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TW201105760A - Ultraviolet curing adhesive composition - Google Patents

Ultraviolet curing adhesive composition Download PDF

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Publication number
TW201105760A
TW201105760A TW099110167A TW99110167A TW201105760A TW 201105760 A TW201105760 A TW 201105760A TW 099110167 A TW099110167 A TW 099110167A TW 99110167 A TW99110167 A TW 99110167A TW 201105760 A TW201105760 A TW 201105760A
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Taiwan
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component
meth
mass
parts
polymer
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TW099110167A
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Chinese (zh)
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TWI485213B (en
Inventor
Manabu Shimizu
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Emulsion Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08K5/07—Aldehydes; Ketones
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5397—Phosphine oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
    • C09J143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently

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

Abstract

The invention relates to an Ultraviolet curing adhesive composition. The Ultraviolet curing adhesive composition includes methacrylate polymer (component A), carboxylic acids having polymeric non-saturated groups (component B), light polymerization initiator (component C), silane coupling agent (component D), and compounds having other polymeric non-saturated groups (component E). The component A includes 0.5 to 20 mmol methylacryloyl functional group in 100 grams of the component A, has a glass transition temperature at -55 to 0 degrees of Celsius, and an average molecular weight of 0.2 millions to 1 million. The component C is acyl phosphine oxide type light polymerization initiator. The component D is silane compound having epoxy systems. The components A to E are included in the Ultraviolet curing adhesive composition according to a specific ratio.

Description

201105760 六、發明說明： 【發明所屬之技術領域】 本發明係關於藉由紫外線照射而表現出黏著力的紫外 線硬化型黏著劑組合物。 【先前技術】 近年來，電漿顯示器、液晶顯示器等電子圖像顯示裝 置（電子顯示器）得到廣泛普及。對於電漿顯示器，需要在 顯示器的表面貼合用於提高可見性的防反射性薄膜，另外 ，對於液晶顯示器，也需要在顯示器的表面、內面貼合偏 光板或其他機能性薄膜。在貼附此等機能性薄膜的用途中 ，利用（甲基）丙烯酸系聚合物的黏著劑的使用急劇增加。 以往，在貼附機能性薄膜的用途中，使用所謂的熱硬 化型黏著劑’該熱硬化型黏著劑以（甲基）丙烯酸系聚合物 溶解在有機溶劑中而成的黏著劑做爲主劑，在使用前向該 主劑添加熱交聯劑，藉由加熱而表現出黏著力（參照專利 文獻1及2)。如此的熱硬化型黏著劑，在主劑中添加熱交 聯劑後’塗佈到機能性薄膜等表面，藉由加熱使主劑所含 有的溶劑成分揮發，然後在常溫或加熱的條件下，經由數 天的熟成使熱交聯劑產生交聯反應，發揮穩定的黏著性能 〇 例如’專利文獻1中揭不了一種光學零件用黏著劑組 合物’其含有丙烯酸系聚合物（A)、丙烯酸系聚合物⑼）、 矽烷偶合劑以及熱交聯劑；其中所述丙烯酸系聚合物（A) 201105760 以（甲基）丙烯酸烷基酯及不飽和羧酸爲單體單元、重量平 均分子量爲50萬以上；所述丙烯酸系聚合物（B)以（甲基） 丙烯酸烷基酯及不飽和羧酸爲單體單元、羧酸當量大於丙 烯酸系聚合物（A)、重量平均分子量爲0.2〜5萬。並且， 在專利文獻1中揭示如下例：在含有溶劑的狀態下調製該 黏著劑組合物，於1 1 0°C乾燥•交聯5分鐘，形成黏著劑 層後，再於50°C的高溫下進行24小時熟成，而得到黏著 型光學零件。 又，在專利文獻2中揭示了含有含乙烯性不飽和基的 丙烯酸系樹脂、光聚合起始劑和矽烷系化合物的光學層合 體用活化能量射線硬化型的黏著劑組合物。並且，在專利 文獻2中，記載了該黏著劑組合物以溶劑稀釋到濃度爲1 0 〜20質量％且較佳爲使用熱交聯劑之內容，且公開了在40 °C的高溫下進行4天的長時間熟成的例子。 此等熱硬化型黏著劑具有黏著性良好、耐久性高、塗 佈精度高等優點，但問題是需要進行如上所述的熟成 (aging)。亦即，產品不能立即使用，並且需要熟成所需之 時間和場地，所以除了產品的處理繁瑣之外，保存成本之 增加亦存在著問題。 因此，提出了藉由使用具有聚合性不飽和基的UV硬 化成分，而不需要高溫•長時間熟成的紫外線硬化型黏著 劑的方案。例如，提出了一種紫外線硬化型樹脂組合物， 其含有規定重量平均分子量的丙烯酸共聚物、在分子內具 有2個不飽和雙鍵、在分子內具有烷撐二醇鏈的單體以及 -6 - 201105760 光聚合起始劑（參照專利文獻3)。 另外’提出了由導入有雙鍵的反應性聚合物（A)、（甲 基）丙烯酸酯單體（B)、能與（B)共聚的單官能單體（c)以及 光聚合起始劑等（D)所構成的紫外線硬化型黏著劑組合物（ 參照專利文獻4)。 進而’本發明人也提出了 一種紫外線硬化型黏著劑組 合物’其含有反應性聚合物、光聚合起始劑、具有聚合性 雙鍵的單體’上述反應性聚合物是在主鏈中含有來自（甲 基）丙烯酸系單體的重複單元且在支鏈中具有（甲基）丙烯醯 系官能基的改性（甲基）丙烯酸系聚合物（參照專利文獻5 ) 〇 專利文獻1:日本特開20〇4-263165號公報 專利文獻2:日本特開2006-316231號公報 專利文獻3:日本特開2006_312664號公報 專利文獻4:日本特開2001-64593號公報 專利文獻5:日本特開2006-282805號公報 【發明內容】 對專利文獻3〜5所記載的紫外線硬化型黏著劑組合 物照射紫外線時，光聚合起始劑產生作用，藉由聚合性單 體或反應性聚合物之聚合反應之進行，表現出黏著力。因 此’具有產生黏著力時不需要加熱，幾乎在照射紫外線的 同時就能夠表現出黏著力的優點。並且，由於黏著劑中不 含有熱交聯劑，所以具有在製造黏著劑時不需要熟成時間 201105760 (無熟成）的這樣的熱硬化型黏著劑所不具有的優異特性。 但是，與熱硬化型黏著劑相比，紫外線硬化型的黏著 劑具有光學耐久性、再剝離性差的傾向，且在高速下的塗 佈適合性和空氣環境下的紫外線硬化性等方面也未能令人 充分滿足。特別是在對電子顯示器貼合功能性薄膜的用途 中使用的黏著劑，要求技術水準的進一步提高，例如提高 生產率（塗佈速度）、提高塗佈精度、黏著劑層隨著產品的 薄層化而薄膜化等，尙存在待解決的課題。 本發明爲解決上述現有技術的課題而完成的，亦即提 供一種紫外線硬化型黏著劑組合物，其在發揮不需要熟成 的紫外線硬化型黏著劑的優點的同時，具有在空氣環境下 的紫外線硬化性優異’在光學耐久性、再剝離性、生產率 (塗佈速度）、塗佈適合性（塗佈精度、黏著劑層的薄膜化等 )方面都具有能與熱硬化型黏著劑匹敵的性能。 本發明人爲解決上述現有技術的課題進行了深入硏究 ’結果想到藉由以規定的組成比使用在支鏈導入有聚合性 (甲基）丙烯醯基的交聯性（甲基）丙烯酸系聚合物、（甲基） 丙烯酸等具有聚合性不飽和基的聚合性羧酸類、醯基氧化 膦系光聚合起始劑以及具有環氧系官能基的矽烷偶合劑來 解決上述課題’遂完成了本發明。具體而言，藉由本發明 ’提供以下的紫外線硬化型黏著劑組合物。 [1 ] 一種紫外線硬化型黏著劑組合物，其含有（甲基）丙 嫌酸系聚合物（A成分）、具有聚合性不飽和基的羧酸及其 寡聚物中的至少一種（B成分）、光聚合起始劑（C成分）、矽 -8- 201105760 烷偶合劑（D成分）以及除上述A成分和上述B成分以外的 具有聚合性不飽和基的化合物（E成分）作爲構成成分， 該A成分是在主鏈中含有來自（甲基）丙烯酸系單體的 重複單元、在支鏈中具有含有（甲基）丙烯醯基骨架的（甲基 )丙烯醯系官能基，且每100g聚合物含有0.5〜20mmol的 前述（甲基）丙烯醯系官能基、玻璃轉移溫度（Tg)爲-55 °C〜 〇°C、重量平均分子量（Mw)在20萬〜100萬範圍內的交聯 性（甲基）丙烯酸系聚合物， 該C成分是醯基氧化膦系光聚合起始劑， 該D成分是具有環氧系官能基的矽烷偶合劑， 以上述A成分和上述B成分的總量爲100質量份時， 含有80〜99·5質量份的上述A成分、0.5〜20質量份的上 述B成分、0.05〜3質量份的上述C成分、0.1〜5質量份 的上述D成分、0〜20質量份的上述E成分。 [2 ]如上述[1 ]所述的紫外線硬化型黏著劑組合物，其 中’上述A成分是在支鏈中具有含有烷氧矽烷基骨架的烷 氧矽烷基系官能基’且每l〇〇g聚合物含有〇.〇4〜4mmol 的上述烷氧矽烷基系官能基的交聯性（甲基）丙烯酸系聚合 物。 [3]如上述[1]或[2]所述的紫外線硬化型黏著劑組合物 ，其中’上述E成分是每丨分子具有2個以上之上述（甲 基）丙烯醯系官能基的多官能寡聚物，以上述A成分和上 述B成分的總夏爲100質量份時，含有〇·5〜20質量份的 上述E成分。 201105760 [4]如上述[3]所述的紫外線硬化型黏著劑組合物，其 中’上述E成分是以脂肪族聚酯爲基本骨架，重量平均分 子量（Mw)在1千〜1萬範圍內的多官能寡聚物。 [5 ]如上述[3 ]所述的紫外線硬化型黏著劑組合物，其 中’上述E成分是以雙酚爲基本骨架，重量平均分子量 (Mw)在400〜2,000範圍內的多官能寡聚物。 [6] 如上述[1]或[2]所述的紫外線硬化型黏著劑組合物 ’其中，含有在350〜400nm波長範圍具有Xmax的二苯 甲酮系化合物作爲紫外線吸收劑（F成分）。 [7] 如上述[1]或[2]所述的紫外線硬化型黏著劑組合物 ，其中’上述C成分是2，4,6-三甲基苯甲醯基-二苯基氧 化膦。 本發明的紫外線硬化型黏著劑組合物不需要熟成，具 有在空氣環境下的紫外線硬化性優異，在光學耐久性、再 剝離性、生產率（塗佈速度）、塗佈適合性（塗佈精度、黏著 劑層的薄膜化等）方面都具有能與熱硬化型黏著劑匹敵的 性能。 【實施方式】 以下’具體說明用於實施本發明紫外線硬化型黏著劑 組合物的方式。但本發明涵蓋具備發明技術特徵的全部實 施方式，而不限於以下所示的實施方式。 [1]定義等： -10- 201105760 在以下的說明中，所謂“（甲基）丙烯酸系聚合物”係 指在主鏈中含有來自（甲基）丙烯酸系單體的重複單元（以下 ，將“來源於單體X的重複單元”簡稱爲“X單元”）的 聚合物。 另外，聚合物（也包括寡聚物）的“主鏈”係指該聚合 物中碳原子數最多的碳鏈。另一方面，“支鏈”係指從聚 合物的主鏈（碳原子數最多的碳鏈）分支的、碳原子數比主 鏈少的碳鏈。 進而’ “聚合性不飽和基”係指具有聚合性的不飽和 鍵，即’乙烯基等聚合性雙鍵、乙炔基等聚合性三鍵等。 這些不飽和鍵只要具有聚合性，對其結構就沒有特別限定 ’例如亦可爲構成環狀結構一部分的如環己烯基。 [2]本發明的構成： 本發明的紫外線硬化型黏著劑組合物是含有（甲基）丙 燃酸系聚合物（A成分）、具有聚合性不飽和基的羧酸及其 寡聚物中至少一種（B成分）、光聚合起始劑（c成分）、矽烷 偶合劑（D成分）以及除上述a成分和上述b成分以外的具 有聚合性不飽和基的化合物（E成分）作爲構成成分的黏著 劑組合物。以下，對各成分進行說明。 [2-1](甲基）丙烯酸系聚合物（A成分）： (甲基）丙稀酸系聚合物”係指在主鏈中含有來自（甲 基）丙稀酸系單體的重覆單位的聚合物。本發明的黏著劑 -11 - 201105760 組合物使用在支鏈具有能交聯的反應性官能基的“交聯性 (甲基）丙烯酸系聚合物”作爲“（甲基）丙烯酸系聚合物” [2-1A]主鏈： “交聯性（甲基）丙烯酸系聚合物”的主鏈含有來自（甲 基）丙烯酸系單體的重覆單位。 一般’ “（甲基）丙烯酸系單體”係指丙烯酸、甲基丙 烯酸或此等之鹽或酯。具體而言，除丙烯酸、甲基丙烯酸 以外’可舉例如（甲基）丙烯酸銨、（甲基）丙烯酸鈉、（甲基 )丙烯酸鉀等（甲基）丙烯酸鹽類；（甲基）丙烯酸甲酯、（甲 基）丙烯酸乙酯、（甲基）丙烯酸正丙酯、（甲基）丙烯酸異丙 酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸異丁酯、（甲基） 丙烯酸叔丁酯、（甲基）丙烯酸正戊酯、（甲基）丙烯酸異戊 酯、（甲基）丙烯酸正己酯、（甲基）丙烯酸正辛酯、（甲基） 丙烯酸2-乙基己酯、（甲基）丙烯酸月桂酯、（甲基）丙烯酸 環己酯等（甲基）丙烯酸酯類；（甲基）丙烯酸2.·羥乙酯、（甲 基）丙烯酸2-羥丙酯、（甲基）丙烯酸3-羥丙酯、（甲基）丙烯 酸4-羥丁酯等含有羥基的（甲基）丙烯酸酯類等。 A成分較佳含有來源於上述（甲基）丙烯酸系單體中的（ 甲基）丙烯酸酯類的重覆單位，更佳含有來源於丙烯酸乙 酯、丙烯酸丁酯或丙烯酸2-乙基己酯的重覆單位，進一步 較佳含有來源於丙烯酸乙酯或丙烯酸丁酯的重覆單位，特 別較佳含有來源於丙烯酸乙酯的重覆單位。這是由於藉$ -12- 201105760 含有這些重覆單位，可以發揮良好的黏著特性。 並且，A成分既可以是主鏈僅含有一種（甲基）丙烯酸 系單體單元的均聚物，或是含有2種以上（甲基）丙烯酸系 單體單元的共聚物。但是，從製成黏著劑或黏接劑時容易 精密地調整其塗膜（黏著劑層）的物性的觀點而言，較佳含 有2種以上（甲基）丙烯酸系單體單元的共聚物。這種情況 下，特別較佳含有來源於丙烯酸乙酯和丙烯酸丁酯的重覆 單位。 此外，A成分只要含有（甲基）丙烯酸系單體單元就足 夠，無需全部的重覆單位都是（甲基）丙烯酸系單體單元。 即，只要不妨礙本發明的效果，或含有（甲基）丙烯酸系單 體以外的單體單元（有時記爲“其他的單體單元”）。 對於"（甲基）丙烯酸系單體以外的單體”的種類沒有 特別限制，例如可以使用具有聚合性不飽和鍵的單體。具 體可舉出（甲基）丙烯醯胺等（甲基）丙烯醯胺類；（甲基）丙 烯腈等（甲基）丙烯腈類；苯乙烯、α -甲基苯乙烯等芳香族 乙烯基類；乙酸乙烯酯、丙酸乙烯酯等羧酸乙烯酯類；馬 來酸酐、衣康酸、富馬酸等不飽和二羧酸類；Ν-乙烯基吡 咯烷酮、Ν-乙烯基己內醯胺等Ν-乙烯基內醯胺類等。 Α成分較佳含有來源於上述“（甲基）丙烯酸系單體以 外的單體”中的（甲基）丙烯腈類、特別是丙烯腈的重覆單 位。藉由含有這些重覆單位，能夠提高黏著劑的凝集力， 進而能夠提高再剝離性。 在A成分的（甲基）丙烯酸系單體單元中，以構成（甲 -13- 201105760 基）丙烯酸系聚合物主鏈的單體單元的合計爲100質量°/。時 ，（甲基）丙烯酸系單體單元的含量較佳爲50質量％以上， 更佳爲60質量％以上，特佳爲70質量％以上。其中，較 佳主鏈全部由（甲基）丙烯酸系單體單元構成。（甲基）丙烯 酸系單體單元的含量小於50質量％時，具有黏著特性降低 的傾向，所以不宜。 作爲含有（甲基）丙烯酸系單體以外的單體的情況下的 具體組成，較佳具有（甲基）丙烯酸酯單元和丙輝腈單元的（ 甲基）丙烯酸系聚合物。其中，特佳如下的（甲基）丙烯酸系 聚合物，即，以構成（甲基）丙烯酸系聚合物主鏈的單體單 元的合計爲100質量％時，含有70〜98.9質量％的（甲基） 丙烯酸酯單元、1〜20質量％的丙烯腈單元、〇.1〜1〇質量 %的其他單體單元的（甲基）丙烯酸系聚合物。 [2-1B]支鏈： "交聯性（甲基）丙烯酸系聚合物”的支鏈具有能交聯 的反應性官能基。由於在支鏈具有能交聯的反應性官能基 ，因此藉由紫外線照射使得A成分與其他的聚合成分（例 如’後述的B成分、E成分等）交聯自不必說，a成分彼此 也都交聯。由此’能夠使形成的黏著層的凝膠成分的濃度 增加，能夠形成黏著性能優異、強度和耐久性（特別是光 學耐濕熱性）高的黏著層。 “交聯性（甲基）丙烯酸系聚合物”在支鏈中至少具有 含有（甲基）丙烯醯基骨架的（甲基）丙烯醯系官能基作爲能 交聯的反應性官能基。換言之，能夠使用對成爲基本骨架 -14 - 201105760 的（甲基）丙烯酸系聚合物藉由化學修飾導入（甲基）丙烯醯 系官能基而進行了改性的（甲基）丙烯酸系聚合物。 本說明書中所稱含有（甲基）丙稀醯基骨架的官能基 係ia含有下述通式（1)所不的“丙嫌醯基骨架”或下述通 式（2)所示的“甲基丙烯醯基骨架”的官能基，也包括構成 丙烯醯基骨架或甲基丙烯醯基骨架的全部或部分氫原子被 其他原子或官能基取代而得的取代衍生物。在本說明書中 ，有時將這些官能基稱爲“（甲基）丙烯醯系官能基”。 【化1】201105760 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to an ultraviolet curable adhesive composition which exhibits an adhesive force by ultraviolet irradiation. [Prior Art] In recent years, electronic image display devices (electronic displays) such as plasma displays and liquid crystal displays have been widely used. For a plasma display, it is necessary to attach an antireflection film for improving visibility on the surface of the display, and for a liquid crystal display, it is also necessary to attach a polarizing plate or other functional film to the surface or the inner surface of the display. In the use of attaching such a functional film, the use of an adhesive using a (meth)acrylic polymer sharply increases. Conventionally, in the use of a functional film, a so-called thermosetting adhesive is used. The thermosetting adhesive is an adhesive prepared by dissolving a (meth)acrylic polymer in an organic solvent. A thermal crosslinking agent is added to the main component before use, and adhesion is exhibited by heating (see Patent Documents 1 and 2). Such a thermosetting adhesive is applied to a surface such as a functional film by adding a thermal crosslinking agent to the main component, and volatilizes the solvent component contained in the main component by heating, and then, under normal temperature or heating, The cross-linking reaction is caused by the thermal crosslinking agent after a few days of aging, and the adhesive property is stabilized. For example, 'Patent Document 1 discloses an adhesive composition for optical parts' which contains an acrylic polymer (A) and an acrylic system. a polymer (9)), a decane coupling agent, and a thermal crosslinking agent; wherein the acrylic polymer (A) 201105760 has a (meth)acrylic acid alkyl ester and an unsaturated carboxylic acid as a monomer unit, and has a weight average molecular weight of 500,000. The acrylic polymer (B) has a (meth)acrylic acid alkyl ester and an unsaturated carboxylic acid as a monomer unit, a carboxylic acid equivalent of the acrylic polymer (A), and a weight average molecular weight of 0.2 to 50,000. . Further, Patent Document 1 discloses an example in which the adhesive composition is prepared in a solvent-containing state, dried and crosslinked at 110 ° C for 5 minutes to form an adhesive layer, and then at a high temperature of 50 ° C. After 24 hours of aging, adhesive optical parts were obtained. Further, Patent Document 2 discloses an active energy ray-curable adhesive composition for an optical layer comprising an acrylic resin containing an ethylenically unsaturated group, a photopolymerization initiator, and a decane compound. Further, Patent Document 2 describes that the adhesive composition is diluted with a solvent to a concentration of 10 to 20% by mass, preferably using a thermal crosslinking agent, and is disclosed at a high temperature of 40 ° C. An example of a long-term maturity of 4 days. These thermosetting adhesives have the advantages of good adhesion, high durability, high coating accuracy, and the like, but the problem is that aging as described above is required. That is, the product cannot be used immediately, and it takes time and space to be matured, so in addition to the cumbersome handling of the product, there is a problem in the increase in the cost of storage. Therefore, there has been proposed a solution of an ultraviolet curable adhesive which does not require high temperature and long-term aging by using a UV hardening component having a polymerizable unsaturated group. For example, an ultraviolet curable resin composition containing an acrylic copolymer having a predetermined weight average molecular weight, a monomer having two unsaturated double bonds in the molecule, an alkylene glycol chain in the molecule, and -6 - 201105760 Photopolymerization initiator (refer to Patent Document 3). Further, a reactive polymer (A) having a double bond, a (meth) acrylate monomer (B), a monofunctional monomer (c) copolymerizable with (B), and a photopolymerization initiator are proposed. The ultraviolet curable adhesive composition composed of (D) (see Patent Document 4). Further, the present inventors have also proposed an ultraviolet curable adhesive composition containing a reactive polymer, a photopolymerization initiator, and a monomer having a polymerizable double bond. The above reactive polymer is contained in the main chain. A modified (meth)acrylic polymer having a repeating unit of a (meth)acrylic monomer and having a (meth)acryl fluorene-based functional group in a branched chain (see Patent Document 5) 〇 Patent Document 1: Japan Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 2006-316. In the case of irradiating ultraviolet rays to the ultraviolet curable adhesive composition described in Patent Documents 3 to 5, the photopolymerization initiator acts to polymerize the polymerizable monomer or the reactive polymer. The reaction proceeds and shows adhesion. Therefore, there is an advantage that it does not require heating when the adhesive force is generated, and the adhesion can be exhibited almost at the same time as the ultraviolet ray is irradiated. Further, since the adhesive does not contain a thermal crosslinking agent, it has excellent characteristics which are not required for such a thermosetting adhesive which does not require aging time 201105760 (no aging). However, the ultraviolet curable adhesive has a tendency to be inferior in optical durability and removability as compared with a thermosetting adhesive, and is also inferable in coating suitability at high speed and ultraviolet curability in an air atmosphere. It is fully satisfying. In particular, adhesives used in the application of functional films to electronic displays require further improvement in technical standards, such as increased productivity (coating speed), improved coating accuracy, and thinning of the adhesive layer with the product. Thin film, etc., have problems to be solved. The present invention has been made to solve the above problems of the prior art, that is, to provide an ultraviolet curable adhesive composition which has ultraviolet ray hardening under an air environment while exhibiting the advantages of an ultraviolet curing adhesive which does not require aging. Excellent in performance, it has performance comparable to that of a thermosetting adhesive in terms of optical durability, removability, productivity (coating speed), coating suitability (coating accuracy, film formation of an adhesive layer, etc.). The present inventors have made intensive studies to solve the problems of the above-described prior art. As a result, it has been considered that a crosslinkable (meth)acrylic acid having a polymerizable (meth)acryl fluorenyl group introduced into a branch is used at a predetermined composition ratio. A polymerizable carboxylic acid having a polymerizable unsaturated group such as a polymer or (meth)acrylic acid, a fluorenylphosphine oxide-based photopolymerization initiator, and a decane coupling agent having an epoxy functional group to solve the above problem has been completed. this invention. Specifically, the following ultraviolet curable adhesive composition is provided by the present invention. [1] An ultraviolet curable adhesive composition comprising at least one of a (meth)acrylic acid-based polymer (component A), a carboxylic acid having a polymerizable unsaturated group, and an oligomer thereof (component B) ), photopolymerization initiator (component C), 矽-8-201105760 alkane coupling agent (component D), and a compound (E component) having a polymerizable unsaturated group other than the above-mentioned A component and the above-mentioned component B as a constituent component The component A is a repeating unit derived from a (meth)acrylic monomer in the main chain, and a (meth)acryl fluorene-based functional group having a (meth)acryl fluorenyl skeleton in the branched chain, and each 100 g of polymer contains 0.5 to 20 mmol of the above (meth) propylene fluorene-based functional group, glass transition temperature (Tg) is -55 ° C to 〇 ° C, and weight average molecular weight (Mw) is in the range of 200,000 to 1,000,000. a crosslinkable (meth)acrylic polymer, wherein the component C is a fluorenylphosphine oxide-based photopolymerization initiator, and the component D is a decane coupling agent having an epoxy functional group, and the component A and the component B described above are used. When the total amount is 100 parts by mass, it contains 80 to 99·5 Parts of the component A, the 0.5~20 parts by mass of said component B, 0.05~3 parts by mass of the component C, D 0.1~5 parts by mass of the component, 0~20 parts by mass of the component E. [2] The ultraviolet curable adhesive composition according to the above [1], wherein the above-mentioned A component is an alkoxyalkyl group-functional group having an alkoxyalkyl group skeleton in a branch, and each of the groups The g polymer contains a crosslinkable (meth)acrylic polymer having 4 to 4 mmol of the above alkoxyalkylalkyl functional group. [3] The ultraviolet curable adhesive composition according to the above [1], wherein the above-mentioned E component is a polyfunctional compound having two or more (meth)acrylonitrile-based functional groups per molecule. When the total amount of the A component and the component B described above is 100 parts by mass, the oligo contains 5 to 20 parts by mass of the above E component. [A] The ultraviolet curable adhesive composition according to the above [3], wherein the above-mentioned E component is an aliphatic polyester as a basic skeleton, and the weight average molecular weight (Mw) is in the range of 1,000 to 10,000. Polyfunctional oligomers. [5] The ultraviolet curable adhesive composition according to the above [3], wherein the above-mentioned E component is a polyfunctional oligomer having a bisphenol as a basic skeleton and a weight average molecular weight (Mw) in the range of 400 to 2,000. . [6] The ultraviolet curable adhesive composition according to the above [1] or [2], wherein the benzophenone compound having Xmax in the wavelength range of 350 to 400 nm is contained as an ultraviolet absorber (F component). [7] The ultraviolet curable adhesive composition according to the above [1] or [2] wherein the above-mentioned C component is 2,4,6-trimethylbenzylidene-diphenylphosphine oxide. The ultraviolet curable adhesive composition of the present invention does not require aging, and is excellent in ultraviolet curability in an air environment, and has optical durability, removability, productivity (coating speed), and coating suitability (coating accuracy, The film of the adhesive layer, etc., has properties comparable to those of the thermosetting adhesive. [Embodiment] Hereinafter, the mode for carrying out the ultraviolet curable adhesive composition of the present invention will be specifically described. However, the present invention encompasses all embodiments having the technical features of the invention, and is not limited to the embodiments shown below. [1] Definitions and the like: -10- 201105760 In the following description, the term "(meth)acrylic polymer" means a repeating unit derived from a (meth)acrylic monomer in the main chain (hereinafter, The polymer "repeating unit derived from monomer X" is abbreviated as "X unit"). Further, the "backbone" of a polymer (including an oligomer) means a carbon chain having the largest number of carbon atoms in the polymer. On the other hand, "branched chain" means a carbon chain having a smaller number of carbon atoms than a main chain branched from a main chain of a polymer (a carbon chain having the largest number of carbon atoms). Further, the term "polymerizable unsaturated group" means a polymerizable unsaturated bond, that is, a polymerizable double bond such as a vinyl group or a polymerizable triple bond such as an ethynyl group. The unsaturated bond is not particularly limited as long as it has polymerizability. For example, it may be a cyclohexenyl group which forms a part of the cyclic structure. [2] The composition of the present invention: The ultraviolet curable adhesive composition of the present invention contains a (meth)acrylic acid-based polymer (component A), a carboxylic acid having a polymerizable unsaturated group, and an oligomer thereof. At least one (component B), a photopolymerization initiator (c component), a decane coupling agent (component D), and a compound (E component) having a polymerizable unsaturated group other than the above-described a component and the above b component as constituent components Adhesive composition. Hereinafter, each component will be described. [2-1] (Meth)acrylic polymer (component A): (meth)acrylic polymer means a repeat containing a (meth)acrylic monomer in the main chain Polymer of the unit. Adhesive of the present invention-11 - 201105760 The composition uses "crosslinkable (meth)acrylic polymer" having a crosslinkable reactive functional group in the branch as "(meth)acrylic acid" "Polymer" [2-1A] Main chain: The main chain of "crosslinkable (meth)acrylic polymer" contains a repeating unit derived from a (meth)acrylic monomer. Generally '(Methyl) "Acrylic monomer" means acrylic acid, methacrylic acid or a salt or ester thereof. Specifically, in addition to acrylic acid and methacrylic acid, for example, ammonium (meth)acrylate or sodium (meth)acrylate may be mentioned. (Meth) acrylate such as potassium methacrylate; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (A) Base) n-butyl acrylate, isobutyl (meth)acrylate, (meth) propyl Tert-butyl acid ester, n-amyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate (meth)acrylates such as esters, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, (hydroxy)ethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (hydroxy)-containing (meth) acrylate such as 3-hydroxypropyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate, etc. The component A preferably contains the above-mentioned (meth)acrylic monomer. The repeating unit of the (meth) acrylate is more preferably a repeating unit derived from ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate, and further preferably contains ethyl acrylate or acrylic acid. The repeating unit of the butyl ester particularly preferably contains a repeating unit derived from ethyl acrylate. This is because the heavy-duty unit is contained in the borrowing unit of $ -12-201105760, and the component A can be used. The main chain contains only one (meth) propylene A homopolymer of a monomer unit or a copolymer containing two or more (meth)acrylic monomer units. However, it is easy to precisely adjust the coating film (adhesive) from the time of making an adhesive or an adhesive. From the viewpoint of physical properties of the layer, a copolymer of two or more kinds of (meth)acrylic monomer units is preferred. In this case, it is particularly preferable to contain a repeating unit derived from ethyl acrylate and butyl acrylate. Further, the component A is sufficient as long as it contains a (meth)acrylic monomer unit, and it is not necessary that all of the repeating units are (meth)acrylic monomer units. That is, as long as the effects of the present invention are not impaired or contained ( A monomer unit other than the methyl group-acrylic monomer (may be referred to as "another monomer unit"). The type of the "method other than the (meth)acrylic monomer" is not particularly limited, and for example, A monomer having a polymerizable unsaturated bond is used. Specific examples thereof include (meth)acrylamide such as (meth)acrylamide; (meth)acrylonitriles such as (meth)acrylonitrile; and aromatic vinyls such as styrene and α-methylstyrene; Vinyl esters of vinyl acetate, vinyl propionate, etc.; unsaturated dicarboxylic acids such as maleic anhydride, itaconic acid, fumaric acid; antimony-vinylpyrrolidone, fluorene-vinyl caprolactam, etc. Ν-vinyl endamides and the like. The bismuth component preferably contains a repeating unit of (meth)acrylonitrile, particularly acrylonitrile, derived from the above-mentioned "monomer other than (meth)acrylic monomer". By including these repeating units, the cohesive force of the adhesive can be improved, and the removability can be improved. In the (meth)acrylic monomer unit of the component A, the total of the monomer units constituting the main chain of the (A-13-201105760-based) acrylic polymer is 100% by mass. The content of the (meth)acrylic monomer unit is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more. Among them, the preferred main chain is composed entirely of (meth)acrylic monomer units. When the content of the (meth)acrylic monomer unit is less than 50% by mass, the adhesive property tends to be lowered, which is not preferable. As a specific composition in the case of containing a monomer other than the (meth)acrylic monomer, a (meth)acrylic polymer having a (meth) acrylate unit and a propionitrile unit is preferable. In particular, when the total amount of the monomer units constituting the main chain of the (meth)acrylic polymer is 100% by mass, the content of the (meth)acrylic polymer is 70% to 89.9% by mass. (meth)acrylic polymer having an acrylate unit, 1 to 20% by mass of an acrylonitrile unit, and 1 to 1% by mass of another monomer unit. [2-1B] Branch: The branch of the "crosslinkable (meth)acrylic polymer" has a reactive functional group capable of crosslinking. Since it has a reactive functional group capable of crosslinking in the branch, It is necessary to crosslink the component A with another polymerization component (for example, 'B component, E component, etc. which will be described later) by ultraviolet irradiation, and it is needless to say that the component a is also cross-linked. Thus, the gel of the formed adhesive layer can be formed. When the concentration of the component is increased, an adhesive layer having excellent adhesion, strength, and durability (especially optical heat and humidity resistance) can be formed. "The crosslinkable (meth)acrylic polymer" has at least a branch in the branch (A) The (meth) acrylonitrile-based functional group of the acrylonitrile-based skeleton serves as a crosslinkable reactive functional group. In other words, it is possible to use a (meth)acrylic polymer which is a basic skeleton-14 - 201105760 by chemistry The (meth)acrylic polymer modified by introducing a (meth)acrylonitrile-based functional group is modified. The functional group ia containing a (meth) acrylonitrile-based skeleton in the present specification contains the following Formula 1 The functional group of the "methacrylic fluorenyl skeleton" represented by the following formula (2) or the propylene fluorenyl skeleton or the methacryl fluorenyl skeleton Or a substituted derivative in which a part of hydrogen atoms are substituted by another atom or a functional group. In the present specification, these functional groups may be referred to as "(meth)acryl oxime-based functional groups."

