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TW201207069A - Acrylic-based resin solution, acrylic-based adhesive composition, acrylic-based adhesive, adhesive sheet, acrylic-based adhesive for optical element, and optical element with adhesive layer - Google Patents

Acrylic-based resin solution, acrylic-based adhesive composition, acrylic-based adhesive, adhesive sheet, acrylic-based adhesive for optical element, and optical element with adhesive layer Download PDF

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Publication number
TW201207069A
TW201207069A TW100114594A TW100114594A TW201207069A TW 201207069 A TW201207069 A TW 201207069A TW 100114594 A TW100114594 A TW 100114594A TW 100114594 A TW100114594 A TW 100114594A TW 201207069 A TW201207069 A TW 201207069A
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Taiwan
Prior art keywords
acrylic
adhesive
acrylic resin
resin solution
adhesive layer
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TW100114594A
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Chinese (zh)
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TWI502043B (en
Inventor
Akira Yamabayashi
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Nippon Synthetic Chem Ind
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A cross-linking agent-curable solvent acrylic-based adhesive, which enables thick coating and from which a thick adhesive layer can be obtained, is provided. The present invention relates to an acrylic-based resin solution; which comprises an acrylic-based resin (A) having the weight-average molecular weight of 50, 000 to 300, 000, and an organic solvent (B) in which the chain transfer constant of the vinyl acctate to the organic solvent at 60 DEG C is 250 or more; and which has the solid content concentration of 60% or more.

