemical Corporation, Hiresta UP). Furthermore, the smaller the surface resistivity, the higher the antistatic property.

[附有黏著劑層之偏光板之製備][Preparation of polarizing plate with adhesive layer]

將實施例1～14、比較例1～4之黏著劑組成物溶液以乾燥後之厚度成為25 μm之方式塗佈於聚酯系脫模片上，並於90℃下乾燥3分鐘，將形成之黏著劑組成物層轉印於偏光板(厚度為190 μm)上，其後，於溫度23℃×相對濕度65%之條件下熟化10天，獲得附有黏著劑層之偏光板。The adhesive composition solutions of Examples 1 to 14 and Comparative Examples 1 to 4 were applied to a polyester release sheet so as to have a thickness of 25 μm after drying, and dried at 90 ° C for 3 minutes to form a solution. The adhesive composition layer was transferred onto a polarizing plate (thickness: 190 μm), and then aged at a temperature of 23 ° C × a relative humidity of 65% for 10 days to obtain a polarizing plate with an adhesive layer.

再者，將上述偏光板以相對於延伸軸成為45°之方式切割並使用。Further, the polarizing plate was cut and used so as to be 45° with respect to the extending axis.

使用以如上所述之方式獲得之附有黏著劑層之偏光板，根據下述所示之各方法測定、評價再加工性、耐漏光性、耐久性(耐熱試驗、耐濕熱試驗、熱循環試驗)。將該等結果示於表2。Using the polarizing plate with the adhesive layer obtained as described above, the reworkability, light leakage resistance, and durability (heat resistance test, moisture heat resistance test, heat cycle test) were measured and evaluated according to the methods described below. ). These results are shown in Table 2.

[再加工性][Reworkability]

對於製作之附有黏著劑層之偏光板，切割成寬度為25 mm之寬度，剝離脫模片，將黏著劑層側按壓至無鹼玻璃板(Corning公司製造，Eagle XG)，將偏光板與玻璃板貼合。其後，進行高壓釜處理(50℃，0.5 MPa，20分鐘)，於50℃環境下放置48小時後，於23℃環境下放置30分鐘後，進行180°剝離試驗。The polarizing plate with the adhesive layer was cut into a width of 25 mm, the release sheet was peeled off, and the adhesive layer side was pressed to an alkali-free glass plate (Eagle XG, manufactured by Corning), and the polarizing plate was The glass plate fits. Thereafter, autoclaving treatment (50 ° C, 0.5 MPa, 20 minutes) was carried out, and the mixture was allowed to stand in an environment of 50 ° C for 48 hours, and then left to stand in an environment of 23 ° C for 30 minutes, and then subjected to a 180 ° peel test.

於再加工性中期望黏著力適度較小，於48小時後以10 N/25 mm左右作為目標。利用下述之基準進行評價。It is expected that the adhesion is moderately small in reworkability, and is targeted at about 10 N/25 mm after 48 hours. Evaluation was performed using the following criteria.

(評價基準)(evaluation benchmark)

◎：未滿10 N/25 mm◎: less than 10 N/25 mm

○：為10 N/25 mm以上，未滿15 N/25 mm○: 10 N/25 mm or more, less than 15 N/25 mm

△：為15 N/25 mm以上，未滿20 N/25 mm△: 15 N/25 mm or more, less than 20 N/25 mm

×：為20 N/25 mm以上×: 20 N/25 mm or more

[耐漏光性][Light leakage resistance]

將所獲得之附有黏著劑層之偏光板於80℃下放置1000小時後，以偏光板成為正交偏光之方式製作於表與背雙面上貼合相同之樣本之漏光觀察用樣本。對著背光進行目測確認，利用下述基準進行評價。The obtained polarizing plate with an adhesive layer was allowed to stand at 80 ° C for 1,000 hours, and then a sample for light leakage observation in which the same sample was attached to both the front and back sides was formed so that the polarizing plate became orthogonally polarized. The backlight was visually confirmed and evaluated by the following criteria.

(評價基準)(evaluation benchmark)

◎：完全未見到漏光。◎: No light leakage was observed at all.

○：稍有觀察到漏光。○: Light leakage was observed slightly.

△：可觀察到對實際使用可能具有障礙之程度之漏光。△: Light leakage to the extent that the actual use may have an obstacle can be observed.

×：漏光較為嚴重。×: Light leakage is more serious.