【化2】 …⑴ …⑵ 作爲代表性的例子，可舉出例如丙烯醯基、甲基丙烯 醯基等。丙烯醯基在能夠賦予優異的聚合性（進而紫外線 硬化性）這一點上是較佳的，與丙烯醯基相比’甲基丙烯 醯基在安全性高這一點上是較佳的。 並且，（甲基）丙烯醯系官能基沒有必要是丙烯醯基骨 架或甲基丙烯醯基骨架能直接與主鏈結合的結構的官能基 ，或是丙烯醯基骨架或甲基丙烯醯基骨架藉由某種原子或 官能基能間接與主鏈結合的結構的官能基（例如’丙烯醯 -15- 201105760 氧基等）。 (甲基）丙烯醯系官能基的含量根據主鏈的結構、重量 平均分子量、玻璃轉移溫度、黏著物性等而異。但每100g 聚合物必須含有0·5〜20mmo1的（甲基）丙烯醯系官能基， 較佳爲含有〇·5〜15mmo1’特佳爲含有0.5〜lOmmol。例 如，重量平均分子量爲42萬的交聯性（甲基）丙烯酸系聚合 物時，則較佳爲每1分子聚合物具有2.1〜84個（甲基）丙 烯醯系官能基，更佳爲具有2.1〜63個，特佳爲具有2.1 〜4 2個。 (甲基）丙烯醯系官能基的含量小於〇.5mmol/l〇〇g時， 不能充分增加凝膠成分，有時黏著劑層的強度變得不足。 於情況下，1)在將塗佈了黏著劑組合物的薄膜產品等卷取 成卷筒時，黏著劑組合物有可能會因薄膜產品的自重而被 壓散壞，出現黏著劑組合物從卷筒的端部、側緣滲出的不 良情況。並且，2)近年來，作爲塗佈了黏著劑組合物的薄 膜產品等的保護膜，有時會使用形成有凹凸的壓紋薄膜， 因此還可能出現上述薄膜產品等上存留壓紋模樣的壓痕的 不良情況。爲了解決這樣的問題，較佳爲使（甲基）丙烯醯 系官能基的含量爲 〇.5mmol/100g以上。但含量超過 2〇mmol/100g時，會有黏著劑的耐濕熱性降低之虞。 “交聯性（甲基）丙烯酸系聚合物”的支鏈，宜爲除具 有（甲基）丙烯醯系官能基作爲反應性官能基之外，還具有 含有下述通式（3)所示的烷氧矽烷基骨架的烷氧矽烷基系官 能基作爲反應性官能基。 -16- 201105760 【化3】 R一Ο ——Si— --(3) (式中，R表示可被取代的烷基）》 在支鏈中具有烷氧矽烷基系官能基的聚合物，在使用 玻璃材料作爲被著物的情況下的耐久性、特別是耐熱性或 耐濕熱性優異。具體而言，其特徵係即使在高溫條件下或 高溫•高濕條件下也能顯示優異的密著性、黏著特性優異 。進而，藉由進行此等改性，即使在B成分量少的情況下 ，也能夠獲得在耐熱•耐濕熱條件下黏著特性也不易下降 的黏著組合物。 本說明書中所稱“烷氧矽烷基骨架”係指如上述通式 (3)所示，在矽原子上至少結合有1個烷氧基的骨架之意。 因此，“含有烷氧矽烷基骨架的官能基”還包括在矽原子 上除烷氧基以外，還結合有某種原子、除烷氧基以外的官 能基的官能基。在本說明書中，將這些官能基稱爲“烷氧 矽烷基系官能基”。 具體可舉如，三烷氧矽烷基、二烷氧矽烷基、單烷氧 矽烷基等。其中，從容易取得的三烷氧基矽烷衍生物進行 導入的理由，特別宜爲選用三烷氧矽烷基。 並且，烷氧矽烷基系官能基沒有必要是烷氧矽烷基骨 -17- 201105760 架能直接與主鏈結合的結構的官能基，或是烷氧矽烷基骨 架藉由某種原子或官能基能間接結合的結構的官能基（例 如，三烷氧矽烷基烷基等）。 烷氧矽烷基系官能基的適當含量根據主鏈結構、重量 平均分子量' 玻璃轉移溫度等而異。但較佳爲每100g聚 合物含有0.04〜4mmol的烷氧矽烷基系官能基，更佳爲含 有 0.04〜2mmol，特佳爲含有 0.04〜lmmol。例如，重量 平均分子量爲42萬的交聯性（甲基）丙烯酸系聚合物時，則 較佳爲每1分子聚合物具有0.17〜17個烷氧矽烷基系官 能基，更佳爲具有0.17〜8.5個，特佳爲具有0.17〜4.2 個。 垸氧砂院基系官能基的含量小於0.04mmol/100g時， 有可能無法充分獲得烷氧矽烷基系官能基帶來的改性效果 (具體而言，如使用玻璃材料作爲被著物的情況下的耐久 性、特別是耐熱性、耐濕熱性優異等效果等）。另一方面 ’含量超過4mmol/l〇〇g時’雖然因聚合物組成等而異， 但有隨時間經過而導致聚合物黏度上升的傾向。 對交聯性（甲基）丙烯酸系聚合物的製造方法沒有特別 限定’例如’對於作爲基本骨架的（甲基）丙烯酸系聚合物 ’可採用藉由化學修飾導入（甲基）丙烯醯系官能基和烷氧 矽烷基系官能基的方法（化學修飾法）來製造。 作爲化學修飾法的具體例，例如可舉出以具有經基的 (甲基）丙嫌酸系聚合物爲基質聚合物，使具有異氰酸酯基 的（甲基）丙烯酸系化合物或具有異氰酸酯基的烷氧基矽烷 -18 - 201105760 系化合物直接結合於該基質聚合物的羥基上，由此導入（ 甲基）丙烯醯系官能基和烷氧矽烷基系官能基的方法（直接 結合法）。 “具有羥基的（甲基）丙烯酸系聚合物”可以藉由使丙 烯酸2-羥乙酯等含有羥基的（甲基）丙烯酸酯類與其他（甲 基）丙烯酸系單體共聚而得到。作爲“具有異氰酸酯基的（ 甲基）丙烯酸系化合物”，可舉出例如2 -甲基丙烯醯氧乙 基異氰酸酯（商品名：Karenz MOI，昭和電工公司製造）、 2-丙烯醯氧乙基異氰酸酯（商品名·· Karenz AOI，昭和電工 公司製造）、2-(2-甲基丙烯醯氧基乙基氧基）乙基異氰酸酯 (商品名：Karenz MOI EG，昭和電工公司製造）等。另一 方面’作爲具有異氰酸酯基的烷氧基矽烷系化合物，可舉 出例如3-異氰酸酯基丙基三乙氧基矽烷（商品名：KBE-9007，信越化學工業公司製造）等。 另外，化學修飾法方面，或採用使聚異氰酸酯化合物 等多官能性化合物結合於基質聚合物的羥基上，藉由該多 官能性化合物間接結合具有羥基的（甲基）丙烯酸系化合物 或具有羥基的烷氧基矽烷系化合物，由此導入（甲基）丙烯 醯系官能基和烷氧矽烷基系官能基的方法（間接結合法）。 作爲“聚異氰酸酯化合物”，可舉出例如亞甲基二苯 基二異氰酸酯（MDI)、甲苯二異氰酸酯（TDI)、二異氰酸異 佛爾酮（IPDI)等。作爲"具有羥基的（甲基）丙烯酸系化合 物” ’可舉例如已述的含有羥基的（甲基）丙烯酸酯類等。 作爲“具有羥基的烷氧基矽烷系化合物”，可舉例如3·羥 -19- 201105760 基丙基三乙氧基矽烷等》 基質聚合物的製造方法沒有特別的限定，能夠使用溶 液聚合、懸浮聚合 '塊狀聚合等現有公知的方法。例如， 如果是使用溶液聚合的情況，則藉由在有機溶劑等適當的 溶劑中添加聚合起始劑，且在氮氣流下加熱攪拌的方法等 ’使（甲基）丙烯酸酯系單體成分，根據需要使用能與其共 聚的乙烯性不飽和單體成分構成的乙烯性不飽和單體混合 物聚合。 另外’作爲基質聚合物，可使用市售的丙烯酸系共聚 物。例如可使用商品名：PARACRON AW4500H(固體成分 :40%，Mw : 32萬’ Tg : -8°C，甲苯溶劑，根上工業公司製 造）、商品名：PARACRON AS3000E(固體成分：30%，Mw :65萬’ Tg : -3 6°C，甲苯溶劑，根上工業公司製造）等。 作爲交聯性（甲基）丙烯酸系聚合物的製造方法，或舉 出如下方法，即，對於烷氧矽烷基系官能基而言，將具有 院氧矽烷基系官能基的單體與其他單體共聚而引入到基質 聚合物的骨架中；對於（甲基）丙烯醯系官能基而言，藉由 將該引入有烷氧矽烷基系官能基的基質聚合物進行化學修 飾來導入之方法（聚合法）。 聚合法更具體的說明，其爲如下的方法：將含有（甲 基）丙烯酸系單體、具有羥基的單體和具有烷氧矽烷基系 官能基的單體的單體混合物進行聚合反應，得到在支鏈中 具有上述烷氧矽烷基系官能基和羥基的第1改性（甲基）丙 稀酸系聚合物，以該第1改性（甲基）丙烯酸系聚合物爲基 -20- 201105760 質聚合物，藉由化學修飾在該基質聚合物的羥基上導入（ 甲基）丙烯醯系官能基，得到第2交聯性（甲基）丙烯酸系聚 合物。 作爲“具有烷氧矽烷基系官能基的單體”，可舉例如 甲基丙烯醯氧基三烷氧基矽烷、丙烯醯氧基三烷氧基矽烷 、乙烯基三烷氧基矽烷等。其中，在聚合時的反應性高這 一點上，較佳爲使用甲基丙烯醯氧基三烷氧基矽烷或丙烯 醯氧基三烷氧基矽烷，特佳爲使用丙烯醯氧基三烷氧基矽 烷。 [2-1C]平均分子量： A成分的重量平均分子量（Mw)在20萬〜100萬的範 圍內。如果重量平均分子量小於2 0萬，則製成黏著劑時 在被著物上殘留的糊料會增加，存在會污染被著物的傾向 ，故不宜。另一方面，如果重量平均分子量超過100萬， 則與溶劑、單體的混合性不良，調製組合物時的附著損失 增加，並且，可能出現塗佈黏著劑時塗佈液的操作性惡化 和塗佈性降低等不良情況之虞。更具體而言，在作爲塗佈 物件的薄膜等上會出現塗佈條痕或塗佈液發生拉絲等狀況 。塗佈液的拉絲會經由塗佈輥的旋轉而使塗佈液的黏度上 升，故不宜。 爲了更切實地獲得上述效果，重量平均分子量在25 萬〜80萬的範圍內爲佳，特佳爲40萬〜60萬的範圍內。 藉由適當控制成爲主鏈的（甲基）丙烯酸系聚合物聚合 -21 - 201105760 時的聚合條件’例如聚合起始劑的種類和量、鏈轉移劑的 種類和量、溶劑的種類和量、反應溫度、反應時間等，能 夠將重量平均分子量調整在上述範圍內。此外，還可以從 市售的（甲基）丙烯酸系聚合物中適當選擇具有所需重量平 均分子量的聚合物，將其改性使用之。 此外’本說明書中所稱“重量平均分子量”係指用 GPC法（凝膠滲透色譜法）測定得到的按聚苯乙烯換算的重 量平均分子量之意。 具體而言，較佳以各試樣的固體成分爲0.025%的方 式將各試樣溶解在四氫呋喃（THF)中，在以下的條件下對 該溶液進行測定。（l)GPC測定裝置：高速GPC裝置HLCN 8 820(商品名，東曹公司製造）、（2)柱：TSK-GEL系列（商 品名’東曹公司製造）、（3)流動相：THF、（4)流量：lml/ 分鐘、（5)柱溫：40°C、（6)檢測器：RI' UV、（7)換算：聚 苯乙烯。 [2-1D]玻璃轉移溫度（Tg): A成分的玻璃轉移溫度（Tg)在-55〜0°C的範圍內。藉 由使玻璃轉移溫度處於該範圍內，在製成黏著劑時會表現 出適度的黏著性能。如果玻璃轉移溫度超過0 °C，則製成 黏著劑時，有黏著強度降低、或塗佈性會隨著與溶劑的混 合性降低而降低的傾向，故不宜。另一方面，如果玻璃轉 移溫度小於-55 °C，則製成黏著劑時，在被著物上殘留的 糊料增加，而有污染被著物的傾向，故不宜。爲了更切實 -22- 201105760 可靠地獲得這些效果，較佳的玻璃轉移溫度在-4 0〜-1 0 °C 的範圍內，更佳在-30〜-20 °C的範圍內。 藉由對構成爲主鏈的（甲基）丙烯酸系聚合物的重覆單 位的種類和比例進行適當控制，能夠將玻璃轉移溫度調整 到上述範圍內。由來源於單體Μ,、M2、...Mn的重覆單位 構成的聚合物P的玻璃轉移溫度（理論値），能夠藉由FOX 公式（下述數學式（1))算出，所以可參考該數學式調整重覆 單位的種類和比例》 l/TgP = ri/TgMi+r2/TgM2"-+r„/TgM„ (1) (其中，TgP :聚合物P的玻璃轉移溫度（K)、Tglvh :單體 的均聚物的玻璃轉移溫度（K)、TgM2:單體M2的均聚 物的玻璃轉移溫度（K) ' TgMn :單體Mn的均聚物的玻璃轉 移溫度（Κ)' η:聚合物P中單體M!單元的質量分率、r2 :聚合物P中單體M2單元的質量分率、rn:聚合物p中 單體]^11單元的質量分率） 下面爲更具體的說明。由於構成A成分的交聯性（甲 基）丙烯酸系聚合物的玻璃轉移溫度較低，爲-55〜0。(：，所 以聚合時’在以均聚物的玻璃轉移溫度較低的單體，例如 丙烯酸丁酯（Tg: -55。(：）、丙烯酸乙酯（Tg: -24。(：）、丙稀 酸2-乙基己酯（Tg:-85t：)等爲主成分的單體混合物中， 適當添加均聚物的玻璃轉移溫度較高的單體，例如甲基丙 稀酸甲酯（Tg : 105。〇）、苯乙烯（Tg ·· 100。〇)等進行聚合反 -23- 201105760 應，能夠得到具有所需玻璃轉移溫度的聚合物。此外，或 從市售的（甲基）丙烯酸系聚合物中適當選擇具有所需坡璃 轉移溫度的聚合物，將其改性使用之。 此外’本說明書中所稱“玻璃轉移溫度”係指基於 J IS K 7 1 2 1 (塑膠的轉變溫度測定方法）測定得到的玻璃轉 移溫度。 [2-1E]含量： 構成A成分的交聯性（甲基）丙烯酸系聚合物的含量， 雖然根據A成分的聚合物的結構、被著物的種類、所要求 的黏著特性等而異，但以A成分和B成分的總量爲1 〇〇質 量份時’必須使該交聯性（甲基）丙烯酸系聚合物爲80〜 99.5質量份。含量小於80質量份時，存在黏著力降低的 傾向，故不宜。另一方面，含量超過99.5質量份時，存 在黏著層的耐久性會因凝集力不足而降低的傾向，故不宜 〇 爲了更切實可靠地得到上述效果，較佳爲使A成分的 含量爲85〜99.5質量份，更佳爲90〜99_5質量份。 [2-2]具有聚合性不飽和基的羧酸類（B成分）： 本發明的組合物含有具有聚合性不飽和基的羧酸及其 寡聚物中的至少一種（B成分）。藉由添加B成分，能夠得 到即使在氧存在下紫外線硬化性也不受損，被膜強度和對 基材的密合性也得到提高，而且，即使不使用熱交聯劑， -24- 201105760 在耐熱•耐濕熱條件下黏著特性也不易下降的黏著組合物 。即，在產生黏著物性方面不需要熟成。 “具有聚合性不飽和基的羧酸”係指具有聚合性雙鍵 或聚合性三鍵的羧酸之意。所謂的不飽和羧酸，更具體而 言’可舉出（甲基）丙烯酸、巴豆酸、馬來酸、馬來酸酐、 富馬酸、檸康酸、戊烯二酸、衣康酸、丙烯醯胺N -乙醇 酸、肉桂酸等。 “具有聚合性不飽和基的羧酸的寡聚物”係指重量平 均分子量爲1萬以下的上述羧酸的聚合物。例如除丙烯酸 二聚體外，還可舉出重量平均分子量爲1萬以下的丙烯酸 聚合物。 B成分的含量雖然根據A成分的聚合物結構、被著物 種類 '所要求的黏著特性等而異，但以A成分和B成分的 總量爲100質量份時，必須使B成分爲0.5〜20質量份。 含量不足0.5質量份時，黏著層的黏著耐久性、光學耐久 性有降低的傾向。另一方面，含量超過20質量份時，再 剝離時的糊料殘留有增多的傾向。爲了更切實可靠地獲得 上述效果，較佳使B成分的含量爲0.5〜15質量份，更佳 爲0 · 5〜1 0質量份。 [2-3]光聚合起始劑（C成分）： 本發明的組合物含有光聚合起始劑（C成分）作爲構成 成分。光聚合起始劑係指具有添加到聚合體系後藉由光照 射而引發聚合反應的作用的添加劑之意。即，C成分以紫 -25- 201105760 外線的照射爲契機，引發A成分和B成分的聚合反應，有 助於來源於B成分的聚合物、A成分與B成分的交聯物、 A成分自身的交聯物的形成。利用這樣的性質，能夠形成 強度高的黏著層。 作爲光聚合起始劑，例如，已知有α -羥蕋苯乙酮（商 品名：Irgacure 184, Ciba Specialty Chemicals 公司製造）、 α-胺基苯乙酮、苯偶姻系化合物等光聚合起始劑。本發 明的組合物中含有醯基氧化膦系化合物作爲光聚合起始劑 。這是因爲，加入醯基氧化膦系化合物，能夠將黏著層的 色調惡化（黃變）抑制在極輕微的水準，能夠形成光學特性 和耐久性優異的黏著劑。此外，亦有可能將本發明的黏著 劑組合物用於將機能性膜貼合於電子顯示器的用途等的情 況’因此有時會添加紫外線吸收劑（F成分），這種情況下 ’較佳爲使用一光聚合起始劑，其透過與F成分之吸收波 長相異的波長領域之紫外線，而能使Β成分產生聚合作用 —般’紫外線吸收劑的吸收波長被設定爲2 5 0〜 380nm左右的範圍。因此，宜選用在波長爲380nm以上的 紫外線的照射時，而能引發聚合反應的醯基氧化膦系化合 物。 此外’作爲在波長爲3 80nm以上的紫外線的照射時能 引發聚合反應的光聚合起始劑，有2 -苄基-2-二甲胺基-1-(4-嗎啉代苯基）-丁酮-i(商品名：irgacure 369，Ciba Specialty Chemicals公司製造）等α_胺基烷基苯酮系化合 -26- 201105760 物等存在。但是，在使用醯基氧化膦系化合物以外的光聚 合起始劑的情況下，會發生紫外線硬化性的降低、黏著層 的黃變。 "醯基氧化膦系化合物”係指具有醯基氧化膦結構（ 參照下述通式（4))的化合物。即，只要其結構的一部分具 有下述通式（4)所示的醯基氧化膦結構，無論其他部分的結 構如何，均包含在本發明所說的“醯基氧化膦系化合物” 中。因此，依據作爲樹脂組合物所要求的性能（紫外線硬 化性、顏色等），從這樣的各種物質中適當選擇最佳的物 質當作C成分即可。 【化4】(2) (2) As a representative example, for example, an acrylonitrile group, a methacryloyl group, or the like can be given. The acrylonitrile group is preferable in that it can impart excellent polymerizability (and further ultraviolet ray curability), and the methacryl fluorenyl group is preferable in that it is safer than the propylene fluorenyl group. Further, the (meth) propylene fluorene-based functional group is not necessarily a functional group of a structure in which an acryl fluorenyl skeleton or a methacryl fluorenyl skeleton can directly bond to a main chain, or an acryl fluorenyl skeleton or a methacryl fluorenyl skeleton. A functional group of a structure indirectly bonded to a main chain by an atom or a functional group (for example, 'acrylofluorene-15-201105760 oxy group, etc.). The content of the (meth)acrylonitrile-based functional group varies depending on the structure of the main chain, the weight average molecular weight, the glass transition temperature, the adhesive property, and the like. However, it is necessary to contain a (meth) acrylonitrile-based functional group of from 0.5 to 20 mmo1 per 100 g of the polymer, and preferably contains 〇5 to 15 mmo1' particularly preferably from 0.5 to 10 mmol. For example, in the case of a crosslinkable (meth)acrylic polymer having a weight average molecular weight of 420,000, it is preferably 2.1 to 84 (meth)acrylonitrile-based functional groups per molecule of the polymer, and more preferably 2.1 to 63, especially good for having 2.1 to 4 2 pieces. When the content of the (meth)acrylonitrile-based functional group is less than 〇5 mmol/l〇〇g, the gel component may not be sufficiently increased, and the strength of the adhesive layer may be insufficient. In the case, 1) when the film product or the like coated with the adhesive composition is taken up into a roll, the adhesive composition may be crushed due to the own weight of the film product, and the adhesive composition may appear from the adhesive composition. The end of the reel and the side edge oozing out. In addition, in recent years, an embossed film in which irregularities are formed may be used as a protective film of a film product or the like to which an adhesive composition is applied. Therefore, there may be a pressure on the above-mentioned film product or the like to retain an embossing pattern. Bad conditions. In order to solve such a problem, the content of the (meth) propylene fluorene functional group is preferably 〇. 5 mmol / 100 g or more. However, when the content exceeds 2 〇 mmol/100 g, the heat and humidity resistance of the adhesive may be lowered. The branch of the "crosslinkable (meth)acrylic polymer" preferably has a (meth) propylene fluorene-based functional group as a reactive functional group, and further has a formula represented by the following formula (3) The alkoxyalkylalkyl functional group of the alkoxyalkyl group has a reactive functional group. -16- 201105760 [Chemical 3] R-Ο-Si(-) (wherein, R represents an alkyl group which may be substituted)" A polymer having an alkoxyalkyl group-functional group in a branched chain, In the case of using a glass material as a target, it is excellent in durability, particularly heat resistance or moist heat resistance. Specifically, it is excellent in adhesion and adhesion characteristics even under high temperature conditions or high temperature and high humidity conditions. Further, by performing such modification, even when the amount of the component B is small, it is possible to obtain an adhesive composition which is less likely to have an adhesive property under heat and humidity resistance. The "alkoxyalkylene skeleton" as used in the specification means a skeleton having at least one alkoxy group bonded to a ruthenium atom as shown in the above formula (3). Therefore, the "functional group containing an alkoxyalkyl group skeleton" further includes a functional group which has a certain atom and a functional group other than the alkoxy group in addition to the alkoxy group. In the present specification, these functional groups are referred to as "alkoxyalkylene functional groups". Specific examples thereof include a trialkoxyalkylene group, a dialkoxyalkylene group, a monoalkyloxyalkylene group and the like. Among them, the reason why the trialkoxy decane derivative is easily introduced is particularly preferably a trialkoxyalkylene group. Further, the alkoxyalkyl group functional group is not necessarily a functional group of a structure in which alkoxyalkylene skeleton 17-201105760 can directly bind to a main chain, or an alkoxyalkyl group skeleton can be bonded by an atom or a functional group. A functional group of an indirectly bonded structure (for example, a trialkoxyalkylalkyl group, etc.). The appropriate content of the alkoxyalkyl group-based functional group varies depending on the main chain structure, the weight average molecular weight 'glass transition temperature, and the like. However, it is preferably contained in an amount of 0.04 to 4 mmol of an alkoxyalkyl group-functional group per 100 g of the polymer, more preferably 0.04 to 2 mmol, particularly preferably 0.04 to 1 mmol. For example, in the case of a crosslinkable (meth)acrylic polymer having a weight average molecular weight of 420,000, it is preferably 0.17 to 17 alkoxyalkylene functional groups per molecule of the polymer, more preferably 0.17~ 8.5, especially good with 0.17~4.2. When the content of the functional group of the oxime sand system is less than 0.04 mmol/100 g, the modification effect by the alkoxyalkyl group-based functional group may not be sufficiently obtained (specifically, if a glass material is used as the object) Durability, in particular, heat resistance, heat and humidity resistance, etc.). On the other hand, the case where the content exceeds 4 mmol/l 〇〇g varies depending on the polymer composition and the like, but the viscosity of the polymer tends to increase as time passes. The method for producing the crosslinkable (meth)acrylic polymer is not particularly limited. For example, the (meth)acrylic polymer as a basic skeleton can be introduced by chemical modification to introduce a (meth)acrylonitrile-based functional group. It is produced by a method (chemical modification method) of a group and an alkoxyalkyl group-based functional group. Specific examples of the chemical modification method include a (meth)acrylic compound having an isocyanate group or an alkane group having an isocyanate group, wherein a (meth)acrylic acid having a warp group is used as a matrix polymer. A method in which a oxy decane-18 - 201105760-based compound is directly bonded to a hydroxyl group of the matrix polymer, thereby introducing a (meth) acrylonitrile-based functional group and an alkoxyalkyl-based functional group (direct bonding method). The "(meth)acrylic polymer having a hydroxyl group" can be obtained by copolymerizing a hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl acrylate with another (meth)acrylic monomer. The "(meth)acrylic compound having an isocyanate group", for example, 2-methylpropenyloxyethyl isocyanate (trade name: Karenz MOI, manufactured by Showa Denko), 2-propenyloxyethyl isocyanate (trade name: Karenz AOI, manufactured by Showa Denko Co., Ltd.), 2-(2-methylpropenyloxyethyloxy)ethyl isocyanate (trade name: Karenz MOI EG, manufactured by Showa Denko Co., Ltd.). In another aspect, the alkoxydecane compound having an isocyanate group may, for example, be 3-isocyanatepropyltriethoxydecane (trade name: KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.). Further, in the chemical modification method, a polyfunctional compound such as a polyisocyanate compound is bonded to a hydroxyl group of a matrix polymer, and a (meth)acrylic compound having a hydroxyl group or a hydroxyl group is indirectly bonded by the polyfunctional compound. A method of introducing a (meth) propylene fluorene-based functional group and an alkoxyalkylene-based functional group into an alkoxy decane-based compound (indirect bonding method). The "polyisocyanate compound" may, for example, be methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI) or isophorone diisocyanate (IPDI). The "(meth)acrylic compound having a hydroxyl group"" may, for example, be a hydroxyl group-containing (meth) acrylate or the like. The "alkoxy decane compound having a hydroxyl group" may, for example, be 3 - hydroxy-19-201105760 propyl triethoxy decane, etc. The method for producing the matrix polymer is not particularly limited, and a conventionally known method such as solution polymerization or suspension polymerization "block polymerization" can be used. For example, if a solution is used In the case of the polymerization, a (meth) acrylate monomer component is added by a method in which a polymerization initiator is added to an appropriate solvent such as an organic solvent and heated and stirred under a nitrogen stream, and if necessary, copolymerization can be used. A mixture of ethylenically unsaturated monomers composed of an ethylenically unsaturated monomer component is polymerized. Further, as the matrix polymer, a commercially available acrylic copolymer can be used. For example, a trade name: PARACRON AW4500H (solid content: 40%, Mw : 320,000 ' Tg : -8 ° C, toluene solvent, manufactured by Kasei Industrial Co., Ltd.), trade name: PARACRON AS3000E (solid content: 30%, Mw: 650,000) 'Tg: -3 6 ° C, toluene solvent, manufactured by Kokusei Kogyo Co., Ltd.), etc. As a method for producing a crosslinkable (meth)acrylic polymer, or a method for alkoxyalkylalkyl functional group a monomer having a oxonium alkyl functional group is copolymerized with another monomer to be introduced into the matrix of the matrix polymer; for the (meth) propylene oxime functional group, by introducing the A method in which a matrix polymer of an alkoxyalkylalkyl functional group is chemically modified and introduced (polymerization method). The polymerization method is more specifically described as a method comprising: a (meth)acrylic monomer having a hydroxyl group; Polymerization of a monomer mixture of a monomer and a monomer having an alkoxyalkylalkyl functional group to obtain a first modified (meth)acrylic acid having the above alkoxyalkylalkyl functional group and a hydroxyl group in a branched chain a polymer, based on the first modified (meth)acrylic polymer, a polymer of 20-201105760, which is introduced into a hydroxyl group on the hydroxyl group of the matrix polymer by chemical modification. , get the second The (meth)acrylic polymer. As the "monomer having an alkoxyalkylalkyl functional group", for example, methacryloxytrialtrialkoxide, propyleneoxytrialkoxydecane And a vinyl trialkoxy decane, etc. Among them, in the case where the reactivity at the time of polymerization is high, it is preferred to use methacryloxytriallutoxy decane or propylene decyloxyalkoxy decane. It is preferred to use propylene decyloxytrialkoxy decane. [2-1C] Average molecular weight: The weight average molecular weight (Mw) of component A is in the range of 200,000 to 1,000,000. If the weight average molecular weight is less than 200,000, When the adhesive is formed, the amount of the paste remaining on the object is increased, and there is a tendency to contaminate the object, which is not preferable. On the other hand, when the weight average molecular weight exceeds 1,000,000, the miscibility with the solvent and the monomer is poor, and the adhesion loss at the time of preparing the composition increases, and the handleability of the coating liquid may be deteriorated and coated when the adhesive is applied. The problem of poor performance such as reduced fabric. More specifically, a coating streak or a coating liquid may be drawn on a film or the like as a coated article. The drawing of the coating liquid causes the viscosity of the coating liquid to rise due to the rotation of the coating roller, which is not preferable. In order to obtain the above effects more reliably, the weight average molecular weight is preferably in the range of 250,000 to 800,000, and particularly preferably in the range of 400,000 to 600,000. By appropriately controlling the polymerization conditions at the time of polymerization of the (meth)acrylic polymer to be the main chain from 21 to 201105760, for example, the kind and amount of the polymerization initiator, the kind and amount of the chain transfer agent, the kind and amount of the solvent, The weight average molecular weight can be adjusted within the above range in terms of reaction temperature, reaction time, and the like. Further, a polymer having a desired weight average molecular weight can be appropriately selected from commercially available (meth)acrylic polymers and used for modification. Further, the term "weight average molecular weight" as used in the specification means the weight average molecular weight in terms of polystyrene measured by the GPC method (gel permeation chromatography). Specifically, each sample is preferably dissolved in tetrahydrofuran (THF) in such a manner that the solid content of each sample is 0.025%, and the solution is measured under the following conditions. (1) GPC measuring device: high-speed GPC device HLCN 8 820 (trade name, manufactured by Tosoh Corporation), (2) column: TSK-GEL series (trade name: manufactured by Tosoh Corporation), (3) mobile phase: THF, (4) Flow rate: lml/min, (5) Column temperature: 40 °C, (6) Detector: RI' UV, (7) Conversion: Polystyrene. [2-1D] Glass transition temperature (Tg): The glass transition temperature (Tg) of the component A is in the range of -55 to 0 °C. By setting the glass transition temperature within this range, a moderate adhesive property is exhibited when the adhesive is formed. When the glass transition temperature exceeds 0 °C, when the adhesive is formed, the adhesive strength is lowered, or the applicability tends to decrease as the compatibility with the solvent is lowered, which is not preferable. On the other hand, if the glass transition temperature is less than -55 °C, when the adhesive is prepared, the paste remaining on the object is increased, and there is a tendency to contaminate the object, which is not preferable. For more practical -22-201105760 These effects are reliably obtained, and the preferred glass transition temperature is in the range of -4 0 to -1 0 °C, more preferably in the range of -30 to -20 °C. By appropriately controlling the type and ratio of the repeating unit of the (meth)acrylic polymer constituting the main chain, the glass transition temperature can be adjusted to the above range. The glass transition temperature (theoretical 値) of the polymer P composed of the repeating units derived from the monomers Μ, M2, ... Mn can be calculated by the FOX formula (the following mathematical formula (1)), so Refer to the mathematical formula to adjust the type and proportion of the repeating unit. l/TgP = ri/TgMi+r2/TgM2"-+r„/TgM„ (1) (where TgP: glass transition temperature of polymer P (K) Tglvh: glass transition temperature (K) of homopolymer of monomer, TgM2: glass transition temperature (K) of homopolymer of monomer M2 'TgMn: glass transition temperature of homopolymer of monomer Mn (Κ) 'η: mass fraction of monomer M! unit in polymer P, r2: mass fraction of monomer M2 unit in polymer P, rn: monomer in polymer p] mass fraction of unit 11) For a more specific explanation. The glass transition temperature of the crosslinkable (meth)acrylic polymer constituting the component A is as low as -55 to 0. (:, therefore, when polymerizing, the monomer having a lower transfer temperature in the glass of the homopolymer, such as butyl acrylate (Tg: -55. (:), ethyl acrylate (Tg: -24. (:), C) In a monomer mixture containing diethyl 2-ethylhexyl diester (Tg: -85t:) as a main component, a monomer having a higher glass transition temperature of a homopolymer such as methyl methacrylate (Tg) is appropriately added. : 105. 〇), styrene (Tg ··100. 