TW201343836A - Adhesive composition for optical films, adhesive layer for optical films, optical film with adhesive layer, and image display device - Google Patents

Adhesive composition for optical films, adhesive layer for optical films, optical film with adhesive layer, and image display device Download PDF

Info

Publication number
TW201343836A
TW201343836A TW102112092A TW102112092A TW201343836A TW 201343836 A TW201343836 A TW 201343836A TW 102112092 A TW102112092 A TW 102112092A TW 102112092 A TW102112092 A TW 102112092A TW 201343836 A TW201343836 A TW 201343836A
Authority
TW
Taiwan
Prior art keywords
group
optical film
formula
meth
weight
Prior art date
Application number
TW102112092A
Other languages
Chinese (zh)
Inventor
Tomoyuki Kimura
Yuusuke Toyama
Atsushi Yasui
Original Assignee
Nitto Denko Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Publication of TW201343836A publication Critical patent/TW201343836A/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—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
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides
    • 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
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2471/00—Presence of polyether

Landscapes

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

Abstract

An adhesive composition for optical films, which contains (A) a (meth)acrylic polymer that contains, as a monomer unit, a hydroxyl group-containing monomer, (B) a polyether compound that has a repeating structure unit composed of an oxyalkylene group and has a reactive silyl group represented by general formula (1) -SiRaM3-a (wherein R represents an optionally substituted monovalent organic group having 1-20 carbon atoms; M represents a hydroxyl group or a hydrolyzable group; and a represents an integer of 0-2. In this connection, in cases where there are a plurality of R moieties, the plurality of R moieties may be the same as or different from each other; and in cases where there are a plurality of M moieties, the plurality of M moieties may be the same as or different from each other) at least one end, and (C) a silane coupling agent that has an acetoacetyl group.

Description

光學薄膜用黏著劑組成物、光學薄膜用黏著劑層、附黏著劑層之光學薄膜及影像顯示裝置 Adhesive composition for optical film, adhesive layer for optical film, optical film with adhesive layer, and image display device 技術領域 Technical field

本發明係有關於可形成兼具可不殘留黏合劑地自液晶面板等輕易地剝除光學薄膜的再製性，與長期保管後之耐久性的黏著劑層之光學薄膜用黏著劑組成物、及藉該黏著劑組成物於光學薄膜之至少一面形成有黏著劑層的附黏著劑層之光學薄膜。甚至，本發明係有關於使用有前述附黏著劑層之光學薄膜的液晶顯示裝置、有機EL顯示裝置、PDP等影像顯示裝置。前述光學薄膜可使用偏光薄膜、阻滯板、光學補償薄膜、亮度提升薄膜、甚至是積層有該等者。 The present invention relates to an adhesive composition for an optical film which is capable of forming an optical film which can be easily peeled off from a liquid crystal panel or the like without leaving a binder, and which is durable with long-term storage. The adhesive composition forms an optical film of an adhesive layer with an adhesive layer on at least one side of the optical film. Further, the present invention relates to a liquid crystal display device, an organic EL display device, a PDP or the like which uses an optical film having the above-mentioned adhesive layer. As the optical film, a polarizing film, a retardation plate, an optical compensation film, a brightness enhancement film, or even a laminate may be used.

背景技術 Background technique

液晶顯示裝置等因其影像形成方式需於液晶顯示元件兩側配置偏光元件，一般係貼附有偏光薄膜。又，於液晶面板上除了偏光薄膜以外，正逐漸使用各種光學元件以提升顯示器之顯示品質。正使用例如，防止著色之阻滯板、用以改善液晶顯示器之視角的視角放大薄膜、及用以提高顯示器之對比的亮度提升薄膜等。將該等薄膜總稱 為光學薄膜。 In the liquid crystal display device or the like, a polarizing element is required to be disposed on both sides of the liquid crystal display element due to the image forming method, and a polarizing film is generally attached. Further, in addition to the polarizing film on the liquid crystal panel, various optical elements are being gradually used to improve the display quality of the display. For example, a retardation plate for preventing coloration, a viewing angle magnifying film for improving the viewing angle of the liquid crystal display, and a brightness enhancement film for improving the contrast of the display are used. General name of these films It is an optical film.

於將前述光學薄膜等光學構件貼附於液晶顯示元件時，通常係使用黏著劑。又，通常為降低光之損失，光學薄膜與液晶顯示元件、或光學薄膜間之接著係使用黏著劑黏著各個材料。此時，因具有不需使光學薄膜固著之乾燥步驟等優點，故一般使用預先於光學薄膜之一側設有作為黏著劑的黏著劑層的附黏著劑層之光學薄膜。 When an optical member such as the optical film is attached to a liquid crystal display element, an adhesive is usually used. Further, in general, in order to reduce the loss of light, the adhesive between the optical film and the liquid crystal display element or the optical film is adhered to each material using an adhesive. In this case, since there is an advantage that a drying step of fixing the optical film is not required, an optical film having an adhesive layer in which an adhesive layer as an adhesive is provided on one side of the optical film is generally used.

一般而言，於將光學薄膜貼合於液晶顯示元件時，於貼合之位置有誤、或異物進入貼合面時，有將光學薄膜自液晶面板剝離，再利用液晶顯示元件的情形。前述黏著劑所要求之必要特性，係例如於如此之剝離步驟中，可不殘留黏合劑地自液晶面板輕易地剝除光學薄膜的再剝離性(再製性)。特別是，近年來，不僅以往之面板作成步驟，使用有經化學處理之玻璃的薄型液晶面板之需求增加，而不易維持自該薄型液晶面板的光學薄膜之再製性、加工性。 In general, when the optical film is bonded to the liquid crystal display element, when the bonding position is incorrect or the foreign matter enters the bonding surface, the optical film may be peeled off from the liquid crystal panel, and the liquid crystal display element may be used. The requisite property (remanufacturability) of the optical film can be easily peeled off from the liquid crystal panel without leaving a binder, for example, in the peeling step as described above. In particular, in recent years, not only the conventional panel forming step, but also the demand for using a thin liquid crystal panel having chemically treated glass has increased, and it has been difficult to maintain the reworkability and processability of the optical film of the thin liquid crystal panel.

又，要求前述黏著劑對於通常進行之利用加熱及加濕等的耐久試驗即環境促進試驗，不會產生起因於黏著劑之剝離或浮起等不良情形。特別是，視製品而有所不同，亦有例如經6個月以上之長期保管後使用的情形，而要求如此之長期保管品仍可防止產生起因於黏著劑之接著力下降的剝離或浮起等不良情形。一般而言，黏著劑之接著力下降時，有再製性提升的傾向，但因長期保管後接著力亦下降，故有其耐久性惡化的傾向。 Further, the pressure-sensitive adhesive is required to be subjected to an environmental resistance test which is usually subjected to an endurance test such as heating and humidification, and does not cause problems such as peeling or floating of the adhesive. In particular, depending on the product, for example, it may be used after long-term storage for 6 months or more, and such long-term storage is required to prevent peeling or floating due to a decrease in the adhesive force of the adhesive. Bad circumstances. In general, when the adhesive force of the adhesive is lowered, there is a tendency for the remanufacturability to be improved. However, since the force is also lowered after long-term storage, the durability tends to be deteriorated.

下述專利文獻1中，記載了一種由包含作為單體 單元之具羧基的乙烯基單體0.5~15重量%之重量平均分子量50萬以上的丙烯酸系共聚物100重量份、2級或3級胺化合物0.1~3重量份、及分子內具1個以上之烷氧基矽基的聚醚及/或丙烯酸聚合物1~50重量份所構成的丙烯酸系黏著劑組成物。又，下述專利文獻2中，記載了一種由聚合於單體成分中包含0.5~15重量%之含羧基之乙烯基單體的單體組成物後形成之，含有重量平均分子量Mw係70萬~200萬、重量平均分子量Mw與數量平均分子量Mn之比Mw/Mn係1.5~4範圍的丙烯酸系聚合物100重量份、選自於由各具有複數個可與羧基交聯鍵結形成之官能基的有機化合物、有機金屬化合物及金屬鹽所構成之群的至少1種交聯劑0.001~5重量份、聚醚改質矽油0.01~5重量份、及1分子中至少具有1個烷氧基矽基之聚醚0.1~10重量份的丙烯酸系黏著劑組成物。然而，由該等文獻記載之黏著劑組成物所得的接著劑之接著力高，有再製性差的傾向。 Patent Document 1 listed below describes a kind of inclusion as a monomer 100 parts by weight of the carboxyl group-containing vinyl monomer, 100 parts by weight of the acrylic copolymer having a weight average molecular weight of 500,000 or more, 0.1 to 3 parts by weight of the second or third-order amine compound, and one or more molecules in the molecule. An acrylic adhesive composition comprising 1 to 50 parts by weight of a polyether and/or acrylic polymer of an alkoxyalkyl group. Further, Patent Document 2 listed below discloses a monomer composition comprising a carboxyl group-containing vinyl monomer in an amount of 0.5 to 15% by weight, and a weight average molecular weight Mw of 700,000. ~2 million, the ratio of the weight average molecular weight Mw to the number average molecular weight Mn, Mw / Mn, 100 parts by weight of the acrylic polymer in the range of 1.5 to 4, selected from the group consisting of a plurality of functional groups capable of cross-linking with a carboxyl group 0.001 to 5 parts by weight of at least one crosslinking agent of the group of the organic compound, the organometallic compound, and the metal salt, 0.01 to 5 parts by weight of the polyether modified eucalyptus oil, and at least one alkoxy group in one molecule 0.1 to 10 parts by weight of an acrylic adhesive composition of a thiol based polyether. However, the adhesive agent obtained from the adhesive composition described in these documents has a high adhesive force and tends to be inferior in reworkability.

另外，下述專利文獻3中，記載了一種含有(甲基)丙烯酸系聚合物及具反應性矽基之聚醚化合物的光學薄膜用黏著劑組成物。由如此之黏著劑組成物所得的黏著劑，可不殘留黏合劑地自液晶面板等輕易地剝除光學薄膜，再製性優異。 Further, Patent Document 3 listed below discloses an adhesive composition for an optical film containing a (meth)acrylic polymer and a polyether compound having a reactive mercapto group. The adhesive obtained from such an adhesive composition can be easily peeled off from a liquid crystal panel or the like without leaving a binder, and is excellent in reworkability.

先前技術文獻 Prior technical literature 專利文獻 Patent literature

專利文獻1：日本專利特開平08-122524號公報 Patent Document 1: Japanese Patent Laid-Open Publication No. Hei 08-122524

專利文獻2：日本專利特開平09-302321號公報 Patent Document 2: Japanese Patent Laid-Open No. 09-302321

專利文獻3：日本專利特開2010-275522號公報 Patent Document 3: Japanese Patent Laid-Open Publication No. 2010-275522

發明概要 Summary of invention

本發明人等鑽研檢討的結果，發現利用(甲基)丙烯酸系聚合物及具反應性矽基之聚醚化合物的組合，所得之黏著劑的再製性雖優異，但例如經6個月以上之長期保管後使用時，於耐久性方面尚有再改良的餘地。 As a result of intensive studies conducted by the present inventors, it has been found that a combination of a (meth)acrylic polymer and a polyether compound having a reactive sulfhydryl group provides excellent remanufacturability of the obtained adhesive, but for example, after 6 months or more When used for long-term storage, there is still room for improvement in durability.

本發明之目的係提供一種可形成兼具可不殘留黏合劑地自液晶面板等輕易地剝除光學薄膜的再製性，與長期保管後之耐久性的黏著劑層之光學薄膜用黏著劑組成物。 An object of the present invention is to provide an adhesive composition for an optical film which can form an adhesive layer which is easy to remove an optical film from a liquid crystal panel or the like without leaving a binder, and which is durable after long-term storage.

又，本發明之目的係提供一種具有藉前述光學薄膜用黏著劑組成物形成之黏著劑層的附黏著劑層之光學薄膜，更提供一種使用有前述附黏著劑層之光學薄膜的影像顯示裝置。 Further, an object of the present invention is to provide an optical film having an adhesive layer formed of an adhesive layer formed of the above-mentioned adhesive composition for an optical film, and an image display apparatus using the optical film having the above-mentioned adhesive layer .

本發明人等為解決前述課題，反覆鑽研檢討的結果，發現下述光學薄膜用黏著劑組成物，而完成本發明。 In order to solve the above-mentioned problems, the present inventors have found the following adhesive composition for an optical film as a result of the investigation and review, and completed the present invention.

換言之，本發明乃有關於一種光學薄膜用黏著劑組成物，係含有：包含作為單體單元之含羥基單體之(甲基)丙烯酸系聚合物(A)；具有氧伸烷基之重複結構單元，且於至少1個末端具有以通式(1)表示之反應性矽基之聚醚化合物(B)，通式(1)：-SiRaM3-a (式中，R係亦可具有取代基之碳數1~20之1價有機基，M係羥基或可水解基，a係0~2之整數；但，存在複數R時，複數之R可互為相同亦可相異，存在複數M時，複數之M可互為相同亦可相異)；及具乙醯乙醯基之矽烷耦合劑(C)。 In other words, the present invention relates to an adhesive composition for an optical film comprising: a (meth)acrylic polymer (A) comprising a hydroxyl group-containing monomer as a monomer unit; and a repeating structure having an oxygen-extended alkyl group a polyether compound (B) having a reactive sulfhydryl group represented by the formula (1) at at least one terminal, and a formula (1): -SiR a M 3-a (wherein the R system may also be used a monovalent organic group having 1 to 20 carbon atoms having a substituent, M being a hydroxyl group or a hydrolyzable group, and a being an integer of 0 to 2; however, when a plural number R is present, the plural Rs may be the same or different from each other. In the presence of a complex number M, the complex numbers M may be the same or different from each other; and the decane coupling agent (C) having an acetamidine group.

上述光學薄膜用黏著劑組成物中，前述含羥基之單體宜為(甲基)丙烯酸4-羥丁酯。 In the above adhesive composition for an optical film, the hydroxyl group-containing monomer is preferably 4-hydroxybutyl (meth)acrylate.

上述光學薄膜用黏著劑組成物中，聚醚化合物(B)宜為以通式(2)表示之化合物， 通式(2)：RaM3-aSi-X-Y-(AO)n-Z In the above adhesive composition for an optical film, the polyether compound (B) is preferably a compound represented by the formula (2): Formula (2): R a M 3-a Si-XY-(AO) n -Z

[式中，R係亦可具有取代基之碳數1~20之1價有機基，M係羥基或可水解基，a係0~2之整數；惟，存在複數R時，複數之R可互為相同亦可相異，存在複數M時，複數之M可互為相同亦可相異；AO係表示包含氧伸烷基作為重複結構單元之直鏈或支鏈結構，n係1~1700，表示氧伸烷基之平均加成莫耳數；X係表示碳數1~20之直鏈或支鏈的伸烷基；Y係表示醚鍵、酯鍵、胺甲酸酯鍵、或碳酸酯鍵；Z係氫原子、1價之碳數1~10之烴基、及以通式(2A)或以通式(2B)表示之基，通式(2A)：-Y1-X-SiRaM3-a [In the formula, R may have a monovalent organic group having 1 to 20 carbon atoms of the substituent, M-based hydroxyl group or hydrolyzable group, and a is an integer of 0 to 2; however, when plural R is present, the plural R may be The same or different from each other, in the presence of a complex number M, the complex M may be the same or different from each other; the AO system represents a linear or branched structure comprising an oxygen alkyl group as a repeating structural unit, n series 1 to 1700 , represents the average addition mole number of the oxygen alkyl group; X represents a linear or branched alkyl group having a carbon number of 1 to 20; Y represents an ether bond, an ester bond, a urethane bond, or a carbonic acid An ester bond; a Z-based hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a group represented by the formula (2A) or the formula (2B), and the formula (2A): -Y 1 -X-SiR a M 3-a

(式中，R、M、X係與前述相同；Y1係表示單鍵、-CO-鍵、-CONH-鍵、或-COO-鍵) (wherein R, M, and X are the same as defined above; Y 1 represents a single bond, a -CO- bond, a -CONH- bond, or a -COO- bond)

通式(2B)：-Q{-(OA)n-Y-X-SiRaM3-a}m General formula (2B): -Q{-(OA) n -YX-SiR a M 3-a } m

(式中，R、M、X、Y係與前述相同；OA係與前述AO相同，n係與前述相同；Q係2價以上之碳數1~10之烴基，m 係與該烴基之價數相同)]。 (In the formula, R, M, X, and Y are the same as described above; OA is the same as the above-mentioned AO, and n is the same as the above; Q is a hydrocarbon group having a carbon number of 1 to 10 or more having a valence of 2 or more, m It is the same as the valence of the hydrocarbon group)].

上述光學薄膜用黏著劑組成物中，聚醚化合物(B)之反應性矽基宜為以下述通式(3)表示之烷氧基矽基， In the above adhesive composition for an optical film, the reactive thiol group of the polyether compound (B) is preferably an alkoxy fluorenyl group represented by the following formula (3).

(式中，R1、R2及R3係碳數1~6之1價烴基，於同一分子中可相同亦可相異)。 (Wherein, R 1, R 2 and R 3 lines 1 to 6 carbon atoms of a monovalent hydrocarbon group, in one molecule may be identical or different).

通式(2)所表示之化合物中，上述聚醚化合物(B)宜為以通式(4)表示之化合物，通式(4)：Z0-A2-O-(AO)n-Z1 In the compound represented by the formula (2), the above polyether compound (B) is preferably a compound represented by the formula (4): general formula (4): Z 0 -A 2 -O-(AO) n -Z 1

[式中，AO係與前述相同，n係1~1700，表示AO之平均加成莫耳數；Z1係氫原子或-A2-Z0；A2係碳數2~6之伸烷基；Z0係以通式(3)表示之烷氧基矽基， [In the formula, the AO system is the same as the above, n is 1 to 1700, and represents the average addition molar number of AO; Z 1 is a hydrogen atom or -A 2 -Z 0 ; A 2 is a 2 to 6 carbon a group; Z 0 is an alkoxy fluorenyl group represented by the formula (3),

(式中，R1、R2及R3係碳數1~6之1價烴基，於同一分子中可相同亦可相異)]。 (In the formula, R 1 , R 2 and R 3 are a monovalent hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different in the same molecule).

又，通式(2)所表示之化合物中，上述聚醚化合物(B)宜為以通式(5)表示之化合物，通式(5)：Z0-A2-NHCOO-(AO)n-Z2 Further, in the compound represented by the formula (2), the polyether compound (B) is preferably a compound represented by the formula (5): a formula (5): Z 0 -A 2 -NHCOO-(AO) n -Z 2

[式中，AO係包含氧伸烷基作為重複結構單元之直鏈或支鏈結構，n係1~1700，表示AO之平均加成莫耳數；Z2係氫原子、或-CONH-A2-Z0；A2係碳數2~6之伸烷基；Z0係以通式(3)表示之烷氧基矽基， [wherein, AO includes a linear or branched structure in which an alkylene group is a repeating structural unit, n is 1 to 1700, and represents an average addition molar number of AO; a Z 2 hydrogen atom, or -CONH-A 2 -Z 0 ; A 2 is an alkylene group having 2 to 6 carbon atoms; and Z 0 is an alkoxyfluorenyl group represented by the formula (3).

(式中，R1、R2及R3係碳數1~6之1價烴基，於同一分子中可相同亦可相異)]。 (In the formula, R 1 , R 2 and R 3 are a monovalent hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different in the same molecule).

又，通式(2)所表示之化合物中，上述聚醚化合物(B)宜為以通式(6)表示之化合物，通式(6)：Z3-(AO)n-O-G-CR4{-G-O-(AO)n-Z3}2 Further, in the compound represented by the formula (2), the polyether compound (B) is preferably a compound represented by the formula (6): (3): Z 3 -(AO) n -OG-CR 4 {-GO-(AO) n -Z 3 } 2

[式中，AO係包含氧伸烷基作為重複結構單元之直鏈或支鏈結構，n係1~1700，表示AO之平均加成莫耳數；Z3係氫原子或-A2-Z0，至少任1個Z3係-A2-Z0；A2係碳數2~6之伸烷基，R4係表示氫原子、或碳數1~3之伸烷基；G係表示單鍵或亞甲基；Z0係以通式(3)所表示之烷氧基矽基， [In the formula, AO includes a linear or branched structure in which an oxygen alkyl group is a repeating structural unit, n is 1 to 1700, and represents an average addition molar number of AO; a Z 3 hydrogen atom or -A 2 -Z 0 , at least one Z 3 -A 2 -Z 0 ; A 2 is an alkylene group having 2 to 6 carbon atoms; R 4 is a hydrogen atom or an alkylene group having 1 to 3 carbon atoms; a single bond or a methylene group; Z 0 is an alkoxy fluorenyl group represented by the formula (3),

(式中，R1、R2及R3係碳數1~6之1價烴基，於同一分子中可相同亦可相異)]。 (In the formula, R 1 , R 2 and R 3 are a monovalent hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different in the same molecule).

上述光學薄膜用黏著劑組成物中，聚醚化合物(B)之數量平均分子量宜為300~100000。 In the above adhesive composition for an optical film, the number average molecular weight of the polyether compound (B) is preferably from 300 to 100,000.

上述光學薄膜用黏著劑組成物中，宜相對於(甲基)丙烯酸系聚合物(A)100重量份，含有0.001~5重量份的具乙醯乙醯基之矽烷耦合劑(C)。 The pressure-sensitive adhesive composition for an optical film preferably contains 0.001 to 5 parts by weight of a decane coupling agent (C) having an ethyl acetonitrile group per 100 parts by weight of the (meth)acryl-based polymer (A).

上述光學薄膜用黏著劑組成物中，宜相對於(甲基)丙烯酸系聚合物(A)100重量份，含有0.001~5重量份之聚醚化合物(B)。 The adhesive composition for an optical film preferably contains 0.001 to 5 parts by weight of the polyether compound (B) based on 100 parts by weight of the (meth)acryl-based polymer (A).

上述光學薄膜用黏著劑組成物中，宜使用相對於(甲基)丙烯酸系聚合物(A)100重量份，更含有0.01~2重量份之作為交聯劑(D)的過氧化物者。 In the above-mentioned adhesive composition for an optical film, it is preferred to use 0.01 to 2 parts by weight of a peroxide as the crosslinking agent (D) per 100 parts by weight of the (meth)acryl-based polymer (A).

又，本發明係有關於一種藉由前述光學薄膜用黏著劑組成物形成之光學薄膜用黏著劑層。 Further, the present invention relates to an adhesive layer for an optical film formed by the above-described adhesive composition for an optical film.

又，本發明係有關於一種於光學薄膜之至少一側形成有前述光學薄膜用黏著劑層的附黏著劑層之光學薄膜。該附黏著劑層之光學薄膜可於光學薄膜與光學薄膜用黏著劑層之間具有易接著層。 Further, the present invention relates to an optical film in which an adhesive layer of the optical film adhesive layer is formed on at least one side of an optical film. The optical film with the adhesive layer can have an easy adhesion layer between the optical film and the adhesive layer for the optical film.

又，本發明係有關於一種使用有至少1個前述附黏著劑層之光學薄膜的影像顯示裝置。 Further, the present invention relates to an image display apparatus using an optical film having at least one of the above-mentioned adhesive layers.

本發明之光學薄膜用黏著劑組成物中，除了作為基質聚合物之(甲基)丙烯酸系聚合物(A)以外，亦含有具有 氧伸烷基之重複結構單元，且於至少1個末端具有反應性矽基的聚醚化合物(B)及具乙醯乙醯基之矽烷耦合劑(C)。具有由本發明之光學薄膜用黏著劑組成物所得的黏著劑層之附黏著劑層之光學薄膜，因該黏著劑層含有聚醚化合物(B)，故將附黏著劑層之光學薄膜貼附於液晶顯示元件等後，即使因歷經各種步驟等而經過長時間、或於高溫下保存，仍可適度地抑制對液晶顯示元件等之接著力增大，並可輕易地自液晶顯示元件等剝離附黏著劑層之光學薄膜，且再製性優異，不會損傷或汙染液晶顯示元件，可再利用。特別是，對大型之液晶顯示元件而言，難以剝離附黏著劑層之光學薄膜，但依據本發明，即使為大型之液晶顯示元件仍可輕易地剝離附黏著劑層之光學薄膜。 The adhesive composition for an optical film of the present invention contains, in addition to the (meth)acrylic polymer (A) as a matrix polymer, a repeating structural unit of an oxyalkylene group, and a polyether compound (B) having a reactive sulfhydryl group at at least one terminal and a decane coupling agent (C) having an acetamidine group. An optical film having an adhesive layer of an adhesive layer obtained from the adhesive composition for an optical film of the present invention. Since the adhesive layer contains the polyether compound (B), the optical film with the adhesive layer is attached thereto. After the liquid crystal display element or the like, even if it is stored for a long period of time or at a high temperature, the adhesion of the liquid crystal display element or the like can be appropriately suppressed, and the liquid crystal display element can be easily peeled off. The optical film of the adhesive layer is excellent in reworkability, and does not damage or contaminate the liquid crystal display element, and can be reused. In particular, in the case of a large liquid crystal display element, it is difficult to peel off the optical film with the adhesive layer, but according to the present invention, the optical film with the adhesive layer can be easily peeled off even for a large liquid crystal display element.

