TW201606017A - Pressure-sensitive adhesive composition, pressure-sensitive adhesive polarizing plate and liquid crystal display device - Google Patents

Abstract

A pressure-sensitive adhesive composition comprises (A) an acrylic acid series polymer and (B) an adhesion modifier, represented in the formula (1) (see the description), comprising an organosilicon compound containing an epoxy group and/or partial hydrolysate or partial condensation product partial, and in the formula (1), X represents an alkyl having 1 to 4 hydrogen atoms or carbon atoms, R represents a monovalence alkyl having 1 to 6 carbon atoms, A represents bivalence alkyl having 6 to 10 carbon atoms, Y represents an epoxy structural group, n represents an integer from 1 to 3. The pressure-sensitive adhesive composition comprises, by mass, 100 parts of (A) and 0.001 to 10 parts of (B). The pressure-sensitive adhesive composition has an essential element, which is a silane coupling agent has a special length as that of a jointing chain containing an epoxy group and hydrolysis silyl, of the adhesion modifier, the reutilization in the initial stage and high adhesive strength at a high temperature or at high temperature and humid environment can be balanced.

Description

黏著劑組成物、黏著偏光板及液晶顯示裝置 Adhesive composition, adhesive polarizing plate and liquid crystal display device

本發明係關於使用新穎接著性改質劑之黏著劑組成物，更詳言之，係關於黏著劑組成物，其藉由使用含有環氧基與水解性矽烷基之連結鍵為特定鏈長之構造的矽烷偶合劑，相較於既有技術使用之矽烷偶合劑，有機部分所佔之比例較多，結果提高與樹脂之相溶性且與具有羥基之基質樹脂之結合力、相互作用優異，故除提高含有基質樹脂之黏著劑與基材之接著性外，亦降低矽烷基之水解性，故可急遽提高初期重工性，及有關具有由該黏著劑組成物形成之黏著劑層之黏著偏光板及含有該黏著偏光板之液晶顯示裝置。 The present invention relates to an adhesive composition using a novel adhesive modifier, and more particularly to an adhesive composition which is a specific chain length by using a bond containing an epoxy group and a hydrolyzable alkylene group. The decane coupling agent having a structure has a larger proportion of the organic portion than the decane coupling agent used in the prior art, and as a result, the compatibility with the resin is improved and the binding force and interaction with the matrix resin having a hydroxyl group are excellent. In addition to improving the adhesion between the adhesive containing the matrix resin and the substrate, the hydrolyzability of the alkylene group is also lowered, so that the initial reworkability can be improved rapidly, and the adhesive polarizing plate having the adhesive layer formed of the adhesive composition can be improved. And a liquid crystal display device including the adhesive polarizing plate.

矽烷偶合劑為分子中具有2個以上不同官能基，且通常以連結不易鍵結之有機質材料與無機質材料之仲介角色發揮作用。官能基之一為水解性矽烷基，係藉由水之存在生成矽烷醇基，使該矽烷醇基與無機材質表面之羥基反應，藉此與無機材質表面形成化學鍵。且，其他官能基為與如各種合成樹脂之有機質材料形成化學鍵之乙烯 基、環氧基、胺基、(甲基)丙烯酸基、巰基等之有機反應基。使用該特性而廣泛使用作為有機‧無機樹脂之改質劑、接著助劑、各種添加劑等。 The decane coupling agent has two or more different functional groups in the molecule, and usually functions as an intermediary function of an organic material and an inorganic material which are not easily bonded. One of the functional groups is a hydrolyzable alkylene group which forms a stanol group by the presence of water, and reacts the stanol group with a hydroxyl group on the surface of the inorganic material to form a chemical bond with the surface of the inorganic material. Moreover, other functional groups are ethylene which form a chemical bond with an organic material such as various synthetic resins. An organic reactive group such as an epoxy group, an epoxy group, an amine group, a (meth)acrylic group or a fluorenyl group. Using this property, a modifier, an auxiliary agent, various additives, and the like as an organic/inorganic resin are widely used.

矽烷偶合劑之用途中，代表者為作為黏著劑之接著性改質劑之用途，例如，貼合液晶胞與光學薄膜時之黏著劑隨著液晶顯示裝置(LCD)之尺寸大型化、寬廣化，而成為高度的要求接著性能者。 In the use of the decane coupling agent, it is used as an adhesive modifier as an adhesive. For example, when the liquid crystal cell and the optical film are bonded together, the size of the liquid crystal display device (LCD) is increased and broadened. And become a highly demanding performance player.

LCD之情況下，不同於當初預測之20吋以上之大型化有困難，已急速朝大型化發展。主要製造商迄今之前均以20吋以下之小型面板之生產為主力，但受到近年來之流行已積極導入最新技術，將製品範圍進展到20吋以上之大型尺寸。 In the case of LCD, it is difficult to increase the size of the 20-inch or more that was originally predicted, and it has rapidly developed toward large-scale development. Major manufacturers have previously focused on the production of small panels of less than 20 inches, but have been actively introducing the latest technology in recent years, and the range of products has progressed to a large size of 20 inches or more.

據此，諸光學薄膜中，液晶顯示板製造時使用之玻璃有大型化之趨勢。不過，在初期貼合時產生不良製品，而自液晶胞去除光學用薄膜，且洗淨液晶胞後再使用時，若使用過去具有高黏著力之黏著劑，則光學薄膜再剝離時因強的接著力不僅難以去除光學薄膜，且破壞昂貴的液晶胞之可能性大，結果使生產成本大幅提高。 Accordingly, among the optical films, the glass used in the production of the liquid crystal display panel tends to be large. However, when an initial product is produced at the time of initial bonding, the optical film is removed from the liquid crystal cell, and when the liquid crystal cell is washed and used, if an adhesive having a high adhesive force in the past is used, the optical film is strongly peeled off. The force is not only difficult to remove the optical film, but also the possibility of destroying the expensive liquid crystal cell is large, and as a result, the production cost is greatly increased.

據此，隨著LCD之大型化，而持續嘗試開發出兼顧接著性、重工性等諸黏著性能之高功能性黏著劑。例如，日本專利第3022993號公報(專利文獻1)中為了提高在高溫多濕環境下之耐久性優異之偏光板，而提案含有環氧基矽烷之丙烯酸系黏著劑組成物。 Accordingly, with the increase in the size of LCDs, attempts have been made to develop highly functional adhesives that have adhesive properties such as adhesion and reworkability. For example, Japanese Patent No. 3022993 (Patent Document 1) proposes an acrylic pressure-sensitive adhesive composition containing epoxy decane in order to improve the durability of the polarizing plate in a high-temperature and high-humidity environment.

此外，日本專利第3533446號公報(專利文 獻2)、日本專利第5262672號公報(專利文獻3)中，為了不僅可以良好的接著強度將偏光板接著於基板表面，且視需要在不對基板造成損傷、不殘留黏著劑下自基板表面剝離偏光板，而提案包含丙烯酸系聚合物、與具有β-酮酯基及水解矽烷基之化合物或其水解縮合物之黏著劑組成物。 In addition, Japanese Patent No. 3533446 (Patent Document) In Japanese Patent No. 5262672 (Patent Document 3), in order to adhere not only to the surface of the substrate but also to the surface of the substrate, it is possible to remove the polarizing plate from the surface of the substrate without damaging the substrate. The polarizing plate is proposed to include an acrylic polymer, an adhesive composition having a β-ketoester group and a hydrolyzed alkyl group or a hydrolysis condensate thereof.

日本專利第4771102號公報(專利文獻4)、日本專利第5365609號公報(專利文獻5)、日本專利第5365610號公報(專利文獻6)、日本特表2008-506028號公報(專利文獻7)中，為了不僅可以良好的接著強度將偏光板接著於基板表面，且視需要在不對基板造成損傷、不殘留黏著劑下自基板表面剝離偏光板，故提案包含丙烯酸系聚合物、與具有雜環構造基、胺基甲酸酯或脲連結基及水解矽烷基之化合物之黏著劑組成物。 Japanese Patent No. 4771102 (Patent Document 4), Japanese Patent No. 5365609 (Patent Document 5), Japanese Patent No. 5,536,610 (Patent Document 6), and Japanese Patent Publication No. 2008-506028 (Patent Document 7) In order to adhere the polarizing plate to the surface of the substrate without good adhesion strength, and if necessary, the polarizing plate is peeled off from the surface of the substrate without damaging the substrate, and it is proposed to include an acrylic polymer and a heterocyclic structure. An adhesive composition of a base, a urethane or urea linkage and a compound which hydrolyzes a decyl group.

此外，日本特開2011-219765號公報(專利文獻8)、日本專利第4840888號公報(專利文獻9)、國際公開第2010/26995號(專利文獻10)中，作為初期接著力低、重工性優異、貼合後在高溫多濕下接著力增強、且長期耐久性優異之黏著劑，提案包含於聚醚末端具有烷氧基矽烷基之有機矽化合物之丙烯酸系黏著劑。 In addition, Japanese Patent Publication No. 2011-219765 (Patent Document 8), Japanese Patent No. 4840888 (Patent Document 9), and International Publication No. 2010/26995 (Patent Document 10) have low initial adhesion and heavy workability. An adhesive which is excellent in bonding strength after high-temperature and high-wetting adhesion and excellent in long-term durability after bonding is proposed to include an acrylic adhesive having an alkoxyalkyl group-containing organic sulfonium compound at a polyether end.

