TW201011081A - Pressure-sensitive adhesive composition, pressure-sensitive adhesive and optical film - Google Patents
Pressure-sensitive adhesive composition, pressure-sensitive adhesive and optical film Download PDFInfo
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- TW201011081A TW201011081A TW098100963A TW98100963A TW201011081A TW 201011081 A TW201011081 A TW 201011081A TW 098100963 A TW098100963 A TW 098100963A TW 98100963 A TW98100963 A TW 98100963A TW 201011081 A TW201011081 A TW 201011081A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Polarising Elements (AREA)
Abstract
Description
201011081 六、發明說明: 【發明所屬之技術領域】 本發明係關於一種光學薄膜用黏著劑組成物、附有該 黏著劑之光學薄膜、及該黏著劑組成物的製造方法,該黏 著劑組成物係用於將偏光膜、相位差膜等的光學薄膜黏貼 於液晶胞等被黏著物。更詳細而言,本發明係關於一種光 學薄膜用黏著劑組成物、附有該黏著劑之光學薄膜、及該 # 黏著劑組成物的製造方法,該黏著劑組成物在高溫高濕下 也有優良的耐久性,同時具有難以產生白缺陷(white defect)之特.性。 【先前技術】 液晶顯示裝置,通常是由在2片玻璃等的支撐基板之 間夾有以規定方向配向之液晶成分的液晶胞、以及偏光膜 參 或相位差膜、亮度提升膜等光學薄膜所構成,而在將光學 薄膜彼此之間予以積層、或是將光學薄膜黏貼在液晶胞上 之際,大多是使用黏著劑。 液晶顯示裝置被作為個人電腦或電視、衛星導航系統 等的顯示裝置而使用於廣大範圍。隨之而來的則是要求有 一種黏著劑,即使在高溫高濕下的嚴苛環境下使用,其耐 久性仍優良,亦即,即使是長期的使用也不會發生剝落或 產生氣泡等。而且,在高溫高濕下的嚴苛的環境下,光學 薄膜會有很大的收縮、膨脹之類的尺寸變化,黏著劑層無 201011081 法緩和由於此尺寸變化而產生的應力,則光學薄膜的殘留 應力變得不均勻。結果’光自液晶顯示裝置的周邊部泡漏 而變白’而成為所謂的Γ白缺陷J的問題。 為了解決此種問題,提案有一種黏著劑,其因為添加 - 低分子量聚合物於黏著劑組成物中,而具有應力緩和性。 例如,在專利文獻丨(曰本特開平10_279907號公報)中,揭 示有一種偏光板用黏著劑組成物,其係由高分子量丙稀酸 φ 系共聚物、重量平均分子量是3萬以下之低分子量丙烯酸 系共聚物、多官能化合物所構成,並記載著該黏著劑組成 物會追隨偏光板的尺寸變化而難以產生白缺陷。然而,專 利文獻1所記載的黏著劑組成物,由於重量平均分子量.是 3萬以下之低分子量丙烯酸系共聚物的添加量多,所以難 以防止高溫高濕下的發泡或剝落。 又’專利文獻2(日本特開2006-133606號公報)揭示一 種黏著劑組成物’其係由:含官能基單體〇5重量。/()以下之 • 低玻璃轉移溫度(Tg)丙烯酸系共聚物與含官能基單體6 重量%以上之高Tg丙烯酸系共聚物的混合物、以及可與官 能基反應的交聯劑和異氰酸酯所構成;其凝膠分率小於30 重量%。此黏著劑組成物,是藉由在高Tg丙烯酸系共聚物 的分子内形成交聯結構,並將低Tg丙烯酸系共聚物的分子 間以異氰酸醋化合物之多聚體(multimer)拘束在一起,而表 現凝集力。然而,此黏著劑組成物雖然藉由在分子間幾乎 未形成交聯構造而難以產生白缺陷,但其在高溫下的凝集 力低,在耐久性評價中難以抑制發泡或剝落的產生。 201011081 又,專利文獻3(日本特開20〇4_224873號公報)則揭示 -種黏著劑組成物’其添加〇.3〜3重量份之異氰酸酯化合 物於具有羧基和羥基之丙烯酸系共聚物中,並記載著該黏 著劑組成物的耐久性及白缺陷抑制性優良。此黏著劑組成 . 物,用於上述公開公報的實施例中的小型液晶顯示裝置 • 時,其耐久性及白缺陷抑制性優良。然而,用於大型液晶 顯示裝置時,則耐久性及白缺陷抑制性不良,因而謀求能 • 有一種黏著劑組成物,其具有更優良的耐久性及更高水準 的白缺陷抑制性。 近年來,隨著液晶顯示裝置的大型化,光學薄膜的尺 寸也變得較大。由於光學薄膜的尺寸越大,光學薄膜的膨 脹或收縮之類的尺寸變化也會越大,所以謀求較高的耐久 性及白缺陷抑制性。已揭示有一種黏著劑組成物其係一 種即使用於大畫面的液晶顯示裝置也能滿足耐久性之黏著 劑,且凝集力高。例如,專利文獻4(曰本特開平 籲號公報)揭示有一種偏光板用黏著劑組成物,其係於以2〇 /80〜50/ 50的重量比將含有羧基或酿胺基而未含有羥基 之丙烯酸系共聚物(A)、以及含有羧基或醯胺基和羥基之 丙烯酸系共聚物(B)混合而成之混合物中,調配異氱酸酯 化合物而成。然而,此專利文獻4所記載的黏著劑組成物, 即使能抑制在高溫高濕下的發泡或剝落,也會由於應力緩 和性不足而容易產生白缺陷β [專利文獻1]曰本專利特開平1〇_2799〇7號公報 [專利文獻2]日本專利特開之⑽卜〗336〇6號公報 5 201011081 [專利文獻3] [專利文獻4] 曰本專利特開2004_224873號公報 曰本專利特開平9-113724號公報 【發明内容】 [發明所欲解決之問題] •㈣專敎獻1〜4之黏著劑組成物,如同上述,難以 提供兼具耐久性及白缺陷抑制性的光學薄膜。例如,用於 籲 *有大畫面之液晶顯示裝置的光學薄膜其尺寸於近年來[Technical Field] The present invention relates to an adhesive composition for an optical film, an optical film with the adhesive, and a method for producing the adhesive composition, the adhesive composition It is used to adhere an optical film such as a polarizing film or a retardation film to an adherend such as a liquid crystal cell. More specifically, the present invention relates to an adhesive composition for an optical film, an optical film with the adhesive, and a method for producing the composition of the adhesive, which is excellent also under high temperature and high humidity. Durability, while having the difficulty of producing white defects. [Prior Art] A liquid crystal display device in which a liquid crystal cell having a liquid crystal component aligned in a predetermined direction is interposed between support substrates such as two sheets of glass, and an optical film such as a polarizing film or a retardation film or a brightness enhancement film is usually used. In the configuration, when the optical films are laminated to each other or the optical film is adhered to the liquid crystal cells, an adhesive is often used. The liquid crystal display device is used in a wide range as a display device such as a personal computer, a television, or a satellite navigation system. Along with this, an adhesive is required, which is excellent in durability even in a severe environment under high temperature and high humidity, that is, it does not peel off or generate bubbles even after long-term use. Moreover, under the severe environment of high temperature and high humidity, the optical film has a large dimensional change such as shrinkage and expansion, and the adhesive layer does not have the 201011081 method to alleviate the stress due to the dimensional change, and the optical film is The residual stress becomes uneven. As a result, "light is bubbled from the peripheral portion of the liquid crystal display device and becomes white", which is a problem of the so-called chalkiness defect J. In order to solve such a problem, it is proposed to have an adhesive which has stress relaxation property by adding a low molecular weight polymer to the adhesive composition. An adhesive composition for a polarizing plate, which is composed of a high molecular weight acrylic acid φ-based copolymer and having a weight average molecular weight of 30,000 or less, is disclosed in Japanese Laid-Open Patent Publication No. Hei 10-279907. It is composed of a molecular weight acrylic copolymer or a polyfunctional compound, and it is described that the adhesive composition tends to follow the dimensional change of the polarizing plate and is less likely to cause white defects. However, in the adhesive composition described in Patent Document 1, since the amount of the low molecular weight acrylic copolymer having a weight average molecular weight of 30,000 or less is large, it is difficult to prevent foaming or peeling under high temperature and high humidity. Further, Patent Document 2 (JP-A-2006-133606) discloses an adhesive composition which is composed of a functional group-containing monomer 〇5 by weight. /() below • a mixture of a low glass transition temperature (Tg) acrylic copolymer and a high Tg acrylic copolymer containing more than 6% by weight of the functional group monomer, and a crosslinking agent and isocyanate reactive with the functional group Composition; its gel fraction is less than 30% by weight. The adhesive composition is formed by forming a crosslinked structure in the molecule of the high Tg acrylic copolymer, and binding the molecules of the low Tg acrylic copolymer to the multimer of the isocyanate compound. Together, it shows agglutination. However, this adhesive composition is less likely to cause white defects by forming a crosslinked structure between molecules, but its cohesive force at a high temperature is low, and it is difficult to suppress the occurrence of foaming or peeling in durability evaluation. Further, Patent Document 3 (Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. It is described that the adhesive composition is excellent in durability and white defect suppressing property. This adhesive composition is excellent in durability and white defect suppressability when used in the small liquid crystal display device of the embodiment of the above publication. However, when it is used in a large-sized liquid crystal display device, durability and white defect suppression are poor, and therefore it is possible to have an adhesive composition which has more excellent durability and a higher level of white defect suppressing property. In recent years, with the increase in size of liquid crystal display devices, the size of optical films has also become large. Since the size of the optical film is larger, dimensional changes such as expansion or contraction of the optical film are also increased, so that high durability and white defect suppressing properties are obtained. An adhesive composition which is an adhesive which satisfies durability even in a liquid crystal display device for a large screen has been disclosed, and has high cohesive force. For example, Patent Document 4 (Japanese Unexamined Patent Publication Publication No. Publication No. Publication No.---------------- An isophthalic acid ester compound is prepared by mixing a hydroxy acrylic copolymer (A) and a mixture of a carboxyl group or a hydrazide group and a hydroxyl group-containing acrylic copolymer (B). However, the adhesive composition described in Patent Document 4 can easily cause white defects due to insufficient stress relaxation properties even when foaming or peeling under high temperature and high humidity is suppressed. [Patent Document 1] [Patent Document 2] Japanese Patent Laid-Open No. (10), No. 336, No. 6, Japanese Patent Publication No. PCT Publication No. JP-A No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. JP-A-H09-113724 SUMMARY OF INVENTION [Problems to be Solved by the Invention] (4) Adhesive Compositions Dedicated to 1 to 4, as described above, it is difficult to provide an optical film having both durability and white defect suppression properties. . For example, an optical film used for a liquid crystal display device having a large screen is sized in recent years.
