TW201134905A - Adhesive, adhesive for optical component, optical component with adhesive layer, image display, active energy ray and/or heat hardening adhesive composite, adhesive composite - Google Patents
Adhesive, adhesive for optical component, optical component with adhesive layer, image display, active energy ray and/or heat hardening adhesive composite, adhesive composite Download PDFInfo
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- TW201134905A TW201134905A TW100102174A TW100102174A TW201134905A TW 201134905 A TW201134905 A TW 201134905A TW 100102174 A TW100102174 A TW 100102174A TW 100102174 A TW100102174 A TW 100102174A TW 201134905 A TW201134905 A TW 201134905A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/04—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J7/35—Heat-activated
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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]
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polarising Elements (AREA)
- Adhesive Tapes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
201134905 六'發明說明: 【發明所屬之技術領域] 本發明係關於黏接劑(感壓接著劑)、及光學構件用黏接劑、使 2其而得到的設有黏接劑層的光學構件、影像顯示裝置、活性能 量射線及/或熱硬化性黏接劑組成物。詳言之,係關於液晶顯示裝 置、有機電致發光顯示裝置、電漿顯示器等影像顯示裝置中較佳 了52巧5學薄膜(偏光薄膜、相位差薄膜、光學補償薄膜、輝度 ,二薄,等)等,尤其具體而言,係關於偏光薄膜以三乙酸纖維素 f巧等保護薄膜被覆而成的光學疊層體與液晶晶胞的玻璃基板 可的光學構制黏接劑,及形成有由該光學構件用黏 接蜊構成的黏接劑層的設有黏接劑層的光學構件,尤並 斑 接劑層的偏光板。 /、 》有*占 【先前技術】 將賦予有偏光性的聚乙烯醇系薄膜等的兩面以纖 光子具有以三乙纖維素系保護膜鱗聚乙稀醇夸偏 面:上層=ir此等材料的特性,欠= 為時間經過而發偏用延伸成形,因此容易因 產生的内邱廂右疋無法將由於如此的尺寸變化而 會變得不均騎於偏光板作用的殘留應力 晶顯示袭置ί中在偏光板的周緣部。其結果,液 晶顯示裝置發生顏:二明亮或者更為黑暗等,在液 51 性優異,而且不易發生漏光等 201134905 的光學特性也優異_接劑,而開始有人進行研究。 巧如’於專利文獻i中記載藉由使用 的丙烯酸麟_絲雜優異_接劑文21 5己載藉由配合含有芳香環之低分子量化合物於丙烯萨 , ^']x^3 ^糸樹月曰的乙烯性不飽和單體(UY硬化單活 γ以交«合而成㈣久性與光料㈣平彳優1=^ [先前技術文獻] [專利文獻] 專利文獻1:日本特開2005-53976號公報 專利文獻2:WO 2007/072799號公報 專利文獻3:日本特開2009-132909號公報 【發明内容】 (發明欲解決的問題) 但是,上述專利文獻i揭示的技術雖顯示一定的光學特性, 但是為了使職技術應付近年來對於光學雜的更高要求, 使芳香族單體多量共聚合。 @ 而,若使用多鮮香族單體進行聚合,則反應液巾的黏度會 、,升,故製造光學用途的黏接劑一般使用的高分子量(例如,重量 平均分子量100萬以上)的丙烯酸系樹脂會有困難’而且,一妒的 =族單體由於難以利用蒸德等除去其製造時產生的雜質的二丙 ^酉夂醋體,因此常會含有雜質的二丙職g旨體,由於該雜質的影 曰,與上述同樣難以製造高分子量的丙烯酸系樹脂。又,當聚合 ,用較谷易進行聚合的丙烯酸苄酯或丙烯酸苯氧基乙酯等低分子 量的芳香族單體時,聚合時殘存的單體可能會在雜劑層形成後 仍然殘留,其臭味也會成為問題。 上述專利文獻2揭示的技術確實可得到不易發生顏色不均、 漏光的結果,但是,專利文獻2使用的具有2個以上苯環的低分 201134905 丙辑黏接劑的凝集力,有液晶顯^置的耐纽ΐί 而,本發明係在如此的背景之下而生,目 生)或光學特性(混優異的黏接齊;, 田貼&偏光板4辟構件與柄基姆 漏光性能臟_接^尤其是綱餅職于特_ (解決問題的方式) ❹ϋ發明人等對於歸事努力研究,絲魏:於雌能量射 ^及ϋ匕型的黏接劑中,就硬化性的乙稀性不 .ΐ =由靖定_含有含1個乙烯性不飽和基的單官能單體盘 ^,ίιίί用乙ίίϊ和基的多官能單體使得單官能賴成為 。 且使用/、有方香環的單官能單體當做單官能單體,則摔 十銜丨生彳火異’乃元成本發明。 糾J!即It發明的要旨係關於一種黏接劑,係將含有丙婦酸系 贫曰()、,有1個乙烯性不飽和基的芳香族化合物㊉)、及含有2 们以上乙烯j·生?飽和基的乙稀性不飽和化合物⑹的黏接劑組成物 [I] ’以活性能量射線及/或熱使硬化而成雜制,其特徵為:芳香 族=合物⑻—的含量,相對於丙稀酸系樹脂⑷勘重量份為3〜3〇〇 重里伤,且芳香族化合物(B)相對於芳香族化合物(B)與乙烯性不飽 和化合物(C)的合計量的含有比例(m〇p/Q)大於5〇m〇i〇/〇。 又,本發明的要旨係關於使用上述黏接劑而成的光學構件用 6 201134905 黏接劑’及含有該光學構件用黏接劑的黏接劑層及 =的設有黏接劑層的光學構件、由該光學構件構;= /又,本發明的要旨係關於-種黏接劑,其特徵在 Ϊ糸Ϊί(Α)、含有1個乙雜不飽和基的料族化合_)^1聚人 物、έ有1個乙烯性不飽和基的芳香族化合物(Β),及有(機)丄;: 又,本發明的要旨係關於一種黏接劑組成物 ^ =脂⑷、含㈣•福 個Ui乙稀性不飽和基的乙烯性不飽和化合物(C)而成 f丙職糸樹脂(A)的光彈性係數為負,且芳香族化么‘: 烯性不飽和化合物(Q的硬化物的光彈性係數為正。物敗、乙 條件ΐ = ί縮^⑽光板暴露在耐熱 系保細,梅折_ 酸基聚合物追隨於偏光板敝、_配向,丙f 而言具有負的光彈性係數)。 Π工《生禝折射(-般 的光= 絲合物與具有正 酸基聚合物來源的複折射較大。、即、,、:光^測丙烯 基聚合物的折射率,吨抿轴方向增大的丙烯酸 性係數。 _M)該讀射,必需在·補強正的光彈 201134905 著劑層的偏光板。 族化此’為單官紅能產生正的複折射的芳香 族:“_乙烯性不芳ί :=:二:==益 -成ii,了甘香族化合物⑻與乙稀性不飽和化合物(〇的量關係 交成相反,财硬化_分支構造會變得非常多,其構造上的自 由度ϋ,變得不易配向,推測因而無法達成本發明的效果。 (發明的效果) 不 請娜制尤其適於光學構件麟,_活性能量射線 版=…硬化後的黏接劑層的操作性(黏性)或光學特性(混濁度) 高濕的,下’光學疊層體’尤其是偏光板 玻璃基板的接雜優異,雜劑層與玻璃基板之間 Ρ生起泡或_,可得到不產生顏色不均或漏光的液晶顯 置。 【實施方式】 (實施發明之形態) 以下詳細說明本發明,但此等係例示希望的實施態樣之一例。 又’本發明中,(甲基)丙烯酸基係指丙稀酸基或甲基丙烯酸 土 (甲基)丙烯基係指丙烯酿基或甲基丙稀酸基,(甲基)丙烯酸 酯係指丙烯酸酯或甲基丙烯酸酯。 首先,說明本發明之黏接劑組成物[J]。 ^發明之黏接劑組成物P],係含有丙烯酸系樹脂(A)、含有1 個乙烯性不飽和基之芳香族化合物⑼、及含有2個以上乙稀性不 飽和基的乙烯性不飽和化合物(〇而成。 π〇本發明可使用的丙烯酸系樹脂(Α),係以(甲基)丙烯酸烷酯系 單體(al)當做主成分,並視需要將含有官能基之單體(a2)當做共聚 合成分而共聚合而成者,又,也可將其他可共聚合的單體(a3)當做 8 201134905 共聚合成分。本發曰月中的丙烯酸系樹脂㈧,使[Technical Field] The present invention relates to an adhesive (pressure-sensitive adhesive), an adhesive for an optical member, and an optical member provided with an adhesive layer obtained therefrom , image display device, active energy ray and/or thermosetting adhesive composition. In particular, it is preferred that the image display device such as a liquid crystal display device, an organic electroluminescence display device, or a plasma display device has a 52-color film (a polarizing film, a phase difference film, an optical compensation film, a luminance, and a thin film). In particular, the optical laminate of the optical laminate in which the polarizing film is coated with a protective film such as cellulose triacetate and the glass substrate of the liquid crystal cell can be optically formed and formed. An optical member provided with an adhesive layer of the adhesive layer composed of the adhesive member for the optical member, and a polarizing plate of the patch layer. /, 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The characteristics of the material, under = the extension of the shape for the passage of time, so it is easy to produce the residual stress crystals that can become uneven due to such dimensional changes due to such dimensional changes. Placed in the peripheral portion of the polarizing plate. As a result, the liquid crystal display device has a color: two bright or darker, and is excellent in liquid 51, and is less likely to cause light leakage. The optical characteristics of 201134905 are also excellent, and some studies have begun. It is described in the patent document i that the use of acrylic acid linings is excellent by the use of a low molecular weight compound containing an aromatic ring in acryl, ^']x^3 ^ eucalyptus Ethylene-unsaturated monomer of the cercariae (UY-hardened single-live γ to be combined into a mixture of (4) long-term and light-based materials (4) 彳 彳 优 1 = ^ [Previous Technical Literature] [Patent Literature] Patent Document 1: Japanese Special Patent Document 2: WO 2007/072799 (Patent Document 3) Japanese Laid-Open Patent Publication No. 2009-132909 (Summary of the Invention) However, the technique disclosed in the above Patent Document i shows a certain The optical properties, but in order to cope with the higher requirements for optical impurities in recent years, the aromatic monomers are copolymerized in a large amount. @且,, if the multi-fresh aromatic monomer is used for polymerization, the viscosity of the reaction liquid towel will be In addition, it is difficult to use an acrylic resin having a high molecular weight (for example, a weight average molecular weight of 1,000,000 or more) which is generally used for the production of optical adhesives, and it is difficult to utilize a steamed German Remove impurities generated during its manufacture Since it is a propylene carbonate, it is often used to contain impurities, and it is difficult to produce a high molecular weight acrylic resin as described above due to the influence of the impurities. When a low molecular weight aromatic monomer such as benzyl acrylate or phenoxyethyl acrylate is used, the monomer remaining during the polymerization may remain after the formation of the impurity layer, and the odor may also become a problem. The disclosed technique can reliably obtain color unevenness and light leakage. However, the cohesive force of the low-grade 201134905 acrylic adhesive having two or more benzene rings used in Patent Document 2 has a liquid crystal display resistance. Ϊ́ί However, the present invention is born under such a background, and the optical characteristics (mixed excellent adhesion; the field paste & polarizing plate 4 and the stalk base light leakage performance dirty _ _ ^ especially It is the specialty of the cake _ (the way to solve the problem) ❹ϋ inventors and other efforts to study the cause, silk Wei: in the female energy shot ^ and ϋ匕 type of adhesive, the hardening of the ethylene is not. ΐ = by Jing Ding _ contains 1 ethyl not A saturated monofunctional monomer disk ^, ίιίί is made with a polyfunctional monomer such as a monofunctional lanthanide. And a monofunctional monomer having a square scented ring is used as a monofunctional monomer.彳火异' is the cost of the invention. Correction J! That is the essence of the invention of the invention is about a kind of adhesive, which will contain the indigo (), an aromatic compound with one ethylenic unsaturated group. And an adhesive composition [I] of an ethylenically unsaturated compound (6) containing two or more ethylene groups, which is characterized by an active energy ray and/or heat, which is characterized by The content of the aromatic compound (8)- is 3 to 3 Torr in weight to the acrylic resin (4), and the aromatic compound (B) is not related to the aromatic compound (B) and ethylene. The content ratio (m〇p/Q) of the total amount of the saturated compound (C) is more than 5 〇m〇i〇/〇. Further, the gist of the present invention relates to an optical member 6 201134905 adhesive used for the optical member, an adhesive layer containing the adhesive for the optical member, and an optical layer provided with an adhesive layer. The member is composed of the optical member; = /, the gist of the present invention relates to a kind of adhesive, which is characterized in that Ϊ糸Ϊί(Α), a compound containing one ethylidene unsaturated group is _)^1 An aromatic compound having an ethylenically unsaturated group and an organic compound; and the subject matter of the present invention relates to an adhesive composition ^=lipid (4), containing (four)• The ethylenically unsaturated compound (C) of the Ui ethylidene unsaturated group is a negative photo-elastic coefficient of the propylene-based resin (A), and is aromaticized: 'ethylenically unsaturated compound (Q The photoelastic coefficient of the hardened material is positive. The material is defeated, the condition B is ί = ί shrinking ^ (10) The light plate is exposed to the heat-resistant system, and the yttrium-based polymer is followed by the polarizing plate 敝, _ alignment, and C is negative. Photoelastic coefficient). Completed 禝 禝 禝 ( - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Increased acryl coefficient. _M) This reading must be done in the reinforced positive beam of light 201134905. Grouping this as a single-red red can produce a positive birefringent aromatic: "_Ethylene not ί :=: two: == Yi-cheng ii, Ganxiang compound (8) and ethylene unsaturated compounds (The relationship between the amount of 〇 is reversed, and the structure of the sclerosing _ branch is very large, and the degree of freedom in construction becomes too difficult to align, and it is presumed that the effect of the present invention cannot be achieved. (Effect of the invention) Especially suitable for optical components, _ active energy ray plate = ... operability (viscosity) or optical properties (turbidity) of the adhesive layer after hardening, high-humidity, lower 'optical laminate' especially polarized light The plate glass substrate is excellent in the adhesion, and foaming or ray is generated between the impurity layer and the glass substrate, and liquid crystal display which does not cause color unevenness or light leakage can be obtained. [Embodiment] (Detailed Embodiment) Hereinafter, the present invention will be described in detail. The invention is exemplified by an example of a desired embodiment. In the present invention, the (meth)acrylic group means an acrylic acid group or a methacrylic acid (meth)acrylyl group means an acrylic acid group or Methyl acrylate, (meth) acrylate refers to acrylic acid Or methacrylate. First, the adhesive composition of the present invention [J]. The adhesive composition of the invention P] contains an acrylic resin (A) and contains one ethylenically unsaturated group. An aromatic compound (9) and an ethylenically unsaturated compound containing two or more ethylenically unsaturated groups. The acrylonitrile resin (Α) which can be used in the present invention is an alkyl (meth)acrylate. The monomer (al) is used as a main component, and if necessary, the monomer (a2) containing a functional group is copolymerized as a copolymerization component, and other copolymerizable monomers (a3) can also be regarded as 8 201134905 Copolymerization ingredients. Acrylic resin (eight) in the month of this hair
ya2)當做共聚合成分,從成為丙烯_樹 ς土 J 材與被接著體的密合性更加上升之觀點為較佳(。)的又U ’使基 尤佳= 2Γ丙it二甲基)丙烯酸第三丁酯、(甲_ 酉旨、(甲基)丙烯酸異癸酯、(甲基)丙婦酸‘西旨(、甲辛 Π甲基)丙烯酸硬脂酉旨、(甲基)丙稀酸環己 異坎酉曰專。該等可單獨使用1種或併用2種以上。土)沐酉夂 人成稀酸燒酯系單體(al)共聚合時的含量,相對於丘聚 I to oti 10^100 ^ *% 5 50^ t ί% :=;二:(。甲基)丙稀酸—^ 而j基的單體(a2),例如藉由含有與後述交聯劑(E)反岸 G成官能基的單體,例如:含錄之單ϊ 體"含體ί 之單體、含異她旨基之單 應的= 酸4iiii之例如:(甲基)丙稀酸2-經基乙酉旨、(曱基)丙烯 酯、%、i )丙稀酸5_經基戊醋、(甲基)丙埽酸基ί 臭)酉夂8_經基辛醋等丙烯酸經基烧酯 '己内醋變性(曱 ;' (^)^ίί;ίίϊ;*Γ,;Γ' 201134905 ΞΪίt等-ΐ有一,級經基之單體;(甲基)丙烯酸2-羥基丙醋、(曱基) 夷旨、(曱基)丙稀酸3'氯經基丙醋等含有2級經 ^ 曱基)丙稀酸2,2-二曱基織乙s旨等含有3級經基之 單體當巾’由與交義⑹的反應性優異的觀 丙嫌級經基之單體’又,較佳為使用雜質的二(曱基) 泰3有比例^ 〇.5%以下者’更佳為0.2%以下者,尤佳為 較佳°。。具體而言’丙稀酸2_經基乙醋,丙稀酸4-經基丁醋 酸、ΐίί基體,例如:(甲基)丙烯酸、丙烯酸二聚物、巴豆 N•甘醇酸、桂皮酸等,其中,又以使用(曱基)丙ti較 和丙體’例如:(甲基)丙烯酸第三丁基胺基乙酯、(甲 酸2 基之單體,例如異氰酸2-丙稀酿氧乙醋、異氰 酉夂2-甲基丙烯醯氧乙醋或此等的氧化烯加成物等。 亂 丙稀igm’.例如:(甲基)丙稀酸環氧丙酿、〇 可單獨使用也可伽2種以上。 =,較佳為㈣重量%,尤佳為01〜10 j更佳H刀 ====的單體_含量過多,黏度“ 酸 獅 酯、⑽丙脚铺_3_苯氧細旨、苯乙婦、 201134905Y2) As a copolymerization component, from the viewpoint that the adhesion between the propylene-tree shale J material and the adherend is further increased, it is preferable that U' makes Kyoujia = 2 Γ it it dimethyl) Tert-butyl acrylate, (methyl ketone, isodecyl (meth) acrylate, (methyl) propyl benzoate oxime (, methyl sulfonium methyl) acrylate), (meth) propyl Dilute acid ring hexanyl arsenic. These may be used alone or in combination of two or more. Earth) Muxi people into a dilute acid-burning ester monomer (al) copolymerization content, relative to the hills I to oti 10^100 ^ *% 5 50^ t ί% :=; 2: (.methyl)acrylic acid-^ and the monomer of the j group (a2), for example, by containing a crosslinking agent (described later) E) a monomer which is a functional group of the anti-shore G, for example, a monomer having a recorded monoterpene "containing a monomer, a homozygous group containing the same as the acid group 4iiii, for example: (meth) propylene Acid 2-by ethyl hydrazide, (mercapto) acrylate, %, i) acrylic acid 5 _ pentyl vinegar, (methyl) propyl phthalate ί 酉夂 8_ by acrylic acid such as octyl vinegar Derivatization of the ketone ester by the base ketone (曱; ' (^)^ίί; ίίϊ; *Γ,;Γ' 201134905 ΞΪίt et al. a monomer of a thiol group; a 2-hydroxypropyl acrylate (meth) acrylate, a thiol amide, a fluorene-based propyl acetonate The acid 2,2-didecyl acetylene s is intended to contain a monomer having a 3-stage radical, and is preferably used as a monomer which is excellent in reactivity with the cross-linking (6). The impurity of the di(indenyl) Thai 3 has a ratio ^ 〇.5% or less, preferably more than 0.2%, and particularly preferably. . Specifically, 'acrylic acid 2_-based ethyl vinegar, acrylic acid 4-pyridinic acid, ΐίί matrix, for example: (meth)acrylic acid, acrylic acid dimer, croton N•glycolic acid, cinnamic acid, etc. , wherein, in addition, the use of (mercapto) ti ti and the propylene 'for example: (meth)acrylic acid tert-butylaminoethyl ester, (formic acid 2-based monomer, such as isocyanate 2-propene Oxyethyl acetoacetate, isocyanide 2-methyl propylene oxime vinegar or such alkylene oxide adducts, etc.. Isopropyl igm'. For example: (meth) acrylic acid propylene propylene, 〇 It can also be used alone or in combination of two or more. =, preferably (four) wt%, especially preferably 01~10 j better H knife ==== monomer _ content too much, viscosity "acid lion ester, (10) propylene foot shop _3_ phenoxy fine purpose, benzene, women, 201134905