藉由含有該矽烷化合物，可使基板與偏光板在實際使用之環境下保持所要求程度之適度接著強度，接著強度不會因加熱等而變得過高，不會對液晶元件造成損傷，且可容易剝離偏光板。 By containing the decane compound, the substrate and the polarizing plate can maintain a moderate degree of bonding strength in a practical use environment, and then the strength is not excessively increased by heating or the like, and damage to the liquid crystal element is not caused, and The polarizing plate can be easily peeled off.

然而，用以支撐LCD大型傾向之黏著劑所要求之性能不僅需要貼合於玻璃時之初期接著力低、重工性優異，且在高溫多濕下必須展現高接著力，非此情況時，產生氣泡或剝離現象等而有耐久性脆弱之虞。 However, the performance required for the adhesive to support the large-scale LCD is not only required to be attached to the glass, but also has excellent initial adhesion, excellent reworkability, and high adhesion at high temperatures and humidity. It is fragile and durable due to bubbles or peeling.

日本特開平8-199144號公報(專利文獻11)中，為提供即使在高溫多濕下凝聚力及接著力之經時變化仍少，彎曲面接著力亦優異之黏著劑組成物，而提案將硬化劑調配於在矽烷系化合物存在下使丙烯酸系單體聚合獲得之丙烯酸矽樹脂中之技術。 Japanese Patent Publication No. 8-199144 (Patent Document 11) proposes an adhesive composition which is excellent in the adhesion of the cohesive force and the adhesive force even under high temperature and high humidity, and has excellent bending surface adhesion. The technique of blending in an acrylic resin obtained by polymerizing an acrylic monomer in the presence of a decane-based compound.

且記載藉由調配該矽烷化合物，可使基板與偏光板在實際使用之環境下保持要求程度之適當接著強度，接著強度不會因加熱等而過度提高，亦不對液晶元件造成損傷，可容易剝離偏光板。 It is also described that by blending the decane compound, the substrate and the polarizing plate can be maintained at a desired bonding strength in an environment where they are actually used, and the strength is not excessively increased by heating or the like, and the liquid crystal element is not damaged, and the film can be easily peeled off. Polarizer.

然而，相較於在高溫多濕下凝聚力及接著力之經時變化較小，更好為接著力高、無氣泡或剝離現象且耐久性優異者。亦即，貼合於玻璃之初期雖顯示可再剝離程度之適當初期接著力，但由於隨著時間經過並無剝離之必要性，故可說必須保持強化、安定化之接著力。 However, compared with the change of the cohesive force and the adhesive force with a small time under high temperature and high humidity, it is more preferable that the adhesive force is high, there is no bubble or peeling phenomenon, and the durability is excellent. In other words, the initial initial adhesion of the re-peelable degree is exhibited in the initial stage of bonding to the glass. However, since it is not necessary to peel off over time, it can be said that it is necessary to maintain the adhesion and stability.

基於該觀點，上述專利文獻2~10所記載之由有機矽化合物所成之接著性改質劑所可改良之重工性、貼合後之耐濕特性、接著力等不能說已充分，尚有改良之餘地。 In view of the above, the reworkability improved by the adhesive modifier made of the organic ruthenium compound described in the above Patent Documents 2 to 10, the moisture resistance after bonding, and the adhesion can not be said to be sufficient. Room for improvement.

基於上述，期望開發出能取得保持初期之重工性及高溫多濕下之高的接著強度之平衡的黏著劑。 Based on the above, it has been desired to develop an adhesive capable of achieving a balance between the initial workability and the high strength at the high temperature and high humidity.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利第3022993號公報 [Patent Document 1] Japanese Patent No. 3022993

[專利文獻2]日本專利第3533446號公報 [Patent Document 2] Japanese Patent No. 3533446

[專利文獻3]日本專利第5262672號公報 [Patent Document 3] Japanese Patent No. 5262672

[專利文獻4]日本專利第4771102號公報 [Patent Document 4] Japanese Patent No. 4771102

[專利文獻5]日本專利第5365609號公報 [Patent Document 5] Japanese Patent No. 5365609

[專利文獻6]日本專利第5365610號公報 [Patent Document 6] Japanese Patent No. 5365610

[專利文獻7]日本特表第2008-506028號公報 [Patent Document 7] Japanese Patent Publication No. 2008-506028

[專利文獻8]日本特開第2011-219765號公報 [Patent Document 8] Japanese Laid-Open Patent Publication No. 2011-219765

[專利文獻9]日本專利第4840888號公報 [Patent Document 9] Japanese Patent No. 4840888

[專利文獻10]國際公開第2010/26995號 [Patent Document 10] International Publication No. 2010/26995

[專利文獻11]日本特開平8-199144號公報 [Patent Document 11] Japanese Patent Laid-Open No. Hei 8-199144

本發明係鑑於上述情況而完成者，其目的係提供一種可形成於貼合於玻璃等被接著體時之初期接著力低且重工性優異、貼合後在高溫或高溫多濕之條件下與玻璃等被接著體之接著力增加且長期耐久性優異之黏著劑層之黏著劑組成物、及具有由該黏著劑組成物形成之黏著劑層之黏著偏光板及具有該黏著偏光板之液晶顯示裝置。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a film which can be formed on a bonded body such as glass and has a low initial adhesion force and excellent reworkability, and is bonded to a high temperature or a high temperature and humidity. Adhesive composition of an adhesive layer which is increased in adhesion by a bonding body such as glass and excellent in long-term durability, and an adhesive polarizing plate having an adhesive layer formed of the adhesive composition and a liquid crystal display having the adhesive polarizing plate Device.

本發明人為達成上述目的而重複積極檢討之結果，發現藉由使用含有環氧基與水解性矽烷基之連結鏈為特定鏈長之構造的矽烷偶合劑作為接著性改質劑，相較於既有技術使用之矽烷偶合劑，有機部分所佔之比例較多，故提高與樹脂之相溶性且與具有羥基之基質樹脂之結合力、相互作用優異，且由於矽烷基之水解性低故獲得可兼顧初期重工性與高溫或高溫多濕下之高接著力之黏著劑，終於完成本發明。 As a result of repeating the positive review, the inventors of the present invention found that a decane coupling agent having a structure in which a linking chain of an epoxy group and a hydrolyzable decyl group is a specific chain length is used as an adhesion modifier. The decane coupling agent used in the art has a large proportion of the organic portion, so that the compatibility with the resin is improved, and the binding force and interaction with the matrix resin having a hydroxyl group are excellent, and since the hydrolyzability of the decyl group is low, it is obtained. The present invention has finally been completed in consideration of an adhesive having an initial reworkability and a high adhesion force under high temperature or high temperature and high humidity.

據此，本發明提供下述黏著劑組成物、黏著偏光板及液晶顯示裝置。 Accordingly, the present invention provides the following adhesive composition, adhesive polarizing plate, and liquid crystal display device.

[1] [1]

一種黏著劑組成物，其特徵係含有下列成分：(A)丙烯酸系聚合物，與(B)由以下述通式(1)表示之含有環氧基之有機矽化合物及/或其部分水解物或部分水解縮合物所成之接著性改質劑， An adhesive composition comprising the following components: (A) an acrylic polymer, and (B) an organic hydrazine compound containing an epoxy group represented by the following general formula (1) and/or a partial hydrolyzate thereof Or a partial hydrolysis modifier formed by hydrolysis of the condensate,

(式中，X為氫原子或碳數1~4之烷基，R為碳數1~6之一價烴基，A為碳數6~10之二價烴基，Y為環氧構造基，n為1~3之整數)，且相對於(A)成分100質量份，(B)成分為0.001~ 10質量份之比例。 (wherein X is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R is a hydrocarbon group having 1 to 6 carbon atoms, A is a divalent hydrocarbon group having 6 to 10 carbon atoms, and Y is an epoxy structural group, n It is an integer of 1 to 3), and the component (B) is 0.001 to 100 parts by mass of the component (A). The ratio of 10 parts by mass.

[2] [2]

如[1]所記載之黏著劑組成物，其中上述式(1)中之Y之環氧構造基為縮水甘油氧基或環氧環己烷(cyclohexene oxide)構造基。 The adhesive composition according to [1], wherein the epoxy structural group of Y in the above formula (1) is a glycidoxy group or a cyclohexene oxide structural group.

[3] [3]

如[1]或[2]所記載之黏著劑組成物，其中(B)成分之含有環氧基之有機矽化合物係以下述通式(2)表示者： The adhesive composition according to [1] or [2], wherein the epoxy group-containing organic oxime compound of the component (B) is represented by the following formula (2):

(式中，X、R、n係如[1]之定義)。 (wherein, X, R, and n are as defined in [1]).