因此’本發明之目的是提供一 種光學薄臈用黏著劑组 成物、附有該黏著劑之光學薄膜、及該黏著劑組成物的製 造方法,使耐久性和白缺陷抑制性並存,特別是該黏著劑 籲.组成物在使用於大尺寸的光學薄膜之際,也具有在高溫高 濕下優良的耐久性,並能抑制白缺陷。 [解決問題之技術手段] 本發明為了達成上述目的,提供了一種具備以下組成 之黏著劑組成物、光學薄膜及黏著劑組成物的製造方法。 (1) 一種黏著劑組成物,其包含:含有反應性官能基 之丙稀酸系共聚物(A);以及異氰酸酯化合物(B),其係 相對於100重量份之丙烯酸系共聚物(A),添加$重量份 201011081 以上、30重量份以下〇 过·之黏著劑組成物,其甲丙烯酸 重量❶/〇以上、5重量%以下的含有 之含羧基單體,來作為共聚物成 ⑺如上述⑴所述之黏著敎絲,其中丙稀酸 系共聚物⑷’進而含有G()()1重量%以上、i重量%以下 的含有羥基來作為反應性官能基之含羥基單體來作為共 聚物成分。 (4) 如上述(1)所述之黏著劑組成物,其中進而包 含與丙烯酸系共聚物(A)相異之含有反應性官能基之丙烯 酸系共聚物(c”異氰酸酯化合物(B),則是相對於1〇〇 重量伤之丙稀酸系共聚物(A)和丙稀酸系共聚物(c)的 混合物而被添加。 (5) 如上述(4)所述之黏著劑組成物,其中丙烯酸Therefore, the object of the present invention is to provide an optical thin film adhesive composition, an optical film with the adhesive, and a method for producing the adhesive composition, which have both durability and white defect suppression, particularly Adhesive agent. When used in a large-sized optical film, the composition also has excellent durability under high temperature and high humidity, and can suppress white defects. [Technical means for solving the problem] In order to achieve the above object, the present invention provides a method for producing an adhesive composition, an optical film, and an adhesive composition having the following composition. (1) An adhesive composition comprising: an acrylic acid-based copolymer (A) containing a reactive functional group; and an isocyanate compound (B) based on 100 parts by weight of the acrylic copolymer (A) Adding a weight-containing composition of 201011081 or more and 30 parts by weight or less of the adhesive composition, and a carboxyl group-containing monomer having a weight of methacrylic acid of ❶/〇 or more and 5% by weight or less is used as a copolymer (7) as described above. (1) The adhesive filament according to the above, wherein the acrylic acid copolymer (4) further contains, as a copolymerization, a hydroxyl group-containing monomer having a hydroxyl group as a reactive functional group of 1% by weight or more and 1% by weight or less of G()(). Composition. (4) The adhesive composition according to the above (1), which further comprises a reactive functional group-containing acrylic copolymer (c" isocyanate compound (B) different from the acrylic copolymer (A). It is added to a mixture of the acrylic acid copolymer (A) and the acrylic acid copolymer (c) in a weight loss of 1 〇〇. (5) The adhesive composition as described in the above (4), Among them acrylic
(2)如上述(1 )所 系共聚物(Α),含有〇5 缓基來作為反應性官能基 分0 系共聚物.(A)’含有0·5.重量%以上、5重量%以下的含有 • . 叛基來作為反應性官能基之含叛基單體,來作為共聚物成 分;丙烯酸系共聚物(C),則含有0.1重量%以上、5重量 。/〇以下的含有叛基來作為反應性官能基之含幾基單體以及 0.01重量%以上、5重量。/。以下的含有羥基來作為反應性官 能基之含羥基單體,來作為共聚物成分。 (6) 如上述(5)所述之黏著劑組成物,其中丙烯酸 系共聚物(Α)和丙烯酸系共聚物(C)之各自的重量平均 分子量,是100萬以上、250萬以下。 201011081 (7) 如上述(6)所述之黏著劑組成物,其中丙烯酸 系共聚物(A)和丙烯酸系共聚物(C)的含有重量比,是 50/ 50以上、99/ 1以下。 (8) —種黏著劑组成物,其包含··含有反應性官能基 之丙烯酸系共聚物(A)、與反應性官能基進行交聯反應之 異氰酸酯化合物(B)、以及由未與反應性官能基進行交聯 反應之異氰酸酯化合物(B)所形成之反應物。 (9) 如上述(8)所述之黏著劑組成物,其中異氰酸 酯化合物(B)的異氰酸酯基的當量,相對於1當量之反應 性官能基,是超過1的量。 (10) —種光學薄膜,其具有由上述(1)〜(9)中 的任一項所述之黏著劑組成物所形成的黏著劑層。 (11) 一種黏著劑組成物的製造方法,其具備:將含 有反應性官能基之丙烯酸系共聚物(A)、和要與反應性官 能基進行交聯反應之異氰酸酯化合物(B)混合的步驟;其 中混合步驟,是以異氰酸酯化合物(B)的異氟酸酯基的當 量,多於丙烯酸系共聚物(A)的反應性官能基的當量的量, 將異氰酸酯化合物(B )混合於丙烯酸系共聚物(A)中。 [功效] 若根據有關本發明之光學薄膜用黏著劑組成物、附有 該黏著劑之光學薄膜、及該黏著劑組成物的製造方法,則 因為凝集力和應力緩和性的平衡良好,所以在高溫高濕的 環境下也有優良的对久性、能抑制白缺陷。 8 201011081 【實施方式】 本發明者專心進行研究,結果發現能提供一種黏著劑 組成物(以下又稱為「單獨系黏著劑組成物」),其藉由使 用添加了含有反應性官能基之丙烯酸系共聚物(A)和特定 量之異氰酸酯化合物(B)而成的黏著劑組成物,而能謀求 •耐久性和白缺陷抑制性的並存。又,本發明者為解決上述 課題而專心研究’結果發現能提供一種黏著劑組成物(以 ❹ 下又稱為「混合系黏著劑組成物」),其藉由使用添加了特 定量之異氰酸酯化合物(C)於含有反應性官能基之丙烯酸 系共聚物(A)和與丙烯酸系共聚物(A)相異之含有反應 性官能基之丙烯酸系共聚物(C)的混合物中而成的黏著劑 組成物,而能謀求耐久性和白缺陷抑制性的並存。 [第一實施形態] (單獨系黏著劑组成物) 馨 有關本發明第一實施形態的黏著劑組成物,係包含·· 含有反應性官能基之丙烯酸系共聚物(A)和特定量之異氱 酸酯化合物(B)»有關第一實施形態的黏著劑組成物,其 丙烯酸系共聚物(A)的反應性官能基和異氰酸酯化合物 (B)進行交聯反應,且異氰酸酯化合物(B)中未進行交 聯反應的異氰酸酯基與環境中的水進行反應而形成有多聚 體’來作為所生成的反應物’藉此被認為具有良好的黏著 特性。 201011081 在第一實施形態中,所謂的丙烯酸系共聚物(A),是 在共聚物中作為共聚物成分而以丙烯酸酯單體、甲基丙稀 酸醋單體(以下合併.記述含「丙烯酸」之詞彙與含「曱基 丙烯酸」之詞彙時,記載為「(曱基)丙烯酸」)為主成分, • 而使(甲基)丙烯酸酯及具有反應性官能基之單體共聚合 - 而成的共聚物。丙烯酸系共聚物(A)是表示含80重量% 以上之(甲基)丙烯酸酯的共聚物,以含9〇重量❶/〇以上之 共聚物為佳。 作為(甲基)丙烯酸酯單體’只要是具有(甲基)丙 烯酸酯構造者則無特別限定,例如可使用··(甲基)丙婦酸 甲酯、(曱基)丙烯酸乙酯、(曱基)丙烯酸正丁酯、(曱基) 丙烯酸異丁酯、(曱基)丙烯酸第三丁酯、(甲基)丙烯酸 正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己 酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基) 丙烯酸正癸酯、(甲基)丙烯酸正十二烷基酯、(甲基)丙 Φ 烯酸十八烷基酯等的(甲基)丙烯酸之碳數1〜18的直鏈 或支鏈烷基酯’進而也可使用這些的各種衍生物1種或2 種以上。 基於使丙烯酸系共聚物(Α)和異氰酸酯化合物(Β) 反應的目的,作為有關第一實施形態之丙烯酸系共聚物(Α) 中的構成成分’而含有具有反應性官能基之單體。另外, 具有反應性官能基之單體(甲基)丙烯酸酯,也會被計入 定義丙烯酸系共聚物之際在丙烯酸系共聚物(Α)中作為共 聚物成分而含有之(曱基)丙烯酸酯單體的量。 201011081 作為具有反應性官能基之單體,例如可使用··含羧基 單體、含羥基單體、含環氧丙基單體、含醢胺基或 N-取代 醯胺基單體、含三級胺基單體等的i種或2種以上。 作為含羧基單體,例如可使用:丙烯酸、曱基丙烯酸、 順丁烯二酸、順丁烯二酸酐、反丁烯二酸、丁烯酸、伊康 酸、檸康酸、桂皮酸、琥珀酸單羥基乙基(甲基)丙烯酸 醋、順丁稀二酸單經基乙基(,基)丙烯酸醋、反丁烯二 • 酸單羥基乙基(甲基)丙烯酸酯、鄰苯二曱酸單羥基乙基 (甲基)丙烯酸酯' 1,2-二羧基環己烷單羥基乙基(甲基) 丙烯酸酯、(甲基)丙烯酸二聚物、^_羧基聚己內酯單(甲 基)丙烯酸酯等。 作為含羥基單體,例如可使用:(甲基)丙烯酸2_羥基 乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3_羥基 丙酯、(甲基)丙烯酸4-羥基丁酯、(曱基)丙烯酸3_甲基 _3-羥基丁酯、(甲基)丙烯酸二甲基_3 丁酯、(甲基) 丙烯酸1,3-二甲基-3-羥基丁酯、(曱基)丙烯酸2,2,4三甲 基-3-羥基戊酯、(甲基)丙烯酸2_乙基_3羥基己酯、(甲基) 丙烯酸甘油單酯、(曱基)丙烯酸聚丙二醇單酯、(甲基) 丙稀酸聚乙二醇單酯、(甲基)丙稀酸聚(乙二醇-丙二酵) 單酯、N-羥甲基丙烯醯胺、烯丙醇、甲基烯丙醇等。 作為含環氧丙基單體,例如可使用:(甲基)丙烯酸環 氧丙酯、(甲基)丙烯酸3,4-環氧基環己基甲酯、環氧丙基 乙烯醚、3,4-環氧基環己基乙烯醚、環氧丙基(曱基)烯丙 _、3,4-環氧基環己基(甲基)烯丙趟等。 11 201011081 作為含醯胺基或N-取代醯胺基單體,例如可使用:丙 烯醯胺、曱基丙烯醯胺、N-甲基(甲基)汚烯醯胺、 基(甲基)丙烯醯胺、N-甲氧基曱基(曱基)丙烯醯胺、 N-乙氧基曱基(甲基)丙稀酿胺、N-丙氧基甲基(甲基) 丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺、…第三丁基 ' 丙烯醯胺、N-辛基丙烯醯胺、二丙酮丙烯醮胺等。 作為含三級胺基單體,例如可使用:(甲基)丙烯酸二 鲁 尹基胺乙知、(甲基)丙稀酸二乙基胺乙醋、(甲基)丙歸 酸二甲基胺丙酯等。 作為共聚物成分的具有各種官能基之單體中,以含缓 基單趙、或是含羧基單體及含羥基單體作為共聚物成分而 含於丙烯酸系共聚物(A)為佳。 基於使黏著劑之凝集力增加、使黏著劑組成物之耐久 性it升的目的’作為共聚物成分而含有含緩基單髏之比例 是相對於丙烯酸系共聚物(A)為0.5重量%以上,較佳為 • 1重量%以上。又’基於抑制黏著劑組成物之點接力而不使 其過高的目的’作為共聚物成分而含有含羧基單體之比例 是相對於丙烯酸系共聚物(A )為5重量%以下,較佳為3 重量%以下。 基於抑制白缺陷的目的,作為共聚物成分而含有含經 基單體之比例是相對於丙烯酸系共聚物(A)為〇·〇01重量 %以上,較佳為0·0 1重量%以上。又’基於抑制在耐久性 試驗中產生剝落的目的,作為共聚物成分而含有含經基單 體之比例是相對於丙烯酸系共聚物(A)為1重量%以下, 12 201011081 較佳為0.5重量%以下。 有關第一實施形態之丙烯酸系聚合物(A),在不超過 丙烯酸系聚合物(A)之定義的範圍内,可含有(甲基)丙 烯酸酯單體以外之單體作為共聚物成分。作為(甲基)丙 烯酸醋單體以外之單體,舉例而言可使用:飽和脂肪酸乙 ‘ 烯酯、芳香族乙烯酯、氰化乙烯單體、順丁烯二酸或反丁 烯二酸之二酯。作為飽和脂肪酸乙烯酯,例如可使用甲酸 φ 乙烯酯、乙酸乙烯酯、丙酸乙烯酯、「十碳酸(versatic acid)」 (商品名)等(較佳為乙酸乙稀酯);作為芳香族乙稀單體, 例如可使用苯乙浠、α -甲基苯乙烯、乙烯甲苯等;作為氰 化乙烯單體’例如可使用丙烯腈、甲基丙烯腈;作為順丁 席一酸或反丁稀一酸之·一醋’例如可使用順丁稀二酸二甲 酯、順丁烯二酸二-Ν-丁酯、順丁烯二酸二_2_乙基己酯、順 丁烯二酸二-Ν-辛醋、反丁稀二酸二甲醋、反丁稀二酸二 丁醋、反丁稀二酸二-2-乙基己醋、反丁婦二酸二-Ν -辛醋等。 β 基於賦予黏著劑組成物充分之凝集力、抑制氣泡產生 的目的,有關第一實施形態之丙烯酸系共聚物(Α)的重量 平均分子量(Mw )為100萬以上,較佳為120萬以上、特 佳為140萬以上。又,基於確保黏著劑組成物之塗刷作業 性的目的,丙烯酸系共聚物(A)之重量平均分子量(mw ) 為250萬以下。 丙烯酸系共聚物之重量平均分子量,是藉由下述方法 所測定的值。 (重量平均分子量(Mw)的測定方法) 13 201011081 依照下述(1 )〜(3 )來測定。 (1) 將丙烯酸系共聚物溶液塗佈於剝離紙,以10(rc 乾燥2分鐘,得到膜狀的丙埽酸系共聚物。 (2) 使上述(A)所得之膜狀的丙烯酸系共聚物溶解 於四氫呋喃並使固形分成為0.2%。 (3 )使用凝膠滲透層析法(gpc,Gel permeation chromatography ),以下述條件測定丙烯酸系共聚物之重量 平均分子量(Mw)。 (條件)(2) The copolymer (Α) according to the above (1), which contains a ruthenium 5 ketone group as a reactive functional group-based O-based copolymer. (A)' contains 0.5% by weight or more and 5% by weight or less. The content of the resin is a copolymer component as a reactive functional group, and the acrylic copolymer (C) contains 0.1% by weight or more and 5 parts by weight. The following group-containing monomer having a reactive group as a reactive functional group and 0.01% by weight or more and 5 parts by weight. /. The following hydroxyl group-containing monomer having a hydroxyl group as a reactive functional group is used as a copolymer component. (6) The adhesive composition according to the above (5), wherein each of the acrylic copolymer (Α) and the acrylic copolymer (C) has a weight average molecular weight of 1,000,000 or more and 2,500,000 or less. (7) The adhesive composition according to the above (6), wherein the weight ratio of the acrylic copolymer (A) to the acrylic copolymer (C) is 50/50 or more and 99/1 or less. (8) An adhesive composition comprising: an acrylic copolymer (A) having a reactive functional group, an isocyanate compound (B) having a crosslinking reaction with a reactive functional group, and an unreactive A reactant formed by the isocyanate compound (B) in which the functional group is subjected to a crosslinking reaction. (9) The adhesive composition according to the above (8), wherein the equivalent of the isocyanate group of the isocyanate compound (B) is more than 1 per equivalent of the reactive functional group. (10) An optical film comprising the adhesive layer formed of the adhesive composition according to any one of the above (1) to (9). (11) A method for producing an adhesive composition comprising the steps of mixing an acrylic copolymer (A) containing a reactive functional group and an isocyanate compound (B) to be subjected to a crosslinking reaction with a reactive functional group The mixing step is such that the equivalent of the isofluoride group of the isocyanate compound (B) is more than the equivalent amount of the reactive functional group of the acrylic copolymer (A), and the isocyanate compound (B) is mixed with the acrylic acid. In the copolymer (A). [Efficacy] According to the adhesive composition for an optical film of the present invention, the optical film with the adhesive, and the method for producing the adhesive composition, since the balance between the cohesive force and the stress relaxation property is good, It also has excellent durability and can suppress white defects in high temperature and high humidity environment. 8 201011081 [Embodiment] The present inventors have conducted intensive studies and found that an adhesive composition (hereinafter also referred to as "separate adhesive composition") can be provided by using an acrylic acid containing a reactive functional group. The adhesive composition of the copolymer (A) and the specific amount of the isocyanate compound (B) can coexist with durability and white defect suppression. Further, the inventors of the present invention have intensively studied to solve the above problems. As a result, it has been found that an adhesive composition (hereinafter referred to as "mixed adhesive composition") can be provided by using a specific amount of an isocyanate compound. (C) an adhesive obtained by mixing a reactive functional group-containing acrylic copolymer (A) and a reactive functional group-containing acrylic copolymer (C) different from the acrylic copolymer (A) The composition is capable of coexisting in durability and white defect suppression. [First Embodiment] (Individual Adhesive Composition) The adhesive composition according to the first embodiment of the present invention contains an acrylic copolymer (A) containing a reactive functional group and a specific amount. The phthalate compound (B)» relates to the adhesive composition of the first embodiment, wherein the reactive functional group of the acrylic copolymer (A) and the isocyanate compound (B) are crosslinked, and the isocyanate compound (B) The isocyanate group which has not undergone the crosslinking reaction reacts with water in the environment to form a polymer 'as a reactant to be produced', whereby it is considered to have good adhesion characteristics. 