Description

201207069 六、發明說明： 【發明所屬之技術領域】 本發明係關於丙稀酸系樹脂溶液、丙稀酸系黏著劑組成 物、丙烯酸系黏著劑、黏著片、光學構件用丙稀酸系黏著劑 及附有黏著綱之光學構件；更詳言之，侧於用於製造適 ^厚塗塗佈之非活性能量射線硬化型之溶劑系丙婦酸系黏 著劑的丙烯酸系樹脂溶液。 【先前技術】 習知以來，丙婦酸系黏著劑中係存在有以使被黏體牢固地 長期間貼合為目的之_著性黏著劑，或以於貼附後由被黏 體進行剝離為前提關離型黏著辦各種類型的黏著劑，並 設計、使用有黏著物性分別最適合於各種領域的黏著劑。 “近年來，作為黏著劑所要求之性能，不僅止於黏著力等黏 著物性，在用於液晶顯示裝置等玻璃基板之貼合時，係對黏 著劑層本身要求透明性、耐衝擊吸收性，而於此種用途中， 係為了提升耐衝擊吸收性，而提案有增加黏著劑層之厚度。 另外，作為使用丙烯酸系樹脂而增厚黏著劑層（厚膜塗佈） 的手法’已知有藉由照射紫外線等之活性能量射線，使黏著 劑硬化’得到厚膜之黏著綱的方法。（例如參照專利文獻 1 及 2)。 上述活性能量射線硬化型之黏著劑，一般並不含有通常之 丙烯酸系黏著劑中用於調整黏度的溶劑，屬於取代溶劑而使 100114594 4 201207069 用光聚合性之不飽合單體作為稀釋單體的無产^ 公月·!糸黏者 劑，故在黏著劑塗佈後不需要用於去除溶劑的# * t·禪步鄉，在 經厚塗塗佈時可在短時間内有效地得到黏著劑層。 專利文獻1 :日本專利特開2007-94191號公報 ' 專利文獻2 :日本專利特開2007-314618號公報 【發明内容】 (發明所欲解決之問題） 然而’一般在對曲面或凹凸面等貼附黏著帶時，為了要托 對被黏體的服貼性，而在黏著帶方面係使用薄且柔軟者作為 黏著劑層所形成之支撐體薄膜。若對此種薄且柔軟的支俨體 薄膜使用上述活性能量射線硬化型之黏著劑並照射活性能 量射線，則有因熱等影響而使支撐體薄膜受到損傷的可^ 性。 從而，在需要對此種曲面或凹凸面等進行貼附的用途中， 即使卻彳寸到厚膜的黏著劑層，仍無法使用活性能量射線硬化 型之黏著劑，而必須使用藉由交聯劑所進行之交聯以形成黏 著劑層之溶劑型丙烯酸系黏著劑，以得到厚膜的黏著劑層。 因此，本發明在此種背景下，以提供可進行厚塗塗佈，可 得到厚膜之黏著劑層’進而可用於製造黏著物性及透明性優 越之交聯劑硬化型之溶劑型丙烯酸系黏著劑的丙烯酸系樹 月曰溶液、使用其之丙烯酸系黏著劑組成物、丙烯酸系黏著 劑、黏著片、光學構件用黏著劑、以及附有黏著劑層之光學 100114594 201207069 構件為目的。 (解決問題之手段） 因此，本案發明者有鑑於上述情況而潛心研究，結果發 現’藉由使用含有相較於一般黏著劑用途所使用之丙烯酸系 樹脂呈較低分子量、黏度較低之丙烯酸系樹脂與顯示特定之 鏈轉移常數的有機溶劑，且為高固形份濃度的丙烯酸系樹脂 溶液（丙烯酸系黏著劑組成物），即使在進行厚塗塗佈、得到 黏著劑時，於塗佈時亦不發生垂液等，可輕易進行溶劑乾 燥，所得之黏著劑層係黏著力、保持力、透明性優越，遂完 成本發明。 亦即，本發明之要旨係關於一種丙烯酸系樹脂溶液，其特 徵為，含有：重量平均分子量5萬〜3G萬之丙_系樹脂 (A)、與60 C中醋酸乙烯酯對有機溶劑的鏈轉移常數為25〇 以上之有機溶劑（B)，且固形份濃度為6〇%以上。 再者’係關於含有此種丙烯酸系樹脂溶液而成之丙烯酸系 黏著劑組成物、使用該丙烯酸系黏著劑組成物所得之丙烯酸 系黏著劑及黏著片、光學構件用丙烯酸系黏著劑以及附有黏 著劑層之光學構件。 本發明包括以下態樣。 Π ] —種丙稀酸系樹脂溶液，其特徵為，含有：重量平均分 子量5萬〜30萬之丙烯酸系樹脂(A)、與6(rc中醋酸乙烯酯 對有機溶劑的鏈轉移常數為25〇以上之有機溶劑(B)，且固 100114594 6 201207069 形份濃度為60%以上。 [2] 如[1]之丙烯酸系樹脂溶液’其+ ’丙稀酸系樹脂溶液之 黏度為 20,000mPa · s/25°C 以下。 [3] 如[1]或[2]之丙婦酸系樹脂溶液，其中，丙稀酸系樹脂(A) 不含酸性基。 - [4]如[1]〜[3]中任一項之丙烯酸系樹脂溶液，其中，有機溶 劑(B)之50重量％以上為曱基乙基酮。 [5] 如[1]〜[4]中任一項之丙烯酸系樹脂溶液，其中，相對於 丙烯酸系樹月旨溶液中之總固形份，6〇重量％以上為丙稀酸系 樹脂(A)。 [6] —種丙烯酸系黏著劑組成物，係含有〜[5]中任一項之 丙烯酸系樹脂溶液。 [7] 如[6]之丙烯酸系黏著劑組成物其中含有交聯劑(c)。 [8] 一種丙稀酸系黏著劑，其特徵為，使[6]或[7]之丙稀酸系 黏著劑組成物進行交聯而成。 [9] 種黏著片’係含有含[8]之丙烯酸系黏著劑的黏著劑層。 [10] -種黏著片’係具有將[6]或[7]之丙稀酸系黏著劑組成 物依80μιη以上的膜厚塗佈於基板上使其乾燥而得之黏著 劑層者’其特徵為，乾燥後之黏著劑層之膜厚為 50μιη以上。 [11] 種光學構件用丙烯酸系黏著劑，係使用[8]之丙烯酸系 黏著劑而成。 [12] 種附有黏著劑層之光學構件，係含有含[8]之丙烯酸系 100114594 201207069 黏著劑之黏著劑層、及光學構件。 (發明效果） =^之丙_系樹脂溶液因為含有特定之系樹 ==故可具有通常用於製造溶劑之丙稀酸系黏著 劑的丙稀酸㈣脂溶液所難以兼顧的高固形份濃度，在使用 此種丙狀系樹I日喊進行厚塗塗佈，得到丙稀酸系黏著劑 時塗佈時亦不發生垂液或塗佈紋等，可輕易進行溶劑乾 燥’再者’所仵之點著劑層的黏著力、保持力、透明性、财 腐食性等優越。 【實施方式】 以下詳細說明本發明，但此等僅為表示較佳實施態樣之一 例。 尚且，本發明中，所謂（曱基）丙烯酸係指丙烯酸或曱基丙 烯酸，所謂（曱基）内缚醯基係指丙烯醯基或曱基丙烯醯基， 所謂（曱基）丙烯酸酯係指丙烯酸酯或曱基丙烯酸酯。 本發明所使用之内稀酸系樹脂(A)，係以（曱基）丙烯酸烷 基酯系單體(al)作為主成分，視需要以含有官能基之單體(a2) 作為共聚合成分共聚合而成，進而亦可以其他共聚合性單體 (a3)作為共聚合成分。本發明中之丙烯酸系樹脂(A)，由進一 步提升與基材或被黏體間之密黏性的觀點而言’係使用官能 基單體(a2)作為共聚合成分。 於此’所謂以（甲基）丙烯酸烷基酯系單體(al)作為主成分 100114594 8 201207069 的共聚物’係指（甲基）丙烯酸烷基酯系單體(al)為含有最多 的共聚物’相對於總共聚合成分，含有（甲基）丙烯酸烷基酯 系單體(al)50重量％以上、特佳55重量％以上、更佳60重 量％以上。 作為此種（甲基）丙烯酸烷基酯系單體(al)，烷基之碳數通 常為1〜20、特佳1〜12、更佳1〜8，具體可舉例如（甲基）丙烯 酸曱醋、（曱基）丙烯酸乙酯、（曱基）丙烯酸正丁酯、（曱基） 丙烯酸異丁酯、（甲基）丙烯酸第三丁酯、（曱基）丙烯酸正丙 酯、（甲基）丙烯酸正己酯、（甲基）丙烯酸2-乙基己酯、（甲基） 丙烯酸正辛酯、（甲基）丙烯酸異癸酯、（甲基）丙烯酸月桂酯、 (甲基）丙烯酸十六基酯、（曱基）丙烯酸硬脂酯、（曱基）丙烯 酸環己i旨、（曱基）丙烯酸異降稻酯等之脂肪族丙烯酸炫基 醋。此等可使用單獨1種或併用2種以上。 此種（曱基）丙烯酸烷基酯系單體(al)中，由共聚合性、黏 者物性、操作容易度及原料取得容易度的觀對而言，較佳係 使用（曱基）丙烯酸正丁酯、（甲基）丙烯酸2_乙基己酯，由耐 久性優越的觀點而言，更佳係使用（甲基）丙烯酸正丁酯。 共聚合成分中之（曱基）丙烯酸烷基酯系單體(al)的比例， 較佳為50〜99.9重量％、特佳55〜99 8重量％、更佳6〇〜99 7 重置％ ’若（曱基）丙烯酸烧基醋系單體⑻過少、，則例如在 使用作為黏著劑時，有黏著力不足的傾向。 作為含有官能基之單體(a2)，可舉例如含祕單體、含胺 100114594 9 201207069 基單體、含乙醯乙醯基單體、含異氰酸酯基單體、含竣基單 體、含環氧丙基單體等，此等之中，由可效率佳地進行交聯 反應的觀點而言，較佳為使用含羥基單體、含竣基單體。 作為含羧基單體，可舉例如（曱基）丙烯酸2-羥基乙醋、（甲 基）丙烯酸4-羥基丁酯、（曱基）丙烯酸5-羥基戊酯、（甲基) 丙稀酸6-羥基己酯、（曱基）丙烯酸8-羥基辛酯等之丙婦酸羥 基烷基酯；己内酯改質（甲基）丙烯酸2-羥基乙酯等之己内酯 改質單體；二乙二醇（曱基）丙烯酸、聚乙二醇（曱基）丙稀酸 等之氧基伸烷基改質單體；另外，可舉2-丙烯醯氧基乙基 2-羥基乙基酞酸、N-羥甲基（甲基）丙烯醯胺等之含丨級羥基 單體，（甲基）丙婦酸2-經基丙酯、（曱基）丙稀酸2_經基丁酯、 (甲基）丙烯酸2-羥基3-苯氧基丙酯、（甲基）丙烯酸3_氣2_ 羥基丙酯、（甲基）丙烯酸2-羥基3-苯氧基丙酯等之含2級羥 基單體；（甲基）丙烯酸2,2-二曱基2-羥基乙酯等之含3級羥 基單體。 尚且，作為本發明所使用之含羧基單體，較佳係使用雜質 之二（甲基）丙烯酸酯的含有比例為〇.5〇/0以下者，更佳為使用 0.2%、特佳0.1%以上者。具體而言，較佳為丙烯酸2_羥基 乙醋、丙稀酸4-經基丁醋。 作為含羧基單體，可舉例如（曱基）丙烯酸、丙烯酸二聚 物、丁烯酸、順丁烯二酸、順丁烯二酸酐、反丁烯二酸、檸 康酸、戊烯二酸、衣康酸、丙烯醯胺N_乙醇酸、桂皮酸等， 100114594 10 201207069 其中較佳為使用（曱基）丙烯酸。 作為含胺基單體，可舉例如（甲基）丙烯酸第三丁基胺基乙 酯、（曱基）丙烯酸乙基胺基乙酯、（曱基）丙烯酸二曱基胺基 乙酯、（曱基）丙烯酸二乙基胺基乙酯等，其中，較佳為使用 (曱基）丙烯酸二曱基胺基乙酯、（曱基）丙烯酸二乙基胺基乙 酉旨。 作為含乙醯乙醯基單體，可舉例如（甲基）丙烯酸2-(乙醯 乙醯氧基）乙酯、乙醯乙酸烯丙基酯等。 作為含異氰酸酯基單體，可舉例如異氰酸酯2-丙烯醯氧 基乙酯、異氰酸2-甲基丙烯醯氧基乙酯或此等之環氧烷加 成物等。 作為含環氧丙基單體，可舉例如（甲基）丙烯酸環氧丙酯、 (曱基）丙烯酸烯丙基環氧丙酯等。 此等含有官能基之單體(a2)可單獨使用，或併用2種以 上，尤其是含羧基單體與含胺基單體的組合、含羧基單體與 含胺基單體的組合，係由因交聯反應快而片形成性優越的觀 點而言屬較佳。 丙烯酸系樹脂(A)之共聚合成分中含有官能基單體(a2)的 含有比例，較佳為0.1〜30重量％、特佳0.2〜25重量％、更 佳0.3〜20重量％，若含有官能基之單體(a2)過少，則因交聯 時之交聯點變得過少，故有交聯後之凝集力不足的傾向，若 過多，則有黏著力過於下降的傾向。 100114594 11 201207069 其中’在使用含I!基單體作為含有官能基單體㈣時，丙 稀酸系樹脂⑷於共聚合成分中之含有比例，係由耐濕熱性 或透明性優越的觀點而言，較佳為2〇重量％以上、特佳 20〜50重量％。 作為其他之共聚合性單體㈣，可舉例如（甲基）丙稀酸苯 醋、（甲基）丙稀酸以旨、（甲基）丙烯酸苯氧基乙醋、⑽) 丙稀酸乙氧基化鄰苯基苯酿、苯氧基二乙二醇（甲基）丙稀 酸、（甲基)丙稀酸2_經基_3·苯氧基丙醋、苯乙稀、仏甲基苯 乙烯等之含芳香環單體；（甲基)丙烯醯基咪琳、二曱基（甲基) __、二乙基（甲基）㈣醯胺、（曱基）丙稀醯胺等之醯 胺系單體；㈣㈣酸2_曱氧基乙s|、㈣)㈣酸2_乙 氧基乙自旨、（甲基㈣酸3_甲氧基丁@|、（甲基)丙烯酸2_丁 氧基乙S旨、2· 丁氧基二乙二醇（甲基)丙_醋、甲氧基二乙 二醇（甲基）丙稀_、甲氧基三乙二醇（甲基）丙職醋、乙 氧基二乙二醇（甲基)丙烯酸騎、曱氧基二丙二醇（甲基)丙稀 酉“曰f氧基聚乙二醇(曱基)丙烯酸酯、辛氧基$乙二醇_ 聚丙二醇·單（甲基）丙烯酸^旨、月桂氧基聚乙二醇單（曱基） 丙烯m脂氧絲乙二醇單（曱基)丙烯㈣等之含有燒 氧基及氧基伸絲的單體；μ腈、曱基㈣腈、醋酸乙烯 醋、丙酸乙烯醋、硬脂酸乙烯醋、氣化乙烯、偏二氣乙烯、 烧基乙烯基喊、乙稀基甲苯、乙烯基^比咬、乙烯基、 衣康酸二絲⑽、反、糾麵、丙稀酸 100114594 12 201207069 氯1基⑽_、N_丙稀_甲基三甲基氯化録、婦丙基 三甲基氯化銨、二甲基婦兩基乙蝉基酮等。 " 共聚合成分中之其他共聚合性單體㈣的含有比例，較佳 為〇〜40重量％、特佳〇〜30重量％、更佳〇〜25重量％，若共 聚合性單體⑹過多，則有點著特性容易降低的傾向。” 如此，對上述（甲基）丙歸酸燒基酯系單體㈣，以較佳含 有官能基之單體㈣、視需要之共聚合成分㈣作為共聚合 成刀而進仃聚合，藉此製造丙婦酸系樹脂⑷；在此聚合時， 可，由溶液自由基聚合、_聚合、塊狀聚合、乳化聚合等 法進仃。例如，於有機溶媒中’混合或滴下（甲基） 丙稀酸燒^系單體㈣、含有官能基之單 體(a2)、其他之 ”聚合性單體㈣等之單體成分、聚合起始劑，於迴流狀態 或50〜98°C下進行聚合2〜2〇小時。 乍士此聚。中所使用之有機溶劑，可舉例如甲苯、二甲苯 之方香族煙類；醋酸乙自旨、醋酸丁 異丙基醇等之脂肪族醇類 嗣、環己嘴之酮類等_、甲基乙基酮、甲基異丁基 由合中所使用之聚合起始劑，可舉例如屬於-般自 由基聚&起始劑的偶氮雙 氮系聚合起始劑；過氧化节曱丁 ^偶氣雙二甲基戍賭等之偶 ^ ^ - -Τ- «. _ 曱醯基、過氧化月桂醯基、過氧 等。i 11化過氣化異丙苯等之過氧化系聚合起始劑 100114594 13 201207069 本發明中，上述所得之丙烯酸系樹脂(A)之重量平均分子 量為5萬〜3 0萬，此為由容易進行為了使丙埽酸系樹脂溶液 之黏度變低並得到厚膜之黏著劑層所必要之高固形份化的 觀點而言所必需的，較佳為6萬〜25萬、特佳7萬〜2〇萬、 更佳8萬〜18萬。若重量平均分子量過小’則有凝集力不足 的傾向，若過大則因丙烯酸系樹脂溶液黏度變高，故有難以 件到平整塗佈面的傾向。 丙烯酸系樹脂(A)之數量平均分子量通常為3,〇〇〇〜15萬、 較佳5,000〜13萬、特佳8,000〜1〇萬、更佳j萬〜8萬。若數 量平均分子量過小，财㈣力从的傾向，若過大則因 丙烯酸_脂雜減變高，故餘平錄佈面的傾 向。 另外，丙烯酸系樹脂⑷之分散度（重量平均分子量/數量平 均分子量)較佳為20以下、特佳㈣下、更佳7以下、再 更佳4以下。若此分散度過高，卿著_之_久性能降 ^進行耐久輯驗時有料發生發、料的傾向。又，由製 以界限的觀點而s ’分散度之下限通常為2。 再者’丙烯酸系樹脂（A) β J之玻璃轉移溫度通常 -75〜-l〇C、較佳-70〜、更佳 μ。 ^ _ 尺佳~60〜-2〇c，若玻璃轉移 度過南，則有難以得到黏著特性 一 ㈣傾向’若過低，則有黏 力降低的傾向。 準聚笨乙烯分子量換算 尚且’上述重量平均分子量係由標 100114594 201207069 所得之重量平均分子量，藉由於高速液體層析儀（日本 Waters 公司製，「Waters 2695(本體）」與「Waters 2414(檢測 器）」），使用管柱：ShodexGPCKF-806L(排除界限分子量： 2xl07，分離範圍：1〇〇〜2χ1〇7，理論段數：1〇,〇〇〇段/根，填 ' 充劑材質：苯乙烯-二乙烯基苯共聚物，填充劑粒徑： ' 串聯3根而測定，數量平均分子量亦可依相同方法予以測 定。又，分散度係由重量平均分子量與數量平均分子量所求 得。又，玻璃轉移溫度(Tg)係由以下Fox [數1] 1 __ Wa Wb Wn τ^ = τ^ + τφ+"' + τ^201207069 VI. Description of the Invention: [Technical Field] The present invention relates to an acrylic resin solution, an acrylic adhesive composition, an acrylic adhesive, an adhesive sheet, and an acrylic adhesive for an optical member. And an optical member to which an adhesive is attached; more specifically, an acrylic resin solution for producing a solvent-based acrylic acid-based adhesive which is suitable for application of a thick coating. [Prior Art] Conventionally, in the acrylic acid-based adhesive, there is a viscous adhesive for the purpose of bonding the adherend firmly for a long period of time, or for peeling off by the adherend after attachment. For the premise, the adhesives of various types are adhered, and the adhesives which are most suitable for various fields are designed and used. "In recent years, the performance required for the adhesive is not limited to adhesive properties such as adhesion, and when it is used for bonding to a glass substrate such as a liquid crystal display device, it is required to have transparency and impact absorption resistance to the adhesive layer itself. In order to improve the impact absorption resistance, it is proposed to increase the thickness of the adhesive layer. In addition, as a method of thickening the adhesive layer (thick film coating) using an acrylic resin, it is known that The method of curing a thick film by irradiating an active energy ray such as ultraviolet rays to cure the adhesive (see, for example, Patent Documents 1 and 2). The active energy ray-curable adhesive generally does not contain a usual one. The solvent used to adjust the viscosity in the acrylic adhesive is a substitute for the solvent and makes 100114594 4 201207069 a photopolymerizable unsaturated monomer as a diluent monomer, which is a non-productive ^ 月 糸 糸 糸 , , , , After the application of the agent, the #*t·Zhangbu Township for removing the solvent is not required, and the adhesive layer can be effectively obtained in a short time by thick coating. Patent Document 1: Japanese Patent [Patent Document 2: Japanese Patent Laid-Open Publication No. 2007-314618] SUMMARY OF INVENTION [Problems to be Solved by the Invention] However, in general, when attaching an adhesive tape to a curved surface or a concave-convex surface, The support is applied to the adherend, and in the adhesive tape, a thin and soft support film formed by the adhesive layer is used. If the thin and soft support film is used, the active energy ray hardening is used. When the type of the adhesive is applied to the active energy ray, the support film may be damaged by the influence of heat or the like. Therefore, in the use of such a curved surface or a concave-convex surface, even if it is used, In the case of a thick film adhesive layer, an active energy ray hardening type adhesive is still not used, and a solvent type acrylic adhesive which is crosslinked by a crosslinking agent to form an adhesive layer must be used to obtain a thick The adhesive layer of the film. Therefore, the present invention provides a thick film adhesive layer in such a background to provide a thick film adhesive layer, which can be used for the manufacture of adhesive properties and transparency. Acrylic tree-based solution of a solvent-based acrylic adhesive of a combination curing type, an acrylic adhesive composition using the same, an acrylic adhesive, an adhesive sheet, an adhesive for an optical member, and an adhesive layer Optical 100114594 201207069 For the purpose of the component. (Means for solving the problem) Therefore, the inventors of the present invention have intensively studied in view of the above circumstances, and as a result, have found that 'the lower molecular weight is obtained by using an acrylic resin which is used in comparison with the general adhesive application. An acrylic resin having a low viscosity and an organic solvent exhibiting a specific chain transfer constant, and an acrylic resin solution (acrylic adhesive composition) having a high solid content concentration, even if a thick coating is applied to obtain an adhesive In the case of coating, no liquid or the like is formed during the coating, and the solvent can be easily dried. The obtained adhesive layer is excellent in adhesion, holding power, and transparency, and the present invention has been completed. That is, the gist of the present invention relates to an acrylic resin solution comprising: a propylene-based resin (A) having a weight average molecular weight of 50,000 to 3 G, and a chain of an organic solvent of vinyl acetate in 60 C; The organic solvent (B) having a transfer constant of 25 Å or more and a solid content concentration of 6 % by weight or more. Further, it is an acrylic pressure-sensitive adhesive composition containing the acrylic resin solution, an acrylic pressure-sensitive adhesive and an adhesive sheet obtained by using the acrylic pressure-sensitive adhesive composition, and an acrylic pressure-sensitive adhesive for an optical member, and An optical component of the adhesive layer. The invention includes the following aspects.