[4] [4]

如[1]~[3]中任一項所記載之黏著劑組成物，其包含下列成分：(A)使(a)具有碳數1~12之烷基之(甲基)丙烯酸酯單體90~99.9質量份、與(b)包含可交聯之官能基之乙烯系單體及/或(甲基)丙烯酸系單體0.1~10質量份共聚合而得之丙烯酸系聚合物：100質量份、(B)如[1]~[3]中任一項所記載之接著性改質劑：0.001~10質量份、(C)多官能***聯劑：0.01~10質量份。 The adhesive composition according to any one of [1] to [3] which comprises the following components: (A) (a) a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms 90 to 99.9 parts by mass, and (b) an acrylic polymer obtained by copolymerizing a vinyl monomer containing a crosslinkable functional group and/or a (meth)acrylic monomer in an amount of 0.1 to 10 parts by mass: 100 mass (B) The adhesive modifier according to any one of [1] to [3], which is 0.001 to 10 parts by mass, and (C) a polyfunctional crosslinking agent: 0.01 to 10 parts by mass.

[5] [5]

如[4]所記載之黏著劑組成物，其中上述(b)成分之包含可交聯之官能基之乙烯系單體或(甲基)丙烯酸系單 體係由下列所組成之群選出之至少一種以上之單體：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、二乙二醇單(甲基)丙烯酸酯、二丙二醇單(甲基)丙烯酸酯、(甲基)丙烯醯氧基丙基三甲氧基矽烷、(甲基)丙烯醯氧基丙基三乙氧基矽烷、(甲基)丙烯醯氧基丙基甲基二甲氧基矽烷、(甲基)丙烯醯氧基丙基甲基二乙氧基矽烷、(甲基)丙烯醯氧基甲基三甲氧基矽烷、(甲基)丙烯醯氧基甲基三乙氧基矽烷、(甲基)丙烯醯氧基甲基甲基二甲氧基矽烷、(甲基)丙烯醯氧基甲基甲基二乙氧基矽烷、(甲基)丙烯酸、(甲基)丙烯酸二聚物、衣康酸、馬來酸及馬來酸酐。 The adhesive composition according to [4], wherein the component (b) contains a crosslinkable functional group of a vinyl monomer or a (meth)acrylic acid single The system comprises at least one or more monomers selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and Ethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, (meth)acryloxypropyltrimethoxydecane, (meth)acryloxypropyltriethoxylate Decane, (meth) propylene methoxy propyl methyl dimethoxy decane, (meth) propylene methoxy propyl methyl diethoxy decane, (meth) propylene methoxy methyl trimethoxy Base decane, (meth) propylene methoxymethyl triethoxy decane, (meth) propylene methoxymethyl methyl dimethoxy decane, (meth) propylene methoxymethyl methyl group Ethoxy decane, (meth)acrylic acid, (meth)acrylic acid dimer, itaconic acid, maleic acid and maleic anhydride.

[6] [6]

如[4]或[5]所記載之黏著劑組成物，其中(C)成分之多官能***聯劑係由異氰酸酯系化合物、環氧系化合物、氮丙啶系化合物及金屬螯合系化合物所組成之群選出之一種以上之交聯劑。 The adhesive composition according to [4] or [5], wherein the polyfunctional crosslinking agent of the component (C) is an isocyanate compound, an epoxy compound, an aziridine compound, or a metal chelate compound. One or more cross-linking agents selected from the group consisting of.

[7] [7]

一種黏著偏光板，其特徵係具有偏光薄膜、與在該偏光薄膜之單面或兩面上由如[1]~[6]中任一項所記載之黏著劑組成物形成之黏著劑層。 An adhesive polarizing plate comprising a polarizing film and an adhesive layer formed of the adhesive composition according to any one of [1] to [6] on one or both sides of the polarizing film.

[8] [8]

如[7]所記載之黏著偏光板，其進而具有由保護層、反射層、相位差板、光視角補償薄膜及亮度提高薄膜所組 成之群選出之一種以上之層。 The adhesive polarizing plate according to [7], further comprising a protective layer, a reflective layer, a phase difference plate, a light viewing angle compensation film, and a brightness enhancement film. One or more layers selected by Cheng Zhiqun.

[9] [9]

一種液晶顯示裝置，其特徵係包含液晶面板，該液晶面板具有在一對玻璃基板間封入液晶而成之液晶胞、與貼合於該液晶胞之單面或兩面上之如[7]或[8]所記載之黏著偏光板。 A liquid crystal display device characterized by comprising a liquid crystal panel having a liquid crystal cell sealed with liquid crystal between a pair of glass substrates and attached to one or both sides of the liquid crystal cell such as [7] or [ 8] The adhesive polarizing plate described.

本發明之黏著劑組成物藉由調配含有環氧基與水解性矽烷基之連結鏈為特定鏈長之構造之矽烷偶合劑作為接著性改質劑必要成分，可兼顧初期重工性與在高溫或高溫多濕下之高接著力。 The adhesive composition of the present invention is prepared by blending a decane coupling agent having a structure in which a linking chain of an epoxy group and a hydrolyzable decyl group is a specific chain length as an essential component of the adhesion modifier, and can attain initial workability and high temperature or High adhesion under high temperature and humidity.

以下針對本發明具體說明。又，本發明中「矽烷偶合劑」包含於「有機矽化合物」中。 The invention is specifically described below. Further, in the present invention, the "decane coupling agent" is included in the "organoquinone compound".

本發明黏著劑組成物含有(A)丙烯酸系聚合物與(B)接著性改質劑。 The adhesive composition of the present invention contains (A) an acrylic polymer and (B) an adhesive modifier.

以下，針對(A)成分之丙烯酸系聚合物及(B)成分之接著性改質劑加以詳述。 Hereinafter, the acrylic polymer of the component (A) and the adhesive modifier of the component (B) will be described in detail.

(A)丙烯酸系聚合物 (A) acrylic polymer

(A)成分之丙烯酸系聚合物較好使用使(a)具有碳數1~12之烷基之(甲基)丙烯酸酯單體90~99.9質量 份；(b)包含可交聯之官能基之乙烯系單體及/或(甲基)丙烯酸系單體0.1~10質量份共聚合而得之丙烯酸系共聚物。 The acrylic polymer of the component (A) is preferably used in an amount of 90 to 99.9 by weight of (a) a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms. (b) an acrylic copolymer obtained by copolymerizing a vinyl monomer having a crosslinkable functional group and/or a (meth)acrylic monomer in an amount of 0.1 to 10 parts by mass.

此處，本發明之組成物中使用之(a)具有碳數1~12之烷基之(甲基)丙烯酸酯單體宜為在共聚合之單體100質量份中，含有90~99.9質量份，尤其91~99質量份者，其含量未達90質量份時會有初期接著力降低之情況，超過99.9質量份時會有因凝聚力降低而使耐久性出現問題之情況。 Here, the (meth) acrylate monomer having (a) an alkyl group having 1 to 12 carbon atoms used in the composition of the present invention is preferably contained in an amount of 90 to 99.9 by mass in 100 parts by mass of the copolymerized monomer. When the content is not more than 90 parts by mass, the initial adhesion is lowered, and when it is more than 99.9 parts by mass, the durability may be lowered due to a decrease in cohesive force.

此外，(a)成分之具有碳數1~12之烷基之(甲基)丙烯酸酯單體為(b)成分之含可交聯之官能基之(甲基)丙烯酸系單體以外者，可使用(甲基)丙烯酸之碳數為1~12之烷酯，更好使用碳數為2~8之烷酯。亦即，前述(甲基)丙烯酸烷酯若烷基為長鏈型態則有黏著劑之凝聚力降低之情況，故為了在高溫下保持凝聚力，烷基之碳數較好為1~12之範圍，更好為2~8之範圍。 Further, the (meth) acrylate monomer having a carbon number of 1 to 12 in the component (a) is a (meth)acrylic monomer having a crosslinkable functional group as the component (b). An alkyl ester of (meth)acrylic acid having a carbon number of 1 to 12 can be used, and an alkyl ester having 2 to 8 carbon atoms can be preferably used. That is, the alkyl (meth)acrylate may have a cohesive force of the adhesive if the alkyl group is in a long-chain form, so that the carbon number of the alkyl group is preferably in the range of 1 to 12 in order to maintain cohesive force at a high temperature. It is better for the range of 2~8.

該(甲基)丙烯酸酯單體列舉為(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯等，該等可單獨使用1種或混合2種以上使用。 The (meth) acrylate monomer is exemplified by butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, (methyl) ) n-propyl acrylate, isopropyl (meth) acrylate, tert-butyl (meth) acrylate, amyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate In the case of isophthalic acid (meth) acrylate or the like, these may be used alone or in combination of two or more.

(b)成分之含可交聯之官能基之乙烯系單體 及(甲基)丙烯酸系單體係以與交聯劑反應而在高溫或高溫多濕條件下不會產生黏著劑之凝聚力破壞之方式進行化學鍵結而賦予凝聚力或接著強度。(b)成分之單體之調配量在共聚合之單體100質量份中較好使用0.1~10質量份，最好使用1~9質量份，若未達0.1質量份，則會有在高溫多濕下容易產生凝聚破壞之情況，超過10質量份時適合性顯著減少，成為引起表面移行之原因，且有流動性減少另一方面會使凝聚力上升且應力緩和能力降低之情況。 (b) a vinyl monomer having a crosslinkable functional group And the (meth)acrylic single system is chemically bonded to react with the crosslinking agent to cause cohesive force or subsequent strength without causing cohesive force destruction of the adhesive under high temperature or high temperature and high humidity conditions. The amount of the monomer of the component (b) is preferably 0.1 to 10 parts by mass, preferably 1 to 9 parts by mass, per 100 parts by mass of the copolymerized monomer, and if it is less than 0.1 part by mass, there is a high temperature. When the amount is more than 10 parts by mass, the suitability is remarkably reduced, and the surface migration is caused, and the fluidity is decreased, and the cohesive force is increased and the stress relaxation ability is lowered.

