200536914 九、發明說明： 【發明所屬之技術領域】 用彼之黏合片與霉占 本叙明係關於麼感黏合劑組合物及使 合光學元件。 【先前技術】200536914 IX. Description of the invention: [Technical field to which the invention belongs] The adhesive sheet and mold are used in this description This description is about the sensation adhesive composition and the optical element. [Prior art]
當設計光學官能膜用之壓感黏合劑組合物時，所用交聯 劑之量會增加俾可防止缺點如在耐熱性、耐溼熱性等之耐 久性試驗時發生勉起或剝離現象。然而，問題是當交聯劑 之量增加時，防止漏光（白點）之能力會降低。反之，當交聯 背J之1減 >、時，防止漏光之能力會增加，但耐久性卻會劣 化。因此，成功平衡耐久性與漏光之能力很困難。 為了解決該等問題，已知使用多官能異氰酸酯化合物作 為交聯劑（日本專利公告案（公開）2002-262103A)。然而，此 等化合物具有—種結構’其中具有複數異氰㈣基於一分 子内’如六亞甲二異氰酸酯或二苯乙烯_2,4_二異氰酸酯之 匕&物加入夕元醇主鏈或聚酯主鏈之終端内。當此等化合 物加入（甲基）丙烯酸酿共聚物時’其為壓感黏合劑之主成 刀，蓉Μ甲基）丙稀酸酉旨共聚物之主鏈與交聯劑之主鏈的相 容性，此等問題會視加入之量引起，如相容性之惡化、塗 佈溶液之渾濁或交聯劑之滲出。 【發明内容】 本發明之目的為提供-種具有耐久性及防止漏光能力之 壓感黏合劑組合物並提供使用彼之黏合片與黏合光學元 件0 99064.doc 200536914 本發明包含以下發明： (1) 壓感黏合劑組合物，其包含⑴由（甲基）丙烯酸酯與含 官能基單體之共聚合所得之共聚物（A)以及（ii)由（甲基） 丙烯酸酯與具有至少一個異氰酸酯基在其分子内之游 離基可聚合單體之共聚合所得之共聚物（B)。 (2) 根據上述（1)之壓感黏合劑組合物，其中共聚物（A)具有 重量平均分子量為500,000與2,0〇〇,〇〇〇之間（根據聚苯 乙烯並由GPC測定）。 ® (3)根據上述（1)或（2)之壓感黏合劑組合物，其中共聚物（B) 具有重量平均分子量為50,000與1，200,000之間（根據 聚苯乙烯並由GPC測定）。 (4) 根據上述（1)至（3)任一項之壓感黏合劑組合物，每丨〇〇 重量份共聚物（A)其包含〇·1至30重量份共聚物（B)。 (5) 根據上述（1)至（4)任一項之壓感黏合劑組合物，其用於 光學元件。 φ (6)黏合劑片，其中包含根據上述（1)至（5)任一項之壓感黏 合劑組合物之層設置在基材片之至少一面上。 (7) 黏合光學元件，其中包含根據上述（〗）至（5)任一項之壓 感黏合劑組合物之層設置在片狀光學元件之至少一面 上。 (8) 上述（7)之黏合光學元件，其中片狀光學元件為偏光板 或相差示板。 本發明之壓感黏合劑組合物之特徵為共聚物（B)用作交 ^ ^共聚物（B)為一種具有類似於由欲用作壓感黏合劑之 99064.doc 200536914 主元件之（甲基）丙烯酸酯與含官能基單體之共聚合所得之 共聚物（A)之主鏈的聚合物，並由（甲基）丙烯酸酯與具有至 少一個異氰酸酯基在其分子内之游離基可聚合單體之共聚 合所得。因此，可避免如交聯劑之滲出的缺點並可成功地 平衡耐久性舆防止漏光之能力。 上述聚合物（A)與上述聚合物（B)所用之（曱基）丙烯酸酯 不义特殊限制’並為（曱基）丙卸酸g旨’其中形成g旨部分之取 代基（如彡元基、方纟元基、方基或烧氧烧基）為c1-2G，較佳為 籲 Cl_18取代基。該（甲基）丙烯酸酯之例包括（甲基）丙烯酸甲 醋、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯酸 丁酉曰、（甲基）丙烯酸戊酯、（甲基）丙烯酸己酯、（甲基）丙烯 酸環己酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸辛酯、 (甲基）丙烯酸異辛酯、（甲基）丙烯酸癸酯、（甲基）丙烯酸十 二烷酯、（甲基）丙烯酸十四烷酯、（甲基）丙烯酸棕櫚酯、（甲 基）丙烯酸硬脂醯酯、（甲基）丙烯酸苄酯、（甲基）丙稀酸苯 φ 酯及（甲基）丙烯酸甲氧乙酯。此等（甲基）丙烯酸酯可單獨使 用或其二種以上型式可組合使用。 用於上述共聚物（A)之含官能基單體不受特殊限制，只要 其提供可由欲用作交聯劑之共聚物（B)交聯之交聯劑’並為 例如具有官能基與活性氫之單體即可。該具有官能基與活 性氫之單體包括：含經基單體，例如，（甲基）丙稀酸2_經基 乙西旨、（甲基）丙烯酸2-經基丙醋、（甲基）丙烯酸3·經基丙g旨、 (甲基）丙烯酸2-經基丁酿、（甲基）丙烯酸3-經基丁醋、（甲基） 丙烯酸4_羥基丁酯及烯丙醇；丙烯醯胺類如丙烯醯胺、甲 99064.doc 200536914 基丙稀酸胺、N-甲其兩、膝於^ τ 土丙稀fe月女、Ν_甲基甲基丙稀醯胺、队 經甲基丙烯醯胺、及Ν-經曱基曱基丙烯醯胺；（曱基）丙稀 酸單烧基胺基㈣如（曱基）丙稀酸單甲基胺基乙醋、（甲基） 丙烯酸早乙基胺基乙醋、（甲基）丙烯酸單曱基胺基丙酿及 (甲基）丙稀酸單乙基胺基丙酿；及乙烯系不飽和缓酸如丙烯 酸、曱基丙烯酸、順丁烯二酸、依康酸及棒康酸。此等單 體可單獨使用或其二種以上型式可組合使用。 （甲基）丙烯酸酯對欲用於製造上述共聚物（Α)之含官能基 單體之重篁比率通常為99 9:0」與8〇:2〇之間，較佳為卯：ι 與90:10之間。 關於上述共聚物（Α)，除了（甲基）丙烯酸酯及含官能基單 體以外，必要時亦可使用其他單體。必要時可用之該，，其他，， 單版之例包括·乙稀酯類如乙酸乙烯酯及丙酸乙烯酯；烯 烴類如乙烯、丙烯、及異丁烯；_化烯烴類如乙烯氯、亞 乙烯氯；苯乙烯單體如苯乙烯及心甲基苯乙烯；二烯單體 士 丁一烯、異戊二烯及氯平；腈單體如乙腈及甲基乙腈； 及ν，ν-二烷基取代丙烯醯胺類如Ν，Ν•二甲基丙烯醯胺及 Ν，Ν-二甲基甲基丙烯醯胺。此等單體可單獨使用或其二種 乂上式可組合使用。必要時欲使用之此等，，其他”單體通 吊'之用里每1〇〇重量份所有包含上述共聚物（Α)之單體通常 為0至20重量份，較佳為0至10重量份。 在本發明之壓感黏合劑組合物中，上述共聚物（Α)之型態 不叉特殊限制，其可為任何無規共聚物、嵌段共聚物及接 枝共聚物之型態。此外，關於分子量，較佳為該等具有重 99064.doc 200536914 量平均分子量範圍為_，_與2，_,_間内者。當重量平 均分子，小於500，_時，黏合之封久性會不足。當重量平 均分子量小於2,〇〇〇 〇〇〇 B主 M ^ t ，U0時，以下基材之膨脹性及收縮性會 劣化。鑑於黏合性、點人 4 钻〇之耐久性及以下基材之膨脹性及 收縮性，較佳為該箄呈古壬0 θ Α寺具有重1平均分子量為8〇〇,〇〇〇與 U0M0G間| ’特佳為該等具有重量平均分子量為 1，200,000與1,7〇()，_間者。此外，上述重量平均分子量為When designing a pressure-sensitive adhesive composition for an optically functional film, the amount of the cross-linking agent to be used is increased, and defects such as embarrassment or peeling during a durability test such as heat resistance, heat and humidity resistance can be prevented. However, the problem is that as the amount of the crosslinking agent increases, the ability to prevent light leakage (white spots) decreases. Conversely, when the cross-linking back J-1 is decreased, the ability to prevent light leakage is increased, but the durability is deteriorated. Therefore, it is difficult to successfully balance the ability of durability and light leakage. In order to solve these problems, it is known to use a polyfunctional isocyanate compound as a cross-linking agent (Japanese Patent Publication (Kokai) 2002-262103A). However, these compounds have a structure 'in which there is a plurality of isocyanates based on one molecule' such as hexamethylene diisocyanate or stilbene 2,4_ diisocyanate. Inside the polyester main chain terminal. When these