1284764 玖、發明說明 [發明所屬之技術領域] 本發明係保護液晶顯示裝置所用液晶偏光板所使用之 勘著膜片，係關於添附在液晶偏光板上直接可透視檢查之 液晶偏光板保護用透明黏著膜片。 [先前技術] 液曰曰』不裝置所用液晶偏光板之致命缺陷就在易受損 傷、污染、附著異物等。因此，在液晶#光板之製造步驟、、 流通步驟和安裝步驟中，-般在液晶偏光板之表面上採用 添附保護黏著膜片等措施以保護液晶偏光板不致於受到損 2:染：附著異物等。添附有保護黏著膜片之液晶偏光 板’係在安裝於液晶顯示裝 褒置之刖，先行缺陷檢查。該項 檢查係在添附有保護膜片 、 μ、* 、 膜片之下進行，因此，該保護黏著膜 片被要求具備高透明性。 、 又’在近來之檢杳作辈φ + 德—、、一* 一卞菜中，保濩黏者膜片上顯現有損 傷或π禾之製品全部做為損 貝祀纹理因此，保護黏荖蹬日 :身也被要求具備耐傷性或防靜電性。為確認表面 黏:膜“身所造成，有時會使用= ^ 斤以也而具備耐水性或耐藥性。 離子:成^電層方面’已往例如使用具有石黃酸鹼等帶吟 气物“曰Γ:: 化之含防靜電性樹脂之含水分 U奎^ , 柰11並不充足（例如參照專利文獻 1和專利文獻2)。又，A裎4w k , 〜又駄 七^ 為耠升黏者性膜片表面之耐傷性，ρ 有例如添加非反鹿刑取 # 已 μ來夕氧烷於耐磨損性層以改善滑動之 315051 5 1284764 方法’但也未能充分改善。更在專利文獻1和專利文獻2中， 也揭示有以紫外光等活性能量線硬化耐磨損性層之方法， 但在反應時會產生臭氧’所以需要排除廢氣設備而不理 想0 構成上述保護黏著膜片之黏接劑，通常重視其透明 性，黏接力易於控制和非污染性等，所以一般採用溶劑型 丙稀系黏接劑（例如參考專利文獻3)。該保護黏著膜片在液 晶顯示製造步驟途中因被㈣，所以該保護黏著膜片要且 備微黏接性且可再剝離性之兩種性質。但在使用_般之微 黏接性黏接劑時’當保護黏著膜片在捲裝狀態之流通途中 會發生隧道狀制離(即黏著保護膜片和剝離薄片之間發生 局㈣離現象），或貼附有該保護黏著膜片之液晶偏光板之 另—面’#塗布黏接劑，乾燥時也容易發生上述随道狀剝 離或膨脹之問題。 上述随道狀剝離或膨脹現象會在黏接劑層留下痕跡， =查步驟中往往被誤以為是液晶偏光板之缺陷之原因等 、:碭存在。又，由於屬於微黏接性，所以例如在雙軸拉伸 明聚S旨膜片等膜片基材和黏接劑之間黏貼性變得不足， 剝離時容易在液晶偏光板表面上有殘糊留存等問題發 Μ黏著膜片用剝離薄片通常使用其黏接劑接觸 =有剝離劑之膜片。該剝離劑可採用㈣氧烧系剝離 -非聚石夕氧烷系剝離劑。例如使用聚石夕氧烧系剝離劑 ，跟保護黏著膜“1之剝離性可設計地非常.…曰是〒 315051 6 1284764 貼時有浮起之 化需用高溫， 致表面處理障 石夕氧烧移行至黏接劑層面致使液晶偏光板黏 問題存在，另外，為充分進行聚矽氧烷之熟 造成膜片之熱收縮，或偏光板表面之污染而 礙之問題發生（例如參考專利文獻4)。 專利文獻1 : 曰本專利特開平11-70629號公報（第4頁） 專利文獻2 : 曰本專利特開平2000-1680 15號公報（第4至5頁） 專利文獻3 : 曰本專利特開平9-2089 10號公報（第2頁） 專利文獻4 : 曰本專利特開平2〇00-239623號公報（第2頁） [發明内容] 連Ai月欲解決夕掘 …本發明之目的乃就保護液晶顯示偏光板而使用透明黏 者膜片以解決上述先前技術上之問題。具體言《，本發明 乃提供具有優異之防靜電性、耐傷性、防污性等，又具有 俊異之耐皿水性'耐藥品性、添附在液晶偏光板上可直接 透視檢查液晶偏光板有無缺點而使用之液晶偏光板保護用 透明黏著膜片者。 本發明之另-目的在提供能維持保護膜片和黏接劑間 之適度黏接性’且自剝離薄片剝離黏接劑之際’剝離性輕， 剝離劑不會移行之黏著膜片。 間題之i法 315051 7 1284764 本發明包括下列各項： ⑴：種液晶偏光板保護用透明黏著膜片，係在雙抽拉 伸· Θ膜片之一面依序設置防靜電層和耐傷性層 另：Γ置有再剝離型黏接劑層之液晶偏光板保護用透明 黏：膜片巾，其特徵為防靜電層係含有氧化； 係由硬化樹脂層所構成。 劳r層 ⑺如第⑴項之液晶偏光板保護用透明黏著膜片，其 中，上述硬化樹脂層係熱硬化型聚石夕氧烷樹脂層：- ⑺如第⑴項或第⑺項之液晶偏光板保護用透明黏著 膜片，其中，_L述防靜電層係含有4〇至8〇質量％之氧化錫 IV(Sn〇2)以及60至2〇質量％之聚酯系樹脂。 ⑷如，⑴項至第（3)項中任意—項之液晶偏光板保護 透明黏者膜片’其中，上述耐傷性層係含有〇1至1〇質量 ^之非反應型聚矽氧烷。 (5)如第⑴項至第（4)項中任意—項之液晶偏光板保護 用透月黏著膜片’其中，上述耐傷性層之表面電阻率為1 X 108 Ω以下。 W如第⑴項至第（5)項中任意—項之液晶偏光板保護 用=明黏著膜片，&中’上述再剝離型黏接劑層係由胺基 甲酉文S曰系黏接劑以聚異氰酸酯系交聯劑交聯之雙液硬化型 胺基甲酸酯系黏接劑所構成，且透明黏著膜片之混濁度在 3 %以下。 (7)如第（6)項之液晶偏光板保護用透明黏著膜片，其 中，對於上述胺基甲酸酯系黏接劑之聚異氰酸酯系交聯劑 315051 8 1284764 系黏接劑固形物1 〇〇質量份計，固 之添加量，以胺基甲酸酯 形物為2至1〇質量份。 (8)如弟（1)項至第X7. 用透明黏著膜片，复項中任意一項之液晶偏光板保護 積有剝離薄片。〃，上述再剝離型黏接劑層之表面層 ()如第(8)項之液晶偏光板保護 中’上述剝離薄片係聚稀煙系膜片。…膜片，其 著膜(片 10)^(8)項或第（9)項之液晶偏光板保護用透明黏 …:，上述剝離薄片之表面電位係_以下。 第（1)項至第（7)項中任意一 護用透明黏著膜月，1 士 、液日日偏先板保 著膜片黏貼在經溫声;、作’將該液晶偏光板保護用透明黏 時之三乙醯笑度50%RH之環境下放置3小 -…義維素膜片，經24小時後依據仍 規-之180度剥離法所測得之黏接力為3至鳥。 1用:⑴項至第(7)項中任意-項之液晶偏光板保 邊用透明黏者膜片，A 士 著膜片黏貼在經溫/2、3c f該液晶偏光板保護用透明點 仕、工概度23C，濕度50%RH之環境下放置3小 乙醯基纖維素膜片，經24小時後，再於90±穴下加 ‘、、、】彳纟Λ依據JIS-Z_〇237所規定之刚度剝離法所測 得黏接力為3至3〇N/m。 [實施方式] 本卷月研九者為解決上述問題經銳意研究結果，發現 藉由在雙軸拉伸透明膜片之—面之表面上，依序設置含有 氧化錫之防靜電層’以及做為耐傷性層之硬化樹脂層，再 315051 9 1284764 於上述雙軸拉伸透明膜片之另—面之表面設置再剝離型黏 接劑層，所得透明黏著膜片做為液晶偏光板保護用黏著膜 片具有優異之適性，而完成本發明。 本卷明之防靜電層係以氧化錫（Sn〇2, ιν價之氧化錫， 以下簡稱為氧化錫)和黏接樹脂為主成分而形成。在導電性 微粒中’氧化錫亦具有優異之導電性、白色度亦高。其中 以使用五氧化銻摻雜之氧化錫為較佳。氧化錫之粒徑以 以下為佳，其中以5至—為更佳。當粒徑大於3〇疆 時’混濁度變高而成問題。另一方面，當粒徑過小時，有 時難以分散於塗料中。 ^防猙毛層中之氧化錫含量以40至80質量％為較佳。