201011081 In the first embodiment, the acrylic copolymer (A) is an acrylate monomer or a methyl acrylate monomer as a copolymer component in the copolymer (the following is a combination. The vocabulary and the word "mercaptoacrylic acid" are described as "(mercapto)acrylic acid) as the main component, and the (meth) acrylate and the monomer having a reactive functional group are copolymerized - and a copolymer. The acrylic copolymer (A) is a copolymer containing 80% by weight or more of a (meth) acrylate, and preferably a copolymer containing 9 Å or more by weight. The (meth) acrylate monomer ' is not particularly limited as long as it has a (meth) acrylate structure, and for example, methyl (methyl) propyl acrylate or ethyl (meth) acrylate can be used. N-butyl acrylate, (butyl) isobutyl acrylate, (butyl) methacrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, (meth) acrylate 2-ethylhexyl ester, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, (methyl) A linear or branched alkyl ester having 1 to 18 carbon atoms of (meth)acrylic acid, such as octadecyl octadecyl acrylate, may be used. One or more of these various derivatives may be used. The monomer having a reactive functional group is contained as a constituent component in the acrylic copolymer (Α) according to the first embodiment for the purpose of reacting the acrylic copolymer (yttrium) with an isocyanate compound. In addition, the monomer (meth) acrylate having a reactive functional group is also included in the acryl-based copolymer, and the (mercapto) acrylic acid is contained as a copolymer component in the acrylic copolymer (Α). The amount of ester monomer. 201011081 As a monomer having a reactive functional group, for example, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, a glycidyl group-containing monomer, a guanamine-containing or N-substituted guanamine group monomer, and a One type or two or more types of the amine group-based monomer. As the carboxyl group-containing monomer, for example, acrylic acid, mercaptoacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, citraconic acid, cinnamic acid, amber can be used. Acid monohydroxyethyl (meth) acrylate, cis-butyl succinate, monoethyl acrylate, transbutenic acid monohydroxyethyl (meth) acrylate, phthalic acid Acid monohydroxyethyl (meth) acrylate ' 1,2-dicarboxycyclohexane monohydroxyethyl (meth) acrylate, (meth) acrylate dimer, ^ carboxy polycaprolactone single ( Methyl) acrylate or the like. As the hydroxyl group-containing monomer, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, or (meth)acrylic acid 4- can be used. Hydroxybutyl ester, (meth)acrylic acid 3-methyl-3-hydroxybutyrate, (meth)acrylic acid dimethyl 3 butyl ester, (meth)acrylic acid 1,3-dimethyl-3-hydroxybutyl Ester, 2,2,4 trimethyl-3-hydroxypentyl (meth)acrylate, 2-ethyl-3-hydroxyhexyl (meth)acrylate, mono(meth)acrylate, (fluorenyl) Polypropylene glycol monoester, (meth)acrylic acid polyethylene glycol monoester, (meth)acrylic acid poly(ethylene glycol-propionate) monoester, N-methylol acrylamide, olefin Propanol, methyl allyl alcohol, and the like. As the epoxy group-containing monomer, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl vinyl ether, 3, 4 can be used. - Epoxycyclohexyl vinyl ether, epoxypropyl (decyl) allyl, 3,4-epoxycyclohexyl (methyl) allylic, and the like. 11 201011081 As the guanamine-containing or N-substituted guanamine-based monomer, for example, acrylamide, decyl acrylamide, N-methyl (methyl) methacrylamide, benzyl (meth) propylene can be used. Indoleamine, N-methoxyindenyl (mercapto) acrylamide, N-ethoxyindenyl (meth) propylamine, N-propoxymethyl (meth) acrylamide, N - Butoxymethyl (meth) acrylamide, ... -butyl butyl propylene amide, N - octyl acrylamide, diacetone acrylamide, and the like. As the tertiary amino group-containing monomer, for example, diruthenylamine (meth)acrylate, diethylamine acetate (meth)acrylate, and dimethyl (meth)propionate can be used. Amine propyl ester and the like. The monomer having various functional groups as the copolymer component is preferably contained in the acrylic copolymer (A) as a copolymer component, or a carboxyl group-containing monomer and a hydroxyl group-containing monomer. For the purpose of increasing the cohesive force of the adhesive and increasing the durability of the adhesive composition, the ratio of containing the slow-containing monoterpene as the copolymer component is 0.5% by weight or more based on the acrylic copolymer (A). Preferably, it is • 1% by weight or more. Further, the ratio of the content of the carboxyl group-containing monomer to the acrylic component (A) is preferably 5% by weight or less based on the acrylic copolymer (A), which is based on the purpose of suppressing the point contact force of the adhesive composition without being excessively high. It is 3 wt% or less. For the purpose of suppressing white defects, the ratio of the monomer-containing monomer to the copolymer component is 重量·〇01% by weight or more, preferably 0·0 1% by weight or more based on the acrylic copolymer (A). In addition, the ratio of containing a vinyl group-containing monomer as a copolymer component is 1% by weight or less based on the weight of the acrylic copolymer (A), and 12 201011081 is preferably 0.5 weight, for the purpose of suppressing the occurrence of peeling in the durability test. %the following. The acrylic polymer (A) according to the first embodiment may contain a monomer other than the (meth) acrylate monomer as a copolymer component within a range not exceeding the definition of the acrylic polymer (A). As the monomer other than the (meth)acrylic acid vinegar monomer, for example, a saturated fatty acid ethyl ethene ester, an aromatic vinyl ester, a vinyl cyanide monomer, maleic acid or fumaric acid can be used. Diester. As the saturated fatty acid vinyl ester, for example, formic acid φ vinyl ester, vinyl acetate, vinyl propionate, "versatic acid" (trade name), etc. (preferably ethyl acetate) can be used; As the dilute monomer, for example, phenethyl hydrazine, α-methyl styrene, vinyl toluene or the like can be used; as the vinyl cyanide monomer, for example, acrylonitrile or methacrylonitrile can be used; as cis-butyric acid or anti-butadiene For example, dimethyl succinate, dimethyl phthalate, bis-butylhexyl maleate, maleic acid, maleic acid can be used. Di-Ν-octyl vinegar, butyl succinate, dibutyl succinate, di-2-ethylhexanoic acid, dibutyl succinate, succinic acid Wait. β The weight average molecular weight (Mw) of the acrylic copolymer (Α) according to the first embodiment is 1,000,000 or more, preferably 1.2 million or more, for the purpose of imparting a sufficient aggregating power to the adhesive composition and suppressing the generation of bubbles. Very good for more than 1.4 million. Moreover, the weight average molecular weight (mw) of the acrylic copolymer (A) is 2.5 million or less for the purpose of ensuring the coating workability of the adhesive composition. The weight average molecular weight of the acrylic copolymer is a value measured by the following method. (Method for Measuring Weight Average Molecular Weight (Mw)) 13 201011081 The measurement was carried out in accordance with the following (1) to (3). (1) The acrylic copolymer solution was applied to a release paper, and dried at 10 (rc for 2 minutes to obtain a film-like propionic acid copolymer). (2) The film-like acrylic copolymer obtained in the above (A) was obtained. The product was dissolved in tetrahydrofuran to have a solid content of 0.2%. (3) The weight average molecular weight (Mw) of the acrylic copolymer was measured by gel permeation chromatography (gpc, Gel permeation chromatography) under the following conditions.
GPC = HLC-8220 GPC [曰本東曹股份有限公司製] 管柱:使用4根TSK-GEL GMHXL 移動相之溶劑:四氳吱η南GPC = HLC-8220 GPC [made by Sakamoto Tosoh Co., Ltd.] Column: 4 TSK-GEL GMHXL mobile phase solvent: Four 氲吱N South
流速:0.6 ml/min 管柱溫度:40°C 基於賦予黏著劑組成物充分之凝集力、使其發揮充分 之耐久性的目的’有關第一實施形態之丙烯酸系共聚物(A) 的玻璃轉移溫度(Tg)為-80°C以上,較佳為-60°C以上。 又’基於使黏著劑組成物發揮對支撐基板之充分之密著 性、及不產生剝落等耐久性的目的,丙烯酸系共聚物(A ) 之玻璃轉移溫度(Tg)為-20°C以下,較佳為-40eC以下。 丙烯酸系共聚物之玻璃轉移溫度(Tg),是將藉由下述 式1之計算所求得之溫度(K)換算為(。(:)之值。 式 1 1/Tg= Ml/Tgl + M2/Tg2+M3/Tg3+...... + Μη/ Tgn 式中,Tgl、Tg2、Tg3…及Tgn分別表示成分1、成分 201011081 2、成分3…及成分 (κ)。又’式中Ml 莫耳分率。 各自的同元聚合物之玻璃轉移溫度 M2、M3 ·’·及Μη是表示各種成分之 用於第—實施形態之丙烯酸系共聚物的聚合方法,並 無特別限制,可藉由:女^ 错由/合液聚合、乳化聚合、懸浮聚合等方 法聚合。另外’使用藉由聚合所得之共聚物的混合物來製 造有關第-實施形態的黏著劑組成物之際,因為其處理步 驟較簡單、且能以短時間進行,所以較佳I藉由溶液聚合 來聚合。 溶液聚合,一般可使用:將有機溶劑、單體、聚合起 始劑、及視需要而使用之鏈轉移劑添加至聚合槽内,在氮 氣氣流中或有機溶劑之回流溫度下,邊攪拌邊使其進行數 小時之加熱反應等方法。另外,有關第一實施形態之丙烯 酸系共聚物(Α)的重量平均分子量,可藉由調整反應溫度、 時間、溶劑量、觸媒之種類或量,而作成所希望的分子量。 有關第一實施形態之黏著劑組成物,是相對於丨〇〇重 量份之丙晞酸系共聚物(Α)而含有5〜30重量份之異氰酸 醋化合物(Β )。 作為異氰酸酯化合物(Β )’例如可使用苯二甲基二異 氰酸酯(xylylene diisocyanate)、二苯甲烷二異氰酸酯、三 苯甲烷三異氰酸酯、甲苯二異氰酸酯等芳香族異氰酸酯; 例如可使用六亞甲基二異氟酸酯、異佛酮二異氰酸酯、該 芳香族異氰酸酯化合物之氫化物等脂肪族或脂環族異氰酸 酿;例如可使用這些異氰酸酯之二聚體或三聚體、或者是 15 201011081 這些異氰酸酯與三羥曱基丙烷等多元醇之加成物等各種來 自異氰酸酯的異氰酸酯化合物。這些可單獨或組合使用。 異氰酸酯化合物(B ),可以適當地使用例如以下述商 品名在市面上販售者:「Coronate L」、「Coronate HX」、 -「Coronate HL-S」、「Coronate 2234」(以上為曰本聚氨醋 工業股份有限公司製);「Desmodur N34〇0」(日本住友拜耳 聚胺酯股份有限公司製)、「DURANATE E-405-80T」、 _ 「DURANATE TSE-100」(日本旭化成工業股份有限公司 製)、「Takenate D -110N」、「Takenate D-120N」、「Takenate M-63 IN」(以上為曰本三井武田化學股份有限公司製)等。 其中’自耐久性及白缺陷性之觀點而言,作為異氰酸 醋化合物(B)’較佳為來自芳香族異氰酸酯之異氰酸酯化 合物’特佳為來自曱苯二異氰酸酯之異氰酸酯化合物。 基於抑制白缺陷的目的,相對於1〇〇重量份之丙烯酸 系共聚物(A)的異氰酸酯化合物(b)用量是5重量份以 • 上。又’基於確保丙烯酸系共聚物(A)和異氰酸酯化合物 (B )之相溶性、使其產生作為黏著劑之充分之膠黏感的目 的’相對於100重量份之丙烯酸系共聚物(A)的異氰酸酯 化合物(B )用量是3〇重量份以下,較佳為2〇重量份以下’ 特佳為15重量份以下。 又’有關第—實施形態之黏著劑組成物,其異氰酸酯 化合物(B)中未與共聚物形成交聯的異氰酸酯基,可能會 與環境中的水進行反應而形成多聚體。雖然異氰酸酯基和 水的反應性較高’即使並未相對於樹脂的反應性官能基而 16 201011081 加入過剩量的異氰酸酯基,部分的異氰酸酯基也可能會和 環境中的水反應而形成多聚體,但是基於使其形成較多之 多聚體以提升白缺陷抑制性和耐久性的目的,而相對於丙 烯酸系共聚物(A)的合計丨當量之反應性官能基,使用多 於1當量的異氰酸酯基,較佳為12當量以上、特佳為15 當量以上的異氰酸酯基。 有關第一實施形態之黏著劑組成物,亦可與異氰酸酯 化合物(B)以外的交聯劑並用。作為異氰酸酯(B)以外 的交聯劑,只要能與丙烯酸系共聚物(A)反應而形成交聯 構造者則無特別限定,可以舉出吖丙啶化合物、環氧化合 物、二聚氰胺甲醛縮合物、金屬鹽、金屬螯合物等。這些 異氰酸酯化合物(B)以外的交聯劑,可各自單獨或將2 種以上組合使用。在第一實施形態中,作為異氰酸酯(B) 以外的交聯劑,較佳為使用吖丙啶化合物及/或環氧化合 物。 作為π丫丙啶化合物’可使用異氰酸酯化合物和伸乙亞 胺之反應生成物,作為異氰餿酯化合物則可使用前述所例 示者。又,亦已知:於三羥甲基丙烷或季戊四醇等多元醇 與(甲基)丙烯酸等的多元酯上,使伸乙亞胺加成而得的 化合物’其亦可使用。 作為吖丙啶化合物,例如可舉出Ν,Ν_六亞甲基雙(卜 吖丙啶甲醯胺)、亞甲基雙[Ν_( ^吖丙啶基羰基)4_苯胺]、 四經甲基甲烧_三(沒_吖丙咬基丙酸酯)、三經甲基丙烧_ 二(冷-吖丙啶基丙酸酯)等,這些之中,例如可適當地使 17 201011081 用以下述商品名在市 A 丄 甸上販售者:「TAZO」、「TAZM」〔以 上為日本相互藥工股 切有限公司製〕;「CHEMITITE PZ-33」 〔日本觸媒股份有限公司製〕等。 作為環氧化合物,如i 。 