compounds are added to the (meth) acrylic copolymer, it is the main knife of the pressure-sensitive adhesive, and the phase of the main chain of the methyl (meth) acrylic acid copolymer and the main chain of the crosslinking agent. Capacitance, these problems will be caused by the amount added, such as deterioration of compatibility, turbidity of the coating solution or bleeding of the crosslinking agent. [Summary of the Invention] The object of the present invention is to provide a pressure-sensitive adhesive composition having durability and light leakage prevention capability, and to provide an adhesive sheet and an optical element using the same. 99 99.doc 200536914 The present invention includes the following inventions: (1 ) A pressure-sensitive adhesive composition comprising a copolymer (A) obtained by copolymerization of a (meth) acrylate and a functional group-containing monomer, and (ii) a copolymer of (meth) acrylate with at least one isocyanate Copolymer (B) obtained by copolymerization of a radical polymerizable monomer having a radical in its molecule. (2) The pressure-sensitive adhesive composition according to the above (1), wherein the copolymer (A) has a weight average molecular weight between 500,000 and 2,000,000 (based on polystyrene and measured by GPC) . ® (3) The pressure-sensitive adhesive composition according to (1) or (2) above, wherein the copolymer (B) has a weight average molecular weight between 50,000 and 1,200,000 (based on polystyrene and measured by GPC). (4) The pressure-sensitive adhesive composition according to any one of (1) to (3) above, which comprises from 0.1 to 30 parts by weight of the copolymer (B) per 1,000 parts by weight of the copolymer (A). (5) The pressure-sensitive adhesive composition according to any one of (1) to (4) above, which is used for an optical element. φ (6) An adhesive sheet in which a layer containing the pressure-sensitive adhesive composition according to any one of (1) to (5) above is provided on at least one side of a substrate sheet. (7) A bonded optical element, wherein the layer containing the pressure-sensitive adhesive composition according to any one of (1) to (5) above is provided on at least one side of a sheet-shaped optical element. (8) The bonded optical element of (7) above, wherein the sheet-shaped optical element is a polarizing plate or a phase difference display plate. The pressure-sensitive adhesive composition of the present invention is characterized in that the copolymer (B) is used as a cross-linking copolymer (B) is a kind of (A) having a main component similar to 99064.doc 200536914 intended to be used as a pressure-sensitive adhesive. A polymer of the main chain of the copolymer (A) obtained by copolymerization of an acrylic acid ester and a functional group-containing monomer, and is polymerizable by a (meth) acrylic acid ester and a free radical having at least one isocyanate group in its molecule. Copolymerization of monomers. Therefore, disadvantages such as bleeding out of the cross-linking agent can be avoided and the ability of the durability to prevent light leakage can be successfully balanced. The (amido) acrylic acid ester used in the aforementioned polymer (A) and the aforementioned polymer (B) is not particularly limited 'and is a (fluorenyl) propionic acid g', wherein a substituent (such as hydrazone) Group, stilbene group, square group or oxo group) is c1-2G, preferably a Cl-18 substituent. Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, (meth) Decyl acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, Benzene (meth) acrylate and methoxyethyl (meth) acrylate. These (meth) acrylates can be used alone or in combination of two or more types. The functional group-containing monomer used for the above-mentioned copolymer (A) is not particularly limited as long as it provides a cross-linking agent that can be cross-linked by the copolymer (B) to be used as a cross-linking agent and has, for example, a functional group and an activity A monomer of hydrogen is sufficient. The monomer having a functional group and active hydrogen