另一方面，於至少1個末端具有反應性矽基之聚醚化合物(B)長期存在於黏著劑層中時，反應性矽基將水解，且疏水性高之反應性矽基將變成親水性高之矽醇。結果，黏著劑層中之聚醚化合物(B)容易移動至黏附體側，黏著劑層與黏附體之接著力下降，可預料長期保管後之耐久性惡化。特別是，如此之耐久性惡化於附黏著劑層之光學薄膜積層於玻璃等時(黏著劑層積層於作為黏附體之玻璃時)，具有親水性高之矽醇的聚醚化合物(B)因容易移動至玻璃側，故可預料於長期保管後，將隨著黏著劑層與玻璃之接著力下降而導致耐久性惡化。然而，本發明之光學薄膜用黏著劑組成物中，藉由使用含有含羥基之單體的(甲基)丙烯酸系聚合物(A)，使具有長期保管後水解之矽醇的聚醚 化合物(B)與(甲基)丙烯酸系聚合物(A)的相互作用升高，如此一來，將阻礙黏著劑層中之聚醚化合物(B)移動至黏附體側。此外，藉由併用具乙醯乙醯基之矽烷耦合劑(C)，聚醚化合物(B)中之氧伸烷基與乙醯乙醯基透過氫鍵等互相作用，將阻礙黏著劑層中之聚醚化合物(B)移動至黏附體側。結果，長期保管後仍可防止黏著劑層與黏附體之接著力下降，可提升耐久性。 On the other hand, when the polyether compound (B) having a reactive mercapto group at at least one terminal is present in the adhesive layer for a long period of time, the reactive mercapto group will be hydrolyzed, and the highly reactive reactive mercapto group will become hydrophilic. High sterols. As a result, the polyether compound (B) in the adhesive layer easily moves to the side of the adherend, and the adhesive force of the adhesive layer and the adherend decreases, and the durability after long-term storage is expected to deteriorate. In particular, when the durability is deteriorated when the optical film with the adhesive layer is laminated on glass or the like (when the adhesive layer is laminated on the glass as the adherend), the polyether compound (B) having a highly hydrophilic sterol is Since it is easy to move to the glass side, it is expected that the durability will deteriorate as the adhesion between the adhesive layer and the glass is lowered after long-term storage. However, in the adhesive composition for an optical film of the present invention, a polyether having a sterol which is hydrolyzed after long-term storage is used by using a (meth)acrylic polymer (A) containing a monomer having a hydroxyl group. The interaction between the compound (B) and the (meth)acrylic polymer (A) is increased, and as a result, the polyether compound (B) in the adhesive layer is prevented from moving to the side of the adherend. Further, by using the decane coupling agent (C) of the ethyl acetonitrile group, the oxygen alkyl group in the polyether compound (B) interacts with the ethyl hydrazide group through a hydrogen bond or the like, which hinders the adhesive layer. The polyether compound (B) moves to the side of the adherend. As a result, the adhesion of the adhesive layer and the adherend can be prevented from being lowered after long-term storage, and durability can be improved.

用以實施發明之形態 Form for implementing the invention

本發明之光學薄膜用黏著劑組成物係包含作為基質聚合物的(甲基)丙烯酸系聚合物(A)。(甲基)丙烯酸系聚合物(A)之單體單元通常係含有烷基(甲基)丙烯酸酯作為主成分。另，(甲基)丙烯酸酯係指丙烯酸酯及/或甲基丙烯酸酯，本發明之(甲基)係相同之意。 The adhesive composition for an optical film of the present invention contains a (meth)acrylic polymer (A) as a matrix polymer. The monomer unit of the (meth)acrylic polymer (A) usually contains an alkyl (meth) acrylate as a main component. Further, (meth) acrylate means acrylate and/or methacrylate, and the (meth) group of the present invention is the same.

構成(甲基)丙烯酸系聚合物(A)之主骨架的烷基(甲基)丙烯酸酯，可舉直鏈狀或支鏈狀烷基之碳數1~18者為例。例如，前述烷基可舉例如，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、異十四基、月桂基、十三基、十五基、十六基、十七基、十八基等。該等可單獨或組合使用。該等烷基之平均碳數以3~9為佳。 The alkyl (meth) acrylate which constitutes the main skeleton of the (meth)acrylic polymer (A) is exemplified by a carbon number of 1 to 18 of a linear or branched alkyl group. For example, the aforementioned alkyl group may, for example, be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl, isooctyl, Sulfhydryl, fluorenyl, isodecyl, dodecyl, isotetradecyl, lauryl, thirteen, fifteen, heptyl, heptadecyl, and octadecyl. These may be used singly or in combination. The average carbon number of the alkyl groups is preferably from 3 to 9.

又，可使用含有如(甲基)丙烯酸苯氧乙酯之芳香 族環的烷基(甲基)丙烯酸酯。含有芳香族環之烷基(甲基)丙烯酸酯可使用將聚合有其之聚合物混合於前述例示的(甲基)丙烯酸系聚合物後使用，但由透明性之觀點來看，含有芳香族環之烷基(甲基)丙烯酸酯以與前述烷基(甲基)丙烯酸酯共聚合後使用為佳。 Also, a fragrance containing phenoxyethyl (meth)acrylate can be used. A family of alkyl (meth) acrylates. The alkyl (meth) acrylate containing an aromatic ring can be used by mixing the polymer polymerized with the (meth)acrylic polymer exemplified above, but contains aromatics from the viewpoint of transparency. The alkyl (meth) acrylate of the ring is preferably used after being copolymerized with the aforementioned alkyl (meth) acrylate.

(甲基)丙烯酸系聚合物(A)係含有作為單體單的含羥基之單體。含羥基之單體，可舉例如，(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-羥月桂酯或(4-羥甲基環己基)-甲基丙烯酸酯等。該等中，亦以(甲基)丙烯酸4-羥丁酯為佳。為提升長期保管後之耐久性，(甲基)丙烯酸系聚合物(A)中包含作為單體單元的含羥基之單體係為重要，以0.3重量份以上為佳，較佳者是0.5重量份以上，更佳者係1重量份以上。但，(甲基)丙烯酸系聚合物(A)中含有過多含羥基之單體時，因接著力上升，再製性不佳，故以10重量份以下為佳，以7重量份以下較佳，以5重量份以下更佳。 The (meth)acrylic polymer (A) contains a hydroxyl group-containing monomer as a monomer. The hydroxyl group-containing monomer may, for example, be 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, or (meth)acrylic acid 6- Hydroxyhexyl ester, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate or (4-hydroxymethylcyclohexyl)-methacrylic acid Ester and the like. Among these, 4-hydroxybutyl (meth)acrylate is also preferred. In order to improve the durability after long-term storage, it is important that the (meth)acrylic polymer (A) contains a hydroxyl group-containing single system as a monomer unit, preferably 0.3 parts by weight or more, preferably 0.5 weight. More preferably, it is 1 part by weight or more. However, when the (meth)acrylic polymer (A) contains a monomer having a large amount of a hydroxyl group, the regrindability is poor due to an increase in the adhesion, and therefore it is preferably 10 parts by weight or less, more preferably 7 parts by weight or less. It is more preferably 5 parts by weight or less.

以改善接著性或耐熱性為目的，前述(甲基)丙烯酸系聚合物(A)中可藉由共聚合導入1種以上之具有具(甲基)丙烯醯基或乙烯基等不飽和雙鍵之聚合性官能基的共聚合單體。如此之共聚合單體的具體例，可舉例如，(甲基)丙烯酸、羧乙基(甲基)丙烯酸酯、羧戊基(甲基)丙烯酸酯、亞甲基丁二酸、順丁烯二酸、反丁烯二酸、巴豆酸等含羧基之單體；順丁烯二酸酐、無水亞甲基丁二酸等含酸酐基之單 體；丙烯酸之己內酯加成物；苯乙烯磺酸或芳基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、磺酸丙基(甲基)丙烯酸酯、(甲基)丙烯醯氧萘磺酸等含磺酸基之單體；2-羥乙丙烯醯磷酸等含燐酸基之單體等。 In the (meth)acrylic polymer (A), one or more kinds of unsaturated double bonds having a (meth)acryl fluorenyl group or a vinyl group may be introduced by copolymerization for the purpose of improving the adhesion or the heat resistance. a copolymerizable monomer of a polymerizable functional group. Specific examples of such a copolymerizable monomer include (meth)acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, methylene succinic acid, and cis-butene. a carboxyl group-containing monomer such as diacid, fumaric acid or crotonic acid; an acid anhydride group such as maleic anhydride or anhydrous methylene succinic acid a caprolactone adduct of acrylic acid; styrenesulfonic acid or arylsulfonic acid, 2-(methyl)acrylamidamine-2-methylpropanesulfonic acid, (meth)acrylamidamine propanesulfonic acid, a sulfonic acid group-containing monomer such as sulfonic acid propyl (meth) acrylate or (meth) propylene sulfonaphthyl sulfonic acid; or a decanoic acid group-containing monomer such as 2-hydroxyethyl propylene phosphonic acid.

前述共聚合單體中，於(甲基)丙烯酸系聚合物(A)中含有含羧基之單體時，黏著劑之接著力上升，長期保管後仍不易產生黏著劑層剝落。然而，(甲基)丙烯酸系聚合物(A)中含羧基之單體的含量變多時，黏著劑層之再製性下降。因此，為更均衡地提升再製性與長期保管後之耐久性，單體單元以(甲基)丙烯酸系聚合物(A)中含有含羧基之單體0~0.5重量份為佳，以(甲基)丙烯酸系聚合物(A)中未含有含羧基之單體為佳。 In the case where the (meth)acrylic polymer (A) contains a monomer having a carboxyl group, the adhesion of the adhesive increases, and the adhesive layer is less likely to peel off after long-term storage. However, when the content of the carboxyl group-containing monomer in the (meth)acrylic polymer (A) is increased, the remanufacturability of the adhesive layer is lowered. Therefore, in order to more uniformly improve the durability of the remanufacturability and long-term storage, the monomer unit preferably contains 0 to 0.5 parts by weight of the carboxyl group-containing monomer in the (meth)acrylic polymer (A). The acrylic polymer (A) preferably contains no carboxyl group-containing monomer.

又，亦可舉下述例作為以改質為目的的單體例：(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺或N-羥甲基(甲基)丙烯醯胺、N-羥甲基丙烷(甲基)丙烯醯胺等(N-取代)醯胺系單體；(甲基)丙烯酸胺基乙基、(甲基)丙烯酸N,N-二甲基胺基乙基、(甲基)丙烯酸t-丁基胺基乙基等(甲基)丙烯酸烷基胺基烷基系單體；(甲基)丙烯酸甲氧基乙基、(甲基)丙烯酸乙氧基乙基等(甲基)丙烯酸烷氧基烷基系單體；N-(甲基)丙烯醯甲醛琥珀醯亞胺或N-(甲基)丙烯醯-6-六亞甲琥珀醯亞胺、N-(甲基)丙烯醯-8-氧伸辛基琥珀醯亞胺、N-丙烯醯啉等琥珀醯亞胺系單體；N-環己基順丁烯二醯亞胺或N-異丙基順丁烯二醯亞胺、N-月桂基順丁烯二醯亞胺或N-苯基順丁烯二醯亞胺等 順丁烯二醯亞胺系單體；N-甲基亞甲基丁二酸醯亞胺、N-乙基亞甲基丁二酸醯亞胺、N-丁基亞甲基丁二酸醯亞胺、N-辛基亞甲基丁二酸醯亞胺、N-2-乙基己基亞甲基丁二酸醯亞胺、N-環己基亞甲基丁二酸醯亞胺、N-月桂基亞甲基丁二酸醯亞胺等亞甲基丁二酸醯亞胺系單體等。 Further, examples of the monomer for the purpose of modification include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, and N-butyl (methyl). (N-substituted) guanamine-based monomer such as acrylamide or N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide; (meth) acrylate a (meth)acrylic acid alkylaminoalkyl-based monomer such as N,N-dimethylaminoethyl (meth)acrylate or t-butylaminoethyl (meth)acrylate; a (meth)acrylic acid alkoxyalkyl monomer such as methoxyethyl acrylate, ethoxyethyl (meth) acrylate, etc.; N-(methyl) propylene oxime formaldehyde amber ylide or N- (Meth) propylene oxime-6-hexamethylene succinimide, N-(methyl) propylene fluorene-8-oxooctyl succinimide, N- propylene oxime Amber quinone imine monomer such as porphyrin; N-cyclohexyl maleimide or N-isopropyl maleimide, N-lauryl maleimide or N-benzene a maleimide monomer such as cis-butenylene imine; N-methylmethylene succinimide, N-ethylmethylene succinate, N- Butyl methylene succinate, N-octylmethylene succinate, N-2-ethylhexylmethylene succinate, N-cyclohexylmethylene A methylene succinimide monomer such as succinimide or N-lauryl methylene succinate.

此外，改質單體亦可使用：乙酸乙烯酯、丙酸乙烯酯、N-乙烯基吡咯啶酮、甲基乙烯基吡咯啶酮、乙烯基吡啶、乙烯基哌啶酮、乙烯基嘧啶、乙烯基哌、乙烯基吡、乙烯基吡咯、乙烯基咪唑、乙烯基唑、乙烯基啉、N-乙烯基羧酸醯胺類、苯乙烯、α-甲基苯乙烯、N-乙烯基己內醯胺等乙烯基系單體；丙烯腈、甲基丙烯腈等氰基丙烯酸酯系單體；(甲基)丙烯酸環氧丙基等含環氧基之丙烯酸系單體；(甲基)丙烯酸聚乙二醇、(甲基)丙烯酸聚丙二醇、(甲基)丙烯酸甲氧基乙二醇、(甲基)丙烯酸甲氧基聚丙二醇等醇系丙烯酸酯單體；(甲基)丙烯酸四氫呋喃甲酯、氟(甲基)丙烯酸酯、矽氧(甲基)丙烯酸酯或2-甲氧基乙基丙烯酸酯等丙烯酸酯系單體。並且，可舉異戊二烯、丁二烯、異丁烯、乙烯醚等為例。 In addition, modified monomers can also be used: vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, vinyl pyrimidine, ethylene Kipi Vinylpyr , vinyl pyrrole, vinyl imidazole, vinyl Azole, vinyl Vinyl, N-vinylcarboxylic acid decylamine, vinyl monomer such as styrene, α-methylstyrene, N-vinyl caprolactam; cyanoacrylate such as acrylonitrile or methacrylonitrile Monomer; epoxy group-containing acrylic monomer such as (meth)acrylic acid epoxy acrylate; (meth)acrylic acid polyethylene glycol, (meth)acrylic polypropylene glycol, (meth)acrylic acid methoxyB An alcohol-based acrylate monomer such as a diol or a (meth)acrylic acid methoxypolypropylene glycol; tetrahydrofuran methyl (meth)acrylate, fluorine (meth) acrylate, oxime (meth) acrylate or 2-methyl An acrylate monomer such as oxyethyl acrylate. Further, examples thereof include isoprene, butadiene, isobutylene, and vinyl ether.

此外，前述以外之可共聚合的單體，可舉含矽原子之矽烷系單體等為例。矽烷系單體，可舉例如：3-丙烯醯氧丙基三乙氧矽烷、乙烯基三甲氧矽烷、乙烯基三乙氧矽烷、4-乙烯基丁基三甲氧矽烷、4-乙烯基丁基三乙氧矽烷、8-乙烯基辛基三甲氧矽烷、8-乙烯基辛基三乙氧矽烷、10-甲基丙烯醯氧癸基三甲氧矽烷、10-丙烯醯氧癸基三甲氧 矽烷、10-甲基丙烯醯氧癸基三乙氧矽烷、10-丙烯醯氧癸基三乙氧矽烷等。 Further, examples of the copolymerizable monomer other than the above may be exemplified by a decane-based monomer containing a halogen atom. The decane-based monomer may, for example, be 3-propenyl methoxypropyltriethoxy decane, vinyltrimethoxy decane, vinyltriethoxy decane, 4-vinylbutyltrimethoxy decane or 4-vinylbutyl group. Triethoxyoxane, 8-vinyloctyltrimethoxydecane, 8-vinyloctyltriethoxydecane, 10-methylpropenyloxydecyltrimethoxydecane, 10-propenyloxydecyltrimethoxy Decane, 10-methylpropenyl fluorenyltriethoxy decane, 10-propenyl fluorenyltriethoxy decane, and the like.

又，共聚合單體，亦可使用：三伸丙二醇二(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、三羥甲基丙烷三(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(甲基)丙烯酸與多元醇的酯化物等具2個以上之(甲基)丙烯醯基、乙烯基等不飽和雙鍵的多官能性單體、或於聚酯、環氧、胺甲酸酯等骨架加成有2個以上作為與單體成分相同之官能基的(甲基)丙烯醯基、乙烯基等不飽和雙鍵的聚酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、胺甲酸酯(甲基)丙烯酸酯等。 Further, a copolymerizable monomer may also be used: tri-propylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, double Phenol A diepoxypropyl ether di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tris(methyl) Acrylate, neopentyl alcohol tetra(meth)acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, caprolactone modified dipentaerythritol a polyfunctional monomer having two or more unsaturated double bonds such as a (meth) acryl fluorenyl group or a vinyl group, such as an esterified product of a (meth)acrylic acid and a polyhydric alcohol such as an alcohol hexa (meth) acrylate; A polyester (methyl) having two or more unsaturated double bonds such as a (meth) acrylonitrile group or a vinyl group which are the same functional groups as the monomer component, such as a polyester, an epoxy or a urethane. Acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and the like.

(甲基)丙烯酸系聚合物(A)於全構成單體之重量比率中，以烷基(甲基)丙烯酸酯作為主成分，並未特別限定(甲基)丙烯酸系聚合物(A)中之前述共聚合單體的比例，但全構成單體之重量比率中前述共聚合單體的比例係0~20%左右，以0.1~15%左右為佳，更以0.1~10%左右為佳。 In the weight ratio of the (meth)acrylic polymer (A) to the total constituent monomer, the alkyl (meth) acrylate is used as a main component, and the (meth)acrylic polymer (A) is not particularly limited. The proportion of the copolymerized monomer, but the ratio of the copolymerized monomer in the weight ratio of the total constituent monomers is about 0 to 20%, preferably about 0.1 to 15%, more preferably about 0.1 to 10%. .

本發明之(甲基)丙烯酸系聚合物(A)通常係使用重量平均分子量為50萬~400萬範圍者。考量到耐久性，特別是耐熱性，以使用重量平均分子量係80萬~300萬者為佳。更以140萬~270萬為佳，更以170萬~250萬較佳，以180萬~240萬更佳。重量平均分子量小於50萬時，由耐熱性之 點來看係不佳。又，重量平均分子量大於400萬時，貼合性、接著力下降亦不佳。另，重量平均分子量係指藉由GPC(凝膠滲透層析法)測定，藉由聚苯乙烯換算所算出之值。 The (meth)acrylic polymer (A) of the present invention is usually one having a weight average molecular weight of from 500,000 to 4,000,000. In view of durability, particularly heat resistance, it is preferred to use a weight average molecular weight of 800,000 to 3,000,000. It is better than 1.4 million to 2.7 million, more preferably 1.7 million to 2.5 million, and better than 1.8 million to 2.4 million. When the weight average molecular weight is less than 500,000, it is made of heat resistance. The point is not good. Further, when the weight average molecular weight is more than 4,000,000, the adhesion and the adhesion are not deteriorated. Further, the weight average molecular weight means a value calculated by GPC (gel permeation chromatography) and converted from polystyrene.

如此之(甲基)丙烯酸系聚合物(A)的製造，可適當地選擇溶液聚合、塊狀聚合、乳化聚合、各種自由基聚合等眾所周知的製造方法。又，所得之(甲基)丙烯酸系聚合物(A)可為隨機共聚物、嵌段共聚物、接枝共聚物等之任一者。 For the production of such a (meth)acrylic polymer (A), a well-known production method such as solution polymerization, bulk polymerization, emulsion polymerization, or various radical polymerization can be appropriately selected. Further, the obtained (meth)acryl-based polymer (A) may be any of a random copolymer, a block copolymer, and a graft copolymer.

另外，於溶液聚合中，聚合溶劑可使用例如，乙酸乙酯、甲苯等。具體之溶液聚合例，係於氮等惰性氣體氣流下加入聚合起始劑，通常，係以50~70℃左右、5~30小時左右的反應條件進行反應。 Further, in the solution polymerization, for example, ethyl acetate, toluene or the like can be used as the polymerization solvent. In the specific solution polymerization example, a polymerization initiator is added under a flow of an inert gas such as nitrogen. Usually, the reaction is carried out under the reaction conditions of about 50 to 70 ° C for about 5 to 30 hours.

不需特別限定所使用之自由基聚合起始劑、鏈轉移劑、乳化劑等，可適當地選擇使用。另，(甲基)丙烯酸系聚合物(A)之重量平均分子量可藉由聚合起始劑、鏈轉移劑之使用量、反應條件控制，可對應該等之種類調整適量的使用量。 The radical polymerization initiator, the chain transfer agent, the emulsifier, and the like to be used are not particularly limited, and can be appropriately selected and used. Further, the weight average molecular weight of the (meth)acrylic polymer (A) can be controlled by the amount of the polymerization initiator, the chain transfer agent, and the reaction conditions, and an appropriate amount can be adjusted depending on the type of the polymer.

聚合起始劑，可舉例如：2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2-甲脒基丙烷)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(和光純藥社製，VA-057)等偶氮系起始劑、過硫酸鉀、過硫酸銨等過硫酸鹽、二(2-乙基己基)過氧二碳酸酯、二(4-三級丁基環己基)過氧二碳酸酯、二-二級丁基過氧二碳酸酯、過癸酸三級丁酯、過氧 異丁酸三級己酯、過氧特戊酸三級丁酯、二過氧化月桂醯基、二正過氧化辛醯基、1,1,3,3-四甲基丁基過氧基-2-乙基己酸、二(4-甲基苯甲醯基)過氧化物、過氧化二苯甲醯基、過異丁酸三級丁酯、1,1-二(三級己基過氧基)環己烷、過氧化三級丁基、過酸化氫等過氧化物系起始劑、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組合有過氧化物與還原劑的氧化還原系起始劑等，但並未限定為該等。 The polymerization initiator may, for example, be 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylamidinopropane) dihydrochloride, 2,2'-azobis [2-(5-Methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis(2-methylpropionamidine) disulfate, 2,2'- Azobis(N,N'-dimethyleneisobutylphosphonium), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate (and pure light) Anthraquinone initiator such as Pharmaceutical Co., Ltd., VA-057), persulfate such as potassium persulfate or ammonium persulfate, di(2-ethylhexyl)peroxydicarbonate, bis(4-tertiary butyl) Cyclohexyl)peroxydicarbonate, di-secondary butylperoxydicarbonate, tert-butyl perrhenate, peroxygen Tert-butylhexanoate, tertiary butyl peroxypivalate, ruthenium laurate, di-n-peroxyoctyl, 1,1,3,3-tetramethylbutylperoxy-2- Ethylhexanoic acid, bis(4-methylbenzhydryl)peroxide, dibenzoguanidinium peroxide, tert-butyl peroxybutyrate, 1,1-di(tri-hexylperoxy) a peroxide-based initiator such as cyclohexane, tributyl peroxide or hydrogen peroxide, a combination of persulfate and sodium hydrogen sulfite, a combination of a peroxide and sodium ascorbate, and the like The redox-based initiator of the agent, etc., is not limited to these.

前述聚合起始劑可單獨使用，亦可混合2種以上使用，但全體之含量相對於單體100重量份，以0.005~1重量份左右為佳，以0.02~0.5重量份左右較佳。 The polymerization initiator may be used singly or in combination of two or more kinds. The total content is preferably from 0.005 to 1 part by weight, preferably from 0.02 to 0.5 part by weight, per 100 parts by weight of the monomer.