例如可使用:乙二醇二環氧丙醚、 二乙二醇二環氧丙醚、 本乙一醇二環氧丙醚、丙二醇二環 氧丙鍵、三丙二醇二 一艰氣丙醚、聚丙二醇二環氧丙醚、新 戊一醇二環氧丙醚、丨一 ’-已—醇二環氧丙驗、聚伸丁二醇二 環氧丙醚、丙三醇_ 鮮—%氧丙醚、丙三醇三環氧丙醚、二丙 二醇聚環氧丙喊、聚丙三醇聚環氧丙鍵、間苯二盼二環氧 二漠新戊二醇二環氧丙醚、三經甲基丙烧三環氧 丙喊' 季戊四醇聚援 裏氧丙鍵、山梨醇聚環氧丙醚、己二酸 二環氧丙酯、鄰裟-田 一甲酸一環氧丙酯、異三聚氰酸三(環 氧丙基)酯、異=护垒故 ,Flow rate: 0.6 ml/min Column temperature: 40 ° C Glass transfer of the acrylic copolymer (A) according to the first embodiment for the purpose of imparting sufficient cohesive force to the adhesive composition to exhibit sufficient durability The temperature (Tg) is -80 ° C or higher, preferably -60 ° C or higher. In addition, the glass transition temperature (Tg) of the acrylic copolymer (A) is -20 ° C or less for the purpose of imparting sufficient adhesion to the support substrate and durability such as peeling off. It is preferably -40 eC or less. The glass transition temperature (Tg) of the acrylic copolymer is converted into a value of (.) by the temperature (K) obtained by the calculation of the following formula 1. Formula 1 1/Tg = Ml/Tgl + M2/Tg2+M3/Tg3+... + Μη/ Tgn where Tgl, Tg2, Tg3, ... and Tgn represent component 1, component 201011081, component 3, and component (κ), respectively. Ml Molar fraction. The glass transition temperatures M2, M3, ', and Μη of the respective homopolymers are polymerization methods for the acrylic copolymers of the first embodiment, which are various components, and are not particularly limited. By the method of: polymerization, liquid polymerization, emulsion polymerization, suspension polymerization, etc., and the use of a mixture of copolymers obtained by polymerization to produce the adhesive composition of the first embodiment, because The treatment step is relatively simple and can be carried out in a short time, so it is preferred to polymerize by solution polymerization. Solution polymerization can generally be carried out by using an organic solvent, a monomer, a polymerization initiator, and, if necessary, a chain transfer. Adding to the polymerization tank, refluxing in a nitrogen stream or organic solvent The method of heating and reacting for several hours while stirring, and the weight average molecular weight of the acrylic copolymer (Α) according to the first embodiment can be adjusted by adjusting the reaction temperature, time, amount of solvent, and touch The adhesive composition of the first embodiment is contained in an amount of 5 to 30 parts by weight based on the weight of the acrylic acid copolymer (Α). Isocyanate compound (Β). As the isocyanate compound (Β), for example, an aromatic isocyanate such as xylylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate or toluene diisocyanate can be used; For example, an aliphatic or alicyclic isocyanic acid such as hexamethylene diisofluoride, isophorone diisocyanate or a hydride of the aromatic isocyanate compound can be used; for example, a dimer or a triester of these isocyanates can be used. Polymer, or 15 201011081 Various isocyanate-like additions such as an adduct of a polyhydric alcohol such as an isocyanate and a trihydroxydecylpropane The acid ester compound may be used singly or in combination. The isocyanate compound (B) may be suitably used, for example, in the market under the trade names "Coronate L", "Coronate HX", - "Coronate HL-S". "Coronate 2234" (above is manufactured by Sakamoto Polyurethane Industry Co., Ltd.); "Desmodur N34〇0" (made by Sumitomo Bayer Polyurethane Co., Ltd.), "DURANATE E-405-80T", _ "DURANATE TSE" -100" (made by Asahi Kasei Industrial Co., Ltd.), "Takenate D-110N", "Takenate D-120N", "Takenate M-63 IN" (above is manufactured by Sakamoto Mitsui Takeda Chemical Co., Ltd.). From the viewpoint of durability and white defect, the isocyanate compound (B)' is preferably an isocyanate compound derived from an aromatic isocyanate, and particularly preferably an isocyanate compound derived from indole diisocyanate. The amount of the isocyanate compound (b) based on 1 part by weight of the acrylic copolymer (A) is 5 parts by weight based on the purpose of suppressing the white defect. Further, 'based on ensuring the compatibility of the acrylic copolymer (A) and the isocyanate compound (B) to produce a sufficient adhesiveness as an adhesive' with respect to 100 parts by weight of the acrylic copolymer (A) The amount of the isocyanate compound (B) is 3 parts by weight or less, preferably 2 parts by weight or less, and particularly preferably 15 parts by weight or less. Further, in the adhesive composition according to the first embodiment, the isocyanate group which is not crosslinked with the copolymer in the isocyanate compound (B) may react with water in the environment to form a polymer. Although the reactivity of the isocyanate group and water is higher 'even if the excess isocyanate group is not added relative to the reactive functional group of the resin, part of the isocyanate group may react with water in the environment to form a polymer. However, based on the purpose of increasing the white defect suppression and durability for the purpose of enhancing the white defect suppression and durability, more than one equivalent is used with respect to the total equivalent weight of the reactive functional group of the acrylic copolymer (A). The isocyanate group is preferably an isocyanate group of 12 equivalents or more, particularly preferably 15 equivalents or more. The adhesive composition of the first embodiment may be used in combination with a crosslinking agent other than the isocyanate compound (B). The crosslinking agent other than the isocyanate (B) is not particularly limited as long as it can react with the acrylic copolymer (A) to form a crosslinked structure, and examples thereof include an aziridine compound, an epoxy compound, and a melamine formaldehyde. a condensate, a metal salt, a metal chelate or the like. The crosslinking agents other than the isocyanate compound (B) may be used alone or in combination of two or more. In the first embodiment, as the crosslinking agent other than the isocyanate (B), an aziridine compound and/or an epoxide is preferably used. As the π-aziridine compound, a reaction product of an isocyanate compound and ethylene thiamine can be used, and as the isocyanurate compound, the above-exemplified one can be used. Further, it is also known that a compound obtained by adding ethyleneimine to a polyhydric alcohol such as trimethylolpropane or pentaerythritol or a polyvalent ester such as (meth)acrylic acid can be used. Examples of the aziridine compound include hydrazine, hydrazine hexamethylene bis(dipyridinium carbamide), methylene bis[Ν_(^ 吖 啶 羰 carbonyl) 4 aniline, and Methyl ketone _ tri (n- 吖 吖 propyl propyl propionate), tri-methyl propyl hydride _ bis (cold-aziridine propionate), etc., among these, for example, may be appropriately made 17 201011081 Sold by the following trade names in the city of Aden: "TAZO", "TAZM" (above is made by Japan Mutual Pharmaceutical Co., Ltd.); "CHEMITITE PZ-33" [made by Nippon Shokubai Co., Ltd. 〕Wait. As an epoxy compound, such as i. For example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, the present ethyl alcohol diglycidyl ether, propylene glycol diepoxypropyl bond, tripropylene glycol propylene glycol, polypropylene glycol can be used. Diglycidyl ether, neopentyl alcohol diglycidyl ether, 丨-'--alcohol propylene oxide test, polybutane diol diglycidyl ether, glycerol _ fresh-% oxypropyl ether , glycerol triglycidyl ether, dipropylene glycol polyepoxy propylene, polyglycerol polyepoxy bond, m-phenylene diepoxide, dioxon neopentyl glycol diglycidyl ether, trimethyl methyl Propylene triacetate propylene s 'pentaerythritol poly propylene carbonate bond, sorbitol polyglycidyl ether, diglycidyl adipate, o-ruthenium-formaldehyde monoglycidyl ester, iso-cyanuric acid Tris(epoxypropyl) ester, iso = barrier,
呉-聚氰酸三(環氧丙氧基乙基)醋、W 雙(Ν,Ν-環氧丙基胺甲基 Τ基)環己烷、ν,Ν,Ν’,Ν,-四環氧丙 基-間苯二甲基二胺等。 物為Γ氧化。物之十以含有3個環氧基以上之環氧化合 :’其中更佳為使用異三聚氰酸三(.環氧丙基)酿、 異一聚氛酸三(環氧丙負其、 丙基胺甲…… 1,3,(Ν,環氧 _ 土)1烷、Ν,Ν,Ν,,Ν’-四環氧丙基-間苯二甲美 二胺等環氧化合物,特佳為 ,. 土 ::)環己燒、沐_’_四環氧丙基_間苯二甲基二胺等。 環氧化合物,例如可使用以下述商品名在市面上販售 者· TETRAD-C」、「TETRAD X Γ -芏 公司製〕等。 Χ」〔二逢瓦斯化學股份有限 18 201011081 本發明之黏著劑組成物,可進而使用矽烷化合物。此 種化合物可使用:例如含巯基之聚矽氧烷氧基募聚物 (silicone alkoxy 〇ngomer)、含環氧基之聚矽氧烷氣基寡聚 物、含胺基之聚矽氧烷氧基募聚物、含苯基之聚矽氣境氧 基寡聚物、含甲基之聚矽氧烷氧基寡聚物等含有機取代基 之聚矽氧烷氧基寡聚物;例如酼基丙基三甲氧基矽烷 7* -巯基丙基三乙氧基矽烷、τ _毓基丙基二甲氧基甲基矽 φ 燒等含巯基之矽烷化合物;例如召-(3,4-環氧基環已基) 乙基三曱氧基矽烷、沒-(3,4-環氧基環己基)乙基三乙氧 基矽烷等含脂環式環氧基矽烷化合物;例如甲基三(環氣 丙基)石夕烧、r-環氧丙氧基丙基甲基二曱氧基矽燒、 環氧丙氧基丙基三甲氧基矽烷、^_環氧丙氧基丙基三乙氣 基矽烧等含環氧基石夕烧化合物;例如3三乙氧基矽基丙基 琥珀酸(酐)、3-三甲氧基矽基丙基琥珀酸(酐)、氕 一 甲基 二甲氧基矽基丙基琥珀酸(酐)、甲基二乙氧基矽基丙基魂 •珀酸(酐)、;U羧基_3_三乙氧基矽基丙基琥珀酸(酐)等含 羧基之矽烷化合物;例如N-(厶-胺乙基)-τ_胺丙基 一 洛甲基 一甲氧基矽烷、Ν-( /3-胺乙基)-r_胺丙基三甲氧基矽烷 N_( /3-胺乙基)_r _胺丙基三乙氧基矽烷、γ _胺丙基三甲 氧基*夕燒、r-胺丙基三乙氧基矽烷、苯基胺兩基一 甲氧基矽烷等含胺基矽烷化合物;例如7-羥基丙基三甲= 基矽烷等含羥基之矽烷化合物;例如r醯胺基丙基三甲氣 基矽烷等含醯胺基之矽烷化合物;例如7_異氰酸酯基丙基 三曱氧基矽烷等含異氰酸酯基之矽烷化合物;例如異三聚 19 201011081 氰酸三(3 -三曱氧基矽基丙基)酯、異三聚氰酸三(3 -三 乙氧基石夕基丙基)酯等含異三聚氱酸酯骨架之石夕烧化合物 等。梦烧化合物之使用,有助於財久性之提升。 基於使黏著劑組成物之耐久性提升的目的,相對於1 〇〇 重量份之丙烯酸系共聚物(A)的矽烷化合物用量是〇 〇1 〜3重量份,較佳為〇.〇1〜2重量份,特佳為〇 〇2〜1重量 份。 φ 有關第一實施形態之黏著劑組成物,除了上述丙稀酸 系共聚物(A )和異氰酸酯化合物(b )、異氰酸醋化合物 以外之交聯劑、石夕烧化合物以外,可以以不損及有關第一 實施形態之黏著劑組成物所發揮效果的範圍内之量,來適 當地調配各種添加劑、溶劑、耐候性安定劑、膠黏劑、塑 化劑、軟化劑、染料、顏料、無機充填劑等。 耐候性安定劑、膠黏劑、塑化劑、軟化劑、染料、顏 料、無機充填劑等的調配量範圍,較佳為相對於1〇〇重量 •伤之丙稀酸系共聚物(A)是30重量份以下,更佳為20 重量份以下’最佳為10重量份以下。藉由將調配量設於該 範圍内,可以適當地保持黏著劑組成物之黏接力、濕潤性、 耐熱性、重貼性的平衡,而可獲得各種物性表現良好的黏 著劑組成物。 有關第一實施形態之黏著劑組成物,其丙烯酸系共聚 物(A)之反應性官能基和異氰酸酯化合物會形成交 聯構造,而未進行父聯反應之異氰酸酯基則可能會跟環境 中的水反應而升々成多聚體。基於抑制在耐久性評價中產生 20 201011081 發泡的目的, 的目的,形成交聯構造及多聚體後的膠質成分是 乂 上,.較佳為 70 重量呉-polycyanuric acid tris(glycidoxyethyl) vinegar, W bis (hydrazine, hydrazine-epoxypropylamine methyl fluorenyl) cyclohexane, ν, Ν, Ν', Ν, - tetracyclic Oxypropyl-m-xylylenediamine and the like. The substance is oxidized by hydrazine. The tenth compound contains three epoxy groups and more epoxidized: 'More preferably, it is made of triisocyanate (.epoxypropyl), and isomeric acid is used. Propylamine A... 1,3,(Ν, epoxy_土)1 alkyl, anthracene, anthracene, anthracene, anthracene--tetraepoxypropyl-m-xylylenediamine and other epoxy compounds, Jiawei,. Earth::) Cyclohexene, Mu___tetraepoxypropyl _m-xylylenediamine. For the epoxy compound, for example, those sold under the trade names: TETRAD-C, "TETRAD X Γ-芏", etc. can be used. Χ"[二逢瓦斯化工有限有限18 201011081 The adhesive of the present invention As the composition, a decane compound can be further used. Such a compound can be used, for example, a fluorenyl-containing polyaluminoxy alkoxy 〇ngomer, an epoxy group-containing polyoxyalkylene gas-based oligomer, and an amine group-containing polyoxyalkylene oxide. a polyoxyalkyloxyalkoxy group containing an organic substituent such as a phenyl group-containing polyfluorene gas oxy oligomer, a methyl group-containing polyoxyalkyloxy oligomer; a decyl-containing decane compound such as propyl-trimethoxydecane 7*-mercaptopropyltriethoxy decane, τ-mercaptopropyldimethoxymethyl hydrazine φ; for example, a call-(3,4-ring) An alicyclic oxirane compound such as ethylcyclodecyloxydecane or bis-(3,4-epoxycyclohexyl)ethyltriethoxydecane; for example, methyltri Cyclopropyl propyl), ruthenium, r-glycidoxypropylmethyldimethoxy oxime, glycidoxypropyltrimethoxydecane, ^-glycidoxypropyltriethyl An epoxy group-containing compound such as gas-based oxime; for example, 3 triethoxymercaptopropyl succinic acid (anhydride), 3-trimethoxydecyl propyl succinic acid (anhydride), fluorenylmethyl dimethyl hydride Oxydecyl propyl a carboxyl group-containing decane compound such as peric acid (anhydride), methyldiethoxymercaptopropyl succinic acid (anhydride); U carboxyl-3-3 triethoxymercaptopropyl succinic acid (anhydride); For example, N-(厶-aminoethyl)-τ_aminopropyl-l-methyl-methoxydecane, Ν-(/3-aminoethyl)-r-aminopropyltrimethoxydecane N_(/3 -Amineethyl)_r_Aminopropyltriethoxydecane, γ-Aminopropyltrimethoxy*, sulphur, r-aminopropyltriethoxydecane, phenylaminediyl-methoxypropane, etc. An amino group-containing decane compound; for example, a hydroxyl group-containing decane compound such as 7-hydroxypropyltrimethyl=pyridin; a decyl group-containing decane compound such as r-guanidinopropyltrimethyl decane; for example, 7-isocyanatepropyl An isocyanate-containing decane compound such as tridecyloxydecane; for example, isotrimeric 19 201011081 tris(3-trimethoxydecyl propyl) cyanate, tris(3 - triethoxy sulphate) A sulfonium compound containing a heterotrimeric phthalate skeleton, such as a propyl) ester. The use of dream burning compounds will help to improve the longevity. For the purpose of improving the durability of the adhesive composition, the amount of the decane compound of the acrylic copolymer (A) is 〇〇1 to 3 parts by weight, preferably 〇.