當 虱化錫含ϊ低於40質量％時，導電性微粒相互間之聯结變 少以致有時防靜電性能變得不足。又，氧化錫含量大於8〇 質量％時’黏接樹脂不足而致和基材之黏接性不足以及混 濁度變高之問題發生。 防蛘電性功能以耐傷性層依照JIS_C_23丨8所規定之 面電阻率為低於1χ108Ω者較佳，其中以低於7χ107Ω下； 更佳。當表面電阻率大於lx 108〇時，透明黏著膜片表面 上有時會容易附著塵埃。 二月’電層所使用黏接性樹脂，一般為聚酯系樹脂、丙 ?樹脂、乙烯-乙酸乙烯系共聚物樹脂、聚乙烯醇 t聚苯乙烯系樹脂、離子鍵聚合物系樹脂、尼龍系樹脂、 伞烯系樹脂、聚胺基曱酸酯系樹脂等。防靜電層中之黏 接樹脂含量以20至60質量％為佳。例如透明黏著膜片用之 31505] 10 1284764 基材為雙轴拉伸读 月t酉曰膜片時，由黏接性之觀點，以 用聚S旨系樹脂为^土 、 ”、、乜，♦酯系樹脂之例舉有不飽和聚酯樹脂 之溶液或分齒：潘 甘+ ^ ，、中亦可添加石臘添加型或非石臘型之 差麻軒油等之弟：、、a 、 油’或添加氟系助劑。其中亦以有機溶 厂丨可命I*生之聚酯系樹脂為佳，其中就塗工後潤濕性或透明 甚f抗黏連性之觀點而言，以添加氟系助劑為更佳。 防靜電層之膜厚以G.G5MG//m為宜，其中以010至 β為軏佳。當膜厚低於0·05 # m時，防靜電性能有不 足之缺點。相及祕，腊@ 也膜；大於5.00// m時，混濁度增高， 效果到達飽和而不經濟。 又置於防靜電層上之做為财傷性層之硬化樹脂層係塗 布更化|±㈣日液經硬化而形成。該硬化性樹脂可使用熱硬 化，樹脂、紫外光硬化性樹脂、電子射線硬化性樹脂以 〇亥樹月曰之冷媒洛液、水分散液、無溶劑單體或低聚物液之 形態而利用。 硬化性樹脂中之熱硬化性樹脂以硬化時不產生臭氧者 為佳。熱硬化性樹脂中’以防污性、滑動性優異之熱硬化 性=矽氧烷樹脂為佳。熱硬化性聚矽氧烷樹脂係藉加熱脫 水縮合反應而硬化，為立體交聯構造者。舉一例而言，一 般是以末端具有羥基之聚烷基矽氧烷化合物和末端具有氫 原子之聚烧基石夕t烧間之混合物Μ成分者，該聚烧基矽 氧烷之典型例舉有聚二甲基矽氧烷。 因應必要而含有溶劑、錫等催化劑之形態之商品名通 常亦稱為熱硬化型聚矽氧烷硬塗布劑。 315051 11 1284764 。亥熱硬化型聚矽氧烷硬塗布劑之例舉有例如東芝矽酮 公司製品之「SHC900」GE(商品名）等。為提升與防靜電層 霉占接性，亦可包含醇酸樹脂或三聚氰胺樹脂等。 紫外光硬化性樹脂可使用丙烯系單體或低聚物之無溶 Μ液、溶媒溶液、水分散液等。就防污性、滑動性之觀點 而言，以紫外光硬化性聚矽氧烷樹脂為佳。 如使侍保護膜片本身不易沾污，或沾污時也容易去 污，則耐傷性層以添加非反應型聚石夕氧烧為佳。該非反應 型聚石夕氧烧係導入直鏈狀二甲基聚石夕氧燒或苯基或高級烧 基而成者。非反應型聚石夕氧烧之例舉有東芝道康寧石夕 綱公司製品之「BT_24_842 Addhive」（商品名）等。 耐傷性層中之非反應型聚石夕氧炫之添加量以 質B為宜，其中以(M至5.0質量％為更佳，尤以〇5至5〇 質篁％為最佳。當添加量少於〇 旦/ 、i貝里/〇時，則防污性時有 不足：相反地，多於1〇質量％時，當保護膜片以捲裝狀態 加工日守，聚矽氧烷會有移往背面之問題，因而不佳。又， 耐傷性層之膜厚以（M至1〇//111為 击乂土 A时r 八于以〇·3至5 // 厚溽於。.…時’耐傷性或耐藥品性時有不 足，相反地，膜厚大於1〇 時 混濁度高之問題。 便有防靜電性能不良或 本發明中，透明黏著膜片用 伸透明膜片，就透明性、财華。性ft片可使用雙軸拉 成了 I。性和耐熱性之觀點而言， 使用k擇自例如聚酯系、聚乙烯、 ^ ^ 7 ^ 3 水丙烯4之聚烯烴系、 …細系、聚偏氯乙稀系、乙缚乙烤醇系、聚氣乙稀系、 315051 12 1284764 聚碳酸酯系、聚醯胺系、聚醯亞胺系、 聚鴨之各樹脂中之至少一種而形成二糸轴，^ 片。其中以使用雙軸拉伸透明聚酯 中透明膜 之耐傷性岸在涂右„ ^马佳。特別是後述 為防止敎二化步驟皆需高溫，因此， 為 …、收縮及皺紋等，在透明黏著膜κ 供古也 、月用之基材上亦要 備有耐熱性專。本發明中之雙軸拉伸透 至3 00 "1!1為宜，其中以1〇至1〇〇#瓜為 、 又以6 胺y 更佳。雙轴拉伸透明 Μ片可施與電暈放電處理等周知之表面處理。 本發明之黏接劑層，對於雙軸拉^明聚醋膜片等之 土材膜片要具有優異之貼緊性，、 戸榀么左W 不列離缚片間之剝離性 良好’無剝離劑之移行便不會污染點接劑層者因此透 明黏著膜片在貼附於液晶偏光板之前之捲卜 過程中，不會發生隧道狀剝離，X，貼：：通 之液晶偏光板之另一面上，再將黏冷呆：黏者膜片 冉將黏接劑塗布、乾燥時，也 所干^随道狀幻離或膨服現象’具備有添附於液晶偏光 、“微㈣性和㈣離性之性質’而且即使再次剝離後 必要在液晶偏光板表面上無殘膠之特性。 〃本發明之黏接劑層最好以胺基甲酸酉旨系黏接劑用聚異 鼠酸酿系交聯劑交聯而成之雙液硬化型胺基甲酸I系黏接 劑所構成’該胺基甲酸醋系黏接劑，例如以聚醋聚醇、聚 ㈣醇' 聚碳酸SI聚醇、聚己内酿聚醇和聚異氣酸醋系交 聯劑藉催化劑反應所得分子量為10，_至·,000之聚胺 基：酸酯聚醇，再調配以聚異氰酸酯系交聯劑而成之溶劑 1基甲酸酯系黏接劑為佳。該黏接劑再藉由聚異氰酸酯 315051 13 1284764 系交聯劑之交聯反應而形 化型胺基甲酸6旨系黏接劑/ 4之層°本發明中之雙液硬 如丙烯酸酯主劑/璟4琉儿 ，又炙又液硬化型黏接劑（例 具有良好的離;性州劑等)比較，對於聚婦煙系膜片 …異鼠酸醋系交聯劑 酸醋、脂肪族聚異氰酸醋 <方香…乳 環族聚異氰酸醋等。哕六"丨s肪^異氰酸醋以及脂 曰寻〇哀又聯劑可適度調柝脸|田μ亦匕么# 接劑之交聯密度，在貼附㈣曰 月控胺基甲酸酯糸黏 90°C > 2 J 、；次日日偏光板後之加熱處理（例如 2 ’2小時)時，剝離之際，點接力亦無變化…能改 妃目士 d胰片間之貼緊性，並且對於偏光 ^微黏接性和再剝離性之性f，可得良好之液晶偏光 板保4用透明黏著膜片而甚理想。 聚異氰酸醋系交聯劑中，以採用交聯反應快速之具有 二異氰酸酯環之多官能聚異氰酸酯化合物做為交聯劑，而 將胺基甲酸酯系黏接劑加以交聯而形成者為佳。以含有多 官能聚異氰酸酯化合物之三聚體所構成之三聚異氰酸酯環 至J 一個之聚氰酸酯系交聯劑為佳，加熱處理後再剝離 時’其黏接性也幾乎無變化。 添加於本發明之胺基甲酸酯系黏接劑之聚異氰酸酯交 聯劑之用量，以胺基甲酸酯系黏接劑固形物丨〇〇質量份計， 使用固形物1.5至11質量份為佳，其中以2至1〇質量份為更 佳。當添加量少於1.5質量份時，交聯度不足，黏接性增強， 特別是加熱後之黏接性增強，自液晶偏光板之再剝離性可 能劣化。相反地，超過1 1質量份時，交聯度過高而黏接性 14 315051 1284764 降低，對於偏光板之微黏接性不足或呈飽和狀態而阻礙交 聯致使凝聚力降低，再剝離性可能不良。 黏接劑層之厚度以5至5Ο μ m為佳，其中以20至3 0 # m 為更佳。當黏接劑層厚度少於5 時，對於被黏接體之黏 接性可能會不足’又，超過5 〇 # m時，黏接力因飽和而變 得不經濟，另外，造成黏接劑之逸出，而可能成為剝離時 破壞凝聚之原因。 