(b)成分之含可交聯之官能基之乙烯系單體或(甲基)丙烯酸系單體之例列舉為(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、二乙二醇單(甲基)丙烯酸酯、二丙二醇單(甲基)丙烯酸酯等含羥基之單體，(甲基)丙烯酸、(甲基)丙烯酸二聚物、衣康酸、馬來酸及馬來酸酐等含羧基之單體，(甲基)丙烯醯氧基丙基三甲氧基矽烷、(甲基)丙烯醯氧基丙基三乙氧基矽烷、(甲基)丙烯醯氧基丙基甲基二甲氧基矽烷、(甲基)丙烯醯氧基丙基甲基二乙氧基矽烷、(甲基)丙烯醯氧基甲基三甲氧基矽烷、(甲基)丙烯醯氧基甲基三乙氧基矽烷、(甲基)丙烯醯氧基甲基甲基二甲氧基矽烷、(甲基)丙烯醯氧基甲基甲基二乙氧基矽烷等含水解性矽烷基之單體等，但並不限於該等。上述單體可單獨使用1種或混合2種以上使用。 Examples of the vinyl monomer or (meth)acrylic monomer having a crosslinkable functional group of the component (b) are exemplified by 2-hydroxyethyl (meth)acrylate and 3-hydroxypropyl (meth)acrylate. a hydroxyl group-containing monomer such as ester, 4-hydroxybutyl (meth)acrylate, diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, (meth)acrylic acid, (methyl) a carboxyl group-containing monomer such as acrylic acid dimer, itaconic acid, maleic acid or maleic anhydride, (meth)acryloxypropyltrimethoxydecane, (meth)acryloxypropyl three Ethoxy decane, (meth) propylene methoxy propyl methyl dimethoxy decane, (meth) propylene methoxy propyl methyl diethoxy decane, (meth) propylene methoxy group Trimethoxy decane, (meth) propylene methoxymethyl triethoxy decane, (meth) propylene methoxymethyl methyl dimethoxy decane, (meth) propylene methoxymethyl A monomer containing a hydrolyzable alkylene group such as methyldiethoxysilane or the like, but is not limited thereto. These monomers may be used alone or in combination of two or more.

又，本發明中在製造丙烯酸系共聚物時，可進而使用其他共聚合性單體以調節黏著劑組成物之玻璃轉移溫度，且賦予其他功能性。具體而言，可使用丙烯腈、苯乙烯、(甲基)丙烯酸縮水甘油酯、乙酸乙烯酯等共聚合性單體。該等共聚合性單體之調配比例在共聚合之單體100質量份中，較好為0.1~9.9質量份，更好為0.5~8質量份。 Further, in the production of the acrylic copolymer in the present invention, other copolymerizable monomers may be further used to adjust the glass transition temperature of the adhesive composition and impart other functionalities. Specifically, a copolymerizable monomer such as acrylonitrile, styrene, glycidyl (meth)acrylate or vinyl acetate can be used. The blending ratio of the copolymerizable monomers is preferably from 0.1 to 9.9 parts by mass, more preferably from 0.5 to 8 parts by mass, per 100 parts by mass of the copolymerized monomer.

黏著劑組成物之黏彈性特性主要是基於高分子鏈之分子量、分子量分佈、或分子構造之存在量，尤其由分子量決定，故本發明中使用之(甲基)丙烯酸系共聚物之分子量(重量平均分子量：Mw)較好為80萬~200萬，更好為90萬~190萬。又，重量平均分子量係以凝膠滲透層析儀(GPC)測定之標準聚苯乙烯換算值。分子量太小時會有無法獲得期望之黏彈特性之虞，太大時聚合物之黏度非常高，處理困難故有生產性降低之情況。 The viscoelastic property of the adhesive composition is mainly based on the molecular weight, molecular weight distribution, or molecular structure of the polymer chain, and is particularly determined by the molecular weight, so the molecular weight (weight) of the (meth)acrylic copolymer used in the present invention The average molecular weight: Mw) is preferably from 800,000 to 2,000,000, more preferably from 900,000 to 1.9 million. Further, the weight average molecular weight is a standard polystyrene equivalent value measured by a gel permeation chromatography (GPC). If the molecular weight is too small, the desired viscoelastic properties may not be obtained. When the molecular weight is too large, the viscosity of the polymer is very high, and the handling is difficult, so that the productivity is lowered.

該等共聚物可經過通常之自由基共聚合過程製造。本發明中聚合物之聚合方法並無特別限制，可藉由溶液聚合法、光聚合法、塊體聚合法、懸浮聚合法、乳化聚合法等一般方法製造。該等中基於生產性之觀點以溶液聚合法較佳。該情況下，較好聚合溫度為50~140℃，反應時間為1~24小時。較好在單體均勻混合之狀態下添加起始劑。 These copolymers can be produced by a conventional free radical copolymerization process. The polymerization method of the polymer in the present invention is not particularly limited, and it can be produced by a general method such as a solution polymerization method, a photopolymerization method, a bulk polymerization method, a suspension polymerization method, or an emulsion polymerization method. Among these, a solution polymerization method is preferred from the viewpoint of productivity. In this case, the polymerization temperature is preferably from 50 to 140 ° C, and the reaction time is from 1 to 24 hours. It is preferred to add an initiator in a state in which the monomers are uniformly mixed.

(B)接著性改質劑[有機矽化合物(矽烷偶合劑)] (B) Adhesive modifier [organic hydrazine compound (decane coupling agent)]

本發明之主幹成分之接著性改質劑係以下述通式(1)表示之含有環氧基之有機矽化合物及/或其部分水解物或部分水解縮合物。 The adhesive modifier of the main component of the present invention is an epoxy group-containing organic hydrazine compound represented by the following formula (1) and/or a partial hydrolyzate or a partially hydrolyzed condensate thereof.

(式中，X為氫原子或碳數1~4之烷基，R為碳數1~6之一價烴基，A為碳數6~10之二價烴基，Y為環氧構造基，n為1~3之整數)。 (wherein X is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R is a hydrocarbon group having 1 to 6 carbon atoms, A is a divalent hydrocarbon group having 6 to 10 carbon atoms, and Y is an epoxy structural group, n It is an integer from 1 to 3.)

接著性改質成分，除上述有機矽化合物單體以外，水解性矽烷基部分經一部分水解之構造，或進而進行分子間縮合成為寡聚物之部分水解縮合物由於亦展現同樣性能故而包含於接著性改質成分中。 Further, in addition to the above organic hydrazine compound, the hydrolyzable decyl group is partially hydrolyzed, or further intermolecularly condensed to form a partially hydrolyzed condensate of the oligomer, since it exhibits the same performance and is included in the subsequent modification. Sexually modified ingredients.

上述X中碳數1~4之烷基之具體例列舉為甲基、乙基、丙基、丁基，該等可為直鏈狀或分支狀。較好基於原料取得之容易性、生產性之觀點，較期望為甲基、乙基。 Specific examples of the alkyl group having 1 to 4 carbon atoms in the above X are exemplified by a methyl group, an ethyl group, a propyl group and a butyl group, and these may be linear or branched. It is preferred to use a methyl group or an ethyl group from the viewpoint of easiness of obtaining raw materials and productivity.

上述R中碳數1~6之一價烴基之具體例，烷基列舉為甲基、乙基、丙基、丁基、戊基、己基。該等為直鏈狀、分支狀、環狀之任一種均可。此外，芳基列舉為苯基。較好基於原料取得之容易性、生產性之觀點，較期望為甲基。 Specific examples of the one-valent hydrocarbon group having 1 to 6 carbon atoms in R, the alkyl group is exemplified by a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. These may be any of a linear chain, a branched shape, and a ring shape. Further, the aryl group is exemplified by a phenyl group It is preferable to use a methyl group because it is easy to obtain raw materials and productivity.

上述A中碳數6~10之二價烴基之具體例列舉為伸己基、伸庚基、伸辛基、伸壬基、伸癸基等伸烷基。該等可為直鏈狀或分支狀。基於原料取得之容易性以直鏈 狀伸辛基較佳。又，該構造部為本發明之主幹構造，既有技術一般為伸丙基，鏈長比其長為必要因子。 Specific examples of the divalent hydrocarbon group having 6 to 10 carbon atoms in the above A are exemplified by an alkyl group such as an exohexyl group, a heptyl group, an exooctyl group, a fluorenyl group, and a fluorenyl group. These may be linear or branched. Based on the ease of obtaining raw materials in a linear chain It is preferred to extend the octyl group. Further, the structural portion is the main structure of the present invention, and the conventional technique is generally a stretching propyl group, and the chain length is an essential factor.

上述Y中環氧構造基之具體例為縮水甘油氧基或環氧環己烷構造基，基於原料取得之容易性以縮水甘油氧基更佳。 A specific example of the epoxy structural group in the above Y is a glycidoxy group or an epoxycyclohexane structural group, and a glycidyloxy group is more preferable because the easiness of the raw material is obtained.