Aril' 二丙二醇酯、(甲基)丙_甲氧基聚乙二_旨 =:=lene)之單體;甲氧基甲基(甲基)丙烯醯胺、乙i基;美 _系單體;(甲基)丙烯酿基味琳^ 基)丙烯 合性單體㈣的含量過多 酯、二(甲基)丙烯匕為目=¥ ’可併用二(甲基)丙烯酸乙二醇 基)丙烯酸聚乙二醇;、::Α2:ί)丙烯酸三乙二醇酯、二(甲 具有2個以上乙烯性不飽―旨、二乙烯基苯等 ⑷: ⑽合單體、聚合起始:並=態 乙酸甲s旨、乙=旨有苯二甲苯等芳香族烴類、 族醇類、响、甲乙= 201134905 該自由基共聚合使用的聚合起始劑, 合起始劑,即偶氮雙異丁腈、偶_ =由f聚 始劑、過氧化苯㈣、過氧化月桂醒、過氧偶=聚合起 苯過氧化鮮艄杨絲合起始鮮#做秘^。二丁基、異丙 丙婦酸系樹脂(A)之重量平均分子量 較佳為30萬〜250萬,尤佳為6〇萬〜2〇〇 =萬〜300萬, 萬。若重量平均分子量過小,則耐久 働萬了 18〇 則需要大量稀釋溶劑,於塗佈性或成本方"不』、的頁,’若過大 子量)又宜為丙的分散度(重量平均分子ί/i量平均分 于里)且為20以下,尤佳為;(〇以下,更 I的S分散度過高,則黏接劑層的耐久性能降低,且 泡的傾向。又,分散度的下限,由製造極限的觀點,通易起 佳為,5, =',Ι(Α)的玻璃轉移溫度,較佳為孤20C,。尤 力的傾向,若過低則耐熱性有降低的傾向。要 而得的重量為^用標準聚苯乙烯分子量換算 司製「驗Μ95(本體)」本=公 使用而測定者:管柱制饮GPC KF_=排= iiii L^^ils:10rxl°7' 均八+ : 一乙知基苯共聚物、填充劑粒徑:ι〇μηι),數量$ 使用同樣的方法。又,分散度可由重量平^ίΐ 平均分子量求得。又,玻璃轉移溫度係由F0X算式=Aril' dipropylene glycol ester, (meth) propyl methoxypolyethylene diol =:=lene) monomer; methoxymethyl (meth) acrylamide, ethyl i; (meth)acrylic styrene-based aryl-based propylene monomer (IV) content of excess ester, di(meth) propylene hydrazine for the purpose = ¥ 'co-di(meth) acrylate glycol group can be used together Acrylic acid polyethylene glycol;,::Α2: ί) Triethylene glycol acrylate, two (A has two or more ethylenic unsaturated, divinylbenzene, etc. (4): (10) monomer, polymerization initiation: And = acetic acid, 甲, B = aromatic hydrocarbons such as benzene xylene, alcohols, ring, methyl b = 201134905 polymerization initiator used in the radical copolymerization, starting agent, azo Double isobutyronitrile, even _ = from f starter, benzene (IV), oxidized laurel, oxidized couple = polymerization benzene oxidized fresh 艄 丝 丝 起始 起始 做 做 做 做 做 做 做 。 。 。 。 The weight average molecular weight of the isopropylidene-acrylic acid resin (A) is preferably from 300,000 to 2.5 million, and particularly preferably from 10,000 to 2,000 to 10,000 to 30,000, and if the weight average molecular weight is too small, it is durable. If you are 18, you need a lot of thin Solvent release, on the page of coating property or cost side, if it is too large, it should be the dispersion of C (the average weight of molecules ί/i is divided equally) and is 20 or less. (In the following, if the S dispersion of I is too high, the durability of the adhesive layer can be lowered, and the tendency of the bubble is. Further, the lower limit of the dispersion is from the viewpoint of the manufacturing limit, 5, = ', Ι (Α) glass transition temperature, preferably solitary 20 C. The tendency of eu, if too low, the heat resistance tends to decrease. The weight obtained is the standard polystyrene molecular weight Conversion system "test Μ 95 (body)" = public use and measured: tube column drink GPC KF_= row = iiii L ^ ^ ils: 10rxl ° 7 ' all eight + : a bis- benzene copolymer, filling Particle size: ι〇μηι), quantity $ Use the same method. Further, the degree of dispersion can be determined from the average molecular weight of the weight. Also, the glass transition temperature is determined by the F0X formula =
Wn . M I ! Tjgn I _ IVa m , + · ·Wn . M I ! Tjgn I _ IVa m , + · ·
Tg:共聚物的玻璃轉移溫度(jgTg: glass transition temperature of copolymer (jg
Sis玻璃轉移溫度(κ) wa:單體A的重量分率 =的玻璃轉移溫度(κ)屬:單體B的重量分率 g 丁_的均聚物的玻璃轉移溫度(Κ_)·:單體N的重量分率 201134905 (Wa+Wb+· · *+Wn=l) 又」本f明巾,由能以良好平衡性滿足耐久性及抑制漏光的 觀點,就輯酸系樹脂(A) ’宜個於側鏈具有紐的丙烯酸系樹 脂(A 1)及於側鏈具有敌基的丙烯酸系樹脂(a〗)。 上述於侧鏈具有羥基的丙烯酸系樹脂(A1)(以下有時簡稱「丙 烯酸系樹脂(A1)」),只要是在側鏈含有羥基的丙烯酸系樹脂即可, 例如’可綱使含雜之單體絲合的方法、使含有官能基的丙 稀酸樹脂的官能基翻時财能與該官能基反應的官能基及經基 的反應化反應(後變性)方法等製造者。 該等之中,使用將含有祕之單體的躲合成分與其他共聚 合成分共聚合而成者’於工業化製造時能簡便地得到於側鍵含有 ,基,丙烯酸細脂(A1)的觀點為較佳,該丙稀酸織脂(A1),可 藉由就構成上述丙烯酸系樹脂(A)的含有官能基之單體言, 使用以含羧基之單體當做必要成分而獲得。 又’丙烯酸系樹脂(A1),就含羥基的單體以外的共聚合成分 而言,宜實質上不含含絲之單體,更佳為也實質上不含魏基以 外的其他含官能基的單體。「實質上不含」,係指上述單體的含有 比例為1重量%以下,較佳為01重量%以下,尤佳為不含。 於上述侧鏈含有羧基的丙烯酸系樹脂(A2)(以下有時簡稱為 「丙烯酸系樹脂(A2)」,/口、要是於側鏈含有缓基的丙稀i系樹脂即 了,例如侧使含贼之單體共聚合之方法、使含有官能基之丙 雄酸系樹脂之官能基與同時具有能與該官能基反應的官能基與缓 基的化合物反應(後變性)的方法等製造者。 s亥等之中’仙將含有含麟之單體的共聚合成分與其他丘 ?^合成分共聚合者,於卫業化製造時關便地得到含有麟的丙 烯酸系樹脂(A2)的觀點為較佳,制烯酸系樹脂(A2),可藉由就構 成上述丙稀酸系樹脂(A)的含官能基的單體㈣而言,使用含 的單體當做必要成分而獲得。 又,,烯酸系樹脂(A2) ’就含羧基之單體以外的共聚合成分 而言,宜實質上不含有含錄之單體,又,實質上也不含缓基以 13 201134905 =其他含官能基之單體較佳。「實質上不含」,係指上述單 3有比例為!重量%以下,較佳為01重量%以下,尤佳為不人。 曰匕“ί?用丙稀酸系樹脂(A1)及丙烯酸系樹脂(A2)時,丙烯酸ί樹 t(Al)與丙烯酸系樹脂(Α2)的重量平均分子量的差異少 ^交聯後的聚合物網絡的凝集力而提高耐久性,故為較佳,^ δ,丙烯酸系樹脂(Α1)與丙烯酸系樹脂(Α2)的重量平均 旦= ((Α1)/(Α2))較佳為(八1)/(八2)=〇 5〜15,更佳為(Α1)/ 〇 二 又更佳為(Α1)/(Α2)=0.9〜1.1。 · · 丙^系樹脂(Α1)與丙烯酸系樹脂(Α2)的配合 承」為(A1WA2)=5G:5G〜99:1,尤佳為(Α1)仏2),4〇〜L.5 更佳為(Α1):(Α2)=70:30〜90:10。 ·5 若丙烯酸系樹脂(Α1)相對於丙烯酸系樹脂(Α2)的含 依存於交聯劑添加量,會發生郷分較幅上升,有耐久性 或耐漏光性降低的傾向’若過少則黏接力有上升過度的 在此,黏接劑組成物Ρ]中含有的經基無基的 =)其宜,基/絲=0.15〜20,尤佳為經基/絲=〇 5〜1〇 竣基-1.5〜2.5。若羥基對羧基的含有比例過多,則依二 如劑添加量,會發生凝夥分率大幅上 | = 低的傾向,若過少職接力有上升過度的傾向。耐漏先性降 黏接劑組成物附的^^基、絲,宜為實質上來- 與丙稀酸系樹脂(A2)的官能基,但也ΐ為來^ 成分贿駐絲。料柿域 可使㈣含有1個乙雜不飽和基料麵化合物 且有「單官驗料舰合物⑻」,只要是分i内 具f方魏與1個乙雜不飽和基的化合物即可 C 2 烯丙基等。 w W基)丙减基、巴五酿基、乙稀基、 以人ϋ能其,芳香ΐ化合物⑹,在其構造中,上述宫能基當尹又 s 土)丙細酿基之化合物,即單(曱基)丙稀酸_系化合物 14 201134905 時’於利用活性能量射、線及/或熱硬化時容易進行反應之觀 單官能性芳香族化合物(B)含有的芳香環的個數,可為丨個^ 可為多個,由可取得黏接物性平衡的觀點,較佳為含有丨個 環的化合物,由效率良好、可控繼接層的折射 點,較佳為含有2姆香_化合物。 的觀 二^等:^絲衍生物#,自旨'㈣單官能性料族化合物 (b2),例如本甲酸衍生物、鄰苯二曱酸衍生物等。 的槿宜為致苯⑩的經基的氮原子在含有(甲基)丙烯酿基 取代的構造的衍生物(bM),二經基苯衍生物,宜為 =一齡具有的2個絲的其巾—個或兩個氫原子在 其 丙烯醯基的構造部位經取代的衍生物(M-2)。 ( 土) 上述單官能性芳香族化合物⑼,具體而言,例如趟系 ,务香族化合物(bl)、S旨系單官能性芳香族化合物(b2)等'、2 ί能ίϊΐ族化合物(bl),例如:苯紛系衍生物、兒茶§分、間^二 R —(X-0)Sis glass transition temperature (κ) wa: weight fraction of monomer A = glass transition temperature (κ) genus: weight fraction of monomer B g glass transition temperature of homopolymer_(Κ_)·: single The weight fraction of the body N is 201134905 (Wa+Wb+· · *+Wn=l). In addition, the f-type wipes are made of acid-based resin (A) from the viewpoint of satisfying durability and suppressing light leakage with good balance. It is preferable to use an acrylic resin (A 1) having a side chain and an acrylic resin (a) having an enemy group in a side chain. The acrylic resin (A1) having a hydroxyl group in the side chain (hereinafter sometimes referred to as "acrylic resin (A1)") may be an acrylic resin having a hydroxyl group in a side chain, and for example, A method of merging a monomer, a method of reacting a functional group having a functional group of a functional group-containing acrylic resin with a functional group, and a reaction reaction (post-denaturation) of a radical. Among these, the use of a copolymerization component containing a monomer containing a secret monomer and other copolymerization components can be easily obtained from the viewpoint of a side bond, a base, and a fine acrylic acid (A1). In the above, the acrylic acid-containing resin (A1) can be obtained by using a monomer having a carboxyl group as an essential component in order to constitute a functional group-containing monomer of the acrylic resin (A). Further, the 'acrylic resin (A1) preferably contains substantially no filament-containing monomer in the copolymerization component other than the hydroxyl group-containing monomer, and more preferably contains substantially no functional group other than the Wei group. Monomer. The term "substantially free" means that the content of the above monomer is 1% by weight or less, preferably 0.1% by weight or less, and particularly preferably not contained. The acrylic resin (A2) having a carboxyl group in the side chain (hereinafter sometimes abbreviated as "acrylic resin (A2)"), or the propyl i-based resin containing a slow-base group in the side chain, for example, A method of copolymerizing a monomer containing a thief, a method of reacting a functional group of a functional group-containing propyl tertyl resin with a compound having a functional group capable of reacting with the functional group and a slow group (post-denaturation), and the like In the case of shai, etc., the scent will contain a copolymer of a monomer containing a lining and a copolymer of other mounds, and will be obtained by the acrylic resin (A2). In view of the above, the olefinic acid-based resin (A2) can be obtained by using the monomer-containing monomer (IV) constituting the above-mentioned acrylic resin (A) as an essential component. Further, the olefinic resin (A2) 'is preferably not contained in the copolymerizable component other than the monomer having a carboxyl group, and substantially does not contain a slow group to be 13 201134905 = other The monomer having a functional group is preferably "substantially free", which means that the ratio of the above single 3 is! The amount is 5% or less, preferably 01% by weight or less, and particularly preferably not. 曰匕 "When using acrylic resin (A1) and acrylic resin (A2), lactic acid t (Al) and acrylic acid The difference in weight average molecular weight of the resin (Α2) is less than the cohesive force of the polymer network after crosslinking, and the durability is improved, so that it is preferably δ, acrylic resin (Α1) and acrylic resin (Α2). The average weight of the denier = ((Α1) / (Α2)) is preferably (eight 1) / (eight 2) = 〇 5 to 15, more preferably (Α 1) / 〇 2 and more preferably (Α 1) / (Α 2 ) = 0.9 to 1.1. · · The combination of the acrylic resin (Α1) and the acrylic resin (Α2) is (A1WA2)=5G:5G~99:1, especially preferably (Α1)仏2),4 〇~L.5 is better (Α1): (Α2)=70:30~90:10. ·5 If the content of the acrylic resin (Α1) relative to the acrylic resin (Α2) depends on the amount of crosslinking agent added, the amount of bismuth will increase, and the durability or light leakage resistance will decrease. Here, the relay has an excessive rise, and the binder composition Ρ] contains a base-free group =), preferably, the base/wire = 0.15 to 20, and particularly preferably a warp group/filament = 〇5~1〇竣Base -1.5~2.5. If the ratio of the hydroxyl group to the carboxyl group is too large, the amount of the condensing agent tends to be significantly lower than the amount of the second addition agent, and the tendency to increase excessively tends to be excessive. Leak-proof first drop The composition of the adhesive attached to the composition of the adhesive is preferably a functional group with the acrylic resin (A2), but it is also a component of bribe. The persimmon field can (4) contain one ethylidene unsaturated base compound and have a "single-sense sample compound (8)", as long as it is a compound having f-square and one ethyl-unsaturated group in the i- It can be C 2 allyl or the like. w W base) propyl group, phenanthrene group, ethylene group, arsenic, aromatic hydrazine compound (6), in its structure, the above-mentioned compound of the uterine energy base, Yin s soil) That is, the number of aromatic rings contained in the monofunctional aromatic compound (B) which is easily reacted by active energy radiation, linear and/or thermal hardening when the single (mercapto)acrylic acid-based compound 14 201134905 It may be a plurality of materials, and may be a plurality of materials. From the viewpoint of obtaining a balance of adhesion properties, it is preferably a compound containing a ring, and the refractive index of the controllable relay layer is preferably 2 m. Fragrance_compound. The view of the two is equal to: ^ silk derivative #, from the purpose of '(4) monofunctional compound compound (b2), such as the present formic acid derivative, phthalic acid derivative and the like. The nitrogen atom of the benzene group 10 is a derivative (bM) containing a (meth) acryl-substituted structure, and the diphenylbenzene derivative is preferably two filaments of the first age. A derivative (M-2) in which one or two hydrogen atoms are substituted at the structural portion of the acryloyl group. (土) The monofunctional aromatic compound (9), specifically, for example, an anthraquinone compound, a scent compound (b1), a S-based monofunctional aromatic compound (b2), etc., and a 2 能 ϊΐ ϊΐ compound ( Bl), for example: benzene derivatives, catechu § points, between ^ two R - (X-0)