〇), etc. Polymerization inverse -23- 201105760 should be able to obtain a polymer having a desired glass transition temperature. In addition, or from commercially available (meth)acrylic acid The polymer having the desired transition temperature of the glass is appropriately selected and used in the polymer. Further, the term "glass transition temperature" as used in the specification refers to the transformation based on J IS K 7 1 2 1 (plastic). Temperature measurement method) The glass transition temperature of the obtained component is measured. [2-1E] content: The content of the crosslinkable (meth)acrylic polymer constituting the component A, although the structure of the polymer of the component A and the object of the object are The type, the required adhesive properties, etc., but the total amount of the A component and the B component When it is 1 part by mass, it is necessary to make the crosslinkable (meth)acrylic polymer 80 to 99.5 parts by mass. When the content is less than 80 parts by mass, the adhesive strength tends to decrease, which is not preferable. When the content is more than 99.5 parts by mass, the durability of the adhesive layer tends to be lowered due to insufficient cohesive force. Therefore, in order to obtain the above effect more reliably, the content of the component A is preferably 85 to 99.5 parts by mass. More preferably, it is 90 to 99_5 parts by mass. [2-2] A carboxylic acid having a polymerizable unsaturated group (component B): The composition of the present invention contains a carboxylic acid having a polymerizable unsaturated group and an oligomer thereof At least one (component B) can be obtained by adding the component B, and the ultraviolet curability is not impaired even in the presence of oxygen, and the film strength and adhesion to the substrate are improved, and even if thermal crosslinking is not used Agent, -24- 201105760 Adhesive composition which is not easily deteriorated in adhesion under heat and humidity resistance, that is, it does not require aging in terms of producing adhesive properties. "Carboxylic acid having a polymerizable unsaturated group" means having The meaning of a carboxylic acid having a double bond or a polymerizable triple bond. The so-called unsaturated carboxylic acid, more specifically, may be exemplified by (meth)acrylic acid, crotonic acid, maleic acid, maleic anhydride, and fumaric acid. , citraconic acid, glutaconic acid, itaconic acid, acrylamide, N-glycolic acid, cinnamic acid, etc. "Oligomer of carboxylic acid having a polymerizable unsaturated group" means a weight average molecular weight of 10,000 or less The polymer of the above carboxylic acid. For example, in addition to the dimerization of acrylic acid, an acrylic polymer having a weight average molecular weight of 10,000 or less may be mentioned. The content of the component B is based on the polymer structure of the component A and the type of the object. The required adhesive properties may vary, but when the total amount of the A component and the B component is 100 parts by mass, the B component must be 0.5 to 20 parts by mass. When the content is less than 0.5 part by mass, the adhesive durability and optical durability of the adhesive layer tend to be lowered. On the other hand, when the content exceeds 20 parts by mass, the amount of the paste remaining at the time of peeling tends to increase. In order to obtain the above effects more reliably, the content of the component B is preferably 0.5 to 15 parts by mass, more preferably 0 to 5 to 10 parts by mass. [2-3] Photopolymerization initiator (component C): The composition of the present invention contains a photopolymerization initiator (component C) as a constituent component. The photopolymerization initiator means an additive having an action of initiating a polymerization reaction by irradiation with light after being added to a polymerization system. In other words, the C component is caused by the irradiation of the violet-25-201105760 external line, and the polymerization reaction of the component A and the component B is initiated to contribute to the polymer derived from the component B, the crosslinked product of the component A and the component B, and the component A itself. The formation of crosslinks. With such a property, an adhesive layer having high strength can be formed. As a photopolymerization initiator, for example, photopolymerization of α-hydroxyindole acetophenone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.), α-aminoacetophenone, benzoin-based compound, and the like is known. Starting agent. The composition of the present invention contains a fluorenylphosphine oxide-based compound as a photopolymerization initiator. This is because the addition of the fluorenylphosphine oxide-based compound can suppress the deterioration of the color tone (yellowing) of the adhesive layer to an extremely slight level, and can form an adhesive having excellent optical properties and durability. Further, the adhesive composition of the present invention may be used in the case of bonding a functional film to an electronic display or the like. Therefore, an ultraviolet absorber (component F) may be added, in which case it is preferable. In order to use a photopolymerization initiator which transmits ultraviolet light in a wavelength region different from the absorption wavelength of the F component, the ruthenium component can be polymerized. The absorption wavelength of the ultraviolet absorber is set to 2500 to 380 nm. The range around. Therefore, a sulfhydryl phosphine oxide-based compound capable of initiating a polymerization reaction when irradiated with ultraviolet rays having a wavelength of 380 nm or more is preferably used. Further, as a photopolymerization initiator capable of initiating a polymerization reaction upon irradiation with ultraviolet rays having a wavelength of 380 nm or more, there is 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)- The α-aminoalkylphenone compound -26-201105760, such as butanone-i (trade name: irgacure 369, manufactured by Ciba Specialty Chemicals Co., Ltd.), is present. However, when a photopolymerization initiator other than the fluorenylphosphine oxide-based compound is used, the ultraviolet curability is lowered and the adhesion layer is yellowed. "Mercapto phosphine oxide-based compound means a compound having a fluorenylphosphine oxide structure (refer to the following general formula (4)). That is, as long as a part of its structure has a fluorenyl group represented by the following formula (4) The phosphine oxide structure is included in the "mercapto phosphine oxide-based compound" of the present invention regardless of the structure of other parts. Therefore, depending on the properties (ultraviolet curability, color, etc.) required for the resin composition, It is sufficient to select the best substance among the various substances as the C component.

Ο Ο II II _P_U_R …（4) (式中，R表示可以被取代的烷基或可以被取代的芳基）。 作爲“醯基氧化膦系化合物”，可舉出例如雙（2,4,6-三甲基苯甲醯基）-苯基氧化膦（商品名：Irgacure 819， Ciba Specialty Chemicals 公司製造）、雙（2，6 -二甲氧基苯 甲醯基）-2,4,4-三甲基-戊基氧化膦（商品名：CGL403， Ciba Specialty Chemicals公司製造）、2,4,6-三甲基苯甲醯 基-二苯基氧化膦（商品名：Lucirin TPO，BASF公司製造） 等。其中，從硬化性優異、塗膜色調幾乎不變化的觀點而 言，特佳爲2,4,6-三甲基苯甲醯基-二苯基氧化膦。 -27- 201105760 此外，“醯基氧化膦系化合物”還包括高分子化合物 。即，在高分子化合物中導入有醯基氧化膦結構的高分子 光聚合起始劑或作爲C成分使用。該高分子光聚合起始劑 不僅包括所謂的聚合物（重量平均分子量大槪爲5萬以上） ，也包括所謂的寡聚物（重量平均分子量爲5 00〜5萬左右） 。這樣的高分子光聚合起始劑必須至少具有醯基氧化膦結 構，但除此之外或具有其他的光聚合起始劑的結構。例如 ，可舉出除具有醯基氧化膦結構外，還具有苯偶姻結構、 羥基苯乙酮結構、胺基苯乙酮結構或二苯甲酮結構等的其 他的光聚合起始劑的結構的高分子光聚合起始劑》 C成分的含量根據A成分的聚合物結構、被著物種類 、所要求的黏著特性等而不同，但以A成分和B成分的總 量爲100質量份時，使C成分爲0.05〜3質量份。如果含 量不足〇.〇5質量份，則有時黏著劑會不硬化或者硬化不 充分，故不宜。另一方面，如果含量超過3質量份，則黏 著劑可能發生黃變，故不宜。爲了更切實可靠地獲得上述 效果，較佳爲使C成分的含量爲0.1〜1質量份，更佳爲 0.1〜0.5質量份。 此外，醯基氧化膦系光聚合起始劑容易被氧抑制，如 果不在層合加工等排除了氧的條件下，則難以實際應用。 本發明人發現了如下事實，即，藉由與B成分（丙烯酸等 具有聚合性不飽和基的羧酸類）共存時，在氧存在下醯基 氧化膦系光聚合起始劑引發的紫外線硬化會快速進行。由 此，在空氣下，並且以少量的光聚合起始劑就能夠進行紫 -28- 201105760 外線硬化，從而能夠用醯基氧化膦系光聚合起始劑產生黏 著性能。與現有的紫外線硬化型黏著劑相比，在本發明的 黏著劑組合物中藉由將起始劑的量減少爲極低，從而能夠 減少殘留起始劑和低分子聚合物的量，可提高黏著劑的光 學特性。 [2-4]矽烷偶合劑（D成分）： 本發明的組合物含有矽烷偶合劑（D成分）作爲構成成 分。藉由掺合D成分，在與玻璃等被著物接合的用途中能 夠發揮良好的黏著性。此外，藉由掺合D成分，即使在B 成分量少的情況下，也能夠獲得在耐熱•耐濕熱條件下黏 著特性也不易下降的黏著組合物。 作爲D成分，可以廣泛使用通常稱作“矽烷偶合劑” 的物質。通常，作爲矽烷偶合劑，可使用具有環氧丙氧基 、甲基丙烯醯氧基、丙烯醯氧基等反應性官能基的矽烷化 合物。但在本發明的黏著劑組合物中使用具有環氧系官能 基的矽烷偶合劑作爲D成分。“環氧系官能基”係指具有 環氧環的官能基，例如可舉出環氧丙氧基等。具有環氧系 官能基的矽烷偶合劑，在能夠提高對電漿顯示器的前面板 等玻璃基材的密合性這—點上是較佳的。 作爲具體化合物，可舉出環氧丙氧丙基三甲氧基 矽烷（商品名：ΚΒΜ-403 (信越化學工業公司製造）等）、r-環氧丙氧丙基三乙氧基矽烷（商品名：KBE-4 03 (信越化學 工業公司製造）等）、r-環氧丙氧丙基甲基二甲氧基矽烷等 -29- 201105760 ，具有環氧丙氧基的烷基烷氧基矽烷類。這些矽烷偶合劑 可單獨使用一種，或組合兩種以上使用。 D成分的含量’根據A成分的聚合物結構、被著物種 類、所要求的黏著特性等而不同，但以A成分和B成分的 總量爲100質量份時，D成分爲0.1〜5質量份爲宜。如果 含量不足〇·1質量份，則在與坡璃等被著物接合用途中產 生黏著性不足。另一方面，如果該含量超過5質量份，則 再剝離時有可能發生糊料殘留。爲了更切實可靠地獲得上 述效果，較佳爲D成分的含量爲0.5〜2質量份。 [2-5 ] Α成分及Β成分以外的具有聚合性不飽和基之化合物 (E成分）： 本發明的組合物除上述成分外，可以進一步含有除上 述A成分和上述B成分以外的具有聚合性不飽和基的化合 物（E成分）作爲構成成分。 此外，所述“化合物”是廣泛涵蓋具有聚合性不飽和 鍵的物質的槪念。即，只要具有聚合性不飽和鍵，則對其 化學結構沒有特別限定，可以是單體，或是寡聚物。 作爲具有聚合性不飽和基的單體，可舉出（甲基）丙烯 酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸正丙酯、（甲基 )丙烯酸異丙酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸異丁 酯、（甲基）丙烯酸叔丁酯、（甲基）丙烯酸正戊酯、（甲基） 丙烯酸異戊酯、（甲基）丙烯酸正己酯、（甲基）丙烯酸正辛 酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸月桂酯、（甲 -30- 201105760 基）丙烯酸環己酯、丙烯酸四氫糠酯等（甲基）丙烯酸酯類； (甲基）丙烯酸2-羥乙酯、（甲基）丙烯酸2-羥丙酯、（甲基） 丙烯酸3-羥丙酯、丙烯酸4-羥基丁酯等含有羥基的（甲基） 丙烯酸酯類；1,6-己二醇二丙烯酸酯、1，9-壬二醇二丙烯 酸酯、季戊四醇三丙烯酸酯' 季戊四醇四丙烯酸酯、二季 戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯等多官能丙烯 酸酯類；乙酸乙烯酯、丙酸乙烯酯等羧酸乙烯酯類；苯乙 烯、甲基苯乙烯等芳香族乙烯基類等。 但是’具有聚合性不飽和基的單體，在如本發明中之 減少了光聚合起始劑量的條件下，有可能會產生紫外線硬 化性降低或黏著劑組合物發生黃變之虞。因此，本發明的 黏著劑組合物中，較佳使用每1分子具有2個以上（甲基） 丙烯醯系官能基的多官能寡聚物作爲E成分。藉由將多官 能寡聚物作爲構成成分，還可進一步促進黏著劑成分交聯 的效果。 對具體的結構沒有特別限制，可舉出在成爲基本骨架 的聚酯型多元醇、聚丙二醇、脂肪族聚酯、雙酚系環氧樹 脂等聚合物上’結合有（甲基）丙烯酸酯類等具有聚合性不 飽和鍵的單體，而成的聚胺酯丙烯酸酯等。雖然根據黏著 劑的要求性能而異’但從與其他成分的相容性、容易對硬 化後的黏著力進行調整的觀點而言，較佳爲使用脂肪族聚 酯骨架的聚胺酯丙烯酸酯和雙酚系環氧丙烯酸酯。 作爲多官能丙烯酸酯，例如有市售的Light tackPSA-8 〇5(商品名’共榮公司化學公司製造；基本骨架：聚酯型 -31 - 201105760 多元醇）、NK OLIGO UA-340P(商品名，新中村化學工業 公司製造；基本骨架：聚丙二醇）、EB270(商品名’ Daicel SciTech公司製造；基本骨架：脂肪族聚酯）、CN-965 (商 品名，日本化藥公司製造；基本骨架：脂肪族聚酯）、 Ripoxy VR-77(商品名，昭和高分子公司製造；基本骨架 :雙酚系環氧樹脂）等。除此之外，還市售有Biscoat #300(商品名，大阪有機化學公司製造；基本骨架：季戊 四醇）等。但或依據所要求的性能，適當合成所期望結構 的物質來使用。 其中，較佳以脂肪族聚酯爲基本骨架、每1分子具有 2個以上（甲基）丙烯醯系官能基、重量平均分子量（Mw)在 1千〜1萬範圍內的多官能寡聚物（例如，上述EB 270等） ，或者以雙酚系環氧樹脂爲基本骨架、每1分子具有2個 以上所述（甲基）丙稀醯系官能基、重量平均分子量（Mw)在 400〜2000範圍內的多官能寡聚物（例如，Rip0Xy VR-77 等）。 E成分可單獨使用上述化合物中之僅一種，或組合2 種以上使用。 E成分的含量，根據A成分的聚合物結構、被著物種 類、所要求的黏著特性等而異，但以A成分和B成分的總 量爲1 0 〇質量份時’必須使E成分爲〇〜2 0質量份。特別 是使用上述多官能寡聚物作爲E成分的情況下，較佳爲含 有0.5〜20質量份的該多官能寡聚物。如果多官能寡聚物 的含量小於〇 . 5質量份’則可能會有黏著強度調整困難的 -32- 201105760 現象發生。另一方面，如果含量超過20質量份，會有黏 著力明顯下降的傾向。爲了更切實可靠地獲得上述效果， 較佳爲使多官能寡聚物的含量爲0.5〜15質量份，更佳爲 0.5〜1 0質量份。 [2-6]紫外線吸收劑（F成分）： 本發明的組合物除上述構成成分以外，還可以含有紫 外線吸收劑（F成分）。藉由掺合F成分，可以發揮如下效 果，即，遮蔽具有強化學作用的紫外線、抑制較黏著層下 層側之物質的氧化和變質、或抑制有機物分解所致的劣化 (變色、退色、脆化等），如此的有益效果（以下，稱爲“紫 外線遮蔽性”）。 作爲F成分，較佳爲含有在35〇〜4〇〇nm的波長範圍 具有λιη ax之二苯甲酮系化合物。所謂“二苯甲酮系化合 物”是具有下述結構式（5)所示的二苯甲酮骨架的化合物。 即’只要在其結構的一部分具有下述結構式（5)所示的二苯 甲酮骨架，則無論其他部分的結構如何，均包含在本發明 的“二苯甲酮系化合物，，中。因此，根據作爲樹脂組合物 所要求的性能（紫外線硬化性、顏色等），從這樣的各種物 質中適當選擇最佳的物質當作F成分即可。 【化5】Ο Ο II II _P_U_R (4) (wherein R represents an alkyl group which may be substituted or an aryl group which may be substituted). The "mercapto phosphine oxide-based compound" may, for example, be bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (trade name: Irgacure 819, manufactured by Ciba Specialty Chemicals Co., Ltd.), double (2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide (trade name: CGL403, manufactured by Ciba Specialty Chemicals), 2,4,6-trimethyl Benzobenzyl-diphenylphosphine oxide (trade name: Lucirin TPO, manufactured by BASF Corporation) and the like. Among them, 2,4,6-trimethylbenzimidyl-diphenylphosphine oxide is particularly preferred from the viewpoint of excellent curability and little change in color tone of the coating film. -27- 201105760 In addition, "mercapto phosphine oxide compound" also includes a polymer compound. In other words, a polymer photopolymerization initiator having a fluorenylphosphine oxide structure introduced into a polymer compound or a component C is used. The polymer photopolymerization initiator includes not only a so-called polymer (having a weight average molecular weight of more than 50,000) but also a so-called oligomer (having a weight average molecular weight of about 50,000 to 50,000). Such a polymer photopolymerization initiator must have at least a mercaptophosphine oxide structure, but otherwise has a structure of another photopolymerization initiator. For example, a structure of another photopolymerization initiator having a benzoin structure, a hydroxyacetophenone structure, an aminoacetophenone structure, or a benzophenone structure in addition to the fluorenylphosphine oxide structure may be mentioned. The content of the component C is different depending on the polymer structure of the component A, the type of the component, the desired adhesive property, and the like, but when the total amount of the component A and the component B is 100 parts by mass. The component C is 0.05 to 3 parts by mass. If the content is less than 质量5 parts by mass, the adhesive may not be hardened or hardened, and it is not suitable. On the other hand, if the content exceeds 3 parts by mass, the adhesive may be yellowed, which is not preferable. In order to obtain the above effect more reliably, the content of the component C is preferably 0.1 to 1 part by mass, more preferably 0.1 to 0.5 part by mass. Further, the fluorenylphosphine oxide-based photopolymerization initiator is easily inhibited by oxygen, and it is difficult to practically use it under conditions in which oxygen is not excluded from lamination processing. The present inventors have found out that, by coexistence with a component B (a carboxylic acid having a polymerizable unsaturated group such as acrylic acid), ultraviolet ray hardening by a fluorenylphosphine oxide-based photopolymerization initiator in the presence of oxygen Go quickly. As a result, the external hardening of violet -28-201105760 can be carried out under air and with a small amount of a photopolymerization initiator, whereby the sulfhydrylphosphine-based photopolymerization initiator can be used to produce adhesive properties. Compared with the conventional ultraviolet curable adhesive, the amount of the initiator and the low molecular polymer can be reduced by reducing the amount of the initiator to be extremely low in the adhesive composition of the present invention, and the amount of the residual initiator and the low molecular polymer can be reduced. The optical properties of the adhesive. [2-4] Decane coupling agent (component D): The composition of the present invention contains a decane coupling agent (component D) as a constituent component. By blending the D component, it is possible to exhibit good adhesion in a joint with a substrate such as glass. Further, by blending the D component, even when the amount of the B component is small, it is possible to obtain an adhesive composition which is not easily deteriorated in adhesion characteristics under heat and humidity resistance. As the component D, a substance generally called a "decane coupling agent" can be widely used. Usually, as the decane coupling agent, a decane compound having a reactive functional group such as a glycidoxy group, a methacryloxy group or a propylene oxy group can be used. However, a decane coupling agent having an epoxy functional group is used as the component D in the adhesive composition of the present invention. The "epoxy functional group" means a functional group having an epoxy ring, and examples thereof include a glycidoxy group and the like. The decane coupling agent having an epoxy functional group is preferable in that it can improve the adhesion to a glass substrate such as a front panel of a plasma display. Specific examples of the compound include glycidoxypropyltrimethoxydecane (trade name: ΚΒΜ-403 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.), r-glycidoxypropyltriethoxydecane (trade name) :KBE-4 03 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc., r-glycidoxypropylmethyldimethoxydecane, etc. -29- 201105760, alkyl alkoxy decane having a glycidoxy group . These decane coupling agents may be used alone or in combination of two or more. The content of the component D is different depending on the polymer structure of the component A, the type of the object to be coated, the desired adhesive property, and the like. However, when the total amount of the component A and the component B is 100 parts by mass, the component D is 0.1 to 5 mass. It is appropriate. If the content is less than 1 part by mass, the adhesion is insufficient in the use of the object to be bonded to a glass or the like. On the other hand, if the content exceeds 5 parts by mass, paste residue may occur at the time of peeling again. In order to obtain the above effect more reliably, the content of the component D is preferably 0.5 to 2 parts by mass. [2-5] A compound having a polymerizable unsaturated group other than the oxime component and the bismuth component (component E): The composition of the present invention may further contain, in addition to the above components, a polymerization other than the component A and the component B described above. The compound of the unsaturated group (component E) is a constituent component. Further, the "compound" is a concept that broadly covers a substance having a polymerizable unsaturated bond. That is, as long as it has a polymerizable unsaturated bond, the chemical structure thereof is not particularly limited, and it may be a monomer or an oligomer. Examples of the monomer having a polymerizable unsaturated group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. Base) n-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate , n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl acrylate (A-30-201105760), tetrahydrofurfuryl acrylate, etc. Methyl) acrylates; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl acrylate, etc. (meth) acrylates; 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, pentaerythritol triacrylate 'pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate Polyfunctional acrylates such as esters; vinyl acetate Vinyl propionate vinyl carboxylate esters and the like; styrene, methyl styrene and other aromatic vinyl and the like. However, the monomer having a polymerizable unsaturated group may have a decrease in ultraviolet hardening property or yellowing of the adhesive composition under the condition that the initial amount of photopolymerization is reduced as in the present invention. Therefore, in the adhesive composition of the present invention, a polyfunctional oligomer having two or more (meth)acrylonitrile-based functional groups per molecule is preferably used as the component E. By using a multi-functional oligomer as a constituent component, the effect of crosslinking of the adhesive component can be further promoted. The specific structure is not particularly limited, and a (meth) acrylate is bonded to a polymer such as a polyester polyol, a polypropylene glycol, an aliphatic polyester or a bisphenol epoxy resin which serves as a basic skeleton. A polyurethane acrylate having a monomer having a polymerizable unsaturated bond. Although it varies depending on the required properties of the adhesive, it is preferably a polyurethane acrylate and bisphenol using an aliphatic polyester skeleton from the viewpoint of compatibility with other components and easy adjustment of adhesion after hardening. It is an epoxy acrylate. As the polyfunctional acrylate, for example, commercially available Light tack PSA-8 〇5 (trade name: manufactured by Kyoei Chemical Co., Ltd.; basic skeleton: polyester type -31 - 201105760 polyol), NK OLIGO UA-340P (trade name) , manufactured by Shin-Nakamura Chemical Industry Co., Ltd.; basic skeleton: polypropylene glycol), EB270 (trade name 'Manufactured by Daicel SciTech Co., Ltd.; basic skeleton: aliphatic polyester), CN-965 (trade name, manufactured by Nippon Kayaku Co., Ltd.; basic skeleton: Aliphatic polyester), Ripoxy VR-77 (trade name, manufactured by Showa Polymer Co., Ltd.; basic skeleton: bisphenol epoxy resin). In addition, Biscoat #300 (trade name, manufactured by Osaka Organic Chemical Co., Ltd.; basic skeleton: pentaerythritol) is commercially available. However, depending on the desired properties, a substance of the desired structure is suitably synthesized for use. Among them, a polyfunctional oligomer having an aliphatic polyester as a basic skeleton, having two or more (meth)acrylonitrile-based functional groups per molecule, and a weight average molecular weight (Mw) in the range of 1,000 to 10,000 is preferable. (for example, the above-mentioned EB 270 or the like), or a bisphenol-based epoxy resin as a basic skeleton, having two or more of the (meth) acryl-based functional groups per molecule, and a weight average molecular weight (Mw) of 400 to 400 Polyfunctional oligomers in the range of 2000 (for example, Rip0Xy VR-77, etc.). The E component may be used alone or in combination of two or more. The content of the component E varies depending on the polymer structure of the component A, the type of the object to be coated, and the desired adhesive properties. However, when the total amount of the component A and the component B is 10 parts by mass, the component E must be made. 〇~2 0 parts by mass. In particular, when the above polyfunctional oligomer is used as the component E, it is preferred to contain 0.5 to 20 parts by mass of the polyfunctional oligomer. If the content of the polyfunctional oligomer is less than 〇 5 parts by mass, there may be a problem that the adhesion strength is difficult to adjust -32-201105760. On the other hand, if the content exceeds 20 parts by mass, there is a tendency that the adhesion is remarkably lowered. In order to obtain the above effects more reliably, the content of the polyfunctional oligomer is preferably from 0.5 to 15 parts by mass, more preferably from 0.5 to 10 parts by mass. [2-6] Ultraviolet absorber (F component): The composition of the present invention may further contain an ultraviolet absorber (F component) in addition to the above constituent components. By blending the F component, it is possible to exhibit an effect of shielding ultraviolet rays having a strong chemical action, suppressing oxidation and deterioration of a substance on the lower layer side of the adhesive layer, or suppressing deterioration due to decomposition of an organic substance (discoloration, discoloration, embrittlement). Etc.) Such a beneficial effect (hereinafter referred to as "ultraviolet shielding"). The F component preferably contains a benzophenone compound having λιη ax in a wavelength range of 35 〇 to 4 〇〇 nm. The "benzophenone-based compound" is a compound having a benzophenone skeleton represented by the following structural formula (5). In other words, as long as the benzophenone skeleton represented by the following structural formula (5) is contained in a part of the structure, it is included in the "benzophenone-based compound of the present invention" regardless of the structure of the other moiety. Therefore, depending on the performance (ultraviolet curability, color, and the like) required for the resin composition, an optimum substance can be appropriately selected from the various substances as the F component.