另外，聚合起始劑，例如，於使用2,2’-偶氮雙異丁腈製造前述重量平均分子量之(甲基)丙烯酸系聚合物(A)時，聚合起始劑之使用量相對於單體成分之全量100重量份，以0.06~0.2重量份左右為佳，更以0.08~0.175重量份左右為佳。 Further, the polymerization initiator, for example, when the (meth)acrylic polymer (A) having the above weight average molecular weight is produced by using 2,2'-azobisisobutyronitrile, the amount of the polymerization initiator used is relative to The total amount of the monomer component is preferably 100 parts by weight, preferably 0.06 to 0.2 parts by weight, more preferably 0.08 to 0.175 parts by weight.

鏈轉移劑，可舉例如：月桂基硫醇、環氧丙基硫醇、巰乙酸、2-巰乙醇、硫乙醇酸、巰乙酸2-乙基己基、2,3-二巰-1-丙醇等。鏈轉移劑可單獨使用，亦可混合2種以上使用，但全體之含量相對於單體成分之全量100重量份，係0.1重量份左右以下。 The chain transfer agent may, for example, be lauryl mercaptan, propylene propyl thiol, hydrazine acetic acid, 2-hydrazine ethanol, thioglycolic acid, 2-ethylhexyl phthalate, 2,3-dipyridin-1-propene Alcohol, etc. The chain transfer agent may be used singly or in combination of two or more kinds, and the total content is about 0.1 part by weight or less based on 100 parts by weight of the total amount of the monomer components.

又，乳化聚合時使用之乳化劑，可舉例如：月桂基硫酸鈉、月桂基硫酸銨、十二烷基苯磺酸鈉、聚氧乙烯烷基醚硫酸銨、聚氧乙烯烷基苯基醚硫酸鈉等陰離子系乳 化劑、聚氧乙烯烷基醚、聚氧乙烯烷基苯基醚、聚氧乙烯脂肪酸酯、聚氧乙烯-聚氧丙烯嵌段聚合物等非離子系乳化劑等。該等乳化劑可單獨使用，亦可併用2種以上。 Further, examples of the emulsifier used in the emulsion polymerization include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate, and polyoxyethylene alkylphenyl ether. Anionic milk such as sodium sulfate A nonionic emulsifier such as a chemical agent, a polyoxyethylene alkyl ether, a polyoxyethylene alkylphenyl ether, a polyoxyethylene fatty acid ester, or a polyoxyethylene-polyoxypropylene block polymer. These emulsifiers may be used singly or in combination of two or more.

此外，反應性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為例，具體而言，有AQUALON HS-10、HS-20、KH-10、BC-05、BC-10、BC-20(以上，均係第一工業製藥社製)、ADEKAREASOAP SE10N(旭電化工社製)等。反應性乳化劑因於聚合後被帶入聚合物鏈中，耐水性變差，而為佳。相對於單體成分之全量100重量份，乳化劑之使用量係0.3~5重量份，由聚合穩定性或機械穩定性來看，以0.5~1重量份較佳。 Further, the reactive emulsifier may be exemplified by an emulsifier having a radical polymerizable functional group such as a propenyl group or an allyl ether group, and specifically, AQUALON HS-10, HS-20, KH-10, BC. -05, BC-10, BC-20 (all of which are manufactured by Daiichi Kogyo Co., Ltd.), ADEKAREASOAP SE10N (made by Asahi Chemical Co., Ltd.), and the like. The reactive emulsifier is preferably incorporated into the polymer chain after polymerization, and the water resistance is deteriorated. The emulsifier is used in an amount of 0.3 to 5 parts by weight based on 100 parts by weight of the total monomer component, and is preferably 0.5 to 1 part by weight in terms of polymerization stability or mechanical stability.

本發明之黏著劑組成物除了前述(甲基)丙烯酸系聚合物(A)以外，亦含有聚醚化合物(B)。 The adhesive composition of the present invention contains a polyether compound (B) in addition to the (meth)acryl-based polymer (A).

聚醚化合物(B)係具有氧伸烷基之重複結構單元，且於至少1個末端具有以下述通式(1)：-SiRaM3-a表示之反應性矽基(式中，R係亦可具有取代基之碳數1~20之1價有機基，M係羥基或可水解基，a係0~2之整數；惟，存在複數R時，複數之R可互為相同亦可相異，存在複數M時，複數之M可互為相同亦可相異)。 The polyether compound (B) is a repeating structural unit having an oxyalkylene group and has a reactive thiol group represented by the following formula (1): -SiR a M 3-a at at least one terminal (wherein R Further, it may have a monovalent organic group having 1 to 20 carbon atoms of the substituent, M-based hydroxyl group or hydrolyzable group, and a is an integer of 0 to 2; however, when plural R is present, the plural R may be the same as each other. Different, when there is a complex number M, the complex numbers M can be the same or different.

前述聚醚化合物(B)係於每1分子之末端至少具有1個前述反應性矽基。聚醚化合物(B)係直鏈狀之化合物時，於末端具有1個或2個前述反應性矽基，以於末端具有2個者為佳。聚醚化合物(B)係支鏈狀之化合物時，末端除了主鏈末端以外亦包含側鏈末端，於該等末端至少具有1個前 述反應性矽基，但對應於末端數量，前述反應性矽基可為2個以上，更以3個以上為佳。 The polyether compound (B) has at least one of the aforementioned reactive sulfhydryl groups per molecule of the terminal. When the polyether compound (B) is a linear compound, it has one or two reactive sulfhydryl groups at the terminal, and it is preferred to have two at the terminal. When the polyether compound (B) is a branched compound, the terminal includes a side chain end in addition to the end of the main chain, and has at least one front end at the end. Although the reactive sulfhydryl group is mentioned, the reactive thiol group may be two or more, and more preferably three or more, depending on the number of terminals.

具有反應性矽基之聚醚化合物(B)係於其分子末端之至少一部分具有前述反應性矽基，且其分子中至少具有1個反應性矽基，以具有1.1~5個為佳，以具有1.1~3個更佳。 The polyether compound (B) having a reactive mercapto group has at least a part of its molecular terminal having the aforementioned reactive mercapto group, and has at least one reactive mercapto group in its molecule, preferably having 1.1 to 5, It has 1.1 to 3 better.

於以前述通式(1)表示之反應性矽基中，R係亦可具有取代基之碳數1~20之1價有機基。R以直鏈或支鏈的碳數1~8之烷基、碳數1~8之氟烷基或苯基為佳，以碳數1~6之烷基較佳，以甲基特佳。於同一分子中存在複數R時，複數之R可互為相同亦可相異。M係羥基或可水解基。可水解基係直接鍵結於矽原子，藉由水解反應及/或縮合反應產生矽氧烷鍵者。可水解基，可舉例如，鹵素原子、烷氧基、醯氧基、烯氧基、胺甲醯基、胺基、胺氧基、酮肟基等。可水解基具有碳原子時，其碳數以6以下為佳，以4以下較佳。特別是，以碳數4以下之烷氧基或烯氧基為佳，以甲氧基或乙氧基特佳。於同一分子中存在複數M時，複數之M可互為相同亦可相異。 In the reactive thiol group represented by the above formula (1), the R group may have a monovalent organic group having 1 to 20 carbon atoms as a substituent. R is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, a fluoroalkyl group having 1 to 8 carbon atoms or a phenyl group, and preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably a methyl group. When a plurality of Rs are present in the same molecule, the plural Rs may be the same or different from each other. M is a hydroxyl group or a hydrolyzable group. The hydrolyzable group is directly bonded to the ruthenium atom, and the oxime bond is produced by a hydrolysis reaction and/or a condensation reaction. The hydrolyzable group may, for example, be a halogen atom, an alkoxy group, a decyloxy group, an alkenyloxy group, an amine carbaryl group, an amine group, an amine oxy group or a ketoximino group. When the hydrolyzable group has a carbon atom, the carbon number is preferably 6 or less, more preferably 4 or less. In particular, an alkoxy group or an alkenyloxy group having a carbon number of 4 or less is preferred, and a methoxy group or an ethoxy group is particularly preferred. When a complex number M exists in the same molecule, the plural Ms may be the same or different from each other.

以前述通式(1)表示之反應性矽基以下述通式(3)所表示之烷氧基矽基為佳： The reactive thiol group represented by the above formula (1) is preferably an alkoxy fluorenyl group represented by the following formula (3):

(式中，R1、R2及R3係碳數1~6之1價烴基，於同一分子 中可相同亦可相異。)。 (In the formula, R 1 , R 2 and R 3 are a monovalent hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different in the same molecule.).

以前述通式(3)表示之烷氧基矽基中，R1、R2及R3，可舉例如，直鏈或支鏈之碳數1~6的烷基、直鏈或支鏈之碳數2~6的烯基、碳數5~6的環烷基、苯基等。式中-OR1、-OR2及-OR3之具體例，可舉例如，甲氧基、乙氧基、丙氧基、丙烯基、苯氧基等。其中，亦以甲氧基、乙氧基為佳，特別以甲氧基為佳。 In the alkoxyfluorenyl group represented by the above formula (3), R 1 , R 2 and R 3 may, for example, be a linear or branched alkyl group having 1 to 6 carbon atoms, a straight chain or a branched chain. An alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, or a phenyl group. Specific examples of the -OR 1 , -OR 2 and -OR 3 in the formula include a methoxy group, an ethoxy group, a propoxy group, a propenyl group, a phenoxy group and the like. Among them, a methoxy group and an ethoxy group are preferred, and a methoxy group is particularly preferred.

具有前述聚醚化合物(B)之氧伸烷骨架，以具有碳數1~10之直鏈或支鏈的氧伸烷基之重複結構單元者為佳。氧伸烷基之結構單元以碳數2~6為佳，更以2為佳。又，氧伸烷基之重複結構單元可為1種氧伸烷基之重複結構單元，亦可為2種以上之氧伸烷基的嵌段單元或隨機單元之重複結構單元。氧伸烷基可舉，氧乙烯基、氧丙烯基、氧丁烯基等為例。該等氧伸烷基中，亦以具有氧乙烯基之結構單元者，因骨架之親水性高，因產生矽醇導致對黏附體的移動量之變化小，故長期保管後之耐久性不易更為下降，特為佳。 The oxyalkylene skeleton having the above polyether compound (B) is preferably a repeating structural unit having a linear or branched oxygen alkyl group having 1 to 10 carbon atoms. The structural unit of the oxygen alkyl group is preferably 2 to 6 carbon atoms, more preferably 2 carbon atoms. Further, the repeating structural unit of the oxygen alkyl group may be a repeating structural unit of one oxygen alkyl group, or may be a block unit of two or more kinds of oxygen alkyl groups or a repeating structural unit of a random unit. The oxygen alkyl group may, for example, be an oxyethylene group, an oxypropylene group or an oxybutenyl group. Among these oxygen-extended alkyl groups, those having a structural unit having an oxyethylene group are highly hydrophilic due to the high hydrophilicity of the skeleton, and the change in the amount of movement of the adherend due to the production of decyl alcohol is small, so that the durability after long-term storage is not easy. For the decline, especially good.

前述聚醚化合物(B)除了前述反應性矽基以外，以主鏈實質上係由氧伸烷基之重複結構單元所構成為佳。此處，主鏈實質上係由氧伸烷基之重複結構單元所構成，係指亦可含有少量其他化學結構之意。其他化學結構係指，例如，亦可包含於製造氧伸烷基之重複結構單元時的起始劑之化學結構及與反應性矽基之連結基等。氧伸烷基之重複結構單元以聚醚化合物(B)全重量的50重量%以上為 佳，以80重量%以上更佳。 The polyether compound (B) is preferably composed of a repeating structural unit in which the main chain is substantially an alkyloxy group in addition to the reactive mercapto group. Here, the main chain is substantially composed of repeating structural units of an oxygen-extended alkyl group, and means that it may contain a small amount of other chemical structures. The other chemical structure means, for example, a chemical structure of a starter and a linking group with a reactive sulfhydryl group when the repeating structural unit of the oxygen alkyl group is produced. The repeating structural unit of the oxygen alkyl group is 50% by weight or more based on the total weight of the polyether compound (B). Preferably, it is more preferably 80% by weight or more.

前述聚醚化合物(B)可舉以通式(2)表示之化合物為例：通式(2)：RaM3-aSi-X-Y-(AO)n-Z The above polyether compound (B) can be exemplified by the compound represented by the formula (2): the formula (2): R a M 3- aSi-XY-(AO) n -Z

[式中，R係亦可具有取代基之碳數1~20之1價有機基，M係羥基或可水解基，a係0~2之整數；惟，存在複數R時，複數之R可互為相同亦可相異，存在複數M時，複數之M可互為相同亦可相異；AO係表示包含氧伸烷基作為重複結構單元之直鏈或支鏈結構，n係1~1700，表示氧伸烷基之平均加成莫耳數；X係表示碳數1~20之直鏈或支鏈的伸烷基；Y係表示醚鍵、酯鍵、胺甲酸酯鍵、或碳酸酯鍵；Z係氫原子、1價之碳數1~10之烴基、及以通式(2A)或以通式(2B)表示之基，通式(2A)：-Y1-X-SiRaM3-a [In the formula, R may have a monovalent organic group having 1 to 20 carbon atoms of the substituent, M-based hydroxyl group or hydrolyzable group, and a is an integer of 0 to 2; however, when plural R is present, the plural R may be The same or different from each other, in the presence of a complex number M, the complex M may be the same or different from each other; the AO system represents a linear or branched structure comprising an oxygen alkyl group as a repeating structural unit, n series 1 to 1700 , represents the average addition mole number of the oxygen alkyl group; X represents a linear or branched alkyl group having a carbon number of 1 to 20; Y represents an ether bond, an ester bond, a urethane bond, or a carbonic acid An ester bond; a Z-based hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a group represented by the formula (2A) or the formula (2B), and the formula (2A): -Y 1 -X-SiR a M 3-a

(式中，R、M、X係與前述相同；Y1係表示單鍵、-CO-鍵、-CONH-鍵、或-COO-鍵) (wherein R, M, and X are the same as defined above; Y 1 represents a single bond, a -CO- bond, a -CONH- bond, or a -COO- bond)

通式(2B)：-Q{-(OA)n-Y-X-SiRaM3-a}m General formula (2B): -Q{-(OA) n -YX-SiR a M 3-a } m

(式中，R、M、X、Y係與前述相同；OA係與前述AO相同，n係與前述相同；Q係2價以上之碳數1~10之烴基，m係與該烴基之價數相同)]。 (In the formula, R, M, X, and Y are the same as described above; OA is the same as the above-mentioned AO, and n is the same as the above; Q is a hydrocarbon group having a carbon number of 1 to 10 or more, and m is a price of the hydrocarbon group; The same number)].

前述通式(2)中之X係碳數1~20的直鏈或支鏈之伸烷基，碳數以2~10為佳，更以3為佳。 In the above formula (2), X is a linear or branched alkyl group having 1 to 20 carbon atoms, and the carbon number is preferably 2 to 10, more preferably 3.

前述通式(2)中之Y係與聚醚骨架之氧伸烷基末端的羥基反應所形成之鏈群，以醚鍵或胺甲酸酯鍵為佳， 更以胺甲酸酯鍵為佳。 The chain group formed by reacting the Y group in the above formula (2) with the hydroxyl group at the alkyl terminal of the oxygen extension chain of the polyether skeleton is preferably an ether bond or a urethane bond. More preferably, a urethane bond is preferred.

前述Z係對應於具有羥基的羥化合物，該化合物係與製造通式(2)所表示之化合物相關的氧伸烷聚合物之起始劑。於前述通式(2)中，於一末端具有1個反應性矽基時，另一末端之Z係氫原子、或1價之碳數1~10之烴基。Z係氫原子時，係使用與氧伸烷聚合物相同之構成單元作為前述羥化合物，Z係1價之碳數1~10之烴基時，係使用具有1個羥基之羥化合物作為前述羥化合物。 The aforementioned Z system corresponds to a hydroxy compound having a hydroxyl group which is an initiator of an oxyalkylene polymer related to the production of the compound represented by the formula (2). In the above formula (2), when one terminal has one reactive sulfhydryl group, the other terminal has a Z-based hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. When a Z-based hydrogen atom is used, the same structural unit as the oxygen-alkylene polymer is used as the above-mentioned hydroxy compound, and when Z is a monovalent hydrocarbon group having 1 to 10 carbon atoms, a hydroxy compound having one hydroxyl group is used as the hydroxy compound. .

另一方面，於前述通式(2)中，於末端具有複數反應性矽基時，Z係與通式(2A)或(2B)的情形相關。Z係通式(2A)時，係使用與氧伸烷聚合物相同的構成單元作為前述羥化合物，Z係通式(2B)時，係使用與氧伸烷聚合物之構成單元相異，且具有2個羥基的羥化合物作為前述羥化合物。另，Z係通式(2A)時，Y1與Y同樣地，係與聚醚骨架之氧伸烷基末端的羥基反應所形成之鏈群。 On the other hand, in the above formula (2), when the terminal has a complex reactive sulfhydryl group, the Z system is related to the case of the formula (2A) or (2B). In the case of the Z-formula (2A), the same structural unit as the oxyalkylene polymer is used as the hydroxy compound, and in the case of the Z-formula (2B), the constituent unit of the oxyalkylene polymer is different, and A hydroxy compound having two hydroxyl groups is used as the aforementioned hydroxy compound. Further, in the case of the Z-formula (2A), Y 1 is a chain group formed by reacting with a hydroxyl group at the terminal of the oxygen-extended alkyl group of the polyether skeleton, similarly to Y.

前述通式(2)所表示之聚醚化合物(B)中，由再製性之點來看，以通式(4)、通式(5)、通式(6)所表示之化合物為佳，通式(4)：Z0-A2-O-(AO)n-Z1 In the polyether compound (B) represented by the above formula (2), a compound represented by the formula (4), the formula (5) or the formula (6) is preferred from the viewpoint of remanufacturability. General formula (4): Z 0 -A 2 -O-(AO) n -Z 1

(式中，AO係包含氧伸烷基作為重複結構單元之直鏈或支鏈結構，n係1~1700，表示AO之平均加成莫耳數；Z1係氫原子或-A2-Z0；A2係碳數2~6之伸烷基)；通式(5)：Z0-A2-NHCOO-(AO)n-Z2 (wherein, AO contains a linear or branched structure in which an oxygen alkyl group is a repeating structural unit, n is 1 to 1700, which represents an average addition molar number of AO; Z 1 is a hydrogen atom or -A 2 -Z 0 ; A2 is a 2 to 6 carbon alkyl group; formula (5): Z 0 -A 2 -NHCOO-(AO) n -Z 2

(式中，AO係包含氧伸烷基作為重複結構單元之直鏈或 支鏈結構，n係1~1700，表示AO之平均加成莫耳數；Z2係氫原子、或-CONH-A2-Z0；A2係碳數2~6之伸烷基)；通式(6)：Z3-(AO)n-O-G-CR4{-G-O-(AO)n-Z3}2 (wherein, AO contains a linear or branched structure in which an alkylene group is a repeating structural unit, n is 1 to 1700, and represents an average addition molar number of AO; a Z 2 hydrogen atom, or -CONH-A 2 -Z 0 ; A 2 is an alkylene group having 2 to 6 carbon atoms; and (3): Z 3 -(AO) n -OG-CR 4 {-GO-(AO) n -Z 3 } 2

(式中，AO係包含氧伸烷基作為重複結構單元之直鏈或支鏈結構，n係1~1700，表示AO之平均加成莫耳數；Z3係氫原子或-A2-Z0，至少任1個Z3係-A2-Z0；A2係碳數2~6之伸烷基，R4係表示氫原子、或碳數1~3之伸烷基)。G係表示單鍵或亞甲基。Z0均係以前述通式(3)表示之烷氧基矽基。AO之氧伸烷基可為直鏈或支鏈。A2之伸烷基可為直鏈或支鏈，尤以乙烯基為佳。 (wherein, AO contains a linear or branched structure in which an alkylene group is a repeating structural unit, n is 1 to 1700, which represents an average addition molar number of AO; a Z 3 hydrogen atom or -A 2 -Z 0 , at least one Z 3 -A2-Z 0 ; A 2 is a 2 to 6 alkylene group; R 4 is a hydrogen atom or a C 1 to 3 alkyl group). G is a single bond or a methylene group. Z 0 is an alkoxyfluorenyl group represented by the above formula (3). The oxyalkylene group of AO may be straight or branched. The alkyl group of A 2 may be a straight chain or a branched chain, and particularly preferably a vinyl group.

另，以前述通式(5)表示之化合物以使用下述通式(5A)所表示之化合物為佳： Further, the compound represented by the above formula (5) is preferably a compound represented by the following formula (5A):

[式中，R1、R2及R3係碳數1~6之1價烴基，於同一分子中可相同亦可相異。n係1~1700，表示氧丙烯基之平均加成莫耳數。 [wherein, R 1 , R 2 and R 3 are a monovalent hydrocarbon group having 1 to 6 carbon atoms, and may be the same or different in the same molecule. The n series is 1 to 1700, and represents the average addition mole number of the oxypropylene group.

Z21係氫原子、或以通式(5B)表示之三烷氧基矽基：[化7] a Z 21 hydrogen atom or a trialkoxycarbonyl group represented by the formula (5B): [Chem. 7]

(式中，R1、R2及R3係與前述相同)]。 (wherein R 1 , R 2 and R 3 are the same as defined above)].

聚醚化合物(B)之數量平均分子量由再製性來看，以300~100000為佳。前述數量平均分子量之下限以500以上為佳，更以1000以上為佳，又以2000以上為佳，更加以3000以上，甚至以4000以上為佳，尤以5000以上為佳，另一方面，上限以50000以下為佳，更以40000以下為佳，又以30000以下為佳，更加以20000以下為佳，甚至以10000以下為佳。前述數量平均分子量可使用前述上限值或下限值設定於較佳之範圍內。前述通式(2)、(4)、(5)或(6)所表示之聚醚化合物(B)中的n係氧伸烷基之平均加成莫耳數，前述聚醚化合物(B)以控制為數量平均分子量於前述範圍者為佳。前述n於聚醚化合物(B)之數量平均分子量為1000以上時，通常係10~1700。 The number average molecular weight of the polyether compound (B) is preferably from 300 to 100,000 in terms of remanufacturability. The lower limit of the number average molecular weight is preferably 500 or more, more preferably 1,000 or more, more preferably 2,000 or more, more preferably 3,000 or more, even more preferably 4,000 or more, particularly preferably 5,000 or more, and on the other hand, the upper limit It is preferably 50,000 or less, more preferably 40,000 or less, and preferably 30,000 or less, more preferably 20,000 or less, and even 10,000 or less. The above number average molecular weight can be set within a preferred range by using the above upper limit value or lower limit value. The average addition mole number of the n-type oxygen alkyl group in the polyether compound (B) represented by the above formula (2), (4), (5) or (6), the above polyether compound (B) It is preferred to control the number average molecular weight to be in the above range. When n the polyether compound (B) has a number average molecular weight of 1,000 or more, it is usually 10 to 1700.

又，聚合物之Mw(重量平均分子量)/Mn(數量平均分子量)以3.0以下為佳，以1.6以下較佳，以1.5以下特佳。為得到Mw/Mn小之具反應性矽基的聚醚化合物(B)，特別是於催化劑中使用下述複合金屬氰化物錯合物，並於起始劑存在下，以使用使環狀醚聚合所得之氧伸烷聚合物特佳，以將如此之原料氧伸烷聚合物的末端變性，作為反應性矽基之方法最佳。 Further, the Mw (weight average molecular weight) / Mn (number average molecular weight) of the polymer is preferably 3.0 or less, more preferably 1.6 or less, and most preferably 1.5 or less. In order to obtain a polyether compound (B) having a small mw/Mn reactive thiol group, the following composite metal cyanide complex is used in particular in the catalyst, and in the presence of an initiator, a cyclic ether is used. The oxygenated alkylene oxide polymer obtained by polymerization is particularly preferred in order to denature the terminal of such a raw material oxygenated alkylene polymer as a reactive mercapto group.