又本毛明之透明黏著膜片之光透過率，雖然會受基 材薄片、防靜電層、耐傷性層以及黏接劑層等各層成分之 影響，但其混濁度以3%以下為宜，添附於液晶偏光板之情 形下，可直接透視檢查液晶偏光板有無缺陷。 本發明之液晶偏光板保護用透明黏著膜片之形成方 法，例如將基材薄片之雙軸拉伸透明膜片之表面上塗布防 靜電層’乾燥後，#塗布以耐傷性層，經乾燥所得防靜電 性雙軸拉伸透明膜片之内側面，塗布以雙液硬化型胺基甲 酸醋系黏接劑，再乾燥而形成黏接縣，然後，該黏接劑 ::貼附以剝離薄片之方法，或在剝離薄片上塗布以該黏 ’經乾餘而形成黏接劑層之後，介以黏接劑層將剝離 靜電性雙軸拉伸透明膜片之内面側而製成之 層’皆可按照已 之早面上。例如 逆向輥塗布機、 氣刀到塗機、逆 /防靜電層’還有其上面層積之耐傷性 i周知方法形成在雙軸拉伸透明聚酯膜片 錯延點塗布機’唇形塗布機、簾式塗布機、 刮塗機、棒材塗布機、縫口模頭塗布機、 315051 15 1284764 :輪軸凹印塗布機、同向輪轉凹印塗布機、微輪轉凹印淹 布機等塗布裝置塗布於雙軸拉伸透明膜片之方法可供： =:玄塗布也可以藉簾式塗布機或縫口模頭塗布機等雙層 5時進行，或使用上述任意方法逐次實施亦可。 黏接劑層也可以和上述防靜電層、耐傷性層同樣使用 :周知方法’直接塗布在防靜電性雙軸拉伸透明聚醋膜 =面之方法’或一旦塗布於剝離薄片之後，再轉錄在防 靜電性雙軸拉伸透明聚醋膜片之方法等均可採用。又，層 =靜電層和耐傷性層之步驟，也可以在形成上述黏接； 便貫施。 片系剝離薄片， 系膜片，（b)其他 本發明之剝離薄片可大別為①塑膠膜 ②其他剝離薄片。 ①塑膠膜片系剝離薄片可分（a)聚烯烴 塑膠膜片。 ⑷聚烯烴系膜片包括聚乙烯、聚丙烯、聚丁烯、聚甲 :戊烯、乙烯-丙烯共聚物樹脂，或其2種以上之樹脂經混 合之樹脂加以層積而成之複合膜片等。上述膜片尚可塗布 以含氟樹脂或聚矽氧烷樹脂’或混合亦可。但是聚烯烴系 膜片具有不必塗布聚矽氧烷等也能使用之優點。 ⑼其他塑膠膜片之例舉有聚乙稀對苯二甲酸醋、聚酿 ，等塑膠膜片上’按照乾燥質量計，以0.1至3.0g/m2左右 量塗布以含氟樹脂或聚錢㈣脂等，經熱硬化或電離放 射線硬化等方法設置剝離劑層’或亦可在膜片巾混合以含 氟樹脂或聚矽氧烷樹脂等。 315051 16 1284764 0其他剝m之例舉有紙、合成紙 物上層積上述①項之膜片而成。 =之織 接塗布聚錢燒樹脂等。 在。成紙上亦可直 也心二聚:烴系膜片可以不使用聚石夕氧烧等剥離劑 離性，因此宜做為剝離薄片使用，且剝離劑不會 移仃至黏接劑層面。 2:料㈣、膜片㈣基甲酸1_接_之剝離性 輕，無剝離劑移行所造成不良 等之優點存在。mu’且有價廉而透明性高 其中以剝離性穩定的表面電位少於100乂之雙軸拉 5^丙婦膜片為最佳。争7白士 y 更以自本發明之剝離薄片剝離黏著膜 片後，剝離薄片之表面電位為少於丨〇〇v者為佳。 又，為不損及剝離後之黏接劑之外觀或透明性，依照 本財政。P印刷局刊行之夾雜物表之順序，以聚烯煙系膜 片中所含長徑0.05mm以上之魚眼個數在〇」個/m2以下，且 按照JISI06G1所規定表面粗度之最高在m以下之剝離 薄片為佳。 將本發明之液晶偏光板保護用透明黏著膜貼附在放置 於溫度23± 2。(：，濕度50± 3%RH環境下3小時之三乙醯基纖 維素膜片上，經過24小時後依照JIS-Z-0237所規定之180度 剝離法所測得之黏接力（A)宜在3至30N/m範圍，其中以5至 20N/m為更佳。又，當該黏接力少於3N/m時，因黏接力不 足’對於需求微黏接性之液晶偏.光板保護用透明黏著膜片 而吕’有缺乏適性之問題。相反地，當黏接力超過3 0N/m 17 315051 1284764 日守’因黏接力過強，對於需求再剝離性之液晶偏光板保護 用透明黏著膜片而言，同樣有欠缺適性之問題。 又’將本發明之液晶偏光板保護用透明黏著膜片貼附 在放置於溫度23± 2°C，濕度50± 3%RH之環境下經3小時之 二乙醯基纖維素膜片上，經過24小時後，再於溫度90t： ±五 C下加熱2小時後依照jis-Z-0237所規定之180度剝離法所 測知黏接力（B)宜在3至30N/m範圍，其中以5至2〇N/m為更 佳又，當該黏接力未滿3N/m時，因黏接力不足，對於需 求微黏接性之液晶偏光板保護用透明黏著膜片而言，有欠 缺適性之缺點。相反地，當該黏接力超過3(^/爪時，因黏 接力過強，對於需求再剝離性之液晶偏光板保護用透明黏 著膜片而言，同樣有欠缺適性之問題。 特別是以按照上述條件所測定之黏接力（A)和黏接力 (B)同時能滿足本發明之需求者為佳，在藉自動或手動方式 自液晶偏光板剝離保護黏著膜片之操作步驟上，才不致於 ^生使液晶偏光板變形，或殘膠等污染物質附著之現象。 技依據本發明之第（6)項，當胺基甲酸酯系黏接劑以聚異 氰酸酯系交聯劑所交聯之雙液硬化型胺基甲酸醋系黏接劑 所構成時’可以同時滿足上述黏接力(A)和黏接力(B)之條 件0 y、 實施例： 本發明藉實施例詳細說明如下。在下述實施例和 U中倘右無特別說明，所使用「份」表示「質量 表示「質量％ 〇」 315051 18 1284764 實施例1 在基材之雙軸拉伸聚乙烯對苯二甲酸酯（PET)膜片上 (商品名為T-100°c，曰本三菱化學聚酯膜片公司製品，厚 度為25//m，全光透過率為88%，混濁度為30%)，將氧化 錫/聚酯樹脂之質量比率為2/1之防靜電劑（商品名為微索 爾巴-Rmd 142，索爾貝克公司製品，氧化錫之平均粒徑為 2〇nm ’含氟系助劑）以乾燥質量計能成為〇 3g/m2量，藉微 輪轉凹印塗布機塗布，然後在100艺下乾燥3〇秒鐘以形成防 靜電層。 其次，在該防靜電層上，以聚矽氧烷硬塗劑（商品名為 SHC900，奇異東芝矽酮公司製品，固形物含量3〇%)1〇〇份 (固形物計）做為熱硬化性樹脂，對之混合非反應型聚矽氧 烷（商品名為BY-24-842 Additive，東麗·道康寧·矽酮公 司製品，固形物含量50%)1份（固形物計）調製塗布液，以乾 燥貝里δ十成為〇· 5g/m2，藉微輪轉凹印塗布機塗布，然後在 1 2〇 C下乾燥30秒鐘，形成耐傷性層，而製得防靜電性雙軸 拉伸透明聚酯膜片。 力汁，以六亞甲基 一，一开乳敗b日心二不體（商品名為「； 2乃付2030」’日本聚胺基甲酸酯工業公司製品）份做；1284764 发明 发明 发明 发明 发明 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 847 Adhesive patch. [Prior Art] The fatal defects of the liquid crystal polarizing plate used in the liquid helium are susceptible to damage, contamination, and foreign matter adhering. Therefore, in the manufacturing step, the flow-through step, and the mounting step of the liquid crystal light panel, measures such as attaching a protective adhesive film are generally applied to the surface of the liquid crystal polarizing plate to protect the liquid crystal polarizing plate from damage. 