[耐久性][durability]

剝離所獲得之附有黏著劑層之偏光板之脫模片，將黏著劑層側按壓於無鹼玻璃板(Corning公司製造，Eagle XG)上，貼合偏光板與玻璃板後，進行高壓釜處理(50℃，0.5 MPa，20分鐘)，其後，於下述(1)～(3)之耐久試驗(耐熱試驗、耐濕熱試驗、熱循環試驗)中進行發泡、剝離、浮起之評價。再者，所使用之試驗片之尺寸為20 cm×15 cm。The release sheet of the polarizing plate with the adhesive layer obtained was peeled off, and the adhesive layer side was pressed against an alkali-free glass plate (Eagle XG, manufactured by Corning, Inc.), and the polarizing plate and the glass plate were attached thereto, and then autoclaved. Treatment (50 ° C, 0.5 MPa, 20 minutes), followed by foaming, peeling, and floating in the durability tests (heat resistance test, moisture heat resistance test, heat cycle test) of the following (1) to (3) Evaluation. Further, the size of the test piece used was 20 cm × 15 cm.

(1)耐熱試驗(1) Heat resistance test

90℃、2000小時之耐久試驗90 ° C, 2000 hours of endurance test

(2)耐濕熱試驗(2) Heat and humidity resistance test

60℃、相對濕度(R.H.)90%、2000小時之耐久試驗Durability test at 60 ° C, relative humidity (R.H.) 90%, 2000 hours

(3)熱循環試驗(3) Thermal cycle test

將於-35℃下放置30分鐘後，於70℃下放置30分鐘之操作設為1個循環，進行1000個循環之耐久試驗After standing at -35 ° C for 30 minutes, the operation at 70 ° C for 30 minutes is set to 1 cycle, and 1000 cycles of endurance test are performed.

[評價基準][evaluation benchmark] (發泡)(foaming)

◎…無發泡◎...no foaming

○…幾乎不可觀察到發泡○... almost no foaming is observed

△…稍可觀察到發泡△... slightly observed foaming

×…較多地觀察到發泡×...More foaming is observed

(剝離)(stripping)

○…產生未滿0.5 mm之剝離，或未滿0.5 mm之浮起痕跡○...leaving a peel of less than 0.5 mm, or a floating trace of less than 0.5 mm

△…產生0.5mm以上未滿10 mm之剝離，或0.5 mm以上未滿10 mm之浮起痕跡△... Produces a peeling of 0.5 mm or more and less than 10 mm, or a floating trace of 0.5 mm or more and less than 10 mm.

×…產生10 mm以上之剝離，或10 mm以上之浮起痕跡×... Produces peeling of 10 mm or more, or floating marks of 10 mm or more

可知於含有N-(烷氧基烷基)(甲基)丙烯醯胺系單體(a2)之實施例1～14之附有黏著劑層之偏光板中，不論何者均可達成再加工性與於長時間曝露於高溫、高濕度下時之耐久性之並存。It is understood that in the polarizing plates with the adhesive layers of Examples 1 to 14 containing the N-(alkoxyalkyl)(meth)acrylamide-based monomer (a2), reworkability can be achieved by any of them. Coexistence with durability when exposed to high temperatures and high humidity for a long time.

另一方面，於使用專利文獻2等所記載之N,N-二烷基(甲基)丙烯醯胺代替N-(烷氧基烷基)(甲基)丙烯醯胺系單體(a2)之比較例1中，再加工性雖優異，但耐久性較差。又，於使用專利文獻1等所記載之含三級胺基之單體(丙烯酸酯、丙烯醯胺)代替單體(a2)之比較例2、3中，再加工性、耐久性均較差。進而，於未使用單體(a2)之比較例4中，再加工性雖優異，但耐久性不充分。On the other hand, N,N-dialkyl(meth)acrylamide as described in Patent Document 2 or the like is used instead of the N-(alkoxyalkyl)(meth)acrylamide monomer (a2). In Comparative Example 1, although the reworkability was excellent, the durability was inferior. In addition, in Comparative Examples 2 and 3 in which a monomer having a tertiary amino group (acrylic acid ester or acrylamide) described in Patent Document 1 or the like was used instead of the monomer (a2), reworkability and durability were inferior. Further, in Comparative Example 4 in which the monomer (a2) was not used, the reworkability was excellent, but the durability was insufficient.