0 (1) (式中’ R為氫原子或曱基,χ為伸烧基,n為丄以上的整數。 —=2)中f x為伸烧基,其中又以碳數1〜_伸關 SI為㈡伸乙基、伸丙基、四亞曱基等碳數1 鏈的以2 f氧化烯基鏈部位的情形,可為同樣的氧化稀! 的均來物’也可為不同的氧化烯基鏈以無規或嵌段狀丘聚人者 輕基又忿Ϊ伸ϊί也可具有取代基’取代基通常為齒、素廣:子、 較佳為經i基基、硫絲(sulfanyl)、芳基、雜芳基等,其斗 上述通式(1)中的n為i以上的整數,較佳為U ,尤佳肩 15 201134905 ;為2 值若過大’則丙稀酸系樹脂的耐濕熱性有降 去ίΛΓ制折射率或複折射,伸絲或氧化烯基構 造以較短者較佳,所以η小較好。 上述(bl-Ι)的具體例’例如:(曱基)丙稀酸苯氧基乙醋、(甲基 ^稀酸苯基二乙^醇S旨、(甲基)丙烯酸苯基三乙二醇醋、(甲基)丙 烯酸苯基四乙二醇醋、(甲基)丙烯酸苯基八乙二醇醋等乙二醇構造 的重複數為2〜8(較佳為2〜4)的(曱基)丙烯酸苯基聚乙二醇酯、(曱 基)丙烯酸苯氧基丙醋、(曱基)丙烯酸苯基二丙二醇醋、(甲基)丙稀 酸,基聚丙二_旨、(甲勤丙稀酸2_錄_3_苯氧基丙g旨、(甲基) 丙烯酸乙氧化苯基苯酯、(曱基)丙烯酸壬基苯氧基乙酯、(甲基)丙 烯酸壬基笨基一乙二醇酯等乙二醇構造的重複數為2〜8(較佳為 2〜4)的(曱基)丙烯酸壬基苯基聚乙二醇酯、(甲基)丙烯酸壬基苯氧 基丙酯、(曱基)丙烯酸壬基苯基二丙二醇酯等丙二醇構造的重複數 為2〜8(較佳為2~4)的(曱基)丙烯酸壬基苯基聚丙二醇酯等,市售 品例如:丙烯酸苯氧基聚乙二醇酯(大阪有機化學公司製,商品名 「visc〇at#193」)、丙烯酸2-羥基-3-苯氧基丙酯(大阪有機化學公司 製’商品名「viscoat#220」、丙烯酸苯氧基二乙二醇酯(共榮公司製, 商品名「Light acrylate P2HA」、丙烯酸苯基三乙二醇酯(日立化成 公司製,商品名「phenoxy triethyleneglycol acrylate」)、丙烯酸苯 基四乙二醇酯(日立化成公司製,商品名r phen〇xy tetraethyleneglycol acrylate」)、(日立化成公司製,商品名 rn〇nyl phenoxy ethyl acrylate」)、丙烯酸壬基苯基二乙二醇酯(日立化成公 司製,商品名「nonyl phenoxy diethylene glycol acrylate」)、丙烯 酸壬基本基四乙二醇g旨(日立化成公司製’商品名「n〇nylphen〇Xy tetraethylene glycol acrylate」)、丙稀酸壬基苯基八乙二醇酯(日立 化成公司製,商品名「nonylphenoxy octaethylene glycol acrylate」)、 (曱基)丙烯酸壬基苯基聚丙二醇醋(日立化成公司製,商品名「nonyl phenoxy plypropylene glycol (meta)acrylate」)、丙烯酸乙氧化鄰苯 基苯酯(新中村化學公司製,商品名「NKesterA-LEN-10」)等。 苯曱酸衍生物,宜為苯甲酸的羧基的氫原子在含有(甲基)丙烯 16 201134905 酿基的構造部位經取代的構造的衍生物(b24) ’鄰苯二甲酸衍生 物,宜為鄰苯二曱酸具有的2個羧基的其中之一或兩個氫原子於 含有(曱基)丙烯醯基的構造部位經取代的構造的衍生物(b2_2)。 該含有(甲基)丙烯醯基之構造部位,宜為以前述通式(丨)表示 者。 ’、 上述衍生物(b2-2)的具體例,就市售品而言,例如鄰苯二甲酸 2-丙烯醯氧乙基_2_羥基丙酯(大阪有機化學公司製,商品名 「viSCOat#2311HP」)、2-丙烯醯氧乙基氫鄰苯二曱酸酯(大阪有機 化學公司製,商品名「viscoat#2〇〇〇」)、2-丙烯醯氧丙基氫鄰苯二 曱曰(大阪有;化學公司製,商品名rvisc〇at#2i〇〇」)、2_曱基丙 稀醯氧乙基鄰苯二曱酸(新中村化學工業公司製,商品名「c 等。 」’ 任、本發明可使用的單官能性芳香族化合物⑼,如前所述,只要 是分子内具有芳香環與丨個乙烯性不飽和基的化合物即無特殊限 制’但—是^έ為分子内含有2個以上芳魏、硫原子或漠原子者。 芳香環、硫原子或溴原子已知為折射率極高的構造且容易導 入丙稀酸基單體的構造,該等構造藉由導人丙烯酸系樹脂的側鍵 (較,為/則鏈上遠離主鏈的位置),當丙烯酸系黏接劑層全體受到應 么呀,旎使產生的複折射成分於拉伸方向側仏軸側)的折射 常良好效率上升。 結果,藉由含有在使相對於垂直於拉伸方向汐軸侧)的折射率 上升的(曱基)丙烯酸烷酯主體的丙烯酸樹脂、與上述單官能性化合 = (Β)的聚合體的合計構成_接射’絲接鬚的複折射^氏 消’可。成為不紐生複折射的黏接爆,能以良好效率抑制漏光。 a单官能性芳香·合物⑻含肴的滿足「含有2個以上芳香 =、硫原子或溴原子」條件的構造部位,例如: 苯造、絲基構造等,其中又以聯苯構造、ΪΪ構 社於可有ί率提供正的複折射提高效果的觀點為較佳。 叫s生方香族化合物⑻,具體而言,例如:含有聯苯構 k勺(甲_丙細酸酯系化合物、含有苯硫構造的(曱基)丙烯酸醋系 17 201134905 化合物、含有萘構造的(甲基)丙烯酸酯系化合物、含有溴苯基構造 、 的(甲基)丙烯酸酯系化合物等。 ,含有聯苯構造的(甲基)丙烯酸酯系化合物,例如:(曱基)丙烯 酸聯苯醋、(甲基)丙烯酸聯苯氧烧醋、(甲基)丙烯酸聯苯聚伸絲 二醇酯等。 該(甲基)丙稀酸聯苯氧烷酯’例如:烧基的碳數為的(甲基) 丙烯酸聯I氧編旨,具體而言,例如:(甲基)丙烯酸聯苯氧曱酷、(甲 基)丙烯酸聯苯氧乙酯、(曱基)丙烯酸聯苯氧丙酯等。 該(甲基)丙烯酸聯苯聚伸烷基二醇酯,例如:伸烷基的碳數為 1〜8,伸烷基二醇鏈的重複單位數為2〜1〇的(甲基)丙烯酸聯苯聚伸 烷^二醇’具體而言,例如:(甲基)丙烯酸聯苯二乙二醇酯、(甲基) 丙烯酸,苯三乙二醇酯、(甲基)丙烯酸聯苯四乙二醇酯、(曱基^ 烯酸聯苯二丙二醇醋、(曱基)丙烯酸聯苯聚乙二醇酯、(甲基)丙稀 酸聯苯聚丙二醇酯等。 ,认°亥專之中,車父佳為(甲基)丙烯酸聯苯聚伸垸基二醇酯,尤佳為 從可有效率地提供正的光彈性效果的觀點,為 二更佳為乙二醇鏈的重複單位數為1〜4的(甲ί丙稀i: 笨聚乙二醇。 西ιϊί有 造的(甲基)丙烯酸酉旨系化合物,例如··(甲基)丙烯 稀酸苯硫烧醋等’該(甲基)丙稀酸苯基硫垸酯, lUit1:12的(甲基)丙稀酸苯基硫烧酉旨,具體而言, ,丙_ 丁酷、(甲基)丙二:): 丙 =本硫己醋、(甲基)丙稀酸苯硫庚酯、(甲基)丙婦酸笨^ 酉曰、丙細酸苯硫壬酯、(甲基)丙烯酸苯硫癸醋等。 从担ft之巾,較佳為(?基)丙職苯魏®旨,尤料從可有效率 3光彈性效果的觀點,為(甲基)丙烯酸苯硫乙酯, 丙烯酸苯硫乙酯。 阳又1土局 該含有萘構造的(甲基)丙稀酸醋化合物,例如.* 丙卸酸酯 < 甲基)丙烯酸萘氧基甲§旨代基)丙烯酸萘氧基&(旨/甲 18 201134905 基)丙婦酸萘氧基丙酯等。 ' μ漠苯,造的(甲基)丙稀酸醋,例如:(甲基)丙烯酸漠 Γ)丙烯酸二漠苯氧基甲酯、(甲基)丙烯酸三溴苯 )丙職喊苯氧基㈣、(甲基)丙烯酸五溴苯氧 i r甲曰其If f烯酸溴苯氧基乙酯、(甲基)丙烯酸二溴苯氧基乙 三鮮氧基乙酯、㈣㈣酸四溴苯氧基乙醋、 氧基乙醋、(甲基)丙稀酸溴苯氧基丙醋、(甲基) 酯、(甲基)丙烯酸三漠苯氧基丙酯、(甲基)丙 基丙醋、(甲基)丙烯酸五溴苯氧基丙醋等苯環經1〜5 们溴原子取代的(甲基)丙烯酸苯烷基烷酯。 又’燒基的碳數通常為1〜12。 又,單官能性料·合物(Β),不含容易 於每成早g此性方香族化合物(切與乙烯性不飽和化人物 的自峨失、耐娜改良效果咖可能性少的觀 -醇物⑻當中,尤佳為丙烯酸苯基聚乙 酸壬基苯氧基丙^^單位數為2♦丙烯 i:二=二酸以' (甲基)丙烯酸聯苯聚乙二 或2 基具體而言,為異_旨基、經基、縣當中任!種 單官能性芳香族化合物(B)的重.1 八 . 2〇〇:1〇,000,21〇^〇〇 , 22^〇; =過念過不易^ 果的傾向。按心w合易揮發’會有難以得到發明效 單官能性芳香族化合物⑻,其弓丨九點在靴以上較佳,尤 19 201134905 344【3ΐ〇0^Ζν^'5〇〜4〇ίη:,^16〇〜3〇〇ΕΐΜ 若過小^由於揮心2增加會有複折射調整能力降低的傾向’ = 上升,黏接劑乾燥時容易揮發,會有難以獲 -5 點:170〜199。〇等。f<來者插/匕郑苯基苯酚丙烯酸酯(引火 點:13t=c):丙_^旨(_:=^。苯氧基乙醋(引火 (A)i〇riS方^的含量,相對於丙稀酸系樹脂 的含量若過乡,紐料·合物⑼ 少則有耐漏紐降低耐/細會有_化的傾向,若過 和物S以月3:^^個官:)生=生不,基的乙烯性不飽 分子内含有2 _上乙烯性不二基的)體=1 丙二醇醋、二(甲基)丙烯酸丁享 ;:(甲基)丙城聚 以二:烯^;==:⑽二•烯 季戍四醇酯、乙二醇二環氧__基)丙烯“7^基=| 20 201134905 i丙鄰苯二情二環氧㈣二(曱基)丙烯酸 :二二S 基?二氧 3=^ 等。 基的單體即可,例如個上乙稀性不飽和 酸季戊四雜、^田:基)細酸三經甲基丙烧、三(甲基)丙稀 " ——曰(甲基)丙烯酸季戊四醇酯、三(甲基;)丙烯酸-李 ' -(^)Λ21;ί 土i, 季戊四醇醋、三基)丙烯醒氧乙氧基 (曱氧丙崎(甲基)丙烯咖旨、異氰尿酸氧乙 ==氧酸 酸西旨基甲酸料化合物,為分子内具有胺基甲 ίίίί Li ,糸化合物’使用將含有織的(曱基)丙烯 二乂 i:二0 /、夕元異氰酸酯系化合物(視需要,多元醇系化合物), 〜=^卩反可絲麟料可,錢好均分子量,通常 ⑽化合物(c)的含量,相對於丙婦酸系樹脂 f二希望為請〜3(3重量份,較佳為G.5〜w重量份, =性、耐漏光性均有降低關向,若過少刺漏^^足^ 本發明中’可適#調整交聯密度,而適當調整又, 二物生的觀點,相對於上述單官能性芳香族化 二化合物(C)的合特,單官紐芳香族化 =:==佳為~,更佳為 相對於單官能性芳香族化合物⑻與多官能性不飽和化合物⑹ 21 201134905 的合計量,單官能性芳香族化合物⑻的含有比例若過小,則多官 能性不飽和化合物(〇的含_對於單官能性芳香族化合物 多,因此交聯密度上升過度,會有欠缺附著感的傾向。又官 能性芳香魏合物⑻相對於單官紐芳香族化合 不,化合物(c)的合計量的含有比例若過大,則多官能性不飽ς 二匕二,^的含量相對於單官能性芳香族化合物⑼變少,因此交聯 始、度上升不多,耐久性有變差的傾向。 Μ·/ ^ ’關於本發明的(Α)〜(C)成分,就利用後述方法測定的光彈 性係數而言,丙烯酸系樹脂(A)的光彈性係數為負,且含有H 稀性不飽和基的芳香族化合物(B)與含有2個以上乙稀性不飽和美 的乙烯性不飽和化合物(c)的硬化物的光彈性係數為正時,於ς 效率地消除複折射的觀點為較佳。 啕 本發明中,係提供將含有上述丙烯酸系樹月旨⑷、單官能性 ,族化合物⑻及乡宫雛不鮮化合物(〇#做必要成分的 ^成物[I],利用活性能量射線及/或熱(活性能量射線照射及/或 接劑。該硬化,_單編峰麵化合物(Β) SiiTb 化合物(C⑽雜能量祕及7或錄合(高分子 a u 酸系樹脂⑷’於涉及反應時,祕於以活性能量射 ==進彳㈣單細_族化合謂及多官紐 ? 口,f)W刀子化,也會伴隨丙烯酸系樹脂(Α)與單官能性芳夫 =化口勿(B) ’及與多官能性不飽和化合物⑹的高分子化而發生硬 上述以'舌性迠量射線及/或熱進行硬化時,黏接劑纟且成物m承 能使活性能量射線照射時及域加熱時的 τ ρ Ϊ/α本ί、明中,將上述黏接劑組成物m硬化的方法,例如除 了述()〜(C)成分或(D)成分以外,尚有更使含有交聯,(Ε) 物[1]利用活性能量射線及職化心S使; 勺方去。又,使用交聯劑(Ε)時,丙烯酸系樹脂(Α)宜為具有 22 201134905 官能基^,藉由該官能基與交聯劑反應可進行硬化(交聯)。 ㈣ft?::上述利用活性能量射線及/或熱(活性能量射線照射 於能以極短時間的紫外線等的活性能量射線照 為較佳,又,併用利用交聯劑使硬化(交聯)亦為較 ίί異ϊ夠獲喊喊接_交聯密度、提高難力而使敎性更 聚合起始劑(D) ’例何使用絲合紗娜1)、熱聚合 =等各種聚合起始劑,尤其使用光聚合起始劑(dl)於能夠 =極短時_紫外線等活性能量射線的照射使硬化的觀點為較 又,使用上述光聚合起始劑(dl)時,利用活性能量射線,昭 t成物[1]硬化,使用熱聚合起始劑(d2)時,利用加熱使黏接 刎組成物[I]硬化,但視需要併用兩者亦為較佳。 δ亥光聚合起始劑(dl),只要是由於光作用而產生自由基者即 y ’無特殊p艮制,可使用分子内自開裂型的光聚合起始劑⑷或 氫提取型光聚合起始劑(犯_2)。 分子Π自開裂型的光聚合起始劑(dl_1),例如:4-苯氧基二氯苯 ^酮、4-第二丁基二氯苯乙酮、二乙氧基苯乙酮、2_羥基_2_甲基 苯基丙^同、H4-異伸丙基苯基>2_羥基_2_曱基丙小g同、H4_+ 一燒基本基)-2-每基-2-曱基丙_1_酮、4_(2_經基乙氧基)_苯基(2_經基 _2_丙基)酮、1-經基環己基苯酮、1曱基小㈣甲硫基)苯基]_2_味琳 ^丙-1·•酮、苯偶因、苯偶因曱醚、苯偶因***、苯偶因異丙醚、 本偶,異了_、卡基—甲基縮酮、α_酿氧基月亏醋、醯基氧化膦、 :基苯基乙醛酸酯、4-(2-羥基乙氧基)苯基_(2_羥基_2_丙基)酮、4_ 苯甲醯基-4’-二曱基二苯硫等’其中較佳為2_羥基_2_曱基苯基 丙-1-酮、1-經基環己基苯_。 #又,氫提取型的光聚合起始劑(dl_2),例如:二苯基酮、苯曱醯 基苯曱酸、苯曱醯基苯曱酸甲酯、4_苯基二苯基酮、羥基二苯基酮、 3^3 -二甲基-4-曱氧基二苯基酮、2,4,6_三曱基二苯基酮、4-曱基二 苯基嗣、。塞4J[S](thk)xanthone)、2-氯噻吨酮、2-曱基噻吨酮、2,4- 23 201134905 二甲基噻吨酮、異丙基噻吨酮、樟腦醌、二苯并環庚酮 (Di^enzosuberone)、2-乙基蒽醌、3,3,,4,4,_四(第三丁基過氧化幾基) 二苯基綱、苄基、9,1〇_菲醌等’其中,較佳為二苯基酮、甲基二 本基明、2,4,6-三T基二苯基酉同。 本發明中,由耐久性優異的觀點,使用氫提取型的光聚合起 始,(dl-2)較佳,尤其,併用分子内自開裂型的光聚合起始劑(⑴」) 與氫提,型的光聚合起始劑(dl_2)兩者,於能使黏接劑層的表面部 分的光交聯與内部的光交聯的平衡性良好,且整體性能提高 點為較佳。 就自開裂型的光聚合起始劑與氫提取型的光聚合起始劑的袓 合而言,宜為自開裂型的1_經基環己基苯酮或2_經基_2_甲基+笨 基丙-1-酮與氫提取型的二苯基酮、甲基二苯基酮或 二 苯基酮的組合。 ,一τ丞一 又’視需要就光聚合起始劑的辅助劑而言,可併 三;丙醇胺、4,m職二苯基_翻)、2_二==乙 ,本甲酸、4-二甲基胺基苯甲酸乙醋、4_二甲基胺基苯甲酸(正丁 氧y乙J、4-二曱基胺基苯曱酸異戊醋、4_二曱基胺基苯甲酸孓 乙基己酯、2,4-二乙基嗟吨酮、2,4_二異丙基嘆吨 用1種或併用2種以上。 卞说寻J便 ^,上述熱,合起始劑(d2),例如可使用:過氧化甲乙嗣 氧化環己酮、過氧化曱基環己酮、過氧化?基乙 —^ 雙〒三己基過氧化>環己烧、U-雙(第三丁基過氧化;_3己f5_= 基環己烷、1,1-雙(第三丁基過氧化)_2_甲基環 — 基過氧龄環己烧、U-雙(第三丁基過雙丁 丁基過氧化)丁烧、2,2-雙(4,4-二-第二丁美、厂’元、雙(第二 薄荷烧細n J絲過碑丙坑、對 化氮、異丙苯過氣化氮、第三己基丁甲上丁:氣 α,α,-雙(第三丁基過氧化)二異丙基苯、過 基過氧化風、 基-㈣第三丁基過_故、第三 24 201134905 訂驢、3^5 5 L甲^^2’5·雙(第二丁基過氧化)己块·3、過氧化 過氧化硬脂醯、過氧化琥輯、化月桂酿、 氧化苯甲酿、二正丙基過氧化二:1甲甲酿、過 酉旨、雙(4_第三丁基環己基)過氧化二碳酸西旨"Tjff i化,酸 乙氧基己基過氧化二碳_ 過虱化二碳酸酿、二_第—Α )甲虱基丁基 其τ其备π 。 基過虱化二碳酸酯、二(3-曱基-3_甲氧 f 丁f)過乳化二碳酸酯、邮,_雙(新癸醯基過氧化一:虱 環己基-1-甲基乙基過氧化靳八抑甲f 丁基過氧化新癸酸醋、1-tr f旨、第三己基過氧化三甲基乙酸醋、第: 弟一丁基過乳化-2-乙基己酸酯、第三己基 ;A;f Iff 丁 、第三τ基過氧化月桂酸自旨、第三 gt 酸酯、第三丁基過氧化_2_乙基己基單碳酸 酉^ 、第三丁基過氧化間曱苯甲酸基苯甲 二2 5甲酯、雙(第三丁基過氧化)間苯二甲酸 化本甲酸醋、2,5-二甲基-2,5-雙(苯甲酿基過氧化)己燒7匕丁 1 過氧化稀丙基單碳_旨、過氧化第三丁基三甲基 =(第三丁基過氧化)二苯基鲷、2,3_二甲基_23_ ’ /等 有Π化物系起始餘苯基勝"氧基_2,4二^工= 田雙(甲基丁腈)、2,2:偶氮雙異丁腈、U,_偶氮雙(24-j基戊腈)、2,2,-偶t^(2_甲基丙肺)二氯化氯、22,_偶氮^ 甲基苯基丙月米)二氯化氫、2,2:偶氮雙砰(4_氯苯基)_2_甲基^米] -鼠化虱、2,2’-偶氮雙[Ν·(4·氫苯基>2_甲基丙脒]二氯化氫、22,_] 25 201134905 "(苯基甲基)丙脉]二氯化氫、2,2,-偶氮雙[2_甲基 =丙脉]二氯化氮、仏偶氮雙陶铺乙基)-2_甲基 |·2 M5,6 7广2"" 2_°級°林1基)丙烧]二氣化氫、2,2,_偶氮雙 34。’,心咬·2·基)丙烧]二氣化氫、2,2’—偶氮雙[2·(5-經基 & 基)秘]二氯化氫、2,2:偶氮削叩-經基乙 Ξΐ 22 3 ΐ -[U_雙(經基甲基)乙基]丙酸胺、2,2,_ 1 基乙基)㈣胺]、2,2’·偶氮雙(2_甲基丙酿 ik 2 2 三曱基姐)、2,2’_偶氮雙(2_甲基丙烧)、二 Ϊ丙酸_)、4,4’.雙(4·氰基戊酸、2,2,_偶 等偶氮系起始劑;等。又,該等熱聚合起始 d 了僅早獨使用1種也可併用2種以上。 重量i这相對於前述丙烯酸系樹脂⑷100 0合3有5物職含細少,臟硬^ °'owo° — 就光聚合起始劑(di)而言,併用分子内 〜1:99(重量比),尤佳為(此_-种 姐),更佳為(dl-l):(dl-2)=45:55〜1_(重量比_入女 均會有黏接劑層全體的交聯平衡性崩潰的^向,可 上述照射活性能量射線時,可彻遠料線、料線、近紫 26 201134905 外線、紅外線等光線、x射線、 束、質子射線、中子射線等,但從硬皮^外可利用電子 度、價格等,利用紫外線照射所 ^有=裝置取得容易 子束照射時,又’進行電子束照射時的。又’進行電 始劑(dl)也可硬化。 、「使不使用上述光聚合起 又,進行上述紫外線照射時的 電極燈、超高壓水銀燈破弧燈$原m雨壓水銀燈、無 10〜lOOOmJ/cm2的條件進行。' 5:3=0mJ/cm,較佳為 2〜150_/cm2,較佳為5〜5〇〇mJ/cm2的^^電極燈例,可於 視光源種類、光源與塗佈面的距離“,订二:、射時間 但是通料數秒奶秒,雜形也可為件而/, 子為f丄=二 度或處理時間,視使用的熱聚合起 類 間通常宜,0.2〜20分鐘,尤佳為〇 5〜1〇分鐘。L處理日守 而劑(E) ’例如··異氰酸醋系交聯劑、環氧系交聯劑、氮 物系父聯劑。該等之中,由提高與基材的密合性的 或物的反應性的觀點,較佳為使用異誠酯系交聯^、。 2述異亂酸醋系交聯劑,例如:2,4_甲革二異氰酸酉旨、a卜甲苯 酸匕氫化甲苯二異氰酸酯、u_二曱苯二異氰酸醋、α 了 y本一兴氰酸酯、六亞▼基二異氰酸酯、二苯基甲烷_44-二異 ^酸醋、異佛爾酉同二異氰酸醋、1,3-雙(異氛酸甲基)環己烧、四^ 曱苯亏異氰酸酯、萘二異氰酸酯、三苯基甲烷三異氰酸 酯,及此等的聚異氰酸酯化合物與三羥〒基丙烷等多元醇化合物 的加成體、此等聚異氰酸酯化合物的雙脲體或異氰尿酸體等。 27 201134905 環氧丙_、1,6-己二醇二環氧丙 一衣乳丙趟、甘油三 梨醇聚環氧丙_、聚甘油聚㈣而;'經甲基丙烧二環氧丙驗、山 糖醇、二甘油聚環氧㈣等。< @、季戍四醇聚環氧丙基赤藻 酯 亡述=口定系交聯劑,例如:四經甲基甲烧.三似丙咬基丙酸 雙°定基丙酸酯、N,N,_二苯基甲烧_4,4’-^(。氣丙讀基《〇、N,N,-六亞甲基♦雙(1_氮丙錄基酿胺) 上述二聚氰胺系交聯劑,例如: 氧基甲基三聚氰胺、六丙氧美甲其_ :巧甲基4統、六乙 氮胺、六戊氧基甲基三甲基f聚 胺樹脂等。 4基甲基二聚緩、三聚氛 上述醛系交聯劑,例如··乙二醛、 醛、戊二路、甲醛、乙路、苯甲酸等。—J 一备、馬來二 交聯! T:六亞甲基二胺、三乙二胺、聚乙亞胺、 二亞曱土四月女、一乙二月女、二乙基四胺、異佛 脂、聚醯胺等。 妝妝丞树 上述金屬螯合物系交聯劑,例如m # ^、録、=、飢、鉻、鱗多價金屬的乙_ 酯配位化合物等。 々Q ^ G暴 又,該等交聯劑(E)可單獨使用,也可併用2種以上。 上述父聯劑(E)的含量,通常相對於丙稀酸系樹脂⑷⑽ 份’宜為0.01〜10重量份’更佳為0 05〜5重量份, 重量份。敍聯劑⑹若少,則凝集力不S,有無法得到充分的耐 久性的傾向,若過多則柔軟性及黏接力降低,且耐久性降低,織 得容易發生剝離,因此有難以當做光學構件使用的傾向。 又 本發明中^含有魏偶· (F)當做黏接敝成_ 成分’於更提南對於光學構件的密合性的觀點為較佳。 該矽烧偶聯劑(F),例如:含環氧基的矽烷偶聯劑、含(曱基)内0 (1) (wherein R is a hydrogen atom or a sulfhydryl group, χ is a stretching group, and n is an integer above 丄. -=2) where fx is a stretching group, wherein the carbon number is 1~_ SI is (2) a case where a carbon number of 1 chain such as an ethyl group, a propyl group or a tetradecyl group is a 2 f oxyalkylene chain moiety, and the same oxidation is rare! The average olefinic chain can also be a different oxidized alkenyl chain with a random or block-like condensate. The light base can also be stretched. ί can also have a substituent. The substituent is usually a tooth, a broad one: Preferably, it is an i-based group, a sulfanyl group, an aryl group or a heteroaryl group, and n in the above formula (1) is an integer of i or more, preferably U, particularly preferred shoulder 15 201134905; If the value of 2 is too large, the heat resistance of the acrylic resin may be lowered to reduce the refractive index or birefringence, and the structure of the wire or the oxyalkylene group is preferably shorter, so η is preferably small. Specific examples of the above (bl-Ι) are, for example, (mercapto) acrylic acid phenoxyacetic acid, (methyl benzoic acid phenyl diethanol), (meth)acrylic acid phenyl triethylene glycol The number of repeats of glycolic acid such as alcoholic vinegar, phenyltetraethylene glycol (meth) acrylate, and phenyl octaethylene glycol vinegar (meth) acrylate is 2 to 8 (preferably 2 to 4) ( Thiophene phenyl acrylate, phenoxy acetoacetate, phenyl dipropylene glycol acrylate, (meth) acrylate Dimethyl acrylate 2_ _3_phenoxy propyl g, (meth) ethoxylated phenyl phenyl acrylate, (mercapto) decyl phenoxy ethyl acrylate, (meth) acrylate thiol (mercapto) decyl phenyl phthalate, (meth) methacrylate, having a repeating number of 2 to 8 (preferably 2 to 4), such as an ethylene glycol ester a nonyl phenylpolypropylene glycol (meth) acrylate having a repeating number of 2 to 8 (preferably 2 to 4) propylene glycol structure such as oxypropyl ester or (mercapto) decyl phenyl dipropylene glycol. Commercial products such as phenoxy acrylate polyethylene glycol (Osaka Machine Chemical Company, trade name "visc〇at #193"), 2-hydroxy-3-phenoxypropyl acrylate (product name "viscoat#220" made by Osaka Organic Chemical Co., Ltd., phenoxydiethylene acrylate) Alcohol ester (trade name "Light acrylate P2HA", phenyl triethylene glycol acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name "phenoxy triethyleneglycol acrylate"), phenyl tetraethylene glycol acrylate (Hitachi Chemical Co., Ltd.) Company name, trade name r phen〇xy tetraethyleneglycol acrylate"), (manufactured by Hitachi Chemical Co., Ltd., trade name rn〇nyl phenoxy ethyl acrylate), decyl phenyl diethylene glycol acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name " Nonyl phenoxy diethylene glycol acrylate"), ruthenium acrylate base tetraethylene glycol g (product name "n〇nylphen〇 Xy tetraethylene glycol acrylate" manufactured by Hitachi Chemical Co., Ltd.), nonylphenyl octaethylene glycol acrylate (Nikkim Chemical Co., Ltd., trade name "nonylphenoxy octaethylene glycol acrylate"), (mercapto) decyl phenyl propylene glycol acrylate (Hitachi Chemical Co., Ltd. , the trade name "nonyl phenoxy plypropylene glycol (meta)acrylate"), ethoxylated o-phenyl phenyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "NKester A-LEN-10"), etc. The hydrogen atom of the carboxyl group of benzoic acid is a derivative of the structure (b24) substituted with a structural moiety containing a (meth)acryl 16 201134905 brewing group, preferably two of phthalic acid. One or two hydrogen atoms of the carboxyl group are a derivative (b2_2) having a structure substituted with a structural moiety of a (fluorenyl) acrylonitrile group. The structural site containing the (meth) acrylonitrile group is preferably represented by the above formula (丨). ', a specific example of the above-mentioned derivative (b2-2), for example, a commercially available product, for example, 2-propenyloxyethyl 2-hydroxypropyl phthalate (manufactured by Osaka Organic Chemical Co., Ltd., trade name "viSCOat" #2311HP"), 2-propylene oxiranyl ethyl hydrogen phthalate (trade name "viscoat #2〇〇〇", manufactured by Osaka Organic Chemical Co., Ltd.), 2-propenyl isopropyloxy hydrogen phthalate曰 (Osaka has a chemical company, trade name rvisc〇at #2i〇〇)), 2_mercapto propylene oxyethyl phthalic acid (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name "c". The monofunctional aromatic compound (9) which can be used in the present invention is not particularly limited as long as it is a compound having an aromatic ring and an ethylenically unsaturated group in the molecule, but is not limited thereto. The molecule contains two or more aromatic, sulfur or oxygen atoms. The aromatic ring, sulfur atom or bromine atom is known as a structure having an extremely high refractive index and is easy to introduce a structure of an acrylic group. Leading the side bond of the acrylic resin (more, the position on the chain away from the main chain), when the acrylic adhesive All what it should be, so that laying birefringence produced in the stretching direction component Fo side shaft side) normally refractive good efficiency rises. As a result, the total of the acrylic resin having a (mercapto)acrylic acid alkyl ester main body which is increased in refractive index with respect to the side perpendicular to the axis of the stretching direction and the monofunctional compound = (Β) The composition of the _ 接 接 丝 丝 丝 丝 丝 丝 丝 丝 丝It becomes a bonded explosion that does not have a birefringence, and can suppress light leakage with good efficiency. a monofunctional aromatic compound (8) is a structural part satisfying the condition of "containing two or more aromatic =, sulfur atom or bromine atom", for example, a benzene-based or silk-based structure, in which a biphenyl structure or a bismuth is used. It is preferable that the organization can provide a positive birefringence improving effect at a rate. It is called s raw fragrant compound (8), specifically, for example, a biphenyl-containing k-spoon (a-propyl acrylate-based compound, a sulfonium-containing thiophene acrylate vinegar 17 201134905 compound, containing a naphthalene structure) a (meth) acrylate type compound, a (meth) acrylate type compound containing a bromophenyl structure, etc., a (meth) acrylate type compound containing a biphenyl structure, for example, (mercapto) acrylate Benzene vinegar, biphenyl oxyacetate (meth) acrylate, biphenyl condensate (meth) acrylate, etc. The biphenyl oxyalkyl (meth) acrylate 'for example: carbon number of the alkyl group For the (meth)acrylic acid I oxygen, specifically, for example, (meth)acrylic acid biphenyl oxyhydrazine, (meth)acrylic acid biphenyloxyethyl ester, (mercapto)acrylic acid phenoxypropane Ester, etc. The (meth)acrylic acid biphenyl polyalkylene glycol ester, for example, the alkyl group has a carbon number of 1 to 8, and the alkylene glycol chain has a repeating unit number of 2 to 1 Å. Acrylic biphenyl polyalkylene glycol diol 'specifically, for example: (meth) acrylate biphenyl diethylene glycol ester, (meth) acrylic acid, benzene Ethylene glycol ester, biphenyl ethylene glycol (meth)acrylate, (biphenyl)biphenyl dipropylene glycol vinegar, biphenyl polyethylene glycol (meth) acrylate, (meth) acrylic acid Biphenyl polypropylene glycol ester, etc., in the recognition of the Hai, the car father Jia (meth) acrylate biphenyl polydecyl diol ester, especially from the point of view of the ability to provide a positive photoelastic effect It is more preferred that the number of repeating units of the ethylene glycol chain is 1 to 4 (methyl propylene i: stupid polyethylene glycol. ϊ ϊ ϊ 有 有 有 有 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉(Methyl) propylene dilute acid benzene sulphur vinegar, etc. 