就該等觀點而言，含環氧基之有機矽化合物之更好構造係以下述通式(2)表示 From such a viewpoint, a better structure of the epoxy group-containing organic ruthenium compound is represented by the following formula (2)

(式中，X、R、n係與上述同義)。 (wherein, X, R, and n are synonymous with the above).

基於原料取得之容易性、生產性之觀點，更好係X為甲基，n=3者。 From the viewpoint of easiness of obtaining raw materials and productivity, it is more preferable that X is a methyl group and n=3.

本發明之黏著劑組成物中，特徵為(B)接著性改質成分相對於(A)丙烯酸系聚合物100質量份係調配0.001~10質量份。未達前述下限值時無法展現期望之接著性改質效果，超過上限值時效果已飽和，除相對費用效果降低以外，原有之矽烷偶合劑所具有之密著性提高效果之影響變大，會有初期密著性突出之虞而不適當。 In the adhesive composition of the present invention, the (B) adhesive composition is formulated in an amount of 0.001 to 10 parts by mass based on 100 parts by mass of the (A) acrylic polymer. When the lower limit value is not reached, the desired adhesion modification effect cannot be exhibited. When the upper limit value is exceeded, the effect is saturated, and the effect of the adhesion improvement effect of the original decane coupling agent is changed in addition to the reduction in the relative cost effect. Large, there will be an initial imperfection and not appropriate.

[黏著劑組成物] [Adhesive composition]

本發明之黏著劑組成物係以上述(A)、(B)成分作為必要成分者，但較好進而含有(C)多官能***聯劑，更具體而言較好含有下列成分： The adhesive composition of the present invention contains the above components (A) and (B) as essential components, but preferably further contains (C) a polyfunctional crosslinking agent, and more specifically preferably contains the following components:

(A)丙烯酸系聚合物：100質量份 (A) acrylic polymer: 100 parts by mass

(B)接著性改質劑：0.001~10質量份 (B) Adhesive modifier: 0.001 to 10 parts by mass

(C)多官能***聯劑：0.01~10質量份 (C) Polyfunctional crosslinking agent: 0.01 to 10 parts by mass

此處，本發明之黏著劑組成物中，(C)成分之多官能***聯劑係扮演與羧基、或羥基等反應而提高黏著劑之凝聚力之角色。交聯劑之含量相對於(A)成分之共聚物100質量份較好使用0.01~10質量份，更好為0.05~5質量份。太多時凝聚加劇，會有成形為黏著劑薄片等變困難之情況，太少時會有無法獲得期望之凝聚力提高效果之情況。 Here, in the adhesive composition of the present invention, the polyfunctional crosslinking agent of the component (C) functions to react with a carboxyl group or a hydroxyl group to increase the cohesive force of the adhesive. The content of the crosslinking agent is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the copolymer of the component (A). When the amount is too much, the aggregation becomes intensive, and it may become difficult to form an adhesive sheet or the like. When the amount is too small, the desired cohesive strength improvement effect may not be obtained.

多官能***聯劑可使用異氰酸酯系、環氧系、氮丙啶系、金屬螯合系交聯劑等，其中異氰酸酯系交聯劑在使用上較容易。異氰酸酯系交聯劑列舉為甲苯二異氰酸酯、二甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、四甲基二甲苯二異氰酸酯、萘二異氰酸酯、該等與三羥甲基丙烷等多元醇之反應物(三羥甲基丙烷甲苯二異氰酸酯加成物等)等。 As the polyfunctional crosslinking agent, an isocyanate-based, epoxy-based, aziridine-based or metal-chelating crosslinking agent can be used, and an isocyanate-based crosslinking agent is easy to use. The isocyanate crosslinking agent is exemplified by toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate, naphthalene diisocyanate, and the like. A reaction product such as a trihydric alcohol such as trimethylolpropane (trimethylolpropane toluene diisocyanate adduct or the like).

環氧系交聯劑列舉為乙二醇二縮水甘油醚、三羥甲基丙烷三縮水甘油醚、N,N,N’,N’-四縮水甘油基乙二胺、丙三醇二縮水甘油醚、丙三醇三縮水甘油醚、聚丙三醇聚縮水甘油醚、山梨糖醇系聚縮水甘油醚等。 The epoxy crosslinking agent is exemplified by ethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, N, N, N', N'-tetraglycidyl ethylene diamine, glycerol diglycidyl Ether, glycerol triglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, and the like.

氮丙啶系交聯劑列舉為N,N’-甲苯-2,4-雙(1-氮丙啶羰基化物)、N,N’-二苯基甲烷-4,4’-雙(1-氮丙啶羰基化物)、三伸乙基三聚氰胺、雙isoprotaloyl-1-(2- 甲基氮丙啶)(bisisoprotaloyl-1-(2-methylaziridine))、三-1-氮丙啶基氧化膦等。 The aziridine crosslinking agent is exemplified by N,N'-toluene-2,4-bis(1-aziridine carbonyl), N,N'-diphenylmethane-4,4'-bis(1- Aziridine carbonyl), tri-ethyl melamine, double isoprotaloyl-1-(2- Bisisoprotaloyl-1-(2-methylaziridine), tri-1-aziridine phosphine oxide, and the like.

金屬螯合系交聯劑列舉為使鋁、鐵、鋅、錫、鈦、銻、鎂、釩等多價金屬配位於乙醯基丙酮或乙醯基乙酸乙酯而成之化合物等。 The metal chelate crosslinking agent is exemplified by a compound obtained by disposing a polyvalent metal such as aluminum, iron, zinc, tin, titanium, ruthenium, magnesium or vanadium in ethyl acetonylacetate or ethyl acetoxyacetate.

此外，本發明之黏著劑組成物中可進一步添加黏著性賦予樹脂以調節黏著性能。其含量相對於(A)(甲基)丙烯酸系共聚物100質量份可在1~100質量份，尤其可在5~90質量份之範圍內使用。此時，若未達1質量份則有調節效果不足之情況，若超過100質量份則有黏著劑之常用性或凝聚性降低之虞。 Further, an adhesive imparting resin may be further added to the adhesive composition of the present invention to adjust the adhesive property. The content thereof may be from 1 to 100 parts by mass, particularly preferably from 5 to 90 parts by mass, per 100 parts by mass of the (A) (meth)acrylic copolymer. In this case, if the amount is less than 1 part by mass, the effect of the adjustment may be insufficient, and if it exceeds 100 parts by mass, the usualness or cohesiveness of the adhesive may be lowered.

黏著性賦予樹脂之例可使用(氫化)烴系樹脂、(氫化)松脂系樹脂、(氫化)松脂酯樹脂、(氫化)萜烯樹脂、(氫化)萜烯酚樹脂、聚合松脂樹脂、聚合松脂酯樹脂等，該等可單獨使用1種或混合2種以上使用。 Examples of the tackifying resin can be used (hydrogenated) hydrocarbon resin, (hydrogenated) rosin resin, (hydrogenated) rosin ester resin, (hydrogenated) terpene resin, (hydrogenated) terpene phenol resin, polymerized rosin resin, polymerized rosin. For the ester resin or the like, these may be used alone or in combination of two or more.

除上述成分外，在不損及本發明目的之範圍內，亦可視需要混合使用可塑劑、調平劑等低分子量體、環氧樹脂及硬化劑等作為追加成分，且可依據一般目的適度添加紫外線安定劑、抗氧化劑、除色劑、補強劑、填充劑、消泡劑、界面活性劑等而使用。 In addition to the above-mentioned components, a low molecular weight body such as a plasticizer or a leveling agent, an epoxy resin, a hardener, or the like may be used as an additional component as needed in addition to the object of the present invention, and may be appropriately added according to general purposes. It is used as an ultraviolet stabilizer, an antioxidant, a color remover, a reinforcing agent, a filler, an antifoaming agent, a surfactant, and the like.

本發明之黏著劑組成物之製造方法並無特別限制，可以通常方法混合前述(A)~(C)成分及其他任意成分而得。混合條件較好為在10~150℃下10分鐘~10 小時。該情況下，上述含多官能環氧基之有機矽化合物可在(甲基)丙烯酸系共聚物聚合後，於調配步驟中添加使用，即使在(甲基)丙烯酸系共聚物之製造步驟中添加亦顯示相同效果。又，多官能***聯劑在為了使黏著劑組成物硬化而得之黏著劑層之形成中實施之調配過程中，可在幾乎不產生交聯劑之官能基交聯反應之情況下均勻塗佈。塗佈後經過乾燥及熟成過程時將形成交聯構造，可獲得有彈性、凝聚力強之黏著劑層。 The method for producing the adhesive composition of the present invention is not particularly limited, and the components (A) to (C) and other optional components may be mixed by a usual method. The mixing condition is preferably 10 minutes to 10 minutes at 10 to 150 °C. hour. In this case, the polyfunctional epoxy group-containing organogermanium compound can be added to the compounding step after polymerization of the (meth)acrylic copolymer, even if it is added in the production step of the (meth)acrylic copolymer. It also shows the same effect. Further, in the compounding process in which the polyfunctional crosslinking agent is carried out in the formation of the adhesive layer obtained by hardening the adhesive composition, it is possible to uniformly coat the functional group crosslinking reaction which hardly produces a crosslinking agent. . After the drying and ripening process after coating, a crosslinked structure is formed, and an adhesive layer having elasticity and cohesive force can be obtained.