〇1 to 2, with respect to 1 part by weight of the acrylic copolymer (A). The parts by weight are particularly preferably 2 to 1 part by weight. φ The adhesive composition according to the first embodiment may be other than the above-mentioned acrylic acid copolymer (A), isocyanate compound (b), cross-linking agent other than isocyanate compound, and cerium compound. Various additives, solvents, weather stabilizers, adhesives, plasticizers, softeners, dyes, pigments, and the like are appropriately blended in an amount within the range of the effect of the adhesive composition of the first embodiment. Inorganic fillers, etc. The range of the formulation of the weathering stabilizer, the adhesive, the plasticizer, the softener, the dye, the pigment, the inorganic filler, etc., is preferably the weight of the acrylic copolymer (A) relative to 1 〇〇. It is 30 parts by weight or less, more preferably 20 parts by weight or less, and most preferably 10 parts by weight or less. By setting the blending amount within this range, the balance of the adhesive force, the wettability, the heat resistance, and the reproducibility of the adhesive composition can be appropriately maintained, and an adhesive composition excellent in various physical properties can be obtained. In the adhesive composition according to the first embodiment, the reactive functional group of the acrylic copolymer (A) and the isocyanate compound form a crosslinked structure, and the isocyanate group which is not subjected to the parental reaction may be in contact with water in the environment. The reaction is promoted to a multimer. Based on the purpose of suppressing the occurrence of foaming in the durability evaluation 20 201011081, the colloidal structure after forming the crosslinked structure and the polymer is 乂, preferably 70 重量
構造及多聚體後的膠質成分是95重量%以下。 特佳為80重量%以上。 剝落的目的,形成交聯 黟質成分可以藉由下述方法測定。 (黏著劑組成物之膠質成分的測定) φ 依照下述(1 )〜(6 )來測定。 (1) 將黏著劑組成物之溶液,塗佈於經聚矽氧系脫模 劑表面處理後的剝離片上,使其乾燥後的塗刷量成為25g ,然後以熱風循環式乾燥機將其在1〇〇π乾燥秒, 形成膜狀的感壓接著劑層。 (2) 將所形成之感壓接著劑層,在23。〇、濕度65%rh 下熟化(curing)lO曰〇 (3) 將約〇.25g之(2)所得的膜狀黏著劑層,黏貼 魯於經精秤之網目數250 mesh的金屬網(i〇〇mmxi〇〇mm ) 上’而將其包覆使膠質成分不漏出。之後,以精密天平正 確地測定重量、製作試料。 (4) 將上述金屬網於乙酸乙酯溶液中浸潰3日。 (5 )浸潰後,取出金屬網,以少量的乙酸乙酯將其洗 淨,並使其在120。(:乾燥24小時。之後,以精密天平正確 地測定重量。 (6 )根據下式計算膠質成分。 膠質成分(重量 %) = (C—A) / (B—A) X100 21 201011081 其中,A是金屬網的重量(g),B是黏貼了黏著劑之 金屬網的重量(黏著劑重量)(g ),C是浸潰後經乾燥之金 屬網的重量(膠質樹脂重量)(g)。 有關第一實施形態之黏著劑組成物,至少是經由將含 有反應性官能基之丙烯酸系共聚物(A)和與反應性官能基 進行交聯反應之異氰酸酯化合物(B )混合的步驟而製作。 然後,在此混合步驟中,是將異氰酸酯化合物(B )混合於 丙烯酸系共聚物(A),其中異氰酸酯化合物(B)之異氰 9 酸酯基當量是多於丙烯酸系共聚物(A)之反應性官能基當 量的量。具體而言’是經由下述步驟而合成:準備一含有 反應性官能基之丙烯酸系共聚物(A)的步驟、準備一與反 應性官能基進行交聯反應之異氰酸酯化合物(B )的步驟、 將所準備的丙烯酸系共聚物(A)和所準備的異氰酸醋化合 物(B)混合的步驟。而且’準備異氰酸酯化合物(b)的 步驟’是準備一異氰酸酯化合物(B),其中異氰酸酯化合 ❿ 物(B)之異氰酸酯基的當量是多於丙烯酸系共聚物(a) 之反應性官能基的當量的量。 又’有關第一實施形態之光學薄膜’係具有由有關第 一實施形態之黏著劑組成物所形成之黏著劑層的光學薄 膜。其具體的製造方法’是藉由在剝離片上塗佈有關第一 實施形態之黏著劑組成物並將其乾燥,而在剝離片上形成 黏著劑層。然後,可以將形成於剝離片上之黏著劑層轉印 至光學薄膜’接著使其熟化而製作。 作為剝離片’可以使用以氟系樹脂、石蠟、聚碎氧等 22 201011081 脫模劑施以脫模處理的聚酯等合成樹脂片。形成於剝離片 上之黏著劑層的厚度,例如在乾燥後的厚度是丨〜1 〇〇 " m,較佳為5〜50/zm,更佳為15〜30/im左右的厚度。 塗佈於剝離片上之黏著劑組成物,可以用熱風乾燥機 以70〜12(TC、1〜3分鐘左右的加熱條件來乾燥。 有關第一實施形態之黏著劑組成物、具備由此黏著劑 組成物所構成黏著劑層之光學薄膜’其對於被黏著物的黏 φ 接力’可藉由調整丙烯酸系共聚物(A)的反應性官能基、 異氰酸酯化合物(B)等的種類或量,而調整為所希望的黏 接力。 (第一實施形態的功效) 有關第一實施形態之黏著劑組成物、具備由此黏著劑 組成物所構成黏著劑層之光學薄膜,因為具備上述結構, 所以可能藉由丙烯酸系共聚物(A )的反應性官能基與交聯 劑之反應所致的化學交聯、以及異氰酸酯化合物(B)中未 ® 進行交聯反應之異氰酸酯基與熟化環境中的水分反應形成 多聚體並拘束丙烯酸系共聚物之分子鏈移動的物理交聯, 而具有高凝集力,因此对久性良好,拘束分子鏈移動的物 理交聯部分則可能因為亦具有流動性而在應力緩和性方面 亦優良,可以兼具高水準的耐久性和白缺陷抑制性。 亦即,在有關第一實施形態之黏著劑組成物中,因為 使用了其異氰酸酯化合物(B)的異氰酸酯基的當量多於丙 婦酸系共聚物(A)的反應性官能基的當量的量之異氰酸酯 化合物(B),所以不僅生成丙烯酸系共聚物(A)的反應 23 201011081 性官能基與交聯劑之反應所致的化學交聯,在添加於丙烯 酸系共聚物(A)中之異氰酸酯化合物(B)中,也會生成 來自於具有未與丙烯酸系共聚物(A)反應之異氰酸酯基的 異氰酸酯化合物(B)之多聚體。藉此,有關第一實施形態 之黏著劑組成物,在藉由丙稀酸系共聚物(A )之反應性官 能基與交聯劑之反應所致的化學交聯而生成之分子鏈纏繞 結構中,存在有異氰酸酯化合物(B)之多聚體。因此,有 關第一實施形態之黏著劑組成物,其多聚體不均勻地分散 於藉由反應性官能基與交聯劑之反應所致的化學交聯而生 成之分子鏈纏繞結構中,例如可以確保對於可見光之良好 的透明性,同時以高水準實現耐久性和白缺陷抑制性。 [第二實施形態] (混合系黏著劑組成物) 有關第二實施形態之黏著劑組成物,含有:含有反應 性官能基之丙烯酸系共聚物(A)、與丙烯酸系共聚物(A) 相異之含有反應性官能基之丙烯酸系共聚物(C)、特定量 之異氰酸酯化合物(B )。亦即,有關第二實施形態之黏著 劑組成物’除了進而含有丙烯酸系共聚物(C)之外,和有 關第一實施形態之黏著劑組成物具備約略相同的組成。因 此’除了相異點之外,省略詳細的說明。另外,有關第二 實施形態之黏著劑組成物中,丙烯酸系共聚物(A )及丙烯 酸系共聚物(C)的反應性官能基舆異氰酸酯化合物(B) 進行交聯反應,且異氰酸酯化合物(B)中未進行交聯反應 24 201011081 之異氰酸酯化合物(B)的異氰酸酯基與環境中的水進行反 應而形成有多聚體,來作為所生成的反應物,藉此而被認 為具有良好的黏著特性。 在第二實施形態中,作為共聚物成分的具有各種官能 基之單體中,特佳為含羧基單體係作為共聚物成分而含於 丙烯酸系共聚物(A)。 又,在第二實施形態中,丙烯酸系共聚物(C)是在共 聚物中作為共聚物成分而以(甲基)丙烯酸酯單體作為主 ❹ 成分,而使(曱基)丙烯酸酯、及具有反應性官能基之單 體共聚合而成之共聚物,其與丙烯酸系共聚物(A)相異。 有關第二實施形態之黏著劑組成物,作為樹脂成分而使用 丙烯酸系共聚物(A)和丙烯酸系共聚物(C)的混合物, 藉此可良好地調整凝集力和應力缓和性之平衡。 作為有關第二實施形態之丙烯酸系共聚物(C)的共聚 物成分,可使用(甲基)丙烯酸酯、具有反應性官能基之 • 單體、以及作為其他單體而使用與在丙烯酸系共聚物(A) 中所例示之共聚物成分同樣的共聚物成分。 作為共聚物成分之具有各種反應性官能基的單體之 中’較佳為含羧基單體及含羥基單體作為共聚物成分而含 • 於丙烯酸系共聚物(C)中。若丙烯酸系共聚物(C)中含 有含羧基單體及含羥基單體,則可實現一種丙烯酸系共聚 物(C)’其在具有高凝集力的同時也易於調整樹脂成分之 凝集力和應力緩和性。 基於使黏著劑之凝集力增加、使黏著劑組成物之耐久 25 201011081 提升的目的,作為共聚物成分而含有含羧基單體之比 例:是相對於丙烯酸系共聚物(C)為0.1重量%以上,較 佳為0.3重量%以上,特佳為〇 5重量%以上。又基於抑 制黏著劑組成物之黏接力而不使其過高的目的,作為共聚 物成分而含有讀基單體之比例是相對於丙烯酸系共聚物 (C)為5重量%以下,較佳為3重量%以下特佳為2重 量%以下。 ❼ 基於抑制白缺陷的目的,作為共聚物成分而含有含經 基單髏之比例,是相對於丙烯酸系共聚物(c)為〇 〇1重 量/◦以上,較佳為〇 · 1重量%以上,更佳為〇 3重量。以上。 又,基於抑制在耐久性試驗中產生剝落的目的,作為共聚 物成分而含有含羥基單體之比例為5重量%以下,較佳為3 重量%以下,特佳為1重量%以下。 基於賦予黏著劑組成物充分之凝集力的目的,有關第 二實施形態之丙烯酸系共聚物(C)的重量平均分子量(Mw ) Φ 是100萬以上,較佳為12〇萬以上,特佳為140萬以上》 .. · 又,基於確保黏著劑組成物之塗刷作業性的目的,丙烯酸 系共聚物(C)的重量平均分子量(M W)是250萬以下。 有關第二實施形態之丙烯酸系共聚物(C)的玻璃轉移 溫度(Tg),較佳為與丙烯酸系共聚物(Α)之玻璃轉移溫 度相等,或是高於丙烯酸系共聚物(A)之玻璃轉移溫度。 丙烯酸系共聚物(A)之Tg與丙烯酸系共聚物(C)之Tg 若具有上述關係,則丙烯酸系共聚物(c )會具有丙烯酸系 聚物(A)以上的凝集力,且易於取得樹脂成分之凝集力和 26 201011081 應力緩和性之平衡。較具體而言,基於賦予黏著劑組成物 充分之凝集力、使其發揮充分之耐久性的目的,丙烯酸系 共聚物(c)的玻璃轉移溫度是_60°c以上,較佳為_5(rc以 上。又,基於使黏著劑組成物發揮對於支撐基板之充分的 密著性、不產生剝落等的耐久性的目的,丙烯酸系共聚物 (C)的玻璃轉移溫度是〇°c以下,較佳為_3〇°c以下。 又’用於第二實施形態之丙烯酸系共聚物(C)的聚合 方法並無特別限制’可以以與丙烯酸系共聚物(A )同樣的 方法來聚合。另外,在使用藉由聚合而得之共聚物的混合 物來製造有關第二實施形態之黏著劑組成物之際,因為其 處理步驟較簡單、且能以短時間進行,所以較佳為藉由溶 液聚合來聚合。另外,溶液聚合可採用與第一實施形態同 樣的方法。然後,關於有關第二實施形態之丙烯酸系共聚 物(C)的重量平均分子量,也可藉由調整反應溫度、時間、 溶劑量、觸媒之種類或量,而獲得所希望的分子量。 • 丙烯酸系共聚物(A)之溶解性參數(SPa )和丙烯酸 系共聚物(C)之溶解性參數(SPB)的差(△ SP= SPa_ SPb)較佳為- 0.5〜0.5’更佳為- 0.4〜0.4,特佳為_〇.2〜〇.2。 溶解性參數的差(ASP)若在上述範圍内,則因為丙烯酸 系共聚物(A)和丙烯酸系共聚物(C)之相溶性極優良, 所以較佳。 溶解性參數是以Fedor的方法來計算。ped〇r的方法例 如記載於「SP值基礎、應用及計算方法J(山本秀樹著, 由株式會社情報機構所發行,2005年在Fedor的方法 ^ 27 201011081 中,溶解性參數是由下述式2所算出。 式2 溶解性參數=[Σ Ecoh/ Σ V]A2 戈2中’ Ecoh是内聚能密度(cohesive energy density )’v是分子體積。基於各原子團固有的Ec〇h及v, 而求出在高分子之重複單位中的Ecoh及v之總和Σ Ecoh 及Σν’藉此可算出溶解性參數❹共聚物之溶解性參數是 如下述般算出:藉由上述式2,先算出構成此共聚物的各 參 結構單位各自的單獨共聚物的溶解性參數,再對這些SP值 各自乘以各結構單位的莫耳分率而得的數值加總。 基於抑制在耐久性試驗中產生剝落的目的,混合丙烯 酸系共聚物(Α)和丙烯酸系共聚物(c)的比例,是重量 比(丙烯酸系共聚物(Α)之重量/丙烯酸系共聚物(〇) 之重量)為50/50以上,較佳為70/30以上,特佳為80 / 20以上。又,基於抑制在耐久性試驗中產生發泡的目的, 混合丙烯酸系共聚物(A )和丙烯酸系共聚物(c )的比例, Φ 是重量比(丙烯酸系共聚物(A)之重量/丙烯酸系共聚物 (C)之重量)為99/1以下,較佳為95/5以下,特佳為 9〇/ 10以下。 然後,有關笫二實施形態之黏著劑組成物,相對於1 〇〇 重量份之丙烯酸系共聚物(A)和丙烯酸異共聚物(C)的 混合物,而含有5〜30重量份之異氰酸酯化合物(B)。異 氰酸酯化合物(B ),是使用與第一實施形態同樣的化合物。 在第二實施形態中,基於抑制白缺陷的目的,相對於 100重量份之丙烯酸系共聚物(A)和丙稀酸異共聚物(C) 28 201011081 之混合物,異氰酸酯化合物(B)用量是5重量份以上。又, 基於確保共聚物和異氰酸酯化合物⑻之相溶性使其產 生作為黏著劑之充分之膠黏感的目的,相對於ι〇〇重量份 之丙烯酸系共聚物(A)和丙烯酸異共聚物(c)之混合物, 異氰酸酯化合物(B)用量是30重量份以下較佳為2〇 重量份以下’特佳為15重量份以下。The colloidal component after the structure and the polymer is 95% by weight or less. It is particularly preferably 80% by weight or more. The purpose of exfoliation to form a crosslinked enamel component can be determined by the following method. (Measurement of Gummy Component of Adhesive Composition) φ is measured in accordance with the following (1) to (6). (1) Applying a solution of the adhesive composition to a release sheet surface-treated with a polyfluorene-based release agent, and drying the coating amount to 25 g, and then applying it in a hot air circulation dryer 1 〇〇 干燥 dry seconds to form a film-like pressure-sensitive adhesive layer. (2) The formed pressure-sensitive adhesive layer is formed at 23. 〇, humidity 65% rh, curing (O) (3) about 〇.25g (2) of the film-like adhesive layer, adhered to the fine mesh of the mesh of 250 mesh mesh (i 〇〇mmxi〇〇mm ) on top and wrap it so that the gel component does not leak out. After that, the weight was accurately measured with a precision balance to prepare a sample. (4) The above metal mesh was immersed in an ethyl acetate solution for 3 days. (5) After the impregnation, the metal mesh was taken out, washed with a small amount of ethyl acetate, and allowed to stand at 120. (: Dry for 24 hours. After that, the weight is accurately measured with a precision balance. (6) The gum component is calculated according to the following formula: Colloidal composition (% by weight) = (C-A) / (B-A) X100 21 201011081 where A It is the weight (g) of the metal mesh, B is the weight of the metal mesh to which the adhesive is applied (weight of the adhesive) (g), and C is the weight (weight of the colloidal resin) (g) of the dried metal mesh after the impregnation. The adhesive composition according to the first embodiment is produced at least by a step of mixing an acrylic copolymer (A) containing a reactive functional group and an isocyanate compound (B) which is crosslinked with a reactive functional group. Then, in this mixing step, the isocyanate compound (B) is mixed with the acrylic copolymer (A), wherein the isocyanate 9 acid ester equivalent of the isocyanate compound (B) is more than the acrylic copolymer (A) The amount of the reactive functional group equivalent is specifically synthesized by the following steps: preparing a reactive functional group-containing acrylic copolymer (A), preparing a crosslinking reaction with a reactive functional group. different a step of the acid ester compound (B), a step of mixing the prepared acrylic copolymer (A) and the prepared isocyanate compound (B), and a step of preparing the isocyanate compound (b) is prepared The isocyanate compound (B) in which the equivalent weight of the isocyanate group of the isocyanate compound (B) is more than the equivalent amount of the reactive functional group of the acrylic copolymer (a). Further, 'the optical film of the first embodiment' An optical film having an adhesive layer formed of the adhesive composition according to the first embodiment. The specific manufacturing method is by coating the adhesive composition of the first embodiment on the release sheet and applying the same. After drying, an adhesive layer is formed on the release sheet. Then, the adhesive layer formed on the release sheet can be transferred to the optical film and then cured. The release sheet can be made of a fluorine-based resin, a paraffin, or a poly Broken oxygen, etc. 22 201011081 Release agent is applied to a synthetic resin sheet such as polyester which is released from the mold. The thickness of the adhesive layer formed on the release sheet, for example, after drying The thickness is 丨~1 〇〇" m, preferably 5 to 50/zm, more preferably about 15 to 30/im. The adhesive composition applied to the release sheet can be 70 with a hot air dryer. ~12 (TC, drying under heating conditions of about 1 to 3 minutes. The adhesive composition of the first embodiment, the optical film having the adhesive layer formed of the adhesive composition, and the adhesive film for the adherend) The φ relay force can be adjusted to a desired adhesive strength by adjusting the type or amount of the reactive functional group of the acrylic copolymer (A), the isocyanate compound (B), etc. (Effect of the first embodiment) The adhesive composition of the embodiment and the optical film comprising the adhesive layer formed of the adhesive composition may have a reactive functional group and a crosslinking agent of the acrylic copolymer (A) because of the above structure. The chemical cross-linking due to the reaction and the isocyanate group in the isocyanate