前述通式(2)、(4)、(5)或(6)所表示之聚醚化合物 (B)可藉由例如，使用於分子末端具有官能基之氧伸烷聚合物作為原料，透過伸烷基等有機基使反應性矽基鍵結於該分子末端地製造。作為原料使用之氧伸烷聚合物，以於催化劑及起始劑之存在下使環狀醚開環聚合反應後所得的羥基末端之聚合物為佳。 a polyether compound represented by the above formula (2), (4), (5) or (6) (B) It can be produced, for example, by using an oxyalkylene polymer having a functional group at a molecular terminal as a raw material, and by bonding an organic group such as an alkyl group to bond a reactive sulfhydryl group to the terminal of the molecule. The oxygen-alkylene polymer used as a raw material is preferably a hydroxyl-terminated polymer obtained by ring-opening polymerization of a cyclic ether in the presence of a catalyst and a starter.

前述起始劑係每1分子具有1個以上之活性氫原子的化合物，可使用例如，每1分子具有1個以上之羥基的羥化合物等。起始劑，可舉例如：乙二醇、丙二醇、二丙二醇、丁二醇、六亞甲二醇、氫化雙酚A、新戊二醇、聚丁二烯醇、二乙二醇、三乙二醇、聚乙二醇、烯丙醇、甲烯丙醇、甘油、三羥甲基甲烷、三羥甲基丙烷、及新戊四醇等、及該等化合物之環氧烷加成物等含羥基之化合物等。起始劑可僅使用1種，亦可併用2種以上。 The above-mentioned initiator is a compound having one or more active hydrogen atoms per molecule, and for example, a hydroxy compound having one or more hydroxyl groups per molecule can be used. The initiator may, for example, be ethylene glycol, propylene glycol, dipropylene glycol, butanediol, hexamethylene glycol, hydrogenated bisphenol A, neopentyl glycol, polybutadienol, diethylene glycol, triethyl ethane. Glycol, polyethylene glycol, allyl alcohol, allyl alcohol, glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol, and alkylene oxide adducts of such compounds A compound containing a hydroxyl group or the like. The initiator may be used alone or in combination of two or more.

欲於起始劑存在下使環狀醚開環聚合時，可使用聚合催化劑。聚合催化劑，可舉例如：氫氧化鉀及甲氧化鉀等鉀化合物、及氫氧化銫等銫化合物等鹼金屬化合物；複合金屬氰化物錯合物；金屬紫質錯合物；及具有P=N鍵之化合物等。 When the cyclic ether is to be subjected to ring-opening polymerization in the presence of an initiator, a polymerization catalyst can be used. Examples of the polymerization catalyst include potassium compounds such as potassium hydroxide and potassium oxychloride, and alkali metal compounds such as ruthenium compounds such as ruthenium hydroxide; composite metal cyanide complexes; metallic violet complexes; and P=N a compound such as a bond.

前述通式(2)、(4)、(5)或(6)所表示之聚醚化合物(B)的聚氧伸烷鏈，以利用碳數2~6之環氧烷的開環聚合形成之氧伸烷的聚合單元所構成者為佳，又以選自於由環氧乙烷、環氧丙烷及環氧丁烷構成群組的1種以上之環氧烷經開環聚合形成之氧伸烷基的重複結構單元所構成者較佳，尤以利用環氧乙烷之開環聚合形成的氧乙烯基之重複結構 單元所構成者更佳。聚氧伸烷鏈係由2種以上之氧伸烷基的重複結構單元構成時，2種以上之氧伸烷基的重複結構單元之排列方法可為嵌段狀，亦可為隨機狀。 The polyoxyalkylene chain of the polyether compound (B) represented by the above formula (2), (4), (5) or (6) is formed by ring-opening polymerization of an alkylene oxide having 2 to 6 carbon atoms. Preferably, the polymerization unit of the oxyalkylene is formed by oxygen ring-opening polymerization of one or more kinds of alkylene oxides selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide. The repeating structural unit of an alkylene group is preferably composed of a repeating structure of an oxyethylene group formed by ring-opening polymerization of ethylene oxide. The unit is better. When the polyoxyalkylene chain is composed of a repeating structural unit of two or more kinds of oxygen-extended alkyl groups, the arrangement method of the repeating structural units of two or more kinds of oxygen-extended alkyl groups may be in the form of a block or a random form.

又，以前述通式(5)表示之聚醚化合物(B)可藉由例如，使具有聚氧伸烷鏈與羥基之聚合物、及具有以通式(1)表示之反應性矽基與異氰酸酯基的化合物進行胺甲酸酯化反應後得到。其他，具不飽和基之氧伸烷聚合物，亦可使用，利用以烯丙醇作為起始劑聚合環氧烷所得之烯丙基末端聚氧伸烷單元醇對不飽和基之氫矽烷或巰矽烷的加成反應，將通式(1)所表示之反應性矽基導入分子末端的方法。 Further, the polyether compound (B) represented by the above formula (5) can be, for example, a polymer having a polyoxyalkylene chain and a hydroxyl group, and a reactive thiol group represented by the formula (1) The isocyanate group-containing compound is obtained after the urethanization reaction. Other, unsaturated alkyloxyalkylene polymers may also be used, which are obtained by polymerizing an alkylene oxide with allyl alcohol as a starting agent to obtain an allyl terminal polyoxyalkylene unit alcohol to an unsaturated group of hydrodecane or A method of introducing a reactive sulfhydryl group represented by the formula (1) into a molecular terminal by an addition reaction of decane.

並未特別限定使用於起始劑存在下使環狀醚開環聚合後所得之羥基末端的氧伸烷聚合物(亦稱為原料氧伸烷聚合物)之末端基，導入通式(1)所表示之反應性矽基之方法，但通常以再透過有機基使反應性矽基連結前述末端基之下述(a)至(c)的方法為佳。 The terminal group of the hydroxy-terminated alkylene oxide polymer (also referred to as a raw material oxygen-alkylene polymer) obtained by ring-opening polymerization of a cyclic ether in the presence of an initiator is not particularly limited, and is introduced into the formula (1). The method of the reactive mercapto group is preferably a method in which the reactive mercapto group is further bonded to the terminal group (a) to (c) by re-passing the organic group.

(a)將不飽和基導入具羥基之原料氧伸烷聚合物的末端後，使反應性矽基鍵結於不飽和基的方法。該方法更可例示如以下2個方法(a-1)及(a-2)。(a-1)使用於鉑化合物等催化劑之存在下，於前述不飽和基中使氫矽烷化合物反應，即矽氫化反應的方法。(a-2)於不飽和基使巰矽烷化合物反應之方法。巰矽烷化合物，可舉例如：3-巰基丙基三甲氧矽烷、3-巰基丙基三乙氧矽烷、3-巰基丙基三異丙烯基氧基矽烷、3-巰基丙基甲基二甲氧矽烷、3-巰基丙基二甲基單甲氧矽烷、3-巰基丙基甲基二乙氧烷等。 (a) A method in which an unsaturated group is introduced into a terminal of a hydroxy group-forming oxyalkylene polymer, and a reactive thiol group is bonded to an unsaturated group. This method can further exemplify the following two methods (a-1) and (a-2). (a-1) A method in which a hydroquinone compound is reacted in the unsaturated group in the presence of a catalyst such as a platinum compound, that is, a hydrogenation reaction. (a-2) A method of reacting a decane compound with an unsaturated group. The decane compound may, for example, be 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, 3-mercaptopropyltriisopropenyloxydecane or 3-mercaptopropylmethyldimethoxy Decane, 3-mercaptopropyldimethylmonomethoxynonane, 3-mercaptopropylmethyldiethoxylate, and the like.

於使不飽和基與巰基反應時，可使用作為自由基聚合起始劑使用之自由基產生劑等化合物，亦可視所需不使用自由基聚合起始劑，而利用放射線或熱進行反應。自由基聚合起始劑，可舉例如，過氧化物系、偶氮系、及氧化還原系之聚合起始劑、及金屬化合物催化劑等，具體而言，可舉例如，2,2’-偶氮雙異丁腈、2,2’-偶氮雙-2-甲基丁腈、過氧化苯甲醯基、過氧三級烷酯、過氧化乙醯基、及過氧碳酸二異丙酯等。使用自由基聚合起始劑使不飽和基與巰基反應時，雖因前述聚合起始劑之分解溫度(半衰期溫度)而異，但一般係20~200℃，以50~150℃的反應溫度進行數小時~數十小時反應為佳。 When the unsaturated group is reacted with a thiol group, a compound such as a radical generator used as a radical polymerization initiator may be used, and the reaction may be carried out by radiation or heat, without using a radical polymerization initiator. The radical polymerization initiator may, for example, be a peroxide-based, azo-based or redox-based polymerization initiator, or a metal compound catalyst. Specifically, for example, 2,2'-couple Nitrogen bisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, benzammonium peroxide, peroxytrialkyl ester, ethyl ethoxylate, and diisopropyl peroxycarbonate Wait. When a radical polymerization initiator is used to react an unsaturated group with a thiol group, the decomposition temperature (half-life temperature) of the polymerization initiator varies depending on the reaction temperature of 50 to 150 ° C at a temperature of 20 to 200 ° C. The reaction is preferably from several hours to tens of hours.

於原料氧伸烷聚合物之末端導入不飽和基的方法，可舉於併有可藉由醚鍵、酯鍵、胺甲酸酯鍵、或碳酸酯鍵等連結之官能基及不飽和基的反應劑中，使原料氧伸烷聚合物之末端羥基與原料氧伸烷聚合物反應的方法為例。又，於起始劑存在下聚合環狀醚時，亦可使用藉使烯丙基環氧丙基醚等含不飽和基之環氧化合物共聚合，將不飽和基導入原料氧伸烷聚合物的末端之至少一部分的方法。以60~120℃之溫度進行為佳，一般係於數小時以內之反應時間充分地進行矽氫化反應。 The method of introducing an unsaturated group to the terminal of the raw material oxygen-alkylene polymer may be a functional group or an unsaturated group which may be bonded by an ether bond, an ester bond, a urethane bond, or a carbonate bond. In the reactant, a method of reacting a terminal hydroxyl group of a raw material oxygen alkylene polymer with a raw material oxygen alkylene polymer is exemplified. Further, when a cyclic ether is polymerized in the presence of an initiator, it is also possible to introduce an unsaturated group into a raw material oxygen-alkali polymer by copolymerizing an unsaturated group-containing epoxy compound such as allyl epoxypropyl ether. The method of at least part of the end. It is preferably carried out at a temperature of from 60 to 120 ° C, and the hydrazine hydrogenation reaction is generally carried out under a reaction time of several hours.

(b)使末端具有羥基之原料氧伸烷聚合物與具有反應性矽基之異氰酸酯矽烷化合物反應的方法。該化合物可舉例如，1-異氰酸酯甲基三甲氧矽烷、1-異氰酸酯甲基三乙氧矽烷、1-異氰酸酯丙基三甲氧矽烷、1-異氰酸酯丙基三 乙氧矽烷、3-異氰酸酯丙基三甲氧矽烷、3-異氰酸酯丙基三乙氧矽烷、1-異氰酸酯甲基甲基二甲氧矽烷、1-異氰酸酯甲基二甲基單甲氧矽烷、1-異氰酸酯甲基甲基二乙氧矽烷、1-異氰酸酯丙基甲基二甲氧矽烷、1-異氰酸酯丙基二甲基單甲氧矽烷、1-異氰酸酯丙基甲基二乙氧矽烷、3-異氰酸酯丙基甲基二甲氧矽烷、3-異氰酸酯丙基二甲基單甲氧矽烷、及3-異氰酸酯丙基甲基二乙氧矽烷等異氰酸酯矽烷系化合物。其中，以3-異氰酸酯丙基三甲氧矽烷、1-異氰酸酯甲基甲基二甲氧矽烷更佳，以3-異氰酸酯丙基三甲氧矽烷特佳。 (b) A method of reacting a raw material oxygenated alkylene polymer having a hydroxyl group at the terminal with an isocyanate decane compound having a reactive mercapto group. The compound may, for example, be 1-isocyanate methyltrimethoxysilane, 1-isocyanate methyltriethoxysilane, 1-isocyanatepropyltrimethoxysilane, 1-isocyanatepropyltri Ethoxy decane, 3-isocyanate propyl trimethoxy decane, 3-isocyanate propyl triethoxy decane, 1-isocyanate methyl methyl dimethoxy decane, 1-isocyanate methyl dimethyl monomethoxy decane, 1- Isocyanate methylmethyldiethoxysilane, 1-isocyanate propylmethyldimethoxydecane, 1-isocyanate propyldimethylmonomethoxynonane, 1-isocyanate propylmethyldiethoxy decane, 3-isocyanate An isocyanate decane compound such as propylmethyldimethoxydecane, 3-isocyanatepropyldimethylmonomethoxynonane or 3-isocyanate propylmethyldiethoxyoxane. Among them, 3-isocyanatepropyltrimethoxysilane, 1-isocyanate methylmethyldimethoxysilane are more preferable, and 3-isocyanatepropyltrimethoxysilane is particularly preferable.

反應以進行至相對於原料氧伸烷聚合物之羥基(OH)，異氰酸酯矽烷系化合物的異氰酸酯基(NCO)以莫耳比計係NCO/OH=0.80~1.05為佳。該方法因製造步驟數少，可大幅地縮短步驟時間，製造步驟途中亦無副生成之不純物，亦不需純化等繁瑣之操作。更佳之NCO基與OH基的比率係NCO/OH(莫耳比)=0.85~1.00。NCO比率少時，剩下之OH基與反應性矽基將產生反應等，儲藏穩定性不佳。此時，以重新使異氰酸酯矽烷化合物或單異氰酸酯化合物反應，消耗過剩之OH基，調整至預定之矽烷化率為佳。 The reaction is carried out until the hydroxyl group (OH) of the starting oxygenate polymer, and the isocyanate group (NCO) of the isocyanate decane compound is preferably NCO/OH = 0.80 to 1.05 in terms of molar ratio. In this method, since the number of manufacturing steps is small, the step time can be greatly shortened, and the impurities generated in the middle of the manufacturing step are not produced, and complicated operations such as purification are not required. A more desirable ratio of NCO groups to OH groups is NCO/OH (Morby ratio) = 0.85 to 1.00. When the NCO ratio is small, the remaining OH group reacts with the reactive sulfhydryl group, and the storage stability is poor. At this time, the isocyanate decane compound or the monoisocyanate compound is reacted again, and the excess OH group is consumed, and the predetermined decane conversion ratio is adjusted.

使原料氧伸烷聚合物之羥基與前述異氰酸酯矽烷化合物反應時，亦可使用眾所周知的胺甲酸酯化反應催化劑。因有無使用胺甲酸酯化反應催化劑及使用量，反應溫度及至反應結束所需之反應時間相異，但一般係20~200℃，以50~150℃之溫度進行數小時反應為佳。 When the hydroxyl group of the raw material oxygenated alkylene polymer is reacted with the above-mentioned isocyanate decane compound, a well-known urethanation reaction catalyst can also be used. The reaction temperature and the reaction time required until the end of the reaction differ depending on whether or not the urethanization catalyst is used or not, but it is usually 20 to 200 ° C, and it is preferred to carry out the reaction at a temperature of 50 to 150 ° C for several hours.

(c)於異氰酸酯基過剩之條件下，使聚異氰酸酯 化合物於分子末端具有羥基之氧伸烷聚合物反應，製造末端之至少一部分具有異氰酸酯基的氧伸烷聚合物，更使具有官能基之矽化合物於前述異氰酸酯基反應的方法。該矽化合物之官能基係選自於由羥基、羧基、巰基、1級胺基、及2級胺基所構成之群的含活性氫之基。該矽化合物可舉例如，N-苯基-3-胺基丙基三甲氧矽烷、3-胺基丙基三甲氧矽烷、3-胺基丙基三乙氧矽烷、N-苯基-3-胺基丙基甲基二甲氧矽烷、3-胺基丙基甲基二甲氧矽烷、及3-胺基丙基甲基二乙氧矽烷等胺基矽烷系化合物；以及3-巰基丙基三甲氧矽烷、3-巰基丙基甲基二甲氧矽烷等巰矽烷系化合物。使原料氧伸烷聚合物之羥基與於前述異氰酸酯基具有官能基之矽化合物反應時，亦可使用眾所周知的胺甲酸酯化反應催化劑。因有無使用胺甲酸酯化反應催化劑及使用量，反應溫度及至反應結束所需之反應時間相異，但一般係20~200℃，以50~150℃之溫度進行數小時反應為佳。 (c) making polyisocyanate under conditions of excess isocyanate groups The compound reacts with an oxyalkylene polymer having a hydroxyl group at a molecular terminal to produce an oxyalkylene polymer having at least a part of a terminal having an isocyanate group, and a method of reacting a ruthenium compound having a functional group with the aforementioned isocyanate group. The functional group of the ruthenium compound is selected from the group consisting of a hydroxyl group, a carboxyl group, a thiol group, a first-order amine group, and a group 2 amine group-containing active hydrogen-containing group. The hydrazine compound may, for example, be N-phenyl-3-aminopropyltrimethoxy decane, 3-aminopropyltrimethoxy decane, 3-aminopropyltriethoxy decane, N-phenyl-3- Amino decane-based compounds such as aminopropylmethyldimethoxydecane, 3-aminopropylmethyldimethoxydecane, and 3-aminopropylmethyldiethoxyoxane; and 3-mercaptopropyl A decane compound such as trimethoxysilane or 3-mercaptopropylmethyldimethoxydecane. When a hydroxyl group of a raw material oxygenated alkylene polymer is reacted with a hydrazine compound having a functional group in the above isocyanate group, a well-known urethanation reaction catalyst can also be used. The reaction temperature and the reaction time required until the end of the reaction differ depending on whether or not the urethanization catalyst is used or not, but it is usually 20 to 200 ° C, and it is preferred to carry out the reaction at a temperature of 50 to 150 ° C for several hours.

聚醚化合物(B)之具體例，可舉例如，Kaneka社製之MS聚合物S203、S303、S810；SILYL EST250、EST280；SAT10、SAT200、SAT220、SAT350、SAT400、旭硝子社製之EXCESTAR S2410、S2420或S3430等、GELEST社製之SIB1824．82、SIB1824．84等。 Specific examples of the polyether compound (B) include MS polymers S203, S303, and S810 manufactured by Kaneka Co., Ltd.; SILYL EST250 and EST280; SAT10, SAT200, SAT220, SAT350, SAT400, and EXCESTAR S2410 and S2420 manufactured by Asahi Glass Co., Ltd. Or S3430, etc., SIB1824.82, SIB1824.84, etc. by GELEST.

本發明之黏著劑組成物的聚醚化合物(B)之比例，相對於(甲基)丙烯酸系聚合物(A)100重量份，以0.001~5重量份為佳。聚醚化合物(B)小於0.001重量份時，有提升再製性之效果並不充分的情形。聚醚化合物(B)以0.005重量份 以上為佳，更以0.01重量份以上為佳。另一方面，聚醚化合物(B)大於5重量份時，耐濕性係不充分，信賴性試驗等中容易產生剝離。聚醚化合物(B)以1重量份以下為佳，更以0.5重量份以下為佳。前述聚醚化合物(B)之比例可使用前述上限值或下限值，設定於較佳的範圍。 The ratio of the polyether compound (B) of the adhesive composition of the present invention is preferably 0.001 to 5 parts by weight based on 100 parts by weight of the (meth)acryl-based polymer (A). When the polyether compound (B) is less than 0.001 part by weight, the effect of improving the remanufacturability is insufficient. Polyether compound (B) in an amount of 0.005 parts by weight The above is preferred, and more preferably 0.01 parts by weight or more. On the other hand, when the polyether compound (B) is more than 5 parts by weight, the moisture resistance is insufficient, and peeling is likely to occur in a reliability test or the like. The polyether compound (B) is preferably 1 part by weight or less, more preferably 0.5 part by weight or less. The ratio of the polyether compound (B) can be set to a preferred range by using the above upper limit or lower limit.

本發明之黏著劑組成物除了前述(甲基)丙烯酸系聚合物(A)及聚醚化合物(B)，亦含有具乙醯乙醯基之矽烷耦合劑(C)。矽烷耦合劑(C)之具體例可舉例如，含有乙醯乙醯基，且含有以下述通式(2)表示之反應性矽基的化合物，-SiRaM3-a (2) The adhesive composition of the present invention contains a decane coupling agent (C) having an acetamidine group in addition to the (meth)acrylic polymer (A) and the polyether compound (B). Specific examples of the decane coupling agent (C) include, for example, a compound containing an ethyl fluorene group and containing a reactive thiol group represented by the following formula (2), -SiR a M 3-a (2)

(式中，R係亦可具有取代基之碳數1~20之1價有機基，M係羥基或可水解基，a係0~2之整數；惟，存在複數R時，複數之R可互為相同亦可相異，存在複數M時，複數之M可互為相同亦可相異)。矽烷耦合劑(C)之市售品可舉綜研化學社的A100等為例。本發明之黏著劑組成物的矽烷耦合劑(C)之比例，相對於(甲基)丙烯酸系聚合物(A)100重量份，以0.001~5重量份為佳。矽烷耦合劑(C)小於0.001重量份時，於長期保管後有產生剝離的情形，大於5重量份時，於製造後及長期保管後的耐久試驗中，均容易產生黏著劑層之剝離。本發明之黏著劑組成物的矽烷耦合劑(C)之比例以0.02重量份以上較佳，以0.1重量份以上更佳。又，以3重量份以下較佳，以2重量份以下更佳。 (In the formula, R may have a monovalent organic group having 1 to 20 carbon atoms of the substituent, M-based hydroxyl group or hydrolyzable group, and a is an integer of 0 to 2; however, when plural R is present, the plural R may be The same or different from each other, when there are multiple M, the complex M can be the same or different. A commercial product of the decane coupling agent (C) can be exemplified by A100 of the Institute of Chemical Research. The ratio of the decane coupling agent (C) of the adhesive composition of the present invention is preferably 0.001 to 5 parts by weight based on 100 parts by weight of the (meth)acryl-based polymer (A). When the decane coupling agent (C) is less than 0.001 part by weight, peeling may occur after long-term storage, and when it is more than 5 parts by weight, peeling of the adhesive layer is likely to occur in the durability test after production and after long-term storage. The ratio of the decane coupling agent (C) of the adhesive composition of the present invention is preferably 0.02 parts by weight or more, more preferably 0.1 parts by weight or more. Further, it is preferably 3 parts by weight or less, more preferably 2 parts by weight or less.

此外，本發明之黏著劑組成物中可含有交聯劑(D)。交聯劑(D)可使用有機系交聯劑或多官能性金屬螯 合。有機系交聯劑，可舉例如，異氰酸酯系交聯劑、過氧化物系交聯劑、環氧系交聯劑、亞胺系交聯劑等。多官能性金屬螯合係多價金屬與有機化合物共價鍵結或配位鍵結者。多價金屬原子，可舉例如，Al、Cr、Zr、Co、Cu、Fe、Ni、V、Zn、In、Ca、Mg、Mn、Y、Ce、Sr、Ba、Mo、La、Sn、Ti等。共價鍵結或配位鍵結之有機化合物中的原子可舉氧原子等為例，有機化合物，可舉例如，烷基酯、醇化合物、羧酸化合物、醚化合物、酮化合物等。 Further, the adhesive composition of the present invention may contain a crosslinking agent (D). The crosslinking agent (D) may use an organic crosslinking agent or a polyfunctional metal chelate Hehe. The organic crosslinking agent may, for example, be an isocyanate crosslinking agent, a peroxide crosslinking agent, an epoxy crosslinking agent, or an imide crosslinking agent. Polyfunctional metal chelates are those in which a polyvalent metal is covalently bonded or coordinated to an organic compound. The polyvalent metal atom may, for example, be Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti. Wait. The atom in the organic compound of the covalent bond or the coordinate bond may be an oxygen atom or the like, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound.