如此所得之本發明之黏著劑組成物可塗佈於玻璃板、塑膠膜、紙等被接著體上，在25~150℃、20~90% RH下硬化5分鐘~5小時，尤其在40~80℃、20~60% RH下硬化10分鐘~3小時而形成黏著劑層。 The adhesive composition of the present invention thus obtained can be applied to a substrate such as a glass plate, a plastic film or a paper, and hardened at 25 to 150 ° C and 20 to 90% RH for 5 minutes to 5 hours, especially at 40 °. The adhesive layer is formed by hardening at 80 ° C and 20 to 60% RH for 10 minutes to 3 hours.

本發明之黏著劑組成物較好充分去除內部之揮發成分、反應殘留物等之誘發氣泡之成分後使用。交聯密度或分子量過低，黏著劑層之彈性率過低時，在高溫狀態下存在於玻璃板等被接著體與黏著劑層之間之小的氣泡會變大，而於黏著劑層之內部形成散射體。此外，長期使用彈性率過大之黏著劑層時，因過度交聯反應而在黏著劑層(薄片)之末端部位產生剝離現象。 The adhesive composition of the present invention is preferably used after sufficiently removing the components of the induced bubbles such as the internal volatile components and reaction residues. When the crosslinking density or the molecular weight is too low, and the elastic modulus of the adhesive layer is too low, the small bubbles existing between the adherend and the adhesive layer such as a glass plate at a high temperature may become large, and the adhesive layer may be A scatterer is formed inside. Further, when the adhesive layer having an excessively high modulus of elasticity is used for a long period of time, peeling occurs at the end portion of the adhesive layer (sheet) due to excessive crosslinking reaction.

且，考慮最適之物理均衡時，黏著劑層之交聯密度以5~95質量%，尤其以7~93質量%之範圍較適當。交聯密度係指以一般已知之黏著劑之凝膠含量測定法，形成未溶解於溶劑中之交聯構造之部分之量以質量%獲得之值。此時，黏著劑層之交聯密度未達5質量%時會 有黏著劑層之凝聚力變低，而發生如氣泡或剝離之黏著耐久性問題之虞，超過95質量%時會有不黏附之耐久性變弱之情況。 Further, in consideration of the optimum physical balance, the crosslinking density of the adhesive layer is suitably in the range of 5 to 95% by mass, particularly 7 to 93% by mass. The crosslink density refers to a value obtained by mass fraction of a crosslinked structure which is not dissolved in a solvent by a gel content measurement method of a generally known adhesive. At this time, when the crosslinking density of the adhesive layer is less than 5% by mass, When the adhesive strength of the adhesive layer is lowered, and the adhesion durability problem such as air bubbles or peeling occurs, when the content exceeds 95% by mass, the durability of non-adhesion becomes weak.

[黏著偏光板] [Adhesive Polarizer]

接著，針對將前述黏著劑組成物塗佈‧硬化於偏光薄膜等之單面或兩面上之含黏著劑層之黏著偏光板加以說明。 Next, an adhesive polarizing plate containing an adhesive layer which is applied to the adhesive composition and cured on one surface or both surfaces of a polarizing film or the like will be described.

本發明之黏著偏光板為具有偏光薄膜或偏光元件、與在該偏光薄膜或偏光元件之單面或兩面上由上述黏著劑組成物形成之黏著劑層者。關於構成偏光板之偏光薄膜或偏光元件並無特別限制。若列舉偏光薄膜之例，則有由聚乙烯醇系樹脂所成之薄膜中含有碘或異色性染料等之偏光成分之經延伸獲得之薄膜等，該等偏光薄膜之厚度亦無限制，可成形成一般之厚度。 The adhesive polarizing plate of the present invention is a polarizing film or a polarizing element, and an adhesive layer formed of the above-described adhesive composition on one or both sides of the polarizing film or the polarizing element. The polarizing film or the polarizing element constituting the polarizing plate is not particularly limited. In the case of a polarizing film, a film obtained from a polyvinyl alcohol-based resin contains a film obtained by stretching a polarizing component such as iodine or a heterochromatic dye, and the thickness of the polarizing film is not limited. Form a general thickness.

聚乙烯醇系樹脂係使用聚乙烯醇、聚乙烯甲縮醛、聚乙烯乙縮醛及乙烯‧乙酸乙烯酯共聚物之鹼化物等。 As the polyvinyl alcohol-based resin, polyvinyl alcohol, polyvinyl formal, polyethylene acetal, and an alkali compound of ethylene/vinyl acetate copolymer are used.

本發明中，於偏光薄膜上形成黏著劑層之方法並無特別限制，可採用直接使用棒塗佈器等將黏著劑組成物塗佈於該偏光薄膜之表面上並乾燥之方法；將黏著劑組成物暫時塗佈於剝離性基材表面上並乾燥後，將該剝離性基材表面上形成之黏著劑層轉印於偏光薄膜表面上，接著經熟成之方法等。此時，乾燥較好在25~150℃、20~ 90% RH下進行5分鐘~5小時，熟成較好在25~150℃、20~90% RH下進行5分鐘~5小時。 In the present invention, the method of forming the adhesive layer on the polarizing film is not particularly limited, and a method of applying an adhesive composition directly onto the surface of the polarizing film by using a bar coater or the like and drying the film may be employed; After the composition is temporarily applied onto the surface of the release substrate and dried, the adhesive layer formed on the surface of the release substrate is transferred onto the surface of the polarizing film, followed by a method of aging. At this time, the drying is preferably at 25~150°C, 20~ It is carried out for 5 minutes to 5 hours at 90% RH, and it is preferably carried out at 25 to 150 ° C and 20 to 90% RH for 5 minutes to 5 hours.

此外，黏著劑層厚度雖無特別限制，但通常較好為0.01~100μm，更好為0.1~50μm。黏著劑層之厚度小於上述範圍時會有作為黏著劑層之效果不足之情況，大於上述範圍大會有黏著劑層之效果飽和，且成本變大之情況。 Further, although the thickness of the adhesive layer is not particularly limited, it is usually preferably from 0.01 to 100 μm, more preferably from 0.1 to 50 μm. When the thickness of the adhesive layer is less than the above range, the effect as an adhesive layer may be insufficient, and the effect that the adhesive layer is saturated and the cost is increased is larger than the above range.

又，如此獲得之具有本發明之黏著劑層之偏光薄膜(黏著偏光板)上可積層一種以上之保護層、反射層、相位差板、光視角補償薄膜、亮度提高薄膜等之提供追加功能之層。 Further, the polarizing film (adhesive polarizing plate) having the adhesive layer of the present invention thus obtained may have an additional function of laminating one or more protective layers, a reflective layer, a phase difference plate, a viewing angle compensation film, and a brightness enhancement film. Floor.

尤其，可於具有黏著劑層之偏光薄膜之兩面積層三乙醯基纖維素等纖維素系薄膜、聚碳酸酯薄膜、聚對苯二甲酸乙二酯薄膜等聚酯系薄膜、聚醚碸系薄膜、如聚乙烯、聚丙烯、該等之共聚物之聚烯烴系薄膜等之保護薄膜而形成多層薄膜。此時，該等保護薄膜之厚度亦無特別限制，可形成通常之厚度。 In particular, it can be used in a cellulose film such as triacetyl cellulose, which is a two-layer layer of a polarizing film having an adhesive layer, a polyester film such as a polycarbonate film or a polyethylene terephthalate film, or a polyether oxime system. A protective film such as a film, a polyolefin film such as polyethylene, polypropylene, or a copolymer of the above is formed into a multilayer film. At this time, the thickness of the protective film is not particularly limited, and a normal thickness can be formed.

[液晶顯示裝置] [Liquid Crystal Display Device]

本發明之黏著偏光板可全盤應用於一般之液晶顯示裝置，其液晶面板之種類並無特別限制。尤其，較好構成為包含將本發明之黏著偏光板貼合於將液晶封入於一對玻璃基板間而成之液晶胞之單面或兩面上而成之液晶面板之液晶顯示裝置。 The adhesive polarizing plate of the present invention can be applied to a general liquid crystal display device as a whole, and the type of the liquid crystal panel is not particularly limited. In particular, a liquid crystal display device including a liquid crystal panel in which the adhesive polarizing plate of the present invention is bonded to one or both sides of a liquid crystal cell in which a liquid crystal is sealed between a pair of glass substrates is preferably used.

本發明之黏著劑組成物除上述偏光薄膜以外，可不限於產業用薄片，尤其是反射薄片、構造用黏著薄片、照片用黏著薄片、車縫線顯示用黏著薄片、光學用黏著製品、電子零件用等用途而使用。此外，亦可使用於多層構造之層合製品，亦即一般商業用黏著薄片製品、醫療用貼片、加熱活性用等作用概念相同之應用領域。 The adhesive composition of the present invention is not limited to the industrial sheet except for the above-mentioned polarizing film, and particularly, a reflective sheet, an adhesive sheet for construction, an adhesive sheet for photographs, an adhesive sheet for sewing thread display, an optical adhesive product, and an electronic component. Used for other purposes. In addition, it can also be used in a laminate product of a multilayer structure, that is, a general commercial adhesive sheet product, a medical patch, and a heating activity, and the like.