丙] an acrylic acid-based resin solution containing an acrylic resin (A) having a weight average molecular weight of 50,000 to 300,000 and a chain transfer constant of 6 (the vinyl acetate in rc to an organic solvent) 〇The above organic solvent (B), and the solid concentration of 100114594 6 201207069 is 60% or more. [2] The acrylic resin solution of [1] has a viscosity of +20,000 mPa of the + 'acrylic resin solution · s / 25 ° C or less. [3] such as [1] or [2] propylene glycol resin solution, wherein the acrylic resin (A) does not contain an acidic group. - [4] such as [1] ~ The acrylic resin solution of any one of [1] to [4], wherein the 50% by weight or more of the organic solvent (B) is a mercaptoethyl ketone. [5] The acrylic system according to any one of [1] to [4] In the resin solution, the acrylic acid resin (A) is 6% by weight or more based on the total solid content in the acrylic resin solution. [6] An acrylic adhesive composition containing ~ [ [5] The acrylic resin solution according to any one of [7], wherein the acrylic adhesive composition contains a crosslinking agent (c). [8] An acrylic adhesive, which is characterized by In order to crosslink the [6] or [7] acrylic acid-based adhesive composition. [9] The adhesive sheet is an adhesive layer containing an acrylic adhesive containing [8]. The adhesive sheet is characterized in that the adhesive layer of the [6] or [7] acrylic adhesive composition is applied to a substrate at a film thickness of 80 μm or more and dried to obtain an adhesive layer. The film thickness of the adhesive layer after drying is 50 μm or more. [11] An acrylic adhesive for optical members is obtained by using an acrylic adhesive of [8]. [12] Optical with an adhesive layer The member includes an adhesive layer containing an acrylic 100114594 201207069 adhesive of [8], and an optical member. (Effect of the invention) The C-based resin solution of the compound has a specific tether == The high solid content concentration which is difficult to achieve in the acrylic acid (tetra) ester solution of the acrylic acid-based adhesive for producing a solvent, and when the acrylic-based adhesive is used, the thick-coating is applied to obtain an acrylic-based adhesive. No dripping or coating lines are formed during coating, and it is easy to carry out solvent drying. The adhesive layer, the holding power, the transparency, the rot, and the like of the agent layer are excellent. The present invention will be described in detail below, but these are merely examples showing preferred embodiments. Further, in the present invention, The fluorenyl group refers to acrylic acid or methacrylic acid, and the so-called (fluorenyl) fluorenyl group refers to an acryl fluorenyl group or a fluorenyl fluorenyl group. The so-called (fluorenyl) acrylate refers to an acrylate or a methacrylate. The dilute acid resin (A) used in the present invention contains a (mercapto)alkyl acrylate monomer (al) as a main component, and a functional group-containing monomer (a2) as a copolymer component, if necessary. It is copolymerized, and further, the other copolymerizable monomer (a3) may be used as a copolymerization component. In the acrylic resin (A) of the present invention, the functional monomer (a2) is used as a copolymerization component from the viewpoint of further improving the adhesion to the substrate or the adherend. Here, the phrase "copolymer having a (meth)acrylic acid alkyl ester monomer (al) as a main component 100114594 8 201207069" means that the (meth)acrylic acid alkyl ester monomer (al) is the most copolymerized. The material ' contains 50% by weight or more of the alkyl (meth) acrylate monomer (al), more preferably 55% by weight or more, and still more preferably 60% by weight or more based on the total polymerization component. The alkyl (meth) acrylate monomer (al) has a carbon number of usually 1 to 20, particularly preferably 1 to 12, more preferably 1 to 8, and specific examples thereof include (meth)acrylic acid. Ethyl vinegar, ethyl (meth) acrylate, n-butyl (decyl) acrylate, isobutyl acrylate (meth) acrylate, n-butyl (meth) acrylate, n-propyl (meth) acrylate, (a Base) n-hexyl acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylate An aliphatic acrylic acetal vinegar such as hexa-ester, stearyl (decyl) acrylate, fluorenyl acrylate or decyl acrylate. These may be used alone or in combination of two or more. In such an alkyl (meth) acrylate monomer (al), it is preferred to use (mercapto) acrylic acid from the viewpoints of copolymerizability, adhesiveness, ease of handling, and ease of obtaining raw materials. N-butyl ester and 2-ethylhexyl (meth)acrylate are more preferably n-butyl (meth)acrylate from the viewpoint of superior durability. The proportion of the (alkyl)alkyl acrylate monomer (al) in the copolymerization component is preferably from 50 to 99.9% by weight, particularly preferably from 55 to 99% by weight, more preferably from 6 to 99. If the amount of the sulfonic acid-based vinegar-based monomer (8) is too small, for example, when it is used as an adhesive, the adhesive strength tends to be insufficient. The functional group-containing monomer (a2) may, for example, contain a secret monomer, an amine-containing 100114594 9 201207069 base monomer, an ethyl ethylene group-containing monomer, an isocyanate group-containing monomer, a fluorenyl group-containing monomer, and the like. Among the above, among the above, from the viewpoint of efficiently performing the crosslinking reaction, it is preferred to use a hydroxyl group-containing monomer or a mercapto group-containing monomer. The carboxyl group-containing monomer may, for example, be 2-hydroxyethyl ketone (acrylic acid), 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth) acrylate or (meth) acrylate 6 a hydroxyalkyl acrylate, a hydroxyalkyl propyl acrylate such as 8-hydroxyoctyl acrylate; a caprolactone modified monomer such as 2-hydroxyethyl (meth) acrylate; An oxyalkylene modified monomer such as diethylene glycol (mercapto)acrylic acid or polyethylene glycol (mercapto)acrylic acid; in addition, 2-propenyloxyethyl 2-hydroxyethyl hydrazine Acid-containing, hydroxy-containing monomer containing N-methylol (meth) acrylamide, etc., 2-methylpropyl propyl acrylate, 2-(butyl) benzoic acid 2 butyl butyl acrylate , 2-hydroxy 3-phenoxypropyl (meth)acrylate, 3-hydroxy-2-propyl hydroxypropyl (meth)acrylate, 2-hydroxy 3-phenoxypropyl (meth)acrylate, etc. a hydroxyl group-containing monomer; a 3-hydroxy group-containing monomer such as 2,2-dimercapto 2-hydroxyethyl (meth)acrylate. Further, as the carboxyl group-containing monomer to be used in the present invention, it is preferred to use a ratio of the di(meth)acrylate of the impurity to 〇.5 〇/0 or less, more preferably 0.2%, particularly preferably 0.1%. The above. Specifically, 2-hydroxyethyl acrylate and 4-butyl acetonate are preferred. Examples of the carboxyl group-containing monomer include (mercapto)acrylic acid, acrylic acid dimer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, and glutaconic acid. , itaconic acid, acrylamide, N-glycolic acid, cinnamic acid, etc., 100114594 10 201207069 Among them, (mercapto)acrylic acid is preferably used. The amine group-containing monomer may, for example, be a tert-butylaminoethyl (meth)acrylate, an ethylaminoethyl (meth)acrylate or a decylaminoethyl (meth)acrylate; Indenyl) diethylaminoethyl acrylate or the like is preferred. Among them, didecylaminoethyl (decyl) acrylate and diethylaminoethyl (meth) acrylate are preferably used. Examples of the ethylidene group-containing monomer include 2-(ethionethoxy)ethyl (meth)acrylate and allyl acetate. The isocyanate group-containing monomer may, for example, be an isocyanate 2-propenyloxyethyl ester, 2-methylpropenyloxyethyl isocyanate or an alkylene oxide adduct thereof. Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate and allyl glycidyl (meth)acrylate. These functional group-containing monomers (a2) may be used singly or in combination of two or more kinds, in particular, a combination of a carboxyl group-containing monomer and an amine group-containing monomer, a carboxyl group-containing monomer, and an amine group-containing monomer. It is preferred from the viewpoint that the crosslinking reaction is fast and the sheet formability is superior. The content ratio of the functional group monomer (a2) in the copolymerization component of the acrylic resin (A) is preferably 0.1 to 30% by weight, particularly preferably 0.2 to 25% by weight, more preferably 0.3 to 20% by weight, if any When the amount of the monomer (a2) of the functional group is too small, the crosslinking point at the time of crosslinking becomes too small, so that the cohesive force after crosslinking tends to be insufficient, and if it is too large, the adhesion tends to be excessively lowered. 100114594 11 201207069 In the case where the I-containing monomer is used as the functional group-containing monomer (IV), the content ratio of the acrylic resin (4) in the copolymerization component is superior to heat and humidity resistance or transparency. It is preferably 2% by weight or more, particularly preferably 20 to 50% by weight. Examples of the other copolymerizable monomer (IV) include (meth)acrylic acid benzene vinegar, (meth)acrylic acid, (meth)acrylic phenoxyacetic acid, and (10) acrylic acid B. Oxylated o-phenylbenzene, phenoxy diethylene glycol (meth) acrylic acid, (meth) acrylic acid 2 _ _ _ 3 · phenoxy propyl vinegar, styrene, armor An aromatic ring-containing monomer such as styrene; (meth) propylene hydrazinyl, dimethyl (methyl) __, diethyl (methyl) (tetra) decylamine, (mercapto) acrylamide, etc. Amidoxime monomer; (iv) (iv) acid 2_decyloxyethyl s|, (iv)) (tetra) acid 2 ethoxy ethoxy, (methyl (tetra) acid 3 methoxy butyl @ |, (meth) acrylic acid 2_butoxy B, 2, butoxy diethylene glycol (methyl) propylene vinegar, methoxy diethylene glycol (methyl) propylene _, methoxy triethylene glycol (A Base) vinegar vinegar, ethoxydiethylene glycol (meth) acrylate, decyl dipropylene glycol (meth) propylene 酉 "曰 f oxypolyethylene glycol (fluorenyl) acrylate, octyloxy Base $ethylene glycol _ polypropylene glycol mono (meth) acrylate ^, lauryl oxy polyethylene glycol single (fluorenyl) a monomer containing an alkoxy group and an oxy-anthracene such as an alkylene oxide methyl glycol mono(indenyl)propene (tetra); a nitrile, a mercapto (tetra) nitrile, a vinyl acetate vinegar, a vinyl vinegar propionate, an ethylene stearate Vinegar, gasified ethylene, partial ethylene, vinyl, vinyl, toluene, vinyl, bite, vinyl, itaconic acid (10), reverse, corrective, acrylic acid 100114594 12 201207069 Chlorine 1 base (10) _, N propylene _ methyl trimethyl chloride, propyl propyl trimethyl ammonium chloride, dimethyl bis ethyl decyl ketone, etc. " other copolymerization of other copolymerization The content ratio of the monomer (4) is preferably from 〇 to 40% by weight, particularly preferably from 3% to 30% by weight, more preferably from 5% to 25% by weight. When the amount of the copolymerizable monomer (6) is too large, the characteristic tends to be lowered. In the above, the (meth)propionic acid ester-based monomer (IV) is polymerized by using a monomer (IV) preferably containing a functional group and, if necessary, a copolymerization component (4) as a copolymerization synthesizing blade. Production of propylene glycol resin (4); during the polymerization, free radical polymerization, _polymerization, bulk polymerization, emulsion polymerization For example, in the organic solvent, 'mix or drop the (meth)acrylic acid burning monomer (4), the functional group-containing monomer (a2), and other "polymerizable monomer (four), etc. The body component and the polymerization initiator are polymerized in a reflux state or at 50 to 98 ° C for 2 to 2 hours. The organic solvent used in the polymerization of the gentleman may be, for example, toluene or xylene. Class; an alcoholic alcohol, an aliphatic alcohol such as butyl isopropyl acetate, a ketone of a cyclohexanyl group, etc., a methyl ethyl ketone, a methyl isobutyl group, and a polymerization start used in the combination The agent may, for example, be an azobis-nitrogen polymerization initiator which is a general-purpose radical poly &initiator; a peroxide 曱 ^ 偶 偶 偶 偶 偶 偶 ^ ^ - - Τ - «. _ 曱醯 、, peroxide lauryl sulfhydryl, peroxygen, etc. In the present invention, the weight average molecular weight of the acrylic resin (A) obtained in the present invention is 50,000 to 300,000, which is easy to be obtained. It is necessary to carry out the high solidification of the adhesive layer of the thick film in order to lower the viscosity of the acrylic acid resin solution, and it is preferably 60,000 to 250,000, and particularly preferably 70,000. 2 million, better 80,000 to 180,000. If the weight average molecular weight is too small, the cohesive force tends to be insufficient. When the weight is too large, the viscosity of the acrylic resin solution becomes high, so that it tends to be difficult to flatten the coated surface. The number average molecular weight of the acrylic resin (A) is usually 3, 〇〇〇 150,000, preferably 5,000 to 130,000, particularly preferably 8,000 to 10,000, and more preferably 10,000 to 80,000. If the average molecular weight of the quantity is too small, the tendency of the force (4) force is too large, because if the acrylic acid_lipid is high, the inclination of the surface is recorded. Further, the degree of dispersion (weight average molecular weight / number average molecular weight) of the acrylic resin (4) is preferably 20 or less, more preferably (four), more preferably 7 or less, still more preferably 4 or less. If the dispersion is too high, the performance of the _ _ _ long-term performance is reduced. Further, the lower limit of the s 'distribution degree is usually 2 from the viewpoint of the limit. Further, the glass transition temperature of the acrylic resin (A) β J is usually -75 to -10 ° C, preferably -70 to 1, more preferably μ. ^ _ 佳佳~60~-2〇c, if the glass transition degree is too south, it is difficult to obtain the adhesive property. (4) The tendency is too low, and the viscosity tends to decrease. The quasi-polystyrene molecular weight conversion is still 'the above weight average molecular weight is the weight average molecular weight obtained from the standard 100114594 201207069, by high-speed liquid chromatography (Waters 2695 (body) and "Waters 2414" manufactured by Japan Waters Co., Ltd. ))), using the column: ShodexGPCKF-806L (excluding the limit molecular weight: 2xl07, separation range: 1〇〇~2χ1〇7, theoretical number of segments: 1〇, 〇〇〇 segment/root, filling' Filling material: benzene Ethylene-divinylbenzene copolymer, filler particle size: 'Measured in series 3, the number average molecular weight can also be determined by the same method. Moreover, the dispersion is determined by the weight average molecular weight and the number average molecular weight. The glass transition temperature (Tg) is determined by the following Fox [number 1] 1 __ Wa Wb Wn τ^ = τ^ + τφ+"' + τ^