-33- 201105760 但在本發明的組合物中，爲了在不妨礙光聚合起始劑 (C成分）的作用的條件下，且能賦予紫外線遮蔽性，c成 分與F成分的吸收光譜圖較佳爲不一致者。在本發明的組 合物中，較佳爲使用在2 00〜44 0nm範圍內具有吸收波長 範圍的物質作爲C成分；使用在200〜415 nm範圍內具有 吸收波長範圍的物質作爲F成分。 換言之’作爲F成分，較佳使用其λιη3χ與C成分的 Xmax具有不同的波長範圍之物質。例如，使用在24〇〜 2 5 0nm範圍內具有Xmax的物質作爲C成分的情況時，則 較佳使用在280〜3 00nm範圍內具有Xmax的紫外線吸收 劑；使用在280〜300nm範圍內具有Xmax的物質作爲C 成分的情況時，較佳使用在310〜330 nm範圍內具有λιη ax 的紫外線吸收劑；使用在3 8 0〜4 1 Onm範圍內具有Xmax 的物質作爲C成分的情況時，較佳使用在3 40〜38 Onm範 圍內具有ληιax的紫外線吸收劑。 作爲吸收波長範圍處於200〜440nm範圍內的光聚合 起始劑’可舉出例如α-經基苯乙嗣（商品名：Irgacure 184 ’ Ciba Specialty Chemicals 公司製造）、α-胺基苯乙酮、 苯偶姻系化合物和醯基氧化膦系化合物（雙（2，4,6-三甲基 苯甲醯基）-苯基氧化膦、2,4,6-三甲基苯甲醯基-二苯基氧 化膦等）等。 另一方面，作爲吸收波長範圍處於200〜415 nm範圍 內的紫外線吸收劑（即，在280〜3 80nm的波長範圍具有 Xmax的紫外線吸收劑），可舉出例如2,2’，4,4'-四羥基二苯 -34- 201105760 甲酮（商品名：DAINSORB P-6，大和化成公司製造）、2,2，_ 二羥基-4,4'-二甲氧基二苯甲酮（商品名：3££3〇118 107， SHIPRO化成公司製造）、2,4-二羥基二苯甲酮（商品名： SEESORB 1〇〇，SHIPRO化成公司製造）等。 因此，本發明的組合物中，較佳爲將上述光聚合起始 劑和上述紫外線吸收劑組合使用。其中，從不易出現色調 惡化（黃變）、光學特性良好的觀點而言，較佳爲2,4,6-三 甲基苯甲醯基-二苯基氧化膦與2,2’-二羥基-4，4’-二甲氧基 二苯甲酮的組合。 F成分的含量，根據C成分的種類和量等而不同，以 A成分和B成分的總量爲100質量份時，較佳爲F成分爲 0.1〜15質量份。含量不足0.1質量份時，可能會有紫外 線遮蔽效果不足之現象。另一方面，如果含量超過15質 量份，則可能會有黏著劑無法硬化或硬化不足之現象。爲 了更切實可靠地獲得上述效果，較佳爲使F成分的含量爲 0.5〜10質量份，更佳爲1〜5質量份。 [2-7]溶劑： 本發明的組合物亦可含有溶劑作爲構成成分。藉由含 有溶劑，能夠提高塗佈性及有效防止塗佈時容易產生塗怖 不均等不良情況。 溶劑的種類無特別限制，只要考慮與其他成分的混合 性進行適當選擇即可。例如可舉出甲苯、二甲苯等芳香族 系溶劑；丙酮、甲基乙基酮、甲基異丁基酮、2 -甲基-5-己 -35- 201105760 酮等酮系溶劑；乙酸乙酯、乙酸丁酯、乳酸乙酯等酯系溶 劑；氯甲烷、二氯甲烷、二氯乙烷等含鹵素系溶劑；乙 醇、異丙醇等醇系溶劑；乙二醇乙醚、丙二醇甲醚、丙二 醇-正丙醚、丙二醇甲基醚乙酸酯等二醇醚系溶劑；乙酸 溶纖劑、甲基溶纖劑、乙基溶纖劑 '正丁基溶纖劑、異丁 基溶纖劑、正丙基溶纖劑等溶纖劑類等。 上述溶劑中，從容易降低殘留溶劑濃度的觀點而言， 較佳爲使用甲基乙基酮、乙酸乙酯，特佳爲使用甲基乙基 酮。這些溶劑可單獨使用一種，或將兩種以上組合使用。 溶劑的含量，根據A成分的聚合物結構、被著物種類 、所要求的黏著特性等而不同，較佳爲使黏著劑組合物的 固體成分濃度爲20〜50質量％範圍的方式含有溶劑。黏著 劑組合物的固體成分濃度不足2〇質量％時，可能難以調整 塗佈膜厚。另一方面，固體成分濃度超過50質量％時，因 組合物的黏度增高，會有導致塗佈性降低之虞。 此外，溶劑的含量以組合物黏度爲標準來進行調整即 可。具體而言，以組合物黏度（25 °C )爲100〜5000mPa . s 、較佳爲300〜2000mPa · s的方式來調整溶劑的量。但溶 劑並不限於在如上所述的組合物的黏度調整時添加。例如 ，將A成分進行溶液聚合時並不將溶劑蒸餾除去，而是將 溶劑用於調製組合物的情況時，A成分的聚合溶劑也應被 包含在溶劑中。 [2-8]其他添加劑·· -36- 201105760 在本發明的組合物中，除上述各成分以外，依需要還 可加入抗老化劑、消泡劑、整平劑、密著性賦予劑、黏著 性賦予劑（增黏劑）、光穩定劑、抗靜電劑、界面活性劑、 保存穩定劑、防止熱聚合劑、可塑劑、潤濕性改善劑等， 有時添加在黏著劑組合物中的添加劑。這些添加劑的含量 ，在不妨礙本發明組合物的目的的範圍內適當決定即可。 另外，本發明的組合物與以往的組合物不同，不需要 添加熱交聯劑。由於不需使用熱交聯劑，2液型溶劑系黏 著劑不需進行2液混合必要的操作和熟成（無熟成性）。 "熱交聯劑”係指藉由加熱促進交聯反應從而使黏著 物性表現出來的物質。但，本發明的組合物，即使在不使 用這些熱交聯劑也能夠使黏著物性表現出來。以下，舉出 2液型溶劑系黏著劑中使用的熱交聯劑的例子用於參考。 雙酚A·表氯醇型環氧樹脂；乙二醇二縮水甘油醚、 聚乙二醇二縮水甘油醚、甘油二縮水甘油醚、甘油三縮水 甘油醚、1,6-己二醇二縮水甘油醚、三羥甲基丙烷三縮水 甘油醚、山梨糖醇多縮水甘油醚、聚甘油多縮水甘油醚、 季戊四醇多縮水甘油基赤蘚醇、一縮二甘油多縮水甘油醚 等環氧系化合物：四羥甲基甲烷-三- /3-氮丙啶基丙酸酯、 三羥甲基丙烷-三·召-氮丙啶基丙酸酯、N，N’-二苯基甲烷_ 4,4’-雙（1-氮丙啶羧醯胺）、n，N'-六亞甲基-1,6-雙（卜氮丙 啶羧醯胺）等氮丙啶系化合物； 六甲氧基甲基三聚氰胺、六乙氧基甲基三聚氰胺、六 丙氧基甲基三聚氰胺、六丁氧基甲基三聚氰胺、六戊氧基 -37- 201105760 甲基三聚氰胺、六己氧基甲基三聚氰胺、三聚氰胺樹脂等 三聚氰胺系化合物；2，4-甲苯二異氰酸酯、2,6-甲苯二異 氰酸酯、氫化甲苯二異氰酸酯、1,3 -苯二亞甲基二異氰酸 酯、1,4-苯二亞甲基二異氰酸酯、二苯基甲烷-4,4-二異氰 酸酯、異佛爾酮二異氰酸酯、1,3 -雙（異氰酸根合甲基）環 己烷、四甲基苯二亞甲基二異氰酸酯、1，5-萘二異氰酸酯 、三羥甲基丙烷的甲苯二異氰酸酯加成物、三羥甲基丙烷 的苯二亞甲基二異氰酸酯加成物、三羥甲基丙烷的二苯基 甲烷-4,4 -二異氰酸酯加成物、三羥甲基丙烷的異佛爾酮二 異氰酸酯加成物、三苯甲烷三異氰酸酯、亞甲基雙（4-苯基 甲烷）三異氰酸酯等異氰酸酯系化合物； 乙二醛、丙二醛、丁二醛、馬來二醛、戊二醛、甲醛 、乙醛、苯甲醛等醛系化合物；六亞甲基二胺、三乙基二 胺、聚乙烯亞胺、六亞甲基四胺、二亞乙基三胺、三乙基 四胺、異佛酮二胺、胺基樹脂、聚醯胺等胺系化合物；在 鋁、鐵、銅、鋅、錫、鈦 '鎳、銻、鎂、釩、鉻、鉻等金 屬上配位元乙醯丙酮、乙醯乙醯基酯等而成的金屬螯合物 等。 [3 ]製造方法： 本發明的組合物可藉由以規定比例混合A成分、B成 分、C成分、D成分、視需要使用的£成分、f成分、溶 劑和其他添加劑而得到。 -38- 201105760 [4]使用方法： 本發明的組合物可直接用於塗佈。例如，利用塗佈器 等現有公知的塗佈裝置塗佈在被著物的表面後，乾燥後除 去有機溶劑，接下來，照射與C成分（光聚合起始劑）的種 類相對應的紫外線，形成黏著劑塗膜即可。 作爲本發明組合物適合的被著物，可舉出例如聚乙烯 、聚丙烯、聚氯乙烯、聚對苯二甲酸乙二醇酯、聚碳酸酯 、聚颯、聚甲基丙烯酸甲酯、聚苯乙烯、聚丁二烯、ABS 樹脂、AS樹脂、AES樹脂、聚醯亞胺樹脂、脂肪族聚醯 胺樹脂（商品名：尼龍）、纖維素、硝化纖維素、三乙醯纖 維素等熱塑性樹脂；酚醛樹脂、甲酚甲醛樹脂、三聚氰胺 樹脂、尿素樹脂等熱硬化性樹脂；玻璃、陶瓷、金屬等無 機材料等。此外，被著物或根據使用用途進行了表面處理 的被著物。 本發明的組合物藉由紫外線的照射而表現出黏著力。 對紫外線的波長沒有特別限制，較佳照射波長爲200〜 400ηπι的紫外線。作爲光源的具體例，可舉出例如超高壓 水銀燈、高壓水銀燈 '金屬鹵化物燈、高功率金屬鹵化物 燈等。對紫外線照射條件也沒有特別限制，高壓水銀燈的 情況時，則較佳爲100〜600mW/cm2(20〜150nU/cm2)» 作爲黏著強度，較佳爲與現有的熱硬化型同樣，即爲 20〜25N/25mm左右，但隨著近年來面板的大型化，有要 求低黏著力的趨勢。這種情況下，較佳黏著強度爲 2〇N/25mm以下，其中特佳爲15N/25mm以下。該黏著強 -39- 201105760 度可以藉由A成分的重量平均分子量（Mw)和玻璃轉移溫 度（Tg)、（甲基）丙烯醯基-烷氧矽烷基的含量、以及E成分 的種類和量來調整。 實施例 以下，利用實施例更具體說明本發明的紫外線硬化型 黏著劑組合物。但這些實施例只不過是用於表示本發明的 —部分實施方式的例子。因此，本發明不應解釋爲限定於 這些實施例。 Π]Α成分的基質聚合物的合成： 首先，調製成爲A成分的基質聚合物的（甲基）丙烯酸 系聚合物。 (参考例1) 在具備回流冷凝器、攪拌器、氮氣吹入口和溫度計的 四口圓底燒瓶中，加入丙烯酸乙酯67質量份、丙烯腈10 質量份、甲基丙烯酸2-羥乙酯23質量份以及甲基乙基酮 2 3 3質量份，在氮氣流下加熱，開始加熱回流。其後，加 入作爲聚合起始劑的 2,2’-偶氮二異丁腈（以下記作 “AIBN”）0.1質量份，於90°C反應5小時，得到（甲基）丙烯 酸系聚合物（P-1)溶液（重量平均分子量19.8萬、玻璃轉移 溫度0°C、固體成分濃度30質量％、黏度600mPa · s/25°C) -40- 201105760 (参考例2) 在具備回流冷凝器、攪拌器 '氮氣吹入口和溫度計的 四口圓底燒瓶中，加入丙烯酸乙酯87質量份、丙稀腈3.5 質量份、丙烯酸2 -羥乙酯9·5質量份以及甲基乙基酮233 質量份，在氮氣流下加熱，開始加熱回流。其後，加入作 爲聚合起始劑的AIBN 0.03質量份，於80°C反應6小時， 由此得到（甲基）丙烯酸系聚合物（P-2)溶液（重量平均分子 量27.4萬、玻璃轉移溫度-20°C、固體成分濃度3〇質量。/D 、黏度 400mPa· s/25°C)。 (参考例3) 在具備回流冷凝器、攪拌器、氮氣吹入口和溫度計的 四口圓底燒瓶中加入水300質量份，攪拌溶解作爲分散穩 定劑的聚乙烯醇0.7質量份。在該溶解液中一次性加入由 丙烯酸乙酯33.4質量份、丙烯酸丁酯50質量份、甲基丙 烯酸甲酯3質量份、甲基丙烯酸2-羥乙酯13.6質量份構 成的單體混合物和作爲聚合起始劑的AIBN 1質量份，製 作成懸浮液。在氮氣流下加熱該懸浮液，開始加熱回流。 於8 0°C反應4小時後，將反應生成物固液分離，用水充分 洗淨後，使用乾燥機在70°C乾燥1 2小時，得到固態樹脂（ 甲基）丙烯酸系聚合物（P-3)(重量平均分子量42.3萬、玻 璃轉移溫度-30°C )。 -41 - 201105760 (参考例4) 在具備回流冷凝器、攪拌器、氮氣吹入口和溫度計的 四口圓底燒瓶中加入水300質量份，攪拌溶解作爲分散穩 定劑的聚乙烯醇0·4質量份。在該溶解液中一次性加入由 丙烯酸乙酯54.4質量份、丙烯酸丁酯29質量份、甲基丙 烯酸甲酯3質量份、丙烯酸2-羥乙酯13.6質量份構成的 單體混合物和作爲聚合起始劑的AIBN 0.5質量份，製作 成懸浮液。在氮氣流下加熱該懸浮液，開始加熱回流。於 8 〇°C反應6小時後，將反應生成物固液分離，用水充分洗 淨後，使用乾燥機於7 0 °C乾燥1 2小時，得到固態樹脂（甲 基）丙烯酸系聚合物（P-4)(重量平均分子量60.3萬、玻璃 轉移溫度-3 0 °C )。 (参考例5)-33-201105760 However, in the composition of the present invention, in order to impart ultraviolet shielding properties without impeding the action of the photopolymerization initiator (component C), the absorption spectrum of the component c and the component F is preferably For inconsistencies. In the composition of the present invention, a substance having an absorption wavelength range of from 200 to 440 nm is preferably used as the C component, and a substance having an absorption wavelength range of from 200 to 415 nm is used as the F component. In other words, as the F component, a substance having a different wavelength range from λιη3χ to the Xmax of the C component is preferably used. For example, when a substance having Xmax in the range of 24 Å to 250 nm is used as the component C, it is preferred to use an ultraviolet absorber having Xmax in the range of 280 to 300 nm; and having Xmax in the range of 280 to 300 nm. When the substance is used as the component C, it is preferred to use an ultraviolet absorber having λιη ax in the range of 310 to 330 nm; and when a substance having Xmax in the range of 380 to 4 1 Onm is used as the component C, It is preferred to use an ultraviolet absorber having ληιax in the range of 3 40 to 38 Onm. The photopolymerization initiator which is in the range of the absorption wavelength in the range of from 200 to 440 nm is exemplified by α- mercaptophenone (trade name: Irgacure 184 'Ciba Specialty Chemicals Co., Ltd.), α-aminoacetophenone, Benzoin-based compound and fluorenylphosphine oxide-based compound (bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 2,4,6-trimethylbenzylidene-II Phenylphosphine oxide, etc.). On the other hand, as an ultraviolet absorber having an absorption wavelength in the range of 200 to 415 nm (that is, an ultraviolet absorber having Xmax in a wavelength range of 280 to 380 nm), for example, 2, 2', 4, 4 may be mentioned. '-Tetrahydroxydiphenyl-34- 201105760 methyl ketone (trade name: DAINSORB P-6, manufactured by Daiwa Kasei Co., Ltd.), 2,2, _ dihydroxy-4,4'-dimethoxybenzophenone (product Name: 3££3〇118 107, manufactured by SHIPRO Chemical Co., Ltd.), 2,4-dihydroxybenzophenone (trade name: SEESORB 1〇〇, manufactured by SHIPRO Chemical Co., Ltd.). Therefore, in the composition of the present invention, it is preferred to use the above photopolymerization initiator in combination with the above ultraviolet absorber. Among them, 2,4,6-trimethylbenzimidyl-diphenylphosphine oxide and 2,2'-dihydroxy group are preferred from the viewpoint that color tone deterioration (yellowing) is less likely to occur and optical characteristics are good. a combination of -4,4'-dimethoxybenzophenone. The content of the component F varies depending on the type and amount of the component C, and when the total amount of the component A and the component B is 100 parts by mass, the component F is preferably 0.1 to 15 parts by mass. When the content is less than 0.1 part by mass, there may be insufficient ultraviolet shielding effect. On the other hand, if the content exceeds 15 parts by mass, there may be a phenomenon that the adhesive cannot be hardened or hardened. In order to obtain the above effects more reliably, the content of the F component is preferably from 0.5 to 10 parts by mass, more preferably from 1 to 5 parts by mass. [2-7] Solvent: The composition of the present invention may further contain a solvent as a constituent component. By containing a solvent, it is possible to improve the coatability and to prevent the occurrence of unevenness in coating unevenness during coating. The type of the solvent is not particularly limited, and may be appropriately selected in consideration of the compatibility with other components. For example, an aromatic solvent such as toluene or xylene; a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone or 2-methyl-5-hexyl-35-201105760; ethyl acetate; , an ester solvent such as butyl acetate or ethyl lactate; a halogen-containing solvent such as methyl chloride, dichloromethane or dichloroethane; an alcohol solvent such as ethanol or isopropanol; ethylene glycol diethyl ether, propylene glycol methyl ether, and propylene glycol; - glycol ether solvent such as n-propyl ether or propylene glycol methyl ether acetate; cellosolve acetate, methyl cellosolve, ethyl cellosolve 'n-butyl cellosolve, isobutyl cellosolve, n-propyl solution Cellulose such as fiber. Among the above solvents, from the viewpoint of easily lowering the concentration of the residual solvent, methyl ethyl ketone or ethyl acetate is preferably used, and methyl ethyl ketone is particularly preferably used. These solvents may be used alone or in combination of two or more. The content of the solvent varies depending on the polymer structure of the component A, the type of the object to be coated, the desired adhesive properties, and the like, and it is preferred to contain the solvent so that the solid content concentration of the adhesive composition is in the range of 20 to 50% by mass. When the solid content concentration of the adhesive composition is less than 2% by mass, it may be difficult to adjust the coating film thickness. On the other hand, when the solid content concentration exceeds 50% by mass, the viscosity of the composition is increased, which may cause a decrease in coatability. Further, the content of the solvent may be adjusted in accordance with the viscosity of the composition. Specifically, the amount of the solvent is adjusted so that the viscosity (25 ° C) of the composition is 100 to 5000 mPa·s, preferably 300 to 2000 mPa·s. However, the solvent is not limited to being added at the time of viscosity adjustment of the composition as described above. For example, when the component A is subjected to solution polymerization, the solvent is not distilled off, but when a solvent is used to prepare the composition, the polymerization solvent of the component A should also be contained in the solvent. [2-8] Other Additives···36-201105760 In the composition of the present invention, in addition to the above components, an anti-aging agent, an antifoaming agent, a leveling agent, an adhesion imparting agent, or an anti-aging agent may be added as needed. Adhesive imparting agent (tackifier), light stabilizer, antistatic agent, surfactant, storage stabilizer, thermal polymerization inhibitor, plasticizer, wettability improver, etc., sometimes added to the adhesive composition Additives. The content of these additives may be appropriately determined within the range not impairing the purpose of the composition of the present invention. Further, unlike the conventional composition, the composition of the present invention does not require the addition of a thermal crosslinking agent. Since it is not necessary to use a thermal crosslinking agent, the two-liquid solvent-based adhesive does not require the necessary operations and ripening (no ripening) of the two-liquid mixing. "Thermal cross-linking agent" means a substance which exhibits an adhesive property by promoting a crosslinking reaction by heating. However, the composition of the present invention can exhibit adhesive properties even without using these thermal crosslinking agents. Hereinafter, an example of a thermal crosslinking agent used in a two-liquid solvent-based adhesive is used for reference. Bisphenol A·epichlorohydrin type epoxy resin; ethylene glycol diglycidyl ether, polyethylene glycol diminishing Glycerol ether, glycerol diglycidyl ether, glycerol triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl Epoxy compounds such as ether, pentaerythritol polyglycidyl erythritol, diglycerin polyglycidyl ether, etc.: tetramethylolethane-tris-/3-aziridine propionate, trimethylolpropane-三·召—Aziridine propionate, N,N′-diphenylmethane _ 4,4′-bis(1-aziridine carboxamide), n,N′-hexamethylene-1 , aziridine-based compound such as 6-bis (aziridine carboxamide); hexamethoxymethyl melamine, hexaethoxymethyl three Melamine compounds such as cyanamide, hexapropoxymethyl melamine, hexabutoxymethyl melamine, hexapentyloxy-37-201105760 methyl melamine, hexahexyloxymethyl melamine, melamine resin; 2,4- Toluene diisocyanate, 2,6-toluene diisocyanate, hydrogenated toluene diisocyanate, 1,3-benzenedimethylene diisocyanate, 1,4-benzenedimethylene diisocyanate, diphenylmethane-4,4- Diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, tetramethylbenzenedimethylene diisocyanate, 1,5-naphthalene diisocyanate, trimethylol Toluene diisocyanate adduct of propane, benzene dimethylene diisocyanate adduct of trimethylolpropane, diphenylmethane-4,4-diisocyanate adduct of trimethylolpropane, trishydroxyl Isocyanate compound such as isophorone diisocyanate adduct of propane, triphenylmethane triisocyanate or methylene bis(4-phenylmethane) triisocyanate; glyoxal, malondialdehyde, succinaldehyde, horse Dialdehyde, glutaraldehyde, formaldehyde, acetaldehyde, An aldehyde compound such as benzaldehyde; hexamethylenediamine, triethyldiamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethyltetramine, isophoronediamine An amine-based compound such as an amine-based resin or a polyamine; a complexing element on the metals such as aluminum, iron, copper, zinc, tin, titanium 'nickel, lanthanum, magnesium, vanadium, chromium, chromium, etc. A metal chelate compound such as a mercaptoester or the like. [3] Production method: The composition of the present invention can be mixed with a component A, a component B, a component C, a component D, and a component as needed, in a predetermined ratio. The component f, the solvent, and other additives are obtained. -38- 201105760 [4] Method of use: The composition of the present invention can be directly used for coating. For example, it is coated by a conventionally known coating device such as an applicator. After the surface of the object is dried, the organic solvent is removed, and then ultraviolet rays corresponding to the type of the component C (photopolymerization initiator) are irradiated to form an adhesive coating film. Suitable examples of the composition of the present invention include polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyfluorene, polymethyl methacrylate, and poly. Thermoplastics such as styrene, polybutadiene, ABS resin, AS resin, AES resin, polyimine resin, aliphatic polyamide resin (trade name: nylon), cellulose, nitrocellulose, triacetyl cellulose Resin; thermosetting resin such as phenol resin, cresol formaldehyde resin, melamine resin, urea resin; inorganic materials such as glass, ceramics, and metals. In addition, the object to be treated or the surface treated according to the intended use. The composition of the present invention exhibits adhesion by irradiation with ultraviolet rays. The wavelength of the ultraviolet light is not particularly limited, and ultraviolet rays having a wavelength of 200 to 400 ηπ are preferably irradiated. Specific examples of the light source include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a high power metal halide lamp, and the like. The ultraviolet irradiation condition is also not particularly limited. In the case of a high pressure mercury lamp, it is preferably 100 to 600 mW/cm 2 (20 to 150 nU/cm 2 ).» As the adhesion strength, it is preferably the same as the conventional thermosetting type, that is, 20 ~25N/25mm or so, but with the recent enlargement of panels, there is a tendency to require low adhesion. In this case, the preferred adhesive strength is 2 〇 N / 25 mm or less, and particularly preferably 15 N / 25 mm or less. The adhesion strength -39-201105760 degrees can be obtained by the weight average molecular weight (Mw) of the component A and the glass transition temperature (Tg), the content of the (meth) acryloyl-alkoxyalkylene group, and the type and amount of the component E. To adjust. EXAMPLES Hereinafter, the ultraviolet curable adhesive composition of the present invention will be more specifically described by way of examples. However, these embodiments are merely examples for representing some embodiments of the present invention. Therefore, the invention should not be construed as being limited to the embodiments. Synthesis of matrix polymer of Α component: First, a (meth)acrylic polymer which is a matrix polymer of component A is prepared. (Reference Example 1) Into a four-necked round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet, and a thermometer, 67 parts by mass of ethyl acrylate, 10 parts by mass of acrylonitrile, and 2-hydroxyethyl methacrylate 23 were added. The mass fraction and 2 3 parts by mass of methyl ethyl ketone were heated under a nitrogen stream to start heating under reflux. Thereafter, 0.1 parts by mass of 2,2'-azobisisobutyronitrile (hereinafter referred to as "AIBN") as a polymerization initiator was added, and the mixture was reacted at 90 ° C for 5 hours to obtain a (meth)acrylic polymer. (P-1) solution (weight average molecular weight: 198,000, glass transition temperature: 0 ° C, solid content concentration: 30% by mass, viscosity: 600 mPa · s / 25 ° C) -40 - 201105760 (Reference Example 2) In a four-neck round bottom flask of a stirrer 'nitrogen gas inlet and a thermometer, 87 parts by mass of ethyl acrylate, 3.5 parts by mass of acrylonitrile, 9.5 parts by mass of 2-hydroxyethyl acrylate, and methyl ethyl ketone 233 were added. The mass fraction was heated under a stream of nitrogen and heated to reflux. Thereafter, 0.03 parts by mass of AIBN as a polymerization initiator was added, and the mixture was reacted at 80 ° C for 6 hours to obtain a (meth)acrylic polymer (P-2) solution (weight average molecular weight: 274,000, glass transition temperature). -20 ° C, solid concentration of 3 〇 mass. / D, viscosity 400 mPa · s / 25 ° C). (Reference Example 3) 300 parts by mass of water was placed in a four-necked round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet, and a thermometer, and 0.7 parts by mass of polyvinyl alcohol as a dispersion stabilizer was stirred and dissolved. A monomer mixture composed of 33.4 parts by mass of ethyl acrylate, 50 parts by mass of butyl acrylate, 3 parts by mass of methyl methacrylate, and 13.6 parts by mass of 2-hydroxyethyl methacrylate was added in one portion to the solution. 1 part by mass of the AIBN of the polymerization initiator was prepared into a suspension. The suspension was heated under a stream of nitrogen and heated to reflux. After reacting at 80 ° C for 4 hours, the reaction product was subjected to solid-liquid separation, washed thoroughly with water, and dried at 70 ° C for 1 hour using a dryer to obtain a solid resin (meth)acrylic polymer (P- 3) (weight average molecular weight of 423,000, glass transition temperature of -30 ° C). -41 - 201105760 (Reference Example 4) 300 parts by mass of water was added to a four-necked round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet, and a thermometer, and stirred to dissolve the polyvinyl alcohol as a dispersion stabilizer. Share. A monomer mixture composed of 54.4 parts by mass of ethyl acrylate, 29 parts by mass of butyl acrylate, 3 parts by mass of methyl methacrylate, and 13.6 parts by mass of 2-hydroxyethyl acrylate was added in one portion to the solution and as a polymerization. 0.5 parts by mass of the AIBN of the starting agent was prepared into a suspension. The suspension was heated under a stream of nitrogen and heated to reflux. After reacting at 8 ° C for 6 hours, the reaction product was subjected to solid-liquid separation, washed thoroughly with water, and dried at 70 ° C for 1 hour using a dryer to obtain a solid resin (meth)acrylic polymer (P). -4) (weight average molecular weight of 603,000, glass transition temperature - 3 0 °C). (Reference example 5)