交聯劑(D)以異氰酸酯系交聯劑及/或過氧化物型交聯劑為佳。異氰酸酯系交聯劑之化合物，可舉例如，甲苯二異氰酸酯、氯伸苯基二異氰酸酯(chlorphenylene diisocyanate)、四亞甲基二異氰酸酯、茬二異氰酸酯、二苯基甲烷二異氰酸酯、經氫化之二苯基甲烷二異氰酸酯等異氰酸酯單體及將該等異氰酸酯單體加成有三羥甲基丙烷等之異氰酸酯化合物或異三聚氰酸酯化物、縮二脲型化合物、更佳者係，聚醚多元醇或聚酯多元醇、丙烯酸多元醇、聚丁二烯多元醇、聚異戊二烯多元醇等經加成反應之胺甲酸酯預聚合物型之異氰酸酯等。特佳者為，聚異氰酸酯化合物，係選自於由六亞甲基二異氰酸酯、氫化茬二異氰酸酯、及異佛酮二異氰酸酯所構成之群的1種或來自於其之聚異氰酸酯化合物。此處，選自於由亞甲基二異氰酸酯、氫化茬二異氰酸酯、及異佛酮二異氰酸酯所構成之群的1種或來自於其之聚異氰酸酯化合物，包含六亞甲基二異氰酸酯、氫化茬二異氰酸酯、異佛酮二異氰酸酯、多元醇變性 六亞甲基二異氰酸酯、多元醇變性氫化茬二異氰酸酯、三聚物型氫化茬二異氰酸酯、及多元醇變性異佛酮二異氰酸酯等。例示之聚異氰酸酯化合物因可迅速地進行與羥基之反應，特別是使聚合物所含之酸、鹽基作為催化劑，有助於交聯的速度係為佳。 The crosslinking agent (D) is preferably an isocyanate crosslinking agent and/or a peroxide crosslinking agent. Examples of the isocyanate crosslinking agent compound include toluene diisocyanate, chlorphenylene diisocyanate, tetramethylene diisocyanate, decyl diisocyanate, diphenylmethane diisocyanate, and hydrogenated diphenyl. An isocyanate monomer such as a methane diisocyanate or an isocyanate compound such as trimethylolpropane or an isomeric cyanurate compound, a biuret type compound, or a polyether polyol. Or a urethane prepolymer type isocyanate which is subjected to an addition reaction such as a polyester polyol, an acrylic polyol, a polybutadiene polyol, or a polyisoprene polyol. Particularly preferred is a polyisocyanate compound selected from the group consisting of hexamethylene diisocyanate, hydrogenated hydrazine diisocyanate, and isophorone diisocyanate, or a polyisocyanate compound derived therefrom. Here, one or a polyisocyanate compound selected from the group consisting of methylene diisocyanate, hydrogenated hydrazine diisocyanate, and isophorone diisocyanate contains hexamethylene diisocyanate and hydrazine hydride. Diisocyanate, isophorone diisocyanate, polyol denaturation Hexamethylene diisocyanate, polyol denatured hydrogenated hydrazine diisocyanate, trimer hydrogenated hydrazine diisocyanate, and polyol denatured isophorone diisocyanate. The exemplified polyisocyanate compound is preferred because it can rapidly react with a hydroxyl group, and particularly, an acid or a salt group contained in the polymer is used as a catalyst to facilitate crosslinking.

過氧化物只要可藉由加熱或光照射產生自由基活性種，使黏著劑組成物之基質聚合物的交聯進行者，即可適當地使用，考量到作業性或穩定性，以使用1分鐘半衰期溫度為80℃~160℃之過氧化物為佳，以使用90℃~140℃之過氧化物較佳。 The peroxide can be suitably used as long as the radical polymerizable species can be generated by heating or light irradiation, and the matrix polymer of the adhesive composition can be appropriately used, and the workability or stability can be considered to be used for 1 minute. A peroxide having a half-life temperature of 80 ° C to 160 ° C is preferred, and a peroxide of 90 ° C to 140 ° C is preferred.

可使用之過氧化物，可舉例如，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℃)、過癸酸三級丁酯(1分鐘半衰期溫度：103.5℃)、過氧異丁酸三級己酯(1分鐘半衰期溫度：109.1℃)、過氧特戊酸三級丁酯(1分鐘半衰期溫度：110.3℃)、二過氧化月桂醯基(1分鐘半衰期溫度：116.4℃)、過氧化二正辛醯基(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(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℃)、過氧化二苯甲醯基(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。其中，特別因交聯反應效率優異，以使用 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℃)、二過氧化月桂醯基(1分鐘半衰期溫度：116.4℃)、過氧化二苯甲醯基(1分鐘半衰期溫度：130.0℃)等為佳。 A peroxide which can be used is, for example, bis(2-ethylhexyl)peroxydicarbonate (1 minute half-life temperature: 90.6 ° C), bis(4-tert-butylcyclohexyl)peroxydicarbonate (1 minute half-life temperature: 92.1 ° C), peroxydicarbonate di(secondary butyl ester) (1 minute half-life temperature: 92.4 ° C), perchloric acid tert-butyl ester (1 minute half-life temperature: 103.5 ° C), peroxygen Tert-butyl hexanoate (1 minute half-life temperature: 109.1 ° C), tertiary butyl peroxypivalate (1 minute half-life temperature: 110.3 ° C), di-peroxidized lauryl thiol (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-ethylhexanoic acid (1 minute half-life temperature: 124.3 ° C), Bis(4-methylbenzimidyl) peroxide (1 minute half-life temperature: 128.2 ° C), benzoyl peroxide (1 minute half-life temperature: 130.0 ° C), tertiary butyl peroxybutyrate ( 1 minute half-life temperature: 136.1 ° C), 1,1-di(tri-hexylperoxy)cyclohexane (1 minute half-life temperature: 149.2 ° C), and the like. Among them, especially because of the excellent crosslinking efficiency Bis(4-tert-butylcyclohexyl)peroxydicarbonate (1 minute half-life temperature: 92.1 ° C), diperoxidic lauryl sulfhydryl (1 minute half-life temperature: 116.4 ° C), diphenylmethyl sulfonate ( 1 minute half-life temperature: 130.0 ° C) is preferred.

另外，過氧化物之半衰期係表示過氧化物之分解速度的指標，指過氧化物之殘留量剩一半的時間。於任意之時間內用以得到半衰期的分解溫度、或任意溫度下之半衰期時間，均記載於製造商目錄等中，記載於例如，日本油脂股份公司之「有機過氧化物目錄第9版(2003年5月)」等。 Further, the half-life of the peroxide is an index indicating the decomposition rate of the peroxide, and means the time remaining in the residual amount of the peroxide. The decomposition temperature for obtaining the half-life at any time or the half-life time at any temperature is described in the manufacturer's catalogue, etc., and is described, for example, in the Organic Peroxide Catalogue, Nippon Oils and Fats Corporation, 9th Edition (2003). May)) and so on.

交聯劑(D)之使用量，相對於(甲基)丙烯酸系聚合物(A)100重量份，以0.01~2重量份為佳，更以0.03~1重量份為佳。另，交聯劑(D)小於0.01重量份時，有黏著劑之凝集力不足的傾向，有加熱時產生發泡的疑慮，另一方面，大於2重量份時，耐濕性並不充分，信賴性試驗等中容易產生剝離。 The amount of the crosslinking agent (D) to be used is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 1 part by weight, per 100 parts by weight of the (meth)acrylic polymer (A). When the crosslinking agent (D) is less than 0.01 part by weight, the cohesive force of the adhesive tends to be insufficient, and there is a concern that foaming occurs during heating. On the other hand, when it is more than 2 parts by weight, the moisture resistance is insufficient. Peeling is likely to occur in a reliability test or the like.

前述異氰酸酯系交聯劑可單獨使用1種，亦可混合2種以上後使用，全體之含量，相對於前述(甲基)丙烯酸系聚合物(A)100重量份，以含有前述聚異氰酸酯化合物交聯劑0.01~2重量份為佳，以含有0.02~2重量份較佳，以含有0.05~1.5重量份更佳。可於考量到阻止凝集力、耐久性試驗的剝離等後適當地含有。 The isocyanate-based crosslinking agent may be used singly or in combination of two or more kinds thereof, and the content of the entire polyisocyanate compound may be contained in an amount of 100 parts by weight based on 100 parts by weight of the (meth)acryl-based polymer (A). The crosslinking agent is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, more preferably 0.05 to 1.5 parts by weight. It can be appropriately contained after considering the prevention of cohesive force, peeling of the durability test, and the like.

前述過氧化物可單獨使用1種，亦可混合2種以上後使用，全體之含量，相對於前述(甲基)丙烯酸系聚合物(A)100重量份，前述過氧化物係0.01~2重量份，以含有0.04~1.5重量份為佳，以含有0.05~1重量份較佳。為調整加 工性、再製性、交聯穩定性、剝離性等，可於該範圍內適當地選擇。 The peroxide may be used singly or in combination of two or more kinds, and the total amount of the peroxide is 0.01 to 2 by weight based on 100 parts by weight of the (meth)acrylic polymer (A). The portion is preferably contained in an amount of 0.04 to 1.5 parts by weight, preferably 0.05 to 1 part by weight. For adjustment plus The workability, the reworkability, the crosslinking stability, the peelability, and the like can be appropriately selected within this range.

另外，反應處理後殘留之過氧化物分解量的測定方法，係例如，可藉由HPLC(高速液體層析)測定。 Further, the method for measuring the amount of decomposition of the peroxide remaining after the reaction treatment can be measured, for example, by HPLC (High Speed Liquid Chromatography).

更具體而言，例如，取出反應處理後之黏著劑組成物各約0.2g，浸漬於乙酸乙酯10ml中，再以搖動機於25℃下，以120rpm搖動萃取3小時後，於室溫下靜置3天。接著，加入乙腈10ml，於25℃下以120rpm搖動30分鐘，將藉膜濾器(0.45μm)過濾後所得之萃取液約10μl注入HPLC後分析，可作為反應處理後的過氧化物量。 More specifically, for example, about 0.2 g of each of the adhesive compositions after the reaction treatment is taken out, immersed in 10 ml of ethyl acetate, and shake-extracted at 120 ° C for 3 hours at 25 ° C with shaking at room temperature. Allow to stand for 3 days. Next, 10 ml of acetonitrile was added, and the mixture was shaken at 120 rpm for 30 minutes at 25 ° C, and about 10 μl of the extract obtained by filtration through a membrane filter (0.45 μm) was injected into HPLC and analyzed, and the amount of peroxide after the reaction treatment was used.

此外，本發明之黏著劑組成物中亦可含有其他眾所周知的添加劑，可視使用之用途適當地添加例如，著色劑、顏料等粉體、染料、界面活性劑、可塑劑、黏著性賦予劑、表面潤潤滑劑、均染劑、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、無機或有機之填充劑、金屬粉、粒子狀、箔狀物等。又，亦可於可控制之範圍內，使用添加有還原劑之氧化還原系。 Further, the adhesive composition of the present invention may contain other well-known additives, and may be appropriately added, for example, a powder such as a coloring agent or a pigment, a dye, a surfactant, a plasticizer, an adhesive imparting agent, or a surface, depending on the intended use. Lubricating lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, particulates, foils, and the like. Further, a redox system to which a reducing agent is added may be used within a controllable range.

藉由前述黏著劑組成物可形成黏著劑層，但形成黏著劑層時，以調整交聯劑全體之添加量並充分地考慮交聯處理溫度或交聯處理時間的影響為佳。 The adhesive layer can be formed by the above-mentioned adhesive composition. However, when the adhesive layer is formed, it is preferable to adjust the addition amount of the entire crosslinking agent and sufficiently consider the influence of the crosslinking treatment temperature or the crosslinking treatment time.

藉由使用之交聯劑可調整交聯處理溫度或交聯處理時間。交聯處理溫度以170℃以下為佳。 The crosslinking treatment temperature or the crosslinking treatment time can be adjusted by using a crosslinking agent. The crosslinking treatment temperature is preferably 170 ° C or less.

又，如此之交聯處理可以黏著劑層的乾燥步驟時之溫度進行，亦可於乾燥步驟後設置其他交聯處理步驟進行。 Further, such crosslinking treatment may be carried out at a temperature at the drying step of the adhesive layer, or may be carried out after the drying step.

又，交聯處理時間可於考量到生產性或作業性後設定，通常係0.2~20分鐘左右，以0.5~10分鐘左右為佳。 Further, the crosslinking treatment time can be set after considering the productivity or workability, and is usually about 0.2 to 20 minutes, preferably about 0.5 to 10 minutes.

本發明之附黏著劑層之光學薄膜等黏著型光學構件，係於光學薄膜之至少一面藉由前述黏著劑形成有黏著劑層者。 The adhesive optical member such as the optical film to which the adhesive layer of the present invention is applied is one in which an adhesive layer is formed on at least one side of the optical film by the above-mentioned adhesive.

形成黏著劑層之方法，係藉由例如，將前述黏著劑組成物塗布於經剝離處理之分離器等，再乾燥去除聚合溶劑等，形成黏著劑層後轉印於光學薄膜的方法、或將前述黏著劑組成物塗布於光學薄膜，再乾燥去除聚合溶劑等後於光學薄膜形成黏著劑層的方法等製作。另，於塗布黏著劑時，亦可適當地重新添加聚合溶劑以外之一種以上的溶劑。 The method of forming the pressure-sensitive adhesive layer by, for example, applying the pressure-sensitive adhesive composition to a separator which has been subjected to a release treatment, drying and removing a polymerization solvent or the like, forming an adhesive layer, and transferring the film to an optical film, or The pressure-sensitive adhesive composition is applied to an optical film, dried to remove a polymerization solvent, and the like, and then formed into an optical film to form an adhesive layer. Further, when the adhesive is applied, one or more solvents other than the polymerization solvent may be appropriately added.

經剝離處理之分離器以使用矽釋離襯墊為佳。於如此之襯墊上塗布、乾燥本發明之接著劑組成物，形成黏著劑層的步驟中，使黏著劑乾燥之方法可視目的，使用適當、適切之方法。以使用過熱乾燥前述塗布膜之方法為佳。加熱乾燥溫度以40℃~200℃為佳，更佳者係50℃~180℃，特佳者為70℃~170℃。藉使加熱溫度為前述範圍，可得具優異黏著特性之黏著劑。 The stripper treated separator is preferably a release liner. In the step of coating and drying the adhesive composition of the present invention on such a liner to form an adhesive layer, the method of drying the adhesive may be carried out according to the purpose, and an appropriate and appropriate method may be used. It is preferred to use a method of drying the aforementioned coating film by using superheat. The heating and drying temperature is preferably from 40 ° C to 200 ° C, more preferably from 50 ° C to 180 ° C, and particularly preferably from 70 ° C to 170 ° C. If the heating temperature is within the above range, an adhesive having excellent adhesive properties can be obtained.

乾燥時間可使用適當、適切之時間。前述乾燥時間以5秒~20分鐘為佳，更佳者係5秒~10分鐘，特佳者為10秒~5分鐘。 The drying time can be used at an appropriate and appropriate time. The drying time is preferably from 5 seconds to 20 minutes, more preferably from 5 seconds to 10 minutes, and particularly preferably from 10 seconds to 5 minutes.

又，可於光學薄膜之表面形成固定層，施行電暈處理、電漿處理等各種易接著處理後，形成黏著劑層。又， 亦可於黏著劑層表面進行易接著處理。 Further, a fixing layer can be formed on the surface of the optical film, and various adhesive treatments such as corona treatment and plasma treatment can be performed to form an adhesive layer. also, It can also be easily treated on the surface of the adhesive layer.

黏著劑層之形成方法可使用各種方法。具體而言，可舉例如，利用輥塗布、接觸輥塗布、凹板塗布、反向塗布、輥刷、噴霧塗布、浸沾輥塗布、棒塗布、刮刀塗布、空氣刀塗布、簾狀塗布、唇狀塗布、模具塗布機等之擠壓塗布法等的方法。 Various methods can be used to form the adhesive layer. Specifically, for example, roll coating, contact roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip coating, bar coating, blade coating, air knife coating, curtain coating, lip A method such as extrusion coating or a die coating method such as a die coater.

並未特別限制黏著劑層之厚度，係例如1~100μm左右。以2~50μm為佳，較佳者是2~40μm，更佳者係5~35μm。 The thickness of the adhesive layer is not particularly limited, and is, for example, about 1 to 100 μm. It is preferably 2 to 50 μm, preferably 2 to 40 μm, and more preferably 5 to 35 μm.

於前述黏著劑層露出時，亦可以經剝離處理之片材(分離器)保護黏著劑層至實用階段。 When the adhesive layer is exposed, the adhesive layer (separator) can also be used to protect the adhesive layer to a practical stage.

分離器之構成材料，可舉例如，聚乙烯、聚丙烯、聚對苯二甲酸乙二酯、聚酯薄膜等塑膠薄膜、紙、布、不織布等多孔質材料、網、發泡片材、金屬箔、及該等之積層體等適當的薄片體等，但由表面平滑性優異之點來看，以使用塑膠薄膜為佳。 The constituent material of the separator may, for example, be a plastic film such as polyethylene, polypropylene, polyethylene terephthalate or polyester film, a porous material such as paper, cloth or non-woven fabric, a mesh, a foamed sheet or a metal. It is preferable to use a plastic film from the viewpoint of excellent surface smoothness, such as a foil and an appropriate sheet such as a laminate.

該塑膠薄膜只要為可保護前述黏著劑層即可，並未特別限定，可舉例如，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、聚氯化乙烯基薄膜、氯化乙烯基共聚物薄膜、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 as long as it can protect the pressure-sensitive adhesive layer, and examples thereof include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, and a poly Vinyl chloride film, chlorinated vinyl copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate film, etc. .

前述分離器之厚度通常係5~200μm，以5~100μm左右為佳。前述分離器中亦可視需要，進行利用矽系、氟 系、長鏈烷基系或脂肪酸醯胺系之脫模劑、二氧化矽粉等之脫模及防污處理、或塗布型、捏揉型、蒸鍍型等之抗靜電處理。特別是，藉於前述分離器表面適當地進行矽處理、長鏈烷基處理、氟處理等剝離處理，可更加提高自前述黏著劑層之剝離性。 The thickness of the separator is usually 5 to 200 μm, preferably about 5 to 100 μm. In the foregoing separator, the use of lanthanide and fluorine may also be carried out as needed. A mold release agent, a long-chain alkyl group or a fatty acid amide-based release agent, a mold release and antifouling treatment of cerium oxide powder, or an antistatic treatment such as a coating type, a kneading type, or a vapor deposition type. In particular, the peeling property from the adhesive layer can be further improved by appropriately performing a release treatment such as a ruthenium treatment, a long-chain alkyl treatment, or a fluorine treatment on the surface of the separator.

另外，於製作前述附黏著劑層之光學薄膜時使用的經剝離處理之片材，可直接作為附黏著劑層之光學薄膜的分離器使用，可使步驟簡略化。 Further, the release-treated sheet used in the production of the optical film with the adhesive layer described above can be directly used as a separator of an optical film with an adhesive layer, and the steps can be simplified.

光學薄膜，可使用用以形成液晶顯示裝置等影像顯示裝置者，並未特別限制其種類。例如，光學薄膜可舉偏光薄膜為例。偏光薄膜一般係使用於偏光片之一面或兩面具有透明保護薄膜者。 The optical film can be used to form an image display device such as a liquid crystal display device, and the type thereof is not particularly limited. For example, the optical film may be exemplified by a polarizing film. The polarizing film is generally used for a transparent protective film on one side or both sides of the polarizer.

並未特別限定偏光片，可使用各種。偏光片可舉例如，於聚乙烯醇系薄膜、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有碘或二色性染料之二色性物質後經單軸延伸者、聚乙烯醇之脫水處理物或聚氯化乙烯基之脫鹽酸處理物等多烯系配向薄膜等。該等中，亦以由聚乙烯醇系薄膜與碘等二色性物質所構成的偏光片為佳。並未特別限制該等偏光片之厚度，但一般係5~80μm左右。 The polarizer is not particularly limited, and various types can be used. The polarizer may, for example, be a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or ethylene. A hydrophilic polymer film such as a partially saponified film of a vinyl acetate copolymer adsorbs a dichroic substance of iodine or a dichroic dye, and is subjected to a uniaxial stretcher, a dehydrated material of polyvinyl alcohol or a polyvinyl chloride. A polyene-based alignment film or the like such as a hydrochloric acid-treated product. Among these, a polarizer composed of a polyvinyl alcohol-based film and a dichroic substance such as iodine is preferred. The thickness of the polarizers is not particularly limited, but is generally about 5 to 80 μm.

以碘染色聚乙烯醇系薄膜並經單軸延伸之偏光片，可藉由例如，將聚乙烯醇浸漬於碘之水溶液中染色，可延伸至原本長度的3~7倍。視需要亦可浸漬於可含有硼酸或硫酸鋅、氯化鋅等之碘化鉀等的水溶液。更亦可視需要 於染色前將聚乙烯醇系薄膜浸漬於水中水洗。藉由水洗聚乙烯醇系薄膜可去除聚乙烯醇系薄膜表面之髒汙或洗淨抗結塊劑，亦有使聚乙烯醇系薄膜膨脹，防止染色不均等不均一的效果。延伸可於經碘染色後進行，亦可一面染色一面延伸，亦可於延伸後以碘染色。於硼酸或碘化鉀等水溶液或水浴中亦可延伸。 A polarizer which is uniaxially dyed with a iodine-dyed polyvinyl alcohol-based film can be dyed to an extent of 3 to 7 times the original length by, for example, immersing the polyvinyl alcohol in an aqueous solution of iodine. If necessary, it may be immersed in an aqueous solution containing potassium iodide such as boric acid, zinc sulfate or zinc chloride. More also needs The polyvinyl alcohol-based film was immersed in water and washed with water before dyeing. By washing the polyvinyl alcohol-based film with water, the surface of the polyvinyl alcohol-based film can be removed or the anti-caking agent can be washed, and the polyvinyl alcohol-based film can be expanded to prevent unevenness in dyeing unevenness. The extension may be carried out after iodine dyeing, or may be extended on one side of the stain, or may be stained with iodine after extension. It can also be extended in an aqueous solution or a water bath such as boric acid or potassium iodide.

《薄型偏光片》 Thin Polarizer

前述偏光片可使用厚度10μm以下之薄型偏光片。由薄型化之觀點來看，該厚度以1~7μm為佳。如此之薄型偏光片之厚度不均少，能見度優異，又因尺寸變化少，故耐久性優異，且作為偏光薄膜之厚度由期待薄型化之點來看係為佳。然而，一般而言，隨著偏光薄膜變薄，將不易兼具再製性與長期保管後之耐久性，特別是起因於使用薄型偏光片，偏光薄膜變薄時，於再製時特別因偏光薄膜容易斷裂，故實際情況係非常不易兼具再製性與長期保管後之耐久性。相對於此，由本發明之黏著劑組成物所得的黏著劑層即便再製性提升，長期保管後之耐久性仍未下降，故由本發明之黏著劑組成物所得的黏著劑層特別可作為具有於一側或兩側積層有透明保護薄膜之薄型偏光片的附黏著劑層之偏光薄膜用的黏著劑層。 As the polarizer, a thin polarizer having a thickness of 10 μm or less can be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. Such a thin polarizer has a small thickness unevenness, is excellent in visibility, and has little dimensional change, so that it is excellent in durability, and it is preferable that the thickness of the polarizing film is expected to be thinner. However, in general, as the polarizing film becomes thinner, it is difficult to achieve both remanufacturability and durability after long-term storage. In particular, when a polarizing film is thinned by using a thin polarizer, it is easy to be particularly polarized film during remanufacturing. Breaking, so the actual situation is very difficult to have both remanufacturing and durability after long-term storage. On the other hand, the adhesive layer obtained from the adhesive composition of the present invention has an improved durability after long-term storage, and the adhesive layer obtained from the adhesive composition of the present invention is particularly useful as one. An adhesive layer for a polarizing film with an adhesive layer of a thin polarizer having a transparent protective film laminated on the side or both sides.

薄型之偏光片可舉具代表性之日本專利特開昭51-069644號公報或日本專利特開2000-338329號公報、WO2010/100917號手冊、PCT/JP2010/001460之說明書、或日本專利特願2010-269002號說明書或日本專利特願 2010-263692號說明書所記載的薄型偏光膜為例。該等薄型偏光膜可藉由將聚乙烯醇系樹脂(以下，亦稱作PVA系樹脂)層與延伸用樹脂基材於積層體之狀態延伸的步驟與染色的步驟之製法而得。若為該製法，即使PVA系樹脂層為薄，藉由延伸用樹脂基材支撐，將未有因延伸造成斷裂的不良情形，而可延伸。 The thin type of polarizer can be exemplified by the Japanese Patent Application Laid-Open No. Hei 51-069644, the Japanese Patent Publication No. 2000-338329, the WO2010/100917 manual, the PCT/JP2010/001460, or the Japanese Patent Patent Application. 2010-269002 specification or Japanese patent The thin polarizing film described in the specification of 2010-263692 is taken as an example. These thin polarizing films can be obtained by a step of stretching a polyvinyl alcohol-based resin (hereinafter also referred to as a PVA-based resin) layer and a resin substrate for stretching in a state of a laminate, and a method of dyeing. According to this production method, even if the PVA-based resin layer is thin, it is supported by the resin substrate for stretching, and it can be stretched without causing breakage due to stretching.