'The (methyl) benzoic acid phenyl thioxanthate, lUit 1: 2 (methyl) acrylate thiophene sulphur, specifically,丙_丁酷, (methyl) propylene 2:): propyl = thiocacetate, (meth) benzoic acid thiop-heptyl ester, (methyl) propyl benzoic acid benzoate, propyl benzoate Anthracene ester, (meth)acrylic acid phenylsulfonate vinegar, etc. From the towel of ft, preferably (? base) propyl benzoic acid, especially from the viewpoint of efficient 3 photoelastic effect, Base) phenyl thioethyl acrylate, phenyl thioethyl acrylate. Yang (1) soil-based (meth) acrylate vinegar compound containing naphthalene structure, for example, **propionate <methyl methacrylate phthalate methoxy group / A 18 201134905 base) propanol naphthyl propyl acetate and the like. ' μ desert benzene, made (methyl) acrylic acid vinegar, for example: (meth)acrylic acid desert) acrylic acid phenoxymethyl ester, (meth)acrylic acid tribromobenzene) (iv), (meth)acrylic acid pentabromophenoxy ir-methyl hydrazide, its f-phenethyl bromophenoxyethyl ester, (di) bromophenoxy ethoxylate, (tetra) (tetra) phenyl bromide Ethyl vinegar, oxyethyl vinegar, (meth) bromo bromophenoxy propyl vinegar, (meth) ester, trimethylphenoxypropyl (meth) acrylate, (methyl) propyl vinegar A phenylalkyl (meth) acrylate substituted with a bromine atom of 1 to 5 benzene rings, such as pentabromophenoxypropyl acrylate. Further, the carbon number of the base is usually from 1 to 12. In addition, the monofunctional compound (Β) does not contain the aromatic compound which is easy to be used in the early stage. Among the oleanols (8), it is especially preferred that the phenyl phenyl phenyl phenoxy propyl acrylate unit is 2 ♦ propylene i: bis = diacid with '(meth) acrylate biphenyl polyethylene or 2 base Specifically, it is a weight of a monofunctional aromatic compound (B) which is a heterogeneous group, a sulfhydryl group, a genus, or a genus. VIII: 2〇, 000, 21〇^〇〇, 22^ 〇; = The tendency to read the fruit is not easy. It is difficult to obtain the monofunctional aromatic compound (8) according to the heart, and the bow is better than the nine points above the boots, especially 19 201134905 344 [3ΐ 〇0^Ζν^'5〇~4〇ίη:,^16〇~3〇〇ΕΐΜ If it is too small ^The tendency to reduce the birefringence adjustment ability due to the increase of the heart 2' = rise, the adhesive will volatilize when dry It will be difficult to get -5 points: 170~199. 〇, etc. f< 来者插/匕 Zheng phenyl phenol acrylate (fire point: 13t = c): C _ ^ purpose (_: = ^. phenoxy Base vinegar (fire) (A)i〇ri If the content of S-square is relative to the content of the acrylic resin, if the content of the acrylic resin (9) is small, there is a tendency to reduce the resistance and the resistance will be thinner. If the material S is in the month 3: ^^官官:) raw = raw, the base of the ethylenic unsaturated molecule contains 2 _ upper vinyl dibasic) body = 1 propylene glycol vinegar, di(meth)acrylic acid Dingxiang;: (methyl)丙城聚二二: 烯^;==:(10) bis-enyl stilbene tetraol ester, ethylene glycol epoxide __ base) propylene "7 ^ base =| 20 201134905 i propyl phthalate epoxide (4) Di(indenyl)acrylic acid: di-S S-group, di-oxygen 3=^, etc. The monomer of the group may be, for example, an ethylene-unsaturated acid, a pentaerythritol, a salt, a base, a fine acid Methylpropane, tris(methyl) propylene " - pentaerythritol (meth) acrylate, tris(methyl;) acrylate - Li' - (^) Λ 21; ί soil i, pentaerythritol vinegar, tribasic ) propylene oxy-ethoxy ethoxy (oxime oxypropyl ketone (meth) propylene coffee, isocyanuric acid oxygen = = oxyacid oxime acid compound, which has an amine group in the molecule, 甲 compound] Use will contain woven (mercapto) propylene dioxime i: 0.25 /, october isocyanic acid Compound (if necessary, polyol compound), ~=^卩反可丝麟料, money good average molecular weight, usually (10) the content of compound (c), relative to the bupropion acid resin f two is desired ~ 3 (3 parts by weight, preferably G. 5~w parts by weight, = sex, light leakage resistance are reduced, if too little punctured ^^ foot ^ In the present invention, 'could adjust # crosslink density, and appropriate In addition, the viewpoint of the two substances is relative to the monofunctional aromatic compound (C), and the single-membered aromaticization =:==good is ~, more preferably relative to the monofunctional aromatic If the content ratio of the monofunctional aromatic compound (8) to the polyfunctional unsaturated compound (6) 21 201134905 is too small, the polyfunctional unsaturated compound (the content of hydrazine is more than that of the monofunctional aromatic compound) Therefore, the crosslink density is excessively increased, and there is a tendency for a lack of adhesion. Further, the functional aromatic wei compound (8) is not aromaticly combined with the mono-initial compound, and if the total content of the compound (c) is too large, the polyfunctional unsaturated is not sufficient, and the content of the compound is relative to the monofunctionality. Since the aromatic compound (9) is small, the degree of crosslinking starts to increase, and the durability tends to be deteriorated. Μ·/ ^ 'About the (Α) to (C) components of the present invention, the photoelastic coefficient measured by the method described later is that the photoelastic coefficient of the acrylic resin (A) is negative and contains H-saturated unsaturated When the photoelastic coefficient of the aromatic compound (B) of the group and the cured product of the ethylenically unsaturated compound (c) containing two or more ethylenically unsaturated are positive, it is preferable to efficiently eliminate the birefringence. . In the present invention, an active energy ray and an active energy ray are used to contain the above-mentioned acrylic tree (4), a monofunctional compound, a compound (8), and a compound of the genus / or heat (active energy ray irradiation and / or contact agent. The hardening, _ monolithic peak compound (Β) SiiTb compound (C (10) hybrid energy secret and 7 or recorded (polymer au acid resin (4)' in response to the reaction At the time, the secret is to use active energy to shoot == into the 彳 (four) single _ _ _ _ _ _ _ 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 (B) 'When the polyfunctional unsaturated compound (6) is polymerized and hardened, the above-mentioned adhesive is entangled with ray and/or heat. τ ρ Ϊ α α α α α α α 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 To contain cross-linking, (Ε) substance [1] using active energy ray and occupational heart S to make a spoon; and, when using cross-linking agent (Ε), C The acid resin (Α) preferably has a functional group of 22 201134905, which can be hardened (crosslinked) by reacting the functional group with a crosslinking agent. (4) ft?:: utilizing active energy ray and/or heat (active energy ray) It is preferable to irradiate an active energy ray which can be ultraviolet rays or the like in a very short time, and to use a crosslinking agent to make the hardening (crosslinking) more squeezing and squeaking _ _ crosslink density, and it is difficult to improve Force to make the oxime more polymerization initiator (D) 'how to use silk yarn yarn 1), thermal polymerization = various polymerization initiators, especially using photopolymerization initiator (dl) in the ability to = very short _The irradiation of active energy rays such as ultraviolet rays makes the viewpoint of hardening more. When the photopolymerization initiator (dl) is used, the active energy ray is used to harden the product [1], and a thermal polymerization initiator (d2) is used. In the case of heating, the adhesive composition [I] is cured by heating, but it is also preferable to use both if necessary. The δ haiguang polymerization initiator (dl) is a y which generates a radical due to the action of light. 'Without special p-type system, it can be used in the intramolecular self-cracking type photopolymerization initiator (4) or hydrogen extraction type photopolymerization. Starting agent (2). Molecular Π self-cracking type photopolymerization initiator (dl_1), for example: 4-phenoxydichlorobenzophenone, 4-second butyldichloroacetophenone, diethyl Oxyacetophenone, 2-hydroxy-2-methylphenylpropane, H4-isopropylpropyl]>2_hydroxy_2_mercaptopropene g, H4_+ a basic base) -2-peryl-2-mercaptopropen-1-one, 4-(2-cyanoethoxy)-phenyl(2-di-yl-2-propyl)one, 1-cyclohexylbenzophenone , 1 fluorenyl small (tetra)methylthio)phenyl]_2_weilin^propan-1·• ketone, benzoin, benzoin oxime ether, benzoin ether, benzoin isopropyl ether, puppet, _, Kaki-methyl ketal, α-stokeoxy vinegar, fluorenylphosphine oxide, phenylphenylglyoxylate, 4-(2-hydroxyethoxy)phenyl _ (2 _hydroxy-2-propyl)one, 4_benzimidyl-4'-dimercaptodiphenylsulfide, etc., wherein 2-hydroxy-2-indoleylpropan-1-one, 1- Base cyclohexylbenzene_. #又, Hydrogen extraction type photopolymerization initiator (dl_2), for example: diphenyl ketone, benzoyl benzoic acid, methyl benzoyl benzoate, 4 phenyl diphenyl ketone, Hydroxydiphenyl ketone, 3^3-dimethyl-4-decyloxydiphenyl ketone, 2,4,6-tridecyldiphenyl ketone, 4-mercaptodiphenyl fluorene. 4J[S](thk)xanthone), 2-chlorothioxanthone, 2-mercaptothioxanthone, 2,4- 23 201134905 dimethylthioxanthone, isopropylthioxanthone, camphorquinone, two Benzocycloheptone (Di^enzosuberone), 2-ethylindole, 3,3,,4,4,_tetra(t-butylperoxy)diphenyl, benzyl, 9,1 Among them, phenanthrenequinone et al. are preferably diphenyl ketone, methyl dibenylamine, and 2,4,6-tri-T-diphenyl fluorene. In the present invention, from the viewpoint of excellent durability, a hydrogen extraction type photopolymerization initiation is used, and (dl-2) is preferable, and in particular, an intramolecular self-cracking type photopolymerization initiator ((1)") is used together with hydrogen extraction. Both types of photopolymerization initiators (dl_2) are preferable in that the balance of photocrosslinking and internal photocrosslinking of the surface portion of the adhesive layer is good, and the overall performance is improved. In the case of the combination of the self-cleaving type photopolymerization initiator and the hydrogen extraction type photopolymerization initiator, it is preferably a self-cleaving type of 1-based cyclohexyl benzophenone or 2-based benzyl 2-methyl group. a combination of a phenylpropan-1-one with a hydrogen extraction type diphenyl ketone, methyl diphenyl ketone or diphenyl ketone. , τ 丞 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 4-Dimethylaminobenzoic acid ethyl acetate, 4-dimethylaminobenzoic acid (n-butoxy y-ethyl J, 4-didecylaminobenzoic acid isovaleric acid, 4-didecylamino group) Ethyl hexyl benzoate, 2,4-diethylxanthone, 2,4-diisopropyl sulphate, 1 type or 2 or more types may be used together. Starting agent (d2), for example, can be used to oxidize cyclohexanone peroxide, cyclohexanone peroxide, cyclohexanone peroxide, ethyl bromide, bismuth trihexyl peroxide, hexene burn, U-double ( Tertiary butyl peroxidation; _3hex f5_= cyclohexane, 1,1-bis(t-butylperoxy)_2-methyl ring-based peroxygen cycline, U-double (third butyl Based on dibutyl butyl peroxy) butyl, 2,2- bis (4,4-di-second butyl, plant 'yuan, double (second mint burning fine n J wire through the pit, pit nitrogen, nitrogen , cumene gasification nitrogen, third hexyl butyl butyl: gas α,α,-bis (t-butyl peroxy) diisopropylbenzene, peroxy peroxide, base - (four) Tributyl group _, the third 24 201134905 order, 3 ^ 5 5 L A ^ 2 '5 · bis (second butyl peroxidation) hex · 3, peroxide peroxide stearin, peroxidation A series, laurel, oxidized styrene, di-n-propyl peroxide 2: 1 nail, brewing, double (4_t-butylcyclohexyl) peroxydicarbonate "Tjff i Acidic ethoxyhexylperoxydicarbonate _ _ 虱 二 二 、 、 二 二 二 二 二 二 虱 τ 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 -3_methoxy f butyl f) over-emulsified dicarbonate, postal, _ double (new fluorenyl peroxide: 虱cyclohexyl-1-methylethyl peroxide 靳 eight inhibitory f butyl peroxidation new Citrate, 1-tr f, third hexylperoxyacetic acid vinegar, first: butyl-butyl emulsified 2-ethylhexanoate, third hexyl; A; f Iff, third Τ-based peroxy lauric acid, third gt acid ester, tert-butylperoxy-2-ethylhexyl sulfonate, and tert-butyl peroxybenzoic acid benzoyl 245 , bis (tertiary butyl peroxidation) isophthalic acid, carboxylic acid vinegar, 2,5-dimethyl-2, 5-Bis(Benzene-based peroxidation), calcined, 7-butylene, peroxyl-propylidene monocarbon, tributyltrimethyl peroxide, (t-butylperoxy)diphenylphosphonium, 2,3_Dimethyl_23_ ' /etc. There is a telluride system starting from the remainder of the phenyl group "oxy 2,4 2^^ = bis (methylbutyronitrile), 2, 2: azo double Isobutyronitrile, U, _ azobis(24-j-valeronitrile), 2,2,-even t^(2_methylpropanol)chlorine chloride, 22,_azo^methylphenyl丙月米)Dihydrogen chloride, 2,2: azobisindole (4_chlorophenyl)_2_methyl^m] - rodent quinone, 2,2'-azobis[Ν·(4·hydrobenzene) Base>2_methylpropionamidine]hydrogen dichloride, 22,_] 25 201134905 "(phenylmethyl)propane]dihydrogen chloride, 2,2,-azobis[2_methyl=丙脉] Nitrogen dichloride, arsenazo double ceramsite ethyl)-2_methyl|·2 M5,6 7 wide 2"" 2_° grade ° forest 1 base) propane burning] dihydrogenated hydrogen, 2, 2 , _ azo double 34. ', heart bite · 2 · base) propane burning] dihydrogenated hydrogen, 2, 2'-azo double [2 · (5-trans group & base) secret] hydrogen dichloride, 2, 2: azo - via acetamidine 22 3 ΐ -[U_bis(transmethylmethyl)ethyl]propionate, 2,2,-1-ylethyl)(tetra)amine], 2,2'-azobis (2 _methyl propyl ik 2 2 曱 曱 )), 2, 2' _ azobis (2-methyl propyl ketone), dipropionate _), 4, 4 '. bis (4 · cyanyl pentane An acid, a 2, 2, or an azo-based initiator; etc. Further, the thermal polymerization initiation d may be used alone or in combination of two or more. The weight i is relative to the aforementioned acrylic resin. (4) 100 0 in 3 with 5 jobs containing fine, dirty and hard ^ ° 'owo ° - in terms of photopolymerization initiator (di), combined with intramolecular ~ 1:99 (weight ratio), especially good (this _ - kind of sister), more preferably (dl-l): (dl-2) = 45:55~1_ (weight ratio _ into the female will have the balance of the cross-linking balance of the entire adhesive layer, can When the active energy ray is irradiated, the material, the material line, the near-violet line 26 201134905, the infrared rays, the x-rays, the beams, the proton rays, the neutron rays, etc. can be used, but the electrons can be used from the hard surface. Price, etc. When the ultraviolet beam is irradiated with the device to obtain an easy beam irradiation, the electron beam irradiation can be performed when the electron beam is irradiated. Further, the electrophoresis agent (dl) can be hardened. The electrode lamp at the time of ultraviolet irradiation, the ultra-high pressure mercury lamp arc-breaking lamp, the original m rain pressure mercury lamp, and the condition without 10 to 100 mJ/cm 2 are carried out. '5:3 = 0 mJ/cm, preferably 2 to 150 mm/cm 2 , preferably For example, the electrode lamp type of 5~5〇〇mJ/cm2 can be used depending on the type of light source, the distance between the light source and the coated surface, and the second time: the shooting time but the material is several seconds of milk seconds, and the hybrid shape can also be used. And /, sub is f丄 = second degree or treatment time, depending on the thermal polymerization used, usually between 0.2~20 minutes, especially preferably 〇5~1〇 minutes. L treatment day defensive agent (E) ' For example, an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, and a nitrogen-based parent-linked agent. Among these, from the viewpoint of improving the reactivity with the substrate or the reactivity of the substance, Good use of iso-ester cross-linking ^, 2. Dissimilar acid vinegar cross-linking agent, for example: 2,4_methyl leather diisocyanate, a yttrium yttrium hydrogenated toluene diisocyanate Ester, u_diphenylene diisocyanate, α, y-cyanate, hexamethylene diisocyanate, diphenylmethane _44-diiso-acid vinegar, isophora Cyanic acid vinegar, 1,3-bis(iso-acid methyl)cyclohexene, tetrahydrophenylene isocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and polyisocyanate compounds and trihydroxyindoles An adduct of a polyol compound such as propane, a diurea or an isocyanuric acid of such a polyisocyanate compound. 