Tg:共聚物之玻璃轉移溫度(κ)Tg: glass transition temperature of copolymer (κ)

Tga:單體Α之均聚物的玻璃轉移溫度(Κ)Tga: glass transition temperature of the homopolymer of the monomer Κ (Κ)

Wa :單體A的重量分率Wa: weight fraction of monomer A

Tgb :單體B之均聚物的玻璃轉移溫度(K)Tgb: glass transition temperature (K) of homopolymer of monomer B

Wb:單體B的重量分率Wb: the weight fraction of monomer B

Tgn :單體N之均聚物的玻璃轉移溫度(κ) - Wn :單體Ν的重量分率 (Wa+Wb+ · · · +Wn=l) 另外’在將本發明之丙烯酸系黏著劑貼合於電子構件、尤 其是精密電子構件而使用的資訊標籤用途、或電子構件固定 用途時’由於要求耐腐蝕性，故較佳為上述丙烯酸系樹脂(A) 不含酸性基。 100114594 15 201207069 亡：中所使用之有機溶劑(b)，6吹中醋酸乙烯醋對有 機糾丨的鏈轉移常數必須為25〇以上。 奶ί發明中所謂鏈轉移常數C，係指在60°c下使醋 體聚合時’將醋酸乙稀酯之生長末端自由基對於 二、下09與有機溶劑的反應速度常數分別設為kp、ktr 砰，依下式所計算者。 [數2] C=(ktr/kp)xi〇5 作為上述鍵轉移常數，較佳為3〇〇以上、特佳_以上、 更佳500以上’通常上限為麵Q。若此鏈轉移常數過小， 則丙稀酸樹脂的分子量變古，品B雜、丨 向 里旻呵，而且難以進行厚膜塗佈的傾 作為有機溶刪，騎機溶卿)之鏈轉料數為25〇以 上，則__可單獨使用，亦可組合制2種以上之有機 溶劑。於此，在有機溶_)為含有2種以上之有機溶劑時， 有機溶劑(取_时_纟平均_財數所表示。 使用2種以上之有機溶劑時的平均鍵轉移常數，係在使用 η種有機溶劑(X卜X2..·、χη)時，將各有機溶劑之鏈轉移常 數設為A1、Α2...Αη，將各有機溶劑之含有比例（重量％)設 為Bl、Β2...Βη，依下式所計算。 [數3] 平均鏈轉移常數=α__)+Α2χ_擎·.—(請〇) 100114594 201207069 一般調配於丙烯系黏著劑中之有機溶劑的鏈轉移常數，例 如為曱基乙基酮（738)、曱苯(208.9)、丙酮（in)、醋酸乙酯 (33)。 尚且’（）内之數值係根據j. brandrup，E.H. Immergut • 編’’Polymer Handbook”，p.II-91, Interscience(1965)的值。 • 本發明中，由容易調整丙烯酸系樹脂(A)之分子量的觀點 而言，有機溶劑(B)之50重量％以上較佳為曱基乙基酮，特 佳為60重量％以上、更佳70重量％以上。作為與此種甲基 乙基鲷組合的溶劑，較佳可舉例如曱苯、丙酮、醋酸乙酯等， 由容易得到良好之塗佈面的觀點而言，特佳為甲苯。 上述有機溶劑(B)可調配至事先調製成的丙烯酸系樹脂(A) 中，亦可使用作為在使構成丙晞酸系樹脂(A)之共聚合成分 進行聚合時之聚合溶媒，但由容易得到適合厚塗塗佈之固带 份濃度之丙_系餘溶__或4生產性的觀點= 吕，特佳係使用作為聚合時之聚合溶媒。 2為有機溶劑(B)之含量，係相較於輯⑽'樹脂(A_ 4量份，較佳為7〇重量份以下、特佳40重量份以下、更佳 .3〇重量份以下。作為此種含量的下限值，通常為H)重量份。 .若有機溶劑⑻之含量過多，則有難以進行厚塗塗佈的 劑:含有本發明之丙 _而成的丙烯酸系樹脂溶液，但本發明中， 酸糸樹脂溶液具有特定範圍之固形份濃度一事，係在作成, 100114594 17 201207069 配有後述交聯劑（c)的丙烯酸系黏著劑組成物，對基材進行 塗佈時，使其可進行厚塗塗佈的必要條件。 本發明之丙烯酸系樹脂溶液之固形份濃度必須為60重量 %以上、較佳65重量％以上、特佳70重量％以上、更佳75 重量％以上，作為此種固形份濃度之上限，通常為90重量 %。 若此種固形份濃度過底，則難以進行厚塗塗.佈，有難以得 到厚膜之黏著劑層的傾向。 於此，丙烯酸系樹脂溶液之固形份濃度（重量％)，可藉由 例如於鋁箔上精秤lg試料，以Kett(紅外線乾燥機，185W， 高5cm)加熱45分鐘後之殘量予以算出。 本發明中，丙烯酸系樹脂溶液中，由可擔保凝集力的觀點 而言’較佳係相對於總固形份之6〇重量％以上為丙烯酸系 樹脂(A)’特佳為7〇重量％以上、更佳8〇重量％以上為丙烯 酸系樹脂(A)。通常，相對於總固形份之丙烯酸系樹脂(A) 之含有比例的上限為1〇〇重量％。 另外’本發明之丙烯酸系樹脂溶液中，由塗佈性之觀點而 言’其黏度較佳為20,000mPa · s/25°C以下，特佳 18,000mPa· S/25°C 以下、更佳 i5,〇〇〇mpa· s/25t：以下。通 常’此種黏度的下限值為l〇〇mPa · s/25°c。 若此黏度過高，則因容易出現塗佈紋等，而有難以進行塗 佈的傾向。 100114594 201207069 本發明中’較佳係於上述丙烯酸系樹脂溶液中進一步調配 交聯劑（c) ’而作成丙烯酸系黏著劑組成物，作成丙烯酸系 黏著劑組成物後，此種丙烯酸系黏著劑組成物係藉由交聯劑 (c)進行交聯而成為丙烯酸系黏著劑。 ' 交聯劑（c)係與來自屬於丙烯酸系樹脂（A)之主要構成單 • 體的含官能基單體(a2)之官能基進行反應，藉此發揮優越的 黏著力，可舉例如異氰酸酯系交聯劑、環氧基系交聯劑、吖 環丙烷系交聯劑、三聚氰胺系交聯劑、醛系交聯劑、胺系交 聯劑、金屬嵌合物系交聯劑。此等之中，由提升與基材間之 #黏性的觀點或與丙烯酸系樹脂(A)之反應性的觀點而言， 適合使用異氰酸酯系交聯劑。 作為上述異氰酸酯系交聯劑，可舉例如：2,4_二異氰酸曱 苯醋、2,6-二異氰酸曱苯酯、氫化二異氰酸曱苯酯、匕^二 異氰酸一甲苯醋、1，4-二異氰酸二曱苯醋、二異氰酸六亞曱 酉曰、一笨基甲烧_4,4_二異氰酸酯、異佛嗣二異氰酸酯、丨，3_ 雙（異氰酸基甲基)環己烷、二異氰酸四曱基二曱苯酯、丨，5_ 二異氰酸甲萘酯、三苯基曱烷三異氰酸酯、及此等之聚異氰 酸酯化合物與三羥曱基丙烷等之多醇化合物的加成體、此等 聚異氰酸酯化合物的雙脲物或三聚異氰酸酯物等；此等之 中，較佳為使用二異氰酸曱苯酯、二異氰酸六亞甲酯之與多 醇化合物的加成體、雙脲物、三聚異氰酸酯物，特佳為使用 三羥甲基丙烷之2,4-二異氰酸曱苯酯加成物、三羥曱基丙烷 100114594 19 201207069 之2,6-二異氰酸甲苯酯加成物、或此等之混合物。 作為上述環氧基系交聯劑，可舉例如N，N，N’，N’-四環氧丙 基-間二曱苯二胺、二環氧丙基苯胺、1,3-雙(N，N-環氧丙基 胺基甲基)環己烷、1，6-己二醇二環氧丙基醚、新戊二醇二環 氧丙基醚、乙二醇二環氧丙基醚、丙二醇二環氧丙基醚、聚 乙二醇二環氧丙基醚、聚丙二醇二環氧丙基醚、山梨醇聚環 氧丙基醚、甘油聚環氧丙基醚、季戊四醇聚環氧丙基醚、聚 甘油聚環氧丙基醚、山梨醇酐聚環氧丙基醚、三羥曱基丙烷 聚環氧丙基醚、己二酸二環氧丙基酯、鄰酞酸二環氧丙基 酯、三環氧丙基-參(2-羥基乙基)三聚異氰酸酯、間苯二酚環 氧丙基醚、雙酚S-二環氧丙基醚、其他於分子内具有2個 以上環氧基的環氧基系樹脂等。 作為上述吖環丙烷系交聯劑，可舉例如四羥曱基甲烷-三 10-丙酸吖環丙烷基酯、三羥曱基丙烷-三/3-丙酸吖環丙烷基 酯、N，N’-二苯基曱烷-4,4’-雙（1-吖環丙烷羰基醯胺）、N，N’-六亞曱基-1,6-雙（1-吖環丙烷羰基醯胺）等。 作為上述三聚氰胺系交聯劑，可舉例如六曱氧基曱基三聚 氰胺、六乙氧基曱基三聚氰胺、六丙氧基曱基三聚氰胺、六 丁氧基曱基三聚氰胺、六戊氧基甲基三聚氰胺、六己氧基曱 基三聚氰胺、三聚氰胺樹脂等。 作為上述醛系交聯劑，可舉例如乙二醛、丙二醛、丁二醛、 順丁烯二醛、戊二醛、曱醛、乙醛、苯醛等。 100114594 20 201207069 作為上述胺系交聯劑，可舉例如六亞曱二胺、三乙基二 胺、聚乙亞胺、六亞曱四胺、二伸乙基三胺、三乙基四胺、 異佛酮二胺、胺基樹脂、聚醯胺等。 作為上述金屬嵌合物系交聯劑，可舉例如鋁、鐵、銅、鋅、 錫、鈦、鎳、銻、鎂、釩、鉻、錯等之多金屬的乙醯丙酮或 乙醯乙醯基酯配位化合物等。 另外’此等交聯劑(C)可單獨使用，亦可併用2種以上。 上述交聯劑（C)之含量，通常相對於丙烯酸系樹脂(A)100 重量份，較佳為〇·〇1〜20重量份、更佳〇 〇5〜15重量份、特 佳0.1〜10重量份。若交聯劑(C)過少，則有凝集力不足、無 法得到充分耐久性的傾向；若過多’則有柔軟性及黏著力容 易降低的傾向。 另外’由厚塗塗佈時之片形成性優越的觀點而言，較佳係 與交聯劑(C) 一起使用交聯促進劑（交聯觸媒）。作為此種交聯 促進劑（交聯觸媒），可舉例如苄基甲基胺、三伸乙二胺等之 3級胺，2-曱基咪唑、2-乙基-4-曱基咪唾等之咪唑化合物， 對甲苯績酸、填酸.等之酸觸媒’錫或鋅之金屬氧化物等。 另外’丙烯酸系黏著劑組成物中，在不損及本發明效果的 範圍内，可進一步調配石夕貌偶合劑、抗靜電劑、其他之丙稀 酸系黏著劑、其他黏著劑、胺基曱酸乙酯樹脂、松香、松香 脂、氫化松香酯、酚樹脂、芳香族改質萜樹脂、脂肪族系石 油樹脂、脂環族系石油樹脂、苯乙稀系樹脂、二甲苯系樹脂 100114594 21 201207069 等之黏著賦予劑、荖A令， , 者色劑、填充劑、杭老化 劑、機能性色素等之習知添加劑，續=紫外線吸收 而發生呈色或變色的化合物；此等添加劑之線或放射線照射 組成物整體之30重量％以下、特佳2()重w配垔’較佳為 性優越的觀點M，較佳為極力鮮含有。=下’由耐久 低分子成分作為調配劑。 里低於1萬之 另外，除了上述添加劑之外，亦可少量地 物之構成成分之製造原料科所含的㈣等1者劑組成 使上迷丙稀gM黏著劑組成物藉由交聯劑⑼進行 (交聯）’而得到丙烯酸系黏著劑。 本發明之丙稀酸系點著劑’較佳係用於含有由 著劑所構成之黏著劑層與基材的黏著片中。 糸黏 此種黏著片可依照公知之一般黏著片製造方法進行製 le例如’將㈣㈣點著劑組成物設於基材上後，予: 燥、硬化而獲得。 & 作為上述設置丙彿酸系點著劑組成物的基材，並無特別限 制’可舉例如聚奈二甲酸乙二醋、聚對苯二曱酸乙二酿、聚 對苯二曱酸丁二s旨、聚對笨二曱酸乙二g|/異酞㈣共聚物 等之聚S旨系樹脂；聚乙稀、聚丙烯、聚曱基箱等之聚稀煙系 樹脂；聚IU匕乙稀基、聚偏二敗乙稀、聚氟化乙料之聚氣 化乙烯樹脂；尼龍6、尼龍6,6等之聚醯胺；聚氣化乙烯基、 聚氯化乙縣/騎乙稀s旨共聚物、乙稀_醋酸乙埽龜共聚 100114594 22 201207069 物、乙烯-乙烯基醇共聚物、聚乙烯醇、維尼綸等之乙烯旯 聚合物；三醋酸纖維素、赛璐凡等之纖維素系樹脂；聚T基 丙烯酸甲醋、”基丙烯酸乙酷、聚丙婦酸乙酿、聚丙烯： 丁酯等之丙烯酸系樹脂；聚苯乙烯；聚碳酸酯、聚芳香酯 (polyarylate);聚醯亞胺等之合成樹脂片，在呂、鋼、鐵之^ 屬箔，道林紙、玻璃紙等之紙，玻璃纖維、天然纖維、合成 纖維等所構成的織物或不織布。此等基材可作為單層使°用， 亦可作成積層了 2種以上的複層體而使用。 另外’本發明中，較佳係將上述丙婦酸系黏著劑使用作為 光學構件用黏著劑，藉由將由此種丙稀酸系黏著劑所構成的 黏著劑層積層形成於光學構件上，則可得到附有黏 光學構件。 曰之 作為此種光學構件，可舉例如ΙΤ〇電極膜等之透明電極 膜、偏光板、相位差板、楕圓偏光板、光學補償薄膜、哀产 提升薄膜、電磁波屏蔽薄膜、近紅外線吸收薄膜、从= 等。此等之中，在透明電極膜時則可顯著發揮本發明效果、 得到高黏著力，而屬較佳，特佳為IT0(氧化銦锡）電極膜。 :=丙—含酸性基的—生 光上光學:7'較佳係於_層之與 進一步設置離型片，在供於音田 時’係將上述離型片_後而將歸劑層與被黏體貼合。作 100114594 23 201207069 為此種離型片，較佳係使用矽系之離型片。 在製造貼合有上述離型片之附有黏著劑層之光學構件 時，關於使丙烯酸系黏著劑組成物交聯的方法，可藉由下述 方法進行：[1]於光學構材上，將丙烯酸系黏著劑組成物進 行塗佈、乾燥後，貼合離型片，進行熟化處理的方法；[2] 於離型片上，將丙烯酸系黏著劑組成物進行塗佈、乾燥後， 貼合光學構件，進行熟化處理的方法。此等之中，[2]之方 法係由不至損傷光學構件、作業性或穩定製造的觀點而言屬 較佳。 尚且，於丙烯酸系黏著劑組成物中使用交聯劑（C)時，較 佳係在使用上述方法製造附有黏著劑層之光學構件後實施 熟化處理。此熟化處理係為了得到黏著物性之均衡而進行 者，作為熟化條件，溫度通常為室溫〜70°C，時間通常為1 日〜30日，具體而言例如23°C下1日〜20日，較佳可依23°C 下3曰〜10曰、40°C下1曰〜7曰等條件進行。 在上述丙烯酸系黏著劑組成物之塗佈時，係由輥塗、棒 塗、凹版印刷塗佈、刮刀塗佈、網版印刷等慣用方法進行。 至此，說明了在製造暫時貼合有離型片之附有黏著劑層之 光學構件後，將上述離型片剝離後並將黏著劑層與被黏體 (其他光學構件）貼合的黏著劑使用方法，但本發明中，使用 上述丙烯酸系黏著劑製作雙面黏著片亦為較佳，亦可使用利 用此種雙面黏著片而將光學構件彼此貼合的方法。 100114594 24 201207069 4作=種雙面黏著片，可使用上述丙婦酸系黏著編用 知一般構成的雙面”片，但由透明性優越、相對於制厚 觀點而言，特佳為作成無基材之雙面黏著 片此種無基材之雙面黏著片，係藉由在 述丙稀酸系黏著劑所構成之黏著劑層後，在該黏著劑= 具離型片_上’進—步貼合其他之離型片而可獲得。使用 方法係將—者之離型片_並貼合至被黏 離型片並貼合錢㈣。 _離另 上述黏著片之黏著劑層、附有黏著劑層之光學構件之黏著 = 的面黏著片之黏著劑層的凝膠分率* 規點而言’較佳為30〜98%、特佳4〇〜95% 佳50〜90%。若凝跋八才… 丈 ，刀率過低，則有因凝集力不足所引起之 曰不足的傾向。又，若凝膠分率過高，則有因凝集力上 幵而黏著力降低的傾向。 ^ 在將+黏著片之黏著劑層、光學構件用黏著劑及雙面 #著片之黏著劑層的凝膠分率調整為上述範圍時，係藉由例 如調整交義之種類與量等而達成。 上述凝膠分率為交聯度(硬化程度)的衡 量標準，例如依下 、乂 Α算出亦即，將在成為基材之高分子片（例如聚對苯 =夂乙一g日;|膜等）上形成黏著劑層而成的黏著片（未設 ^刀離^者），由200網目之SUS製金屬網包覆，於甲苯中 /又潰2 3 c X 2 4小時’將金屬财殘存之不溶解之黏著劑成分 100114594 25 201207069 相對於甲苯浸潰前之黏 率。其中，事先減去基材重量曰。f百分比作為凝膠分 f ^ i =附有點者劑層之光學構件、雙面黏著片中之 # 的厚度(乾燥後臈厚)，通常較佳為3〜2 5〜150/rni、更佳10〜1〇〇μηι。 寻佳 若此種黏著劑層之厚产坍簡 向，·若過户，則古止 有黏著物性不易穩定的傾 ’予構件整體之厚度過於增加的傾向。 尚且，本發明之丙締酸系點著劑組成物中，係如上述，由 ^該組成物所含有之⑽㈣、樹脂顧之固形份濃度高、且 呈低黏度，故可得到—般為了低黏度化而經溶劑稀釋之低固 形伤濃度之丙稀酸系黏著劑组成物進行塗佈、乾燥所不可能 獲得的厚膜黏著劑層。 在得到上述厚膜之黏著劑層時，較佳係依卿爪以上之膜 厚進行塗佈，特佳為11G/an以上、更佳14_以上；乾燥 後所得之黏著劑層的膜厚，較佳為卿m以上特佳叫爪 以上、更佳ΙΟΟμηι以上。 作為此膜厚之上限，塗料之轉通常為屬帅，乾燥 後之膜厚通常為2〇〇〇pm。 另外’在使用於吸收衝擊或埋填空氣層等之空隙的用途 時’乾燥後之黏著劑層的膜厚較佳為刚㈣以上、特佳 120μιη以上，上限通常為2〇〇〇μπι。 本發明之黏著騎之黏著力係、配合被黏體之材料等而適 100114594 26 201207069 當決定，例如在貼黏至玻璃基板、聚碳酸酯板、聚甲基丙烯 酸曱酯板、經蒸鍍了 ITO層之PET片的情況，較佳為具有 5N/25mm〜500N/25mm 之黏著力’更佳為 1〇N/25mm〜1〇〇N /25mm ° 尚且’上述黏者力（N/25min)係如下述般所算出。於厚 100Mm之聚對苯二曱酸乙二酯（PET)片上依乾燥後厚度為 25μιη之方式形成黏著劑層，將此附有黏著劑層之ρΕτ片裁 斷為寬25mm寬。接著，剝離離型片，將25mmxl〇〇mm之 上述附有黏著劑層之PET片之黏著劑層側，於23t：、相對 濕度50%之環境下藉2kg橡膠輥來回2次加壓貼附至鈉玻螭 等上，並於相同環境下放置30分鐘。其後，於常溫依剝離 速度300mm/min測定180度剝離強度(N/25mm)，將所得值 设為黏者力（N/25mm)。 本發明之黏著劑層的總光線穿透率較佳為9〇%以上、特佳 92%以上。若此總光線穿透率過低，則因穿透性低而有難以 使用於顯示器用途的傾向。又，總光線穿透率之上限通 95%。 ’、、 本^明之黏著劑層的霧值，較佳為以下、特佳以 下、右此霧值過高，則在使用作為顯示器用時，有影像變得 不鮮明的傾向。又’霧值之下限通常為〇.〇〇%。 於此，上述總光線穿透率及霧值係使用根據JIS K7361 i 的霧值計所測定的值。 100114594 27 201207069 例如，黏著劑層之總光線穿透率可使用根據JIS κ7361-1 的HAZA MATER NDH2000(日本電色工業公司製）進行測 定。 另外，黏著劑層之擴散穿透率亦同樣地可使用例如根據 JIS K7361-1的HAZE MATERNDH2000(曰本電色工業公司 製）進行測定。黏著劑層之霧值可由所得之總光線穿透率及 擴散穿透率之值，依霧值(％)=(擴散穿透率/總光線穿透率）X 100而算出。 尚且，本發明中，霧值、總光線穿透率之測定，係僅將黏 著層貼黏於光學PET(總光線穿透率=91.6%，霧值=0.7%)所 測定的值》 由本發明之黏著劑組成物所構成的黏著劑，可適合使用作 為雙面黏著片、尤其是不具有基材（無基材）雙面黏著片’尤 其可用於黏著力高、耐熱可靠性或耐衝擊可靠性優越，具有 較高之光穿透性，不易發生起霧，玻璃或汀〇透明電極片、 聚對苯二甲酸乙二酯(PET)、聚碳酸酯(pc)、聚曱基丙烯酸 曱醋(PMMA)等之光學片類、偏光薄膜、相位差薄膜、光學 補償薄膜、壳度提升薄膜等之光學構件貼附用途。再者，可 適合用於含有料光學構件而成_控面板中。 (實施例） 以下列舉貫施例更具體說明本發明，但本發明在不超過其 要旨之下並不限定於以下實施例。又，例中之「份」、「％」 100114594 28 201207069 係指重量基準。 首先，如下述般調製各種丙烯酸系樹脂溶液（以下有時記 載^丙稀I系樹脂溶液(1)」。又，丙婦酸系樹脂溶液⑴之 重里平均分子量、數量平均分子量、玻璃轉移溫度之測定， 係依上述方法所測定。 尚且，丙烯酸系樹脂溶液⑴之固形份濃度，係於鋁箔上取 丙稀酸Μ脂溶液K2g’藉〖刪紅外線乾燥機 ，185W，高Tgn : glass transition temperature (κ) of homopolymer of monomer N - Wn : weight fraction of monomer ( (Wa + Wb + · · · · + Wn = l) Further 'adhesive of the acrylic adhesive of the present invention In the case of an information tag used for an electronic component, particularly a precision electronic component, or when the electronic component is used for fixing, 'the corrosion resistance is required. Therefore, the acrylic resin (A) preferably does not contain an acidic group. 100114594 15 201207069 Death: The organic solvent used in (b), 6 blowing vinyl acetate vinegar to the organically corrected chain transfer constant must be 25 〇 or more. Milk 发明 The chain transfer constant C in the invention means that when the vinegar is polymerized at 60 ° C, the reaction rate constants of the growth end radicals of ethylene glycol to the organic solvent are set to kp, respectively. Ktr 砰, according to the calculation of the following formula. [Expression 2] C=(ktr/kp)xi〇5 The bond transfer constant is preferably 3 Å or more, particularly preferably _ or more, and more preferably 500 or more. The upper limit is usually the surface Q. If the chain transfer constant is too small, the molecular weight of the acrylic resin becomes old, the product B is miscellaneous, the ruthenium is ruined, and it is difficult to carry out the thick film coating as the organic solvent, and the chain material is transferred. When the number is 25 Å or more, __ may be used singly or in combination of two or more organic solvents. Here, when the organic solvent _) contains two or more kinds of organic solvents, the organic solvent (indicated by _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In the case of η kinds of organic solvents (X Bu X2.., χη), the chain transfer constant of each organic solvent is A1, Α2...Αη, and the content ratio (% by weight) of each organic solvent is B1, Β2 ...Βη, calculated according to the following formula. [Equation 3] Average chain transfer constant = α__) + Α 2 χ _ engine ·. - (please 〇) 100114594 201207069 Chain transfer constant of organic solvent generally formulated in propylene-based adhesives For example, mercaptoethyl ketone (738), toluene (208.9), acetone (in), ethyl acetate (33). The value in '() is based on the value of j. brandrup, EH Immergut • ed. 'Polymer Handbook', p. II-91, Interscience (1965). • In the present invention, the acrylic resin (A) is easily adjusted. From the viewpoint of the molecular weight, 50% by weight or more of the organic solvent (B) is preferably mercaptoethyl ketone, particularly preferably 60% by weight or more, more preferably 70% by weight or more. The solvent to be combined is preferably, for example, toluene, acetone, ethyl acetate or the like, and is preferably toluene from the viewpoint of easily obtaining a good coated surface. The organic solvent (B) can be adjusted to be prepared in advance. In the acrylic resin (A), a polymerization solvent which is used to polymerize a copolymer component constituting the propionic acid resin (A) may be used, but it is easy to obtain a concentration of a solid portion suitable for thick coating. _ _ _ _ _ or 4 productive point of view = Lu, particularly used as a polymerization solvent in the polymerization. 