compound (B) which is not cross-linked by reacting with the moisture in the curing environment to form a polymer and restrict the molecular chain shift of the acrylic copolymer Physical cross-linking, and high cohesion, so the physical cross-linking part of the molecular chain movement may be excellent, and it may be excellent in stress relaxation, and it may have high level of durability. And white defect inhibition. That is, in the adhesive composition according to the first embodiment, the equivalent amount of the isocyanate group of the isocyanate compound (B) is more than the equivalent amount of the reactive functional group of the acrylic acid-based copolymer (A). The isocyanate compound (B), so that not only the reaction of the acrylic copolymer (A) is produced 23 201011081 The chemical crosslinking by the reaction of the functional group with the crosslinking agent, and the isocyanate added to the acrylic copolymer (A) In the compound (B), a polymer derived from an isocyanate compound (B) having an isocyanate group which is not reacted with the acrylic copolymer (A) is also produced. Thereby, the molecular chain winding structure formed by the chemical crosslinking of the adhesive composition of the first embodiment in the reaction of the reactive functional group of the acrylic acid copolymer (A) and the crosslinking agent is formed. Among them, a polymer of the isocyanate compound (B) is present. Therefore, in the adhesive composition according to the first embodiment, the polymer is unevenly dispersed in the molecular chain-wound structure formed by chemical crosslinking by the reaction of the reactive functional group and the crosslinking agent, for example, It is possible to ensure good transparency to visible light while achieving durability and white defect suppression at a high level. [Second Embodiment] (Mixed Adhesive Composition) The adhesive composition according to the second embodiment contains an acrylic copolymer (A) containing a reactive functional group and an acrylic copolymer (A). The acrylic copolymer (C) having a reactive functional group or a specific amount of the isocyanate compound (B) is different. In other words, the adhesive composition of the second embodiment has substantially the same composition as the adhesive composition according to the first embodiment except that the acrylic copolymer (C) is further contained. Therefore, the detailed description is omitted except for the difference. Further, in the adhesive composition of the second embodiment, the reactive functional group 舆 isocyanate compound (B) of the acrylic copolymer (A) and the acrylic copolymer (C) is subjected to a crosslinking reaction, and the isocyanate compound (B) The isocyanate group of the isocyanate compound (B) which is not subjected to the crosslinking reaction 24 201011081 reacts with water in the environment to form a polymer, and is considered as a reaction product, whereby it is considered to have good adhesion characteristics. . In the second embodiment, among the monomers having various functional groups as the copolymer component, a carboxyl group-containing single system is particularly preferably contained as a copolymer component in the acrylic copolymer (A). Further, in the second embodiment, the acrylic copolymer (C) is a (meth) acrylate monomer as a main quinone component as a copolymer component in the copolymer, and (mercapto) acrylate, and A copolymer obtained by copolymerizing a monomer having a reactive functional group, which is different from the acrylic copolymer (A). In the adhesive composition of the second embodiment, a mixture of the acrylic copolymer (A) and the acrylic copolymer (C) is used as the resin component, whereby the balance between the cohesive force and the stress relaxation property can be favorably adjusted. As the copolymer component of the acrylic copolymer (C) according to the second embodiment, a (meth) acrylate, a monomer having a reactive functional group, and a monomer which is used as a monomer and copolymerized with acrylic acid can be used. The copolymer component of the copolymer component exemplified in the object (A) is the same. Among the monomers having various reactive functional groups as the copolymer component, it is preferred that the carboxyl group-containing monomer and the hydroxyl group-containing monomer are contained as a copolymer component in the acrylic copolymer (C). If the acrylic copolymer (C) contains a carboxyl group-containing monomer and a hydroxyl group-containing monomer, an acrylic copolymer (C) can be realized which has a high cohesive force and is easy to adjust the cohesive force and stress of the resin component. Alleviation. The ratio of the carboxyl group-containing monomer as a copolymer component is 0.1% by weight or more based on the acrylic copolymer (C), for the purpose of increasing the adhesion of the adhesive to the durability of the adhesive composition 25 201011081. Preferably, it is 0.3% by weight or more, and particularly preferably 5% by weight or more. Further, for the purpose of suppressing the adhesive force of the adhesive composition without excessively high, the ratio of the monomer having a read group as a copolymer component is 5% by weight or less based on the acrylic copolymer (C), preferably 3% by weight or less is particularly preferably 2% by weight or less.比例 For the purpose of suppressing white defects, the ratio of the base group contained in the copolymer component is 〇〇1 by weight/◦ or more, preferably 〇·1% by weight or more based on the acrylic copolymer (c). More preferably 〇 3 weight. the above. In addition, the ratio of the hydroxyl group-containing monomer to the copolymer component is 5% by weight or less, preferably 3% by weight or less, and particularly preferably 1% by weight or less, for the purpose of suppressing the occurrence of flaking in the durability test. The weight average molecular weight (Mw) Φ of the acrylic copolymer (C) according to the second embodiment is 1,000,000 or more, preferably 120,000 or more, particularly preferably for the purpose of imparting sufficient cohesive force to the adhesive composition. Further, the weight average molecular weight (MW) of the acrylic copolymer (C) is 2.5 million or less for the purpose of ensuring the coating workability of the adhesive composition. The glass transition temperature (Tg) of the acrylic copolymer (C) according to the second embodiment is preferably equal to or higher than the glass transition temperature of the acrylic copolymer (A). Glass transfer temperature. When the Tg of the acrylic copolymer (A) and the Tg of the acrylic copolymer (C) have the above relationship, the acrylic copolymer (c) has a cohesive force of the acrylic polymer (A) or more, and the resin is easily obtained. The agglutination of the ingredients and the balance of 26 201011081 stress relaxation. More specifically, the glass transition temperature of the acrylic copolymer (c) is _60 ° C or more, preferably _5 (for the purpose of imparting sufficient cohesive force to the adhesive composition to exhibit sufficient durability. In addition, the glass transition temperature of the acrylic copolymer (C) is 〇°c or less, for the purpose of exhibiting sufficient adhesion to the support substrate and durability against peeling of the adhesive composition. Further, the polymerization method of the acrylic copolymer (C) used in the second embodiment is not particularly limited, and it can be polymerized in the same manner as the acrylic copolymer (A). When the adhesive composition of the second embodiment is produced by using a mixture of copolymers obtained by polymerization, since the treatment step is simple and can be carried out in a short time, it is preferably by solution polymerization. Further, the solution polymerization may be carried out in the same manner as in the first embodiment. Then, regarding the weight average molecular weight of the acrylic copolymer (C) according to the second embodiment, it may be adjusted by The desired molecular weight is obtained by temperature, time, amount of solvent, type or amount of catalyst. • Solubility parameter (SPa) of acrylic copolymer (A) and solubility parameter of acrylic copolymer (C) (SPB) The difference (Δ SP = SPa_ SPb) is preferably -0.5 to 0.5', more preferably - 0.4 to 0.4, and particularly preferably _〇.2 to 〇.2. The difference in solubility parameter (ASP) is in the above range. In addition, since the compatibility between the acrylic copolymer (A) and the acrylic copolymer (C) is extremely excellent, the solubility parameter is calculated by the method of Fedor. The method of ped〇r is described, for example, in "SP". Value basis, application, and calculation method J (Yamamoto Hideki, issued by the company's information agency, and in the method of Fedor 2005 27 201011081, the solubility parameter is calculated by the following formula 2. Equation 2 Solubility parameter = [Σ Ecoh/ Σ V] A2 Ge 2 ' Ecoh is the cohesive energy density 'v is the molecular volume. Based on the inherent Ec〇h and v of each atomic group, it is determined in the repeating unit of the polymer. The sum of Ecoh and v, Ecoh and Σν', can be used to calculate the solubility parameter❹ The solubility parameter of the polymer is calculated as follows: by the above formula 2, the solubility parameter of each individual copolymer constituting each of the reference structural units of the copolymer is first calculated, and each of the SP values is multiplied by each structural unit. The sum of the values obtained by the molar fraction is based on the purpose of suppressing the occurrence of peeling in the durability test, and the ratio of the mixed acrylic copolymer (Α) to the acrylic copolymer (c) is a weight ratio (acrylic copolymerization). The weight of the substance (Α) / the weight of the acrylic copolymer (〇) is 50/50 or more, preferably 70/30 or more, and particularly preferably 80 / 20 or more. Further, the ratio of the acrylic copolymer (A) to the acrylic copolymer (c) is mixed for the purpose of suppressing foaming in the durability test, and Φ is a weight ratio (weight of the acrylic copolymer (A) / acrylic acid The weight of the copolymer (C) is 99/1 or less, preferably 95/5 or less, and particularly preferably 9 Å / 10 or less. Then, the adhesive composition of the second embodiment contains 5 to 30 parts by weight of an isocyanate compound per 1 part by weight of the mixture of the acrylic copolymer (A) and the acryl-isomeric copolymer (C). B). The isocyanate compound (B) is the same as the compound of the first embodiment. In the second embodiment, the amount of the isocyanate compound (B) is 5 based on the mixture of 100 parts by weight of the acrylic copolymer (A) and the acrylic acid isopolymer (C) 28 201011081 for the purpose of suppressing white defects. More than the weight. Further, based on the purpose of ensuring the compatibility of the copolymer and the isocyanate compound (8) to give a sufficient adhesiveness as an adhesive, the acrylic copolymer (A) and the isomeric copolymer (c) are iv by weight. The mixture of the isocyanate compound (B) is used in an amount of 30 parts by weight or less, preferably 2 parts by weight or less, and particularly preferably 15 parts by weight or less.