2: dyeing: adhesion of foreign matter Wait. The liquid crystal polarizing plate attached with the protective adhesive film is attached to the liquid crystal display device to perform defect inspection first. This inspection is carried out with the protective film, μ, *, and diaphragm attached. Therefore, the protective adhesive film is required to have high transparency. And in the recent inspections of φ + 得 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Next day: The body is also required to be resistant to injury or anti-static. In order to confirm the surface stickiness: the film is caused by the body, and sometimes it is used to have water resistance or resistance. [Ion: Into the electrical layer] In the past, for example, a helium gas with a rhein base has been used. "曰Γ: The moisture content of the antistatic resin containing the antibacterial resin is not sufficient (for example, refer to Patent Document 1 and Patent Document 2). Also, A裎4w k , ~ 駄 ^ ^ ^ 耠 耠 耠 耠 耠 耠 耠 耠 耠 耠 耠 耠 者 者 者 者 者 者 者 者 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有The 315051 5 1284764 method 'but has not been fully improved. Further, in Patent Document 1 and Patent Document 2, a method of hardening an abrasion resistant layer by an active energy ray such as ultraviolet light is also disclosed, but ozone is generated during the reaction. Therefore, it is necessary to remove the exhaust gas device, which is not preferable. The adhesive for the adhesive film generally pays attention to transparency, and the adhesion is easy to control and non-contaminating. Therefore, a solvent-type acryl-based adhesive is generally used (for example, refer to Patent Document 3). Since the protective adhesive film is (4) in the middle of the liquid crystal display manufacturing step, the protective adhesive film has two properties of micro-adhesiveness and re-peelability. However, when using the _like micro-adhesive adhesive, 'the tunneling separation occurs when the protective adhesive film is in the package state (that is, the local (four) separation phenomenon occurs between the adhesive protective film and the peeling sheet). Or the other surface of the liquid crystal polarizing plate for protecting the adhesive film is coated with an adhesive, and the problem of peeling or swelling accompanying the above-mentioned manner is also likely to occur during drying. The above-mentioned peeling or swelling phenomenon may leave marks on the adhesive layer, and the inspection step is often mistaken for the cause of the defects of the liquid crystal polarizing plate, etc.: 砀 exists. In addition, since it is micro-adhesive, for example, the adhesiveness between the film substrate such as the biaxially stretched film and the adhesive is insufficient, and it is easy to be disfigured on the surface of the liquid crystal polarizing plate during peeling. Problems such as retention of the paste, etc. The release sheet for the adhesive film is usually contacted with its adhesive = a film having a release agent. The release agent may be a (iv) oxy-fired release-non-polyoxanene release agent. For example, the use of poly-stone oxidizing agent stripping agent, and the protective adhesive film "1 stripping property can be designed very .... 