includes: a monomer containing a warp group, for example, (meth) acrylic acid 2-mercaptoethoxy, (meth) acrylic acid 2-mercaptopropionate, (methyl ) Acrylic acid 3 · propyl acrylate, 2- (meth) acrylic acid 2-butyl butyl, (meth) acrylic acid 3- butyl vinegar, (meth) acrylic acid 4-hydroxybutyl acrylate and allyl alcohol; propylene Amines such as acrylamide, methyl 99064.doc 200536914 methacrylic acid amine, N-methyl methacrylate, and acetone Allyl acrylamide, and N-methyl amidyl acrylamide; (fluorenyl) acrylic acid monoalkylamino, such as (fluorenyl) acrylic acid monomethylamino ethyl acetate, (methyl) Early ethylamine ethyl acrylate, monomethylamino acrylate (meth) acrylate and monoethylamine acrylate (meth) acrylic acid; and ethylenic unsaturated slow acids such as acrylic acid and methacrylic acid , Maleic acid, itaconic acid and clavonic acid. These monomers can be used alone or in combination of two or more types. The weight ratio of the (meth) acrylate to the functional group-containing monomer to be used in the production of the above-mentioned copolymer (A) is usually between 99 9: 0 "and 80:20, preferably 卯: ι and 90:10. Regarding the copolymer (A), in addition to the (meth) acrylate and the functional group-containing monomer, other monomers may be used as necessary. Examples of this, other, and single editions that can be used include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene, and isobutylene; olefins such as ethylene chloride, vinylene Chlorine; styrene monomers such as styrene and methylolstyrene; diene monomers butadiene, isoprene, and chloropine; nitrile monomers such as acetonitrile and methylacetonitrile; and ν, ν-dioxane Acrylamines such as N, N-dimethylacrylamide and N, N-dimethylmethacrylamine. These monomers may be used singly or two of the above formulas may be used in combination. These are to be used when necessary. For other "monomer suspension" applications, the content of each of the monomers containing the above copolymer (A) is usually 0 to 20 parts by weight, preferably 0 to 10 parts by weight. In the pressure-sensitive adhesive composition of the present invention, the type of the copolymer (A) described above is not particularly limited, and it can be any type of random copolymer, block copolymer, and graft copolymer. In addition, as for the molecular weight, it is preferable that the weight average molecular weight ranges between 99,64.doc 200536914 and _, _ and 2, _, _. When the weight average molecular weight is less than 500, _, the adhesion is sealed for a long time. When the weight-average molecular weight is less than 2,000,000 B, the main M ^ t, U0, the swelling properties and shrinkage properties of the following substrates are deteriorated. In view of adhesion, the durability of the point 4 diamond is 0. The swelling and shrinkage properties of the following substrates are preferred. The shogunate is ancient. 0 θ A temple has a weight of 1 and an average molecular weight of 80,00,00 and U0M0G. It is between 1,200,000 and 1,70 (), and the weight average molecular weight is
根據聚苯乙烯藉由凝膠渗透色層分離法（GPC)_者。在本 發明中’可使用一種型式之共聚物㈧，或其二種以上型式 可組合使用。 用於上述共聚物（B)之具有至少一個異氰酸酯基在其分 子内之游離基可聚合單體不受特殊限制，只要其賦予交聯 劑之功能在共聚物（B)上即可。該游離基可聚合單體之例包 括具有至乂個氰酸酯基之（甲基）丙稀酸酯衍生物（例如， (甲基）丙烯酸2-異氰酸基乙醋，或使用具有羧基或羥基如 (甲基）丙烯酸、（甲基）丙烯酸2_羥基乙酯或（甲基）丙烯酸扣 搜基丁酯及多官能異氰酸酯化合物如二異氰酸甲苯酯或二 異氰酸二甲苯酯之游離基可聚合單體獲得之游離基可聚合 單體）。此等單體可單獨使用或其二種以上型式可組合使 用。 (甲基）丙烯酸酯對欲用於製造上述共聚物（B)之具有至少 一個異氰酸酯基在其分子内之游離基可聚合單體之重量比 率通常為99·9··0·1與80:20之間，較佳為99:1與90:10之間。 關於上述共聚物（Β)’除了（甲基）丙烯酸酯及具有至少一 99064.doc 10 200536914 個異氰酸酯基在其分子内之游離基可聚合單體以外，必要 時亦可使用其他單體。必要時可用之該”其他"單體之例包 括：乙烯酯類如乙酸乙烯酯及丙酸乙烯酯；烯烴類如乙烯、 丙烯、及異丁烯；函化烯烴類如乙烯氣、亞乙稀氯；苯乙 烯單體如苯乙烯及α_甲基苯乙烯；二烯單體如丁二烯、異 戊二烯及氣平；腈單體如乙腈及甲基乙腈；及Ν，Ν·二烷基 取代丙烯醯胺類如Ν，Ν_二甲基丙烯醯胺及Ν，Ν•二甲基$基 _ 丙烯醯胺。此等單體可單獨使用或其二種以上型式可組合 使用。必要時欲使用之此等”其他”單體通常之用量每丨⑼重 量份所有包含上述共聚物（Β)之單體通常為〇至1〇重量份， 較佳為0至5重量份。 在本發明之壓感黏合劑組合物中，上述共聚物⑺）之型態 不叉特殊限制，其可為任何無規共聚物、嵌段共聚物及接 枝共聚物之型態。此外，關於分子量，較佳為該等具有重 量平均分子量範圍為50,〇〇〇與！，200,000間内者（根據聚苯 • 乙烯並藉由GpC測定）。當重量平均分子量小於5〇,〇〇〇時， 壓感黏合劑之凝結力無法獲得及耐久性劣化。當重量平均 刀子里超過於2,000,000時，塗佈溶液之黏度會顯著增加而 塗佈能力會劣化。鑑於此等因素，較佳為重量平均分子量 為100,000與1，000,000之間，特佳為重量平均分子量2 15 0,000與9500,000之間。在本發明中，可使用一種型式2 共聚物（B)，或其二種以上型式可組合使用。