在具備回流冷凝器、攪拌器、氮氣吹入口和溫度計的 四口圓底燒瓶中，加入丙烯酸丁酯97質量份、丙烯酸2-羥乙酯3質量份和甲基乙基酮233質量份，在氮氣流下加 熱，開始加熱回流。其後，加入作爲聚合起始劑的AIBN 〇·5質量份，於80°C反應6小時，由此得到（甲基）丙烯酸 系聚合物（P-5)溶液（重量平均分子量79.8萬、玻璃轉移溫 度-55t、固體成分濃度30質量％、黏度4500mPa · s/25°C (参考例6) -42- 201105760 在具備回流冷凝器、攪拌器、氮氣吹入口和溫度計的 四口圓底燒瓶中，加入丙烯酸2 -乙基己醋7〇質量份、丙 嫌膳15質里份 '甲基丙煉酸2 -經乙醋15質量份以及甲基 乙基酮400質量份，在氮氣流下加熱，開始加熱回流。其 後’加入作爲聚合起始劑的AIBN 0.01質量份，於8〇°c反 應8小時’由此得到（甲基）丙烯酸系聚合物（p_6)溶液（重 量平均分子量152.3萬、玻璃轉移溫度_55t：、固體成分濃 度 20 質量 ％、黏度 8000mPa. s(25°C))。 (参考例7) 將市售的丙稀酸系共聚物（商品名：ARUFON UH2000 ’固體成分100質量％，重量平均分子量K1萬，玻璃轉 移溫度-55°C，東亞合成公司製造）作爲聚合物（P_7)。 (参考例8) 在具備回流冷凝器、攪拌器、氮氣吹入口和溫度計的 四口圓底燒瓶中，加入甲苯100質量份，接下來，在氮氣 流下用2小時滴加丙烯酸2-乙基己酯97.5質量份、丙烯酸 2-經乙酯1 .5質量份、丙烯酸1質量份和AIBN 2質量份的 混合液’同時在l〇〇t反應8小時，由此得到（甲基）丙烯酸 系聚合物（P-8)溶液（重量平均分子量48.6萬，玻璃轉移溫 度- 83°C，固體成分濃度50質量％，黏度74〇〇mPa · s/25°C ) -43- 201105760 (参考例9) 在具備回流冷凝器、攪拌器、氮氣吹入口和溫度計的 四口圓底燒瓶中，加入丙烯酸5質量份、丙烯酸丁酯95 質量份和乙酸乙酯80質量份、丙酮40質量份、作爲聚合 起始劑的AIBN 0.03質量份，在氮氣流下於乙酸乙酯回流 溫度反應3小時後，用乙酸乙酯稀釋，得到（甲基）丙烯酸 系聚合物（P-9)溶液（重量平均分子量183.6萬，玻璃轉移 溫度- 50°C，固體成分濃度16質量％，黏度9000mPa . s/25 °C )。 [2]交聯性（甲基）丙烯酸系聚合物（A成分）的合成： 接下來’在基質聚合物中導入反應性感應基，得到交 聯性（甲基）丙烯酸系聚合物（A -1 )。 (参考例10) 在參考例1中合成的（甲基）丙烯酸系聚合物（P-丨）溶液 中’加入相對於100質量份（按固體成分換算）的（甲基）丙 嫌酸系聚合物（P-1)爲0.05質量份的月桂酸二丁基錫和〇.3 質量份的2-甲基丙烯醯氧乙基異氰酸酯（商品名·· Karenz Μ ΟI ’昭和電工公司製造），於5 〇乞反應8小時。藉由反應 液的滴定分析’由異氰酸酯基的消失而確認反應終止。由 此’在丙嫌酸系聚合物（!>_〗）中導入（甲基）丙烯醯基，得到 交聯性（甲基）丙烯酸系聚合物（A—丨）溶液（重量平均分子量 19.9萬’玻璃轉移溫度，固體成分濃度3〇質量％，黏 -44 - 201105760 度 600mPa · s/25 °C ) 0 (参考例11〜2 3 ) 除了改變基質聚合物的種類、具有萆_ 月異氰酸酯基的（甲 基）丙烯酸系化合物的種類和量以外，跑兴去伽 八參考例8進行同 樣地操作’得到交聯性（甲基）丙烯酸系聚合物（A ^ 10)、（A-!2)〜（Α-15)β表丨、表3、表5和表7中顯示出 其投料比。 (參考例24) 使參考例3中合成的（甲基）丙烯酸系聚合物（ρ_3)溶解 在甲基乙基酮23 3質量份中，得到（甲基）丙烯酸系聚合物 溶液（固體成分濃度30質量％)。相對於（甲基）丙稀酸系聚 合物100質量份（按固體成分換算），加入月桂酸二丁基錫 0.05質量份、2-丙烯醯氧乙基異氰酸酯（商品名：Karenz AOI，昭和電工公司製造）0.25質量份和烷氧基矽烷系化合 物（3-異氰酸酯基丙基三乙氧基矽烷，商品名：KBE-9007 ，信越化學公司製造）0.1質量份，於50°C反應8小時。藉 由反應液的滴定分析，以確認到異氰酸酯基消失的時刻作 爲反應終止，得到交聯性（甲基）丙烯酸系聚合物（A-l 1)溶 液（重量平均分子量42.5萬，玻璃轉移溫度-3(TC，黏度 500mPa · s/25〇C)° (参考例25) -45- 201105760 在參考例8中合成的（甲基）丙烯酸系聚合物（p_8)溶液 中加入2-甲基丙烯醯氧乙基異氰酸酯（昭和電工公司製造 ;Karenz M〇i)2質量份、氫醌〇.〇4質量份和月桂酸二丁 基錫0·04質量份，在同一溫度下進行8小時改性反應。 接下來’蒸餾除去甲苯’使殘留溶劑爲1 %以下，由此得 到交聯性（甲基）丙烯酸系聚合物（Α-16)(重量平均分子量 49.3萬，玻璃轉移溫度-83 °C)。 (参考例26) 在參考例9中合成的（甲基）丙燃酸系聚合物（p_9)溶液 中’相對於1〇〇質量份（按固體成分換算）的（甲基）丙烯酸 系聚合物（P-9)加入乙酸乙酯50質量份/甲苯50質量份的 混合溶劑、二月桂酸二丁基錫0.08質量份和2-甲基丙稀 醯氧乙基異氣酸醋5.4質量份，於65 °C反應8小時。最後 ’用甲苯稀釋該反應溶液，得到交聯性（甲基）丙烯酸系聚 合物（A-17)溶液（重量平均分子量185.3萬，玻璃轉移溫 度- 5(TC，固體成分濃度13質量％，黏度9500mPa · s/25t： )。 另外，對於A成分的品質，採用以下的方法進行評儐 [重量平均分子量] 以GPC法測定聚合物的聚苯乙烯換算的重量平均分 子量。 -46- 201105760 [玻璃轉移溫度] 依照JIS Κ7121(塑膠的轉移溫度測定方 物的玻璃轉移溫度。 [甲基丙烯醯基含量•三乙氧基甲矽烷基含量] 藉由酸鹼滴定法對聚合物的甲基丙烯醯ί 氧基矽烷基含量進行定量。具體而言，將得5 二正丁胺（DBA)混合，使（甲基）丙烯酸系化洽 矽烷系化合物的未反應的異氰酸酯基與DBA 酸對所消耗的DBA的量進行反滴定，從而進ί 法）測定聚合 含量和三乙 的聚合物與 物和院氧基 反應，用鹽 定量。 -47- 201105760 i 比 22-1 比 22-2 比 22-3 1_A-17_I 1 MAC 1 1 5400 1 1__1 未修飾 | 185.3 萬 | s 1 o \ 1 1 ι I 1 o 1 \ 1 1 \ \ 1 1 1 1空氣下1 癍 m in ο 戚 «Η 1 m < xr 丑 Γα^Ί 1 ρ-6 1 1 MAc 1 ο CO σ> 未修飾 丨152.4萬| \r> m 1 CO σ> t-m 1 U) l \ 1 \ — 1 1 1 1 1 { 1 1 1 厂空氣下1 Ϊ 摧 to A L a-5 1 1 - P-5 J 1 MAc | 1 500 1 w CO 未修飾 丨80.0萬Ί n ifi \ CO ¢7) 卜 t l/d d 1 1 1 1 — ) 1 1 1 \ \ 1 1 1 Γ空氣下1 1 摧 辟 1 A-4 1 丨 p-4 1 | MAc | ο CO Oi 未修飾 丨60.4萬| g 1 CO σ> 卜 1 ΙΟ ο 1 1 1 1 1 1 1 1 1 1 1 ί 1 1空氣下1 無熟化 CO 艇 1 A-3 I 1 p-3 . 1 | MAc 1 ο η σι ••N 未修飾 1 42.4 萬 | g i to 〇> 1 to d 1 幽 i 1 1 1 1 I 1 1 1 1 » i空氣下1 無熟化 P«J fc i | MAc ] ο 〇> — 未修飾 1 27.5 萬 j o C|4 CO ⑦ 卜 1 U) o 1 1 1 1 1 1 1 1 1 咖 I 1 1 1空氣下1 無熟化 K 1 A-l I l_p-i J | MAc 1 1 300 1 Oi — 未修飾 濉 σ> σ> 〇 CO σ* 卜 1 U) ό 1 1 1 1 •N 幽 \ 1 1 1 1 1 K- 碱 無熟化 ±J A-13 I 丨卜7 1 | MAc 1 ο σ> — 未修飾 1 1.2 萬 1 iA in CO 卜 1 (A 〇 1 1 1 I •H J 1 1 1 1 1 1 1 Υ~ 搣 丨無熟化 丨 種類 _1 1 基質聚合物種類 1 駿 w (mg/聚合物 100g) 1 (mmol/聚合物lOOg) | (mg/聚合物1〇〇β) (mmol/聚合物 100g) 1 ίΓ η- ιίττη PI P (質量份） 價量份） (質量份） (質量份） L (質量份） 1 i _ 咖 m m • m (甲基)丙烯酸基 三乙氧基矽烷基 丨 …——B-1__1 eg m 1 c-i _J 1 C二2 _J 1 C-3 1 | C-4— _| 1 — C-5 1 1 D-l 1 1 D-2 1 D-3 D-4 1 E-l I CS UJ 1 . 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S Κ 戚 @ @ 3 © £ Ο @ 舀 @ © S 2 @ © PS ® CO ® Γ» © αΐ © S ® s © 卜· © c> ◎ 1 «η La-3 ΐ 1 300 P> 未修飾 觸 ο S & 炒 1 @ @ S ◎ ο ◎ Ν ◎ @ 2 μ @ © *? ® !·> ⑪ « ❾ σ> @ 5： ⑫ a @ 卜· @ f C4 缽 s Μ I MAc § 〇» 未修飾 擁 in ri S S Y- 喊 猱 1 ◎ ❾ 5 〇 <3 S @ @ S @ © 5 0 «» ιη Ο s Θ S @ S @ © 1«. @ r· ◎ 1 fD I A·丨丨 ΐ 1 MAc 1 300 Ot 未修飾 滩 〇> ο S 搣 猱 © 〇 S 〇 <3 ◎ B © @ S @ @ 5 0 ΙΟ Ο «η Ο & 0 S @ S © © *» ◎ 1 CM 1 A-13 t MAc 1 〇· 未修飾 婢 Ν ? S 臧 疾 薜 @ © 辑 X - X X eg | 1200 1 X X 〇 ο X X O X U3 X «ο X s 〇 W X CO X 00 ◎ <v X X 1 m 睡 鼷 u 雔 1 <Bg/聚合场io〇g) Ruo 1/聚合物 100C) | i «έ Η |<uo丨/聚合物100g)| 电 (? 系 1¾ S 画 i t Μ § 社 m & i 細 S 1 i <! i > ! Π δ a ® 链 1 § 1 « a < a N ί i D i I m I 5 <π 抜 黏合保持率(％) 钿 i 初期 ί < < 1 3 Β t ι ) i ι 銳七 蟀8 初期 i < < t 3 Β t 1 耐濕熱 IDOO/J^rM_ 初期 1 i ϋ ί > j } 耐濕熱 _LQQQ/b^·_ 7Y0380nm | 艇1 <Π m » (甲基)丙 烯醢基 三乙氧基 矽烷基_； Μ 伽 ijn 凝膝成分 初期 耐熱 耐濕熱 色差b* 1 I總光線透射率 « 1 箱度 瑤 η (甲基)丙烯i 酸系聚合物^ 1 黏合物性 光學特性 -49- 201105760 r- 1 A-10 1 2 υ [i5〇〇_l 1_ί〇·6_| 未修飾 婢 * η σ* 卜 1 tn i 1 1 1 — I 1 t in » 1 1 i 1 00 β La-11 1 L上3…1 | 250 I 00 s — 碑 1/3 I Λ σ> 卜 1 m ο t 1 1 1 — 1 1 1 to 1 1 1 1 唯 嫉 ΙΟ β 1 A-9 1 1. ρ-3Π § βο 未修飾 摊 <· <Ό σ> 1— » m ο \ 1 1 » — 1 \ \ in 1 1 \ » \ Y- 喊 a | A-14 |P-3 J ! MAc | | 4000 1 1 25.8 1 未修飾 Φ ή 1 η 〇> Γ- I U) 1 1 1 1 1 1 1 U) 1 1 1 1 1 喊 U9 御3 1 A·8 1 「^ ] | MAc | 3000 I 丨 19.4 ι 未修飾 睥 CO 5 Ο V ο σ> 卜 1 u> o 1 1 1 1 — 1 \ 幽 in 1 1 1 1 1 卜 ρ r A-；.. i 丨 Ρ-3_Ί | MAc 1 1 750 1 00 未修飾 摊 in n 男 1 Λ 〇> 卜 i in 1 1 1 1 *4 1 1 幽 in 卜’ 1 1 \ 1 t Y- 嫉 CO κ Γ A-3 I <*> i | MAc 1 〇 σι — η Ά χτ τ CO σ* r— 1 (A o 1 1 » 1 i 1 1 1 1 J 1 1 K- OJ 廢？ 1 Α-ΐ 1 1- P-3 1 i 〇 to 未修飾 m cn ? η σ> 卜 1 tn 幽 I 1 1 — 1 1 1 tn 1 1 I 1 1 Y- 喊 5 I -A-15 1 l-P-3 J | MAc | S 'β; 未修飾 濉 r> 另 1 «η σ> 卜 U) ό 1 1 1 I 1 1 唯 in 1 幽 1 1 1 F 丨比13丨 L __P^3_」 I (P-3) | 未修飾 未修飾 m CO « η σ> 卜 1 U5 1 1 1 t - 1 1 1 in 1 1 1 1 1 嫉 5 I "」 I (P-3) | 未修飾 未修飾 婢 «〇 ? ΡΟ σ> 卜 1 u> d 1 1 1 1 1 1 1 1 in 1 1 1 1 1 C4 h ΰ Λ C4 a 1_m_I | (P-3) 1 未修飾 未修飾 i« C9 <N s 1 ο 1 1 1 1 1 o 1 1 1 1 m d 嫉 F R 駿 m Γ> Umi w | (mg/聚合物 100g> 1 |(naol/聚合物lOOg) | | (mg/聚合物 100g) I |(刪"聚合物I00g)| Hi|s] ΐ 逛 ΙΊ δ i (質量份） (質量份） (質量份） (質量份） i 咖 /«— Φ 0ι _ 1 嵌 IK m (甲基)丙烯醢基 S fi 扣 J8 卜 1 j ϊ ί 0 1 ΡΓ _ Μ φΠι 03 1. __1 1 c-i I C-2_ C-3 I L C-4 _1 | 05 --」 1 D"1 1 丨 D-2 D-3 D-4 . ω Ε-2 | Ε-3 I Ε-4 U. 趣 IS 酿 嵌 m 画 (甲基)丙烯 酸系聚合物 聚合性羧酸類 光聚合起始劑 矽烷偶合劑 其他聚合 性化合物 m 越 執 交聯劑 。W蹉娛K长谳-ν-w題发KM&UUVN-^W。莩鎰丑胺谳..丑-匡握_长*..<-旮揪※ -50- 201105760 寸^ 卜 牺 〇 < ΓΪ ο I (D 〇 i i 4 1 蝴 σι ? 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Heating under a nitrogen stream and heating to reflux. Thereafter, 5 parts by mass of AIBN® as a polymerization initiator was added, and the mixture was reacted at 80° C. for 6 hours to obtain a (meth)acrylic polymer (P-5) solution (weight average molecular weight: 798,000, glass). Transfer temperature -55t, solid content concentration 30% by mass, viscosity 4500mPa · s/25°C (Reference Example 6) -42- 201105760 In a four-neck round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet, and a thermometer Adding 7 parts by mass of 2-ethylhexyl acrylate, adding 15 parts of 'methyl succinic acid 2 - 15 parts by weight of ethyl vinegar and 400 parts by mass of methyl ethyl ketone, heating under a nitrogen stream, Heating and refluxing were started. Thereafter, 0.01 part by mass of AIBN as a polymerization initiator was added, and the reaction was carried out at 8 ° C for 8 hours to obtain a (meth)acrylic polymer (p_6) solution (weight average molecular weight of 1,233,000, Glass transition temperature _55t: solid content concentration 20% by mass, viscosity 8000 mPa·s (25 ° C)) (Reference Example 7) Commercially available acrylic acid copolymer (trade name: ARUFON UH2000 'solid content 100 Mass%, weight average molecular weight K1 million, glass transfer temperature -55 ° C, manufactured by Toagosei Co., Ltd.) as a polymer (P_7). (Reference Example 8) 100 parts by mass of toluene was added to a four-necked round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet, and a thermometer. Next, a mixture of 97.5 parts by mass of 2-ethylhexyl acrylate, 1.5 parts by weight of ethyl acrylate, 1 part by mass of acrylic acid, and 2 parts by mass of AIBN was added dropwise under a nitrogen stream for 2 hours. 〇〇t reaction for 8 hours, thereby obtaining a (meth)acrylic polymer (P-8) solution (weight average molecular weight of 486,000, glass transition temperature - 83 ° C, solid content concentration of 50% by mass, viscosity 74 〇〇) mPa · s / 25 ° C ) -43- 201105760 (Reference Example 9) 5 parts by mass of acrylic acid, butyl acrylate 95 mass in a four-neck round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet, and a thermometer 80 parts by weight of ethyl acetate, 40 parts by mass of acetone, 0.03 parts by mass of AIBN as a polymerization initiator, and reacted at reflux temperature of ethyl acetate for 3 hours under a nitrogen stream, and then diluted with ethyl acetate to obtain (methyl). Acrylic polymer (P-9) solution The weight average molecular weight is 1.836 million, the glass transition temperature is -50 ° C, the solid content concentration is 16% by mass, and the viscosity is 9000 mPa. s / 25 ° C. [2] Crosslinkable (meth)acrylic polymer (component A) Synthesis: Next, a reactive inductive group was introduced into a matrix polymer to obtain a crosslinkable (meth)acrylic polymer (A-1). (Reference Example 10) (Methyl) synthesized in Reference Example 1. In the acrylic polymer (P-丨) solution, 'dibutyltin laurate is added in an amount of 0.05 parts by mass based on 100 parts by mass of the (meth)acrylic acid (P-1) in terms of solid content.质量. 3 parts by mass of 2-methyl propylene oxirane ethyl isocyanate (trade name · Karenz Μ ' I's manufactured by Showa Denko Co., Ltd.), and reacted at 5 Torr for 8 hours. The reaction was terminated by titration analysis of the reaction solution by the disappearance of the isocyanate group. Thus, a (meth)acrylonitrile group was introduced into the acrylic acid-based polymer (!>_) to obtain a crosslinkable (meth)acrylic polymer (A-fluorene) solution (weight average molecular weight 19.9) 10,000 'glass transfer temperature, solid content concentration 3% by mass, viscous -44 - 201105760 degrees 600 mPa · s / 25 ° C) 0 (Reference Example 11~2 3 ) In addition to changing the type of matrix polymer, having 萆 _ isocyanate In addition to the type and amount of the (meth)acrylic compound, the same procedure as in Reference Example 8 was carried out to obtain a crosslinkable (meth)acrylic polymer (A ^ 10), (A-! 2) ~(Α-15)β 丨, Table 3, Table 5 and Table 7 show their feed ratios. (Reference Example 24) The (meth)acrylic polymer (ρ_3) synthesized in Reference Example 3 was dissolved in 23 parts by mass of methyl ethyl ketone to obtain a (meth)acrylic polymer solution (solid content concentration). 30% by mass). To 100 parts by mass of the (meth)acrylic acid polymer (in terms of solid content), 0.05 parts by mass of dibutyltin laurate and 2-propenyloxiranyl ethyl isocyanate (trade name: Karenz AOI, manufactured by Showa Denko Co., Ltd.) 0.25 parts by mass and alkoxydecane-based compound (3-isocyanatepropyltriethoxydecane, trade name: KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.1 parts by mass, and reacted at 50 ° C for 8 hours. By the titration analysis of the reaction liquid, it was confirmed that the time at which the isocyanate group disappeared was terminated as a reaction, and a crosslinkable (meth)acrylic polymer (Al 1) solution (weight average molecular weight of 425,000, glass transition temperature -3 (g) was obtained. TC, viscosity 500 mPa · s / 25 〇 C) ° (Reference Example 25) -45- 201105760 2-methylpropene oxy-oxygen B was added to the (meth)acrylic polymer (p_8) solution synthesized in Reference Example 8. 2 parts by mass of the isocyanate (manufactured by Showa Denko Co., Ltd.; Karenz M〇i), 4 parts by mass of hydroquinone, and 4 parts by mass of dibutyltin laurate, and subjected to a modification reaction at the same temperature for 8 hours. The toluene was distilled off to make the residual solvent 1% or less, thereby obtaining a crosslinkable (meth)acrylic polymer (Α-16) (weight average molecular weight: 493,000, glass transition temperature - 83 ° C). 26) (meth)acrylic polymer (P- relative to 1 part by mass (calculated as solid content) in the (meth)propionic acid-based polymer (p_9) solution synthesized in Reference Example 9 9) Adding 50 parts by mass of ethyl acetate / 50 parts by mass of toluene Solvent, 0.08 parts by mass of dibutyltin dilaurate and 5.4 parts by mass of 2-methylpropane oxirane ethyl oxalate, and reacted at 65 ° C for 8 hours. Finally, the reaction solution was diluted with toluene to obtain crosslinkability. (meth)acrylic polymer (A-17) solution (weight average molecular weight 1.855 million, glass transition temperature - 5 (TC, solid content concentration 13% by mass, viscosity 9500 mPa · s / 25t:). The quality was evaluated by the following method [weight average molecular weight] The polystyrene-equivalent weight average molecular weight of the polymer was measured by GPC method. -46- 201105760 [Glass transfer temperature] According to JIS Κ7121 (plastic transfer temperature measurement method) Glass transfer temperature of the product [Methyl propylene sulfhydryl content • Triethoxymethyl decyl content] The methacrylic acid oxime alkyl content of the polymer is quantified by acid-base titration. The mixture of 5 di-n-butylamine (DBA) is obtained, and the amount of the DBA consumed by the unreacted isocyanate group of the (meth)acrylic phthalic acid compound and the DBA acid is back-titrated. 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• W嫿跋K^^-v-s^^Mgi-vw-i^^s^qi^^'-^siK^F^.tf^JiE -51 - 201105760 i •φ ϋ A-4 | <L MAc | ο 另 σ* ψ·^ 未修飾 LUl Ο ? in ΙΟ CN3 1 u> ο 1 1 1 J I 1 1 i 1 1 I 1 ] 1空氣下1 無熟化1 t— ft A~4 1 η i MAc Ο CO σ» 未修飾 I 60.4 萬 I 1 -30 S s 1 m ο 1 1 1 1 1 1 1 1 1 1 1 1 1 1空氣下1 無熟化 GO A-4 丨 Μ 1 MAc Ο CO σ* 未修飾 I 60.4 萬 I 1 -30 CO O) 1 卜 tn ο 1 1 1 1 1 1 1 1 1 1 1 1 1 1空氣下1 無熟化 寸 触 1 A-4 I P-4 MAc ο s Ο) 未修飾 I 60.4 萬 I ο ? CO σ> h- 1 in ο 1 1 1 1 1 1 1 1 1 1 1 1 1 厂空氣下1 無熟化 i〇 κ 1 A-4 1 1 .μ丨 MAc g CO Ο) 未修飾 60.4 萬 | 99.5 | in d 1 in d 1 1 1 1 1 1 1 1 1 1 1 1 1 「空氣下1 無熟化 CO a 1__^：4_J I MAc o σ> 未修飾 I 60.4 萬 I -30 o 1 1 in 1 1 1 1 1 1 1 1 1 1 1 1 1 y~ 嫉 無熟化 種類 基質聚飾種類 n ifwil 卿 (mg/聚合物lOOg) (omo丨/聚备物100g) (mg/聚合物100g) (omol/聚合物 100g) ρ«Μ] 屮 _ tlrnll 職 (質量份） (質量份） (質量份） (質量份） (質量份） (質量份） (質量份） (溫度、時間） (甲基)丙烯醢基 三乙氧基矽烷基 B-l B-2 C-l C-2 C-3 C-4 C-5 D-l D-2 D-3 D-4 E-l E-2 cp ω γ cu i 聚異氛酸酯 固化環境 離條件 (甲基)丙烯 酸系聚合物 聚合性羧酸類 光聚合起始劑 矽烷偶合劑 其他聚合 性化合物 紫外線吸收劑 交聯劑 。«窗歧^®^·^2··"^。^^^^"·^"^*^""-^^※ -52- 201105760 9¾ ·«· U3 c>i 1 ◎ ◎ jj ◎ CO N < X 〇 CO ◎ X σ> CO σ> CO ◎ X CO ◎ « © r> ◎ 5ί ◎ 〇! ◎ s ◎ t»- o ◎ ί ο ◎ t— d ◎ 1 in； s 1 ◎ @ S ◎ CO CM <3 ◎ 芑 Μ ◎ ◎ S σ> tr> ◎ ◎ « ◎ C0 〇 ◎ η ό ◎ at ◎ 〇> ◎ cS ◎ ◎ t— o ◎ Ϊ- Ο ◎ 1 CO 魏 1 卜 ◎ ◎ ΰ ◎ 1Λ ◎ ◎ S c*> «ο — ◎ ◎ 00 § ◎ ◎ η ◎ CO 〇 ◎ CO ο ◎ 〇> ◎ σί ◎ cri ◎ r*. 〇 ◎ 卜 d ◎ ί— d @ 1 i r— 1 ◎ ◎ s ◎ to 〇 ◎ Μ IT) ◎ ◎ 00 ¢0 ◎ @ CO ◎ Ρ0 d @ CO ο ◎ σϊ © σ> ◎ σί ◎ t- o ◎ 卜 d ◎ d ◎ 1 i〇 駟 U3 〇 1 ◎ ◎ s 〇 2 ◎ ◎ 00 σ> ◎ ◎ 2 Ο ◎ ◎ η ο ◎ 〇 «· d 〇 s ◎ 8 ◎ St ◎ r- o ◎ 00 o ο oo 〇 1 CO ϋ o 1 ◎ ◎ 萃 X 2 ◎ ◎ 2 o — ◎ ◎ m Ο» X X eo Ο ◎ 〇> d X '«r X s ◎ CO X oo X r- 〇 ◎ 二 X Γ> X 1 (質量份） 1 s _ « 黏合力(N/25mm) 班 菜 詆 1 ΙΑ Ζ <π 黏合保持率(％) m 竑 m 1 2 <Π 黏合保持率(％) 班 頌 要 初期 耐熱 1000小時後 耐濕熱 1000小時後 初期 耐熱 1000小時後 耐濕熱 1000小時後 耐熱 1000小時徬 耐濕熱 1000小時後 T%@380nm | m 1 B-2 凝膠成分 _1 1 初期 _1 耐熱 耐濕熱 色差>>* 總光線透射率 (%) 霧度 1 UV遮蔽性 丨 聚合性羧_ 璉 m 黏合物性 光學特性 -53- 201105760 比10 1 CO i MAc | ο μ σ> 未修飾 丨42.4萬丨 ο ej5 CO σ» 卜 \ 1 \ 1 1 m d 1 1 1 m 1 1 1 1 1 1空氣下1 無熟化1 σ> 1 Α-3 1 1 P-3 1 MAc ο CO σ» 未修飾 雔 oi 寸 Ο cp CO σ> 卜 \ 1 1 1 in o 1 1 1 1 IT) 1 1 1 1 ί 「空氣下1 丨無· 1 οο ±J 1 Α-3 1 1 p-3 1 MAc Ο 另 σ» 未修飾 崦 ο CO CO Ο) 卜 1 1 1 in ο 1 1 — 1 1 t in 1 1 1 1 1 1空氣下1 無熟化 r» 1 Α-3 1 1 p-3 1 MAc Ο CO σ> 未修飾 1 «.4 萬 | ο cp CO σ» 卜 踰 1 m 〇 I l 1 1 1 1 tn 1 1 1 1 1 1空氣下1 無熟化 CO Β L Α-3 1 P-3 MAc Ο CO σ> — 未修飾 雔 eg ο CJ> CO σ> f— 1 iq d 1 I I 1 1 1 1 u> 1 1 1 1 1 1空氣下1 疾 摧 φ a 1 Α-4 1 1 m i MAc Ο CO I—· 未修飾 丨60.4萬| ο cp CO σ> 卜 肅 in 1 I 1 1 1 1 1 1 1 1 1 1 1 i空氣下 丨無熟化 丨實ιι 1 Α-4 卜4 MAc Ο 另 σ> 未修飾 1 60.4 萬 1 ο CO C5 σ> 卜 1 1 I 1 1 — 1 1 1 1 1 1 1 1 1 1空氣下1 丨無齡 CO κ 丨卜3 1 MAc ο σ» 未修飾 丨42.4萬| ο to CO σ> 卜 1 in ο 1 1 \ 1 — ( 1 1 1 1 1 t 1 1 嫉 !