又,在有關第二實施形態之黏著劑組成物中,也與有 關第一實施形態之黏著劑組成物同樣,異氰酸酯化合物(b ) 中未與共聚物形成交聯的異氰酸酯基,可能會與環境中的 水進行反應而形成多聚體。然後,在第二實施形態中,基 於使其形成較多之多聚體以提升白缺陷抑制性和耐久性的 目的’而相對於丙烯酸系共聚物(A)和丙烯酸系共聚物(c) 的合計1當量之反應性官能基,使用多於丨當量的異氰酸 酯基,較佳為1·01當量以上、特佳為12當量以上的異氰 酸酿基。 又,基於提升黏著劑組成物之耐久性的目的,相對於 100重量份之丙烯酸系共聚物(Α)和丙烯酸系共聚物(C) 之混合物的矽烷化合物之用量是101〜3重量份,較佳為 0.01〜2重量份,特佳為〇.〇2〜1重量份。進而,有關第二 實施形態之黏著劑組成物,除了上述丙烯酸系共聚物(A )、 丙烯酸系共聚物(C)、異氰酸酯化合物(B)、異氰酸酯化 合物以外之交聯劑、矽烷化合物以外,可以以不損及有關 第二實施形態之黏著劑組成物所發揮效果的範圍内之量, 來適當地調配各種添加劑等。 29 201011081 進而,在有關第二實施形態之黏著劑組成物中,丙烯 酸系共聚物(A)及丙烯酸系共聚物(C)之反應性官能基 和異氰酸酯化合物(C)會形成交聯構造’而未進行交聯反 應之異氰酸酯基則可能會跟環境中的水反應而形成多聚 體。基於抑制在耐久性評價中產生發泡的目的,形成交聯 構造及多聚體後的膠質成分是60重量%以上,較佳為7〇 重量%以上,特佳為80重量%以上。又,基於抑制在耐久 Φ 性評價中產生剝落的目的,形成交聯構造及多聚體後的膠 質成分是95重量%以下。 (實施例) , T入1 J 〜,· Λ卿I7.J久PCi权列' 所使用之試驗片的製作,以及各種試驗方法及評價方法 是如同以下所述。 (1)試驗用光學薄膜之製作 _ 作為光學薄膜之—例而使用偏光膜來製作具有黏著$ 層之偏光膜。將黏著劑組成物塗佈於經聚矽氧系脫模们 面?理的剝離膜上’使其乾燥後的塗刷量成為25g/ cm2 接著以熱風循環式乾燥機將其在i〇〇t乾燥秒形) 黏著劑層。接下來,將黏㈣層所在之面貼合於偏光基』 =〔將纖維素三乙酸醋(TAC)膜積層於以聚 光子的兩面而成之膜L〕的内面,: 輥(niproller)而壓接。壓接後在23。。、_ ·,、 0日,而得到具有黏著劑層的偏光膜。 30 201011081 (2 )黏接力之測定 將在「(1)試驗用光學薄臈之製作」中所製作的偏光 膜切成25mmx 15 0mm後,用桌上型積層機將此偏光膜片壓 接於厚度0.7mm之康寧公司製的無鹼玻璃板「# 1737」, 而作成試驗樣品。將此樣品予以熱壓處理(5〇<>c、5kg/ em、20分鐘)。接著將此樣品在23它、65%RH的條件下 放置24小時後,測定在180度剝離時的黏接力(剝離速度: 鲁 300mm/分鐘)。 (3 )财久性之評價 使用積層機將14〇mmX260mm (長邊)的試驗片黏貼於 之康寧公司製的無鹼玻璃板「# 1737」的單面,該 試驗片是將「( 1)試驗用光學薄膜之製作」中所製作之具 有黏著劑層的偏光膜’以相對於吸收軸使長邊呈之角 度來裁切者。接著’將此樣品施以熱壓處理(、5 kg /⑽^^^分鐘广並在^^:^以尺^的條件下放置以小 •時。之後’在後續的溫度及濕度條件下放置1〇〇〇小時,以 目視觀察發泡、剝落、浮起的狀態來進行評價。評價基準 是如同下述。 (耐久性評價基準) a )發泡 ◎:完全未發現發泡 〇:幾乎未發現發泡 X :顯著發現發泡 b)剝落 31 201011081 ◎:在四邊中,無剝落者 〇在四邊中,距外緣端部0.8mm以上的位置無剝落者 X .在四邊中任一邊,距外緣端部0.8mm以上的位置有剝 落者 (4)白缺陷現象之評價試驗 製作試驗樣品,該試驗樣品是將具有與「(3)耐久性 之評價」同樣尺寸之黏著劑層的偏光膜,黏貼於〇 7mm之 鲁康寧a司製的無驗玻璃板「#1737」的兩面,並使具有黏 著劑層之偏光膜與其偏光軸互相垂直相交。接著,將此樣 品施以熱壓處理(50。(:、5kg//cm2、2〇分鐘),並在23<>c、 65%RH的條件下放置24小時。之後,纟_、乾燥條件 下放置500小時。放置後,在23°C、65°/❶RH的條件下使用 均一光源,藉由目視來觀察白缺陷狀態。評價基準是如同 下述。 ◎:完全未察覺白缺陷。 鲁 〇:幾乎未察覺白缺陷。 X :白缺陷之面積大。 (丙烯酸系共聚物之製造) (製造例1 ) 在具備溫度計、攪拌機、氮導入管及回流冷卻管的反 應器内,置入97重量份之丙烯酸正丁酯(BA)、3重量份 之丙烯酸(AA)、1〇〇重量份之乙酸乙酯(EAc)、及〇.2 重量份之偶氮雙異丁腈(AIBN ),以氮氣取代反應容器之 空氣後’在氮氣環境中攪拌下,使該反應容器之内容物溫 32 201011081 度升溫至65°C並反應6小時’再進而使其升溫至70°C並反 應2小時。之後’於其中歷時1小時滴加將〇 4重量份之 AIBN溶解於20重量份之EAc而成的溶液,進一步反應2 小時。反應結束後’以甲苯稀釋反應混合物,而得到固形 分22.68重量%、黏度51400 mPa · s之丙烯酸系共聚物溶 液。丙烯酸系聚合物之重量平均分子量為172萬。 (製造例8 ) ^ 在與製造例1同樣的反應器内,置入98.975重量份之 丙烯酸正丁酯(BA)、0.025重量份之丙烯酸2-羥基乙酯 (2HEA)、100重量份之乙酸乙酯(EAc)、及0.2重量份 之偶氮雙異丁腈(AIBN ),以氮氣取代反應容器之空氣後, 在氮氣環境中擾拌下,使該反應容器之内容物溫度升溫至 65°C並反應6小時,再進而使其升溫至70°C並反應2小時。 之後’於其中歷時1小時滴加將〇·4重量份之AIBN溶解於 20重量份之EAc而成的溶液’進一步反應2小時。反應結 籲 束後以甲苯稀釋反應混合物,而得到固形分19.79重量 %、黏度12200 mPa · s之丙烯酸系共聚物溶液。丙烯酸系 聚合物之重量平均分子量為141萬。 (製造例2〜7及製造例9) 除了將共聚物組成設作表1之各製造例所示之單體組 成,來代替在製造例1所使用之共聚物組成以外,以與製 造例1同樣的方式進行聚合。在表1中顯示各製造例之共 聚物組成、固形分、玻璃轉移溫度(Tg )、溶解性參數(sp 值)、重量平均分子量(Mw)、黏度(mPa · s )。 33 201011081 L衣 項目 製造例 1 製造例 2 製造例 3 製造例 4 製造例 5 製造例 6 製造例 7 製造例 8 製造例 9 共 聚 合 組 成 BA(重量份) 97 99 95 83.5 83.5 83 100 98.975 98.95 t-BA(重量份) 0 0 0 0 15 15 0 0 0 MA(重量份) 0 0 0 15 0 0 0 0 0 AA(重量份) 3 1 5 1 1 1 0 1 1 2HEA(重量份) 0 0 0 0.5 0.5 1 0 0.025 0.05 特 性 值 固形分(重量%) 22.68 22.49 18.87 19.45 18.68 19.04 22.81 19.79 22.87 Tg(°C) -51 -55 -47 -44 -45 -45 57 -55 -55 SP值 (J1/2/cm3/2) 20.44 20.14 20.74 20.51 20.07 20.12 19.99 20.14 20.15 Mw (萬) 172 177 155 136 143 189 153 141 140 黏度(mPa · s)_ 51400 102000 11320 7400 11680 19800 30400 12200 18420 (光學薄膜用黏著劑組成物之製造) (實施例1 ) 以3 97重量份之製造例1所合成的丙烯酸系共聚物溶 液(丙烯酸系共聚物(A)是90重量份)作為丙烯酸系共 聚物(A)、以51重量份之製造例5所合成的丙烯酸系共聚 物溶液(丙烯酸系共聚物(C)是10重量份)作為丙烯酸 系共聚物(C)、以13.4重量份之Coronate L (曰本聚氨酯 工業股份有限公司製之聚異氰酸酯化合物,有效成分是1〇 重量份)作為異氰酸酯化合物(B)、以〇2重量份之異三 聚乳酸二(3 -三甲氧基梦基丙基)S旨(信越化學工業股份 有限公司製之矽烷化合物,商品名X-12-965,有效成分是 0.2重量份)和〇·〇5重量份之3-環氧丙氧基丙基三甲氧基 石夕烧(信越化學工業股份有限公司製之矽烷化合物,商品 名ΚΒΜ-403,有效成分是0.05重量份)作為矽烷化合物, 34 201011081 將上述成分充分地攪拌混合’而得到黏著劑組成物。相對 於丙稀酸系共聚物(A)和丙烯酸系共聚物(c)的合計1 當量之反應性官能基,異氰酸酯基之量(在表2-1、表2-2、 表2-3是記載為「NCO/樹脂官能基」)是κ6當量。 (實施例11 ) ❿ 又’以505重量份之製造例1所合成的丙烯酸系共聚 物溶液(丙烯酸系共聚物(A)是1〇〇重量份)作為丙烯酸 系共聚物(A)、以13.3重量份之Coronate L (曰本聚氨醋 工業股伤有限公司製之聚異鼠酸醋化合物,有效成分是 重量份)作為異氰酸酯化合物(B)、以〇2重量份之異三 聚氰酸二(3 -三甲氧基矽基丙基)酯(信越化學工業股份 有限公司製之矽烷化合物,商品名χ_12 965,有效成分是 〇.2重量份〇.〇5重量份之3·環氧丙氧基丙基三甲氧基 珍烧(信越化學工業股份有⑯公司製之石夕烧化合物,商品 名KBM-403,有效成分是〇.〇5重量份)作為㈣化合物, 將上述成分充分地挽拌混合,而得到黏著劑組成物。相對 於丙烯酸系共聚物(A)的合計!當量之反應性官能基,異 氛酸醋基之量(在表W、表2_2、表2_3是記載為「則 /樹脂官能基」)是2.96當量。 (實施例2〜10、實施例12〜17、比較例 除了採用表2-1及表29沉·-·»· λ & 衣2-2所不之各實施例、及表2-3 所示之比較例的調配组成’來代替在實施例ι中之調配組 成以外*以與實施例1、1 1 接^ 1同樣的方式製作黏著劑組成物Further, in the adhesive composition according to the second embodiment, similarly to the adhesive composition according to the first embodiment, the isocyanate group which is not crosslinked with the copolymer in the isocyanate compound (b) may be in contact with the environment. The water in the reaction reacts to form a polymer. Then, in the second embodiment, the acrylic copolymer (A) and the acrylic copolymer (c) are relative to each other based on the purpose of forming a large amount of the polymer to enhance the white defect suppressing property and durability. A total of one equivalent of the reactive functional group is used, and an isocyanate group having more than an equivalent of an isocyanate group is used, and preferably an amount of 1 to 01 equivalents or more, particularly preferably 12 equivalents or more. Further, for the purpose of improving the durability of the adhesive composition, the amount of the decane compound relative to 100 parts by weight of the mixture of the acrylic copolymer (Α) and the acrylic copolymer (C) is 101 to 3 parts by weight. Preferably, it is 0.01 to 2 parts by weight, and particularly preferably 〇.〇 2 to 1 part by weight. Further, the adhesive composition according to the second embodiment may be other than the acrylic copolymer (A), the acrylic copolymer (C), the isocyanate compound (B), the crosslinking agent other than the isocyanate compound, or the decane compound. Various additives and the like are appropriately blended in an amount within a range that does not impair the effects of the adhesive composition of the second embodiment. 29 201011081 Further, in the adhesive composition according to the second embodiment, the reactive functional group of the acrylic copolymer (A) and the acrylic copolymer (C) and the isocyanate compound (C) form a crosslinked structure. Isocyanate groups which are not subjected to a crosslinking reaction may react with water in the environment to form a polymer. For the purpose of suppressing the occurrence of foaming in the durability evaluation, the gel component after forming the crosslinked structure and the polymer is 60% by weight or more, preferably 7% by weight or more, and particularly preferably 80% by weight or more. Further, the gel component after forming the crosslinked structure and the polymer is 95% by weight or less for the purpose of suppressing the occurrence of peeling in the evaluation of the durability Φ. (Examples), the production of test pieces used in TJ1, ············································ (1) Production of optical film for test _ As an optical film, a polarizing film was used to produce a polarizing film having a layer of adhesion. Applying the adhesive composition to the polyfluorene-based mold release? On the release film, the amount of the coating after drying was 25 g/cm2, and then it was dried in a hot air circulation dryer to form a second layer of the adhesive layer. Next, the surface on which the adhesive layer is placed is bonded to the polarizing substrate. The inner surface of the film of the cellulose triacetate (TAC) laminated on both sides of the photon is formed by a roll (niproller). Crimp. After crimping at 23. . , _,,, 0, to obtain a polarizing film having an adhesive layer. 30 201011081 (2) Measurement of adhesive force After the polarizing film produced in "(1) Fabrication of optical enamel for testing" was cut into 25 mm x 150 mm, the polarizing film was crimped to the surface by a desktop laminator. An alkali-free glass plate "#1737" manufactured by Corning Co., Ltd. having a thickness of 0.7 mm was prepared as a test sample. This sample was subjected to hot pressing treatment (5 〇 <>c, 5 kg/em, 20 minutes). Then, the sample was allowed to stand under conditions of 23% and 65% RH for 24 hours, and the adhesion at 180 degree peeling (peeling speed: 300 mm/min) was measured. (3) Evaluation of financial durability The test piece of 14〇mmX260mm (long side) was adhered to one side of the alkali-free glass plate "#1737" manufactured by Corning Co., Ltd. using a laminator. The test piece is "(1) The polarizing film 'having an adhesive layer produced in the production of the optical film for testing' is cut at an angle with respect to the absorption axis at the long side. Then 'this sample is subjected to hot pressing treatment (5 kg / (10) ^ ^ ^ minutes wide and placed under ^^: ^ in the condition of a small ^ hour. After 'subject in the subsequent temperature and humidity conditions The evaluation was carried out by visual observation of the state of foaming, peeling, and floating. The evaluation criteria were as follows. (Standard of durability evaluation) a) Foaming ◎: No foaming enamel was found at all: almost no Found foaming X: Significantly found foaming b) Peeling off 31 201011081 ◎: In the four sides, no peeling squats in the four sides, no peeling off from the end of the outer edge of 0.8 mm or more. On either side of the four sides, the distance At the position of the outer edge of the outer edge of 0.8 mm or more, there is a peeling tester (4) for the evaluation of the white defect phenomenon. The test sample is a polarizing film having an adhesive layer having the same size as the "(3) durability evaluation". Adhesively adhered to both sides of the non-inspective glass plate "#1737" manufactured by Lukangning A, 7 mm, and the polarizing film having the adhesive layer and its polarization axis perpendicularly intersect each other. Next, this sample was subjected to hot pressing treatment (50: (:, 5 kg//cm 2 , 2 〇 minutes), and left under conditions of 23 <>, 65% RH for 24 hours. Thereafter, 纟_, dried After standing for 500 hours, after standing, a uniform light source was used under conditions of 23 ° C and 65 ° / RH, and the white defect state was observed by visual observation. The evaluation criteria were as follows. ◎: White defects were not observed at all. 〇: The white defect was hardly observed. X: The area of the white defect was large. (Production of acrylic copolymer) (Production Example 1) In a reactor equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a reflux cooling tube, 97 was placed. Parts by weight of n-butyl acrylate (BA), 3 parts by weight of acrylic acid (AA), 1 part by weight of ethyl acetate (EAc), and 2 parts by weight of azobisisobutyronitrile (AIBN), After replacing the air in the reaction vessel with nitrogen, the temperature of the reaction vessel was raised to 65 ° C and reacted for 6 hours under stirring in a nitrogen atmosphere, and then the temperature was raised to 70 ° C and reacted for 2 hours. After that, it was dissolved in 1 hour, and 4 parts by weight of AIBN was dissolved. A solution of 20 parts by weight of EAC was further reacted for 2 hours. After the completion of the reaction, the reaction mixture was diluted with toluene to obtain an acrylic copolymer solution having a solid content of 22.68% by weight and a viscosity of 51,400 mPa·s. The weight average molecular weight was 1.72 million. (Manufacturing Example 8) ^ In the same reactor as in Production Example 1, 98.975 parts by weight of n-butyl acrylate (BA) and 0.025 parts by weight of 2-hydroxyethyl acrylate (2HEA) were placed. 