曰 is 315 315051 6 1284764 when affixed to float high temperature, the surface treatment barrier stone oxygen The problem of sticking to the layer of the adhesive causes the liquid crystal polarizing plate to be viscous, and the problem of the heat shrinkage of the film caused by the ripening of the polyoxyalkylene or the contamination of the surface of the polarizing plate occurs (for example, refer to Patent Document 4). Patent Document 1: Japanese Patent Laid-Open No. Hei 11-70629 (page 4) Patent Document 2: Japanese Patent Laid-Open No. 2000-1680 No. 15 (pages 4 to 5) Patent Document 3: Patent Japanese Laid-Open Patent Publication No. Hei 9-2089 No. 10 (P. 2) Patent Document 4: Japanese Patent Laid-Open No. Hei No. Hei No. 2-00-239623 (page 2) [Summary of the Invention] The transparent adhesive film is used to protect the liquid crystal display polarizing plate to solve the above-mentioned prior art problems. Specifically, the present invention provides excellent antistatic property, scratch resistance, antifouling property, and the like. The water resistance of the dish is 'chemical resistance, Attached to the liquid crystal polarizing plate, the liquid crystal polarizing plate can be directly inspected for the presence or absence of the liquid crystal polarizing plate, and the transparent polarizing film for liquid crystal polarizing plate protection is used. The other object of the present invention is to provide a moderate adhesion between the protective film and the adhesive. When the adhesive is peeled off from the peeling sheet, the peeling property is light, and the peeling agent does not migrate to the adhesive film. The method of the method is 315051 7 1284764 The present invention includes the following items: (1): Liquid crystal polarizing plate protection A transparent adhesive film is used to sequentially provide an antistatic layer and a scratch-resistant layer on one side of the double-stretching and bismuth film. Further, a transparent polarizing film for protecting the liquid crystal polarizing plate with a re-peelable adhesive layer is provided. And a transparent adhesive film for protecting a liquid crystal polarizing plate according to Item (1), wherein the hardened resin layer is thermosetting type, wherein the antistatic layer is made of a oxidized layer; The transparent adhesive film for liquid crystal polarizing plate protection according to Item (1) or (7), wherein the antistatic layer contains 4 to 8% by mass of tin oxide IV ( Sn〇2) and 60 to 2〇 (4) The liquid crystal polarizing plate of any one of items (1) to (3) protects the transparent adhesive film, wherein the above-mentioned damage resistant layer contains 〇1 to 1〇. (5) The