27 201134905 Ethylene acrylate, 1,6-hexanediol, diepoxypropene, propylene glycol, glycerol sorbitol, glycerol, polyglycerol, poly(glycerol), and methacrylic acid , sorbitol, diglycerol polyepoxy (four) and so on. < @, Quaternary tetraol polyepoxypropyl red algae said = mouth-based cross-linking agent, for example: tetramethyl-methyl-burning. three-like propionate propionic acid bis-propionyl propionate, N , N, _diphenyl-methyl _4,4'-^ (. 丙, N, N, N, - hexamethylene ♦ bis (1 - aziridine-enylamine) An amine-based crosslinking agent, for example, oxymethyl melamine, hexapropoxymethylene y: carboxymethyl 4, hexaethylamine, hexamethoxymethyltrimethyl f polyamine resin, etc. The aldehyde-based cross-linking agent, such as glyoxal, aldehyde, pentane, formaldehyde, ethylbenzene, benzoic acid, etc. - J-prepared, Malay-two cross-linking! T: Hexamethylenediamine, triethylenediamine, polyethyleneimine, diammine, April female, unEuropean female, diethyltetramine, isophor, polyamine, etc. The above metal chelate-based crosslinking agent, for example, an alkyl group complex compound of m # ^, 录, =, hunger, chromium, scaly polyvalent metal, etc. 々Q ^ G storm, the crosslinking agent (E) ) may be used singly or in combination of two or more. The content of the above parent (E) is usually relative to acrylic acid. The resin (4) (10) part is preferably 0.01 to 10 parts by weight, more preferably 0 05 to 5 parts by weight, and parts by weight. If the amount of the crosslinking agent (6) is small, the cohesive force is not S, and sufficient durability may not be obtained. Then, the flexibility and the adhesive force are lowered, the durability is lowered, and the woven fabric is easily peeled off, so that it is difficult to use it as an optical member. In the present invention, Wei is contained (F) as a bond _ component _ Further, the viewpoint of the adhesion of the optical member is preferable. The oxime coupling agent (F) is, for example, an epoxy group-containing decane coupling agent or a (fluorene-containing) group.
2S 201134905 $酿的梦燒偶·劑、含織基的梦炫偶聯劑、含·基的梦貌偶聯 .f基的魏偶聯劑、含絲的雜侧劑、含ϋ胺基的石夕 H如蜊、、含異氰酸酯基的矽烷偶聯劑等。該等可單獨使用也可 人f ^重以上。該等之中,較佳為使用含環氧基之石夕規偶聯劍、 聯劑,併时縣基之魏偶·與含縣的石夕 m於提^濕熱耐久性及黏接力不過分升高的觀點為較佳。 兩其-=ί環氧基的石夕燒偶聯劑的具體例,例如:丫-環氧丙氧基 ϊΐ夕ί、γ_環氧丙氧基丙基三乙氧基魏、丫.環氧丙氧 ΐ Α=基魏,環氧丙氧基丙基甲基二τ氧基石夕燒、 β m4環氧環己基)乙基三甲氧基魏、 H里基基三歹氧基石夕烧等’其中較佳為个環氧丙a ΪΑί;Ιί^' ;:;^ ^基丙基甲基二乙氧基魏、Ρ_(3,4環氧環己基)乙基三甲氧基石夕 述含的魏偶聯劑的具體例,例如:γ-縣丙基:甲4 m基丙基三乙氧基魏、㈣基丙 烷或此等化合物的寡聚物型的矽烷偶聯劑等。 土 土 通當相對於丙_系樹脂_〇重量份, 重量份。該·ίΐί;)::ίί:·:重::二 =凝丙缔酸系樹脂㈧的互溶性降低 ’有彳寻不到接著 又,於黏接劑組成物[η中,在不損及本發明#要沾 也可進-步配合抗靜電劑、其他的丙烯酸系 ^圍内, 劑、胺基曱酸醋樹脂、松香、松香醋、氣化松夭&二他,接 芳产變性_樹脂、脂肪族系石油樹脂、脂二二本恥,旨、 本乙烯系樹脂、二甲苯系樹脂等黏接日:f、石油樹脂、 抗=劑、紫外線吸收劑、機能性色素等=往填充劑、 因為紫外線或放射線照射而呈色或變色的化合二口、从、加劑,或 又’上述添加劑以外,也可少量含有^劑組成物_構成 29 201134905 成分的製造原料等所含的雜質等。 上述抗靜電劑,例如:咪唑鏽鹽、四烷基銨磺酸鹽等四級 ,陽離子型抗靜電劑、脂肪族磺酸鹽、高級醇硫酸g鹽、高級^ 氧化烯加成物硫酸酯鹽、高級醇磷酸酯鹽、高級醇氧;f忐= ,酸酯鹽等陰離子型抗靜電劑、鉀雙(氟磺醯基)醯亞胺、鐘錐 ^磺醯基)醯亞胺,或氯化鋰等鹼金屬鹽、鹼土類金屬鹽、言 氧化烯加成物、聚烷撐二醇脂肪酸酯等。 |同、、-予 黏接=而言之,本發明可制將上述雜敝成物[1]硬化而成的 在此,具有使本發明的黏接劑組成物硬化而得的 接片,其黏接劑(層)由含有丙烯酸系樹脂(A)、含有i個 飽和基的芳香族化合物⑻的聚合物、含有i個乙稀性 ===有__接_斜,棘㈣揮本i明 /〇,有機溶劑的含量為0.5重量ppm〜5重量%,較佳為''' 二 量Ppm,尤佳為1〇〜1〇〇重量ppm。 為1000重 ^上述黏接劑,宜含有丙烯酸烧酯系單 係來自於丙烯酸系樹脂(A)的製造。 H 此寻 含有丙烯·酯系單體(al)時,含量為lppm lOppm〜1000ppm,尤佳為5〇〜1〇〇ppm。 較佺為 又,藉由將由上述黏接劑構成的黏接劑層疊芦形忐/ 件(光學疊層體)上,可獲得設有黏接劑層的光曰學;^;成在先學構 於上述設有黏接劑層的光學構件中,較佳 光學構件面相反的面,更設置離型片。 ”、、沾接浏層的 上述設有黏接劑層的光學構件的製造方法,於旦 及加熱當中至少射之—進行硬化時,有 光子構件上塗佈黏接敝成物P]並使乾燥後,貼H 活性能量射線照射及加埶當中14、苴巾 口離孓片,利用 ,、、、中至人/、中之—進行處理;[2]在離型 30 201134905 片上塗佈黏接船域师]並使乾燥, 雜 .能量射線照射及加熱當中至少其中之一進利用活性 加熱當中至少其中之—進行處理後,貼合燦照射及 片上塗佈黏接劑組成物[η並使乾燥後 勺m]在離型 加熱當中至少其中之-進行處理後,貼崎射線照射及 的方法於照射活性能量射線日林損傷基 =子=,[2] 製造的觀點為較佳。 J硯點作業性或安定 又,勒接劑組成物[I]使用交聯劑時( ,)時)’宜在使用上述方法製造匕 施熟成處理。該熟成處理中, 的學構件後實 性而進行者,就熟⑶ ;===二=進例“ 等的條件實施。 口 % 4υ C進仃1日〜7曰 量%,尤佳Λ 10〜舌曰。/ . '又而〇,車父佳為5〜60重 能使,劑組成物 milt' ^ 用乙酸乙酷、甲乙〆輸佳。攸/谷解性、乾燥性、價格等觀點,使 凹版上組成物[1]之塗佈,可利用輥塗、模塗、 利用上述方等慣用的方法進行。 親點,宜為30〜99%,尤佳為 二?几 分率過低,__力不足 向。又’若凝膠分率過高,合由於气隹a L ,陧义侍不足的傾 31 201134905 —利用上述方法製造的黏接劑層,當以手指接觸時,有良好附 著感者由於實際貼在被黏著體時的透濕性佳,有提升作 向故為較佳。 八 又,當調整光學構件用黏接劑的凝膠分率為上述範圍時, =可利用輕活性能量射線的照射量或照概度、調整含不飽和 基的化合物__量、雛聚合起始劑的翻貞及其併用比例、 調整聚合起始劑的配合量、調整交聯劑的種類與量等而達成。又, 上述活性能;t麟賴射量或照射強度、聚合起始躺组成比、 祕各綱交互作㈣使凝膠分較變,需要各 上述,分率,係度量交聯度(硬化程度)的指標,例如可用以 下方法計异。亦即,將在成為基材的高分子片 ^乙二義薄膜等)形成轉劑層而成的黏接片(未;有 者),以20〇mesh的SUS製金屬網包裹,在23。〇於 牛 24小時,以殘留在金屬網中的不溶解的 當做凝膠分率。惟,先減去基材重量。我刀的重里百分率 ^,利用上述方法製造的黏接劑層的折射 1.470〜L575,尤佳為撕〜⑽’更佳為i仍〜i 52 j 1.480〜1·5〇〇。若該折射率過低,則光學疊 雕 =二二2S 201134905 $ brewed dream burning agent, woven base-containing dream coupling agent, containing base-based dream coupling. f-based Wei coupling agent, silk-containing side agent, sulfonamide-containing stone eve H such as hydrazine, an isocyanate group-containing decane coupling agent, and the like. These can be used alone or in a larger amount. Among these, it is preferred to use an epoxy group-containing stone-like coupling sword and a jointing agent, and the Weiji of the county base and the Shixi m of the county have not excessively damp heat durability and adhesion. An elevated view is preferred. Specific examples of the sulphur coupling agent of the two -? ε epoxy group, for example, 丫-glycidoxy ethoxylate, γ-glycidoxypropyltriethoxy Wei, oxime. Oxypropoxypurine Α = kewei, glycidoxypropylmethyl dimethyl τ oxime, β m4 epoxy cyclohexyl) ethyl trimethoxy wei, H rylate trimethoxy sulphur, etc. ' Among them, it is preferably a propylene oxide a ΪΑ ί; Ιί^' ;:; ^ ^ propyl propyl diethoxy wei, Ρ _ (3,4 epoxy cyclohexyl) ethyl trimethoxy sulphur Specific examples of the thio coupling agent include, for example, γ-county propyl group: methyl 4 m propyl triethoxy wei, (tetra) propyl propane or an oligomer type decane coupling agent of these compounds. The soil is generally in parts by weight relative to the amount of propylene resin. The ··ίΐί;)::ίί:·:Heavy::2=Condensation of the acrylic acid resin (8) The mutual solubility is reduced, 'I can’t find it, and in the adhesive composition [η, without damaging The invention can also be used in combination with an antistatic agent, other acrylics, an agent, an amine vinegar resin, a rosin, a rosin vinegar, a gasified pine mites & _Resin, aliphatic petroleum resin, fat two or two shame, purpose, this vinyl resin, xylene resin and other bonding days: f, petroleum resin, anti-agent, UV absorber, functional pigment, etc. a filler, a combination of coloring or discoloration due to ultraviolet light or radiation, a dosing agent, or an additive, or a small amount of a composition of the above-mentioned additive. Impurities, etc. The above antistatic agent, for example, an imidazole rust salt, a tetraalkylammonium sulfonate or the like, a cationic antistatic agent, an aliphatic sulfonate, a higher alcohol sulfate g salt, a higher alkylene oxide adduct sulfate salt , higher alcohol phosphate salt, higher alcohol oxygen; f忐 =, anionic antistatic agent such as ester salt, potassium bis(fluorosulfonyl) quinone imine, bell cone sulfonyl sulfonium imide, or chlorine An alkali metal salt such as lithium, an alkaline earth metal salt, an alkylene oxide adduct, a polyalkylene glycol fatty acid ester, or the like. In the present invention, the present invention can be obtained by curing the above-mentioned hybrid material [1], and has a tab for curing the adhesive composition of the present invention. The adhesive (layer) is a polymer containing an acrylic resin (A) and an aromatic compound (8) containing i saturated groups, and contains i ethylene === __ _ oblique, spine (four) The content of the organic solvent is from 0.5 ppm by weight to 5% by weight, preferably from 2% by weight, more preferably from 1 to 1% by weight. It is preferable that the above-mentioned adhesive is 1000 parts by weight of the above-mentioned adhesive, and it is preferable to contain the acrylate-based ester-based single-system from the production of the acrylic resin (A). When the propylene/ester monomer (al) is contained, the content is from 1 ppm to 10 ppm, more preferably from 5 to 1 ppm. Further, by laminating a bonding agent composed of the above adhesive agent on a reed 忐/piece (optical laminate), a photonics provided with an adhesive layer can be obtained; In the optical member provided with the adhesive layer described above, it is preferable that the surface of the optical member opposite to the surface is provided with a release sheet. ", the method of manufacturing the optical member provided with the adhesive layer on the lining layer, and at least when it is fired during heating and curing, the photonic member is coated with the adhesive composition P] After drying, paste H active energy ray irradiation and twisting, 14. 苴 口 孓 , , , , , , , , , , , 利用 利用 利用 利用 利用 [ [ [ [ 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 Receiving the ship's division] and making at least one of the dry, miscellaneous, energy ray irradiation and heating into at least one of the active heating treatments, bonding the glazing and the on-chip coating of the adhesive composition [η After the drying spoon m] is subjected to at least one of the treatments in the release heating, the method of irradiating the ray radiation is effective in irradiating the active energy ray, and the viewpoint of manufacturing [2] is preferable.作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业 作业For the implementer, the conditional implementation of (3); === two = example "in case"Mouth % 4υ C into the 1st ~ 7曰 volume%, especially good Λ 10 ~ tongue 曰. / . 'And then, the car father is 5 to 60 heavy, the composition of the agent milt' ^ with acetic acid, cool, and acetaminophen. The application of the composition [1] on the intaglio plate can be carried out by roll coating, die coating, or the like by a conventional method such as ruthenium/glutinability, drying property, and price. Relatively, it should be 30~99%, especially good for two? The percentage is too low, __power is insufficient. Also, if the gel fraction is too high, due to the gas 隹 a L, 陧 侍 侍 31 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 When it is adhered, the moisture permeability is good, and it is preferable to improve it. 8. When the gel fraction of the adhesive for optical members is adjusted to the above range, the irradiation amount or the degree of illumination of the light active energy ray can be adjusted, and the amount of the compound containing the unsaturated group can be adjusted. The turning of the starting agent and the ratio of the combined use thereof, adjusting the amount of the polymerization initiator, adjusting the type and amount of the crosslinking agent, and the like are achieved. Moreover, the above-mentioned activity energy; t-ray radiation amount or irradiation intensity, polymerization initiation composition ratio, and secret interaction (4) make the gel fraction change, and each of the above-mentioned fractions is required to measure the degree of crosslinking (hardening degree). The indicator can be calculated, for example, by the following method. In other words, a bonding sheet (not used) in which a transfer layer is formed on a polymer sheet which is a base material, and the like, is wrapped in a metal mesh of SUS made of 20 mesh. The cows were simmered for 24 hours, and the insoluble matter remaining in the metal mesh was used as the gel fraction. However, first subtract the weight of the substrate. The percentage of the weight of my knife ^, the refraction of the adhesive layer made by the above method 1.470~L575, especially for tearing ~ (10)' better for i still ~i 52 j 1.480~1·5〇〇. If the refractive index is too low, the optical overlay = two two