共聚物⑺）對共 聚物（A)之化合比率每〗00重量份共聚物（A)通常為〇· 1至儿 重量份，較佳為〇·5至15重量份共聚物（B)。 99064.doc 200536914 產生上述共聚物（A)及（以之γ人 取入々所曰 之來合係糟傳統聚合法如溶液 1較佳為坑至帆。反應，度通常為贼至85 :實施溶液聚合時，單體係在通常為〇.5與6〇重量％，較 ^與5°重量%濃度(固體含量)，使用聚合引發劑如偶氮 又異丁腈或過氧化节醯於溶劑如丙酮、苯、甲[乙酸乙 醋、己烧、庚烧或異丙醇内聚合。化合之聚合引發劑之量 母100重量份全部單體量通常為〇 〇5至〗重量份。 本發明之麼感黏合劑組合物，必要時，V進一步補充有 各種已知傳統上用於壓感黏合劑組合物的添加劑，例如， 塑化劑、石夕烧偶合劑、紫外線吸收劑及抗氧化劑，只要添 加劑不會不利地影響本發明之對象即可。 本發明之壓感黏合劑組合物適用於光學元件。 當本發明之壓感黏合劑組合物用於光學元件時，該组人 物最好是光學上透明。 " 本發明之黏合劑片材包含—層（以下縮寫為"黏合層”），盆 =含上述壓感黏合劑組合物，其中—層設置在基材片之I 少-面上。基材片之例包括：紙張基材如玻璃紙、塗佈紙 及鑄塗紙；包含熱塑性樹脂如聚乙烯之層壓紙層壓在紙基 材上；聚酷膜如聚對醜酸乙二醋、聚對敗酸丁二醋及蔡酸 乙二醋之膜；聚稀烴膜如聚丙烯與聚甲基戍稀之膜塑膠 膜如聚擁旨與乙酸纖維素之膜；及包含此等膜之層壓 片。基材片適合根據黏合片之應用選擇。本發明之黏合片 可用作元件供轉移黏合層至被黏物或作為元件以固定黏合 "064.doc -12- 200536914 層至所欲被黏物。當黏合層用於前者應用時，通常，基材 片塗佈有脫模劑如矽酮樹脂。在此情況下，基材片之厚度 不受特殊限制，通常為約20微米與15〇微米之間。當黏合層 用於後者應用時，基材片之類型與厚度端視其應用而適當 述擇。在此情況下，必要時，一般脫模劑可設置在黏合層 上。在本發明之黏合片之情況下，黏合層之厚度通常為約$ 微米與150微米之間，較佳為約1〇微米與9〇微米之間。 其次，本發明之黏合光學元件設有一包含上述壓感黏合 劑組合物在片狀光學元件之至少一面上之層。上述片狀光 學元件之例不受特殊限制並包括偏光板、相差示板、抗反 射板及放大視角之膜。其中’最佳為偏光板。偏光板之例 包括液晶顯示器用之偏光板、調整光量用之偏光板、使用 偏光干擾之裝置用之偏光板及光學缺陷之檢測器用之偏光 板。其中，特別有利為黏合層設置在液晶顯示器之液晶電 池用之偏光板。 【實施方式】 實例 以下參照不希望限制本發明範圍之實例與比較例詳述本 發明。 此外’聚合物之重量平均分子量測定如下。 (測定重量平均分子量之方法） 使用1重量％聚合物於四氫吱喃（THF)溶液内作為樣品， 在4CTC及丨毫升THF溶劑/分鐘之條件下使用HLc_8〇2〇(由 TOSOH CORPORATION製造；三重管才主由管柱微㈣ 99064.doc -13- 200536914 GMHXL . TSKgel GMHXL^TSKgel G2000HXLm # ^ )^J ^ 〇 [參考例1】 99重$份丙烯酸正丁酯、丨重量份丙烯酸4_羥基丁酯及〇·2 重里份偶氮雙異丁腈作為聚合引發劑加入2〇〇重量份乙酸 乙酯内。溶液在6(TC下攪拌17小時，可得具有重量平均分 子ΐ為1，600,000之丙烯酸酯共聚物之溶液。 [參考例2] 99重;f份丙稀酸正丁醋、工重量份甲基丙稀酸2·異氰酸基 乙S曰及〇·2重里份偶氮雙異丁腈作為聚合引發劑加入重 里伤乙酸乙酯内。溶液在6〇〇c下攪拌丨7小時，可得具有重 里平均分子量為850,〇〇〇之丙烯酸酯共聚物之溶液。 [參考例3] 95重量份丙烯酸正丁酯、5重量份曱基丙烯酸入異氰酸基 乙S曰及〇·2重ϊ份偶氮雙異丁腈作為聚合引發劑加入2〇〇重 量份乙酸乙酯内。溶液在6〇它下攪拌17小時，可得具有重 φ 里平均分子1為92〇,〇〇〇之丙烯酸酯共聚物之溶液。 [參考例4 ] 90重里伤丙烯酸正丁酯、10重量份甲基丙烯酸2_異氰酸 基乙酯及0.2重量份偶氮雙異丁腈作為聚合引發劑加入2〇〇 重量份乙酸乙醋内。溶液在6〇t下授掉17小時，可得具有 重量平均分子量為900,000之丙烯酸酯共聚物之溶液。 [參考例5】 9〇重量份丙烯酸正丁酯、1〇重量份曱基丙烯酸2_異氰酸 基乙酯及0.5重量份偶氮雙異丁腈作為聚合引發劑加入2〇〇 99064.doc -14- 200536914 重^分乙酸乙醋内。溶液在6〇t下授掉17小時，可得具有 重置平均分子量為41G，_之丙烯酸§旨共聚物之溶液。 [參考例6】 ㈣量份丙稀酸正丁 s旨、1G重量份甲基丙烯酸2•異氛酸 =知及0.2重量份偶氮雙異丁腈作為聚合引發劑加入_ 重置伤乙酸乙S旨及⑽重量份甲苯内。溶液在㈣下7 小犄’可得具有重量平均分子量為18〇，_之丙烯酸 物之溶液。 、知 [實例1】 ii.o重量份參考例2所得之共聚物加人⑽ 1所得之共聚物内。溶 β例 夜係用乙酸乙酯稀釋以製備具有濃声 為25%之溶液，藉此可得黏合劑Α。 又 [實例2】 2·〇2重量份參考例3所得之共聚物加入_ 1所得之共聚物内 里 考例 用乙酸乙酯稀釋以製備具有濃戶 為/°之溶液，藉此可得黏合劑Β。 又 [實例3】 L〇〇重量份參考例4所得之共聚物加幻 1所得之共聚物内。溶液传用7 t “考例 為挪之溶液，藉此可得黏合劑c。 m辰度According to polystyrene by gel permeation chromatography (GPC) method. In the present invention, one type of copolymer ㈧ may be used, or two or more types thereof may be used in combination. The polymerizable monomer having at least one isocyanate group in its molecule for use in the above-mentioned copolymer (B) is not particularly limited as long as it imparts the function of a crosslinking agent to the copolymer (B). Examples of the free-radically polymerizable monomer include a (meth) acrylic acid ester derivative (for example, (meth) acrylic acid 2-isocyanatoethyl acetate) having up to 20 cyanate groups, or use having a carboxyl group Or a hydroxyl group such as (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate or butyl butyl (meth) acrylate and a polyfunctional isocyanate compound such as toluene diisocyanate or dimethyl diisocyanate Free radical polymerizable monomer). These monomers may be used alone or in combination of two or more types. The weight ratio of the (meth) acrylic acid ester to the polymerizable monomer having at least one isocyanate group in the molecule to be used in the above-mentioned copolymer (B) is usually 99 · 9 ···· 1 and 80: Between 20, preferably between 99: 1 and 90:10. Regarding the above-mentioned copolymer (B) ', in addition to (meth) acrylate and a polymerizable monomer having at least one 99064.doc 10 200536914 free radical in its molecule, other monomers may be used as necessary. Examples of such "other" monomers that may be used when necessary include: vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene, and isobutylene; functional olefins such as ethylene gas, ethylene chloride ; Styrene monomers such as styrene and α-methylstyrene; diene monomers such as butadiene, isoprene, and gas balance; nitrile monomers such as acetonitrile and methylacetonitrile; and