100 parts by weight of ethyl acetate (EAc), and 0.2 parts by weight of azobisisobutyronitrile (AIBN), after replacing the air of the reaction vessel with nitrogen, and then scrambled under a nitrogen atmosphere to make the reaction vessel The temperature of the contents was raised to 65 ° C and reacted for 6 hours, and then the temperature was further raised to 70 ° C and reacted for 2 hours. Then, 4 parts by weight of AIBN was dissolved in 20 parts by weight in 1 hour. The solution of EAc was further reacted for 2 hours. After the reaction was completed, the reaction mixture was diluted with toluene to obtain an acrylic copolymer solution having a solid content of 19.79% by weight and a viscosity of 12,200 mPa·s. The weight of the acrylic polymer. The average molecular weight was 1.41 million. (Production Examples 2 to 7 and Production Example 9) The copolymer composition was used as the monomer composition shown in each of the production examples of Table 1, instead of the copolymer composition used in Production Example 1. The polymerization was carried out in the same manner as in Production Example 1. Table 1 shows the copolymer composition, the solid content, the glass transition temperature (Tg), the solubility parameter (sp value), the weight average molecular weight (Mw), and the weight average molecular weight (Mw) of each of the production examples. Viscosity (mPa · s ) 33 201011081 L-cloth article manufacturing example 1 Manufacturing example 2 Manufacturing example 3 Manufacturing example 4 Manufacturing example 5 Manufacturing example 6 Manufacturing example 7 Manufacturing example 8 Production example 9 Copolymerization composition BA (parts by weight) 97 99 95 83.5 83.5 83 100 98.975 98.95 t-BA (parts by weight) 0 0 0 0 15 15 0 0 0 MA (parts by weight) 0 0 0 15 0 0 0 0 0 AA (parts by weight) 3 1 5 1 1 1 0 1 1 2HEA (parts by weight) 0 0 0 0.5 0.5 1 0 0.025 0.05 Characteristic value solid content (% by weight) 22.68 22.49 18.87 19.45 18.68 19.04 22.81 19.79 22.87 Tg(°C) -51 -55 -47 -44 -45 -45 57 - 55 -55 SP value (J1/2/cm3/2) 20.44 20.14 20.74 20.51 20.07 20.12 19.99 20.14 20.15 Mw (million) 172 1 77 155 136 143 189 153 141 140 Viscosity (mPa · s) _ 51400 102000 11320 7400 11680 19800 30400 12200 18420 (Manufacture of adhesive composition for optical film) (Example 1) Manufactured in Example 1 of 3 97 parts by weight Acrylic copolymer solution (acrylic copolymer (A): 90 parts by weight) as acrylic copolymer (A), 51 parts by weight of the acrylic copolymer solution (acrylic copolymer) synthesized in Production Example 5 (C) is 10 parts by weight of the acrylic copolymer (C), and 13.4 parts by weight of Coronate L (polyisocyanate compound manufactured by Hashimoto Polyurethane Co., Ltd., the active ingredient is 1 part by weight) as an isocyanate compound ( B), in an amount of 2 parts by weight of isomeric trisodium lactic acid bis(3-trimethoxymethylpropyl)S (a decane compound manufactured by Shin-Etsu Chemical Co., Ltd., trade name X-12-965, the active ingredient is 0.2 parts by weight) and 〇·〇 5 parts by weight of 3-glycidoxypropyltrimethoxy zebao (a decane compound manufactured by Shin-Etsu Chemical Co., Ltd., trade name ΚΒΜ-403, active ingredient is 0.05 Parts by weight as a decane compound, 34 201011081 The above components are thoroughly stirred and mixed to obtain an adhesive composition. The amount of the isocyanate group relative to the total of 1 equivalent of the reactive functional group of the acrylic copolymer (A) and the acrylic copolymer (c) (in Table 2-1, Table 2-2, Table 2-3 is The description "NCO/resin functional group" is κ6 equivalent. (Example 11) ❿ An acrylic copolymer solution (acrylic copolymer (A) is 1 part by weight) synthesized in 505 parts by weight of Production Example 1 as an acrylic copolymer (A), 13.3 Coonate L (polyisophthalic acid vinegar compound manufactured by Sakamoto Polyurethane Industrial Co., Ltd., active ingredient is part by weight) as an isocyanate compound (B), 2 parts by weight of isomeric cyanuric acid (3-trimethoxydecylpropyl) ester (a decane compound manufactured by Shin-Etsu Chemical Co., Ltd., trade name χ12 965, active ingredient is 〇.2 parts by weight 〇. 〇 5 parts by weight of 3·glycidoxy Propyl propyl trimethoxy sulphur (Shinjuku Chemical Industry Co., Ltd. has a 16-company Shihwa-baked compound, trade name KBM-403, the active ingredient is 重量. 〇 5 parts by weight) as (4) compound, the above ingredients are fully mixed The mixture was mixed to obtain an adhesive composition. The total amount of the reactive functional group and the alicyclic vine group based on the equivalent of the acrylic copolymer (A) (described in Table W, Table 2_2, and Table 2_3) / resin functional group") is 2.96 equivalents. Examples 2 to 10 and Examples 12 to 17 and Comparative Examples are the same as those in Tables 2-1 and 29, and the examples shown in Table 2-3 and Table 2-3. The compounding composition of the comparative example was used instead of the compounding composition in the example ι. * The adhesive composition was produced in the same manner as in the example 1, 1 1
(有關實施例2〜1 0、實施彻! o H X死例12〜17之黏著劑組成物、及 35 201011081 、你用所得之黏著劑組 有關比較例卜6之黏㈣組成物)° 來製作試驗用 成物’藉由上述試驗用光學薄膜之製“狀結果是表 光學薄膜,並實施上述各種測定。關於實》 表3_3。 日,丨其夹7P於承·(In relation to Examples 2 to 10, the implementation is complete! o HX deadly examples 12 to 17 of the adhesive composition, and 35 201011081, the adhesive group obtained by you, the comparative example of the adhesive (4) composition) The test article 'made by the optical film for the test described above is a surface optical film, and various measurements described above are carried out. About the actual table. Table 3_3. Japanese, 丨其夹7P于承·
[表 2-2][Table 2-2]
36 201011081 [表 2-3]36 201011081 [Table 2-3]
項目 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 丙烯酸系 共聚物(A) 種類 製造例1 製造例1 製造例1 製造例1 製造例7 製造例1 添加量 (重量份) 100 100 90 90 90 90 丙烯酸系 共聚物(B) 種類 — — 製造例4 製造例4 製造例5 製造例7 添加量 (重量份) — — 10 10 10 10 Coronate L 添加量 (重量份) 1 40 1 40 15 15 NCO/ 樹脂官能基 0.10 4.01 0.11 4.25 34.36 1.67 TETRAD-X — — — — — — TAZM — — 一 — — — TMSI 0.2 0.2 0.2 0.2 0.2 0.2 KBM-403 0.05 0.05 0.05 0.05 0.05 0.05 X-41-1805 — — — — — — 膠質成分(重量%) 32 91 76 90 60 76 NCO/ 樹脂官能基 2.96 1.50 2.01 4.52 2.92 4.44 4.44 TETRAD-X — — — — — 0.04 — TAZM — — — — — — 0.04 TMSI 0.2 0.2 0.2 0.2 0.2 — — KBM-403 0.05 0.05 0.05 0.05 0.05 — — X-41-1805 — — — — — 0.1 0.1 膝質成分(重量%) 85 91 93 83 86 88 92 另外,表2-1〜表2-3中各調配物之略稱如同下述,各 成分之添加量是有效成分的重量份。Item Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Acrylic copolymer (A) Type Production Example 1 Production Example 1 Production Example 1 Production Example 1 Production Example 7 Production Example 1 Adding amount (parts by weight) 100 100 90 90 90 90 Acrylic copolymer (B) Type - Production Example 4 Production Example 4 Production Example 5 Production Example 7 Adding amount (parts by weight) - 10 10 10 10 Coronate L Adding amount (parts by weight) 1 40 1 40 15 15 NCO/ Resin Functional Group 0.10 4.01 0.11 4.25 34.36 1.67 TETRAD-X — — — — — TAZM — — — — — TMSI 0.2 0.2 0.2 0.2 0.2 0.2 KBM-403 0.05 0.05 0.05 0.05 0.05 X- 41-1805 — — — — — — Gummy component (% by weight) 32 91 76 90 60 76 NCO/ Resin functional group 2.96 1.50 2.01 4.52 2.92 4.44 4.44 TETRAD-X — — — — — 0.04 — TAZM — — — — — — 0.04 TMSI 0.2 0.2 0.2 0.2 0.2 — — KBM-403 0.05 0.05 0.05 0.05 — — X-41-1805 — — — — — 0.1 0.1 Knee component (% by weight) 85 91 93 83 86 88 92 In addition, Table 2 1~ Table 2-3 in each formulation Abbreviated as follows, the added amount of each component is parts by weight of the active ingredient.
Coronate L:日本聚氨酯工業股份有限公司製之三羥曱 基丙烷的甲苯二異氰酸酯加成物,有效成分為75重量%, 異氰酸酯化合物(B ) TMSI :信越化學工業股份有限公司製之矽烷化合物, 37 201011081 商品名:X-12-965,化學名:異三聚氰酸三(3-三曱氧基 矽基丙基)酯,有效成分為100%,矽烷化合物 KBM —403 :信越化學工業股份有限公司製之石夕烧化合 物,商品名:KBM-403,化學名:3-環氧丙氧基丙基三曱 氧基矽烷,有效成分為1 00%,矽烷化合物 TETRAD-X : '三菱瓦斯化學股份有限公司製之環氧化 合物,商品名:TETRAD-X,化學名:N,N,N’,N’-四環氧丙 基-間苯二曱基二胺,有效成分為100重量%,環氧化合物 參 TAZM :日本相互藥工股份有限公司製之吖丙啶化合 物,商品名:TAZM,化學名:三羥甲基丙烷-三(召-吖丙 啶基丙酸酯),有效成分為100重量%,吖丙啶化合物 實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 實施例 6 實施例 7 實施例 8 實施例 9 實施例 10 23°C、24小時之 黏接力(N/25mm) 5 4 8 1 15 3 3 3 3 2 财久性 (80。。) 發泡 ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ 剝落 ◎ ◎ 〇 〇 〇 ◎ ◎ ◎ ◎ ◎ 耐久性 (60〇Cx90%RH) 發泡 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 剝落 ◎ ◎ ◎ 〇 ◎ 〇 ◎ ◎ ◎ ◎ 白缺陷 ◎ ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ X-41-1 805 :信越化學工業股份有限公司製之矽烷化合 物,商品名:X-41-1805,是含有疏基作為有機取代基、含 有曱氧基和乙氧基作為烷氧基之聚矽氧烷氧基募聚物,有 效成分為100重量%,矽烷化合物 參 [表3-1]_ 38 201011081 [表 3-2] 實施例11 實施例12 實施例13 實施例14 實施例15 實施例16 實施例17 23°C、24小時之 黏接力(N/25mm) 8 6 3 5 6 6 5 耐久性 發泡 ◎ ◎ ◎ 〇 ◎ ◎ ◎ (80°〇 剝落 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 耐久性 發泡 ◎ ◎ ◎ ◎ ◎ ◎ ◎ (60°Cx90%RH) 剝落 ◎ ◎ 〇 ◎ ◎ ◎ ◎ 白缺陷 ◎ ◎ ◎ 〇 ◎ ◎ ◎ [表 3-3]Coronate L: Toluene diisocyanate adduct of trihydroxy decylpropane manufactured by Nippon Polyurethane Industry Co., Ltd., having an active ingredient of 75% by weight, isocyanate compound (B) TMSI: decane compound manufactured by Shin-Etsu Chemical Co., Ltd., 37 201011081 Product Name: X-12-965, Chemical Name: Tris(3-trisethoxydecylpropyl) isocyanurate, 100% active ingredient, decane compound KBM-403: Shin-Etsu Chemical Co., Ltd. The company's Shixi burning compound, trade name: KBM-403, chemical name: 3-glycidoxypropyl tridecyloxydecane, active ingredient is 100%, decane compound TETRAD-X: 'Mitsubishi gas chemistry Epoxy compound manufactured by Co., Ltd., trade name: TETRAD-X, chemical name: N, N, N', N'-tetraepoxypropyl-m-phenylenediamine diamine, the active ingredient is 100% by weight, Epoxy compound ginseng TAZM: Aziridine compound manufactured by Japan Mutual Pharmaceutical Co., Ltd., trade name: TAZM, chemical name: trimethylolpropane-tris(callo-aziridinylpropionate), the active ingredient is 100% by weight, aziridine compound Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Adhesion at 23 ° C, 24 hours (N/25 mm) 5 4 8 1 15 3 3 3 3 2 Long-lasting (80.) Foaming ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ 脱 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Durability (60〇Cx90%RH) Foaming ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ X-41-1 805: 矽 化学 化学 化学 化合物 化合物 化合物 , , X-41-1805 is a polyoxyalkyloxy alkoxy polymer containing a sulfhydryl group as an organic substituent and a decyloxy group and an ethoxy group as an alkoxy group, the active ingredient is 100% by weight, and the decane compound is ginseng [Table 3-1]_38 201011081 [Table 3-2] Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Adhesion at 23 ° C for 24 hours (N/25 mm) 8 6 3 5 6 6 5 Durable foaming ◎ ◎ ◎ 〇 ◎ ◎ ◎ (80° 〇 peeling ◎ ◎ 〇 ◎ ◎ ◎ ◎ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎
項目 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 23°C ' 24小時之 黏接力(N/25mm) 18 0.3 25 0.5 20 9 财久性 (80°〇 發泡 X ◎ X ◎ X X 剝落 〇 X 〇 X 〇 〇 对久性 (60〇Cx90%RH) 發泡 ◎ ◎ ◎ ◎ ◎ ◎ 剝落 X X 〇 〇 X X 白缺陷 X 〇 〇 〇 〇 〇 另外,第一及第二實施形態、以及具有有關實施例之 光學薄膜用黏著劑的光學薄膜,因為耐久性良好、能抑制 _ 白缺陷,所以可適用於個人電腦、電視、衛星導航系統等 顯示裝置所用的光學薄膜。 以上說明本發明之實施形態及實施例,但申請專利範 圍中之發明並不受記載於上述之實施形態及實施例所限 定。又,應注意的是,實施形態及實施例中所說明之特徵 組合,並非全部都是解決發明之課題的手段所必須。 39Item Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 23 ° C '24-hour adhesion (N/25 mm) 18 0.3 25 0.5 20 9 Long-lasting (80°〇foaming X ◎ X ◎ XX 脱 〇 X 〇 X 〇〇 〇〇 ( (60〇Cx90%RH) ◎ ◎ ◎ ◎ ◎ ◎ ◎ 脱 XX XX XX White defect X 〇〇〇〇〇 In addition, the first and second embodiments The optical film having the adhesive for an optical film according to the embodiment is excellent in durability and can suppress white defects, and is therefore applicable to an optical film used in a display device such as a personal computer, a television, or a satellite navigation system. The embodiments and examples of the invention are not limited to the above-described embodiments and examples, and it should be noted that the combinations of features described in the embodiments and examples are not All are necessary to solve the problem of invention. 39
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JP5562173B2 (en) * | 2010-08-19 | 2014-07-30 | リンテック株式会社 | Adhesive composition, adhesive and adhesive sheet |
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JP2008069202A (en) * | 2006-09-12 | 2008-03-27 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive composition for optical member surface protective film and optical member surface protective film |
JP2008144126A (en) * | 2006-11-17 | 2008-06-26 | Fujifilm Corp | Acrylate-based pressure-sensitive adhesive, and polarizing plate and liquid crystal display device obtained using the same |
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JP2009221324A (en) * | 2008-03-14 | 2009-10-01 | Soken Chem & Eng Co Ltd | Pressure-sensitive adhesive for optical member and protection film for optical member using the same |
-
2008
- 2008-12-25 JP JP2008330230A patent/JP5923231B2/en active Active
-
2009
- 2009-01-12 TW TW098100963A patent/TWI487763B/en active
- 2009-02-13 KR KR1020090011824A patent/KR101748873B1/en active IP Right Grant
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2014
- 2014-09-03 JP JP2014179489A patent/JP5972326B2/en active Active
Also Published As
Publication number | Publication date |
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JP5923231B2 (en) | 2016-05-24 |
KR20100026951A (en) | 2010-03-10 |
JP5972326B2 (en) | 2016-08-17 |
JP2015025132A (en) | 2015-02-05 |
TWI487763B (en) | 2015-06-11 |
JP2010090354A (en) | 2010-04-22 |
KR101748873B1 (en) | 2017-06-19 |
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