perforated adhesive film for liquid crystal polarizing plate protection according to any one of items (1) to (4), wherein the surface resistivity of the above-mentioned damage-resistant layer is 1 X 108 Ω or less. W. For the protection of liquid crystal polarizing plates of any of items (1) to (5) = brightly adhered film, & 'the above-mentioned re-peelable adhesive layer is composed of amino-based methacrylate The S-based adhesive is composed of a two-liquid hardening type urethane-based adhesive which is crosslinked by a polyisocyanate crosslinking agent, and the turbidity of the transparent adhesive film is 3% or less. (7) The transparent adhesive film for protecting a liquid crystal polarizing plate according to Item (6), wherein the polyisocyanate crosslinking agent for the above urethane-based adhesive is 315051 8 1284764 adhesive solid 1 The amount of the solid is added in an amount of 2 to 1 part by mass based on the amount of the carbamate. (8) Rudi (1) to X7. With a transparent adhesive film, the liquid crystal polarizing plate of any of the above items is protected by a peeling sheet. That is, the surface layer of the above-mentioned re-peelable adhesive layer () is protected by the liquid crystal polarizing plate of the item (8), and the above-mentioned peeling sheet is a thin flue-cured film. The film has a transparent adhesive for protecting the liquid crystal polarizing plate of the film (Piece 10) (8) or (9), and the surface potential of the peeling sheet is _ or less. For any of the items (1) to (7), the transparent adhesive film is used for the month, and the 1st, the liquid, and the first plate are used to protect the film and adhere to the temperature; and the liquid crystal polarizing plate is protected. When the transparent sticky time, the three-dimensional 醯 度 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 1 Use: (1) to (7) of any of the items of the liquid crystal polarizer for the edge of the transparent adhesive film, A Shi film attached to the temperature of 2 / 3c f liquid crystal polarizer protection transparent point 3 small acetonitrile-based cellulose membranes were placed under the environment of 23C and humidity 50% RH. After 24 hours, add ',, and 彳纟Λ at 90± points. According to JIS-Z_ The adhesion measured by the stiffness peeling method specified in 〇237 is 3 to 3 〇N/m. [Embodiment] In order to solve the above problems, the research results of the above-mentioned research and development have found that the antistatic layer containing tin oxide is sequentially disposed on the surface of the surface of the biaxially stretched transparent film. The hardened resin layer of the scratch-resistant layer is further provided with a re-peelable adhesive layer on the other surface of the above-mentioned biaxially-stretched transparent film, and the obtained transparent adhesive film is used as a protective layer for liquid crystal polarizing plates. The film has excellent suitability to complete the present invention. The antistatic layer of the present invention is