2 is the content of organic solvent (B), compared to the series (10) 'resin (A 4 parts, It is preferably 7 parts by weight or less, more preferably 40 parts by weight or less, more preferably 3 parts by weight. The lower limit of the content is usually H) by weight. If the content of the organic solvent (8) is too large, there is an agent which is difficult to apply thick coating: an acrylic resin solution containing the C of the present invention. However, in the present invention, the acid bismuth resin solution has a specific range of solid content concentration, and is prepared, 100114594 17 201207069, an acrylic adhesive composition containing a crosslinking agent (c) to be described later, when the substrate is coated. It is necessary to carry out thick coating. The solid content of the acrylic resin solution of the present invention must be 60% by weight or more, preferably 65% by weight or more, particularly preferably 70% by weight or more, and more preferably 75% by weight. The upper limit of the solid content concentration is usually 90% by weight. If the solid content concentration is too low, it is difficult to apply a thick coating, and it is difficult to obtain a thick film adhesive layer. The solid content concentration (% by weight) of the acrylic resin solution can be calculated by, for example, finely measuring the lg sample on an aluminum foil and heating it in Kett (infrared dryer, 185 W, height 5 cm) for 45 minutes. In the acrylic resin solution, from the viewpoint of securing the cohesive force, it is preferable that the acrylic resin (A) is more preferably 7% by weight or more, and more preferably 8% by weight or more based on the total solid content. The 5% by weight or more is the acrylic resin (A). The upper limit of the content ratio of the acrylic resin (A) to the total solid content is usually 1% by weight. Further, in the acrylic resin solution of the present invention, From the viewpoint of coatability, the viscosity is preferably 20,000 mPa·s/25 ° C or less, particularly preferably 18,000 mPa·s/25 ° C or less, more preferably i5, and 〇〇〇mpa·s/25t: or less. Usually, the lower limit of such viscosity is l〇〇mPa · s/25°c. If the viscosity is too high, coating embossing or the like tends to occur, and it tends to be difficult to apply. 100114594 201207069 In the present invention, it is preferable to further prepare a crosslinking agent (c) in the acrylic resin solution to form an acrylic adhesive composition, and to form an acrylic adhesive composition, the acrylic adhesive composition The system is crosslinked by a crosslinking agent (c) to form an acrylic adhesive. The crosslinking agent (c) reacts with a functional group derived from the functional group-containing monomer (a2) which is a main constituent monomer belonging to the acrylic resin (A), thereby exerting an excellent adhesion, and is, for example, an isocyanate. A crosslinking agent, an epoxy group crosslinking agent, an anthracycline crosslinking agent, a melamine crosslinking agent, an aldehyde crosslinking agent, an amine crosslinking agent, and a metal chiral crosslinking agent. Among these, an isocyanate crosslinking agent is suitably used from the viewpoint of improving the adhesion between the substrate and the acrylic resin (A). The isocyanate crosslinking agent may, for example, be 2,4-diisocyanatobenzene vinegar, 2,6-diisocyanatophenyl ester, hydrogenated diphenylphenylisocyanate or oxime diisocyanate. Acid-toluene vinegar, 1,4-diisocyanate diphenyl benzene vinegar, hexamethylene diisocyanate, benzoic acid -4-4,4-diisocyanate, isophora diisocyanate, hydrazine, 3_ Bis(isocyanatomethyl)cyclohexane, tetradecyldiphenyl phenyl diisocyanate, hydrazine, methyl naphthyl 5-isocyanate, triphenyldecane triisocyanate, and polyisocyanates thereof An adduct of a compound with a polyhydric alcohol compound such as trishydroxypropylpropane, a diurea or a trimeric isocyanate of such a polyisocyanate compound; among these, preferably, phenylphenyl diisocyanate is used. An adduct of a hexamethylene diisocyanate with a polyol compound, a diurea, a trimeric isocyanate, particularly preferably a 2,4-diisocyanate addition using trimethylolpropane , 3,6-diisocyanate toluene adduct, or a mixture of these, trihydroxymercaptopropane 100114594 19 201207069. The epoxy group-based crosslinking agent may, for example, be N,N,N',N'-tetraepoxypropyl-m-diphenylene diamine, diepoxypropylaniline or 1,3-bis(N). , N-glycidylaminomethyl)cyclohexane, 1,6-hexanediol diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, ethylene glycol diepoxypropyl ether , propylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, polypropylene glycol diepoxypropyl ether, sorbitol polyepoxypropyl ether, glycerol polyepoxypropyl ether, pentaerythritol polyepoxy Propyl ether, polyglycerol polyepoxypropyl ether, sorbitan polyepoxypropyl ether, trishydroxypropyl propane polyepoxypropyl ether, diepoxypropyl adipate, phthalic acid bicyclo Oxypropyl propyl ester, triepoxypropyl- cis (2-hydroxyethyl) trimeric isocyanate, resorcinol glycopropyl ether, bisphenol S-diepoxypropyl ether, others having 2 in the molecule More than one epoxy group-containing epoxy resin or the like. Examples of the above-mentioned anthracene-based propane-based crosslinking agent include tetrahydrofurfuryl methane-tris-10-propionic acid cyclopropylpropanyl ester, trishydroxypropyl propane-tris/3-propionic acid decyl cyclopropyl ester, and N. N'-diphenyldecane-4,4'-bis(1-indolylcyclocarbonylcarbonylguanamine), N,N'-hexa-indenyl-1,6-bis(1-indolylcyclopropanecarbonylguanamine) )Wait. The melamine-based crosslinking agent may, for example, be hexamethoxy fluorenyl melamine, hexaethoxy decyl melamine, hexapropoxy decyl melamine, hexabutoxy decyl melamine or hexapentoxymethyl melamine. , hexahexyloxymercapto melamine, melamine resin, and the like. Examples of the aldehyde crosslinking agent include glyoxal, malondialdehyde, succinaldehyde, maleic aldehyde, glutaraldehyde, furfural, acetaldehyde, and benzaldehyde. 100114594 20 201207069 The amine crosslinking agent may, for example, be hexamethylenediamine, triethyldiamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine or triethyltetramine. Isophorone diamine, amine resin, polyamine, and the like. Examples of the metal chimera-based crosslinking agent include acetamidine or acetamidine of a polymetallic such as aluminum, iron, copper, zinc, tin, titanium, nickel, ruthenium, magnesium, vanadium, chromium, or the like. A base complex compound or the like. Further, these crosslinking agents (C) may be used singly or in combination of two or more. The content of the above-mentioned crosslinking agent (C) is usually from 1 to 20 parts by weight, more preferably from 5 to 15 parts by weight, particularly preferably from 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic resin (A). Parts by weight. When the amount of the crosslinking agent (C) is too small, the cohesive force is insufficient and sufficient durability is not obtained. If the amount is too large, the flexibility and the adhesive strength tend to be lowered. Further, from the viewpoint of excellent sheet formability at the time of thick coating, it is preferred to use a crosslinking accelerator (crosslinking catalyst) together with the crosslinking agent (C). Examples of such a crosslinking accelerator (crosslinking catalyst) include a tertiary amine such as benzylmethylamine or triethylenediamine, 2-mercaptoimidazole and 2-ethyl-4-fluorenylamine. An imidazole compound such as saliva, an acid catalyst such as p-toluene acid, acid, etc., or a metal oxide of tin or zinc. Further, in the 'acrylic adhesive composition, it is possible to further mix the Shixia coupler, the antistatic agent, other acrylic adhesives, other adhesives, and the amine base in the range which does not impair the effects of the present invention. Acid ethyl ester resin, rosin, rosin, hydrogenated rosin ester, phenol resin, aromatic modified oxime resin, aliphatic petroleum resin, alicyclic petroleum resin, styrene resin, xylene resin 100114594 21 201207069 Ordinary additives such as adhesion-imparting agents, sputum A, toners, fillers, aging agents, functional pigments, etc., continued = UV-absorbing compounds that develop color or discolor; lines of such additives or The viewpoint M which is preferably 30% by weight or less of the entire radiation-irradiating composition and which is particularly preferable in that it is preferably excellent in the content of the composition is preferably contained. = Lower 'by durable low molecular weight as a blending agent. In addition to the above-mentioned additives, in addition to the above-mentioned additives, the composition of the constituents of the constituents of a small amount of the constituents may be composed of (4) and the like, and the composition of the propylene-gM adhesive is passed through the cross-linking agent. (9) Conducting (crosslinking) to obtain an acrylic adhesive. The acrylic acid dot applicator of the present invention is preferably used in an adhesive sheet containing an adhesive layer composed of a coating agent and a substrate. The adhesive sheet can be produced according to a conventional method for producing a conventional adhesive sheet. For example, after the (four) (four) dot composition is placed on a substrate, it is obtained by drying and hardening. & The substrate on which the composition of the propofol-based dot-agent is provided is not particularly limited, and examples thereof include, for example, polyethylene naphthalate, polyethylene terephthalate, and polyethylene terephthalate. Dings s, poly-p-benzoic acid Ethylene g | / isoindole (tetra) copolymer and other poly S-type resin; polythene, polypropylene, poly-base box and other poly-smoke resin; poly IU Polyethylene-based resin, nylon 6, nylon 6,6, etc.; poly-glycolated vinyl, polychlorinated bi-country/riding Ethylene s-copolymer, ethylene-acetic acid acetaminophen copolymer 100114594 22 201207069, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, vinylon and other vinyl fluorene polymers; cellulose triacetate, 赛璐凡, etc. Cellulose resin; poly-T-based acrylic acid vinegar, acrylic acid based on acrylic acid, polyacrylic acid ethyl acetate, polypropylene: butyl ester, etc.; polystyrene; polycarbonate, polyarylate ; synthetic resin sheets such as polyimine, in Lv, steel, iron foil, dalin paper, cellophane, etc., glass fiber, day a woven fabric or a non-woven fabric composed of fibers, synthetic fibers, etc. These substrates may be used as a single layer or as a laminate of two or more layers. When a acrylic acid-based adhesive is used as an adhesive for optical members, an adhesive layer formed of such an acrylic-based adhesive is formed on an optical member, whereby a viscous optical member can be obtained. Examples of such an optical member include a transparent electrode film such as a ruthenium electrode film, a polarizing plate, a phase difference plate, a circularly polarizing plate, an optical compensation film, a wading film, an electromagnetic wave shielding film, and a near-infrared absorbing film. Among these, in the case of a transparent electrode film, the effect of the present invention can be remarkably exhibited, and a high adhesion is obtained, which is preferable, and an IT0 (indium tin oxide) electrode film is particularly preferable. - Raw light optics: 7' is preferably attached to the _ layer and further provided with the release sheet. When used for the sound field, the above release sheet is attached to the adherend layer. 