熟習本案相關技藝者應明白，以上雖詳細地且參照特定之實施態樣對本發明進行了說明，但可不脫離本發明之精神與範圍而施加各種變化或修正。It will be apparent to those skilled in the art that the present invention is described in detail hereinabove.

本申請案係基於2010年10月12日申請之日本專利申請案(日本專利特願2010-229885)，其內容係作為參照而併入於此。The present application is based on Japanese Patent Application No. 2010-229885, filed on Jan.

(產業上之可利用性)(industrial availability)

藉由使用本發明之光學構件用黏著劑組成物，可獲得再加工性與耐久性優異之光學構件用黏著劑。進而，藉由使用本發明之光學構件用黏著劑，可於液晶顯示板等影像顯示裝置中抑制色彩不均、漏光現象。By using the adhesive composition for an optical member of the present invention, an adhesive for an optical member excellent in reworkability and durability can be obtained. Further, by using the optical member adhesive of the present invention, it is possible to suppress color unevenness and light leakage in an image display device such as a liquid crystal display panel.

Claims (8)

一種光學構件用黏著劑組成物，其係含有使以(甲基)丙烯酸烷基酯系單體(a1)作為主成分之共聚合成分[1]進行共聚合而獲得之丙烯酸系樹脂(A)而成者，其中係含有N-(烷氧基烷基)(甲基)丙烯醯胺系單體(a2)及含羧基之單體(a4)作為共聚合成分[1]而成；相對於共聚合成分[1]整體，N-(烷氧基烷基)(甲基)丙烯醯胺系單體(a2)之含有比例為0.5~2重量%；相對於共聚合成分[1]整體，N-(烷氧基烷基)(甲基)丙烯醯胺系單體(a2)及含羧基之單體(a4)之合計之含有比例為4重量%以下；上述丙烯酸系樹脂(A)之重量平均分子量為40萬~159萬。 An adhesive composition for an optical member, which comprises an acrylic resin obtained by copolymerizing a copolymerized component [1] containing a (meth)acrylic acid alkyl ester monomer (a1) as a main component (A) The composition is composed of an N-(alkoxyalkyl)(meth)acrylamide monomer (a2) and a carboxyl group-containing monomer (a4) as a copolymer component [1]; The copolymerization component [1] as a whole, the content ratio of the N-(alkoxyalkyl)(meth)acrylamide monomer (a2) is 0.5 to 2% by weight; relative to the copolymerized component [1] as a whole, The content ratio of the total of the N-(alkoxyalkyl)(meth)acrylamide monomer (a2) and the carboxyl group-containing monomer (a4) is 4% by weight or less; and the acrylic resin (A) The weight average molecular weight is 400,000 to 1.59 million. 如申請專利範圍第1項之光學構件用黏著劑組成物，其中，進而含有含芳香環之單體(a3)，作為共聚合成分[1]。 The adhesive composition for an optical member according to claim 1, further comprising an aromatic ring-containing monomer (a3) as a copolymer component [1]. 如申請專利範圍第1項之光學構件用黏著劑組成物，其係含有交聯劑(B)而成。 An adhesive composition for an optical member according to the first aspect of the invention, which comprises a crosslinking agent (B). 如申請專利範圍第1項之光學構件用黏著劑組成物，其係含有矽烷偶合劑(C)而成。 An adhesive composition for an optical member according to the first aspect of the invention, which comprises a decane coupling agent (C). 一種光學構件用黏著劑，其特徵在於，係使申請專利範圍第1至4項中任一項之光學構件用黏著劑組成物交聯而成。 An adhesive for an optical member, which is obtained by crosslinking an optical member for an optical member according to any one of claims 1 to 4. 如申請專利範圍第5項之光學構件用黏著劑，其中，光學構件為偏光板。 The adhesive for optical members according to claim 5, wherein the optical member is a polarizing plate. 一種附有黏著劑層之光學構件，其特徵在於含有包含申請專利範圍第5或6項之光學構件用黏著劑之黏著劑層、及光學構件之積層結構。 An optical member with an adhesive layer characterized by comprising an adhesive layer comprising an adhesive for an optical member according to claim 5 or 6 and a laminated structure of the optical member. 一種影像顯示裝置，其特徵在於含有申請專利範圍第7項之附有黏著劑層之光學構件。 An image display apparatus comprising the optical member with an adhesive layer of claim 7 of the patent application.
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