formed by tin oxide (Sn〇2, tin oxide, hereinafter referred to as tin oxide) and a binder resin as main components. In the conductive fine particles, tin oxide also has excellent electrical conductivity and high whiteness. Among them, tin oxide doped with antimony pentoxide is preferred. The particle size of the tin oxide is preferably as follows, with 5 to - being more preferred. When the particle size is larger than 3 〇, the turbidity becomes high. On the other hand, when the particle diameter is too small, it is sometimes difficult to disperse in the coating material. The tin oxide content in the anti-cork layer is preferably 40 to 80% by mass. When the content of bismuth telluride is less than 40% by mass, the conductive particles are less linked to each other such that the antistatic property sometimes becomes insufficient. Further, when the tin oxide content is more than 8% by mass, the problem that the adhesion resin is insufficient and the adhesion to the substrate is insufficient and the degree of turbidity becomes high occurs. The anti-mite function is preferably such that the surface resistivity of the scratch-resistant layer in accordance with JIS_C_23丨8 is less than 1χ108Ω, and more preferably less than 7χ107Ω; more preferably. When the surface resistivity is greater than lx 108 ,, dust may easily adhere to the surface of the transparent adhesive film. In February, the adhesive resin used in the electric layer is generally polyester resin, acrylic resin, ethylene-vinyl acetate copolymer resin, polyvinyl alcohol t polystyrene resin, ionomer resin resin, nylon. A resin, an umbrella resin, a polyamine phthalate resin, or the like. The content of the adhesive resin in the antistatic layer is preferably from 20 to 60% by mass. For example, in the case of a transparent adhesive film, 31505] 10 1284764, when the substrate is a biaxially stretched read-on-teptium film, from the viewpoint of adhesion, the poly-S resin is used as the soil, ",," ♦ Examples of ester-based resins include solutions of unsaturated polyester resins or split teeth: Pangan + ^, and may also add paraffin-added or non-paraffin-type smashed oils, etc.:,, a , oil' or add fluorine-based auxiliaries. Among them, it is also preferred to use polyester-based resin which can be produced by organic solvent, in terms of wettability after coating or transparency. It is more preferable to add a fluorine-based auxiliary agent. The film thickness of the antistatic layer is preferably G.G5MG//m, and preferably 010 to β. When the film thickness is less than 0·05 # m, antistatic The performance has insufficient shortcomings. The phase and the secret, wax @also film; when it is greater than 5.00 / / m, the turbidity is increased, the effect reaches saturation and is not economical. It is also placed on the antistatic layer as the hardening resin of the financial damage layer The layer coating is further modified. The (±) day liquid is formed by hardening. The curable resin can be thermally cured, resin, ultraviolet curable resin, or electron beam