前述薄型偏光膜，於包含積層體之狀態下延伸的步驟與染色的步驟之製法中，由可高倍率地延伸提升偏光性能的觀點來看，以如WO2010/100917號手冊、PCT/JP2010/001460之說明書、或日本專利特願2010-269002號說明書或日本專利特願2010-263692號說明書記載的包含於硼酸水溶液中延伸之步驟的製法所得者為佳，特別是，如日本專利特願2010-269002號說明書或日本專利特願2010-263692號說明書記載之藉由包含於硼酸水溶液中延伸前補助地於空中延伸的步驟之製法所得者為佳。 The above-mentioned thin polarizing film, in the step of extending the state including the laminated body and the step of dyeing, from the viewpoint of being able to extend the polarizing performance at a high magnification, as in the manual of WO2010/100917, PCT/JP2010/001460 The method of the method of the step of extending in an aqueous solution of boric acid described in the specification of Japanese Patent Application No. 2010-269002 or the specification of Japanese Patent Application No. 2010-263692 is preferred, in particular, as disclosed in Japanese Patent Application No. 2010- It is preferred that the method described in the specification of No. 269002 or Japanese Patent Application No. 2010-263692 is carried out by a method comprising the step of extending in the air before extending in an aqueous solution of boric acid.

前述PCT/JP2010/001460說明書中記載之薄型高機能偏光膜係與樹脂基材一體地製膜，且由配向有二色性物質之PVA系樹脂所構成的厚度係7μm以下之薄型高機能偏光膜，具有單質透射率42.0%以上及偏光度99.95%以上的光學特性。 The thin high-performance polarizing film described in the above-mentioned PCT/JP2010/001460 is a thin high-performance polarizing film having a thickness of 7 μm or less, which is formed by integrally forming a film with a resin substrate and having a PVA resin having a dichroic material. It has an optical characteristic of a single transmittance of 42.0% or more and a polarization degree of 99.95% or more.

前述薄型高機能偏光膜可藉由下述製造，於至少具有20μm厚度之樹脂基材藉由塗布及乾燥PVA系樹脂，生成PVA系樹脂層，將經生成之PVA系樹脂層浸漬於二色性物質的染色液中，使PVA系樹脂層吸附二色性物質，將吸附 有二色性物質之PVA系樹脂層於硼酸水溶液中與樹脂基材一體地延伸至總延伸倍率為原本長度之5倍以上。 The thin high-performance polarizing film can be produced by coating and drying a PVA-based resin on a resin substrate having a thickness of at least 20 μm to form a PVA-based resin layer, and immersing the formed PVA-based resin layer in dichroism. In the dyeing solution of the substance, the PVA-based resin layer adsorbs the dichroic substance and adsorbs The PVA-based resin layer having a dichroic substance is integrally extended with the resin substrate in a boric acid aqueous solution to a total stretching ratio of 5 times or more of the original length.

又，製造包含配向有二色性物質之薄型高機能偏光膜的積層體薄膜之方法，係包含下述步驟，而可製造前述薄型高機能偏光膜；該製造方法之步驟為：生成包含至少具有20μm厚度之樹脂基材，與於樹脂基材之一面塗布及乾燥含PVA系樹脂的水溶液所形成的PVA系樹脂層之積層體薄膜的步驟；將包含樹脂基材與於樹脂基材之一面形成的PVA系樹脂層之前述積層體薄膜浸漬於包含二色性物質的染色液中，使積層體薄膜所含之PVA系樹脂層吸附二色性物質的步驟；將包含吸附有二色性物質之PVA系樹脂層的前述積層體薄膜於硼酸水溶液中延伸至總延伸倍率為原本長度之5倍以上的步驟；及藉由一體地延伸吸附有二色性物質之PVA系樹脂層與樹脂基材，於樹脂基材之一面製造由配向有二色性物質的PVA系樹脂層所構成之厚度7μm以下、並具有單質透射率42.0%以上且偏光度99.95%以上之光學特性的薄型高機能偏光膜之製造積層體薄膜的步驟。 Further, a method for producing a laminate film comprising a thin high-performance polarizing film having a dichroic material, comprising the steps of: producing the thin high-performance polarizing film; the manufacturing method comprises the steps of: generating at least a resin substrate having a thickness of 20 μm and a step of coating and drying a laminate film of a PVA-based resin layer formed of an aqueous solution containing a PVA resin on one surface of the resin substrate; forming a resin substrate and a surface of the resin substrate The laminated film of the PVA-based resin layer is immersed in a dyeing liquid containing a dichroic substance, and the PVA-based resin layer contained in the laminated thin film is adsorbed with a dichroic substance; and the dichroic substance is adsorbed; a step of extending the laminated film of the PVA-based resin layer in a boric acid aqueous solution to a total stretching ratio of at least 5 times the original length; and integrally extending the PVA-based resin layer and the resin substrate to which the dichroic substance is adsorbed; A PVA-based resin layer having a dichroic material is formed on one surface of the resin substrate to have a thickness of 7 μm or less, and has a single-element transmittance of 42.0% or more and a degree of polarization of 99.95%. A step of manufacturing a thin high performance polarizing optical characteristics of the laminate film.

本發明中，厚度10μm以下之偏光片，係由配向有二色性物質之PVA系樹脂所構成的連續網(continuous web)之偏光膜，包含製膜於熱可塑性樹脂基材之聚乙烯醇系樹脂層的積層體，可使用藉由空中補助延伸與硼酸水中延伸所構成之2階段延伸步驟延伸所得者。前述熱可塑性樹脂基材以非晶性酯系熱可塑性樹脂基材或結晶性酯系熱可塑性樹脂基材為佳。 In the present invention, the polarizer having a thickness of 10 μm or less is a continuous web polarizing film composed of a PVA resin having a dichroic material, and includes a polyvinyl alcohol film formed on a thermoplastic resin substrate. The laminate of the resin layer can be obtained by using a two-stage extension step consisting of an air-assisted extension and an extension of boric acid water. The thermoplastic resin substrate is preferably a non-crystalline ester-based thermoplastic resin substrate or a crystalline ester-based thermoplastic resin substrate.

前述特願2010-269002號說明書或特願2010-263692號說明書之薄型偏光膜係由配向有二色性物質之PVA系樹脂所構成的連續網之偏光膜，包含製膜於非晶性酯系熱可塑性樹脂基材之PVA系樹脂層的積層體，藉由空中補助延伸與硼酸水中延伸所構成之2階段延伸步驟延伸，可作成10μm以下的厚度。如此之薄型偏光膜以單質透射率為T、以偏光度為P時，以具有滿足P>-(100.929T-42.4-1)×100(但，T<42.3)、及P≧99.9(但，T≧42.3)之條件的光學特性者為佳。 The thin polarizing film of the specification of the Japanese Patent Application No. 2010-269002 or the specification of the Japanese Patent Application No. 2010-263692 is a polarizing film of a continuous web composed of a PVA resin having a dichroic material, and comprises a film formed on a non-crystalline ester system. The laminate of the PVA-based resin layer of the thermoplastic resin substrate can be formed to have a thickness of 10 μm or less by extending in a two-stage extension step of extending the air-assisted extension and boric acid water. Such a thin polarizing film has a single transmittance of T and a polarization degree of P, and has a P>-(10 0.929T-42.4 -1)×100 (however, T<42.3), and P≧99.9 (but The optical characteristics of the condition of T≧42.3) are preferred.

具體而言，前述薄型偏光膜可藉由下述之薄型偏光膜之製造方法製造，包含藉由對製膜於連續網之非晶性酯系熱可塑性樹脂基材的PVA系樹脂層進行空中高溫延伸，生成由經配向之PVA系樹脂層所構成的延伸中間生成物之步驟；藉由對延伸中間生成物吸附二色性物質，生成由配向有二色性物質(以碘或碘與有機染料之混合物為佳)之PVA系樹脂層所構成的著色中間生成物之步驟；及藉由對著色中間生成物進行硼酸水中延伸，生成由經配向有二色性物質之PVA系樹脂層所構成的厚度10μm以下之偏光膜的步驟。 Specifically, the thin polarizing film can be produced by the following method for producing a thin polarizing film, and includes a high temperature in the air by a PVA-based resin layer of a non-crystalline ester-based thermoplastic resin substrate formed on a continuous web. Extending to form an extended intermediate product composed of the aligned PVA-based resin layer; by adsorbing a dichroic substance to the extended intermediate product, a dichroic substance (with iodine or iodine and an organic dye) is formed a step of forming a colored intermediate product of a PVA-based resin layer of a mixture; and forming a PVA-based resin layer having a dichroic substance by stretching the colored intermediate product in water in boric acid A step of a polarizing film having a thickness of 10 μm or less.

於該製造方法中，利用空中高溫延伸與硼酸水中延伸，製膜於非晶性酯系熱可塑性樹脂基材之PVA系樹脂層的總延伸倍率以5倍以上為佳。用以硼酸水中延伸之硼酸水溶液的液溫可設為60℃以上。硼酸水溶液中於延伸著色中間生成物前，以對著色中間生成物施行不溶解化處理為 佳，此時，以藉由將前述著色中間生成物浸漬於液溫不大於40℃之硼酸水溶液進行為佳。前述非晶性酯系熱可塑性樹脂基材可為共聚合有間苯二甲酸之共聚合聚對苯二甲酸乙二酯、共聚合有環己烷二甲醇之共聚合聚對苯二甲酸乙二酯或包含其他共聚合聚對苯二甲酸乙二酯的非晶性聚對苯二甲酸乙二酯，以由透明樹脂所構成者為佳，其厚度可為製膜之PVA系樹脂層厚度的7倍以上。又，空中高溫延伸之延伸倍率以3.5倍以下為佳，空中高溫延伸之延伸溫度以PVA系樹脂的玻璃轉移溫度以上，具體而言，以95℃~150℃之範圍為佳。以自由端單軸延伸進行空中高溫延伸時，製膜於非晶性酯系熱可塑性樹脂基材之PVA系樹脂層的總延伸倍率以5倍以上7.5倍以下為佳。又，以固定端單軸延伸進行空中高溫延伸時，製膜於非晶性酯系熱可塑性樹脂基材之PVA系樹脂層的總延伸倍率以5倍以上8.5倍以下為佳。 In the production method, it is preferable that the PVA-based resin layer formed on the amorphous ester-based thermoplastic resin substrate has a total stretching ratio of 5 times or more by stretching in the air at a high temperature and extending in boric acid water. The liquid temperature of the boric acid aqueous solution extended in boric acid water can be set to 60 ° C or more. In the aqueous boric acid solution, the insoluble treatment of the colored intermediate product is performed before the coloring intermediate product is extended. Preferably, in this case, it is preferred to immerse the colored intermediate product in a boric acid aqueous solution having a liquid temperature of not more than 40 °C. The amorphous ester-based thermoplastic resin substrate may be a copolymerized polyethylene terephthalate copolymerized with isophthalic acid, or a copolymerized polyethylene terephthalate copolymerized with cyclohexanedimethanol. An ester or an amorphous polyethylene terephthalate containing other copolymerized polyethylene terephthalate, preferably composed of a transparent resin, the thickness of which may be the thickness of the PVA-based resin layer of the film-forming film. More than 7 times. Further, the stretching ratio in the air high temperature extension is preferably 3.5 times or less, and the stretching temperature in the air high temperature stretching is equal to or higher than the glass transition temperature of the PVA resin, and specifically, it is preferably in the range of 95 ° C to 150 ° C. When the high-temperature extension in the air is carried out by uniaxial stretching at the free end, the total stretching ratio of the PVA-based resin layer formed on the amorphous ester-based thermoplastic resin substrate is preferably 5 times or more and 7.5 times or less. Further, when the high-temperature extension in the air is carried out by the uniaxial stretching at the fixed end, the total stretching ratio of the PVA-based resin layer formed on the amorphous ester-based thermoplastic resin substrate is preferably 5 times or more and 8.5 times or less.

更具體而言，可藉由以下方法製造薄型偏光膜。 More specifically, a thin polarizing film can be produced by the following method.

製作共聚合有6mol%之間苯二甲酸的間苯二甲酸共聚合聚對苯二甲酸乙二酯(非晶性PET)之連續網的基材。非晶性PET之玻璃轉移溫度係75℃。如以下地製作由連續網之非晶性PET基材與聚乙烯醇(PVA)層所構成的積層體。又，PVA之玻璃轉移溫度係80℃。 A substrate in which a continuous web of ethylene terephthalate copolymerized polyethylene terephthalate (amorphous PET) was copolymerized with 6 mol% of phthalic acid was produced. The glass transition temperature of amorphous PET is 75 °C. A laminate comprising a continuous PET amorphous PET substrate and a polyvinyl alcohol (PVA) layer was produced as follows. Further, the glass transition temperature of PVA was 80 °C.

準備200μm厚之非晶性PET基材，與於水溶解有聚合度1000以上、皂化度99%以上之PVA粉末的4~5%濃度之PVA水溶液。接著，於200μm厚之非晶性PET基材塗布PVA水溶液，以50~60℃之溫度乾燥，得到於非晶性PET基材製 膜有7μm厚之PVA層的積層體。 An amorphous PET substrate having a thickness of 200 μm was prepared, and a PVA aqueous solution having a concentration of 4 to 5% of a PVA powder having a polymerization degree of 1,000 or more and a degree of saponification of 99% or more was dissolved in water. Next, a PVA aqueous solution was applied to a 200 μm thick amorphous PET substrate, and dried at a temperature of 50 to 60 ° C to obtain an amorphous PET substrate. The film had a laminate of a 7 μm thick PVA layer.

將包含7μm厚之PVA層的積層體經由包含空中補助延伸及硼酸水中延伸之2階段延伸步驟的以下步驟，製造3μm厚之薄型高機能偏光膜。藉由第1段之空中補助延伸步驟，將包含7μm厚之PVA層的積層體與非晶性PET基材一體地延伸，生成包含5μm厚之PVA層的延伸積層體。具體而言，該延伸積層體係將包含7μm厚之PVA層的積層體放入配備於設定成130℃之延伸溫度環境的烘箱之延伸裝置，自由端單軸延伸至延伸倍率為1.8倍者。藉由該延伸處理，將延伸積層體所含之PVA層改變成配向有PVA分子的5μm厚之PVA層。 A laminate of a 7 μm thick PVA layer was subjected to the following steps including a two-stage extension step of airborne extension extension and boric acid water extension to produce a thin high-performance polarizing film of 3 μm thickness. The laminate of the PVA layer having a thickness of 7 μm was integrally extended with the amorphous PET substrate by the air-assisted extension step of the first stage to form an extended laminate including a PVA layer having a thickness of 5 μm. Specifically, the extended laminated system placed a laminate including a 7 μm thick PVA layer in an extension device equipped with an oven set to an extended temperature environment of 130 ° C, and the free end was uniaxially extended to a stretching ratio of 1.8 times. By this stretching treatment, the PVA layer contained in the extended laminated body was changed to a 5 μm thick PVA layer which was provided with PVA molecules.

接著，藉由染色步驟，生成於配向有PVA分子之5μm厚的PVA層吸附有碘之著色積層體。具體而言，該著色積層體係藉由將延伸積層體浸漬於包含液溫30℃之碘及碘化鉀的染色液中任意時間，使延伸積層體所含之PVA層吸附有碘，使最終生成之構成高機能偏光膜的PVA層之單質透射率為40~44%者。於本步驟中，染色液係以水作為溶劑，將碘濃度設為0.12~0.30重量%之範圍內，將碘化鉀濃度設為0.7~2.1重量%之範圍內。碘與碘化鉀之濃度比係1比7。換言之，為使碘溶解於水係需碘化鉀。更詳而言之，藉將延伸積層體浸漬於碘濃度0.30重量%、碘化鉀濃度2.1重量%之染色液60秒鐘，生成於配向有PVA分子的5μm厚度之PVA層吸附有碘的著色積層體。 Next, a coloring layer body in which iodine was adsorbed on a 5 μm-thick PVA layer having PVA molecules was formed by a dyeing step. Specifically, the colored layered system is formed by immersing the extended layered body in a dyeing liquid containing iodine and potassium iodide at a liquid temperature of 30 ° C for any time, so that the PVA layer contained in the extended laminated body adsorbs iodine to form a final composition. The PVA layer of the high-performance polarizing film has a single-element transmittance of 40 to 44%. In this step, the dyeing liquid is water as a solvent, the iodine concentration is in the range of 0.12 to 0.30% by weight, and the potassium iodide concentration is in the range of 0.7 to 2.1% by weight. The concentration ratio of iodine to potassium iodide is 1 to 7. In other words, potassium iodide is required to dissolve iodine in the water system. More specifically, the extended layered body was immersed in a dyeing liquid having an iodine concentration of 0.30% by weight and a potassium iodide concentration of 2.1% by weight for 60 seconds to form a colored layered body in which iodine was adsorbed on a PVA layer having a thickness of 5 μm in which PVA molecules were aligned. .

此外，藉由第2階段之硼酸水中延伸步驟，更可 將著色積層體與非晶性PET基材一體地延伸，生成包含構成3μm厚之高機能偏光膜的PVA層之光學薄膜積層體。具體而言，該光學薄膜積層體係將著色積層體放入配備於設定成包含硼酸與碘化鉀之液溫範圍60~85℃的硼酸水溶液之處理裝置的延伸裝置，自由端單軸延伸至延伸倍率為3.3倍者。更詳細而言，硼酸水溶液之液溫係65℃。又，相對於水100重量份將硼酸含量設為4重量份，相對於水100重量份將碘化鉀含量設為5重量份。於本步驟中，首先將經調整碘吸著量之著色積層體浸漬於硼酸水溶液5~10秒鐘。之後，將該著色積層體直接通過配置於處理裝置之延伸裝置的圓周速度相異之複數組軋輥間，自由端單軸延伸30~90秒鐘，使延伸倍率為3.3倍。藉由該延伸處理，經吸附之碘作為聚碘離子錯合物，將著色積層體中所含之PVA層改變成於單向高階地配向之3μm厚的PVA層。該PVA層將構成光學薄膜積層體之高機能偏光膜。 Further, by the step of extending the boric acid water in the second stage, the colored layered product and the amorphous PET substrate can be integrally extended to form an optical film layered body including a PVA layer constituting a high functional polarizing film having a thickness of 3 μm. Specifically, the optical film layering system places the colored layered body in an extension device equipped with a treatment device set to a boric acid aqueous solution having a liquid temperature range of 60 to 85 ° C containing boric acid and potassium iodide, and a free end uniaxial Extend to a stretch ratio of 3.3 times. More specifically, the liquid temperature of the aqueous boric acid solution was 65 °C. Further, the boric acid content was 4 parts by weight based on 100 parts by weight of water, and the potassium iodide content was 5 parts by weight based on 100 parts by weight of water. In this step, the colored layered body having the adjusted iodine absorption amount is first immersed in a boric acid aqueous solution for 5 to 10 seconds. Thereafter, the colored laminated body was directly passed between the multiple array rolls having different circumferential speeds disposed in the stretching device of the processing apparatus, and the free end was uniaxially stretched for 30 to 90 seconds to have a stretching ratio of 3.3 times. By this stretching treatment, the adsorbed iodine is used as the iodonium ion complex, and the PVA layer contained in the colored layered body is changed into a 3 μm thick PVA layer which is aligned in a unidirectional high order. The PVA layer will constitute a high-performance polarizing film of an optical film laminate.

雖非光學薄膜積層體之製造所需步驟，但以藉由洗淨步驟，將光學薄膜積層體自硼酸水溶液取出，以碘化鉀水溶液洗淨附著於經製膜於非晶性PET基材之3μm厚的PVA層表面之硼酸為佳。之後，利用60℃之暖風進行乾燥步驟，乾燥洗淨之光學薄膜積層體。另，洗淨步驟係用以解決硼酸析出等外觀不良的步驟。 Although the steps required for the production of the optical film laminate are not carried out, the optical film laminate is taken out from the aqueous boric acid solution by a washing step, and washed with a potassium iodide aqueous solution to adhere to a 3 μm thick film formed on the amorphous PET substrate. The boric acid on the surface of the PVA layer is preferred. Thereafter, the drying step was carried out by using a warm air of 60 ° C to dry the washed optical film laminate. Further, the washing step is a step of solving the appearance defect such as boric acid precipitation.

同樣地雖非光學薄膜積層體之製造所需步驟，但亦可藉由貼合及/或轉印步驟，一面於製膜於非晶性PET基材之3μm厚的PVA層表面塗布接著劑，一面貼合80μm厚之 三乙酸纖維素薄膜後，剝離非晶性PET基材，將3μm厚之PVA層轉印至80μm厚的三乙酸纖維素薄膜。 Similarly, although the steps required for the production of the optical film laminate are not required, the adhesive may be applied to the surface of the 3 μm thick PVA layer formed on the amorphous PET substrate by a bonding and/or transfer step. One side is attached to 80μm thick After the cellulose triacetate film, the amorphous PET substrate was peeled off, and a 3 μm thick PVA layer was transferred to a 80 μm thick cellulose triacetate film.

[其他步驟] [other steps]

前述薄型偏光膜之製造方法除了前述步驟以外，亦可包含其他步驟。其他步驟可舉不溶解化步驟、交聯步驟、乾燥(水分率之調節)步驟等為例。其他步驟可於任意適當之時機進行。 The method for producing the above-mentioned thin polarizing film may include other steps in addition to the above steps. Other steps may be exemplified by a non-dissolving step, a cross-linking step, a drying (adjustment of moisture content) step, and the like. Other steps can be performed at any suitable time.

前述不溶解化步驟具代表性的係藉由將PVA系樹脂層浸漬於硼酸水溶液地進行。藉由施行不溶解化處理，可賦與PVA系樹脂層耐水性。該硼酸水溶液之濃度，相對於水100重量份，以1重量份~4重量份為佳。不溶解化浴(硼酸水溶液)之液溫以20℃~50℃為佳。以於製作積層體後、染色步驟或水中延伸步驟前進行不溶解化步驟為佳。 The insolubilization step is typically carried out by immersing the PVA-based resin layer in an aqueous boric acid solution. By performing the insolubilization treatment, the water resistance of the PVA-based resin layer can be imparted. The concentration of the aqueous boric acid solution is preferably from 1 part by weight to 4 parts by weight per 100 parts by weight of water. The liquid temperature of the insoluble bath (aqueous boric acid solution) is preferably 20 ° C to 50 ° C. It is preferred to carry out the insolubilization step after the production of the laminate, the dyeing step or the water stretching step.

前述交聯步驟具代表性的係藉由將PVA系樹脂層浸漬於硼酸水溶液地進行。藉由施行交聯處理，可賦與PVA系樹脂層耐水性。該硼酸水溶液之濃度，相對於水100重量份，以1重量份~4重量份為佳。又，於前述染色步驟後進行交聯步驟時，更以混合碘化物為佳。藉由混合碘化物，可抑制吸附於PVA系樹脂層之碘的溶出。碘化物之混合量，相對於水100重量份，係1重量份~5重量份。碘化物之具體例係如上述。交聯浴(硼酸水溶液)之液溫以20℃~50℃為佳。以於前述第2硼酸水中延伸步驟之前進行交聯步驟為佳。於較佳之實施形態中，係依序進行染色步驟、交聯步驟及第2硼酸水中延伸步驟。 The crosslinking step is typically carried out by immersing the PVA-based resin layer in an aqueous boric acid solution. The water resistance of the PVA-based resin layer can be imparted by performing the crosslinking treatment. The concentration of the aqueous boric acid solution is preferably from 1 part by weight to 4 parts by weight per 100 parts by weight of water. Further, when the crosslinking step is carried out after the dyeing step, it is preferred to further mix the iodide. By mixing the iodide, elution of iodine adsorbed to the PVA-based resin layer can be suppressed. The compounding amount of the iodide is 1 part by weight to 5 parts by weight based on 100 parts by weight of water. Specific examples of the iodide are as described above. The liquid temperature of the crosslinking bath (aqueous boric acid solution) is preferably 20 ° C to 50 ° C. It is preferred to carry out the crosslinking step before the step of extending the second boric acid water. In a preferred embodiment, the dyeing step, the crosslinking step, and the second boric acid water extension step are sequentially performed.