該折射率,係使用ATAG0公司製「Ab 線於23°c測定之值。 丨对了 °τ丨丨」,以NaD 又,獲得的設有黏接劑層的光學構件中 ^ ^ 5^3〇〇,m , , 若該黏_層解度太薄,減物財不易Ι^Ομπχ。 則光學構件全體的厚度有增加過度_向。、、° ’右過厚, 本發明的設有黏接劑層的光學構件 合於玻璃基板’或有離型片者將離型片剥離:層面貼 於玻璃基板,並供作例如液晶顯示板使用]。字越·面貼合 32 201134905 黏接劑層的起始黏接力,可因應被黏著體的材料等適 二ί ^ /貼附在玻璃基板時,宜具有a2N/25mm〜2GN/25mm 的4接力,又,更佳為0 5N/25mm〜1〇N/25mm。 料接力’可以下列方法計算。將設有黏接劑層的偏 ,成見為25mm,將離型_剝離,將黏制層侧推壓到無 呙反(康宁公司製,「CommgXG」),而貼合偏光板與玻璃板。 之後,進行高廢爸處理(50t、〇.5MPa、2〇分鐘)後,於抑、5〇%rh. 放置24小時後,進行180°C剝離試驗。 ^本發明^,光學構件不特別限定,例如液晶顯示裝置、有機 發光顯7F裝置、電槳齡科影像騎裝置合適使用的光學 薄巧,,如偏光板或相位差板、橢圓偏光板、光學補償薄膜、輝 度提升薄膜,又,該等疊層而成者等。其中,尤其偏光板於本發 明中為有效。 本龟明可使用的偏光板,通常係在偏光薄膜的兩面疊層三乙 酸纖維素系薄膜當做保護薄膜,上述偏光薄膜,係以平均聚合度 為i,500~10,000、驗化度為85〜100莫耳%的聚乙烯醇系樹脂構成 的缚膜¥做原始結構薄膜’並利用峨_埃化卸的水溶液或二色性染 料染色成的單軸延伸薄膜(通常延伸倍率為2〜10倍,較佳為約3〜7 倍)。 上述聚乙烯醇系樹脂,通常係將聚合乙酸乙烯酯而成的聚乙 酸乙烯酯予以鹼化而製造,但是也可含有少量不飽和羧酸(含鹽、 酯、醯胺、腈等)、烯烴類、乙烯醚類、不飽和磺酸鹽等可與乙酸 乙烯酯共聚合的成分。又,例如於酸存在下使聚乙烯醇與醛類反 應成的例如聚丁縮醛樹脂、聚乙烯基曱縮醛樹脂等所謂的聚乙烯 基縮搭樹脂及聚乙稀醇衍生物。 又’本發明中,也可使用含有丙烯酸系樹脂(A)、及含有1個 乙烯性不飽和基的芳香族化合物(B),及含有2個以上乙烯性不飽 和基的乙烯性不飽和化合物(C)而成,丙烯酸系樹脂(A)的光彈性係 數為負,且芳香族化合物(B)與乙烯性不飽和化合物(C)的硬化物的 光彈性係數為正的黏接劑組成物。 33 201134905 又,本發明中,光彈性係數的正負 〈光彈性係數的正負的測定條件> 竹乂下財八獻 _ X(UNTQPT(股)公销:PEL_3A_1G2R)設置薄 膜狀的5式鉍片,測定光彈性係數的正負。 正負’係於含寬度及長度的舶,當定延伸方 it^垂直 =延伸方向的方向為90。時,主軸方位位在0。方 向時疋為正,主軸方位位在9〇。方向時定為負。 /杯定時的試驗片的厚度’光彈性係數的正負取決於 ί 率差,光彈性係數的正負不受厚度影響,因此 ,鬥=定時士的試驗片的尺寸,只要是在能設置於試驗裝置的 =内即可,不特別限定,通常使用長度2〇〜5〇麵,寬度1〇〜2〇麵 骨〇 ’ ί*彈性係指物質由於受到應力而使得構成物質的分子發 ,造成複折射大小改變的現象,於單軸延伸的情形,由於 身伸方向一致,因此測定當延伸試驗片時展現的複折 光彈性係數的正負。因此,關於上述測定 趣片的延伸鲜,只要設定錄方位為安定的倍率即可, 如,接劑的柔軟物質由於容易發生配向緩和或應力緩和,若延 仏率小則有時無法安定地測定主軸方位,因此可延伸約 長的2〜5倍’若是如薄膜的硬物質,則延伸原試驗片長的約i 01〜2 倍左右即可。 ’ 實施例 以下舉實施例更具體說明本發明,但本發明只要不超過並 首先,以下列方式製備各種丙烯酸系樹脂(A)。又,丙 相 =(A)的重4平均分子量、分散度、_轉移溫度_定^依 知别述方法。 ,、 34 201134905The refractive index was measured by the ATAG0 company "Ab line measured at 23 ° C. 丨 ° ° ° 丨丨", and the optical member provided with the adhesive layer obtained by NaD was ^^ 5^3 〇〇,m , , If the viscosity of the viscous layer is too thin, it is not easy to reduce the wealth Ι^Ομπχ. Then, the thickness of the entire optical member is excessively increased. , ° 'right too thick, the optical member provided with the adhesive layer of the present invention is combined with the glass substrate' or the release sheet peels off the release sheet: the layer is attached to the glass substrate, and is used as, for example, a liquid crystal display panel use]. Words and Faces 32 201134905 The initial adhesion of the adhesive layer can be adapted to the material of the adhesive body, etc. / attached to the glass substrate, should have a 4N force of a2N/25mm~2GN/25mm And, more preferably, it is 0 5N/25mm~1〇N/25mm. The material relay ' can be calculated in the following manner. The adhesive layer layer will be provided with a bias of 25 mm, and the release layer will be peeled off, and the side of the adhesive layer will be pushed to the side of the adhesive layer ("CommgXG" manufactured by Corning Co., Ltd.), and the polarizing plate and the glass plate will be attached. . After that, after high waste treatment (50 t, 〇. 5 MPa, 2 〇 minutes), after standing for 24 hours at 5 〇 % rh., a 180 ° C peel test was performed. In the present invention, the optical member is not particularly limited, and for example, a liquid crystal display device, an organic light-emitting display device, and an optically thin image-based device are suitably used for optical thinness, such as a polarizing plate or a phase difference plate, an elliptically polarizing plate, and optical. A compensation film, a brightness enhancement film, and the like. Among them, especially polarizing plates are effective in the present invention. The polarizing plate that can be used by the turtle is usually a laminated film of cellulose triacetate on both sides of the polarizing film as a protective film, and the polarizing film has an average polymerization degree of i, 500 to 10,000, and a degree of test is 85~ 100 mm% of a polyvinyl alcohol-based resin is used as a film of the original structure and is a uniaxially stretched film dyed with an aqueous solution or a dichroic dye. (The stretching ratio is usually 2 to 10 times. Preferably, it is about 3 to 7 times). The polyvinyl alcohol-based resin is usually produced by alkalizing a polyvinyl acetate obtained by polymerizing vinyl acetate, but may contain a small amount of an unsaturated carboxylic acid (salt, ester, guanamine, nitrile, etc.) or an olefin. A component which can be copolymerized with vinyl acetate, such as a vinyl ether or an unsaturated sulfonate. Further, for example, a so-called polyvinyl condensed resin such as a polybutyral resin or a polyvinyl acetal resin which is obtained by reacting polyvinyl alcohol with an aldehyde in the presence of an acid, and a polyethylene derivative. In the present invention, an acrylic resin (A), an aromatic compound (B) containing one ethylenically unsaturated group, and an ethylenically unsaturated compound containing two or more ethylenically unsaturated groups may be used. (C), the photo-elastic coefficient of the acrylic resin (A) is negative, and the photo-elastic coefficient of the cured product of the aromatic compound (B) and the ethylenically unsaturated compound (C) is positive. . 33 201134905 In addition, in the present invention, the positive and negative of the photoelastic coefficient <the measurement condition of the positive and negative of the photoelastic coefficient> The bamboo 乂 财 八 _ X (UNTQPT (share): PEL_3A_1G2R) is provided with a film-shaped 5 type cymbal , measuring the positive and negative of the photoelastic coefficient. Positive and negative ' is attached to the ship with the width and length, and the direction of the extension is it vertical = the direction of the extension is 90. When the spindle orientation is at 0. The direction is positive and the spindle orientation is 9〇. The direction is set to negative. /The thickness of the test piece of the cup timing 'The positive and negative of the photoelastic coefficient depends on the difference in ί, and the positive and negative of the photoelastic coefficient are not affected by the thickness. Therefore, the size of the test piece of the bucket = chronograph can be set in the test device as long as it is The inside of the = can not be particularly limited, usually the length of 2 〇 ~ 5 〇 face, the width of 1 〇 ~ 2 〇 face bone 〇 ' ί * elastic means that the material is caused by stress, causing the molecules of the material, causing birefringence The phenomenon of the change in size, in the case of uniaxial stretching, since the body extension directions are uniform, the positive and negative of the complex photoelastic coefficient exhibited when the test piece is extended is measured. Therefore, as for the extension of the above-mentioned measurement interesting film, it is only necessary to set the recording orientation to a stable magnification. For example, the soft substance of the adhesive is likely to be relieved by the alignment or the stress is relieved, and if the elongation is small, the measurement may not be performed stably. The orientation of the spindle can be extended by about 2 to 5 times of the length. If it is a hard substance such as a film, the length of the original test piece can be extended by about i 01 to 2 times. EXAMPLES Hereinafter, the present invention will be more specifically described by way of Examples, but the present invention is to prepare various acrylic resins (A) in the following manner as long as they do not exceed. Further, the weight average molecular weight, the degree of dispersion, and the _transfer temperature of the C phase = (A) are determined according to the method. ,, 34 201134905
又,關於丙烯酸系樹脂(A)的黏度的 Κ5400(1900)的4.5.3旋轉黏度計法測定。 疋係依…HS 方式i行丙烯酸系樹脂(Α)的光彈性係數的正負的败,係依下述 <光彈性係數的正負的測定1> 將丙烯酸系樹脂(A)塗佈在SP_01(輕剝離pET),於1〇〇 3分鐘層合㈣03(重剝離pET)。將獲得的片材於攸熟成 1 ^到黏接層的厚度為25μιη的黏接片材。將該黏接 3:2=後,僅將黏_層設置於光彈性測定裝置(iM〇pt(股)公 司衣.PEL-3A-102R」。拉伸黏接劑層的兩端並測定延伸2倍 主轴方位,判定光彈性係數的正負。 錄在G°方向者為正,主__方位 位在90 方向者為負。 [丙烯酸系樹脂(A)之製備](參照表u [丙烯酸系樹脂(A-1)] 於配備回流冷卻器、攪拌器、氮氣吹入口及溫度計的四口圓 底燒瓶中,放入丙烯酸丁酯(al)98.5份、丙烯酸2_羥基乙酯(&2)1 份^丙烯酸(a2)0.5份及乙酸乙酯75份、丙酮45份,開始加熱回 流後’加入當做聚合起始劑的偶氮雙異丁腈(AIBN)〇〇3份,於乙 酸乙酯回流溫度反應3小時後,以乙酸乙酯稀釋,得到丙烯酸系 樹脂(A-1)溶液(重量平均分子量(Mw)2〇〇萬、分散度(Mw/Mn)3 ^ 玻璃轉移溫度-54°C、固體成分16%、黏度8,〇〇〇mPa.s(25t:))。 [丙烯酸系樹脂(A-2)] 於配備回流冷卻器、攪拌器、氮氣吹入口及溫度計的四口圓 底燒瓶中,放入丙烯酸丁酯(al)97份、丙烯酸(功3份及乙酸乙酯 1^)0份、丙酮45份’開始加熱回流後,加入當做聚合起始劑的偶 氮雙異丁腈(AIBN)0.03份,於乙酸乙酯回流溫度反應3小時後, 以乙酸乙酯稀釋,得到丙烯酸系樹脂(A_2)溶液(重量平均分子量 (Mw)180萬、分散度(Mw/Mn)3.2、玻璃轉移溫度-53°C、固體成分 18%、黏度 8,000mPa.s(25t:))。 35 201134905 [丙烯酸系樹脂(A-3)] 於配備回流冷卻盗、授拌器、氮氣吹入口及溫度計的四口圓 底燒瓶中,放入丙烯酸丁酯(al)98.5份、丙烯酸2_經基乙酯(a2)1.5 份及乙酸乙酯120份、丙酮45份,開始加熱回流後,加入當做聚 合起始劑的偶氮雙異丁腈(AIBN)0.03份,於乙酸乙酯回流溫度反 應3小時後,以乙酸乙酯稀釋’得到丙烯酸系樹脂(A_3)溶液(重量 平均为子a(Mw)150萬、分散度㈣、玻璃轉移溫度 -53°C、固體成分 23%、黏度 8,〇〇〇mPa.s(25°C))。 [丙烯酸系樹脂(A-4)] 於配備回流冷卻器、攪拌器、氮氣吹入口及溫度計的四口圓 底燒瓶中,放入丙烯酸丁酯(al)95份、丙烯酸(a2)5份及乙酸乙酯 120份、丙酮45份,開始加熱回流後,加入當做聚合起始劑的偶 氮雙異丁腈(AIBN)0‘03份,於乙酸乙酯回流溫度反應3小時後, 以乙酸乙酷稀釋,得到丙稀酸系樹脂(A_4)溶液(重量平均分子量 (Mw)150萬、分散度(Mw/Mn)3.4、玻璃轉移溫度_51。〇、固體成分 23%、黏度8,00〇111?&.3(25。(:))。 丑刀 [丙烯酸系樹脂(Α-5)] 於配備回流冷卻器、擾拌器、氮氣吹入口及溫度計的四口圓 底燒瓶中’放入丙烯酸丁 I旨(al )95份、丙烯酸(a2)5份及乙酸乙酉旨 100份、丙酮45份’開始加熱回流後,加入當做聚合起始劑的^ 氮雙異丁腈(AIBN)0.03份,於乙酸乙酯回流溫度反應3小&後, 以乙酸乙酯稀釋’得到丙烯酸系樹脂(A-5)溶液(重量平均分子量 (Mw)170萬、分散度(Mw/Mn)3.2、玻璃轉移溫度-5Γ(:、固體成^ 18%、黏度 8,000mPa.s(25t:))。 月丑刀 [丙烯酸系樹脂(A-6)] 於配備回流冷卻器、攪拌器、氮氣吹入口及溫度計的四口圓 底燒瓶中’放入丙烯酸丁酯(al)61.3份、丙烯酸苄酯35份、丙愉 酸2-輕基乙酯(a2)3.5份、丙烯酸〇·2份(a2)及乙酸乙酯I%份、丙 酮45份’開始加熱回流後,加入當做聚合起始劑的偶氮雙異丁产 (AIBN)0.03份’於乙酸乙酯回流溫度反應3小時後,以乙&乙^ 36 201134905 , 稀釋,得到丙烯酸系樹脂(A-6)溶液(重量平均分子量(Mw)15〇萬、 . 分散度(Mw/Mn)3.5、玻璃轉移溫度_36〇c、固體成分2〇%、黏度 8,000mPa-s(25〇C))。 ^ [丙烯酸系樹脂(A-7)] 玻璃轉移溫度-51°C、固體成分23%、黏度8,000mPa.s(25t:y) [表11 丙婦酸 系樹脂 BA(份) HEA(份) AAc(份) BzA(份) 重量平均分 子量(Mw) 分散度 (Mw/Mn) 玻璃轉移 溫度(°c) 光彈性係 數的正負 A-1 98.5 1 0.5 - 200萬 3.1 -54 i A-z A-3 97 98.5 1.5 3 - 180萬 3.2 Γ -53 只 負 A-4 95 5 - 1J U 150萬 3.4 3.4 -53 卜-51 負 备 A-j 95 * 5 - 150萬 3.2 -51 刍 A-0 61.3 3.5 0.2 35 150萬 3.5 -45 貝 ip A- / 94.8 0.2 5 - 150萬 3.3 -51 負— 於配備回流冷卻器、攪拌器、氮氣吹入口及溫度計的四口圓 底燒槪中’放入丙烯酸丁酯(al)94.8份、丙烯酸2-經基乙酯(a2)〇.2 彳刀、丙烯酸(a2)5份及乙酸乙酯120份、丙g同45份,開始加熱回 流後,加入當做聚合起始劑的偶氮雙異丁腈(AIBN)〇 〇3份,於乙 酸乙酯回流溫度反應3小時後,以乙酸乙酯稀釋,得到丙烯酸系 樹脂(A-7)溶液(重量平均分子量(Mw)15〇萬、分散度(Mw/Mn)3 4 註:BA:丙烯酸丁酯 HEA:丙烯酸2-經基乙酯 AAc:丙稀酸 BzA:丙烯酸苄酯 [單官能性芳香族化合物(B)] 準備以下者當做單官能性芳香族化合物(B-1)。 •丙烯酸苯基二乙二醇酯(共榮社製,商品名「Lightacrylatep2HA 分子量236.3) 準備以下者當做單官能性芳香族化合物(B_2)。 •乙氧化鄰苯基苯酚丙烯酸酯(曰立化成工業公司製,商品名 「FAJ01A」:分子量268、引火點17(M9^c,揮發殘份1〇〇%) 準備以下者當做單官能性芳香族化合物(B-3)。 37 201134905 •丙烯酸鄰聯苯氧乙酯(新中村化學公司製,商品名「A-LEN-IOT」: 分子量268) 準備以下者當做單官能性芳香族化合物(B_4)。 •丙烯酸苯基硫乙酯(大阪有機社製,商品名rphSEA」:分子量207) [多官能不飽和化合物(〇] 準備以下者當做多官能不飽和化合物(C-1)。 •三羥曱基丙烷三丙烯酸酯(分子量296.3) [聚合起始劑(D)] 準備以下者當做光聚合起始劑(D_i)。 •二苯基酮與1-羥基環己基苯酮的質量比1:1的混合物(chibaFurther, the viscosity of the acrylic resin (A) was measured by a 4.5.3 rotational viscometer method of Κ 5400 (1900). The 光 疋 依 HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS HS The pET was lightly stripped and laminated (4) 03 (heavy peeled pET) at 1 〇〇 3 minutes. The obtained sheet was bonded to a bonded sheet having a thickness of 25 μm to the adhesive layer. After bonding 3:2 =, only the adhesive layer was placed on a photoelastic measuring device (iM〇pt Co., Ltd. PEL-3A-102R). Both ends of the adhesive layer were stretched and the extension was measured. 2 times the spindle orientation, the positive or negative of the photoelastic coefficient is judged. The one recorded in the G° direction is positive, and the main __ orientation is negative in the 90 direction. [Preparation of acrylic resin (A)] (Refer to Table u [Acrylic Resin (A-1)] In a four-neck round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet, and a thermometer, 98.5 parts of butyl acrylate (al) and 2-hydroxyethyl acrylate (&2) were placed. 1 part of acrylic acid (a2) 0.5 parts and 75 parts of ethyl acetate, 45 parts of acetone, after heating and refluxing, 'addition of azobisisobutyronitrile (AIBN) as a polymerization initiator to 3 parts, in acetic acid After reacting for 3 hours at the reflux temperature of the ester, it was diluted with ethyl acetate to obtain a solution of an acrylic resin (A-1) (weight average molecular weight (Mw) 2 million, degree of dispersion (Mw/Mn) 3 ^ glass transition temperature - 54 °C, solid content 16%, viscosity 8, 〇〇〇mPa.s (25t:)) [Acrylic resin (A-2)] 4 with reflux cooler, stirrer, nitrogen inlet and thermometer In a round bottom flask, 97 parts of butyl acrylate (al), 0 parts of acrylic acid (3 parts by weight and ethyl acetate 1 ), and 45 parts of acetone were added to start heating and refluxing, and then azo double as a polymerization initiator was added. 0.03 parts of isobutyronitrile (AIBN), reacted at reflux temperature of ethyl acetate for 3 hours, and then diluted with ethyl acetate to obtain an acrylic resin (A 2 ) solution (weight average molecular weight (Mw) 1.8 million, dispersion (Mw/Mn) 3.2, glass transfer temperature -53 ° C, solid content 18%, viscosity 8,000 mPa.s (25t:)). 35 201134905 [acrylic resin (A-3)] with reflow cooling thief, agitator, nitrogen In a four-necked round bottom flask with a water inlet and a thermometer, 98.5 parts of butyl acrylate (al), 1.5 parts of 2-ethyl acrylate (a2), 120 parts of ethyl acetate, and 45 parts of acetone were placed, and heating was started. Adding 0.03 parts of azobisisobutyronitrile (AIBN) as a polymerization initiator, reacting at reflux temperature of ethyl acetate for 3 hours, and diluting with ethyl acetate to obtain a solution of acrylic resin (A_3) (weight average a (Mw) 1.5 million, dispersion (four), glass transition temperature -53 ° C, solid content 23%, viscosity 8, 〇〇〇mPa.s (25 ° C) [Acrylic Resin (A-4)] In a four-neck round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet, and a thermometer, 95 parts of butyl acrylate (al) and acrylic acid (a2) 5 were placed. 120 parts of ethyl acetate and 45 parts of acetone, after heating and refluxing, adding 0'03 parts of azobisisobutyronitrile (AIBN) as a polymerization initiator, and reacting at reflux temperature of ethyl acetate for 3 hours, Ethyl acetate was diluted to obtain an acrylic resin (A_4) solution (weight average molecular weight (Mw) 1.5 million, dispersion (Mw/Mn) 3.4, glass transition temperature _51. 〇, solid content 23%, viscosity 8,00〇111?&.3 (25. (:)). Ugly knife [acrylic resin (Α-5)] In a four-necked round bottom flask equipped with a reflux cooler, a scrambler, a nitrogen gas inlet, and a thermometer, 'into a butyl acrylate I (al) 95 parts, acrylic acid (a2) 5 parts and 100 parts of ethyl acetate and 45 parts of acetone' were heated and refluxed, and then 0.03 parts of nitrogen diisobutyronitrile (AIBN) was added as a polymerization initiator, and reacted at a reflux temperature of 3 hours & , diluted with ethyl acetate to obtain an acrylic resin (A-5) solution (weight average molecular weight (Mw) 1.7 million, dispersion (Mw / Mn) 3.2, glass transition temperature -5 Γ (:, solid formation ^ 18%, Viscosity 8,000 mPa.s (25t:)). Ugly knife [acrylic resin (A-6)] in a four-neck round bottom flask equipped with a reflux cooler, a stirrer, a nitrogen gas inlet and a thermometer 61.3 parts of ester (al), 35 parts of benzyl acrylate, 3.5 parts of 2-light ethyl ethyl acrylate (a2), 2 parts of bismuth acrylate (a2) and 1% of ethyl acetate, 45 parts of acetone 'start heating After refluxing, 0.03 parts of azobisisobutyric acid (AIBN) as a polymerization initiator was added and reacted at reflux temperature of ethyl acetate for 3 hours, and then B & E 36 36 34 34 Dilute to obtain an acrylic resin (A-6) solution (weight average molecular weight (Mw) 15 million, . Dispersity (Mw/Mn) 3.5, glass transition temperature _36 〇 c, solid content 2 〇%, viscosity 8,000 mPa-s(25〇C)) ^ [Acrylic resin (A-7)] Glass transition temperature -51 ° C, solid content 23%, viscosity 8,000 mPa.s (25 t: y) [Table 11 propylene glycol acid Resin BA (parts) HEA (parts) AAc (parts) BzA (parts) Weight average molecular weight (Mw) Dispersity (Mw/Mn) Glass transition temperature (°c) Positive and negative photoelastic coefficient A-1 98.5 1 0.5 - 2 million 3.1 -54 i Az A-3 97 98.5 1.5 3 - 1.8 million 3.2 Γ -53 only negative A-4 95 5 - 1J U 1.5 million 3.4 3.4 -53 Bu-51 Negative Aj 95 * 5 - 1.5 million 3.2 -51 刍A-0 61.3 3.5 0.235 1.5 million 3.5 -45 Bei ip A- / 94.8 0.2 5 - 1.5 million 3.3 -51 Negative - four round bottom with reflux cooler, stirrer, nitrogen inlet and thermometer In the simmering simmer, put 94.8 parts of butyl acrylate (al), 2-isoethyl acrylate (a2) 〇.2 trowel, 5 parts of acrylic acid (a2), 120 parts of ethyl acetate, and 45 parts of propylene g, After heating and refluxing, add azo as a polymerization initiator 3 parts of bis-isobutyronitrile (AIBN), reacted at reflux temperature of ethyl acetate for 3 hours, and then diluted with ethyl acetate to obtain a solution of acrylic resin (A-7) (weight average molecular weight (Mw) 150,000, Dispersion (Mw/Mn) 3 4 Note: BA: butyl acrylate HEA: Acrylic acid 2-ethylidene ethyl ester AAc: Acrylic acid BzA: benzyl acrylate [monofunctional aromatic compound (B)] Prepare the following as Monofunctional aromatic compound (B-1). • Phenyl diethylene glycol acrylate (trade name "Lightacrylatep2HA molecular weight 236.3") Prepared as the monofunctional aromatic compound (B_2). • Oxidized o-phenylphenol acrylate (曰立化成工业) Company name, trade name "FAJ01A": molecular weight 268, ignition point 17 (M9^c, volatile residue 1%) Prepare the following as a monofunctional aromatic compound (B-3). 37 201134905 • Acrylic neighboring Phenoxyethyl ester (product name "A-LEN-IOT": molecular weight 268) The following is prepared as a monofunctional aromatic compound (B_4). , trade name rphSEA": molecular weight 207) [Polyfunctional unsaturated compound (〇) Prepare the following as a polyfunctional unsaturated compound (C-1). • Trihydroxydecylpropane triacrylate (molecular weight 296.3) [Initiation of polymerization Agent (D)] Prepare the following as a photopolymerization initiator (D_i). • A mixture of diphenyl ketone and 1-hydroxycyclohexyl ketone in a mass ratio of 1:1 (chiba)