Ν, Ν · dioxane Group substituted acrylamides such as N, N_dimethylacrylamide and N, N • dimethyl $ yl_acrylamide. These monomers can be used alone or two or more types can be used in combination. Necessary These "other" monomers to be used are usually used in an amount of usually 0 to 10 parts by weight, preferably 0 to 5 parts by weight, per 1 part by weight of all the monomers containing the above copolymer (B). In the pressure-sensitive adhesive composition of the present invention, the type of the copolymer ii) is not particularly limited, and it can be any type of random copolymer, block copolymer, and graft copolymer. In addition, regarding the molecular weight, It is preferred that these have a weight average molecular weight in the range of 50,000 and 200,000. (Based on polystyrene • ethylene and measured by GpC). When the weight average molecular weight is less than 50,000, the cohesive force of the pressure-sensitive adhesive cannot be obtained and the durability is deteriorated. When the weight average knife exceeds 2,000,000, The viscosity of the coating solution will increase significantly and the coating ability will deteriorate. In view of these factors, it is preferred that the weight average molecular weight is between 100,000 and 1,000,000, and particularly preferred is between 2 15 0,000 and 9500,000. In the present invention, one type 2 copolymer (B) may be used, or two or more types thereof may be used in combination. The compounding ratio of the copolymer ii) to the copolymer (A) per 00 parts by weight of the copolymer (A) It is usually from 0.1 to 1 part by weight, preferably from 0.5 to 15 parts by weight of the copolymer (B). 99064.doc 200536914 produces the above-mentioned copolymer (A) and (where γ is taken by the person) The traditional polymerization method such as solution 1 is preferably from pit to sail. The degree of reaction is usually from thief to 85: When implementing solution polymerization, the single system is usually 0.5 and 60% by weight, which is more than ^ and 5 °. Concentration by weight (solid content), using a polymerization initiator such as azo Butyronitrile or peroxide is polymerized in a solvent such as acetone, benzene, methyl acetate, hexane, heptane, or isopropanol. The amount of the combined polymerization initiator is usually 100 parts by weight of the total monomer amount. 〇5 ～ parts by weight. The mesogenic adhesive composition of the present invention, when necessary, V is further supplemented with various additives conventionally known for pressure-sensitive adhesive compositions, such as plasticizers, stone sintered couples, etc. Mixtures, ultraviolet absorbers and antioxidants, as long as the additives do not adversely affect the objects of the present invention. The pressure-sensitive adhesive composition of the present invention is suitable for optical elements. When the pressure-sensitive adhesive composition of the present invention is used in optical When it comes to components, this group of people is preferably optically transparent. " The adhesive sheet of the present invention includes a layer (hereinafter abbreviated as " adhesive layer "), and the pot = contains the above pressure-sensitive adhesive composition, wherein the-layer is disposed on the I-side of the substrate sheet. Examples of sheet materials include: paper substrates such as cellophane, coated paper, and cast coated paper; laminated paper containing a thermoplastic resin such as polyethylene laminated on the paper substrate; poly film such as polyethylene terephthalate, Films of polybutylene diacetate and ethylene diacetate; polyhydrocarbon films such as polypropylene and polymethyl phthalate; plastic films such as polyethylene and cellulose acetate; and films containing these films Laminated sheet. The substrate sheet is suitable for selection according to the application of the adhesive sheet. The adhesive sheet of the present invention can be used as a component for transferring an adhesive layer to an adherend or as a component for fixed adhesion " 064.doc -12- 200536914 layer to all To be