構成透明保護薄膜之材料，可使用例如，透明性、機械的強度、熱穩定性、水份截取性、等向性等優異之熱可塑性樹脂。如此之熱可塑性樹脂的具體例，可舉例如，三乙酸纖維素等纖維素樹脂、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(降莰烯系樹脂)、聚芳酯樹脂、聚苯乙烯樹脂、聚乙烯醇樹脂、及該等之混合物。另，偏光片之一側係藉由接著劑層貼合透明保護薄膜，於另一側則可使用(甲基)丙烯酸系、胺甲酸酯系、丙烯酸胺甲酸酯系、環氧系、矽系等熱硬化性樹脂或紫外線硬化型樹脂，作為透明保護薄膜。透明保護薄膜中亦可含有1種以上任意適當之添加劑。添加劑可舉例如，紫外線吸收劑、抗氧化劑、潤滑劑、可塑劑、脫模劑、褪色劑、阻焰劑、核劑、抗靜電劑、顏料、著色劑等。透明保護薄膜中之前述熱可塑性樹脂的含量以50~100重量%為佳，較佳者是50~99重量%，更佳者係60~98重量%，特佳者為70~97重量%。透明保護薄膜中前述熱可塑性樹脂的含量為50重量%以下時，有熱可塑性樹脂未能充分地顯現原本具有之高透明性等的疑慮。 As the material constituting the transparent protective film, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, water interception property, isotropic property, and the like can be used. Specific examples of such a thermoplastic resin include a cellulose resin such as cellulose triacetate, a polyester resin, a polyether oxime resin, a polyfluorene resin, a polycarbonate resin, a polyamide resin, and a polyimide resin. A polyolefin resin, a (meth)acrylic resin, a cyclic polyolefin resin (northene-based resin), a polyarylate resin, a polystyrene resin, a polyvinyl alcohol resin, and a mixture thereof. Further, on one side of the polarizer, a transparent protective film is bonded by an adhesive layer, and on the other side, (meth)acrylic, urethane, urethane, epoxy, or the like can be used. A thermosetting resin such as a lanthanum resin or an ultraviolet curable resin is used as a transparent protective film. One or more optional additives may be contained in the transparent protective film. The additives may, for example, be ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, fading agents, flame retardants, nucleating agents, antistatic agents, pigments, colorants and the like. The content of the thermoplastic resin in the transparent protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. When the content of the thermoplastic resin in the transparent protective film is 50% by weight or less, there is a concern that the thermoplastic resin does not sufficiently exhibit high transparency and the like.

又，光學薄膜可舉用以形成反射板或反透射板、阻滯板(包含1/2或1/4等波長板)、視角補償薄膜、亮度提升薄膜等液晶顯示裝置等之光學層者為例。該等可單獨作為光學薄膜使用，亦可於實際使用時於前述偏光薄膜積層1層或2層以上使用。 Further, the optical film may be an optical layer such as a liquid crystal display device such as a reflective plate or a reverse transmission plate, a retardation plate (including a 1/2 or 1/4 wavelength plate), a viewing angle compensation film, or a brightness enhancement film. example. These may be used alone as an optical film, or may be used in one or two or more layers of the polarizing film layer in actual use.

於偏光薄膜積層有前述光學層之光學薄膜，可於液晶顯示裝置等製造過程中以依序個別積層的方式形成，但預先積層作成光學薄膜者，有品質穩定性或組裝作業等優異，可提升液晶顯示裝置等製造步驟之優點。積層可使用黏著層等適當之接著方法。於接著前述偏光薄膜與其他光學層時，該等之光學軸可對應於目的之相位差特性等為適當的配置角度。 The optical film in which the optical layer is laminated on the polarizing film can be formed by sequentially laminating in a manufacturing process such as a liquid crystal display device. However, if an optical film is laminated in advance, it is excellent in quality stability and assembly work, and can be improved. Advantages of manufacturing steps such as a liquid crystal display device. As the laminate, an appropriate bonding method such as an adhesive layer can be used. When the polarizing film and the other optical layers are continued, the optical axes may correspond to the phase difference characteristics of the object and the like as an appropriate arrangement angle.

本發明之附黏著劑層之光學薄膜可較佳地使用以形成液晶顯示裝置等各種影像顯示裝置。液晶顯示裝置之形成係依據習知地進行。換言之，液晶顯示裝置一般係藉由適當地組裝液晶顯示元件等顯示面板與附黏著劑層之光學薄膜、及視需要之照明系統等構成零件後，裝入驅動電路等形成，於本發明中除了使用利用本發明之附黏著劑層之光學薄膜以外，並未特別限定，可依據習知進行。液晶顯示元件可使用例如，TN型或STN型、π型、VA型、IPS型等任意型態之任一種者。 The optical film with an adhesive layer of the present invention can be preferably used to form various image display devices such as liquid crystal display devices. The formation of the liquid crystal display device is carried out in accordance with a conventional method. In other words, the liquid crystal display device is generally formed by appropriately assembling a display panel such as a liquid crystal display element, an optical film with an adhesive layer, and an illumination system as necessary, and then incorporating the components into a drive circuit or the like, in addition to the present invention. The optical film using the adhesive layer of the present invention is not particularly limited and can be carried out according to conventional methods. For the liquid crystal display element, for example, any of the TN type, the STN type, the π type, the VA type, and the IPS type can be used.

可形成於液晶顯示元件等顯示面板之一側或兩側配置有附黏著劑層之光學薄膜的液晶顯示裝置、或於照明系統使用有背光源或反射板者等適當之液晶顯示裝置。此時，本發明之光學薄膜可設置於液晶顯示元件等顯示面板的一側或兩側。於兩側設置光學薄膜時，該等可相同亦可相異。此外，於形成液晶顯示裝置時，可於適當之位置配置1層或2層以上的例如，擴散板、防眩光層、抗反射膜、保護板、稜鏡陣列、透鏡陣列片材、光擴散板、背光源等適當之 零件。 A liquid crystal display device in which an optical film with an adhesive layer is disposed on one side or both sides of a display panel such as a liquid crystal display element, or a liquid crystal display device such as a backlight or a reflector used in an illumination system can be used. In this case, the optical film of the present invention may be disposed on one side or both sides of a display panel such as a liquid crystal display element. When the optical film is disposed on both sides, the same may be the same or different. Further, when forming a liquid crystal display device, one or two or more layers, for example, a diffusion plate, an anti-glare layer, an anti-reflection film, a protective plate, a tantalum array, a lens array sheet, and a light diffusing plate can be disposed at appropriate positions. , backlight, etc. Components.

實施例 Example

以下，藉由實施例具體地說明本發明，但本發明並非受該等實施例所限定者。另，各例中之份及%均係重量基準。以下未特別規定之室溫放置條件全係23℃ 65%RH。 Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited by the examples. In addition, the parts and % in each case are based on the weight basis. The room temperature setting conditions not specifically defined below are all 23 ° C 65% RH.

<(甲基)丙烯酸系聚合物(A)之重量平均分子量的測定> <Measurement of Weight Average Molecular Weight of (Meth)Acrylic Polymer (A)>

(甲基)丙烯酸系聚合物(A)之重量平均分子量係藉由GPC(凝膠滲透層析法)測定。 The weight average molecular weight of the (meth)acrylic polymer (A) is measured by GPC (gel permeation chromatography).

．分析裝置：Tosoh社製、HLC-8120GPC . Analytical device: Tosoh company, HLC-8120GPC

．管柱：Tosoh社製、G7000HXL+GMHXL+GMHXL . Pipe column: made by Tosoh, G7000H XL +GMH XL +GMH XL

．管柱大小：各7.8mm ×30cm共90cm . Column size: 7.8mm each ×30cm total 90cm

．管柱溫度：40℃ . Column temperature: 40 ° C

．流量：0.8ml/min . Flow rate: 0.8ml/min

．注入量：100μl . Injection volume: 100μl

．溶析液：四氫呋喃 . Lysate: tetrahydrofuran

．檢測器：微差折射計(RI) . Detector: differential refractometer (RI)

．標準試料：聚苯乙烯 . Standard sample: polystyrene

<聚醚化合物(B)之數量平均分子量的測定> <Measurement of Number Average Molecular Weight of Polyether Compound (B)>

聚醚化合物(B)之數量平均分子量係藉由GPC(凝膠滲透層析法)測定。 The number average molecular weight of the polyether compound (B) is determined by GPC (gel permeation chromatography).

．分析裝置：Tosoh社製，HLC-8120GPC . Analytical device: manufactured by Tosoh, HLC-8120GPC

．管柱：TSKgel,SuperHZM-H/HZ4000/HZ2000 . Column: TSKgel, SuperHZM-H/HZ4000/HZ2000

．管柱大小：6.0mmI.D.×150mm . Column size: 6.0mmI.D.×150mm

．管柱溫度：40℃ . Column temperature: 40 ° C

．流量：0.6ml/min . Flow rate: 0.6ml/min

．注入量：20μl . Injection volume: 20μl

．溶析液：四氫呋喃 . Lysate: tetrahydrofuran

．檢測器：微差折射計(RI) . Detector: differential refractometer (RI)

．標準試料：聚苯乙烯 . Standard sample: polystyrene

(偏光薄膜1(SEG)之作成) (made by polarizing film 1 (SEG))

於速度比相異之軋輥間將厚度80μm之聚乙烯醇薄膜，一面於30℃、0.3%濃度之碘溶液中染色1分鐘，一面延伸至3倍。之後，於60℃、包含4%濃度之硼酸、10%濃度之碘化鉀的水溶液中，一面浸漬0.5分鐘一面延伸至總合延伸倍率為6倍。接著，於30℃、包含1.5%濃度之碘化鉀的水溶液中浸漬10秒鐘並洗淨後，以50℃進行乾燥4分鐘，得到偏光片(厚度30μm)。於該偏光片之兩面藉由聚乙烯醇系接著劑貼合經皂化處理之厚度80μm的三乙酸纖維素薄膜，作成偏光薄膜1(SEG)。 A polyvinyl alcohol film having a thickness of 80 μm was dyed between the rolls having different speed ratios and dyed in a 0.3% iodine solution at 30 ° C for 1 minute while extending to 3 times. Thereafter, the mixture was further immersed in an aqueous solution containing 4% of boric acid and 10% of potassium iodide at 60 ° C for 0.5 minutes while extending to a total stretching ratio of 6 times. Subsequently, the mixture was immersed in an aqueous solution containing potassium iodide at a concentration of 1.5% at 30 ° C for 10 seconds, washed, and then dried at 50 ° C for 4 minutes to obtain a polarizer (thickness: 30 μm). A saponified cellulose triacetate film having a thickness of 80 μm was bonded to both surfaces of the polarizer by a polyvinyl alcohol-based adhesive to form a polarizing film 1 (SEG).

(偏光薄膜2(薄型偏光薄膜)之作成) (Preparation of polarizing film 2 (thin polarizing film))

為製作薄型偏光膜，首先，於非晶性PET基材製膜有24μm厚的PVA層之積層體藉由進行延伸溫度130度之空中補助延伸，生成延伸積層體，接著，藉由染色延伸積層體，生成著色積層體，更藉由將伸著色積層體進行延伸溫度65度之硼酸水中延伸至總延伸倍率為5.94倍，生成經與非晶性PET基材一體地延伸之包含3μm厚之PVA層的光學薄膜積層體。藉由如此之2階段延伸，經製膜於非晶性PET基材的PVA層之PVA分子係高階地配向，可生成構成藉由染色吸 附之碘係作為聚碘離子錯合物單向地高階配向之高機能偏光膜，並包含厚度10μm之PVA層的光學薄膜積層體。 In order to produce a thin polarizing film, first, a laminate of a PVA layer having a thickness of 24 μm formed on an amorphous PET substrate is formed by extending an extension of a temperature of 130 degrees to form an extended laminate, followed by dyeing and stretching. The body is formed into a colored layered body, and further extended to a total stretching ratio of 5.94 times by extending the colored layered body to boric acid water having an extension temperature of 65 degrees, thereby producing a PVA having a thickness of 3 μm which is integrally extended with the amorphous PET substrate. A layer of optical film laminate. By such a two-stage extension, the PVA molecules formed on the PVA layer of the amorphous PET substrate are aligned in a high order, and the composition can be formed by dyeing. The iodine is a high-performance polarizing film which is a unidirectional high-order alignment of the iodine ion complex, and includes an optical thin film laminate of a PVA layer having a thickness of 10 μm.

此外，於該光學薄膜積層體之偏光膜表面一面塗布聚乙烯醇系接著劑，一面貼合經皂化處理之80μm厚的三乙酸纖維素薄膜後，剝離非晶性PET基材，製作偏光薄膜2(薄型偏光薄膜)。 Further, a polyvinyl alcohol-based adhesive was applied to the surface of the polarizing film of the optical film laminate, and a saponified 80 μm-thick cellulose triacetate film was attached thereto, and then the amorphous PET substrate was peeled off to prepare a polarizing film 2 (Thin polarizing film).

製造例1 Manufacturing example 1

<丙烯酸系聚合物(A1)之調製> <Modulation of Acrylic Polymer (A1)>

於具有攪拌葉片、溫度計、氮氣導入管、冷卻器之4口燒瓶，一同裝入丙烯酸丁酯99份、4-羥丙烯酸丁酯1份、作為聚合起始劑之2,2’-偶氮雙異丁腈0.1份與乙酸乙酯100g，一面緩慢地攪拌一面導入氮氣，經氮取代後，將燒瓶內之液溫保持在55℃左右，進行聚合反應8小時，調製重量平均分子量160萬之丙烯酸系聚合物(A1)的溶液。 In a 4-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a cooler, 99 parts of butyl acrylate, 1 part of 4-butyl hydroxyacrylate, and 2,2'-azo double as a polymerization initiator were charged together. After 0.1 part of isobutyronitrile and 100 g of ethyl acetate, nitrogen gas was introduced while slowly stirring, and after replacing with nitrogen, the temperature in the flask was maintained at about 55 ° C, and polymerization was carried out for 8 hours to prepare acrylic acid having a weight average molecular weight of 1.6 million. A solution of the polymer (A1).

製造例2 Manufacturing Example 2

<丙烯酸系聚合物(A2)之調製> <Modulation of Acrylic Polymer (A2)>

於具有攪拌葉片、溫度計、氮氣導入管、冷卻器之4口燒瓶，一同裝入丙烯酸丁酯95份、4-羥丙烯酸丁酯5份、作為聚合起始劑之2,2’-偶氮雙異丁腈0.1份與乙酸乙酯100g，一面緩慢地攪拌一面導入氮氣，經氮取代後，將燒瓶內之液溫保持在55℃左右，進行聚合反應8小時，調製重量平均分子量160萬之丙烯酸系聚合物(A2)的溶液。 In a 4-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a cooler, 95 parts of butyl acrylate, 5 parts of 4-butyl hydroxyacrylate, and 2,2'-azo double as a polymerization initiator were charged together. After 0.1 part of isobutyronitrile and 100 g of ethyl acetate, nitrogen gas was introduced while slowly stirring, and after replacing with nitrogen, the temperature in the flask was maintained at about 55 ° C, and polymerization was carried out for 8 hours to prepare acrylic acid having a weight average molecular weight of 1.6 million. A solution of the polymer (A2).

製造例3 Manufacturing Example 3

<丙烯酸系聚合物(A3)之調製> <Modulation of Acrylic Polymer (A3)>

於具有攪拌葉片、溫度計、氮氣導入管、冷卻器之4口燒瓶，一同裝入丙烯酸丁酯90份、4-羥丙烯酸丁酯10份、作為聚合起始劑之2,2’-偶氮雙異丁腈0.1份與乙酸乙酯100g，一面緩慢地攪拌一面導入氮氣，經氮取代後，將燒瓶內之液溫保持在55℃左右，進行聚合反應8小時，調製重量平均分子量160萬之丙烯酸系聚合物(A3)的溶液。 In a 4-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a cooler, 90 parts of butyl acrylate, 10 parts of 4-butyl hydroxyacrylate, and 2,2'-azo double as a polymerization initiator were charged together. After 0.1 part of isobutyronitrile and 100 g of ethyl acetate, nitrogen gas was introduced while slowly stirring, and after replacing with nitrogen, the temperature in the flask was maintained at about 55 ° C, and polymerization was carried out for 8 hours to prepare acrylic acid having a weight average molecular weight of 1.6 million. A solution of the polymer (A3).

製造例4 Manufacturing Example 4

<丙烯酸系聚合物(A4)之調製> <Modulation of Acrylic Polymer (A4)>

於具有攪拌葉片、溫度計、氮氣導入管、冷卻器之4口燒瓶，一同裝入烯酸丁酯99.9份、4-羥丙烯酸丁酯0.1份、作為聚合起始劑之2,2’-偶氮雙異丁腈0.1份與乙酸乙酯100g，一面緩慢地攪拌一面導入氮氣，經氮取代後，將燒瓶內之液溫保持在55℃左右，進行聚合反應8小時，調製重量平均分子量160萬之丙烯酸系聚合物(A4)的溶液。 In a 4-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a cooler, 99.9 parts of butyl acrylate, 0.1 part of 4-butyl hydroxyacrylate, and 2,2'-azo as a polymerization initiator were charged together. 0.1 part of diisobutyronitrile and 100 g of ethyl acetate were introduced, and nitrogen gas was introduced while slowly stirring. After replacing with nitrogen, the temperature in the flask was maintained at about 55 ° C, and polymerization was carried out for 8 hours to prepare a weight average molecular weight of 1.6 million. A solution of an acrylic polymer (A4).

製造例5 Manufacturing Example 5

<丙烯酸系聚合物(A5)之調製> <Modulation of Acrylic Polymer (A5)>

於具有攪拌葉片、溫度計、氮氣導入管、冷卻器之4口燒瓶，一同裝入丙烯酸丁酯99份、4-羥乙丙烯酸酯1份、作為聚合起始劑之2,2’-偶氮雙異丁腈0.1份與乙酸乙酯100g，一面緩慢地攪拌一面導入氮氣，經氮取代後，將燒瓶內之液溫保持在55℃左右，進行聚合反應8小時，調製重量平均分子量160萬之丙烯酸系聚合物(A1)的溶液。 In a 4-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a cooler, 99 parts of butyl acrylate, 1 part of 4-hydroxyethyl acrylate, and 2,2'-azo double as a polymerization initiator were charged together. After 0.1 part of isobutyronitrile and 100 g of ethyl acetate, nitrogen gas was introduced while slowly stirring, and after replacing with nitrogen, the temperature in the flask was maintained at about 55 ° C, and polymerization was carried out for 8 hours to prepare acrylic acid having a weight average molecular weight of 1.6 million. A solution of the polymer (A1).

實施例1 Example 1

(黏著劑組成物之調製) (modulation of the adhesive composition)

相對於製造例1所得之丙烯酸系聚合物(A1)溶液的固形分100份，混合0.001份之作為聚醚化合物(B)的Kaneka社製Silyl SAT10、0.095份之異氰酸酯交聯劑(三武田化學社製之TAKENATE D110N、三羥甲基丙烷二甲苯二異氰酸酯)、及0.3份之過氧化苯甲醯基(日本油脂社製之NYPER BMT)，調製丙烯酸系黏著劑組成物之溶液(固形分15%)。 100 parts of the solid content of the acrylic polymer (A1) solution obtained in Production Example 1 was mixed with 0.001 part of Silyl SAT10 manufactured by Kaneka Co., Ltd. as a polyether compound (B), and 0.095 part of an isocyanate crosslinking agent (three). TAKENATE D110N, trimethylolpropane xylene diisocyanate manufactured by Takeda Chemical Co., Ltd., and 0.3 part of benzoyl peroxide (NYPER BMT manufactured by Nippon Oil & Fats Co., Ltd.) to prepare a solution of an acrylic adhesive composition (solid form) 15%).

(附黏著劑層之偏光薄膜之製作) (Production of polarizing film with adhesive layer)

接著，將前述丙烯酸系黏著劑溶液塗布於經施行矽處理之38μm的聚對苯二甲酸乙二酯(PET)薄膜(三菱化學聚酯薄膜(股)製，MRF38)之一面，使乾燥後之黏著劑層的厚度為23μm，以155℃進行乾燥1分鐘，轉印至偏光薄膜1(日東電工製，SEG)或偏光薄膜2(日東電工製，薄型偏光薄膜)，製作附黏著劑層之偏光薄膜。 Next, the acrylic pressure-sensitive adhesive solution was applied to one side of a 38 μm polyethylene terephthalate (PET) film (MRF38 manufactured by Mitsubishi Chemical Co., Ltd., MRF38) which was subjected to ruthenium treatment, and dried. The thickness of the adhesive layer was 23 μm, and the film was dried at 155 ° C for 1 minute, and transferred to a polarizing film 1 (made by Nitto Denko, SEG) or a polarizing film 2 (manufactured by Nitto Denko, thin polarizing film) to prepare a polarizing layer with an adhesive layer. film.

實施例2~23及比較例1~8 Examples 2 to 23 and Comparative Examples 1 to 8

於實施例1中，除了將(甲基)丙烯酸系聚合物(A)種類、聚醚化合物(B)之種類及量、矽烷耦合劑(C)之種類及量變更為表1記載者以外，與實施例1同樣地製作附黏著劑層之偏光薄膜。 In Example 1, except for the (meth)acrylic polymer (A) A polarizing film with an adhesive layer was produced in the same manner as in Example 1 except that the type and amount of the polyether compound (B) and the type and amount of the decane coupling agent (C) were changed as shown in Table 1.

對前述實施例1~23及比較例1~8中所得之附黏著劑層之偏光薄膜(試樣)進行以下評價。於表1顯示評價結果。 The polarizing film (sample) with the adhesive layer obtained in the above Examples 1 to 23 and Comparative Examples 1 to 8 was subjected to the following evaluation. The evaluation results are shown in Table 1.

<再製性> <remanufacturing>

將試樣(使用有偏光薄膜1之附黏著劑層之偏光薄膜)切斷成縱420mm×橫320mm，再使用貼合機貼附於厚度0.7mm之無鹼玻璃板(Corning社製，EG-XG)，接著，以50℃、5atm 進行高壓釜處理15分鐘，使其完全地密著(初期)。之後，於60℃乾燥條件下施行加熱處理48小時(加熱後)。測定如此之試樣的接著力。接著力係藉由抗拉試驗機(Autograph SHIMAZU AG-1 1OKN)測定以剝離角度90°、剝離速度300mm/min抗拉試驗剝除該試樣時的接著力(N/25mm，測定時80m長度)求出。測定係以1次/0.5s之間隔取樣，將其平均值作為測定值。 The sample (using a polarizing film with an adhesive layer of the polarizing film 1) was cut into a vertical length of 420 mm × a width of 320 mm, and attached to an alkali-free glass plate having a thickness of 0.7 mm using a laminator (manufactured by Corning Co., Ltd., EG- XG), then, at 50 ° C, 5 atm The autoclave treatment was carried out for 15 minutes to make it completely closed (initial). Thereafter, heat treatment was carried out under dry conditions at 60 ° C for 48 hours (after heating). The adhesion of such a sample was measured. Then, the force was measured by a tensile tester (Autograph SHIMAZU AG-1 1OKN). The adhesion force at the peeling angle of 90° and the peeling speed of 300 mm/min was used to remove the sample (N/25 mm, 80 m length during measurement). ) Find. The measurement was performed at intervals of 1 time/0.5 s, and the average value thereof was used as a measurement value.

又，對與測定前述接著力之對象相同的試樣，藉由人的手自無鹼玻璃板(Corning社製，EG-XG)剝除試樣，以下述基準評價再製性。再製性之評價係以前述順序製作3片、重複3次地實施。 In addition, the sample which was the same as the object of the measurement of the above-mentioned adhesive force was peeled off from an alkali-free glass plate (EG-XG, manufactured by Corning Co., Ltd.) by a human hand, and the reworkability was evaluated by the following criteria. The evaluation of the remanufacturability was carried out by making three pieces in the above-described order and repeating three times.

◎：3片均無黏合劑殘留或薄膜斷裂，可良好地剝離。 ◎: None of the three sheets remained adhesive or the film was broken, and the film was well peeled off.

○：3片中有一部分之薄膜斷裂，但可藉由再次之剝離剝除。 ○: A part of the film of 3 pieces was broken, but it was peeled off by peeling again.

△：3片均薄膜斷裂，但可藉由再次之剝離剝除。 △: Three sheets of the film were broken, but they were peeled off by peeling again.

×：3片均產生黏合劑殘留、或無論剝離幾次薄膜仍斷裂無法剝除。 ×: All of the three sheets were caused to remain as a binder, or the film was broken even if it was peeled off several times.