23 201207069 For this kind of separation For the sheet, it is preferred to use a release sheet of the enamel type. When manufacturing the optical member with the adhesive layer attached to the above-mentioned release sheet, the method for crosslinking the acrylic adhesive composition can be carried out by The method is as follows: [1] A method of applying an acrylic adhesive composition to an optical member, drying the composition, and bonding the release sheet to perform aging treatment; [2] applying acrylic on the release sheet After applying and drying the adhesive composition, the optical member is bonded to the aging treatment. Among these, the method of [2] is based on the viewpoint of not damaging the optical member, workability, or stable manufacturing. Further, when the crosslinking agent (C) is used in the acrylic pressure-sensitive adhesive composition, it is preferred to carry out the aging treatment after the optical member having the pressure-sensitive adhesive layer is produced by the above method. This curing treatment is carried out in order to obtain a balance of adhesive properties. As a curing condition, the temperature is usually from room temperature to 70 ° C, and the time is usually from 1 day to 30 days, specifically, for example, from 1 day to 20 days at 23 ° C. Preferably, it can be carried out under the conditions of 3曰~10曰 at 23°C and 1曰~7曰 at 40°C. In the application of the above acrylic pressure-sensitive adhesive composition, it is carried out by a conventional method such as roll coating, bar coating, gravure coating, blade coating, or screen printing. Heretofore, an adhesive which peels off the release sheet and bonds the adhesive layer to the adherend (other optical member) after manufacturing the optical member with the adhesive layer temporarily attached to the release sheet is described. Although the method of use is used, in the present invention, it is preferable to form a double-sided adhesive sheet using the above-mentioned acrylic pressure-sensitive adhesive, and a method of bonding the optical members to each other by using such a double-sided adhesive sheet can also be used. 100114594 24 201207069 4 for the double-sided adhesive sheet, it is possible to use the above-mentioned double-sided "sheet" which is generally composed of the above-mentioned acrylic acid-based adhesive, but it is excellent in transparency and is excellent in terms of thickness. Double-sided adhesive sheet of the substrate, such a non-substrate double-sided adhesive sheet, is formed by the adhesive layer composed of the acrylic acid adhesive, and the adhesive is placed on the adhesive sheet - It can be obtained by laminating other release sheets. The method of use is to attach the release sheet to the detached sheet and attach the money (4). _ From the adhesive layer of the other adhesive sheet, The adhesion of the optical member with the adhesive layer = the gel fraction of the adhesive layer of the surface-adhesive sheet * is preferably 30 to 98%, particularly preferably 4 to 95%, preferably 50 to 90%. If the scalpel rate is too low, there is a tendency for sputum deficiency due to insufficient cohesion. Also, if the gel fraction is too high, the adhesion is lowered due to the cohesive force. The tendency is to adjust the gel fraction of the adhesive layer of the adhesive sheet, the adhesive for the optical member, and the adhesive layer of the double-sided sheet. In the case of the circumference, it is achieved by, for example, adjusting the type and amount of the intersection, etc. The gel fraction is a measure of the degree of crosslinking (degree of hardening), for example, it is calculated as follows, that is, it becomes a substrate. An adhesive sheet formed by forming an adhesive layer on a polymer sheet (for example, polyparaphenylene; 夂乙一g日;|膜, etc.) is coated with a metal mesh of SUS mesh of 200 mesh. Toluene / breaks 2 3 c X 2 4 hours 'Insoluble component of the metal residue 100114594 25 201207069 Relative to the viscosity before impregnation of toluene. Among them, the weight of the substrate minus 曰. Gel fraction f ^ i = optical member attached to the layer of the agent layer, thickness of # in the double-sided adhesive sheet (thickness after drying), usually preferably 3 to 2 5 to 150 / rni, more preferably 10 to 1 〇〇μηι. 寻佳 If the adhesive layer is thick and easy to produce, if the transfer is made, the adhesiveness of the adhesive is not easy to stabilize, and the thickness of the whole component tends to increase too much. Moreover, the present invention The propionic acid-based dot composition is as described above, and the (10) (four) resin is contained in the composition. Gu's solid concentration is high and it has a low viscosity, so it is possible to obtain a thick coating which is not possible for coating and drying of a low-solids emulsion concentration of a low-solids wound concentrate which is low in viscosity. When the adhesive layer of the thick film is obtained, it is preferably coated with a film thickness of not less than 11 G/an, more preferably 14 or more; and the adhesive obtained after drying. The film thickness of the layer is preferably more than the above, preferably more than 爪μηι. As the upper limit of the film thickness, the transfer of the paint is generally handsome, and the film thickness after drying is usually 2 〇〇〇pm. Further, the thickness of the adhesive layer after drying is preferably just above (four) or more, particularly preferably 120 μm or more, and the upper limit is usually 2 μm μm when used for absorbing an impact or filling a void such as an air layer. The adhesive force of the adhesive rider of the present invention is suitable for the material of the adherend, etc. 100114594 26 201207069 When determined, for example, sticking to a glass substrate, a polycarbonate plate, a polymethyl methacrylate plate, and being vapor-deposited. In the case of the PET sheet of the ITO layer, it is preferable to have an adhesive force of 5N/25 mm to 500 N/25 mm, preferably 1 〇N/25 mm to 1 〇〇N /25 mm ° and the above-mentioned adhesive force (N/25 min). It is calculated as follows. An adhesive layer was formed on a 100 Mm polyethylene terephthalate (PET) sheet to a thickness of 25 μm after drying, and the ρΕτ sheet with the adhesive layer was cut to a width of 25 mm. Next, the release sheet was peeled off, and the adhesive layer side of the PET sheet with the adhesive layer attached thereto was 25 mm×10 mm, and the pressure was applied twice by a 2 kg rubber roller at 23 t: and a relative humidity of 50%. Sodium bromide, etc., and placed in the same environment for 30 minutes. Thereafter, the 180-degree peel strength (N/25 mm) was measured at a peeling speed of 300 mm/min at room temperature, and the obtained value was defined as the adhesive force (N/25 mm). The total light transmittance of the adhesive layer of the present invention is preferably 9% or more, and particularly preferably 92% or more. If the total light transmittance is too low, there is a tendency that it is difficult to use it for display applications because of low penetrability. Also, the upper limit of the total light transmittance is 95%. The haze value of the adhesive layer of the present invention is preferably such that the following haze values are particularly high or low, and when the haze value is too high, the image tends to be unclear when used as a display. Also, the lower limit of the fog value is usually 〇.〇〇%. Here, the total light transmittance and the haze value are values measured by a haze value according to JIS K7361 i. 100114594 27 201207069 For example, the total light transmittance of the adhesive layer can be measured using HAZA MATER NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS κ 7361-1. Further, the diffusion transmittance of the adhesive layer can also be measured by, for example, HAZE MATERNDH2000 (manufactured by Sakamoto Denshoku Industries Co., Ltd.) according to JIS K7361-1. The haze value of the adhesive layer can be calculated from the values of the total light transmittance and the diffusion transmittance obtained by the fog value (%) = (diffusion transmittance / total light transmittance) X 100. Further, in the present invention, the measurement of the haze value and the total light transmittance is a value measured by sticking only the adhesive layer to optical PET (total light transmittance = 91.6%, haze value = 0.7%). The adhesive composed of the adhesive composition can be suitably used as a double-sided adhesive sheet, especially a double-sided adhesive sheet having no substrate (without substrate), especially for high adhesion, heat resistance reliability or impact resistance. Superiority, high light penetration, no fogging, glass or Ting transparent electrode sheet, polyethylene terephthalate (PET), polycarbonate (pc), polyacrylic acid vinegar (PMMA) Optical members such as optical sheets, polarizing films, retardation films, optical compensation films, and shell-lifting films are used for attachment to optical members. Furthermore, it can be suitably used in a control panel containing a material optical member. (Embodiment) The present invention will be more specifically described by the following examples, but the present invention is not limited to the following examples without departing from the scope of the invention. Also, in the examples, "parts" and "%" 100114594 28 201207069 are the weight basis. First, various acrylic resin solutions are prepared as follows (hereinafter, the propylene-based resin solution (1) may be described.) The weight average molecular weight, the number average molecular weight, and the glass transition temperature of the propylene glycol resin solution (1). The measurement was carried out according to the above method. Further, the solid content concentration of the acrylic resin solution (1) was obtained by taking an acrylic acid glutamate solution K2g' on the aluminum foil, 〖deleting the infrared dryer, 185W, high.