adhered. When the adhesive layer is used in the former application, the substrate sheet is usually coated with a release agent such as a silicone resin. In this case, the thickness of the substrate sheet is not particularly limited, and is usually about 20 microns Between 15 μm. When the adhesive layer is used in the latter application, the type and thickness of the substrate sheet are viewed from the end. Its application is appropriately selected. In this case, a general release agent can be provided on the adhesive layer when necessary. In the case of the adhesive sheet of the present invention, the thickness of the adhesive layer is usually between about $ micron and 150 microns. , Preferably between about 10 μm and 90 μm. Second, the bonded optical element of the present invention is provided with a layer containing the pressure-sensitive adhesive composition on at least one side of the sheet-shaped optical element. The sheet-shaped optical element Examples are not particularly limited and include polarizing plates, phase difference display plates, anti-reflection plates, and films with enlarged viewing angles. Among them, 'best is a polarizing plate. Examples of polarizing plates include polarizing plates for liquid crystal displays, polarizing plates for adjusting light amount, A polarizing plate for a device using polarized light interference and a polarizing plate for an optical defect detector. Among them, a polarizing plate for a liquid crystal cell with an adhesive layer provided on a liquid crystal display is particularly advantageous. [Embodiment] Examples The following reference is not intended to limit the present invention. Examples of ranges and comparative examples describe the present invention in detail. In addition, the weight average molecular weight of a polymer is determined as follows. (Method for measuring weight average molecular weight) A 1% by weight polymer was used as a sample in a tetrahydrofuran (THF) solution, and HLc_8020 (manufactured by TOSOH CORPORATION was used under the conditions of 4 CTC and 1 ml of THF solvent / minute; a triple tube was mainly composed of a column micro 064 99064.doc -13- 200536914 GMHXL. TSKgel GMHXL ^ TSKgel G2000HXLm # ^) ^ J ^ 〇 [Reference Example 1] 99 parts by weight of n-butyl acrylate, 丨 parts by weight of 4-hydroxybutyl acrylate and 0.2 weight Parts of azobisisobutyronitrile were added as polymerization initiators to 200 parts by weight of ethyl acetate. The solution was stirred at 6 ° C for 17 hours to obtain a solution of an acrylate copolymer having a weight average molecular weight of 1,600,000. . [Reference Example 2] 99 parts by weight; f parts of n-butyl acrylic acid, 2 parts by weight of methyl acrylic acid 2 isocyanatoethene, and 0.2 parts by weight of azobisisobutyronitrile as polymerization initiators Add ethyl acetate. The solution was stirred at 600 ° C for 7 hours to obtain a solution of an acrylate copolymer having a weight average molecular weight of 850,000. [Reference Example 3] 95 parts by weight of n-butyl acrylate, 5 parts by weight of methacrylic acid, isocyanatoethyl, and 0.2 parts by weight of azobisisobutyronitrile were added as polymerization initiators. In ethyl acetate. The solution was stirred at 60 ° C for 17 hours to obtain a solution having an acrylate copolymer having an average molecular weight of 920,000 in weight φ. [Reference Example 4] 90 parts of n-butyl acrylate, 10 parts by weight of 2-isocyanatoethyl methacrylate, and 0.2 parts by weight of azobisisobutyronitrile were added as polymerization initiators, and 200 parts by weight of ethyl acetate was added. Inside. The solution was allowed to stand for 17 hours at 60 t to obtain a solution of an acrylate copolymer having a weight average molecular weight of 900,000. [Reference Example 5] 90 parts by weight of n-butyl acrylate, 10 parts by weight of 2-isocyanatoethyl fluorenylacrylate, and 0.5 parts by weight of azobisisobutyronitrile were added as polymerization initiators. 