本發明之黏著劑組成物為含有具有配位性官能基之矽烷偶合劑之(甲基)丙烯酸系黏著劑，由於貼合於玻璃等時初期接著力低，故重工性優異，貼合後之濕熱處理後之接著力成為充分高者，長期耐久性優異。 The adhesive composition of the present invention is a (meth)acrylic adhesive containing a decane coupling agent having a coordinating functional group, and has excellent initial workability when bonded to glass or the like, so that it is excellent in reworkability, and after lamination The adhesion force after the wet heat treatment is sufficiently high, and the long-term durability is excellent.

[實施例] [Examples]

以下，例示合成例、實施例及比較例更詳細說明本發明，但本發明並不受限於該等實施例。 Hereinafter, the present invention will be described in more detail by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the Examples.

[(A)丙烯酸系聚合物合成例] [(A) Acrylic Polymer Synthesis Example]

將丙烯酸正丁酯(BA)98.1g、丙烯酸(AA)0.6g、甲基丙烯酸2-羥基乙酯(2-HEMA)1.3g置於具備攪拌機、回流冷卻器、滴加漏斗及溫度計之1L可分離燒瓶中，饋入乙酸乙酯100g作為溶劑予以溶解。隨後，進行通入氮氣泡1小時以去除氧，反應系統中經氮氣置換且保持在62℃。於其中，邊攪拌邊投入0.03g之偶氮雙異丁腈作為聚合起始劑，在62℃反應8小時，獲得基底聚合物之(甲基)丙烯酸系共聚物。 98.1 g of n-butyl acrylate (BA), 0.6 g of acrylic acid (AA), and 1.3 g of 2-hydroxyethyl methacrylate (2-HEMA) were placed in a 1 L mixer equipped with a reflux condenser, a dropping funnel, and a thermometer. In the separation flask, 100 g of ethyl acetate was fed as a solvent to dissolve. Subsequently, nitrogen gas bubbles were introduced for 1 hour to remove oxygen, and the reaction system was replaced with nitrogen and kept at 62 °C. Thereto, 0.03 g of azobisisobutyronitrile was added as a polymerization initiator while stirring, and the mixture was reacted at 62 ° C for 8 hours to obtain a (meth)acrylic copolymer of a base polymer.

[實施例、比較例] [Examples, Comparative Examples]

相對於合成例中獲得之(A)丙烯酸系聚合物：(甲基)丙烯酸系共聚物100質量份，以表1所示之調配組成分別混合(B)接著性改質劑：下述A-1~4、B-1~3所示之矽烷偶合劑、作為(C)多官能***聯劑之三羥甲基丙烷甲苯二異氰酸酯加成物(TDI)，作成黏著劑組成物。 With respect to 100 parts by mass of the (A) acrylic polymer: (meth)acrylic copolymer obtained in the synthesis example, the blending compositions shown in Table 1 were separately mixed. (B) Adhesive modifier: The following A- A decane coupling agent represented by 1 to 4 and B-1 to 3, and a trimethylolpropane toluene diisocyanate adduct (TDI) as a (C) polyfunctional crosslinking agent are used as an adhesive composition.

將所得黏著劑組成物塗佈於脫模紙上並乾燥後，獲得25μm之均勻黏著劑層。將如此製造之黏著劑層黏著加工於厚度185μm之碘系偏光板上後，將所得偏光板切斷成適度大小，使用於各評價中。 The obtained adhesive composition was coated on a release paper and dried to obtain a uniform adhesive layer of 25 μm. After the adhesive layer thus produced was adhered to an iodine-based polarizing plate having a thickness of 185 μm, the obtained polarizing plate was cut into an appropriate size and used for evaluation.

針對製造之偏光板之試驗片，透過以下所示之評價試驗方法，針對耐久性、玻璃接著性、重工性、耐熱或耐濕熱條件下之接著力變化進行評價，其結果示於表2~4。 The test piece of the manufactured polarizing plate was evaluated for the change in adhesion under durability, glass adhesion, reworkability, heat resistance, or heat and humidity resistance by the evaluation test method shown below. The results are shown in Tables 2 to 4. .

又，表1中，縮寫如下。 Also, in Table 1, the abbreviations are as follows.

TDI：交聯劑，三羥甲基丙烷之甲苯二異氰酸酯加成物 TDI: crosslinker, toluene diisocyanate adduct of trimethylolpropane

矽烷A-1：縮水甘油氧基辛基三甲氧基矽烷 矽A-1: glycidyloxyoctyltrimethoxydecane

矽烷A-2：縮水甘油氧基辛基甲基二甲氧基矽烷 Decane A-2: glycidoxyoctylmethyldimethoxydecane

矽烷A-3：縮水甘油氧基辛基三乙氧基矽烷 Decane A-3: glycidoxyoctyltriethoxydecane

矽烷A-4：縮水甘油氧基己基三甲氧基矽烷 Decane A-4: glycidoxyhexyltrimethoxydecane

矽烷B-1：縮水甘油氧基丙基三甲氧基矽烷 Decane B-1: glycidoxypropyltrimethoxydecane

(信越化學工業(股)製之KBM-403) (KBM-403, Shin-Etsu Chemical Industry Co., Ltd.)

矽烷B-2： 矽B-2:

矽烷B-3：兩末端烷氧基矽烷基改質之PO型聚醚化合物 Decane B-3: a PO-type polyether compound modified with a terminal alkoxyalkyl group

(KANEKA(股)製造之SYRIL SAT10) (SYRIL SAT10 manufactured by KANEKA)

評價試驗 Evaluation test <耐久性> <Durability>

將塗佈有黏著劑之偏光板(90mm×170mm)以使光學吸收軸交叉之狀態貼合於玻璃基板(110mm×190mm×0.7mm)之兩面上，獲得試驗片。此時，施加之壓力約為5kgf/cm³，以不產生氣泡或異物之方式在無塵室中進行作業。 A polarizing plate (90 mm × 170 mm) coated with an adhesive was attached to both surfaces of a glass substrate (110 mm × 190 mm × 0.7 mm) in such a manner that the optical absorption axes were crossed to obtain a test piece. At this time, the applied pressure was about 5 kgf/cm ³ , and the operation was performed in the clean room so as not to generate bubbles or foreign matter.

為評價該試驗片之耐濕耐熱特性，在60℃/90%相對濕度之條件下放置1,000小時後，確認有無產生氣泡或剝離。耐熱特性係在80℃/30%相對溼度下放置1,000小時後，觀察氣泡或剝離之樣態。又，評價試驗片狀態前，在室溫(25℃)靜置24小時。結果示於表2。 In order to evaluate the moisture- and heat-resistance characteristics of the test piece, it was allowed to stand for 1,000 hours under conditions of 60 ° C / 90% relative humidity, and it was confirmed whether or not bubbles were generated or peeled off. The heat resistance was observed after being left at 80 ° C / 30% relative humidity for 1,000 hours, and the state of bubbles or peeling was observed. Further, it was allowed to stand at room temperature (25 ° C) for 24 hours before the state of the test piece was evaluated. The results are shown in Table 2.

耐久性評價之評價基準如下。 The evaluation criteria of the durability evaluation are as follows.

○：無氣泡或剝離現象 ○: no bubble or peeling phenomenon

△：稍有氣泡或剝離現象 △: slight bubble or peeling phenomenon

×：有多數氣泡或剝離現象 ×: There are many bubbles or peeling phenomenon

<玻璃接著力、高溫及高溫多濕條件下之接著力變化> <Change in adhesion of glass under force, high temperature and high temperature and humidity>

使塗佈有黏著劑之偏光板在常溫(23℃/60% RH)熟成7天後，將該偏光板分別切斷成1英吋×6英吋之尺寸，使用2kg之橡膠輥貼合於0.7mm厚之無鹼玻璃上。在常溫保管後，於1小時後測定初期接著力，接著在50℃老化4小時，隨後在常溫保管1小時後，測定接著力。結果示於表2。 After the polarizing plate coated with the adhesive was aged at normal temperature (23 ° C / 60% RH) for 7 days, the polarizing plate was cut into a size of 1 inch × 6 inches, and bonded with a 2 kg rubber roller. 0.7mm thick alkali-free glass. After storage at room temperature, the initial adhesion was measured after 1 hour, followed by aging at 50 ° C for 4 hours, and then stored at room temperature for 1 hour, and then the adhesion was measured. The results are shown in Table 2.

又，為觀察高溫及高溫多濕條件下之接著力上升之程度，分別在60℃/30% RH與60℃/90% RH之條件下根據時間熟成後，在常溫放冷1小時，測定接著力。結果示於表3、4。 Further, in order to observe the degree of increase in the adhesion force under high temperature and high temperature and high humidity conditions, the mixture was aged at 60 ° C / 30% RH and 60 ° C / 90% RH, respectively, and then allowed to stand at room temperature for 1 hour, and then measured. force. The results are shown in Tables 3 and 4.

此時，接著力之測定係使用拉伸試驗機，以300mm/分鐘之速度、180°之角度測定剝離強度。 At this time, the force was measured by using a tensile tester, and the peel strength was measured at a speed of 300 mm/min and an angle of 180°.