5cm)加熱乾燥45分鐘，測定乾燥前後之重量變化而予以算 出關於丙稀酸系樹脂溶液(I)之黏度測定，係根據JIS K5400(199G)之4.5.3旋轉黏度計法所測定。 〔丙烯酸系樹脂溶液⑴之調製〕（參照表U [丙稀酸系樹脂溶液 於具備度a十、搜拌機、滴下漏斗及迴流冷卻器的反應器 内，填充甲基乙基酮28份、甲苯8份，一邊攪拌、一邊昇 溫，成為90°C後，在歷時2小時滴下在丙烯酸丁酯（al)95 份、丙烯酸2-羥基乙酯（a2)5份中，溶解作為聚合起始劑之 偶氮雙異丁腈(AIBN)0.16份的混合物。進而於聚合途中， 一邊逐次追加在醋酸乙酯2份中溶解AIBN0.06份的聚合觸 媒液、一邊進行聚合7小時’得到丙烯酸系樹脂溶液(丨_1)(固 形份濃度72.5%，黏度4,700 mPa · s/25t，重量平均分子 量127,000，數量平均分子量47,200，分散度2.69，玻璃轉 移溫度-53.3°C)。 100114594 29 201207069 [丙烯酸系樹脂溶液(Ι_2χ| 於具備溫度計、攪拌機、滴下漏斗及迴流冷卻器的反應器 内，填充甲基乙基g同28份、甲苯8份，一邊攪拌、一邊昇 溫’成為9(TC後，在歷時2小時滴下在丙烯酸丁酯（al)55 份、丙烯酸曱酯（al)4〇份、丙烯酸2_羥基乙酯（a2)5份中， 溶解作為聚合起始劑之偶氮雙異丁腈(AIBN)〇 16份的混合 物。進而於聚合途中，一邊逐次追加在醋酸乙酯2份中溶解 AIBN0.06份的聚合觸媒液、一邊進行聚合7小時，得到丙 婦酸系樹脂溶液（1_2)(固形份濃度72.5%，黏度14,400 mPa · S/25°C，重量平均分子量134,000，數量平均分子量 50,200，分散度2.67，玻璃轉移溫度_315。〇。 [丙烯酸系樹脂溶液(1_3)] 於具備溫度計、攪拌機、滴下漏斗及迴流冷卻器的反應器 内，填充甲基乙基酮3〇份、甲苯10份，一邊攪拌、一邊昇 溫’成為90。(：後，在歷時2小時滴下在丙烯酸丁酯（al)88 份、丙烯酸甲酯（al)i〇份、丙烯酸2-羥基乙酯（a2)2份中， 溶解作為聚合起始劑之偶氮雙異丁腈(AIBN)〇 16份的混合 物。進而於聚合途中’一邊逐次追加在醋酸乙g旨2份中溶解 AIBN0.06份的聚合觸媒液、一邊進行聚合7小時，得到丙 烯酸系樹脂溶液（1-3)(固形份濃度70%，黏度8,000 mPa · s/25°C ’重量平均分子量235 〇〇〇，數量平均分子量 78,900，分散度2.98，玻璃轉移溫度_49 3。〇)。 100114594 201207069 [丙烯酸系樹脂溶液(1-4)] 於具備溫度计、攪拌機、滴下漏斗及迴流冷卻器的反應器 内’填充甲基乙基_ 21份、曱苯19份，一邊攪拌、一邊昇 μ，成為90°C後’在歷時2小時滴下在丙烯酸丁酯(al)8〇 伤、丙烯酸曱酯（al)1〇份、丙烯酸2羥基乙酯（&2)1〇份中， /合解作為聚合起始劑之偶氮雙異丁腈(AlBN)〇丨6份的混合 物進而於聚合途中，-邊逐次追加在醋酸乙醋13份中溶 解AIBN0.06份的聚合觸媒液、一邊進行聚合7小時，得到 丙稀酸系樹脂溶液（1_4)(固形份濃度65% ’黏度7,8〇〇 mPa · s/25 C ’重量平均分子量262,〇〇〇，數量平均分子量 84,500 ’分散度3.12，玻璃轉移溫度_49 3。〇。 [丙烯酸系樹脂溶液(1-5)] 於具備溫度計、攪拌機、滴下漏斗及迴流冷卻器的反應器 内，填充曱基乙基酮28份、甲笨8份，一邊攪拌、一邊昇 溫，成為90°C後，在歷時2小時滴下在丙烯酸丁酯（al)54.8 份、丙烯酸曱酯（al)40份、丙烯酸2_羥基乙酯（a2)5份中， 溶解丙烯酸二曱基胺基乙酯（a2)〇.2份、作為聚合起始劑之 偶氮雙異丁腈(AIBN)0.16份的混合物。進而於聚合途中， 一邊逐次追加在醋酸乙酯2份中溶解AIBN0.06份的聚合觸 媒液、一邊進行聚合7小時，得到丙烯酸系樹脂溶液(1_5)(固 形份》辰度72.5%，黏度1〇,4〇〇 mPa · s/25°C，重量平均分子 量118,000，數量平均分子量43,700，分散度2.70，玻璃轉 100114594 31 201207069 移溫度-31.5°C)。 [丙稀酸系樹脂溶液(I_6)] 於具備溫度計、攪拌機、滴下漏斗及迴流冷卻器的反應器 内，填充曱基乙基蜩30份、曱苯10份，一邊攪拌、一邊昇 溫’成為90C後’在歷時2小時滴下在丙烯酸丁酯（ai)60 份、丙烯酸曱酯01)1〇份、丙烯酸2羥基乙酯（a2)3〇份中， 溶解作為聚合起始劑之偶氮雙異丁腈(A丨B N) 〇」6份的混合 物。進而於聚合途中’一邊逐次追加在醋酸乙酯2份中溶解 AIBN0.G6份的聚合觸媒液、—邊進行聚合7小時，得到丙 稀酸系樹脂溶液（!_6)(固形份濃度7〇0/〇，黏度8,9〇〇 mPa · S/25C ’重量平均分子量ι〇7 〇〇〇，數量平均分子量 40,200 ’分散度2.66 ’玻璃轉移溫度-38 9。〇。 [丙烯酸系樹脂溶液(1_7)] 於具備溫度計、攪拌機、滴下漏斗及迴流冷卻器的反應器 内，填充甲基乙基酮3〇份、甲苯1〇份，一邊攪拌、一邊昇 溫’成為90°C後，在歷時2小時滴下在丙烯酸丁酯(al)88 份、丙烯酸曱酯（al)1〇份、丙烯酸4-羥基丁酯(a2)2份中， 溶解作為聚合起始劑之偶氮雙異丁腈(AIB N) 0.16份的混合 物。進而於聚合途中，一邊逐次追加在醋酸乙酯2份中溶解 ΑΙΒΝ0.06份的聚合觸媒液、一邊進行聚合7小時，得到丙 烯酸系樹脂溶液（1_7)(固形份濃度70%，黏度8,200 mPa · s/25°C ’重量平均分子量215,000，數量平均分子量 100114594 32 201207069 76,800，分散度2.80，玻璃轉移溫度_5〇 6。〇。 [丙烯酸系樹脂溶液(1_8)] 於具備溫度計、攪拌機、滴下漏斗及迴流冷卻器的反應器 内，填充醋酸乙酯60份，一邊攪拌、一邊昇溫，成為78。〇 後，在歷時2小時滴下在丙烯酸丁酯（al)9〇份、醋酸乙烯酯 . (a3)5份、丙烯酸2_羥基乙酯（a2)5份中，溶解作為聚合起始 劑之偶氮雙異丁腈(AIBN)0.05份的混合物。進而於聚合途 中，一邊逐次追加在曱苯6份中溶解AmN〇〇5份的聚合觸 媒液、一邊進行聚合7小時之後，以84份甲苯稀釋，而得 到丙烯酸系樹脂溶液0-8)(固形份濃度4〇%，黏度7,5〇〇 mPa · s/25 C ’重量平均分子量752,〇〇〇，數量平均分子量 176,900 ’分散度4.25，玻璃轉移溫度_5〇1。〇。 [丙烯酸系樹脂溶液(1-9)] 於具備溫度計、攪拌機、滴下漏斗及迴流冷卻器的反應器 内填充醋酸乙酯60份、曱基乙基酮1〇份，一邊攪拌、一 邊昇飢’成為75 C後，在歷時2小時滴下在丙烯酸丁酯(ai)55 伤、丙烯酸甲酯（al)4〇份、丙烯酸2·羥基乙酯（a2)5份中， '合解作為聚合起始劑之偶氮雙異丁腈(ΑΙΒΝ)0.06份的混合 物進而於聚合途中，一邊逐次追加在醋酸乙酯10份中溶 解AIBNo %份的聚合觸媒液、一邊進行聚合7小時，其後 以甲苯86份稀釋，得到丙烯酸系樹脂溶液(1-9)(固形份濃度 37·5/° ’ 黏度 7,800 mPa · s/25°C ’ 重量平均分子量 570,000， 100114594 33 201207069 數量平均分子量122,100，分散度4.67，玻璃轉移溫度 -31.5t：)。 尚且，丙烯酸系樹脂溶液(1-1)〜(1-9)中，有機溶劑(B)之種 類及重量比、鏈轉移常數及調配量（份)係示於表1。 100114594 34 9 6 70207 1X20 【Il 黏度 (mPa · s/25〇C) 〇 寸η o o 寸" 〇 〇Λ od 7,800 〇 o o' 1—^ 〇 od o 异 oo 7,500 7,800 固形份濃度 (%) ——__ yri Η o iTi v〇 〇 o o in S ro cn CO in 1-H cn -49.3 -49.3 C\ 00 cn Ό 〇 in o vp yn ΓΛ 分散度 〇\ VD v〇 CN 00 〇\ cs <N l-H fW o (N \〇 v〇 csi s cs <N 寸· vq — 重量平均 分子量 (Mw) O O O o ολ irT CO <s o o s CN 〇 o ocT o o o 〇 o <νλ 卜 o o o iri @ 敏 m 調配量 (份） 00 00 . CO in 00 \D v〇 平均鏈移 動常數 g 00 iT) JQ 冢 00 ir> 00 Os VO 種類及 重量比 MEK/ToVAcOEt =74/21/5 MEK/Tol/AcOEt =74/21/5 MEK/Tol/AcOEt =74/24/5 § |i It MEKyTol/AcOEt =74/21/5 MEK/Tol/AcOEt =71/24/5 MEK/Tol/AcOEt =71/24/5 ! ToI/AcOEt 1 =60/40 MEK/ToVAcOEt =6/52/42 單體 !§! 1 1 1 1 1 1 1 1 4HBA (32) (份） 1 1 1 1 1 1 (N 1 1 DMAEA (a2) (份） 1 1 1 1 (N 〇 1 1 1 1 HEA (a2) (份） in CM 〇 沄 1 揺 1 〇 o 〇 o o o 1 〇 〇\ in 00 00 § oo 文 § 00 00 . g in 丙烯酸系 樹脂溶液 (I) _I r-H (N rn 2 in v〇 rp 00 On °e 呀 6·0-52 s 201207069 其中，表1中各簡稱如下。 B A :丙烯酸丁酯 MA :丙烯酸曱酯 HEA :丙烯酸2-羥基乙酯 4HBA:丙烯酸4-羥基丁酯 DMAEA:丙烯酸二甲基胺基乙酯 VAc :醋酸乙烯酯5 cm) was dried by heating for 45 minutes, and the change in weight before and after drying was measured to determine the viscosity of the acrylic resin solution (I), which was measured in accordance with the 4.5.3 rotational viscometer method of JIS K5400 (199G). [Preparation of Acrylic Resin Solution (1)] (Refer to Table U [Acrylic acid-based resin solution in a reactor having a degree a, a mixer, a dropping funnel, and a reflux condenser, filled with 28 parts of methyl ethyl ketone, 8 parts of toluene was heated while stirring, and after 90 ° C, 95 parts of butyl acrylate (al) and 5 parts of 2-hydroxyethyl acrylate (a2) were added dropwise as a polymerization initiator for 2 hours. a mixture of azobisisobutyronitrile (AIBN) in an amount of 0.16 parts. Further, in the middle of the polymerization, a polymerization catalyst liquid in which 0.06 parts of AIBN was dissolved in 2 parts of ethyl acetate was added, and polymerization was carried out for 7 hours to obtain an acrylic system. Resin solution (丨_1) (solids concentration 72.5%, viscosity 4,700 mPa · s/25t, weight average molecular weight 127,000, number average molecular weight 47,200, dispersion 2.69, glass transition temperature -53.3 ° C). 100114594 29 201207069 [Acrylic Resin solution (Ι_2χ| in a reactor equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, filled with methyl ethyl g and 28 parts, 8 parts of toluene, and heated while stirring to become 9 (after TC, Lasted 2 hours Dissolving azobisisobutyronitrile (AIBN) as a polymerization initiator in 55 parts of butyl acrylate (al), 4 parts of decyl acrylate (al), and 2 parts of 2-hydroxyethyl acrylate (a2) In the middle of the polymerization, a polymerization solvent solution in which 0.06 parts of AIBN was dissolved in 2 parts of ethyl acetate was added, and polymerization was carried out for 7 hours to obtain a propylene glycol resin solution (1_2) (solid form). The concentration is 72.5%, the viscosity is 14,400 mPa · S/25 ° C, the weight average molecular weight is 134,000, the number average molecular weight is 50,200, the dispersion is 2.67, and the glass transition temperature is _315. 〇. [Acrylic resin solution (1_3)] In a reactor equipped with a stirrer, a dropping funnel, and a reflux condenser, 3 parts of methyl ethyl ketone and 10 parts of toluene were charged, and while stirring, the temperature was increased to 90. (: After that, butyl acrylate was dropped over 2 hours. Al) A mixture of 88 parts of azobisisobutyronitrile (AIBN) ruthenium as a polymerization initiator dissolved in 88 parts of methyl acrylate (al) and 2 parts of 2-hydroxyethyl acrylate (a2). Further, in the middle of the polymerization, one part of the acetic acid is added one by one. The polymerization catalyst solution of 0.06 parts of AIBN was dissolved and polymerization was carried out for 7 hours to obtain an acrylic resin solution (1-3) (solid content concentration: 70%, viscosity: 8,000 mPa · s/25 ° C 'weight average molecular weight 235 〇〇 〇, number average molecular weight 78,900, dispersion 2.98, glass transition temperature _49 3. 〇). 100114594 201207069 [Acrylic resin solution (1-4)] in a reactor equipped with a thermometer, a mixer, a dropping funnel and a reflux cooler 'Packed with methyl ethyl _ 21 parts and 19 parts of decene, and stirred while stirring, and became 90 ° C. After dripping for 2 hours, butyl acrylate (al) 8 〇, decyl acrylate (al) 1 part, 2 parts of 2-hydroxyethyl acrylate (& 2), and a mixture of 6 parts of azobisisobutyronitrile (AlBN) as a polymerization initiator, and further in the middle of polymerization, Further, a polymerization catalyst solution in which 0.06 parts of AIBN was dissolved in 13 parts of ethyl acetate was added and polymerization was carried out for 7 hours to obtain an acrylic resin solution (1_4) (solid content concentration: 65% 'viscosity 7, 8 〇〇 mPa) · s/25 C 'weight average molecular weight 262, 〇〇〇, number average molecular weight 84,500 'Dispersion 3.12, glass transition temperature _49 3. Hey. [Acrylic resin solution (1-5)] In a reactor equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, 28 parts of mercaptoethyl ketone and 8 parts of thiophene were filled, and the temperature was raised while stirring, and it became 90. After °C, the dibutylaminoethyl acrylate was dissolved in 54.8 parts of butyl acrylate (al), 40 parts of decyl acrylate (al), and 5 parts of 2-hydroxyethyl acrylate (a2). (a2) 2. 2 parts, a mixture of 0.16 parts of azobisisobutyronitrile (AIBN) as a polymerization initiator. In the middle of the polymerization, a polymerization catalyst solution in which 0.06 parts of AIBN was dissolved in 2 parts of ethyl acetate was added, and polymerization was carried out for 7 hours to obtain an acrylic resin solution (1_5) (solid content) 72.5%, viscosity. 1 〇, 4 〇〇 mPa · s / 25 ° C, weight average molecular weight 118,000, number average molecular weight 43,700, dispersion 2.70, glass to 100114594 31 201207069 shift temperature -31.5 ° C). [Acrylic acid resin solution (I_6)] In a reactor equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, 30 parts of mercaptoethyl hydrazine and 10 parts of fluorene were added, and the temperature was raised while stirring to become 90C. After the dropwise addition of butyl acrylate (ai) (60 parts, decyl acrylate 01), and 2 parts of 2-hydroxyethyl acrylate (a2) in 3 hours, the azo double is dissolved as a polymerization initiator. A mixture of 6 parts of butyronitrile (A丨BN). Further, while adding a polymerization catalyst liquid in which 6 parts of AIBN0.G was dissolved in 2 parts of ethyl acetate in the middle of the polymerization, the polymerization was carried out for 7 hours to obtain an acrylic resin solution (!_6) (solid concentration: 7〇) 0/〇, viscosity 8,9〇〇mPa · S/25C 'weight average molecular weight ι〇7 〇〇〇, number average molecular weight 40,200 'dispersion 2.66 'glass transition temperature -38 9. 〇. [acrylic resin solution ( 1_7)] In a reactor equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, 3 parts of methyl ethyl ketone and 1 part of toluene were charged, and the temperature was raised while stirring, and the temperature was increased to 90 ° C. Dissolve azobisisobutyronitrile (AIB) as a polymerization initiator in an amount of 88 parts of butyl acrylate (al), 1 part of decyl acrylate (al), and 2 parts of 4-hydroxybutyl acrylate (a2). N) 0.16 parts of the mixture. Further, while adding 0.06 parts of the polymerization catalyst liquid in 2 parts of ethyl acetate, the polymerization was carried out for 7 hours to obtain an acrylic resin solution (1-7) (solid content). Concentration 70%, viscosity 8,200 mPa · s/25°C 'weight average The amount of 215,000, the number average molecular weight of 100114594 32 201207069 76,800, the dispersion of 2.80, the glass transition temperature _5 〇 6. 〇. [Acrylic resin solution (1_8)] in a reactor equipped with a thermometer, a mixer, a dropping funnel and a reflux cooler The inside was filled with 60 parts of ethyl acetate, and the temperature was raised while stirring, and it became 78. After that, 9 parts of butyl acrylate (al) and vinyl acetate were dropped over 2 hours, (a3) 5 parts, acrylic acid 2_ A mixture of 0.05 parts of azobisisobutyronitrile (AIBN) as a polymerization initiator was dissolved in 5 parts of hydroxyethyl ester (a2). Further, in the middle of the polymerization, AmN〇〇5 was dissolved in 6 parts of toluene. The polymerization catalyst solution was subjected to polymerization for 7 hours, and then diluted with 84 parts of toluene to obtain an acrylic resin solution 0-8) (solid content concentration: 4% by weight, viscosity 7, 5 〇〇 mPa · s / 25 C) 'Weight average molecular weight 752, 〇〇〇, number average molecular weight 176,900 'Dispersity 4.25, glass transition temperature _5 〇 1. 〇. [Acrylic resin solution (1-9)] with thermometer, mixer, dropping funnel and reflux Reactor reactor filling 60 parts of ethyl acetate and 1 part of mercaptoethyl ketone, while stirring, while simmering into 75 C, drip in butyl acrylate (ai) 55 wounds, methyl acrylate (al) 4 after 2 hours. A mixture of 0.06 parts of azobisisobutyronitrile (ΑΙΒΝ) as a polymerization initiator in a mixture of 5 parts of 2 parts of hydroxyethyl acrylate (a2) was further added to ethyl acetate in the middle of the polymerization. 10 parts of the polymerization catalyst solution in which AIB No % was dissolved, and polymerization was carried out for 7 hours, and then diluted with 86 parts of toluene to obtain an acrylic resin solution (1-9) (solid content concentration 37·5/° 'viscosity 7,800 mPa) · s/25 ° C ' Weight average molecular weight 570,000, 100114594 33 201207069 Number average molecular weight 122,100, dispersion 4.67, glass transition temperature -31.5t:). Further, in the acrylic resin solutions (1-1) to (1-9), the types and weight ratios of the organic solvent (B), the chain transfer constant, and the blending amount (parts) are shown in Table 1. 100114594 34 9 6 70207 1X20 [Il viscosity (mPa · s / 25〇C) 〇 inch η oo inch " 〇〇Λ od 7,800 〇oo' 1—^ 〇 od o different oo 7,500 7,800 solid concentration (%) — —__ yri Η o iTi v〇〇oo in S ro cn CO in 1-H cn -49.3 -49.3 C\ 00 cn Ό 〇in o vp yn ΓΛ Dispersion 〇 \ VD v〇CN 00 〇\ cs <N lH fW o (N \〇v〇csi s cs <N inch · vq - weight average molecular weight (Mw) OOO o ολ irT CO <soos CN 〇o ocT ooo 〇o <νλ 卜ooo iri @ 敏m Amount (parts) 00 00 . CO in 00 \D v〇 average chain shift constant g 00 iT) JQ 冢00 ir> 00 Os VO Type and weight ratio MEK/ToVAcOEt =74/21/5 MEK/Tol/AcOEt =74 /21/5 MEK/Tol/AcOEt =74/24/5 § |i It MEKyTol/AcOEt =74/21/5 MEK/Tol/AcOEt =71/24/5 MEK/Tol/AcOEt =71/24/5 ! ToI/AcOEt 1 =60/40 MEK/ToVAcOEt =6/52/42 Monomer!§! 1 1 1 1 1 1 1 1 4HBA (32) (Parts) 1 1 1 1 1 1 (N 1 1 DMAEA ( A2) (part) 1 1 1 1 (N 〇1 1 1 1 HEA (a2) (part) in CM 〇沄1 揺1 〇o 〇ooo 1 〇〇\ in 00 00 Oo § 00 00 . g in Acrylic resin solution (I) _I rH (N rn 2 in v〇rp 00 On °e 呀 6·0-52 s 201207069 where the abbreviations in Table 1 are as follows. BA: butyl acrylate Ester MA: decyl acrylate HEA: 2-hydroxyethyl acrylate 4HBA: 4-hydroxybutyl acrylate DMAEA: dimethylaminoethyl acrylate VAc: vinyl acetate