20000964.doc -14- 200536914 heavy acetic acid in ethyl acetate. The solution was allowed to stand for 17 hours at 60 t to obtain a solution having an acrylic acid copolymer with a reset average molecular weight of 41G. [Reference Example 6] ㈣Amounts of n-butyl acrylic acid, 1G parts by weight of methacrylic acid 2 • isopropanoic acid = 0.2 parts by weight of azobisisobutyronitrile was added as a polymerization initiator. S purpose and ⑽ parts by weight of toluene. The solution was 7 hrs below 可 to obtain a solution of an acrylic compound having a weight average molecular weight of 18 °. [Example 1] ii.o The copolymer obtained in Reference Example 2 was added to the copolymer obtained in ⑽1 by weight. Example of dissolution β The system was diluted with ethyl acetate at night to prepare a solution having a strong sound of 25%, whereby the adhesive A was obtained. [Example 2] 2 · 02 parts by weight of the copolymer obtained in Reference Example 3 was added to the copolymer obtained in Example 1. The test case was diluted with ethyl acetate to prepare a solution with a concentration of / °, thereby obtaining an adhesive Β. [Example 3] L00 weight part of the copolymer obtained in Reference Example 4 plus the copolymer obtained in Example 1. The solution is transferred with 7 t.
[實例4J ^重此量份參考例5所得之共聚物加入⑽重量份參考例 A/于八聚物内。溶液係用乙酸乙酯稀釋以製備且有漠戶 為25%之溶液，藉此可得點合劑D。 有，辰度 99064.doc 200536914 [實例5] 1·00重量份參考例6所得之共聚物加入100重量份參考例 1所彳于之共聚物内。浴液係用乙酸乙酯稀釋以製備具有濃度 為2 5 %之溶液’精此可得黏合劑ε。 [比較例1] 2.50重i份以5甲苯二異氰酸醋為主之三官能加成物（由 Soken Chemical & Engineering Co.，Ltd 製造· TD 75)加入 100重罝份麥考例1所得之共聚物内。溶液係用乙酸乙酯稀 釋以製備具有濃度為25%之溶液，藉此可得黏合劑F。 [比較例2】 〇·50重量份以二甲苯二異氰酸酯為主之三官能加成物（由[Example 4J ^ This part by weight of the copolymer obtained in Reference Example 5 was added to ⑽ parts by weight of Reference Example A / in an octamer. The solution was prepared by diluting with ethyl acetate and a 25% solution was obtained, whereby Point D was obtained. Yes, Chen degree 99064.doc 200536914 [Example 5] 1. 00 parts by weight of the copolymer obtained in Reference Example 6 was added to 100 parts by weight of the copolymer prepared in Reference Example 1. The bath solution was diluted with ethyl acetate to prepare a solution having a concentration of 25%, and the adhesive ε was obtained. [Comparative Example 1] 2.50 parts by weight of 5 toluene diisocyanate-based trifunctional adducts (manufactured by Soken Chemical & Engineering Co., Ltd. · TD 75) were added to 100 parts by weight of wheat case 1 In the obtained copolymer. The solution was diluted with ethyl acetate to prepare a solution having a concentration of 25%, whereby the adhesive F was obtained. [Comparative Example 2] 0. 50 parts by weight of a trifunctional adduct containing xylene diisocyanate (from
Soken Chemical & Engineering Co.，Ltd.製造：td-75)加入 100重里伤參考例1所得之共聚物内。溶液係用乙酸乙酯稀 釋以製備具有濃度為25%之溶液，藉此可得黏合劑G。 [比較例3】 0.10重量份以二甲苯二異氰酸酯為主之三官能加成物（由Soken Chemical & Engineering Co., Ltd. (manufactured: td-75) was added to the copolymer obtained in Reference Example 1 with 100 heavy trauma. The solution was diluted with ethyl acetate to prepare a solution having a concentration of 25%, whereby the adhesive G was obtained. [Comparative Example 3] 0.10 parts by weight of a trifunctional adduct mainly composed of xylene diisocyanate (from
Soken Chemical & Engineering Co.，Ltd.製造：TD-75)加入 100重量份參考例丨所得之共聚物内。溶液係用乙酸乙酯稀 釋以製備具有濃度為25%之溶液，藉此可得黏合劑H。 [比較例4] 0.75重里份以異佛爾酮二異氰酸酯為主之二官能加成物 (由 MITSUBISHI CHEMICAL CORP〇rATION 製造： NY-T-35C)加入loo重量份參考例}所得之共聚物内。溶液係 用乙酸乙酯稀釋以製備具有濃度為25%之溶液，藉此可得 99064.doc 16 200536914 黏合劑I。Soken Chemical & Engineering Co., Ltd. (TD-75) was added to 100 parts by weight of the copolymer obtained in Reference Example 丨. The solution was diluted with ethyl acetate to prepare a solution having a concentration of 25%, whereby a binder H was obtained. [Comparative Example 4] 0.75 parts by weight of a bifunctional adduct containing isophorone diisocyanate (manufactured by MITSUBISHI CHEMICAL CORPOration: NY-T-35C) was added to the copolymer obtained by loo parts by weight of reference example} . The solution was diluted with ethyl acetate to prepare a solution having a concentration of 25%, whereby 99064.doc 16 200536914 Binder I was obtained.