Speciality Chemicals 公司製,「lrgacure 5〇〇」)。 [交聯劑(E)] 使用以下者當做交聯劑(E4)。 一輕曱基丙烧的曱苯二異氰酸酯加成物的55%乙酸乙酯溶液 (Japanpolyurethane 公司製,「Coronate L-55E」)。 [石夕烷偶聯劑(F)] 準備以下者當做矽烷系化合物(F-1)。 •γ-環氧丙氧基丙基三甲氧基矽烷(信越化學公司製,「KBM4〇3」)。 準備以下者當做石夕烷系化合物(F-2)。 ·γ_巯基丙基三甲氧基石夕烷(信越化學公司製,「KBM803」)。 準備以下者當做矽烷系化合物(F-3)。 •疏基^矽烷偶聯劑(寡聚物型)(信越化學公司製,「χ_41_18〇5」)。 [實施例1〜13、比較例1〜6] 入將以+上述方式製備、準備的各配合成分,以下表2所示比例 ,稭此製備成為光學構件用黏接劑形成材料的黏接劑組成 物’將其以乙酸乙酯稀釋(黏度[5〇〇〜1〇〇〇〇mPa.s(25。 接劑組成物溶液。 ^ 並且,將上述得到的黏接劑組成物溶液塗佈 上,使得乾燥後的厚度成為25μιη,於9(TC賴3分鐘後 的黏接劑組成物層轉印在聚對苯二曱酸乙二醇酯(pET)薄臈(厚度 38 201134905 38μιη)上,以Fusion公司製無電極燈[LH6UV燈 值照度:6〇2〇mW/Cm2、累積曝光量:24〇mJ/cm2線2 (120mJ/cm、2 次脈衝),於 23。〇、65%r h 的 ^ 射 獲得設有黏接劑層的PET薄膜。 ’、下无、成10曰’ 干夂的/咖妾劑層的PET薄膜,依照以下所 率。該等結果合併顯示於下表2。 此濁度折射 I;操作性] 將得到的設有黏接劑層的ΡΕΤ薄膜切成25聰x4〇m 除離型片,以手指接觸黏接劑層’町列基準評鮮附。J 〇:有良好附著感 〃 " x:不太有附著感 [耐臭性] 將獲得的設有黏接劑層的PET薄膜於2沈、5〇%r. 條件下放置3树後’獅_片,嗅其味道独下列 感覺不出單體臭 x:感覺得到單體臭 [凝膠分率] 將獲得的設有黏接劑層的PET薄膜切成4〇mmx4〇mm 除離型片,並將黏接劑層側貼合在5〇mmxl〇〇mm的sus片 (200meSh),之後從中央部對SUS網片的長邊方向反折以將樣本 入後,以於裝有甲苯250g的密封容器於23〇c浸泡24小時 改變’進行凝膠分率的測定。 里 [混濁度] •混濁度測定用樣本的製造 。將上述黏接劑組成物溶液塗佈在聚酯系輕剝離離型片,使 乾耜後的厚度成為25μηι ’於9〇t乾燥3分鐘後,將形成的黏接兩j 組成物層側以聚酯系重剝離離型片貼合,以Fusi〇n公司製無電^ 燈[LH6UV燈的Η燈泡]’以峰值照度:6〇〇mW/cm2、累積曝光 39 201134905 量:240mJ/Cm2進行紫外線照射(120mJ/cm2、2次脈 50〇/〇R.H.的條件下熟*10曰,獲得無基材的黏接劑乂二2 無基材的雜麟娜3emx4em,嫌輕剝_型^ =、 層側推制紐玻璃板(康寧公司製,EagleXG) 重^ = 型片,獲得混濁度測定用樣本。 輝夏獅離 •混濁度值的測定 使用HAZE MATER NDH2000(曰本電色工業公司製)測定上 述混濁度測定用樣本的擴散穿透率及全光線穿透率。又,本機係 依據 JISK7361-1。 將獲付的擴散穿透率及全光線穿透率的值代入下式,計算混 濁度值。 混濁度值(%)=(擴散穿透率/全光線穿透率)x 1 〇〇 [折射率] 使用上述混濁度測定用樣本,使用Atago公司製「Abt>e折射Speciality Chemicals, "lrgacure 5〇〇"). [Crosslinking agent (E)] The following was used as the crosslinking agent (E4). A 55% ethyl acetate solution of a fluorene-based propylene terephthalate adduct (manufactured by Japan Polyurethane Co., Ltd., "Coronate L-55E"). [Astraestane coupling agent (F)] The following was prepared as a decane-based compound (F-1). • γ-glycidoxypropyltrimethoxydecane ("KBM4〇3", manufactured by Shin-Etsu Chemical Co., Ltd.). The following was prepared as the alkane compound (F-2). - γ-mercaptopropyltrimethoxy oxacyclohexane ("KBM803", manufactured by Shin-Etsu Chemical Co., Ltd.). The following was prepared as the decane compound (F-3). • Silane-based coupling agent (oligomer type) (manufactured by Shin-Etsu Chemical Co., Ltd., "χ_41_18〇5"). [Examples 1 to 13 and Comparative Examples 1 to 6] Each of the compounding components prepared and prepared in the above manner, in the ratio shown in Table 2 below, was prepared as an adhesive for forming an adhesive for an optical member. The composition 'diluted it with ethyl acetate (viscosity [5 〇〇 〜1 〇〇〇〇 mPa.s (25. The composition of the sorbent composition. ^), and the solution of the adhesive composition obtained above was coated So that the thickness after drying is 25 μm, and the adhesive composition layer after 9 minutes of TC is transferred onto polyethylene terephthalate (pET) thin layer (thickness 38 201134905 38 μιη), Electroless lamp made by Fusion [LH6UV lamp illumination: 6〇2〇mW/Cm2, cumulative exposure: 24〇mJ/cm2 line 2 (120mJ/cm, 2 pulses), at 23. 〇, 65% rh A PET film provided with an adhesive layer was obtained. The PET film of the dried/currant layer was formed in the following manner. The results are shown in Table 2 below. The turbidity refraction I; operability] The obtained ruthenium film provided with the adhesive layer is cut into 25 sin x4 〇m release sheets, and the finger contacts the adhesive layer The standard evaluation is attached. J 〇: There is a good adhesion 〃 " x: Not very attached [odor resistance] The PET film with the adhesive layer obtained will be under the conditions of 2 sinks and 5 〇 % r. After placing 3 trees, 'Lion _ film, smelling the taste alone, does not feel the monomer odor x: feeling the monomer odor [gel fraction] The obtained PET film with the adhesive layer is cut into 4〇mmx4 〇mm remove the release sheet, and attach the adhesive layer side to the sus piece (200meSh) of 5〇mmxl〇〇mm, and then fold back from the center to the long side of the SUS mesh to put the sample into the back. The sealed container containing 250 g of toluene was immersed in 23 ° C for 24 hours to change the 'measurement of the gel fraction. 》 [turbidity] • Manufacture of the sample for measuring turbidity. Coating the above-mentioned adhesive composition solution After peeling off the release sheet in the polyester, the thickness after drying is 25 μm, and after drying for 3 minutes at 9 〇t, the formed two-component layer side is bonded with a polyester-based heavy release release sheet. , with Fusi〇n company's non-electrical lamp [LH6UV lamp's xenon bulb]' with peak illumination: 6〇〇mW/cm2, cumulative exposure 39 201134905 Quantity: 240mJ/Cm2 for UV irradiation Shooting (120mJ/cm2, 2 times pulse 50〇/〇RH under the condition of cooked *10曰, obtaining a non-substrate adhesive 乂2 2 no substrate, 麟麟娜3emx4em, suspected light peeling _ type ^ =, The side glass is made of a glass plate (EagleXG, manufactured by Corning Co., Ltd.). The film is used for the measurement of turbidity. The turbidity value of the lion is measured using HAZE MATER NDH2000 (manufactured by Sakamoto Electric Co., Ltd.). The diffusion transmittance and the total light transmittance of the sample for turbidity measurement were measured. Also, this unit is based on JISK7361-1. The value of the diffusion transmittance and the total light transmittance are substituted into the following equation to calculate the haze value. Haze value (%) = (diffusion transmittance / total light transmittance) x 1 〇〇 [refractive index] The above turbidity measurement sample was used, and "Abt>e refraction manufactured by Atago" was used.
*—---- 丙烯酸系樹脂 ㈧ 單官能 性芳香 族化合 物(B) 多官能 性不飽 和化合 物(C) (B)/[( B)+(C )](mol %) 聚合 起始 _) 交聨 劑0¾ *夕炫 偶聯 剖(F) 操 作 性 fit 臭 性 凝膠 分率 (%) 混濁 度 (%) 折射率 ------ 實施例1 A-1 100 B-1 30 C-1 1 97.4 D-l 3 E-l 0.15 F-l 0.1 0 ο 77 0.2 1-481 實施例2 A-L 100 - B-1 50 C-1 2.5 96.2 D-l 5 E-l 0.15 F-l 0.1 0 ο 77 0.2 1.485 1—___ 實施例3 A-2 100 B-1 '30 C-1 1 97.4 D-l 3 E-l 1.5 F-2 0.1 ο ο 77 0.2 1.481 f施例4 A-1 100 - B-1 40 C-1 2.5 95.3 D-l 4 H-l 0.15 F-l 0.1 ο ο 77 0.2 ι·483 ------ 實施例5 A-I 100 - B-I 30 C-1 2.5 93.8 D-l 3 E-l 0.15 F-l 0.1 ο ο 77 0.2 1.481 --- 實施例6 A-1 100 - B-2 10 C-1 2.5 81.6 D-l 1 E-l 0.15 F-l 0.1 ο ο 78 0.2 1-476 實施例7 A-3 90 A-4 10 B-1 30 C-1 1 97.4 D-l 3 ΕΊ 1.5 F-l 0.1 ο ο SO 0.2 1.481 ------- 實施例8 A-3 90 A-4 10 B-2 10 C-1 1 91.7 D-l 1 E-l 1.5 F-l 0.1 ο ο 81 0.2 U75 實施例9 A-1 100 - B-3 10 C-1 1 91.7 D-l 1 E-l 0.2 F-l 0.1 ο ο 78 0.2 1-47?^ 實施例10 A-5 100 - Β·3 10 C-1 1 91.7 D-l 1 ΕΊ 1 F-3 0.1 —---- F-l 0.1 ο 0 76 0.2 1-475 ο ο 74 0.2 1472^ ------ 贲施例11 A-1 100 - Β-4 10 CM 1 93.5 D-l l E-l 0.2 贲施例12 A-1 100 - Β-4 15 CM 1 95.5 D-l 1.5 E-l 0.2 F-l 0.1 ο 0 73 0.2 1.475 --J 計1T」’以NaD射線測定於23°C之值。 [表2] 201134905*—————-- Acrylic resin (8) Monofunctional aromatic compound (B) Polyfunctional unsaturated compound (C) (B) / [( B) + (C )] (mol %) Starting of polymerization _) Intercontracting agent 03⁄4 *Xi Xing coupling section (F) Operational fit Odor gel fraction (%) Haze (%) Refractive index ------ Example 1 A-1 100 B-1 30 C -1 1 97.4 Dl 3 El 0.15 Fl 0.1 0 ο 77 0.2 1-481 Example 2 AL 100 - B-1 50 C-1 2.5 96.2 Dl 5 El 0.15 Fl 0.1 0 ο 77 0.2 1.485 1—___ Example 3 A -2 100 B-1 '30 C-1 1 97.4 Dl 3 El 1.5 F-2 0.1 ο ο 77 0.2 1.481 f Example 4 A-1 100 - B-1 40 C-1 2.5 95.3 Dl 4 Hl 0.15 Fl 0.1 ο ο 77 0.2 ι·483 ------ Example 5 AI 100 - BI 30 C-1 2.5 93.8 Dl 3 El 0.15 Fl 0.1 ο ο 77 0.2 1.481 --- Example 6 A-1 100 - B- 2 10 C-1 2.5 81.6 Dl 1 El 0.15 Fl 0.1 ο ο 78 0.2 1-476 Example 7 A-3 90 A-4 10 B-1 30 C-1 1 97.4 Dl 3 ΕΊ 1.5 Fl 0.1 ο ο SO 0.2 1.481 ------- Example 8 A-3 90 A-4 10 B-2 10 C-1 1 91.7 Dl 1 El 1.5 Fl 0.1 ο ο 81 0.2 U75 Example 9 A-1 100 - B-3 10 C-1 1 91.7 Dl 1 El 0.2 Fl 0.1 ο ο 78 0.2 1-47?^ Example 10 A-5 100 - Β·3 10 C-1 1 91.7 Dl 1 ΕΊ 1 F-3 0.1 —---- Fl 0.1 ο 0 76 0.2 1- 475 ο ο 74 0.2 1472^ ------ 贲 Example 11 A-1 100 - Β-4 10 CM 1 93.5 Dl l El 0.2 贲 Example 12 A-1 100 - Β-4 15 CM 1 95.5 Dl 1.5 El 0.2 Fl 0.1 ο 0 73 0.2 1.475 --J 1T"' measured by NaD ray at a value of 23 °C. [Table 2] 201134905
C-1 3 94.4 D-1 4 E-1 1.5 F-1 0.1 〇 〇 85 0.2 1.483 C-1 2.5 0 D-1 1 E-1 0.15 F-1 0.1 0 0 81 0.2 1.467 C-1 15 0 D-1 E-1 1.5 F-1 0.1 X 0 98 0.4 1,473 C-1 15 16.7 D-1 1 E-I 1.5 F-1 0.1 X 〇 97 0.4 1.473 E-1 0.2 F-2 0.1 〇 X 80 0.2 1.500 ' E-1 0.2 F-1 0.1 0 X 65 0.5 - E-1 0.2 F-1 0.1 〇 X 55 37 - ,一 · ^ V |J=U + 田,|刀 ο •表中,「-」代表未配合。 •比較例5中,配合第15份,比較例6中,配合第3〇份。 接卹ο 中’使用上述設有黏接劑層的ΡΕΤ薄膜測定黏 ΐ早官能性芳香族化合_及乙酸乙酉旨濃度,結 25番曰月b性方曰私化合物⑻的濃度為4重量%,:酸乙醋濃度為 乃亶1 ppm。 又’測定方法如下。 [單官能性芳香族化合物(B)之濃度之測定方法] ^將上述設有黏接劑層的PET薄膜切成4〇mmx4〇mm後,剝除 片,並將黏接劑層側貼合在50mmxl〇〇mm的sus網片 (20—sh) ’之後從十央部對sus網片的長邊方向反折以將樣本包 入後,於裝有丙酮250g的密封容器於23ΐ浸泡24小時後,將獲 得的丙酮溶液以液體自動注射器注入Agile^ ^chnologies公司製7683B系列)’使用氣相層析儀/質量片段偵測 器(GC: Agilent Technologies 公司製,689〇N Netw〇rk GC system, MSD.Agilent Technologies 公司製 5973inert),測定溶液中的單官 能性芳香族化合物(B)的濃度。使用的管柱為Agilent公司製 DB-17MS(3〇mx25(^m(px〇.25pm),載流氣體為 He,流量為 l.Oml/min,壓力為7.0psi(40°C時)。又,分流比30:1,注入口溫度 2201。烤箱的溫度條件為40°C5分鐘後,以1(rc/min升溫,到達 220°C後,維持10分鐘。往MSD的傳輸線溫度22〇〇c,掃描模式 41 201134905 (質量範圍:1〇〜600,掃描次數:2.52/sec)。又,單官能性芳香於化人 物(B)的濃度’係利用上述測定獲得的丙酵j溶液中的單官能性“二 族化合物(B)的濃度、上述40mmx40mm的設有黏接劑層的^ 薄膜的重量、40mmx40mm的PET薄膜的重量計算求得。 [乙酸乙酯濃度的測定方法] 將得到的設有黏接劑層的PET薄膜切成25mmx25mm,剝p/v 離型PET後稱重。將該樣本放入容量20mL的小樣品瓶並鎖緊二 將該瓶以頂部空間自動取樣器(Agilent Technologies公司f headspacesampler G1888)於120°C加熱30分鐘,將加熱狀態的氣^ 以(15psix4分鐘)的條件取出,並使用氣相層析儀/質量片段偵測^ (GC: Agilent Technologies 公司製,6890N Network GC sySte二 MSD:Agilent Technologies公司製5973inert),測定該氣體中所含 的乙酸乙酿濃度。使用的管柱為Agilem公司^ DB-17MS(30mx25(^mcpx〇.25pm) ’ 載流氣體為 He,流量& l.Oml/min,壓力為7.0Psi(40t:時)。又,分流比30:1,注入口溫度 220p。烤箱的溫度條件為40〇C5分鐘後,以1〇t:/min升溫, 220°C後,維持10分鐘。往MSD的傳輸線溫度22CTC,掃描模式 (質量範圍:10〜_,掃描次婁文:2.52/sec)。 又,本次僅測定乙酸乙酯係屬一般,且將本次的實施例中以 代表使用的乙酸乙醋為代表測定。 <光彈性係數的正負的測定2> 又’測定單官能性芳香族化合物(H〜B_4)的光彈性係數的正 負。單官能性芳香族化合物單獨不會將硬化物交聯,因此操作困 難,係配合少量的多官能性不飽和化合物並判定其硬化物的光彈 性係數的正負當做單官能性芳香族化合物的光彈性係數的正負。 亦即,配合單官能性芳香族化合物(B4〜B_4)1〇〇份、多官能性不 飽和化合物(c-i)io份與光聚合起始劑(D_1)1〇份,並塗佈在厚 400μπι的设有分離件的玻璃板上,從上面層合玻璃板,以Fusi〇n 公司製無電極燈[LH6UV燈的η燈泡],以峰值照度:600mW/cm2、 累積曝光量:240mJ/cm2進行紫外線照射(12〇mJ/cm2、2次脈衝)使 42 201134905 硬化。獲得的硬化物的厚度約為3〇〇 3咖2⑽,㈣於光彈性測^ 化物切成 2為触轴方位,與前述關樣方式判定光雜絲的正 性係ίΪ;正單官能性芳香族化合物(㈣)的各硬化物的光彈 在聚ίΐ離、比較例1〜6的黏接劑組成物溶液塗佈 曰糸财片上’使乾燥後的厚度成為25卿,於如 =後.’將接劑組成物層(厚度190—轉印在偏光板1, i Lum製無電極燈[lh6uv燈的h燈泡],以峰值昭 (mm2累積曝光量:24〇mj/cm2進行紫外線照射 3 ’力 23°G、65%R.朗餅了誠 1〇 日, 獲付5又有黏接劑層的偏光板。 4UM又i上福光板係使用美館imagillg公司製「狐卩观」切成 對於延伸軸成為45。後使用。 取 女士 ΐ用!!此方式獲得的紗黏接懸的偏光板,健以下所示 二ίΐ測定並評價耐久性(耐濕熱試驗、熱循環試驗、耐熱試驗)、 黏接力。此等的結果一併顯示於後述表3。 [耐久性] 川^離所得_設有黏接綱的偏光板的離型#,將黏接劑層 無驗玻璃板(康寧公司製,EagleXG),貼合偏光板與以 ,、後μ、進仃局,金處理(5(rc、〇.5MPa、20分鐘〕,之後,於下列 〜()的耐久試驗(耐濕熱試驗、熱循環試驗、耐熱試驗)中進行起 ί雜ΐ離的評價。又,於以下(4)的耐熱試驗中,除了上述起泡、 外,也製作表面與背面兩面貼合有相同樣本使得偏 成為直交偏光鏡(crossed Nichd)的漏光觀察用樣本,進 現象的評價。 又’使用的試驗片的尺寸,係下料為如⑽…⑽後使用。 [耐久試驗] 43 201134905 (1) 耐濕熱試驗 6〇°C、90%R.H. 150小時的耐久試驗 (2) 熱循環試驗 ^ 以於放置60分鐘後於70°C放置60分鐘的操作當做1個 循環’進行75個循環的耐久試驗。 (3) 耐熱試驗(A) 於9CTC、150小時的耐久試驗 (4) 耐熱試驗(B) 於80°C、150小時的耐久試及漏光 [評價基準] (起泡) 〇…幾乎未觀察到起泡 △…觀察到些微起泡 x…觀察到多量起泡 (剝離) 么生小於0.5mm的剝離,或小於〇.5ιηπι的浮起痕 △•“發生0.5mm以上且小於10mm的剝離,或0 5_以上且 小於l〇mm的淨起痕 發生10mm以上的剝離’或i〇mm以上的浮起痕 (漏光) ◎…幾乎未發生漏光 〇…發生些微漏光 △…發生少許漏光 χ·“四邊大量發生漏光 [黏接力] 將製備的IS:有黏接劑層的偏光板切成宽為25麵,雜荆 ,备丨办雜薄C-1 3 94.4 D-1 4 E-1 1.5 F-1 0.1 〇〇85 0.2 1.483 C-1 2.5 0 D-1 1 E-1 0.15 F-1 0.1 0 0 81 0.2 1.467 C-1 15 0 D -1 E-1 1.5 F-1 0.1 X 0 98 0.4 1,473 C-1 15 16.7 D-1 1 EI 1.5 F-1 0.1 X 〇97 0.4 1.473 E-1 0.2 F-2 0.1 〇X 80 0.2 1.500 ' E -1 0.2 F-1 0.1 0 X 65 0.5 - E-1 0.2 F-1 0.1 〇X 55 37 - ,1· ^ V |J=U + field,|knife ο • In the table, "-" stands for unmatched . In Comparative Example 5, the 15th portion was blended, and in Comparative Example 6, the third portion was blended. In the t-shirt ο', using the above-mentioned enamel film provided with an adhesive layer, the concentration of the early functional aromatic compound _ and the acetaminophen was determined, and the concentration of the bismuth compound (8) was 4% by weight. ,: The concentration of acid vinegar is 1 ppm. Further, the measurement method is as follows. [Method for Measuring Concentration of Monofunctional Aromatic Compound (B)] ^ After cutting the PET film provided with the adhesive layer to 4 mm x 4 mm, peeling off the sheet and bonding the adhesive layer side After susiling the mesh (20-sh) of 50mmxl〇〇mm, the product was folded in the direction of the long side of the sus mesh from the ten central part to be wrapped in the sample, and then immersed in a sealed container containing acetone 250g for 24 hours at 23 ΐ. After that, the obtained acetone solution was injected into a liquid auto-injector into a 7838B series manufactured by Agile Co., Ltd.) using a gas chromatograph/mass fragment detector (GC: Agilent Technologies, 689 〇N Netw〇rk GC system) , MSD. Agilent Technologies, Inc., 5973 inert), to determine the concentration of the monofunctional aromatic compound (B) in the solution. The column used was DB-17MS manufactured by Agilent Co., Ltd. (3 〇mx25 (^m (px 〇.25 pm), the carrier gas was He, the flow rate was 1.0 ml/min, and the pressure was 7.0 psi (at 40 ° C). Further, the split ratio was 30:1, and the inlet temperature was 2201. After the