無熟化 實10 1 Α-4 1 丨Μ 1 MAc ο 另 σν 未修飾 1 60.4 萬 1 ο «ρ CO σ> 卜 1 1 0.25 1 1 I 1 1 1 1 1 1 1 \ \ 1 1 丨空氣下丨 無熟化 σ> κ Α-4 P-4 MAc ο CO σ> 未修飾 1 60.4 萬 | ο cp CO σ> 卜 1 0.05 1 I 1 1 1 1 1 1 1 1 1 1 V- 嫉 無熟化 ιη α 1 Α"4__1 丨tM | MAc Ο 另 σ> 未修飾 60.4 萬 ο CJ5 CO Ο) 卜 1 丨 o-oi 1 1 1 1 1 1 1 i ( 1 1 1 1空氣下1 無熟化 種類. 膝 w m <n 联 « 種類 (mg/聚合物10 0g) (mmol/聚合物 100g> (mg/聚合物 100g) 1 (mao 1 / 聚合物 100g) Λ Wn <-Ν μ (質量份） (質量份） (質量份） (質量份） (質量份） 1 (質量份） (質量份） 度、時間） (甲基)丙烯醯基 三乙氧基矽烷基1 (ϊ B-1 B-2 C-1 C-2 03 C-4 C-5 Λ D-2 D-3 D-4 山 CO UJ 2； i 聚異氰酸酯 固化環境 m 漆 (甲基)丙烯 酸系聚合物 聚合性羧酸類 光聚合起始劑 矽烷偶合劑 其他聚合 性化合物 紫外線吸收劑 交聯劑 D 糊題跋^^g。匡^Η'^^-Ή·/^辑魏'"""=-φ 谳※ -54- 201105760 s«• W婳跋K^^-vs^^Mgi-vw-i^^s^qi^^'-^siK^F^.tf^JiE -51 - 201105760 i •φ ϋ A-4 | <L MAc | ο σ* ψ·^ Unmodified LUl Ο ? in ΙΟ CN3 1 u> ο 1 1 1 JI 1 1 i 1 1 I 1 ] 1 Under air 1 No aging 1 t — ft A~4 1 η i MAc Ο CO σ» unmodified I 600.4 million I 1 -30 S s 1 m ο 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 under air 1 no ripening GO A-4 丨Μ 1 MAc Ο CO σ* unmodified I 60.4 million I 1 -30 CO O) 1 Bu tn ο 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Under air 1 No maturity Touch 1 A-4 I P-4 MAc ο s Ο) Unmodified I 60.4 million I ο ? CO σ> h- 1 in ο 1 1 1 1 1 1 1 1 1 1 1 1 1 Under the factory air 1 no aging i〇κ 1 A-4 1 1 .μ丨MAc g CO Ο) Unmodified 604,000 | 99.5 | in d 1 in d 1 1 1 1 1 1 1 1 1 1 1 1 1 "Under air 1 no aging CO a 1__^: 4_J I MAc o σ> Unmodified I 600.4 million I -30 o 1 1 in 1 1 1 1 1 1 1 1 1 1 1 1 1 y~ 嫉Non-maturing type of matrix aggregation type n ifwil qing (mg/polymer lOOg) (omo丨/polymer preparation 100g) (mg/polymerization 100g) (omol/polymer 100g) ρ«Μ] 屮_ tlrnll (parts by mass) ( Parts by mass (parts by mass) (parts by mass) (parts by mass) (parts by mass) (parts by mass) (temperature, time) (methyl) propylene decyl triethoxy fluorenyl Bl B-2 Cl C-2 C -3 C-4 C-5 Dl D-2 D-3 D-4 El E-2 cp ω γ cu i Polyisocyanate curing environment Conditional (meth)acrylic polymer polymerizable carboxylic acid photopolymerization Starting agent decane coupling agent Other polymeric compound UV absorber crosslinker. «Window ^^^^^^··"^.^^^^"·^"^*^""- ^^※ -52- 201105760 93⁄4 ·«· U3 c>i 1 ◎ ◎ jj ◎ CO N < X 〇CO ◎ X σ> CO σ> CO ◎ X CO ◎ « © r> ◎ 5ί ◎ 〇! ◎ s ◎ t»- o ◎ ί ο ◎ t - d ◎ 1 in; s 1 ◎ @ S ◎ CO CM <3 ◎ 芑Μ ◎ ◎ S σ >tr> ◎ ◎ « ◎ C0 〇 ◎ η ό ◎ at ◎ 〇 ◎ cS ◎ ◎ t— o ◎ Ϊ- Ο ◎ 1 CO Wei 1 ◎ ◎ ΰ ◎ 1 Λ ◎ ◎ S c*> «ο — ◎ ◎ 00 § ◎ ◎ η ◎ CO 〇 ◎ CO ο ◎ 〇 gt ◎ σί ◎ cri ◎ r*. 〇◎ 卜d ◎ ί— d @ 1 ir— 1 ◎ s ◎ to 〇 ◎ Μ IT) ◎ ◎ 00 ¢ 0 ◎ @ CO ◎ Ρ 0 d @ CO ο ◎ σϊ © σ> ◎ σί ◎ t- o ◎ 卜 d ◎ d ◎ 1 i〇驷U3 〇1 ◎ ◎ s 〇2 ◎ ◎ 00 σ> ◎ ◎ 2 Ο ◎ ◎ η ο ◎ 〇 «· d 〇 s ◎ 8 ◎ St ◎ r- o ◎ 00 o ο oo 〇 1 CO ϋ o 1 ◎ ◎ Extraction X 2 ◎ ◎ 2 o — ◎ ◎ m Ο» XX eo Ο ◎ 〇> d X '«r X s ◎ CO X oo X r- 〇 ◎ 2 X Γ> X 1 (mass) 1 s _ « Adhesion (N/25mm)班菜诋1 ΙΑ Ζ <π Adhesion retention rate (%) m 竑m 1 2 <Π Adhesion retention rate (%) After the initial heat resistance for 1000 hours, the heat resistance is 1000 hours after the initial heat resistance for 1000 hours and the heat resistance is 1000 After 1000 hours, heat resistance for 1000 hours, heat and humidity resistance for 1000 hours, T%@380nm | m 1 B-2 gel composition_1 1 initial _1 heat and humidity resistance color difference >>* total light transmittance (%) haze 1 UV Shielding 丨polymerizable carboxy _ 琏m adhesive optical properties -53- 201105760 than 10 1 CO i MAc | ο μ σ> unmodified 丨424,000 丨ο ej5 CO σ» 卜\ 1 \ 1 1 md 1 1 1 m 1 1 1 1 1 1 Under air 1 No ripening 1 σ> 1 Α-3 1 1 P-3 1 MAc ο CO σ» Unmodified 雔 oi Ο Ο cp CO σ> 卜 \ 1 1 1 in o 1 1 1 1 IT ) 1 1 1 1 ί "Under the air 1 丨 no · 1 οο ±J 1 Α-3 1 1 p-3 1 MAc Ο Another σ» Unmodified 崦ο CO CO Ο) Bu 1 1 1 in ο 1 1 — 1 1 t in 1 1 1 1 1 1 Under air 1 No ripening r» 1 Α-3 1 1 p-3 1 MAc Ο CO σ> Unmodified 1 «.4 million | ο cp CO σ» Bu more than 1 m 〇I l 1 1 1 1 tn 1 1 1 1 1 1 1 under air 1 no ripening CO Β L Α-3 1 P-3 MAc Ο CO σ> — unmodified 雔eg ο CJ> CO σ> f-1 iq d 1 II 1 1 1 1 u> 1 1 1 1 1 1 Under air 1 Disease φ a 1 Α-4 1 1 mi MAc Ο CO I—· Unmodified 丨 604,000 | ο cp CO σ> Bu Su in 1 I 1 1 1 1 1 1 1 1 1 1 1 i Air 丨 丨 熟 熟 丨 ι ι ι MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA MA 6 6 6 6 1 1 1 1 1 1 1 Under air 1 丨 No age CO κ 丨 3 3 MAc ο σ» Unmodified 丨 424,000 | ο to CO σ> 卜 1 in ο 1 1 \ 1 — ( 1 1 1 1 1 t 1 1 嫉! 无熟化实10 1 Α-4 1 丨Μ 1 MAc ο another σν unmodified 1 60.4 million 1 ο «ρ CO σ> 卜1 1 0.25 1 1 I 1 1 1 1 1 1 1 \ \ 1 1 丨Air 丨 no aging σ> κ Α-4 P-4 MAc ο CO σ> Unmodified 16.04 million | ο cp CO σ> Bu 1 0.05 1 I 1 1 1 1 1 1 1 1 1 1 V- 嫉Uncooked iι α 1 Α"4__1 丨tM | MAc Ο another σ> unmodified 604,000 ο CJ5 CO Ο) 卜 1 丨o-oi 1 1 1 1 1 1 1 i ( 1 1 1 1 under air 1 no aging type. knee wm <n 联« (mg/polymer 100 g) (mmol/polymer 100 g) (mg/polymer 100 g) 1 (mao 1 / polymer 100 g) Λ Wn <-Ν μ (parts by mass) (parts by mass) (parts by mass) (Parts by mass) (parts by mass) 1 (parts by mass) (mass parts) Degree, time) (Methyl) acrylonitrile triethoxy sulfonyl group 1 (ϊ B-1 B-2 C-1 C-2 03 C-4 C-5 Λ D-2 D-3 D-4 Mountain CO UJ 2; i Polyisocyanate curing environment m lacquer (meth)acrylic polymer polymerizable carboxylic acid photopolymerization initiator decane coupling agent other polymerization Sex compound UV absorber crosslinker D paste problem 跋 ^ ^ g.匡^Η'^^-Ή·/^辑魏'"""=-φ 谳※ -54- 201105760 s«

ο £ 1 » 1 1 U3 ◎ ◎ ίο ◎ ◎ ◎ <〇 3 — ◎ @ «Ο 2 ◎ ◎ <D d X 00 〇 σ> X § © s ◎ 卜 d ◎ eo 0 p X 1 σ> a t 1 1 ιή 1 ◎ ◎ X - ◎ X 〇> ◎ © 00 ro X X 00 X X X ◎ 茬 ◎ s ◎ 卜 d ® 0% 〇 «〇 •-H X 1 CO i ( in 1 I ◎ s ◎ n ◎ ◎ 00 CO n ◎ ◎ CV| »-* M 〇> X ◎ ΙΟ X X r> X S ◎ S ◎ 苗 ◎ t- d ◎ q o — X 1 卜 1 tn 1 1 i @ ◎ CO m o n ◎ ◎ <〇 <n CJ ◎ ◎ 2 1 ◎ ◎ u> X 00 〇 o X g ◎ @ s ◎ ◎ 卜 d ◎ 卜· ◎ 1 2 ΙΟ I i 1 I ◎ ◎ s ◎ μ ◎ ◎ ΙΑ U3 — ◎ ◎ ΙΟ — u> ◎ CO ◎ r> ® CJ ◎ α> © S ◎ 5> ◎ 卜 d ◎ r-； ◎ I"-· ◎ 1 ο £ ΙΩ j 1 1 1 ◎ ◎ s ◎ CSJ cs < ◎ CM C*5 CM ® ◎ N s ◎ ◎ to X 00 O cn X ◎ S ◎ s 0 r— d σ» 0 二 X 1 ή » 1 1 t ◎ ◎ 这 ◎ σ> ο ◎ 誃 (O ◎ ◎ N M — ◎ ◎ «〇 ◎ 穴 O fl； ο m ◎ σ> ◎ A ◎ 卜， ◎ P· ◎ I"»· ◎ 1 η Μ 6 I 1 1 1 ◎ ◎ 3 ◎ 〇 ◎ CO N ◎ <n C4 — ◎ @ n o r> o ◎ CO d ◎ σ> ◎ S ◎ σ! ◎ t- o ® 〜 o ◎ *-· ◎ 1 ο 侧 U) CN) Ο I t t 1 ◎ ◎ s o ◎ ◎ <〇 2 ◎ @ «〇 ◎ ◎ CM 〇 ◎ w ◎ Cl ◎ η ◎ A ® σΐ r»； ◎ ί ο ◎ t-; ◎ 1 σ» 御1 g ο I 1 1 1 ◎ ◎ s o C4 ◎ ◎ r~ C*3 •V — ◎ ◎ CJ s ◎ ® CM 〇 © CJ ◎ ◎ σ> ◎ σΐ ◎ r*； o ◎ 卜 e P*. o ◎ t υ> ο I 1 1 1 ◎ ◎ (O X O) ◎ X 00 i ◎ X 卜 09 X X CO d ◎ IA 〇 o 二 X S ◎ s X φ X r· o ◎ X X 1 § _ tt 琏 埕 g 豳 1 m 1 鈿 燄 或 m 3 •I 5 •R <D ¢: m <n «§ 羧 或 龚 Jl δ <Π 1 <Π S 1 装 1 m 〆 癱i ®s 銳< 踩8 ®Ξ 1 ffi «=Ι iS2 t 銳令 蜂g fiS 顆 t ms B2 游 i 銳令 m§ ®2 e s 英 I ϋ S s z 2 <k· 链 m m I 1 m m % ¢3 趾 粕a 璨2 键 « m i toil W <Π 嵌 <Π 坦 & m /7W -55- 201105760 i 1 比 19 1 CO ? MAc ο 另 σ» 未修飾 1 42.4 萬 1 〇 CO σ> 卜 1 w> d 1 1 1 1 1 1 1 ^-4 m 1 i 1 1 1 丨空氣下1 無熟化 比18 e〇 CO ά MAc ο CO σ> — 未修飾 | 42.4 萬 | 〇 er> CO σ> 卜 1 u? ο 1 1 1 1 1 1 1 U9 1 1 1 1 1 1空氣下1 無熟化 比17 CO CO MAc ο 异 σ> — 未修飾 1 42·4 萬 1 芑 1 CO σ) 1 U) ο 1 \ \ 1 ο \ 1 l in 1 ( 1 1 1 1空氣下1 無熟化 實20 cp CO i MAc ο CO σ» *·< 未修飾 丨42·4萬| 〇 CJ> CO σ> 卜 1 in ο 1 1 1 1 1 1 1 in 1 1 1 1 1 1空氣下1 無熟化 實21 CO CO i MAc ο s σ» 未修飾 丨42.4萬| 〇 CO CO σ> 卜 1 in ο 1 1 1 1 1 t 1 in 1 1 1 1 1 1空氣下I 無熟化 I 實 19 I CO CO i MAc ο s σν — 未修飾 丨42.4萬| ο cp CO σ> 卜 1 in d 1 1 1 1 6 1 1 1 ΙΛ 1 1 1 l 1 1空氣下1 無熟化 比16 cp CO MAc ο CO σ> 未修飾 丨42.4萬| 另 1 CO σ> 卜 1 in o 1 1 1 1 1 1 t 1 1 i 1 1 1空氣下1 無熟化 比15 1 CO i MAc ο (Ο Ο 未修飾 I 42.3 萬 1 ο ? CO σι 卜 1 CD o 1 1 1 1 1 1 1 1 in r*·· 1 1 1 1 1 1空氣下 無熟化 種類 基質聚合物_ 種類 (mg/聚合物lOOg) (_〇1/聚合物 100g) (mg/聚合物100g) (_〇1/聚合物 100g) 重量平均分子量 Β (質量份） (質量份） (質量份） (質量份） (質量份） (質量份） (質量份） (溫度、時間） (甲基)丙烯醯基 三乙氧基矽烷基 fS? m CQ •Η ύ eja ύ cp ό ύ S ώ CO i CO ώ y* 〇 ίϋ Ν 山 s ώ 丄 聚異氰酸酯 固化環境 熟化條件 (甲基)丙烧 酸系聚合物 聚合性羧酸類 光聚合起始劑 矽烷偶合劑 <Π^ 紫外線吸收劑 交聯劑 。《魍tfHS^-pv21·^^。匡鎰丑长谳，.丑=·匡捶舾长«=«-廿*※ -56- 201105760 2« 9) 5 » 1 "· ◎ ◎ O «〇 ◎ tD Ο ◎ 00 2 ◎ η όο X ◎ w o ◎ «ο X ID 〇 X ◎ s ◎ g ◎ r* d ◎ OJ ο tT) 〇 1 1 比 18 I t 1 ◎ ◎ (O ◎ ΙΟ ◎ ◎ cn Μ ◎ ◎ s X ◎ Ο 卜_ X CO o X g ◎ s ◎ s ◎ r- 〇 ◎ (7) ο cn 〇 1 ί ο 1 1 1 ◎ ◎ e>j iO ◎ ο X S 00 ◎ ◎ a ◎ X <n o ◎ f*» d ◎ « ◎ S ◎ s ◎ § ◎ Ρ» o ◎ ◎ r— d ◎ 1 ° Κ to 1 1 1 ◎ ◎ i〇 ◎ r- ο ◎ N 00 ◎ ◎ σ> ◎ ◎ o o fO o ◎ rs o ◎ O) 〇> ◎ s ◎ o ◎ N· d ◎ P- o ◎ 1 Ν 獅 1 «Η 1 1 ◎ ◎ es lO ◎ u> ◎ ◎ (O ◎ ◎ σ> N ◎ ◎ rt ◎ n ◎ CO ◎ a? m @ σ! ◎ ◎ ◎ ◎ 1 麵 d 1 1 t ◎ ◎ e*» (〇 ◎ IA ◎ ◎ 卜 2 ◎ ◎ o ◎ ◎ o o ◎ m ◎ in d 〇 ◎ σ! ◎ ◎ P«; o ◎ f- o ◎ 00 ◎ 1 (JD S 1 » 1 ί ◎ ◎ to ◎ LA ◎ ◎ 00 ◎ ◎ «2 X ◎ CQ ◎ CO ◎ CO ◎ 茗 ◎ B ◎ 袞 ◎ ◎ P· o ◎ r- o ◎ J in ΰ 1 1 1 1 ◎ ◎ U3 〇 (X- ο ◎ w ◎ ◎ in 00 CO X © CO 〇 ◎ *? O ◎ CO ◎ s 3 ◎ ◎ ◎ r- o ◎ 1 (質量份） m I” m ,Wa _ 黏合力(N/25ram) 燄 或 m 1 in S R 黏合保持率(％) 班 1 要 M <n 黏合保持率(％) a 像 s m 初期 耐熱 1000小時後 耐濕熱 1000小時後 初期 耐熱 1000小時後 耐濕熱 1000小時後 初期 :耐熱 1000小時後 耐濕熱 1000/fN^_ T%®380nm | 1_D-l_1 __ 1__1 Γ__Ί 凝膠成分 初期 耐熱 耐溻熱 色差b* 總光線透射率 (%) i 1霧度 1 t 瑤 矽烷偶合劑 链 •tt m 黏合物性 光學特性 i -57- 表11 —cn8_ 實23 實25 實24 實26 實22 比20 實27 比 21-1 比2卜2 (甲基)丙烯 酸系聚合物 種類 A-9 A-9 A-9 A-9 A-9 A-9 A-9 A-16 ΑΊ6 基質聚合物種類 P-3 P-3 P-3 P-3 P-3 P-3 P-3 P-8 P-8 (甲基)丙烯醯基 麵 Ac Ac Ac Ac Ac Ac Ac MAc MAc (mg/聚合物lOOg) 250 250 250 250 250 250 250 2000 2000 (mmol / 聚合物 lOOg) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 12.9 12.9 三乙氧基矽院基 (mg/聚合物l〇〇g) (mmol/聚合物 lOOg) 未修飾 未修飾 未修飾 未修飾 未修飾 未修飾 未修飾 未修飾 未修飾 重a平均分子量 42.4 萬 42.4 萬 42.4 萬 42.4 萬 42.4 萬 42.4 萬 42.4 萬 沾-3萬 49_3 萬 Tg rc) -30 -30 -30 -30 -30 -30 -30 -83 -83 (質删 93 93 93 93 93 93 93 97.1 97.1 聚潍羧酸類 B-1 (質量份） 7 7 7 7 7 7 7 2.9 2.9 B'2 光聚合起始劑 C-l (質量份） 0.5 0.5 0.5 0.5 0.5 0.5 3 - - 02 C-3 C-4 05 - - - - - - - 2.9 2.9 矽烷偶合劑 D-l (質量份） 1 1 1 1 1 1 1 - - D-2 D-3 D-4 其他聚合 性化合物 ΕΊ (質量份） - 7.5 - 10 15 25 15 - - E-2 0.5 1 10 2 - - 5 - - E-3 - - - - - - - 191.3 191.3 E-4 - - - - - - - 2.9 2.9 紫外線吸收劑 F-l (質量份） - - - - - - 3 - - 交聯劑 聚異氰酸酯 (質量份） - - - - - - - - - 固化環境 空氣下 空氣下 空氣下 空氣下 空氣下 空氣下 空氣下 空氣下 空氣下 熟化條件 (溫度、時間） 無熟化 無熟化 無熟化 無熟化 無熟化 無熟化 無熟化 無熟化 無熟化 201105760 ※表中，"實"表示實施例，"比"表示比較例。另外,"MAc"甲基丙烯醯基,"Ac"表示丙烯醯基。 201105760 -« CJ, r* s Ο) Ν US 摧 X X η X X X 2 | 1400 1 X X d 〇 X ◎ 2 X X to r» X X ο S X X X ao X 1 ί 1 1 1 191.3 1 〇t ci <Π is 漆 « X X CO © S 〇 « S δ ◎ X 卜 tn η X ◎ CO X — X n c4 X £5 X S Ο 沿 X Λ X pi X X 1 Κ m ΙΑ 1 1 卜 嫉 创 症 鞋 ◎ ◎ s ◎ 〇 ◎ CJ ◎ ◎ s αο ◎ ◎ »*. ♦ 1 r>j ◎ ◎ 8 ◎ Β @ S © 卜 ◎ t· ◎ t— <6 ◎ Μ S ΪΙ t ( 1 K- HS 创 m 摧 ◎ ◎ ο ◎ « ◎ ◎ 二 茺 ◎ X (Ο in X X 2 ο ◎ 'ψ ◎ S 〇 S © S ◎ 卜· ◎ 00 d ◎ ao ◎ t 獅 V» 1 1 1 H- ¥ « @ ◎ N ◎ ο ◎ ◎ § ◎ ◎ w ◎ ◎ ，· 0 *r ◎ ◎ S Ο S ◎ @ r- ο ◎ r- o ◎ r~ O ◎ 1 獅 ο CNJ 1 1 i 两 1 ◎ ◎ E3 ◎ 〇 ◎ g ◎ φ 宕 00 ◎ @ ca ◎ 3 ◎ N 目 ◎ S ◎ S ◎ ◎ r*^ ◎ r- ◎ 1 獅 1 〇 1 1 痣 摧 ◎ ◎ 铝 © « < ◎ 筘 s ◎ ◎ η to CM ◎ ® C4 ◎ w ◎ « ◎ S ◎ σι ◎ σ! ◎ r- c» ◎ ◎ ◎ 1 Μ 蟲 ιη — 1 1 法 « ◎ ◎ μ ◎ 2 ◎ ◎ σ> B ◎ @ 2 H ◎ @ C4 ◎ ca ◎ CM 〇 ◎ m ◎ σ> ◎ ◎ @ ◎ r· ◎ 1 S3 Μ 1 in 1 1 Y- 碱 摧 ◎ ◎ S ◎ 2 ◎ ◎ S § ◎ @ 00 I ◎ ◎ CM o ◎ « ◎ CM 6 ◎ σι ◎ σί ◎ 〇> ◎ Ϊ-; ◎ ◎ r«； ◎ 1 (質量份） Μ | 匪 i & fe i i ϊ * m 埕 g _ 黏合力CN/25mra) Μ 实 憩 1 S Ζ ί <C 黏合保持率(％) a tust m ·? 1 黏合保持率(％) 函 ftK 踩 或 m 初期 耐熱1000 小時後_ 耐濕熱1000 _ 初期 耐熱1000 小時後 耐濕熱1000 小時後一 初期 耐熱1000 小時後^ 耐濕熱1000 小時後_ 1 T%9380nra | ζ 1__1 η 山 ώ 凝膠成分 初期 耐熱 耐濕熱 色差於 總光線透射率 (%) 霧度 * 其他聚合 性化合物 黏合物性 光學特性 增味-腾辰砮盛锯忒採炱昍* 。匡窗丑胳揪=妇-匡辑«胳谳._£1="谳※ -59- 201105760 [紫外線硬化性黏著劑組合物的調製] (實施例1) 相對於參考例1 〇的交聯性（甲基）丙烯酸系聚合物（A_ J 成分）溶液（固體成分30質量％)中的固體成分93質量份， 混合丙烯酸（B-1成分）7質量份、2,4,6-三甲基苯甲醯基_二 苯基氧化膦（C-1成分，商品名：Lucirin TPO，BASF公司 製造）〇.5質量份、3-環氧丙氧丙基三甲氧基矽烷（Dq成分 ’商品名：KBM-403，信越化學工業公司製造n質量份， 調製紫外線硬化性黏著劑組合物。 (實施例2〜2 7、比較例1〜2 3 ) 使用參考例10〜26中合成的A成分（A-1〜A-15成分） ，將各成分的種類和量變更爲表1〜12所記載的組成，除 此以外與實施例1同樣地製備紫外線硬化性黏著劑組合物 。另外，作爲各成分，係使用以下物質。 <B成分> B-1 :丙烯酸（大阪有機工業化學公司製造） B-2:丙烯酸二聚體（商品名：SIPOMER β -CEA-J, Rhodia日華公司製造） <C成分> C-l : 2,4,6-三甲基苯甲醯基-二苯基氧化膦（商品名： Lucirin TPO，BASF 公司製造） -60- 201105760 C-2:氧基-苯基-乙酸2-[2-氧代-2-苯基-乙醯氧基-乙 氧基]-乙基酯與氧基-苯基-乙酸2-[2-羥基-乙氧基]-乙基酯 的混合物（商品名：Irgacu re 754，Ciba Specialty Chemicals 公司製造） C-3: 2-甲基- l-[4-(甲硫基）苯基]-2-嗎啉基丙烷-1-酮（ 商品名：Irgacure 907，Ciba Specialty Chemicals 公司製造 ) C-4: 2,2-二甲氧基-1，2-二苯基乙烷-1-酮（商品名： Irgacure 651，Ciba Specialty Chemicals 公司製造） C-5: 1-羥基-環己基-苯基-酮（商品名：lrgacure 184, Ciba Specialty Chemicals 公司製造） <D成分> D-l : 3-環氧丙氧丙基三甲氧基矽烷（商品名：ΚΒΜ-403，信越化學工業公司製造） D-2 : 3-環氧丙氧丙基三乙氧基矽烷（商品名：κβΕ-403，信越化學工業公司製造） D-3 : Ν-2-(胺基乙基）3-胺基丙基三甲氧基矽烷（商品 名：ΚΒΜ-603，信越化學工業公司製造） D-4: 3 -疏基丙基三甲氧基砂院（商品名：ΚΒΜ-803， 信越化學工業公司製造） <Ε成分> Ε-1:脂肪族聚酯骨架聚胺酯丙烯酸酯（商品名： -61 - 201105760 EB270，Daicel SciTech 公司製造） E-2 :雙酚系環氧樹脂骨架聚胺酯丙烯酸酯（商品名： RipoxyVR-77，昭和高分子公司製造） E-3 :丙烯酸2-乙基己酯 E-4: 1，6 -己二醇二丙烯酸酯（商品名_· NK ESTER A-HD’新中村化學工業製造） <F成分> F-1: 2,2·，4,4’ -四羥基-二苯甲酮（商品名：DAINSORB Ρ-6 ’大和化成公司製造） <熱交聯劑> 聚異氰酸酯（商品名：CORONATE L，日本聚胺酯工業 公司製造） <溶劑> 甲基乙基酮（Kishida Chemical公司製造） 甲苯（Kishida Chemical公司製造） 乙酸乙醋（Kishida Chemical公司製造） 丙酮（Kishida Chemical公司製造） 另外’採用以下的方法評價紫外線硬化型黏著劑組合 物的品質。 [操作性（液體拉絲性）] -62- 201105760 將作爲評價物件的組合物製成固體成分濃度爲 量％的塗佈液，使塗佈液附著於玻璃棒上，觀察塗 玻璃棒落下時的狀態，進行目視評價。塗佈液從玻 下時，塗佈液與玻璃棒完全分離，以液滴狀態落下 下評價爲“ ”（良好）；塗佈液與玻璃棒沒有完全 以拉絲狀態落下的情況下評價爲“ X”（不良）。 [塗佈性（塗佈條痕）] 將作爲評價物件的組合物製成固體成分濃度爲 塗佈液，利用塗佈器將該塗佈液塗佈在一面已實施 處理的厚度38μιη的PET膜（剝離膜）的矽酮處理面 80°C 乾燥 2 分鐘後，以 500mW/cm2、80mJ/cm2 的 射紫外線，使塗膜進行紫外線硬化，形成黏著劑層 ，藉由將上述剝離膜的黏著劑層貼合在成爲基材的 (厚度1 〇〇 μιη，總光線透射率91 %，霧度値0.3。以 “基材膜”）上，從而在上述基材膜的表面形成厚度 的黏著劑層。此外，上述紫外線的照射利用高壓汞 。藉由闻壓萊燈，照射波長200〜400nm的紫外線。 塗佈性的評價如下進行，利用塗佈器將塗佈液 上述剝離膜的表面，確認塗佈時有無產生塗佈條痕 而言’調節塗佈器的狹縫寬度，以使得塗膜的 1 5 μπι ’以20m/分鐘的速度實施塗佈。此時產生的 痕的根數利用每15cm的塗佈寬度中產生的根數來 塗佈條痕爲0根時評價爲"◎ ”（極好），1根時評 30質 佈液從 璃棒落 的情況 分離， 3 0 %的 了矽酮 上，於 條件照 。其後 PET膜 下記作 15 mm 燈進行 塗佈在 。具體 厚度爲 塗佈條 評價。 價爲“ -63- 201105760 〇” ，2根以上時評價爲“ x” （不良）。 [凝膠成分] 利用索氏提取法稱量作爲評價物件的組合物的凝膠成 分。具體而言，以四氫呋喃爲溶劑，進行8小時索氏提取 ，將未被提取而殘留的不溶成分的質量％表示爲凝膠成分（ 質量％)。凝膠成分爲60質量％以上時評價爲“ ”（極好） ，55質量％以上且小於60質量％時評價爲“〇”（良好）， 小於55質量％時評價爲“ X”（不良）。凝膠成分爲55質量 %以上的情況下，卷取黏著膜時不發生黏著劑滲出，也沒 有壓紋膜等保護膜留下的壓痕。 [黏著膜的製作] 在上述剝離膜的矽酮處理面上塗佈實施例和比較例的 紫外線硬化性黏著劑組合物的溶液（固體成分濃度爲30%) ，於80°C乾燥2分鐘後，用高壓汞燈照射紫外線（UV照射 條件：500mW/cm2、80mJ/cm2)，形成厚度15μιη的黏著劑 層。接下來，將上述剝離膜的黏著劑層貼合在上述基材膜 上，剝離上述剝離膜，由此得到形成有黏著劑層的基材膜 (黏著膜）。 但是，對於比較例2 1 -1，在上述剝離膜的矽酮處理面 上直接塗佈未用溶劑稀釋的比較例2 1 -1的紫外線硬化性 黏著劑組合物（固體成分濃度爲1 〇〇%)，貼合上述基材膜， 製成層合狀態，將黏著劑層調整爲2(^m的厚度，用高壓 -64- 201105760 汞燈照射紫外線（UV照射條件：500mW/cm2、80mJ/cm2)。 其後，剝離上述剝離膜，由此得到形成有黏著劑層的基材 膜（黏著膜）。 另外，對於比較例21-2，在上述剝離膜的矽酮處理面 直接塗佈未用溶劑稀釋的比較例2 1 -2的紫外線硬化性黏 著劑組合物（固體成分濃度爲1 00%)，用高壓汞燈照射紫外 線（UV照射條件：500mW/cm2、80mJ/cm2)，形成厚度 2 0μπι的黏著劑層。接下來，將上述剝離膜的黏著劑層貼 合在上述基材膜上，剝離上述剝離膜，由此得到形成有黏 著劑層的基材膜（黏著膜）。 此外’對於比較例22-1，在上述剝離膜的矽酮處理面 上塗佈比較例22- 1的紫外線硬化性黏著劑組合物的溶液（ 固體成分濃度爲30%)，於90 °C加熱3分鐘，形成厚度 2 Ομπι的黏著劑層。接下來，將上述剝離膜的黏著劑層貼 合在上述基材膜上製成層合狀態後，用高壓汞燈進行紫外 線照射。在4 0 °C、乾燥的條件下熟成4天，剝離上述剝離 膜，得到形成有黏著劑層的基材膜（黏著膜）。 另外’對於比較例22-2、22-3，對上述剝離膜的黏著 劑層進行紫外線照射後，貼合在上述基材膜上，剝離上述 剝離膜，由此得到形成有黏著劑層的基材膜（黏著膜）。並 且，不進行上述熟成。 另外，對於比較例23-1，在上述剝離膜的矽酮處理面 上塗佈比較例2 3 -1的熱硬化型黏著劑組合物的溶液（固體 成分濃度爲30%)，於90°C加熱3分鐘，形成厚度20μηι -65- 201105760 的黏著劑層。接下來，將上述剝離膜的黏著劑層貼合在上 述基材膜上後’不進行熟成，剝離上述剝離膜，得到形成 有黏著劑層的基材膜（黏著膜）。將該黏著膜貼合在驗性玻 璃上。對於比較例23-2 ’在401、乾燥條件下熟成4天 ’除此以外與比較例2 3 -1同樣地操作，得到黏著膜。 [黏著性] 除比較例 21-1〜21-2、22-1 〜22-3、23-1 〜23-2 外， 與上述塗佈性評價同樣地在上述基材膜的表面形成厚度 15μηι的塗膜（黏著劑層）。 其後’在無熟成下（具體而言，在塗膜形成2小時後） ’將該形成有黏著劑層的基材膜（黏著膜）貼合在鹼性玻璃（ 普通硬質玻璃）上’形成層積體。形成該層積體後，用JIS Ζ0237(黏著膠帶-黏著片試驗方法）記載的ι8(Γ剝離試驗測 定經過1小時時的上述黏著膜與鹼性玻璃之間的黏著力（ 初期黏著力）。並且’目視評價此時的鹼性玻璃表面的糊 料殘留。 將初期黏著力爲5N/25mm以上、15N/25mm以下的情 況評價爲“ ”（極好），初期黏著力爲3N/25mm以上且小 於5N/25mm的情況以及超過i5N/25mm且在20N/25mm以 下的情況評價爲“〇”（良好），超過 20N/25mm且在 30N/25mm以下的情況評價爲“ ” （稍差），小於 3 N / 2 5 m m的情況和超過3 0 N / 2 5 m m的情況評價爲“ X ”（不 良）。對於糊料殘留，目視確認完全沒有糊料殘留的情況 -66 - 201105760 評價爲”（良好），目視確認到稍有糊料殘留的情況評 價爲“ X” （不良）。 [耐熱性] 與上述黏著性的評價相同，將形成有黏著劑層的基材 膜（黏著膜）貼合在鹼性玻璃（普通硬質玻璃）上，形成層積 體。將該層積體在高溫（8 (TC )的各種條件下暴露1 000小時 ’利用JIS Z0237(黏著膠帶-黏著片試驗方法）記載的180。 剝離試驗測定上述暴露後的上述黏著膜與鹼性玻璃之間的 黏著力。並且，目視評價此時的鹼性玻璃表面的糊料殘留 〇 根據下述數學式（2)由上述黏著性評價中常態下暴露後 的黏著力ΤΊ和高溫條件下暴露後的黏著力τ2計算出的黏 著保持率1爲100〜200%範圍內的情況評價爲“◎”（良 好），Ri小於1 00%的情況和超過200%的情況評價爲“ χ” (不良）。並且，對於糊料殘留，目視確認沒有糊料殘留的 情況評價爲“ ”（良好），目視確認存在糊料殘留的情況 評價爲“ X”（不良）。 R,=(T2/T1)x100 (2) (其中’ T,:常態下的初期黏著力（N/25mm)，τ2 :高溫條 件下暴露後的黏著力（N/25mm) ’ Ri :黏著保持率（％)) -67- 201105760 [耐濕熱性] 與上述黏著性評價同樣，將形成有黏著劑層的基材膜 (黏著膜）貼合在鹼性玻璃（普通硬質玻璃）上，形成層積體 。將該層積體在高溫高濕（溫度：60°C、濕度：90%)的各 種條件下暴露1 000小時，利用JIS Z02 3 7 (黏著膠帶-黏著 片試驗方法）記載的180°剝離試驗測定上述暴露後的上述 黏著膜與鹼性玻璃之間的黏著力。 根據下述數學式（3)由上述黏著性評價中常態下暴露後 的黏著力ΤΊ和高溫高濕條件下暴露後的黏著力τ3計算出 的黏著保持率112爲100〜200%範圍內的情況評價爲“◎ ’’（良好），R2小於1 0 0 %的情況和超過2 0 0 %的情況評價爲 “ X” （不良）。並且，對於糊料殘留，目視確認沒有糊料殘 留的情況評價爲“ ”（良好），目視確認存在糊料殘留的 情況評價爲“ X”（不良）。 R2=(T3/T,)xl00 (3) (其中’ T,:常態下的初期黏著力（N/25mm)，T3 :高溫高 濕條件下暴露後的黏著力（N/25mm)，T2(N/25mm)，R2 :黏 著保持率（％)) [色差] 與上述黏著性的評價同樣，將形成有黏著劑層的基材 膜（黏著膜）貼合在鹼性玻璃（普通硬質玻璃）上，形成層積 •68- 201105760 體。利用色差計（商品名：分光光度計SQ-2000，日本電色 工業公司製造）測定該層積體在25 t的色差（b*)(以下有時 記作“初期色差”）。初期色差（b*)爲0.3以下的情況評價 爲“ ”（極好）’超過0.3且在0.5以下的情況評價爲“ 〇”（良好）’超過0.5的情況評價爲“ X”（不良）。但是， 對於添加有紫外線吸收劑的實施例2 7的組合物，由於紫 外線吸收劑本身帶黃色，色差指標不同，所以將初期色差 (b*)爲1以下的情況評價爲“ ◎” ，超過1的情況評價爲 « »» X ° 並且’對於耐熱性試驗後的層積體和耐濕熱性試驗後 的層積體也利用相同的方法測定色差（以下有時記作"耐 久色差”）。對於耐久色差（b*)，將與初期色差之差小於 0.1的情況評價爲“ ”（極好），差値在ο. 1以上且在0.2 以下的情況評價爲“〇”（良好），超過0 · 2的情況評價爲 “ X” （不良）。 [總光線透射率] 與上述黏著性的評價相同，將形成有黏著劑層的基材 膜（黏著膜）貼合在鹼性玻璃（普通硬質玻璃）上，形成層積 體。利用濁度計（商品名：霧度計HM-150，村上色彩技術 硏究所公司製造）測定該層積體在25°C的總光線透射率（以 下有時記作“初期總光線透射率”）。初期總光線透射率 爲90%以上的情況評價爲“◎”（極好），初期總光線透射 率爲88%以上的情況評價爲“〇”（良好），小於88%的情 -69- 201105760 況評價爲“ X"(不良）。 並且，對於耐熱性試驗後的層積體和耐濕熱性試驗後 的層積體也藉由相同的方法測定總光線透射率（以下有時 記作“耐久總光線透射率”）。對於耐久總光線透射率’ 將與初期總光線透射率之差小於1 %的情況評價爲“ ”（ 極好），在1 %以上且在2 %以下的的情況評價爲“〇”（良 好），超過2%的情況評價爲“ X”（不良）。 [霧度] 與上述黏著性的評價相同，將形成有黏著劑層的基材 膜（黏著膜）貼合在鹼性玻璃（普通硬質玻璃）上，形成層積 體。利用濁度計（商品名：霧度計HM-150，村上色彩技術 硏究所公司製造）測定該層積體在25°C的霧度（以下有時記 作“初期霧度”）。將初期霧度爲1 ·〇以下的情況評價爲“ ◎ ”（極好），超過1.0且在2_0以下的情況評價爲“〇”（ 良好），超過2.0的情況評價爲“X”（不良）。 並且，對於耐熱性試驗後的層積體和耐濕熱性試驗後 的層積體也採用相同的方法測定霧度（以下有時記作“耐 久霧度”）。對於耐久霧度，將其與初期霧度之差小於〇.1 的情況評價爲“ ” （極好），該差値爲〇· 1以上且在〇·3 以下的情況評價爲“〇”（良好），超過〇 . 3的情況評價爲 ’’ X” （不良）。 [紫外線遮蔽性] -70- 201105760 對於實施例27中得到的組合物，藉由以下的方法評 價紫外線遮蔽性。 首先，與上述黏著性的評價相同，將形成有黏著劑層 的基材膜（黏著膜）貼合在鹼性玻璃（普通硬質玻璃）上’形 成層積體。其後，使用紫外可見分光光度計（商品名：·^-best V-570，日本分光公司製造），測定波長300〜8 00nm 的分光光譜，測定該層積體的紫外線透射率（表中記作“ UV遮蔽性”）。波長爲3 80nm以下的紫外線透射率均爲 5%以下的情況評價爲“〇”（良好），超過5%的情況評價 爲“ X” （不良）。 (評價） 實施例1〜27的黏著劑組合物在空氣下不進行層合保 護並且在無熟成下發揮黏著性，在操作性、塗佈性、凝膠 成分、黏著物性、光學特性、糊料殘留（再剝離性）的所有 方面都顯示出良好的結果。實施例27的黏著劑組合物進 而在紫外線遮蔽性方面也顯示出良好的結果。 這些黏著劑組合物中，滿足A成分的重量平均分子量 爲40萬〜60萬、A成分的含量爲90〜99.5質量份、B成 分的量爲0.5〜10質量份、C成分的量爲〇.〇5〜0.5質量 份的範圍的條件的實施例3、4、6、8、9、1 0的黏著劑組 合物在空氣下的硬化性、15N/25mm左右的初期黏著力、 耐熱/耐濕熱條件下的黏著力以及光學特性方面都顯示出 良好的結果。 -71 - 201105760 並且’含有E成分的黏著劑組合物中，滿足A成分的 重量平均分子量爲40萬〜60萬、A成分的含量爲90〜 99.5質量份、（甲基）丙烯醯基官能基的量爲〇.6〜 10_6mmol/100g、B成分的量爲0.5〜10質量份、使用E-1 成分和/或E-2成分作爲E成分的條件的實施例12、13、 14、16、17、23、25、26 顯示出 5 〜15N/25mm 的初期黏 著力，在耐熱/耐濕熱條件下的黏著力和光學特性方面顯 示出良好的結果。 其中，特別是實施例4、8、1 3、14、1 6、2 1、2 3、2 5 的黏著劑組合物發揮出包括具有5〜15N/25mm左右的低 黏著力在內的優異的黏著物性，在光學特性、凝膠成分、 塗佈性等評價專案中全都表現出極佳的結果。 藉由添加B成分，可以在空氣下使用醯基氧化膦系起 始劑，並能夠減少其用量。使用醯基氧化膦系起始劑並降 低了其用量的實施例 3〜5、7〜10、12〜14、16〜18、20 〜21、23〜27的黏著劑組合物在光學特性、特別是色差方 面將初期色差的値抑制在低値，並且，耐久試驗後的色差 的値與初期値相比也幾乎沒有變化，顯示同等的値，表現 出極佳的結果。 另一方面，比較例1的黏著劑組合物由於A成分的分 子量過大，黏度和黏性高，所以是塗佈性差的結果。比較 例2由於A成分的分子量過小，所以是凝膠成分少（SP， 紫外線硬化後的膜強度差），並且糊料殘留（再剝離性）差的 結果。 -72- 201105760 比較例3〜6的黏著劑組合物由於B成分或C成分的 含量在本發明的範圍以外，所以在空氣下使之硬化時，是 黏著物性、光學特性差的結果。另外，比較例7〜10的黏 著劑組合物由於使用非醯基氧化膦系的光聚合起始劑作爲 C成分，所以是光學特性差的結果。 比較例1 1〜1 4的黏著劑組合物由於A成分的（甲基） 丙烯醯基官能基的含量在本發明的範圍以外，所以是黏著 物性、光學特性和凝膠成分（膜強度）差的結果。 比較例15〜17的黏著劑組合物由於D成分的含量在 本發明的範圍以外，所以出現黏著物性差的結果。另外， 藉由與比較例1 3〜1 4的黏著劑組合物的比較可知，在不 將具有（甲基）丙烯醯系官能基的A成分與D成分並用的情 況下，出現在耐濕熱條件下的黏著保持力差的結果。 比較例18〜19的黏著劑組合物由於D成分是不具有 環氧系官能基的矽烷偶合劑，所以出現黏著物性差的結果 。另外，比較例20的黏著劑組合物由於E成分的含量在 本發明的範圍以外，所以出現黏著物性差的結果。 比較例21-1、21-2的黏著劑組合物由於使用丙烯酸酯 單體作爲E成分，並且其用量在本發明的範圍以外，所以 出現塗佈性、光學特性差的結果。 比較例22-2的黏著劑組合物由於使用熱交聯劑且未 熟成，所以顯示出黏著物性差的結果。比較例22-1的黏 著劑組合物由於使用熱交聯劑且在層合保護下進行硬化， 所以黏著物性、光學特性較好。但是，由於A成分的重量 -73- 201105760 平均分子量大，所以操作性和塗佈性差。另外， 22-3的黏著劑組合物那樣的具有與比較例22-1 樣的組成，且不添加熱交聯劑的情況下，黏著衫 特性都差。 進而，比較例23-2的黏著劑組合物使用熱 獲得了良好的黏著物性，但需要在4〇°C熟成4天 進行上述熟成時，如比較例23所示，黏著物性 性都差。 [產業利用性] 本發明的紫外線硬化型黏著劑組合物能夠很 電子材料、光學材料等用途，特別是在等離子 (PDP)、液晶顯示器（LCD)等的表面上貼附防反躬 能性膜的用途。 在比較例 、22-2 同 性和光學 交聯劑， 。即，不 、光學特 好地用於 體顯示器 性膜等功 -74-ο £ 1 » 1 1 U3 ◎ ◎ ίο ◎ ◎ ◎ <〇3 — ◎ @ «Ο 2 ◎ ◎ <D d X 00 〇σ> X § © s ◎ 卜 d ◎ eo 0 p X 1 σ> at 1 1 ιή 1 ◎ ◎ X - 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CO σι 卜 1 CD o 1 1 1 1 1 1 1 1 in r*·· 1 1 1 1 1 1 Unmatured type matrix polymer under air _ Type (mg/polymer 100 g) (_〇1/polymer 100g) (mg/polymer 100g) (_〇1/polymer 100g) Weight average Molecular weight Β (parts by mass) (parts by mass) (parts by mass) (parts by mass) (parts by mass) (parts by mass) (parts by mass) (temperature, time) (methyl) acrylonitrile-triethoxydecyl fS? m CQ •Η ύ eja ύ cp ό ύ S ώ CO i CO ώ y* 〇ίϋ Ν s s 丄 polyisocyanate curing environment curing conditions (methyl) propionate polymer polymerizable carboxylic acid photopolymerization initiator Decane coupling agent <Π^ UV absorber crosslinker. 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O ◎ CO ◎ s 3 ◎ ◎ ◎ r - o ◎ 1 (mass) m I" m , Wa _ Adhesion (N/25ram) Flame or m 1 in SR Adhesion retention (%) Class 1 To M <n Bond retention (%) a Like sm After initial heat resistance for 1000 hours, heat resistance after 1000 hours, initial heat resistance for 1000 hours, heat resistance after 1000 hours, initial stage: heat resistance after 1000 hours, heat resistance 1000/fN^_ T%®380nm | 1_D-l_1 __ 1__1 Γ__Ί溻Hot color difference b* Total light transmittance (%) i 1 Haze 1 t Yaoxane coupling agent chain • tt m Adhesive optical characteristics i -57- Table 11 —cn8_ Real 23 Real 25 Real 24 Real 26 Real 22 to 20 Real 27 to 21-1 than 2 2 2 (meth)acrylic polymer type A-9 A-9 A-9 A-9 A-9 A-9 A-9 A-16 ΑΊ6 Matrix polymer type P- 3 P-3 P-3 P-3 P-3 P-3 P-3 P-8 P-8 (Meth)acrylonitrile base Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac Ac 250 250 250 250 250 250 2000 2000 (mmol / polymer lOOg) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 12.9 12.9 Triethoxy oxime (mg/polymer l〇〇g) (mmol/polymer 100g) unmodified unmodified unmodified unmodified unmodified unmodified unmodified unmodified unmodified heavy a The average molecular weight is 424,000, 424,000, 424,000, 424,000, 42.4 million, 424,000, 42.4 million dip-3 million 49_3 million Tg rc) -30 -30 -30 -30 -30 -30 -30 -83 -83 (Quality deleted 93 93 93 93 93 93 93 97.1 97.1 Polyfluorinated carboxylic acid B-1 (parts by mass) 7 7 7 7 7 7 7 2.9 2.9 B'2 Photopolymerization initiator Cl (parts by mass) 0.5 0.5 0.5 0.5 0.5 0.5 3 - - 02 C- 3 C-4 05 - - - - - - - 2.9 2.9 decane coupling agent Dl (parts by mass) 1 1 1 1 1 1 1 - - D-2 D-3 D-4 Other polymerizable compound 质量 (parts by mass) - 7.5 - 10 15 25 15 - - E-2 0.5 1 10 2 - - 5 - - E-3 - - - - - - - 191.3 191.3 E-4 - - - - - - - 2.9 2.9 UV absorber Fl (quality Parts) - - - - - - 3 - - Cross-linking agent polyisocyanate (parts by mass) - - - - - - - - - Curing ambient air under air under air Under air, air, under air, under air, curing conditions (temperature, time), no ripening, no ripening, no ripening, no ripening, no ripening, no ripening, no ripening, no ripening, no ripening. 201105760 ※ In the table, "real" indicates an example, " Than "quote". In addition, "MAc"methacrylic acid, "Ac" means acrylonitrile. 201105760 - «CJ, r* s Ο) Ν US XX XX XXX 2 | 1400 1 XX d 〇X ◎ 2 XX to r» XX ο SXXX ao X 1 ί 1 1 1 191.3 1 〇t ci <Π is lacquer « XX CO © S 〇 « S δ ◎ X 卜 tn η X ◎ CO X — X n c4 X £5 XS Ο along X Λ X pi XX 1 Κ m ΙΑ 1 1 嫉 嫉 症 shoes ◎ ◎ s ◎ 〇 ◎ CJ ◎ ◎ s αο ◎ ◎ »*. ♦ 1 r>j ◎ ◎ 8 ◎ Β @ S © 卜 ◎ t· ◎ t— <6 ◎ Μ S ΪΙ t ( 1 K- HS 创 m ◎ ◎ ο ◎ « ◎ ◎ 二茺◎ X (Ο in XX 2 ο ◎ 'ψ ◎ S 〇S © S ◎ 卜 · ◎ 00 d ◎ ao ◎ t lion V» 1 1 1 H- ¥ « @ ◎ N ◎ ο ◎ ◎ § ◎ ◎ w ◎ ◎ , · 0 *r ◎ ◎ S Ο S ◎ @ r- ο ◎ r- o ◎ r~ O ◎ 1 lion ο CNJ 1 1 i two 1 ◎ ◎ E3 ◎ 〇 ◎ g ◎ φ 宕 00 ◎ @ ca ◎ 3 ◎ N ◎ ◎ S ◎ ◎ ◎ r*^ ◎ r- ◎ 1 lion 1 〇 1 1 痣 ◎ ◎ Aluminum © « < ◎ 筘 s ◎ ◎ η to CM ◎ ® C4 ◎ w ◎ « ◎ S ◎ σι ◎ σ! ◎ r- c» ◎ ◎ ◎ 1 Μ 虫 ιη — 1 1 method « ◎ ◎ μ ◎ 2 ◎ ◎ σ > B ◎ @ 2 H ◎ @ C4 ◎ ca ◎ CM 〇 ◎ m ◎ σ > ◎ ◎ @ ◎ r· ◎ 1 S3 Μ 1 in 1 1 Y- alkali ◎ ◎ S ◎ 2 ◎ ◎ S § ◎ @ 00 I ◎ ◎ CM o ◎ « ◎ CM 6 ◎ σι ◎ σί ◎ 〇> ◎ Ϊ-; ◎ ◎ r«; ◎ 1 (mass) Μ | 匪i & fe ii ϊ * m 埕g _ Adhesion CN/25mra) 憩 Real 1 S Ζ ί <C Adhesion retention rate (%) a tust m ·? 1 Adhesion retention rate (%) ftK step or m initial heat resistance 1000 hours later _ Moisture-resistant heat 1000 _ Initial heat resistance 1000 hours after heat and humidity resistance 1000 hours after an initial heat resistance 1000 hours ^ After heat-resistant heat 1000 hours _ 1 T%9380nra | ζ 1__1 η Hawthorn Gel composition initial heat and humidity resistance to total light transmittance (%) Haze* Other polymeric compounds, adhesive optical properties, flavoring - Tengchen Yusheng sawing picking *.匡 丑 丑 揪 妇 妇 妇 妇 妇 妇 妇 妇 妇 _ _ _ _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 93 parts by mass of a solid component in a solution of a (meth)acrylic polymer (A_J component) (solid content: 30% by mass), 7 parts by mass of mixed acrylic acid (B-1 component), 2, 4, 6-three Methylbenzhydryl-diphenylphosphine oxide (component C-1, trade name: Lucirin TPO, manufactured by BASF Corporation) 55 parts by mass, 3-glycidoxypropyltrimethoxydecane (Dq component' Product name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd., n parts by mass, and prepared with an ultraviolet curable adhesive composition. (Examples 2 to 27, Comparative Examples 1 to 2 3) The A synthesized in Reference Examples 10 to 26 was used. The ultraviolet curable adhesive composition was prepared in the same manner as in Example 1 except that the components (A-1 to A-15) were changed to the compositions described in Tables 1 to 12. The following substances were used as the respective components. <B component> B-1: Acrylic (manufactured by Osaka Organic Industrial Chemical Co., Ltd.) B-2: C Acid dimer (trade name: SIPOMER β -CEA-J, manufactured by Rhodia Rihua Co., Ltd.) <C component> Cl : 2,4,6-trimethylbenzimidyl-diphenylphosphine oxide Name: Lucirin TPO, manufactured by BASF) -60- 201105760 C-2: Oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-ethyloxy-ethoxy]-ethyl ester Mixture with oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester (trade name: Irgacu re 754, manufactured by Ciba Specialty Chemicals) C-3: 2-methyl-l- [4-(Methylthio)phenyl]-2-morpholinylpropan-1-one (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) C-4: 2,2-dimethoxy-1, 2-Diphenylethane-1-one (trade name: Irgacure 651, manufactured by Ciba Specialty Chemicals Co., Ltd.) C-5: 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: lrgacure 184, Ciba Specialty Chemicals, Inc.) Manufactured <D component> Dl : 3-glycidoxypropyltrimethoxydecane (trade name: ΚΒΜ-403, manufactured by Shin-Etsu Chemical Co., Ltd.) D-2 : 3-glycidoxypropyltriethyl Oxydecane (trade name: κβΕ-403, Shin-Etsu Chemical Industry Manufactured by the company) D-3 : Ν-2-(aminoethyl) 3-aminopropyltrimethoxy decane (trade name: ΚΒΜ-603, manufactured by Shin-Etsu Chemical Co., Ltd.) D-4: 3 - Sparpy Base trimethoxy sand court (trade name: ΚΒΜ-803, manufactured by Shin-Etsu Chemical Co., Ltd.) <Ε ingredients> Ε-1: Aliphatic polyester skeleton polyurethane acrylate (trade name: -61 - 201105760 EB270, Daicel SciTech Manufactured by the company) E-2: Bisphenol-based epoxy resin skeleton polyurethane acrylate (trade name: RipoxyVR-77, manufactured by Showa Polymer Co., Ltd.) E-3: 2-ethylhexyl acrylate E-4: 1,6 - Hexanediol diacrylate (trade name _· NK ESTER A-HD' manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) <F component> F-1: 2,2·,4,4'-tetrahydroxy-benzophenone (trade name: DAINSORB Ρ-6 'Manufactured by Daiwa Kasei Co., Ltd.) <Hot crosslinker> Polyisocyanate (trade name: CORONATE L, manufactured by Japan Polyurethane Industry Co., Ltd.) <Solvent> Methyl ethyl ketone (Kishida Chemical Manufactured by the company) Toluene (Kishida Chemical Co., Ltd.) Ethyl acetate (manufactured by Kishida Chemical Co., Ltd.) Acetone (K Manufactured by Ishida Chemical Co., Ltd.) The quality of the ultraviolet curable adhesive composition was evaluated by the following method. [Operability (Liquid Wire Drawing Property)] -62- 201105760 A composition for evaluating an article was prepared as a coating liquid having a solid content concentration of a % by weight, and the coating liquid was adhered to a glass rod, and the glass coating rod was observed to fall. State, visual evaluation. When the coating liquid was under glass, the coating liquid was completely separated from the glass rod, and it was evaluated as " " (good) in the state of droplet drop; the coating liquid and the glass rod were evaluated as "X" when they were not completely dropped in the drawn state. "(bad). [Coating property (coating streak)] The composition as an evaluation article was prepared into a coating liquid having a solid content concentration as a coating liquid, and the coating liquid was applied to a PET film having a thickness of 38 μm which was subjected to treatment by an applicator. (The release film) The anthrone treatment surface was dried at 80 ° C for 2 minutes, and then the coating film was ultraviolet-cured at 500 mW/cm 2 , 80 mJ/cm 2 to form an adhesive layer, and the adhesive of the release film was removed. The layer is bonded to the substrate (thickness 1 〇〇μηη, total light transmittance 91%, haze 値0.3. to "substrate film") to form a thickness of the adhesive layer on the surface of the substrate film. . Further, the above ultraviolet rays are irradiated with high-pressure mercury. The ultraviolet light having a wavelength of 200 to 400 nm is irradiated by squeezing the light. The evaluation of the coating property was carried out by using the applicator to coat the surface of the above-mentioned release film of the coating liquid, and confirming the presence or absence of the coating streaks at the time of coating, and adjusting the slit width of the applicator so that the coating film 1 5 μπι 'coating was carried out at a speed of 20 m/min. The number of the marks generated at this time was evaluated as "quote" (extra) when the number of scratches was 0 per 1 cm of the coating width produced per 15 cm, and the quality of the 30 liquids from the glass rod was evaluated. The falling condition was separated, 30% of the fluorenone was applied to the condition, and then the PET film was coated as a 15 mm lamp. The specific thickness was evaluated by the coating strip. The price was "-63-201105760 〇", When it is two or more, it is evaluated as "x" (poor). [Gel component] The gel component of the composition as the evaluation article was weighed by Soxhlet extraction. Specifically, Soxhlet was used for 8 hours using tetrahydrofuran as a solvent. In the extraction, the mass % of the insoluble component remaining without being extracted is expressed as a gel component (% by mass), and when the gel component is 60% by mass or more, it is evaluated as " " (excellent), 55 mass % or more and less than 60 mass When it is less than 55% by mass, it is evaluated as "X" (poor). When the gel component is 55 mass% or more, when the adhesive film is wound, no adhesive bleed out, and there is no An indentation left by a protective film such as an embossed film. Preparation of a film] A solution (solid content concentration: 30%) of the ultraviolet curable adhesive composition of the examples and the comparative examples was applied to the anthrone-treated surface of the release film, and dried at 80 ° C for 2 minutes, and then used. The high-pressure mercury lamp is irradiated with ultraviolet rays (UV irradiation conditions: 500 mW/cm 2 , 80 mJ/cm 2 ) to form an adhesive layer having a thickness of 15 μm. Next, the adhesive layer of the release film is bonded to the base film to peel off the peeling. The film was used to obtain a base film (adhesive film) on which an adhesive layer was formed. However, in Comparative Example 21-1, Comparative Example 2, which was not diluted with a solvent, was directly applied to the anthrone-treated surface of the release film. The 1:1 curable adhesive composition (solid content concentration: 1% by weight) is bonded to the base film to form a laminated state, and the adhesive layer is adjusted to a thickness of 2 (m), and a high pressure is used. -64- 201105760 The mercury lamp is irradiated with ultraviolet rays (UV irradiation conditions: 500 mW/cm2, 80 mJ/cm2). Thereafter, the release film is peeled off to obtain a base film (adhesive film) on which an adhesive layer is formed. Comparative Example 21-2, at the oxime of the above-mentioned release film The ultraviolet curable adhesive composition of Comparative Example 2 1 -2 (solid content concentration: 100%) diluted with a solvent was directly applied to the surface, and ultraviolet rays were irradiated with a high pressure mercury lamp (UV irradiation conditions: 500 mW/cm 2 , 80 mJ / Cm2), an adhesive layer having a thickness of 20 μm is formed. Next, an adhesive layer of the release film is bonded to the base film, and the release film is peeled off to obtain a base film on which an adhesive layer is formed ( Further, in Comparative Example 22-1, a solution (solid content concentration: 30%) of the ultraviolet curable adhesive composition of Comparative Example 22-1 was applied to the anthrone treatment surface of the release film. The mixture was heated at 90 ° C for 3 minutes to form an adhesive layer having a thickness of 2 μm. Next, the adhesive layer of the release film was bonded to the base film to form a laminated state, and then irradiated with ultraviolet rays using a high pressure mercury lamp. The film was aged for 4 days at 40 ° C under dry conditions, and the release film was peeled off to obtain a base film (adhesive film) on which an adhesive layer was formed. In addition, in Comparative Examples 22-2 and 22-3, the adhesive layer of the release film was irradiated with ultraviolet rays, and then bonded to the base film to peel off the release film, thereby obtaining a base on which the adhesive layer was formed. Film (adhesive film). Further, the above ripening is not carried out. Further, in Comparative Example 23-1, a solution (solid content concentration: 30%) of the thermosetting adhesive composition of Comparative Example 2 3 -1 was applied to the anthrone-treated surface of the release film, at 90 ° C. The mixture was heated for 3 minutes to form an adhesive layer having a thickness of 20 μm -65 to 201105760. Then, after the pressure-sensitive adhesive layer of the release film is bonded to the base film, the release film is peeled off, and the release film is peeled off to obtain a base film (adhesive film) on which an adhesive layer is formed. The adhesive film is attached to the test glass. An adhesive film was obtained in the same manner as in Comparative Example 2 3 -1 except that Comparative Example 23-2' was cooked at 401 and dried for 4 days. [Adhesiveness] In addition to Comparative Examples 21-1 to 21-2, 22-1 to 22-3, and 23-1 to 23-2, a thickness of 15 μm was formed on the surface of the base film as in the evaluation of the coating property. Coating film (adhesive layer). Thereafter, 'under the ripening (specifically, after the coating film was formed for 2 hours) 'the base film (adhesive film) on which the adhesive layer was formed was bonded to the alkali glass (ordinary hard glass) to form Laminated body. After the laminate was formed, the adhesion (primary adhesion) between the adhesive film and the alkali glass at the time of one hour was measured by ι8 (Γ peeling test) described in JIS Ζ0237 (adhesive tape-adhesive sheet test method). Further, the residue of the alkaline glass surface at this time was visually evaluated. The initial adhesion was 5 N/25 mm or more and 15 N/25 mm or less, and the initial adhesion was 3 N/25 mm or more. When it is less than 5N/25mm and more than i5N/25mm and 20N/25mm or less, it is evaluated as "〇" (good), and when it exceeds 20N/25mm and is less than 30N/25mm, it is evaluated as "" (slightly worse), less than The case of 3 N / 2 5 mm and the case of more than 30 N / 2 5 mm was evaluated as "X" (defective). For the residue of the paste, it was confirmed visually that there was no residue remaining in the paste -66 - 201105760 The evaluation was "( (Good), it was confirmed by visual observation that the case of a slight paste residue was evaluated as "X" (poor). [Heat resistance] The base film (adhesive film) on which the adhesive layer was formed was bonded in the same manner as the evaluation of the above adhesiveness. In alkaline glass (ordinary hard glass) A laminate was formed on the glass. The laminate was exposed to high temperature (8 (TC) under various conditions for 1 000 hours" using JIS Z0237 (adhesive tape-adhesive sheet