Tol :曱苯Tol: Benzene

AcOEt :醋酸乙醋 MEK :曱基乙基酮 36 100114594 201207069 [交聯劑(c)] 準備以下者作為交聯劑（ο 1) •三羥曱基丙烷之異氰酸曱苯酯加成物的55%醋酸乙酯溶 液（日本 Polyurethane 公司製’「CORONATE L-55E」） 〔貝施例1〜7、比較例1、2〕 - 於如上述般調製、準備之丙烯酸系樹脂溶液(I)中，依下述 表2所示之比例調配交聯劑(〇 ’藉此調製成丙烯酸系黏著 劑組成物。 然後’將上述所得之丙烯酸系黏著劑組成物，依厚25〇μιη 塗佈於聚酯系離型片上，以9〇〜100¾乾燥3分鐘，形成乾 燥後膜厚為175/xm的黏著劑層。其後，將所形成之黏著劑 層侧以聚酯系離型片貼合，於40¾條件下使其熟化1〇曰， 而得到無基材之雙面黏著片。 使用上述所得之無基材雙面黏著片，如下述製作附有黏著 背J層之PET薄膜，依以下所示方法測定•評價凝膠分率、 黏著力、保持力、耐腐蝕性。將此等結果一併示於下表2。 [附有黏著劑層之PET薄膜的製作] 由上述無基材雙面黏著片之黏著劑剝離其中一面的離型 片，並按壓至膜厚1〇〇μηι的pET薄膜，得到附有黏著劑層 之PET薄膜。 〔凝膠分率〕 將上述附有黏著劑層之pET薄膜裁斷為4〇x4〇mn^i，剝 100114594 37 201207069 除離型片，將黏著劑層貼合至50x100mm之SUS網目片（200 網目），相對於SUS網目片之長度方向由中央部對折而包覆 樣本後，將其浸潰於裝有甲苯250g的密封容器中，藉由甲 苯浸潰前後之黏著劑層的重量變化進行凝膠分率（％)的測 定。 [黏著力] 針對上述附有黏著劑層之PET薄膜，裁斷為寬25mmx長 100mm，剝離離塑片’將黏著劑層側於23°C、相對濕度50% 的環境下，藉2kg橡膠輥來回2次加壓貼附於聚碳酸酯（pC) 薄膜或鈉玻璃’於相同環境下放置30分鐘後，常溫下依制 離速度300mm/min測定180度剝離強度(N/25mm)。 [保持力] 將上述附有黏者劑層之PET薄膜裁斷為25mmx25mm，制 離離型片，將黏著劑層侧貼黏至研磨SUS板，於80°c條件 下施加負重lkg，根據Z 0237之保持力測定法評價偏 移。評價基準如下。 〇：經1440分鐘後不發生偏移 △:經1440分鐘後發生偏移 X :在經1440分鐘前落下 〔外觀〕 將上述所得之丙嫦酸糸黏著劑組成物，依厚250/im塗佈 於聚酯系離型片上，以90〜100°C乾燥3分鐘，形成乾燥後 100114594 38 201207069 之膜厚為175μπι的黏著劑層，以目視觀察黏著劑層狀態。 (評價） 〇：塗膜未見到氣泡發生 △:上述條件下，塗膜中僅發生些微氣泡，但若進一步以 ' l〇〇°C乾燥2分鐘，則氣泡消失。 X :塗膜中發生氣泡。即使延長乾燥時間氣泡仍不消失。 〔耐腐蝕性評價方法〕 將上述附有黏著劑層之PET薄膜裁斷為5mmx 12mm，剝 離離型片’將黏著劑層侧貼合至銅板上後，於6〇°c、相對 濕度90%之環境下保存7日。其後，由PET薄膜側以目視 觀察銅箔表面’確認銅板表面有無腐蝕。評價基準如下。 〇：未確認到腐|虫 X :確認到腐姓 使用上述所得之無基材雙面黏著片’如下述般製作附有黏 著劑層之光學PET薄膜，並依下述所示各方法測定•評價 總光線穿透率、霧值。此等結果一併示於下表2。 [附有黏著劑層之光學PET薄膜的製作] 將上述無基材雙面黏著片裁斷為3cmx4cm，剝除其中一 面的離型片，將黏著劑層側按壓於光學PET薄膜，再剝離 另一離型片’得到總光學穿透率及霧值測定用樣本。 [總光線穿透率]及[霧值] 將上述附有黏著劑層之光學PET薄膜之離型片剝離，使 100114594 201207069 用HAZE MATER NDH2000(曰本電色工業公司製）測定擴散 穿透率及總光線穿透率。又，本機係根據JIS K7361-1者。 尚且，霧值係將所得之擴散穿透率與總光線穿透率之值代 入下式而算出。 霧值(％)=(擴散穿透率/總光線穿透率)x 100 尚且，針對僅有光學PET薄膜時，測定上述總光線穿透 率、霧值時的值，係總光線穿透率=91.6%，霧值=0.7%。 100114594 40 201207069 鬥(Nd 耐腐蝕性 〇 〇 〇 〇 〇 〇 〇 〇 〇 外觀 〇 〇 〇 < 〇 〇 〇 X X ?/? 0.30 0.35 0.32 0.37 0.34 0.36 0.32 ※ ※ 總光線穿 透4 __(%)__ ΓΟ 〇\ 92.8 92.8 92.5 92.8 92.5 92.8 ※ ※ 保持力 〇 〇 〇 〇 〇 〇 〇 〇 〇 B ^Τί JN Ζ 柳 OQ 玻璃 00 ΓΟ CO (N OO 〇\ d ro 1-H CN CN o r-H ON 28.9 U Ah CM 37.4 1 <N 1-H i〇 <d> T-H 35.3 24.2 12.2 00 00 32.1 凝膠分率 (%) fN oo <N 〇 00 V〇 00 On 00 V〇 o 00 00 OO 交聯劑 (C) r-H s —/—N 0C r' CN U 一 ό 二 ό 二 • f-H U 一 ό已 /«—S 丙烯酸系 樹脂溶灰 (Ώ_ 1 O »—< »—( csg HH — 'w 1 'w /—s 彳§ 1 Ο »—< 1-H 〇 T o l—i ^ Η — 'S—✓ °?§ 'w HH r—1 實施例1 1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 比較例1 比較例2 。螽紱^铆丧 墉赵< 頊禚吩散埤♦噼蘅砌揚WT^玻13<1#采衾噠染矣¥长啭「※」w-9-cs< - Y。牟¥¥齧踩_埏碱WM()-fi-CN<*-&-妹 »—I寸 寸 65HI001 201207069 201207069 將實施例 劑層 -7 m之丙㈣系勘著劑組成物硬化而得_ ，即使為較一般進行更厚 许的勘著 仍均得到良好的塗面，總光線上塗佈而付的厚膜勒著劑層， 越，且黏著祕亦優越。透率或霧值等之光學物性優 另一方面’比較例1及2中， 丙烯酸系樹脂的重量平均分 私m錢所含有之 于夏較高、黏度較高，# 有機溶劑予以稀釋成可進行 °故必須藉 液的固形份濃度變低。因此黏度而丙婦酸系樹脂溶 ，即使如同實施例沁7 佈，於乾燥時無法完全去除有 進仃厗塗 層塗面發生多數氣泡，光學物^、化^在所生成之黏著劑 以上雖參照特定實施態樣詳細說明本發明，但本領域從举 者當知，在不麟本發明精神與_之下，可加以各種變更 或修正。 本申請案係根據2_年4月27日中請之日本專利申过 (特願2_._，將其内容⑽於此作為參照。" (產業上之可利用性） 由本發明之黏著劑組成物所構成的黏著劑，可適合使用作 為雙面黏著片、尤其是不具有基材（無基材）之雙面黏著片， 由接黏力高、耐熱可靠性或耐衝擊可靠性優越、具有較高之 光穿透性、不易發生起霧、對於金屬或金屬氧化物等不使其 發生腐蝕的觀點而言，在玻璃或ITO透明電極片、聚對苯 二曱酸乙二酯（PET)、聚碳酸酯（PC)、聚曱基丙烯酸甲醋 100114594 42 201207069 (PMMA)等之光學片類、偏光薄膜、相位差薄膜、光學補償 薄膜、亮度提升薄膜等之光學構件貼附用途特別有用。再 者，可適合用於含有此等光學構件而成的觸控面板。 100114594 43AcOEt: Acetate Acetate MEK : Mercaptoethyl ketone 36 100114594 201207069 [Crosslinking agent (c)] Prepare the following as a crosslinking agent (ο 1) • Trihydroxydecyl propane isocyanate isocyanate adduct 55% ethyl acetate solution ("CORONATE L-55E" manufactured by Polyurethane Co., Ltd., Japan) [Bei Shi Examples 1 to 7, Comparative Examples 1, 2] - Acrylic resin solution prepared and prepared as described above (I) In the above, the crosslinking agent was prepared in a ratio shown in the following Table 2, thereby preparing an acrylic pressure-sensitive adhesive composition. Then, the acrylic pressure-sensitive adhesive composition obtained above was applied to a thickness of 25 μm. The polyester release sheet was dried at 9 〇 to 1003⁄4 for 3 minutes to form an adhesive layer having a film thickness of 175/xm after drying. Thereafter, the formed adhesive layer side was laminated with a polyester release sheet. And aging it under the condition of 403⁄4 to obtain a double-sided adhesive sheet without a substrate. Using the substrate-free double-sided adhesive sheet obtained above, a PET film with an adhesive back J layer is prepared as follows, The method shown determines and evaluates gel fraction, adhesion, retention, and corrosion resistance. The results are shown in the following Table 2. [Production of PET film with adhesive layer] The release sheet of one side of the above-mentioned substrate-free double-sided adhesive sheet is peeled off and pressed to a film thickness of 1 〇〇 μηι The pET film is obtained as a PET film with an adhesive layer. [Gel fraction] The above pET film with an adhesive layer is cut into 4〇x4〇mn^i, stripped 100114594 37 201207069, and the release sheet will be The adhesive layer was bonded to a 50×100 mm SUS mesh sheet (200 mesh), and the sample was coated with a central portion folded in the longitudinal direction of the SUS mesh sheet, and then immersed in a sealed container containing 250 g of toluene. The gel fraction (%) was measured by the change in the weight of the adhesive layer before and after the impregnation of the toluene. [Adhesive strength] For the PET film with the adhesive layer described above, the cut was 25 mm wide and 100 mm long, and the peeled off plastic sheet was Adhesive layer side under 23 ° C, relative humidity 50% environment, 2kg rubber roller back and forth attached to polycarbonate (pC) film or soda glass in the same environment for 30 minutes, room temperature The 180-degree peel strength (N/25 mm) was measured at a separation speed of 300 mm/min. [Retention] The PET film with the adhesive layer described above was cut into 25 mm x 25 mm, and the release sheet was attached. The adhesive layer side was adhered to the ground SUS plate, and a load lkg was applied at 80 ° C according to Z 0237. The retention force evaluation method was used to evaluate the offset. The evaluation criteria were as follows: 〇: no shift occurred after 1440 minutes Δ: offset occurred after 1440 minutes X: dropped before 1440 minutes [appearance] The above obtained propionic acid The adhesive composition was applied to a polyester release sheet at a thickness of 250/im, and dried at 90 to 100 ° C for 3 minutes to form an adhesive layer having a film thickness of 175 μm after drying at 100114594 38 201207069, and visually observed. Adhesive layer state. (Evaluation) 〇: No bubbles were observed in the coating film. Δ: Under the above conditions, only some microbubbles occurred in the coating film, but if it was further dried at '10 ° C for 2 minutes, the bubbles disappeared. X: Air bubbles occur in the coating film. Even if the drying time is extended, the bubbles do not disappear. [Method for Evaluating Corrosion Resistance] The PET film with the adhesive layer described above was cut into 5 mm x 12 mm, and the release release sheet was attached to the copper plate with the adhesive layer side at 6 ° C and a relative humidity of 90%. Save for 7 days in the environment. Thereafter, the surface of the copper foil was visually observed from the PET film side to confirm the presence or absence of corrosion on the surface of the copper plate. The evaluation criteria are as follows. 〇: Unrecognized rot | Insect X: It was confirmed that the non-substrate double-sided adhesive sheet obtained as described above was used to prepare an optical PET film with an adhesive layer as described below, and was measured and evaluated according to the following methods. Total light transmittance, fog value. These results are shown together in Table 2 below. [Production of Optical PET Film with Adhesive Layer] The above-mentioned substrate-free double-sided adhesive sheet was cut into 3 cm x 4 cm, and one of the release sheets was peeled off, and the adhesive layer side was pressed against the optical PET film, and the other was peeled off. The release sheet' gave a sample for total optical transmittance and haze value measurement. [Total Light Transmittance] and [Fog Value] The release sheet of the optical PET film with the above adhesive layer was peeled off, and 100114594 201207069 was used to measure the diffusion transmittance of HAZE MATER NDH2000 (manufactured by Sakamoto Denshoku Industries Co., Ltd.). And total light penetration. Also, this unit is based on JIS K7361-1. Further, the haze value was calculated by substituting the obtained values of the diffusion transmittance and the total light transmittance into the following formula. Fog value (%) = (diffusion transmittance / total light transmittance) x 100 Also, for the case where only the optical PET film is used, the total light transmittance and the value of the fog value are measured, and the total light transmittance is = 91.6%, fog value = 0.7%. 100114594 40 201207069 Bucket (Nd corrosion resistance 〇〇〇〇〇〇〇〇〇 appearance 〇〇〇 < 〇〇〇XX ?/? 0.30 0.35 0.32 0.37 0.34 0.36 0.32 ※ ※ Total light penetration 4 __(%)__ ΓΟ 〇 \ 92.8 92.8 92.5 92.8 92.5 92.8 ※ ※ Retention force B ^Τί JN Ζ Liu OQ glass 00 ΓΟ CO (N OO 〇\ d ro 1-H CN CN o rH ON 28.9 U Ah CM 37.4 1 <N 1-H i〇<d> TH 35.3 24.2 12.2 00 00 32.1 Gel fraction (%) fN oo <N 〇00 V〇00 On 00 V〇o 00 00 OO Crosslinking Agent (C) rH s —/—N 0C r' CN U 一ό 二ό 二• fH U 一ό已/«—S Acrylic resin dissolved ash (Ώ_ 1 O »—< »—( csg HH — ' w 1 'w /—s 彳§ 1 Ο »—< 1-H 〇T ol—i ^ Η — 'S—✓ ° § 'w HH r—1 Example 1 1 Example 2 Example 3 Implementation Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 螽绂^ 铆 墉 墉 & & 顼禚 顼禚 顼禚 埤 噼蘅 噼蘅 噼蘅 噼蘅 噼蘅 噼蘅 噼蘅 噼蘅 WT WT WT WT WT WT WT WT WT WT WT WT WT WT WT WT WT WT WT WT WT WT长啭"※"w-9-cs< - Y.牟¥¥啮踏踩_埏碱 WM()-f i-CN<*-&- sister»-I inch inch 65HI001 201207069 201207069 The embodiment layer -7 m of C (four) is a hardening agent composition, even if it is thicker than the general Still, a good coating surface is obtained, and the thick film lacquer layer coated on the total light is superior in adhesion and adhesion. The optical properties such as the transmittance or the fog value are excellent. On the other hand, Comparative Examples 1 and 2 In the middle, the weight of the acrylic resin is higher than that in the summer, and the viscosity is high. # The organic solvent is diluted to a concentration, so the solid content of the liquid must be lowered. Therefore, the viscosity is high. If the resin is dissolved, even if it is as in the example 沁7 cloth, most of the bubbles may not be completely removed during the drying process. The optical material and the optical agent are formed in detail above the specific embodiment. The present invention has been described, but it is apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent filed on April 27, 2010 (Japanese Patent Application No. 2_._, the contents of which are hereby incorporated by reference. " Industrial Applicability) Adhesives of the Invention The adhesive composed of the composition can be suitably used as a double-sided adhesive sheet, in particular, a double-sided adhesive sheet having no substrate (without a substrate), and has excellent adhesion, heat resistance reliability, and impact resistance reliability. It has high light transmittance, is less prone to fogging, and does not cause corrosion of metal or metal oxide, etc., in glass or ITO transparent electrode sheets, polyethylene terephthalate (PET), It is particularly useful for attaching optical members such as optical sheets, polarizing films, retardation films, optical compensation films, and brightness enhancement films such as polycarbonate (PC) and polymethyl acrylate vinegar 100114594 42 201207069 (PMMA). It can be suitably used for a touch panel containing such optical members. 100114594 43

Claims (1)

201207069 七、申請專利範圍： 1. 一種丙烯酸系樹脂溶液，其特徵為含有：重量平均分子 量5萬〜30萬之丙烯酸系樹脂⑷、與阶中醋酸乙稀醋對 有機溶劑的鏈轉移常數為250以上之有機溶劑(B)，且固形 份濃度為60%以上。 2. 如申請專利範圍第丨項之丙烯酸系樹脂溶液其中，丙 烯酸系樹脂溶液之黏度為2〇,〇〇〇mPa ·以25。(：以下。 3. 如申請專利範圍第i或2項之丙稀酸系樹脂溶液，其 中，丙烯酸系樹脂(A)不含酸性基。 4. 如申5青專利範圍第1至3項中任一項之丙烯酸系樹脂溶 液，其中，有機溶劑(B)之50重量％以上為甲基乙基酮。 5. 如申請專利範圍第項中任—項之丙稀酸系樹脂溶 液’其中，相對於丙烯酸系樹脂溶液中之_形份，6〇重 量％以上為丙烯酸系樹脂(A)。 6. -種㈣酸系黏著劑組成物，係含有申請專利範圍第i 至5項中任一項之丙烯酸系樹脂溶液。 7. 如申請專利範圍第6項之_酸系黏著顏成物，其 中，含有交聯劑(〇。 、 &-種__㈣劑’其特徵為，係使申請專利範圍第 6或7項之丙烯酸系黏著劑組成物進行交聯而成。 9·種黏著片，係含有黏著劑層，該黏著劑層含有申請專 利範圍第8項之丙烯酸系黏著劑。 100114594 44 201207069 ιο·—種黏著片，係具有黏著劑層，該黏著劑層係將申請 專利範圍第6或7項之丙稀酸系黏著劑組成物依80μιη以上 的膜厚塗佈於基板上並使其乾燥而得，乾燥後之黏著劑層之 膜厚為50jnm以上。 11. 一種光學構件用丙烯酸系黏著劑，係使用申請專利範 圍第8項之丙烯酸系黏著劑而成。 12. —種附有黏著劑層之光學構件，係含有含申請專利範 圍第8項之丙烯酸系黏著劑之黏著劑層、及光學構件。 100114594 45 201207069 四、指定代表圖： (一) 本案指定代表圖為：無 (二) 本代表圖之元件符號簡單說明： 無 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： 無 100114594 3201207069 VII. Patent application scope: 1. An acrylic resin solution characterized by containing: an acrylic resin (4) having a weight average molecular weight of 50,000 to 300,000, and a chain transfer constant of 250 with respect to an organic solvent of ethylene acetate in the order. The above organic solvent (B) has a solid content concentration of 60% or more. 2. The acrylic resin solution according to the scope of the patent application, wherein the acrylic resin solution has a viscosity of 2 〇 and 〇〇〇mPa · 25 . (: The following. 3. For the acrylic resin solution of the i or 2 of the patent application, wherein the acrylic resin (A) does not contain an acidic group. 4. In the first to third paragraphs of the application The acrylic resin solution of any one of the above, wherein 50% by weight or more of the organic solvent (B) is methyl ethyl ketone. 5. The acrylic acid resin solution according to any one of the above claims. 6% by weight or more based on the _ component in the acrylic resin solution is the acrylic resin (A). 6. The seed material of the (four) acid type adhesive contains any of the items i to 5 of the patent application range. The acrylic resin solution of the item 7. The acid-based adhesive pigment of the sixth aspect of the patent application, wherein the cross-linking agent (〇., &-species__(四) agent' is characterized by The acrylic adhesive composition of the sixth or seventh aspect of the patent is crosslinked. 9. The adhesive sheet contains an adhesive layer containing the acrylic adhesive of claim 8 of the patent application. 44 201207069 ιο·—Adhesive sheet with adhesive layer, the stick The coating layer is obtained by applying a film thickness of 80 μm or more to a substrate and applying a film thickness of 80 μm or more to the substrate, and drying the adhesive layer to a thickness of 50 jnm. 11. An acrylic adhesive for optical members, which is obtained by using an acrylic adhesive according to item 8 of the patent application. 12. An optical member with an adhesive layer containing the patent application scope 8 Adhesive layer of acrylic adhesive and optical component. 100114594 45 201207069 IV. Designation of representative figure: (1) The representative representative of the case is: No (2) Simple description of the symbol of the representative figure: No. 5 If there is a chemical formula, please reveal the chemical formula that best shows the characteristics of the invention: None 100114594 3
TW100114594A 2010-04-27 2011-04-27 Acrylic-based resin solution, acrylic-based adhesive composition, acrylic-based adhesive, adhesive sheet, acrylic-based adhesive for optical element, and optical element with adhesive layer TWI502043B (en)

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