聚對酞酸乙二酯膜之矽酮_樹脂_釋放-處理面（由LINTEC c〇rporat議製造：SP_PET3811)，具有厚度為38微米並設置 有石夕酮樹脂之釋放層在一面上之轉移元件係使用到刀塗佈 機塗佈上述實例及比較例製備之各黏合劑。用黏合劑塗佈 之面係在90°C下乾燥！分鐘，得以形成具有厚度姑微米之 黏合層。隨後，上述轉移元件之黏合層面藉由層壓放在偏 _ 光板上，可得具有暫時貼附轉矛多元件之黏合層之偏光板。 所得偏光板有關相容性、财久性及防止漏光之能力試驗如 下。其結果顯不於表1。 1) 相容性：目視在上述轉移元件之塗佈後之經製備塗佈 溶液及經乾燥塗佈層。（〇：外觀未變；χ ••渾濁或變白） 2) 耐久性：具有轉移元件自其剝除之黏合劑之偏光板（尺 寸：233毫米Χ309毫米）之黏合層面接附至非鹼性玻璃。然 後玻璃受到熱壓為處理，然後在乾燥條件下在g 〇 下靜 φ 置200小時。目視方式評估偏光板之外觀改變。（〇··無缺 陷；Δ :具有小氣泡；χ :具有氣泡） 3) 防止漏光之能力：具有轉移元件自其剝除之黏合劑之 偏光板（尺寸：233毫米χ309毫米）之黏合層面接附至具有正 交尼科耳（Nicols)稜鏡之非鹼性玻璃。然後，玻璃受到熱壓 器處理，然後在乾燥條件下在8(TC下靜置200小時。使用下 述 MCPD-2000(〇tsuka Electronics Co·，Ltd.製造）根據亮度 差異评估漏光程度。 4) 党度差異·測定自偏光板之各端中心向内之亮度1厘米 99064.doc 200536914 及在偏光板之中心的亮度，然後可得在自各端測定之平均 亮度與在中心之亮度間之差異。 表1 相容性υ 耐久性2) 防止漏光能力3) 塗佈溶液/ 經乾燥塗佈層 80°c乾燥 亮度差異ΔΙ；4) 實例1 :黏合劑A 〇/〇 Δ 1.24 實例2 :黏合劑B 〇/〇 〇 1.13 實例3 :黏合劑C 〇/〇 〇 0.85 實例4 :黏合劑D 0/0 〇 1.58 實例5 :黏合劑E 〇/〇 〇 1.92 比較例1 :黏合劑F 〇/〇 剝除 不可測定 比較例2 :黏合劑G 〇/〇 〇 9.36 比較例3 ··黏合劑Η 〇/〇 X 1.33 比較例4 :黏合劑I χ/χ 〇 1.20 本發明之功效 根據本發明，可提供一種壓感黏合劑組合物，其可防止 混濁、滲出等有關塗佈溶液且其具有優異耐久性及防止漏 光之能力；及使用彼之黏合片及黏合光學元件。 99064.doc 18-Silicone_resin_release-treated surface of polyethylene terephthalate film (manufactured by LINTEC Corporat: SP_PET3811), having a thickness of 38 micrometers and a release layer provided with aspartone resin, transferred on one side The element was applied to each of the adhesives prepared in the above examples and comparative examples using a knife coater. The surface coated with the adhesive is dried at 90 ° C! In minutes, an adhesive layer having a thickness of about 1 micrometer was formed. Subsequently, the adhesive layer of the above-mentioned transfer element is laminated on the polarizing plate to obtain a polarizing plate having an adhesive layer temporarily attached to the multi-element of the spear. The obtained polarizers were tested for compatibility, longevity and ability to prevent light leakage as follows. The results are shown in Table 1. 1) Compatibility: The prepared coating solution and the dried coating layer after the coating of the transfer element are visually observed. (〇: No change in appearance; χ •• Cloudiness or whitening) 2) Durability: Adhesive layer of polarizing plate (size: 233 mm x 309 mm) with adhesive from which the element is removed is attached to non-alkali glass. The glass was then subjected to hot pressing for treatment, and then placed under a dry condition at φ for 200 hours. The appearance of the polarizer was evaluated visually. (0 ·· no defect; Δ: with small bubbles; χ: with bubbles) 3) Ability to prevent light leakage: Adhesive layer of polarizing plate (size: 233 mm x 309 mm) with transfer adhesive from which the component is peeled off Attached to non-alkaline glass with crossed Nicols. Then, the glass was subjected to an autoclave, and then left to stand at 8 (TC for 200 hours under dry conditions. The following MCPD-2000 (manufactured by Otsuka Electronics Co., Ltd.) was used to evaluate the degree of light leakage based on the difference in brightness. 4) Difference in party degree · Measure the brightness inward from the center of each end of the polarizer 1 cm 99064.doc 200536914 and the brightness at the center of the polarizer, and then obtain the difference between the average brightness measured at each end and the brightness at the center. Table 1 Compatibility υ Durability 2) Light leakage prevention ability 3) Coating solution / Dried coating layer 80 ° c Dry brightness difference ΔI; 4) Example 1: Adhesive A 〇 / 〇Δ 1.24 Example 2: Adhesive B 〇 / 〇〇1.13 Example 3: Adhesive C 〇 / 〇〇0.85 Example 4: Adhesive D 0/0 〇1.58 Example 5: Adhesive E 〇 / 〇〇1.92 Comparative Example 1: Adhesive F 〇 / 〇 Peel Except for non-measurable Comparative Example 2: Adhesive G 〇 / 〇〇9.36 Comparative Example 3 ·· Adhesive Η 〇 / 〇X 1.33 Comparative Example 4: Adhesive I χ / χ 〇1.20 The efficacy of the present invention can be provided according to the present invention. A pressure-sensitive adhesive composition, which can prevent turbidity, bleeding, and other related coating solutions, has excellent durability and the ability to prevent light leakage, and uses an adhesive sheet and an adhesive optical element. 99064.doc 18-