<塗布後之耐久性試驗> <Endurance test after coating>

將試樣(使用有偏光薄膜1的附黏著劑層之偏光薄膜或使用有偏光薄膜2的附黏著劑層之偏光薄膜)作成37吋大小，並使用貼合機貼附於厚度0.7mm的無鹼玻璃(Corning社製，EG-XG)。接著，以50℃、0.5MPa進行高壓釜處理15分鐘，使前述試樣完全地密著於無丙烯酸玻璃。於經施行如此處理之試樣，於80℃、90℃之各環境氣體下施行500小 時處理後(加熱試驗)、於60℃/90%RH、65℃/95%RH之各環境氣體下施行500小時處理後(加濕試驗)、於85℃與-40℃之環境下以1循環1小時施行300循環後(熱衝擊試驗)，以目視依據下述基準評價偏光板與玻璃之間的外觀。 The sample (the polarizing film with the adhesive layer of the polarizing film 1 or the polarizing film with the adhesive layer of the polarizing film 2) was made to have a size of 37 inches, and attached to a thickness of 0.7 mm using a bonding machine. Alkali glass (manufactured by Corning, EG-XG). Next, the autoclave treatment was carried out at 50 ° C and 0.5 MPa for 15 minutes to completely adhere the sample to the acrylic-free glass. For the sample treated as described above, 500 small is applied at 80 ° C and 90 ° C ambient gas. After the treatment (heating test), after 500 hours of treatment in each ambient gas of 60 ° C / 90% RH, 65 ° C / 95% RH (humidification test), at 85 ° C and -40 ° C environment to 1 After 300 cycles of one cycle (thermal shock test), the appearance between the polarizing plate and the glass was evaluated visually in accordance with the following criteria.

◎：完全無發泡、剝離、浮起等外觀上之變化。 ◎: There is no change in appearance such as foaming, peeling, and floating.

○：僅於端部產生一點點剝離、或發泡，但無實用上之問題。 ○: There was only a little peeling or foaming at the end, but there was no practical problem.

△：於端部產生剝離、或發泡，若無特別用途，無實用上之問題。 △: Peeling or foaming occurred at the end portion, and there was no practical problem if there was no special use.

×：於端部有顯著之剝離，有實用上之問題。 ×: There is a significant peeling at the end, which has practical problems.

<長期保管後之耐久性試驗> <Endurance test after long-term storage>

將使用有偏光薄膜1的附黏著劑層之偏光薄膜或使用有偏光薄膜2的附黏著劑層之偏光薄膜於23℃/55%RH之條件下保管12個月。將如此之試樣作成37吋大小，再使用貼合機貼附於厚度0.7mm的無鹼玻璃(Corning社製，EG-XG)。接著，以50℃、0.5MPa進行高壓釜處理15分鐘，使前述試樣完全地密著於無丙烯酸玻璃。於經施行如此處理之試樣，於80℃、90℃之各環境氣體下施行500小時處理後(加熱試驗)、於60℃/90%RH、65℃/95%RH之各環境氣體下施行500小時處理後(加濕試驗)、於85℃與-40℃之環境下以1循環1小時施行300循環後(熱衝擊試驗)，以目視依據下述基準評價偏光板與玻璃之間的外觀。 The polarizing film with the adhesive layer of the polarizing film 1 or the polarizing film with the adhesive layer of the polarizing film 2 was stored at 23 ° C / 55% RH for 12 months. The sample was made to have a size of 37 Å, and attached to an alkali-free glass (manufactured by Corning Co., Ltd., EG-XG) having a thickness of 0.7 mm using a laminator. Next, the autoclave treatment was carried out at 50 ° C and 0.5 MPa for 15 minutes to completely adhere the sample to the acrylic-free glass. The sample subjected to such treatment is subjected to 500 hours of treatment under ambient gas at 80 ° C and 90 ° C (heating test), and is carried out under ambient gases of 60 ° C / 90% RH and 65 ° C / 95% RH. After 500 hours of treatment (humidification test), after 300 cycles of 1 cycle for 1 hour in an environment of 85 ° C and -40 ° C (thermal shock test), the appearance between the polarizing plate and the glass was evaluated visually according to the following criteria. .

◎：完全無發泡、剝離、浮起等外觀上之變化。 ◎: There is no change in appearance such as foaming, peeling, and floating.

○：僅於端部產生一點點剝離、或發泡，但無實用上 之問題。 ○: only a little peeling or foaming occurs at the end, but it is not practical. The problem.

△：於端部產生剝離、或發泡，若無特別用途，無實用上之問題。 △: Peeling or foaming occurred at the end portion, and there was no practical problem if there was no special use.

×：於端部有顯著之剝離，有實用上之問題。 ×: There is a significant peeling at the end, which has practical problems.

於表1中，聚醚化合物(B)中，「SAT10」係表示Kaneka社製之Silyl SAT10、「SAT350」係表示Kaneka社製之Silyl SAT350、「SAX220」係表示Kaneka社製之Silyl SAX220、「SAT400」係表示Kaneka社製之Silyl SAT400、「SIB82」係表示GELEST社製之「SIB1824.82」、「SIB84」係表示GELEST社製之「SIB1824.84」，均係具有反應性矽基之聚醚化合物(B)。 In Table 1, in the polyether compound (B), "SAT10" means Silyl SAT10 manufactured by Kaneka, "SAT350" means Silyl SAT350 manufactured by Kaneka, and "SAX220" is Silyl SAX220 manufactured by Kaneka. SAT400" is a Silyl SAT400 manufactured by Kaneka, "SIB82" is a "SIB1824.82" manufactured by GELEST, and "SIB844.8" is a GELEST company. Ether compound (B).

另外，SAT10、SAT350及SAX220均係通式(4)所表示之化合物，A2係-C3H6-、Z1係-C3H6-Z0，反應性矽基(Z0-)係R1、R2及R3均係甲基的二甲氧基甲基矽基，AO係直鏈結構之氧丙烯基(特別係-CH2CH(CH3)O-)。又，SAT400係以通式(6)表示之化合物，Z3係-C3H6-Z0，反應性矽基(Z0-)係R1、R2及R3均係甲基的二甲氧基甲基矽基，AO係氧丙烯基(-CH2CH(CH3)O-)。SIB82係以通式(5)表示之化合物，A2係-C3H8-、Z2係-CONH-A2-Z0，反應性矽基(Z0-)係R1、R2及R3均係乙基的三乙氧矽基，AO係包含氧乙烯基之骨架。又，SIB84係以通式(4)表示之化合物，A2係-C3H8-，Z1係-C3H8-Z0，反應性矽基(Z0-)係R1、R2及R3均係乙基的三乙氧矽基，AO係包含氧乙烯基之骨架。 In addition, SAT10, SAT350, and SAX220 are all compounds represented by the formula (4), A 2 is -C 3 H 6 -, Z 1 -C 3 H 6 -Z 0 , and reactive thiol (Z 0 -) The dimethoxymethyl fluorenyl group wherein R 1 , R 2 and R 3 are each a methyl group, and the oxypropylene group of an AO linear structure (particularly -CH 2 CH(CH 3 )O-). Further, SAT400 is a compound represented by the formula (6), Z 3 is -C 3 H 6 -Z 0 , and a reactive thiol group (Z 0 -) is a group in which R 1 , R 2 and R 3 are each a methyl group. Methoxymethyl fluorenyl, AO oxypropylene (-CH 2 CH(CH 3 )O-). SIB82 is a compound represented by the formula (5), A 2 is -C 3 H 8 -, Z 2 -CONH-A 2 -Z 0 , and reactive thiol (Z 0 -) is R 1 and R 2 and R 3 is an ethyl triethoxy fluorenyl group, and AO is a skeleton containing an oxyethylene group. Further, SIB84 is a compound represented by the formula (4), A 2 is -C 3 H 8 -, Z 1 is -C 3 H 8 -Z 0 , and reactive thiol (Z 0 -) is R 1 and R. 2 and R 3 are each a triethoxy sulfonyl group of an ethyl group, and AO is a skeleton containing an oxyethylene group.

Claims (15)

一種光學薄膜用黏著劑組成物，其特徵在於，係含有：包含作為單體單元之含羥基單體之(甲基)丙烯酸系聚合物(A)；具有氧伸烷基之重複結構單元，且於至少1個末端具有以通式(1)表示之反應性矽基之聚醚化合物(B)，通式(1)：-SiRaM3-a(式中，R係亦可具有取代基之碳數1~20之1價有機基，M係羥基或可水解基，a係0~2之整數，惟，存在複數R時，複數之R可互為相同亦可相異，存在複數M時，複數之M可互為相同亦可相異)；及具乙醯乙醯基之矽烷耦合劑(C)。 An adhesive composition for an optical film, comprising: a (meth)acrylic polymer (A) comprising a hydroxyl group-containing monomer as a monomer unit; a repeating structural unit having an oxygen alkyl group; a polyether compound (B) having a reactive mercapto group represented by the formula (1) at at least one terminal, and a formula (1): -SiR a M 3-a (wherein the R system may have a substituent The carbon number is 1 to 20, the monovalent organic group, the M is a hydroxyl group or a hydrolyzable group, and the a is an integer of 0 to 2. However, when there is a plurality of R, the plural Rs may be the same or different from each other, and the plural M is present. In the meantime, the plural Ms may be the same or different from each other; and the decane coupling agent (C) having an acetamidine group. 如申請專利範圍第1項之光學薄膜用黏著劑組成物，其中前述含羥基之單體係(甲基)丙烯酸4-羥丁酯。 An adhesive composition for an optical film according to claim 1, wherein the hydroxyl group-containing single system (4-hydroxybutyl) (meth)acrylate. 如申請專利範圍第1或2項之光學薄膜用黏著劑組成物，其中聚醚化合物(B)係以通式(2)表示之化合物，通式(2)：RaM3-aSi-X-Y-(AO)n-Z[式中，R係亦可具有取代基之碳數1~20之1價有機基，M係羥基或可水解基，a係0~2之整數，惟，存在複數R時，複數之R可互為相同亦可相異，存在複數M時，複數之M可互為相同亦可相異，AO係表示包含氧伸烷基作為重複結構單元之直鏈或支鏈結構，n係1~1700，表示氧伸烷基之平均加成莫耳數，X係表示碳數1~20之直 鏈或支鏈的伸烷基，Y係表示醚鍵、酯鍵、胺甲酸酯鍵、或碳酸酯鍵，Z係氫原子、1價之碳數1~10之烴基、及以通式(2A)或以通式(2B)表示之基，通式(2A)：-Y1-X-SiRaM3-a(式中，R、M、X係與前述相同，Y1係表示單鍵、-CO-鍵、-CONH-鍵、或-COO-鍵)通式(2B)：-Q{-(OA)n-Y-X-SiRaM3-a}m(式中，R、M、X、Y係與前述相同，OA係與前述AO相同，n係與前述相同，Q係2價以上之碳數1~10之烴基，m係與該烴基之價數相同)]。 An adhesive composition for an optical film according to claim 1 or 2, wherein the polyether compound (B) is a compound represented by the formula (2): (a): R a M 3-a Si- XY-(AO) n -Z [wherein, R may have a monovalent organic group having 1 to 20 carbon atoms of a substituent, M-based hydroxyl group or hydrolyzable group, and a is an integer of 0 to 2, but exists In the case of a complex number R, the plural Rs may be the same or different from each other. When a complex number M is present, the complex numbers M may be the same or different from each other, and the AO system represents a linear chain or a branch containing an oxygen alkyl group as a repeating structural unit. Chain structure, n series 1~1700, indicating the average addition mole number of oxygen alkyl group, X series means linear or branched alkyl group with 1 to 20 carbon atoms, Y series means ether bond, ester bond, a urethane bond or a carbonate bond, a Z-based hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and a group represented by the formula (2A) or the formula (2B), and the formula (2A) :-Y 1 -X-SiR a M 3-a (wherein R, M, and X are the same as described above, and Y 1 represents a single bond, a -CO- bond, a -CONH- bond, or a -COO- bond) general formula (2B): - Q {- (OA) n -YX-SiR a m 3-a} m ( wherein, R, the same as m, X, Y and the line, the same line OA and the AO, n lines The same, Q-based or more of the divalent hydrocarbon group having 1 to 10 carbon atoms, the hydrocarbon groups with the same number of valence m lines)]. 如申請專利範圍第1或2項之光學薄膜用黏著劑組成物，其中聚醚化合物(B)之反應性矽基係以下述通式(3)表示之烷氧基矽基， (式中，R1、R2及R3係碳數1~6之1價烴基，於同一分子中可相同亦可相異)。 The adhesive composition for an optical film according to claim 1 or 2, wherein the reactive thiol group of the polyether compound (B) is an alkoxy fluorenyl group represented by the following formula (3), (wherein R 1 , R 2 and R 3 are a monovalent hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different in the same molecule). 如申請專利範圍第3項之光學薄膜用黏著劑組成物，其中聚醚化合物(B)係以通式(4)表示之化合物，通式(4)：Z0-A2-O-(AO)n-Z1 [式中，AO係與前述相同，n係1~1700，表示AO之平均加成莫耳數，Z1係氫原子或-A2-Z0，A2係碳數2~6之伸烷基，Z0係以通式(3)表示之烷氧基矽基， (式中，R1、R2及R3係碳數1~6之1價烴基，於同一分子中可相同亦可相異)]。 An adhesive composition for an optical film according to claim 3, wherein the polyether compound (B) is a compound represented by the formula (4), and the formula (4): Z 0 -A 2 -O- (AO) n -Z 1 [wherein, the AO system is the same as the above, n is 1 to 1700, and represents the average addition molar number of AO, Z 1 hydrogen atom or -A 2 -Z 0 , and A 2 carbon number 2 ~6 alkylene, Z 0 is an alkoxy fluorenyl group represented by the general formula (3), (In the formula, R 1 , R 2 and R 3 are a monovalent hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different in the same molecule). 如申請專利範圍第3項之光學薄膜用黏著劑組成物，其中聚醚化合物(B)係以通式(5)表示之化合物，通式(5)：Z0-A2-NHCOO-(AO)n-Z2[式中，AO係包含氧伸烷基作為重複結構單元之直鏈或支鏈結構，n係1~1700，表示AO之平均加成莫耳數，Z2係氫原子、或-CONH-A2-Z0，A2係碳數2~6之伸烷基，Z0係以通式(3)表示之烷氧基矽基， (式中，R1、R2及R3係碳數1~6之1價烴基，於同一分子中可相同亦可相異)]。 An adhesive composition for an optical film according to claim 3, wherein the polyether compound (B) is a compound represented by the formula (5): (0): Z 0 -A 2 -NHCOO-(AO n - Z 2 [wherein, AO contains a linear or branched structure in which an alkylene group is a repeating structural unit, and n is a system of 1 to 1700, which represents an average addition molar number of AO, a Z 2 hydrogen atom, Or -CONH-A 2 -Z 0 , A 2 is an alkylene group having 2 to 6 carbon atoms, and Z 0 is an alkoxyfluorenyl group represented by the formula (3). (In the formula, R 1 , R 2 and R 3 are a monovalent hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different in the same molecule). 如申請專利範圍第3項之光學薄膜用黏著劑組成物，其中聚醚化合物(B)係以通式(6)表示之化合物，通式(6)：Z3-(AO)n-O-G-CR4{-G-O-(AO)n-Z3}2[式中，AO係包含氧伸烷基作為重複結構單元之直鏈或支鏈結構，n係1~1700，表示AO之平均加成莫耳數，Z3係氫原子或-A2-Z0，至少任1個Z3係-A2-Z0，A2係碳數2~6之伸烷基，R4係表示氫原子、或碳數1~3之伸烷基，G係表示單鍵或亞甲基，Z0係以通式(3)表示之烷氧基矽基， (式中，R1、R2及R3係碳數1~6之1價烴基，於同一分子中可相同亦可相異)]。 An adhesive composition for an optical film according to claim 3, wherein the polyether compound (B) is a compound represented by the formula (6): (3): Z 3 -(AO) n -OG- CR 4 {-GO-(AO) n -Z 3 } 2 [wherein, AO contains a linear or branched structure of an oxygen-extended alkyl group as a repeating structural unit, and n is a system of 1 to 1700, indicating an average addition of AO. Moir number, Z 3 -based hydrogen atom or -A 2 -Z 0 , at least one Z 3 -A 2 -Z 0 , A 2 is an alkylene group having 2 to 6 carbon atoms, and R 4 is a hydrogen atom. Or an alkylene group having 1 to 3 carbon atoms, G represents a single bond or a methylene group, and Z 0 is an alkoxythio group represented by the formula (3). (In the formula, R 1 , R 2 and R 3 are a monovalent hydrocarbon group having 1 to 6 carbon atoms, which may be the same or different in the same molecule). 如申請專利範圍第1或2項之光學薄膜用黏著劑組成物，其中聚醚化合物(B)之數量平均分子量係300~100000。 The adhesive composition for an optical film according to claim 1 or 2, wherein the polyether compound (B) has a number average molecular weight of 300 to 100,000. 如申請專利範圍第1或2項之光學薄膜用黏著劑組成物，係相對於(甲基)丙烯酸系聚合物(A)100重量份，含 有0.001~5重量份的具乙醯乙醯基之矽烷耦合劑(C)。 The adhesive composition for an optical film according to claim 1 or 2, which is based on 100 parts by weight of the (meth)acrylic polymer (A), There are 0.001 to 5 parts by weight of a decane coupling agent (C) having an ethyl acetonitrile group. 如申請專利範圍第1或2項之光學薄膜用黏著劑組成物，係相對於(甲基)丙烯酸系聚合物(A)100重量份，含有0.001~5重量份之聚醚化合物(B)。 The adhesive composition for an optical film according to claim 1 or 2, which contains 0.001 to 5 parts by weight of the polyether compound (B) based on 100 parts by weight of the (meth)acryl-based polymer (A). 如申請專利範圍第1或2項之光學薄膜用黏著劑組成物，係相對於(甲基)丙烯酸系聚合物(A)100重量份，更含有0.01~2重量份之作為交聯劑(D)的過氧化物 The adhesive composition for an optical film according to the first or second aspect of the invention is further contained in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the (meth)acrylic polymer (A) as a crosslinking agent (D). Peroxide 一種光學薄膜用黏著劑層，其特徵在於，係藉由如申請專利範圍第1~11項中任一項之光學薄膜用黏著劑組成物形成。 An adhesive layer for an optical film, which is formed by using an adhesive composition for an optical film according to any one of claims 1 to 11. 一種附黏著劑層之光學薄膜，其特徵在於，係於光學薄膜之至少一側形成有如申請專利範圍第12項之光學薄膜用黏著劑層。 An optical film with an adhesive layer, characterized in that an adhesive layer for an optical film according to claim 12 is formed on at least one side of the optical film. 如申請專利範圍第13項之附黏著劑層之光學薄膜，其於光學薄膜與光學薄膜用黏著劑層之間具有易接著層。 An optical film comprising an adhesive layer according to claim 13 of the patent application, which has an easy adhesion layer between the optical film and the adhesive layer for the optical film. 一種影像顯示裝置，其特徵在於，係使用有至少1個如申請專利範圍第13或14項之附黏著劑層之光學薄膜。 An image display apparatus characterized in that an optical film having at least one adhesive layer as disclosed in claim 13 or 14 is used.
TW102112092A 2012-04-04 2013-04-03 Adhesive composition for optical films, adhesive layer for optical films, optical film with adhesive layer, and image display device TW201343836A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2012085628A JP2013216719A (en) 2012-04-04 2012-04-04 Pressure-sensitive adhesive agent composition for optical film, pressure-sensitive adhesive agent layer for optical film, optical film with pressure-sensitive adhesive agent layer, and image display device

Publications (1)

Publication Number Publication Date
TW201343836A true TW201343836A (en) 2013-11-01

Family

ID=49300508

Family Applications (1)

Application Number Title Priority Date Filing Date
TW102112092A TW201343836A (en) 2012-04-04 2013-04-03 Adhesive composition for optical films, adhesive layer for optical films, optical film with adhesive layer, and image display device

Country Status (5)

Country Link
JP (1) JP2013216719A (en)
KR (1) KR20140142346A (en)
CN (1) CN104220550A (en)
TW (1) TW201343836A (en)
WO (1) WO2013151027A1 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2953870B2 (en) * 1992-07-28 1999-09-27 松下電工株式会社 Earth leakage breaker
JP5970950B2 (en) * 2012-05-15 2016-08-17 セメダイン株式会社 Moisture curable adhesive composition and laminate using this adhesive composition
KR20160088064A (en) * 2015-01-15 2016-07-25 동우 화인켐 주식회사 Polarizing plate and image display device comprising the same
KR20170105012A (en) * 2015-01-16 2017-09-18 디아이씨 가부시끼가이샤 Polymerizable composition and optically anisotropic body using same
JP6822813B2 (en) * 2016-09-29 2021-01-27 日東電工株式会社 Adhesive layer for organic conductive layer, adhesive composition, polarizing film with adhesive layer, and image display device
KR102296012B1 (en) * 2018-02-15 2021-08-30 후지필름 가부시키가이샤 Binder composition, binder layer, optical laminate and image display device
KR102505149B1 (en) * 2018-11-28 2023-02-28 후지필름 가부시키가이샤 Optical orientation copolymer, binder composition, binder layer, optical laminate and image display device

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4279944B2 (en) * 1999-06-01 2009-06-17 株式会社サンリッツ Manufacturing method of polarizing plate
JP4849625B2 (en) * 2004-12-02 2012-01-11 日東電工株式会社 Method for producing pressure-sensitive adhesive layer for optical film and method for producing pressure-sensitive adhesive optical film
JP5511148B2 (en) * 2008-02-12 2014-06-04 テクノポリマー株式会社 Alcohol-resistant molding materials and molded products
JP5379409B2 (en) * 2008-02-15 2013-12-25 日東電工株式会社 Adhesive composition for optical film, adhesive optical film, and image display device
JP5187973B2 (en) * 2009-04-30 2013-04-24 日東電工株式会社 Optical film adhesive composition, optical film adhesive layer, adhesive optical film, and image display device
JP4691205B1 (en) * 2010-09-03 2011-06-01 日東電工株式会社 Method for producing optical film laminate including thin high-performance polarizing film

Also Published As

Publication number Publication date
KR20140142346A (en) 2014-12-11
WO2013151027A1 (en) 2013-10-10
JP2013216719A (en) 2013-10-24
CN104220550A (en) 2014-12-17

Similar Documents

Publication Publication Date Title
TWI537352B (en) Adhesive composition for optical film, adhesive layer for optical film, adhesive type optical film and image display device (1)
JP4820443B2 (en) Optical film adhesive composition, optical film adhesive layer, adhesive optical film, and image display device
CN108873139B (en) Polarizing film with adhesive layer and image display device
TWI606105B (en) Adhesive composition for optical film, adhesive layer for optical film, optical film with adhesive layer, and image display device
TW201343836A (en) Adhesive composition for optical films, adhesive layer for optical films, optical film with adhesive layer, and image display device
KR102649521B1 (en) Optical adhesive layer, manufacturing method of optical adhesive layer, optical film with adhesive layer, and image display device
WO2010126054A1 (en) Adhesive composition for optical film, adhesive layer for optical film, and adhesive optical film, and image display device
JP6916196B2 (en) Optical adhesive layer, manufacturing method of optical adhesive layer, optical film with adhesive layer, and image display device
WO2019031496A1 (en) Pressure-sensitive adhesive layer, optical film having pressure-sensitive adhesive layer, optical laminate, and image display device
JP7128945B2 (en) Optical adhesive layer, method for producing optical adhesive layer, optical film with adhesive layer, and image display device
WO2019031486A1 (en) Pressure-sensitive adhesive layer, optical film provided with pressure-sensitive layer, optical laminate, and image display device
KR102405461B1 (en) Polarizing film and image display device provided with an adhesive layer
WO2018062280A1 (en) Polarizing film adhesive composition, manufacturing method of polarizing film adhesive layer, polarizing film with adhesive layer, and image display device
JP5951323B2 (en) Optical film pressure-sensitive adhesive composition, optical film pressure-sensitive adhesive layer, optical film with pressure-sensitive adhesive layer, and image display device
WO2022024579A1 (en) Polarizing film with pressure-sensitive-adhesive layer, image display panel, method for manufacturing image display panel, and pressure-sensitive-adhesive layer
KR102375987B1 (en) Polarizing film with adhesive layer and image display device
WO2024106486A1 (en) Adhesive composition, adhesive sheet, optical multilayer body, and image display device
JP2024073945A (en) Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, optical laminate, and image display device