<重工性> <Reworkability>

將塗佈有黏著劑之偏光板(90mm×170mm)貼合於玻璃基板(110mm×190mm×0.7mm)上後，在常溫經過1小時(初期接著力)及在50℃×4小時熟成，且在常溫放冷1小時後，自玻璃剝離偏光板。結果示於表2。 After bonding a polarizing plate (90 mm × 170 mm) coated with an adhesive to a glass substrate (110 mm × 190 mm × 0.7 mm), it was aged at room temperature for 1 hour (initial adhesion) and at 50 ° C for 4 hours, and After cooling at room temperature for 1 hour, the polarizing plate was peeled off from the glass. The results are shown in Table 2.

對重工性之評價基準如下。 The evaluation criteria for heavy workability are as follows.

○：可容易再剝離 ○: It can be easily peeled off again

△：再剝離稍有困難 △: It is difficult to peel again.

×：無法剝離，玻璃破損 ×: Cannot be peeled off, broken glass

關於應用實施例及比較例之黏著劑之偏光板，針對通過前述之評價方法獲得之耐久性、玻璃接著力、重工性、高溫下及高溫多濕下之接著力變化之評價結果示於下述表2~4。 With respect to the polarizing plates to which the adhesives of the examples and the comparative examples are applied, the evaluation results of the durability, the glass adhesion, the workability, the change in the adhesion force under high temperature and high temperature and high humidity obtained by the above-described evaluation method are shown below. Table 2~4.

比較例1係未調配接著性改質劑，熱硬化後未展現充分之接著性。比較例2係使用既有技術之環氧矽烷偶合劑之情況，該化合物之環氧-矽烷基連結鏈為伸丙基，由於分子整體之疏水性低故初期接著力過高而無法展現重工性。比較例3、4雖為有助於重工性與硬化後之密 著之既有矽烷材料，但硬化後之最終密著強度不充分，缺乏信賴性。比較例5由於使用之接著性改質劑成分過少故效果不充分。另一方面，比較例6由於使用量過多故初期即展現不必要之密著性，使重工性變得不充分。 Comparative Example 1 was not formulated with an adhesion modifier, and did not exhibit sufficient adhesion after thermal curing. In Comparative Example 2, in the case of using an epoxy decane coupling agent of the prior art, the epoxy-nonylalkyl chain of the compound is a propyl group, and since the overall hydrophobicity of the molecule is low, the initial adhesion force is too high to exhibit reworkability. . Comparative Examples 3 and 4 are useful for rework and hardening. There are both decane materials, but the final adhesion strength after hardening is insufficient and lacks reliability. In Comparative Example 5, since the amount of the adhesive modifier used was too small, the effect was insufficient. On the other hand, in Comparative Example 6, since the amount of use was too large, unnecessary adhesion was exhibited early, and the reworkability was insufficient.

由上述，證明本發明之組成物為初期重工性優異，經高溫及高溫多濕處理能展現與玻璃充分之接著力，且長期耐久性優異之黏著劑組成物者。 From the above, it has been confirmed that the composition of the present invention is excellent in initial workability, and exhibits an adhesive composition which exhibits sufficient adhesion to glass and high durability over a long period of time by high-temperature and high-temperature and high-humidity treatment.

Claims (9)

一種黏著劑組成物，其特徵係含有下列成分：(A)丙烯酸系聚合物，與(B)由以通式(1)表示之含有環氧基之有機矽化合物及/或其部分水解物或部分水解縮合物所成之接著性改質劑， (式中，X為氫原子或碳數1~4之烷基，R為碳數1~6之一價烴基，A為碳數6~10之二價烴基，Y為環氧構造基，n為1~3之整數)，且相對於(A)成分100質量份，(B)成分為0.001~10質量份之比例。 An adhesive composition characterized by the following components: (A) an acrylic polymer, and (B) an organic hydrazine compound containing an epoxy group represented by the general formula (1) and/or a partial hydrolyzate thereof or a partial modification agent formed by partially hydrolyzing a condensate, (wherein X is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R is a hydrocarbon group having 1 to 6 carbon atoms, A is a divalent hydrocarbon group having 6 to 10 carbon atoms, and Y is an epoxy structural group, n The component (B) is a ratio of 0.001 to 10 parts by mass based on 100 parts by mass of the component (A). 如請求項1之黏著劑組成物，其中上述式(1)中之Y之環氧構造基為縮水甘油氧基或環氧環己烷(cyclohexene oxide)構造基。 The adhesive composition of claim 1, wherein the epoxy structural group of Y in the above formula (1) is a glycidoxy group or a cyclohexene oxide structural group. 如請求項1或2之黏著劑組成物，其中(B)成分之含有環氧基之有機矽化合物係以下述通式(2)表示者： (式中，X、R、n係如請求項1之定義)。 The adhesive composition according to claim 1 or 2, wherein the epoxy group-containing organic oxime compound of the component (B) is represented by the following formula (2): (where X, R, and n are as defined in claim 1). 如請求項1~3中任一項之黏著劑組成物，其包含下列成分： (A)使(a)具有碳數1~12之烷基之(甲基)丙烯酸酯單體90~99.9質量份、與(b)包含可交聯之官能基之乙烯系單體及/或(甲基)丙烯酸系單體0.1~10質量份共聚合而得之丙烯酸系聚合物：100質量份、(B)如請求項1~3中任一項之接著性改質劑：0.001~10質量份、(C)多官能***聯劑：0.01~10質量份。 The adhesive composition according to any one of claims 1 to 3, which comprises the following components: (A) 90 to 99.9 parts by mass of (a) a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms, and (b) a vinyl monomer containing a crosslinkable functional group and/or Acrylic polymer obtained by copolymerization of 0.1 to 10 parts by mass of a (meth)acrylic monomer: 100 parts by mass, (B) an adhesive modifier according to any one of claims 1 to 3: 0.001 to 10 Parts by mass, (C) polyfunctional crosslinking agent: 0.01 to 10 parts by mass. 如請求項4之黏著劑組成物，其中上述(b)成分之包含可交聯之官能基之乙烯系單體或(甲基)丙烯酸系單體係由下列所組成之群選出之至少一種以上之單體：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、二乙二醇單(甲基)丙烯酸酯、二丙二醇單(甲基)丙烯酸酯、(甲基)丙烯醯氧基丙基三甲氧基矽烷、(甲基)丙烯醯氧基丙基三乙氧基矽烷、(甲基)丙烯醯氧基丙基甲基二甲氧基矽烷、(甲基)丙烯醯氧基丙基甲基二乙氧基矽烷、(甲基)丙烯醯氧基甲基三甲氧基矽烷、(甲基)丙烯醯氧基甲基三乙氧基矽烷、(甲基)丙烯醯氧基甲基甲基二甲氧基矽烷、(甲基)丙烯醯氧基甲基甲基二乙氧基矽烷、(甲基)丙烯酸、(甲基)丙烯酸二聚物、衣康酸、馬來酸及馬來酸酐。 The adhesive composition according to claim 4, wherein the vinyl-based monomer or the (meth)acrylic mono-system containing the crosslinkable functional group of the component (b) is at least one selected from the group consisting of the following: Monomer: 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, diethylene glycol mono(meth)acrylate, Propylene glycol mono (meth) acrylate, (meth) propylene methoxy propyl trimethoxy decane, (meth) propylene methoxy propyl triethoxy decane, (meth) propylene methoxy propyl Methyldimethoxydecane, (meth) propylene methoxy propyl methyl diethoxy decane, (meth) propylene methoxymethyl trimethoxy decane, (meth) propylene methoxy group Triethoxy decane, (meth) propylene methoxymethyl methyl dimethoxy decane, (meth) propylene methoxymethyl methyl diethoxy decane, (meth) acrylic acid, ( Methyl)acrylic acid dimer, itaconic acid, maleic acid and maleic anhydride. 如請求項4或5之黏著劑組成物，其中(C)成分之多官能***聯劑係由異氰酸酯系化合物、環氧系化合物、氮丙啶系化合物及金屬螯合系化合物所組成之群選出 之一種以上之交聯劑。 The adhesive composition of claim 4 or 5, wherein the polyfunctional crosslinking agent of the component (C) is selected from the group consisting of an isocyanate compound, an epoxy compound, an aziridine compound, and a metal chelate compound. More than one crosslinking agent. 一種黏著偏光板，其特徵係具有偏光薄膜、與在該偏光薄膜之單面或兩面上由如請求項1~6中任一項之黏著劑組成物形成之黏著劑層。 An adhesive polarizing plate characterized by comprising a polarizing film and an adhesive layer formed of the adhesive composition according to any one of claims 1 to 6 on one or both sides of the polarizing film. 如請求項7之黏著偏光板，其進而具有由保護層、反射層、相位差板、光視角補償薄膜及亮度提高薄膜所組成之群選出之一種以上之層。 The adhesive polarizing plate of claim 7, which further comprises one or more layers selected from the group consisting of a protective layer, a reflective layer, a phase difference plate, a light viewing angle compensation film, and a brightness enhancement film. 一種液晶顯示裝置，其特徵係包含液晶面板，該液晶面板具有在一對玻璃基板間封入液晶而成之液晶胞、與貼合於該液晶胞之單面或兩面上之如請求項7或8之黏著偏光板。 A liquid crystal display device, comprising: a liquid crystal panel having a liquid crystal cell sealed with liquid crystal between a pair of glass substrates and attached to one or both sides of the liquid crystal cell as claimed in claim 7 or 8 Adhesive polarizing plate.