temperature condition of the oven was 40 ° C for 5 minutes, the temperature was raised at 1 (rc/min, and after reaching 220 ° C, the temperature was maintained for 10 minutes. The transfer line temperature to the MSD was 22 〇〇. c, scan mode 41 201134905 (mass range: 1〇~600, number of scans: 2.52/sec). Further, the concentration of the monofunctional aromatic character (B) is determined by using the above-mentioned measurement in the solution of the yeast J solution. The concentration of the monofunctional "bi-group compound (B), the weight of the 40 mm x 40 mm film provided with the adhesive layer, and the weight of the PET film of 40 mm x 40 mm were calculated. [Method for Measuring Ethyl Acetate Concentration] The PET film with the adhesive layer was cut into 25mmx25mm, and the p/v release PET was peeled off and weighed. The sample was placed in a small vial with a capacity of 20 mL and the bottle was locked to the top space autosampler (Agilent). Technologies f headspacesampler G1888) is heated at 120 ° C for 30 minutes, and the condition of the heated state is (15 psi x 4 minutes). The mixture was taken out and analyzed by gas chromatography/mass fragment detection (GC: Agilent Technologies, 6890N Network GC sySte II MSD: 5973 inert made by Agilent Technologies), and the concentration of acetic acid contained in the gas was measured. The column is Agilem's DB-17MS (30mx25(^mcpx〇.25pm)', the carrier gas is He, the flow rate is 1.0mml/min, the pressure is 7.0Psi (40t: hour), and the split ratio is 30. :1, the inlet temperature is 220p. The temperature condition of the oven is 40〇C for 5 minutes, then the temperature is raised at 1〇t:/min, and after 220°C, it is maintained for 10 minutes. The transmission line temperature to the MSD is 22CTC, the scanning mode (mass range: 10~_, scanning sub-text: 2.52/sec). In this case, only the ethyl acetate system is generally measured, and the acetic acid acetate represented by the representative in the present embodiment is used as a representative. Measurement of the positive and negative of the coefficient 2> The measurement of the photoelastic coefficient of the monofunctional aromatic compound (H to B_4) is positive or negative. The monofunctional aromatic compound does not crosslink the cured product alone, so the operation is difficult, and a small amount is blended. Polyfunctional unsaturated compound and judge its hardened substance Negative negative photoelastic coefficient as the monofunctional aromatic compound photoelastic coefficient. That is, a monofunctional aromatic compound (B4 to B_4) is blended with 1 part by weight, a polyfunctional unsaturated compound (ci) io part and a photopolymerization initiator (D_1) are 1 part by weight, and coated in a thickness of 400 μm. On the glass plate with the separator, the glass plate was laminated from above, and the electrodeless lamp made of Fusi〇n company [η light bulb of LH6UV lamp] was used for peak illumination: 600 mW/cm2, cumulative exposure: 240 mJ/cm2. Ultraviolet irradiation (12〇mJ/cm2, 2 pulses) hardens 42 201134905. The obtained cured product has a thickness of about 3 〇〇 3 coffee 2 (10), and (4) the photoelastic measurement is cut into 2 as the tentacity orientation, and the positive relationship of the optical hybrid yarn is determined in the same manner as the above; the positive monofunctional aromatic The photoelasticity of each of the cured products of the compound ((4)) was on the film of the adhesive composition of Comparative Examples 1 to 6 and the thickness of the cured product was changed to 25 qing, after Ru. 'Connecting agent composition layer (thickness 190 - transferred to polarizing plate 1, i Lum electrodeless lamp [hh bulb of lh6uv lamp], ultraviolet irradiation with peak exposure (mm2 cumulative exposure: 24〇mj/cm2) '力23°G, 65% R. Long cake, 1 day, 5 polarizers with adhesive layer. 4UM and i-Fushang board are cut with the fox 卩 卩 ima The extension axis is 45. It is used later. Take the lady's use!! The yarn obtained by this method is adhered to the polarizing plate, and the durability is measured and evaluated (wet heat resistance test, heat cycle test, heat resistance test). ), the adhesion force. The results of these are also shown in Table 3 below. [Durability] The result of the separation of the polarized plate Type #, the adhesive layer is not tested glass plate (made by Corning Co., Ltd., EagleXG), attached to the polarizing plate and the, after, μ, into the bureau, gold treatment (5 (rc, 〇. 5MPa, 20 minutes), After that, the evaluation of the durability test (heat-resistant test, heat cycle test, heat resistance test) of the following ~() was carried out. In addition, in the heat resistance test of the following (4), in addition to the above foaming, Also, the same sample was attached to both surfaces of the surface and the back surface so that the sample for light leakage observation of the crossed Nichd was evaluated. The size of the test piece used was as follows (10)...(10) [Endurance test] 43 201134905 (1) Heat and humidity resistance test 6 〇 ° C, 90% RH 150 hours endurance test (2) Thermal cycle test ^ After 60 minutes of standing at 70 ° C for 60 minutes As a cycle of '75 cycles of endurance test. (3) Heat resistance test (A) Endurance test at 9CTC, 150 hours (4) Heat resistance test (B) Endurance test and light leakage at 80 ° C, 150 hours [ Evaluation criteria] (bubble) 〇... almost no blistering was observed △... slight blisters x were observed... A large amount of blistering (peeling) was observed. The peeling was less than 0.5 mm, or the floating mark was less than 〇.5 ηηπι. △ "The peeling occurred 0.5 mm or more and less than 10 mm, or the net of 0 5_ or more and less than 10 mm. When the scratches occur, the peeling of 10 mm or more occurs or the floating marks of the above i〇mm or more (light leakage) ◎...There is almost no light leakage 〇...a slight light leakage occurs △...a slight light leakage occurs ““a large amount of light leakage occurs on the four sides [adhesive force] will be prepared IS: The polarizing plate with the adhesive layer is cut into a width of 25 faces, and the hybrids are prepared.
膜, 1737 0.5ΜMembrane, 1737 0.5Μ
180°C 44 201134905 ▼ 為10N/25mm以下。 [表3]180°C 44 201134905 ▼ is 10N/25mm or less. [table 3]
※:比較例6的黏接劑,當做非硬化性芳香 »與丙烯酸系樹脂的互溶性差,第漏出而白化,而且無法貼人^ 玻璃板’無法進行上述耐久性試驗。 α 貫施例的黏接劑,當貼合偏光板與玻璃板時的耐久性、 光性、黏接力為非常高的位準且平衡性相當優異,而且制 桩 劑層a寸的附著感、混濁度、耐臭性亦為優異,相對於此,比 1〜6於以下觀點未能滿足要求的性能。 •未配合單官能性芳香族化合物(B])的比較例j巾,黏 的物性雖紐異’但是貼合偏光板與綱板時的性能差,&配 合單官能性芳香族化合物(B-1)而增加多官能性不飽和化人物— 的酉己合量的比較例2中,貼合偏光板與玻璃板時的口^, 但是黏接劑層本身的物性差。 b ^目對於(Β-1)與(C-1)的合計量,僅配合單官能性芳香族化入物 ㈣15.7_%的比較例3中’貼合偏光板與玻璃板時的性能雜 45 201134905 —單體的 5、6中環f低分子化合賴的比較例 子化合 度鍋化,再者,低分 僅為解的具體形態,但上述實施例 的變更,均在本發明的。’屬於申請專利範圍的均等範圍 [產業上利用性] 本發明的黏接劑,利用活性能量射 作性(祕)料學雜 濕的每丨兄下,光學疊層體尤其偏光板 阿脈同 著性仍優異,在黏接劑層與玻璃基板基板的ΐ 得不發生顏色^;均或漏光的液晶顯示 y巧離,可& 構件用黏接财效,而且#做此^、對於光學 光學構件及用於獲得影像顯示裝用有黏接劑層的 【圖式簡單說明】 益。 * »»\ 【主要元件符號說明】 益。 * »»、 46*: The adhesive of Comparative Example 6 is a non-curable fragrance. The miscibility with the acrylic resin is poor, the first leakage is whitened, and the glass plate cannot be attached. The durability test cannot be performed. The adhesion agent of the α example is a very high level of durability, lightness, and adhesion when the polarizing plate and the glass plate are attached, and the balance is excellent, and the adhesion of the pile layer is a inch. The turbidity and the odor resistance are also excellent. On the other hand, the performance is not satisfied in the following aspects from 1 to 6. • Comparative Example j without a monofunctional aromatic compound (B)), although the viscosity of the adhesive is different, but the performance when the polarizing plate and the plate are attached is poor, & a monofunctional aromatic compound (B) In Comparative Example 2 in which the amount of the polyfunctionally unsaturated person was increased by -1), the mouth of the polarizing plate and the glass plate was bonded, but the physical properties of the adhesive layer itself were inferior. b ^ For the total amount of (Β-1) and (C-1), only the monofunctional aromatic compound (4) 15.7_% of the comparative example 3 in the performance of the polarizing plate and the glass plate 45 201134905 - Comparative Example of 5, 6 Central Ring f Low Molecular Weightation of Monomers The compounding degree is a potting method. Further, the low score is only a specific form of the solution, but the modifications of the above embodiments are all in the present invention. 'Equal range of patent application scope】 [Industrial Applicability] The adhesive of the present invention utilizes active energy injection (secret) material to learn the wetness of each brother, and the optical laminate, especially the polarizing plate The property is still excellent, and the color of the adhesive layer and the glass substrate substrate does not occur; the liquid crystal display of the light leakage or the light leakage is y, and the component can be bonded with the financial effect, and #做此^, for optics The optical member and the [simplified description of the figure] for obtaining the image display device have an adhesive layer. * »»\ [Main component symbol description] Benefit. * »», 46
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JP2010252719A JP5729973B2 (en) | 2010-11-11 | 2010-11-11 | Acrylic adhesive, adhesive for optical members, optical member with adhesive layer, image display device |
JP2010270374 | 2010-12-03 |
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Publication number | Priority date | Publication date | Assignee | Title |
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US10377926B2 (en) | 2012-10-10 | 2019-08-13 | Samsung Sdi Co., Ltd. | Adhesive film, adhesive composition for the same, and display member including the same |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5844589B2 (en) * | 2011-09-21 | 2016-01-20 | デクセリアルズ株式会社 | Anisotropic conductive film, connection method using the same, and connection structure |
JP2013125077A (en) * | 2011-12-13 | 2013-06-24 | Nitto Denko Corp | Adhesive for polarizing plate, polarizing plate, manufacturing method of the same, optical film, and image display device |
JP6027850B2 (en) * | 2012-10-26 | 2016-11-16 | 日東電工株式会社 | Manufacturing method of polarizing plate |
JP5901548B2 (en) * | 2013-01-17 | 2016-04-13 | 藤森工業株式会社 | Adhesive layer and adhesive film |
KR101468475B1 (en) * | 2013-03-08 | 2014-12-04 | 우암피앤씨 주식회사 | Adhesive Agent for Film Lamination and Production Method Thereof |
JP6325777B2 (en) * | 2013-06-28 | 2018-05-16 | リンテック株式会社 | Adhesive sheet and laminate |
KR20150017650A (en) * | 2013-08-07 | 2015-02-17 | 동우 화인켐 주식회사 | Adhesive composition |
KR20150017649A (en) * | 2013-08-07 | 2015-02-17 | 동우 화인켐 주식회사 | Adhesive composition and complexed polarization plate using the same |
CN105492564B (en) * | 2013-08-30 | 2018-12-11 | 日东电工株式会社 | Polarizing coating curing type adhesive, polarizing coating, optical film and image display device |
JP6002701B2 (en) * | 2014-01-27 | 2016-10-05 | 藤森工業株式会社 | Adhesive layer and adhesive film |
KR101622019B1 (en) * | 2014-02-28 | 2016-05-17 | 제일모직주식회사 | Adhesive composition for polarizing plate, polarizing plate comprising the same and optical display comprising the same |
JP6519988B2 (en) * | 2014-05-30 | 2019-05-29 | 住友化学株式会社 | Optical film with adhesive and optical laminate |
KR102375988B1 (en) * | 2014-08-08 | 2022-03-17 | 주식회사 쿠라레 | Adhesive, bonded object and bonded object manufacturing method |
KR102016512B1 (en) * | 2017-08-24 | 2019-08-30 | 건국대학교 산학협력단 | Acrylic adhesive composition having dual curing system, Preparation method thereof, Adhesive film comprising the composition, and display device comprising the same |
WO2019054751A1 (en) | 2017-09-13 | 2019-03-21 | 주식회사 엘지화학 | Optical laminate |
EP3686258A4 (en) | 2017-11-10 | 2020-11-11 | LG Chem, Ltd. | Optical laminate |
EP3715428B1 (en) | 2017-11-30 | 2022-10-26 | Shanjin Optoelectronics (Suzhou) Co.,LTD. | Optical laminate |
CN108944111A (en) * | 2018-07-23 | 2018-12-07 | 库尔兹压烫科技(合肥)有限公司 | The notebook decoration transfer printing foil of high temperature resistant toughness |
KR102352953B1 (en) * | 2018-12-14 | 2022-01-18 | 삼성에스디아이 주식회사 | Adhesive film, optical member comprising the same and optical display apparatus comprising the same |
JP7326958B2 (en) * | 2019-07-22 | 2023-08-16 | コニカミノルタ株式会社 | LAMINATED FILM AND METHOD FOR MANUFACTURING THE SAME |
JP7340998B2 (en) * | 2019-09-05 | 2023-09-08 | リンテック株式会社 | Backlight unit and display device |
WO2021193718A1 (en) * | 2020-03-24 | 2021-09-30 | 日東電工株式会社 | Adhesive sheet and adhesive sheet with release liner |
TWI790849B (en) | 2021-12-09 | 2023-01-21 | 財團法人工業技術研究院 | Adhesive composition and liquid crystal display and method of disassembling the same |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5817555B2 (en) * | 1979-03-19 | 1983-04-07 | 東亞合成株式会社 | Active energy beam-curable adhesive composition |
JPH02248482A (en) * | 1989-03-23 | 1990-10-04 | Fujikura Kasei Co Ltd | Photocurable pressure-sensitive adhesive composition |
JP2612077B2 (en) * | 1989-11-09 | 1997-05-21 | 早川ゴム 株式会社 | Active energy ray-curable adhesive composition |
JP2642077B2 (en) * | 1995-02-24 | 1997-08-20 | 王子製紙株式会社 | Equipment to ultrasonically bond paper saw blades to cartons |
JP4516632B2 (en) * | 1999-04-20 | 2010-08-04 | 日東電工株式会社 | Acrylic pressure-sensitive adhesive composition and its adhesive sheets |
US6800366B2 (en) * | 2000-12-21 | 2004-10-05 | Lg Chem, Ltd. | Acrylic adhesive compositions for polarizing film and the polarizer film using the same |
JP4906196B2 (en) * | 2001-04-25 | 2012-03-28 | スリーエム イノベイティブ プロパティズ カンパニー | Plasticizer-resistant adhesive composition and adhesive article |
US7744998B2 (en) * | 2001-04-25 | 2010-06-29 | 3M Innovative Properties Company | Plasticizer-resistant pressure-sensitive adhesive composition and adhesive article |
JP2009191149A (en) * | 2008-02-14 | 2009-08-27 | Soken Chem & Eng Co Ltd | Adhesive composition for polarizing plate and polarizing plate using it |
JP2009235388A (en) * | 2008-03-03 | 2009-10-15 | Aica Kogyo Co Ltd | Composition |
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US10377926B2 (en) | 2012-10-10 | 2019-08-13 | Samsung Sdi Co., Ltd. | Adhesive film, adhesive composition for the same, and display member including the same |
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WO2011090090A1 (en) | 2011-07-28 |
CN102639663A (en) | 2012-08-15 |
CN102639663B (en) | 2015-04-01 |
CN104046281A (en) | 2014-09-17 |
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CN104046281B (en) | 2016-08-31 |
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