test method) 180. The adhesive force between the above-mentioned adhesive film and the alkali glass after the exposure. Further, the paste residue on the surface of the alkaline glass at this time was visually evaluated, and was exposed under the normal state in the above-mentioned adhesion evaluation according to the following formula (2). The adhesion retention ΤΊ and the adhesion retention rate τ2 after exposure under high temperature conditions are in the range of 100 to 200%, and the evaluation is "◎" (good), and Ri is less than 100% and more than 200%. In the case of the paste residue, the case where the paste residue was not visually confirmed was evaluated as " " (good), and the case where the paste residue was visually confirmed was evaluated as "X" (bad). R,=(T2/T1)x100 (2) (where 'T,: initial adhesion under normal conditions (N/25mm), τ2: adhesion after exposure at high temperature (N/25mm) ' Ri: adhesive Retention rate (%)) -67- 201105760 [Heat and heat resistance] and above Adhesive evaluation Similarly, a base film (adhesive film) on which an adhesive layer was formed was bonded to an alkali glass (ordinary hard glass) to form a laminate. The laminate was subjected to high temperature and high humidity (temperature: 60). The exposure was carried out for 1 000 hours under various conditions of ° C, humidity: 90%), and the above-mentioned exposed adhesive film and alkaline glass were measured by a 180° peel test described in JIS Z02 3 7 (adhesive tape-adhesive sheet test method). The adhesion between the two. According to the following formula (3), the adhesion retention ratio 112 calculated from the adhesion state after exposure in the normal adhesion evaluation and the adhesion force τ3 after exposure under high temperature and high humidity conditions is in the range of 100 to 200%. The evaluation was "◎" (good), and the case where R2 was less than 100% and the case where it exceeded 200% was evaluated as "X" (poor). Further, for the residue of the paste, it was visually confirmed that there was no residue of the paste. The evaluation was " " (good), and the presence of paste residue was visually confirmed as "X" (bad). R2 = (T3/T,) xl00 (3) (where 'T,: initial adhesion under normal conditions ( N/25mm), T3: Adhesion (N/25mm) after exposure to high temperature and high humidity, T2 (N/25mm), R2: Adhesion retention (%)) [Color difference] Similar to the evaluation of adhesion described above, The base film (adhesive film) on which the adhesive layer is formed is bonded to an alkali glass (ordinary hard glass) to form a laminated body. 68-201105760. Using a color difference meter (trade name: spectrophotometer SQ-2000, Measured by the color difference (b*) of the laminate at 25 t (hereinafter sometimes referred to as "Initial color difference". When the initial color difference (b*) is 0.3 or less, it is evaluated as "" (excellent)" when it exceeds 0.3, and when it is 0.5 or less, it is evaluated as "〇" (good). X" (defect). However, in the composition of Example 27 in which the ultraviolet absorber was added, since the ultraviolet absorber itself was yellowish and the color difference index was different, the initial color difference (b*) was 1 or less. " ◎", the case of more than 1 was evaluated as « »» X ° and the chromatic aberration was measured by the same method for the laminate after the heat resistance test and the laminate after the heat and humidity resistance test (hereinafter sometimes referred to as " ; Durable color difference"). In the case of the endurance chromatic aberration (b*), the case where the difference from the initial color difference is less than 0.1 is evaluated as "" (excellent), and the case where the difference is ο. 1 or more and 0.2 or less is evaluated as "〇" (good), and exceeds The case of 0 · 2 is evaluated as "X" (bad). [Total Light Transmittance] As in the evaluation of the above adhesiveness, a base film (adhesive film) on which an adhesive layer was formed was bonded to an alkali glass (ordinary hard glass) to form a laminate. The total light transmittance of the laminate at 25 ° C was measured by a turbidimeter (trade name: haze meter HM-150, manufactured by Murakami Color Technology Co., Ltd.) (hereinafter sometimes referred to as "initial total light transmittance" "). When the initial total light transmittance was 90% or more, it was evaluated as "◎" (excellent), and when the initial total light transmittance was 88% or more, it was evaluated as "〇" (good), and less than 88% -69-201105760 The evaluation was "X" (defective). Further, the total light transmittance was measured by the same method for the laminate after the heat resistance test and the laminate after the heat and humidity resistance test (hereinafter sometimes referred to as "durability". The total light transmittance "). The case where the difference in the total total light transmittance 'will be less than 1% from the initial total light transmittance is evaluated as " " (excellent), and is evaluated in the case of 1% or more and 2% or less. "〇" (good), more than 2% of cases were evaluated as "X" (poor). [Haze] The base film (adhesive film) on which the adhesive layer was formed was bonded in the same manner as the above adhesion evaluation. A layered body was formed on an alkali glass (ordinary hard glass), and the laminate was measured at 25 ° C by a haze meter (trade name: haze meter HM-150, manufactured by Murakami Color Technology Co., Ltd.). Haze (hereinafter sometimes referred to as "initial haze"). The case where the haze was 1 · 〇 or less was evaluated as " ◎ " (excellent), and when it was more than 1.0 and 2 _0 or less, it was evaluated as "〇" (good), and when it exceeded 2.0, it was evaluated as "X" (bad). Further, the laminate after the heat resistance test and the laminate after the heat and humidity resistance test were also measured for haze by the same method (hereinafter referred to as "durable haze"). For durable haze, The case where the initial haze difference is less than 〇.1 is evaluated as " " (excellent), and the difference is 〇·1 or more and 〇·3 or less is evaluated as "〇" (good), which exceeds 〇. The situation is evaluated as ''X' (bad). [Ultraviolet shielding property] -70-201105760 With respect to the composition obtained in Example 27, the ultraviolet shielding property was evaluated by the following method. First, in the same manner as the evaluation of the above adhesiveness, a base film (adhesive film) on which an adhesive layer was formed was bonded to an alkali glass (ordinary hard glass) to form a laminate. Thereafter, an ultraviolet-visible spectrophotometer (trade name: ·^-best V-570, manufactured by JASCO Corporation) was used, and a spectroscopic spectrum of a wavelength of 300 to 800 nm was measured, and the ultraviolet transmittance of the laminate was measured (in the table) "UV shielding"). When the ultraviolet transmittance of the wavelength of 380 nm or less is 5% or less, it is evaluated as "〇" (good), and when it exceeds 5%, it is evaluated as "X" (poor). (Evaluation) The adhesive compositions of Examples 1 to 27 were not subjected to lamination protection under air and exhibited adhesiveness without aging, and workability, applicability, gel composition, adhesive properties, optical properties, and paste. All aspects of residual (re-peelability) showed good results. The adhesive composition of Example 27 also showed good results in terms of ultraviolet shielding properties. In these adhesive compositions, the weight average molecular weight of the component A is 400,000 to 600,000, the content of the component A is 90 to 99.5 parts by mass, the amount of the component B is 0.5 to 10 parts by mass, and the amount of the component C is 〇. The adhesion of the adhesive composition of Examples 3, 4, 6, 8, 9, 10 in the range of 5 to 0.5 parts by mass in the air, the initial adhesion at 15 N/25 mm, and the heat/moisture resistance Both the adhesion under the conditions and the optical properties showed good results. -71 - 201105760 Further, in the adhesive composition containing the component E, the weight average molecular weight of the component A is 400,000 to 600,000, and the content of the component A is 90 to 99.5 parts by mass, and the (meth)acryloyl functional group is used. The amounts of 〇.6 to 10_6 mmol/100 g, the amount of the B component are 0.5 to 10 parts by mass, and the conditions of using the E-1 component and/or the E-2 component as the component E are carried out in Examples 12, 13, 14, and 16. 17, 23, 25, and 26 showed an initial adhesion of 5 to 15 N/25 mm, and showed good results in terms of adhesion and optical properties under heat/moisture resistance. Among them, in particular, the adhesive compositions of Examples 4, 8, 13, 3, 14, 16, 2, 2, and 2 5 are excellent in that they have a low adhesion of about 5 to 15 N/25 mm. Adhesive properties have shown excellent results in evaluation projects such as optical properties, gel composition, and coating properties. By adding the component B, a sulfhydrylphosphine oxide-based initiator can be used under air, and the amount thereof can be reduced. The adhesive composition of Examples 3 to 5, 7 to 10, 12 to 14, 16 to 18, 20 to 21, and 23 to 27 using a fluorenylphosphine oxide-based initiator and reducing the amount thereof is in optical characteristics, particularly In terms of chromatic aberration, the enthalpy of the initial color difference was suppressed to a low level, and the enthalpy of the chromatic aberration after the endurance test hardly changed from the initial enthalpy, and the same enthalpy was exhibited, and excellent results were exhibited. On the other hand, in the adhesive composition of Comparative Example 1, since the molecular weight of the component A was too large, the viscosity and the viscosity were high, and this was a result of poor coatability. In Comparative Example 2, since the molecular weight of the component A was too small, the gel component was small (SP, the film strength after ultraviolet curing was poor), and the paste residue (repeelability) was inferior. -72-201105760 The adhesive composition of Comparative Examples 3 to 6 is outside the range of the present invention because the content of the component B or the component C is hardened, and when it is cured under air, it is a result of poor adhesive properties and optical properties. Further, in the adhesive compositions of Comparative Examples 7 to 10, since a non-fluorenylphosphine oxide-based photopolymerization initiator was used as the C component, the optical properties were inferior. In the adhesive composition of Comparative Example 1 1 to 1 4, since the content of the (meth) acrylonitrile functional group of the component A is outside the range of the present invention, it is a difference in adhesive properties, optical properties, and gel component (film strength). the result of. In the adhesive compositions of Comparative Examples 15 to 17, since the content of the D component was outside the range of the present invention, the adhesiveness was poor. Further, by comparison with the adhesive compositions of Comparative Examples 13 to 14 , it is understood that when the A component having the (meth)acryl fluorene functional group is not used in combination with the D component, it occurs in the heat and humidity resistance condition. The result of poor adhesion retention. In the adhesive compositions of Comparative Examples 18 to 19, since the component D was a decane coupling agent having no epoxy functional group, the adhesiveness was poor. Further, in the adhesive composition of Comparative Example 20, since the content of the component E was outside the range of the present invention, the adhesiveness was poor. In the adhesive compositions of Comparative Examples 21-1 and 21-2, since an acrylate monomer was used as the E component, and the amount thereof was outside the range of the present invention, the coating property and the optical characteristics were inferior. The adhesive composition of Comparative Example 22-2 showed a poor adhesion property due to the use of a thermal crosslinking agent and was not matured. The adhesive composition of Comparative Example 22-1 was cured by using a thermal crosslinking agent under lamination protection, so that the adhesive properties and optical properties were good. However, since the weight of the component A is -73 to 201105760, the average molecular weight is large, so workability and coatability are inferior. Further, when the composition of Comparative Example 22-1 was the same as the adhesive composition of 22-3, and the thermal crosslinking agent was not added, the characteristics of the adhesive shirt were inferior. Further, the adhesive composition of Comparative Example 23-2 obtained good adhesive properties by using heat, but it was necessary to carry out the above-mentioned ripening at 4 °C for 4 days, and as shown in Comparative Example 23, the adhesive properties were inferior. [Industrial Applicability] The ultraviolet curable adhesive composition of the present invention can be used for applications such as electronic materials and optical materials, and particularly for attaching an anti-reflective film to the surface of a plasma (PDP) or a liquid crystal display (LCD). the use of. In Comparative Example, 22-2 isotropic and optical crosslinker, . That is, no, optically, it is excellently used for body display film, etc. -74-

Claims (1)

201105760 七、申請專利範圍： 1 · 一種紫外線硬化型黏著劑組合物，其係含有（甲基） 丙烯酸系聚合物（A成分）、具有聚合性不飽和基的羧酸及 其寡聚物中之至少一種（B成分）、光聚合起始劑（C成分）、 矽烷偶合劑（D成分）以及前述A成分和前述B成分以外的 具有聚合性不飽和基之化合物（E成分）作爲構成成分， 前述A成分係在主鏈中含有來自（甲基）丙烯酸系單體 之重複單元’在支鏈中具有含有（甲基）丙烯醯基骨架的（甲 基）丙烯醯系官能基，且每l〇〇g聚合物含有0.5〜20mmol 之前述（甲基）丙烯醯系官能基、玻璃轉移溫度Tg爲-55 〜〇°C、重量平均分子量Mw在20萬〜100萬之範圍內的 交聯性（甲基）丙烯酸系聚合物， 前述C成分係醯基氧化膦系光聚合起始劑， 前述D成分係具有環氧系官能基的矽烷偶合劑， 以前述A成分和前述B成分的總量爲100質量份時， 含有80〜99.5質量份之前述A成分、0.5〜20質量份之前 述B成分、〇·〇5〜3質量份之前述c成分、0.1〜5質量份 之前述D成分、〇〜20質量份之前述Ε成分。 2.如專利申請範圍第1項所記載之紫外線硬化型黏著 劑組合物’其中’前述Α成分係在支鏈中具有含有烷氧矽 烷基骨架之烷氧矽烷基系官能基，且每1 〇〇g聚合物含有 〇·〇4〜4mmol之前述烷氧矽烷基系官能基的交聯性（甲基） 丙烯酸系聚合物。 3 .如專利申請範圍第〗或2項所記載之紫外線硬化型 -75- 201105760 黏著劑組合物，其中，前述E成分係每1分子具有2個以 上之前述（甲基）丙烯醯系官能基之多官能寡聚物， 以前述A成分和前述B成分的總量爲1〇〇質量份時， 含有0.5〜20質量份之前述E成分。 4. 如專利申請範圍第3項所記載之紫外線硬化型黏著 劑組合物，其中，前述E成分係以脂肪族聚酯爲基本骨架 ，且重量平均分子量Mw在1千〜1萬之範圍內的多官能 寡聚物。 5. 如專利申請範圍第3項所記載之紫外線硬化型黏著 劑組合物，其中，前述E成分係以雙酚型環氧樹脂爲基本 骨架，且重量平均分子量Mw在40 0〜2000之範圍內的多 官能寡聚物。 6 ·如專利申請範圍第1或2項所記載之紫外線硬化型 黏著劑組合物，其係含有在3 50〜4〇〇nm波長範圍具有 Xniax的二苯甲酮系化合物作爲紫外線吸收劑（F成分）。 7.如專利申請範圍第1或2項所記載之紫外線硬化型 黏著劑組合物，其中，前述C成分係2,4,6-三甲基苯甲醯 基-二苯基氧化膦。 -76- 201105760 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 201105760 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 -4-201105760 VII. Patent application scope: 1 · An ultraviolet curable adhesive composition containing a (meth)acrylic polymer (component A), a carboxylic acid having a polymerizable unsaturated group, and an oligomer thereof At least one (component B), a photopolymerization initiator (component C), a decane coupling agent (component D), and a compound (component E) having a polymerizable unsaturated group other than the component A and the component B, as a constituent component. The above-mentioned A component contains a (meth)acrylic fluorene-based functional group having a (meth)acryl fluorenyl skeleton in a branched chain, and a repeating unit derived from a (meth)acrylic monomer in the main chain, and each of l The 〇〇g polymer contains 0.5 to 20 mmol of the above (meth) propylene fluorene-based functional group, the glass transition temperature Tg is -55 〇 ° C, and the weight average molecular weight Mw is in the range of 200,000 to 1,000,000. a (meth)acrylic polymer, the C component is a fluorenylphosphine oxide photopolymerization initiator, and the D component is a decane coupling agent having an epoxy functional group, and the total amount of the component A and the component B is Is 100 In the amount of 80 parts by weight to 99.5 parts by mass of the above-mentioned A component, 0.5 to 20 parts by mass of the above-mentioned B component, 〇·〇 5 to 3 parts by mass of the above-mentioned c component, and 0.1 to 5 parts by mass of the above-mentioned D component, 〇~ 20 parts by mass of the aforementioned bismuth component. 2. The ultraviolet curable adhesive composition according to the first aspect of the invention, wherein the bismuth component has an alkoxyalkyl group-functional group having an alkoxyalkyl group skeleton in a branch, and each 〇 The 〇g polymer contains a crosslinkable (meth)acrylic polymer having 4 to 4 mmol of the alkoxyalkylalkyl functional group. The ultraviolet-curing type-75-201105760 adhesive composition according to the invention, wherein the E component has two or more (meth) acrylonitrile-based functional groups per molecule. In the polyfunctional oligomer, when the total amount of the component A and the component B is 1 part by mass, the component E is contained in an amount of 0.5 to 20 parts by mass. 4. The ultraviolet curable adhesive composition according to the third aspect of the invention, wherein the E component is an aliphatic polyester as a basic skeleton, and the weight average molecular weight Mw is in the range of 1,000 to 10,000. Polyfunctional oligomers. 5. The ultraviolet curable adhesive composition according to the third aspect of the invention, wherein the E component is a bisphenol type epoxy resin as a basic skeleton, and the weight average molecular weight Mw is in the range of 40 to 2,000. Polyfunctional oligomers. The ultraviolet curable adhesive composition according to claim 1 or 2, which contains a benzophenone compound having Xniax in a wavelength range of 3 50 to 4 nm as an ultraviolet absorber (F) ingredient). 7. The ultraviolet curable adhesive composition according to claim 1 or 2, wherein the component C is 2,4,6-trimethylbenzylidene-diphenylphosphine oxide. -76- 201105760 Four designated representatives: (1) The representative representative of the case is: None (2) The symbol of the representative figure is simple: No 201105760 V. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention. :No -4-
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