curable resin. It is used in the form of a refrigerant liquid, an aqueous dispersion, a solvent-free monomer or an oligomer liquid of the eucalyptus tree. The thermosetting resin in the curable resin is preferably such that it does not generate ozone upon hardening. In the resin, the thermosetting property which is excellent in antifouling property and slidability is preferably a decane resin. The thermosetting polysiloxane resin is cured by a heat dehydration condensation reaction and is a three-dimensional crosslinked structure. Generally speaking, it is generally a mixture of a polyalkyl siloxane compound having a hydroxyl group at the terminal end and a polyalkyl siloxane having a hydrogen atom at the end. The polyalkylene oxide is typically exemplified by polydimethylene. The product name of a form containing a catalyst such as a solvent or tin, which is necessary, is also commonly referred to as a thermosetting polyoxyalkylene hard coating agent. 315051 11 1284764. A thermosetting type polyoxyalkylene hard coating agent For example, "SHC900" GE (trade name) of Toshiba Ketone Co., Ltd., and the like are exemplified. In order to improve the adhesion to the antistatic layer, an alkyd resin or a melamine resin may be included. As the ultraviolet curable resin, an sol-free solution of a propylene-based monomer or oligomer, a solvent solution, an aqueous dispersion or the like can be used. From the viewpoint of antifouling properties and slidability, an ultraviolet curable polydecane resin is preferred. If the protective film itself is not easily stained or stained easily, it is preferable to add a non-reactive polysulfide. The non-reactive polysulfide is introduced into a linear dimethyl polysulfide or a phenyl group or a high-grade alkyl group. For example, the "BT_24_842 Addhive" (trade name) of the product of Toshiba Dow Corning Shihsang Co., Ltd. is exemplified. The amount of non-reactive polysulfide in the damage-resistant layer is preferably B, wherein (M to 5.0% by mass is more preferable, especially 〇5 to 5 篁% 为% is optimal. When added When the amount is less than 〇 / /, i berry / 〇, the antifouling property is insufficient: conversely, when more than 1 〇 mass%, when the protective film is processed in a package state, the polyoxane will There is a problem of moving to the back, which is not good. Moreover, the film thickness of the scratch-resistant layer is (M to 1 〇 / / 111 for the smashing soil A when r 八 〇 〇 3 to 5 / 溽 thick 溽. When there is a deficiency in the damage resistance or chemical resistance, on the contrary, the problem of high turbidity when the film thickness is more than 1 。 is poor in antistatic property or in the present invention, the transparent adhesive film is used to stretch the transparent film. Transparency and wealth. The ft film can be biaxially drawn to I. From the viewpoint of properties and heat resistance, k is selected from polyolefins such as polyester, polyethylene, and ^^3^3 water propylene. Department, ... fine system, polyvinylidene chloride, Ethylene Baked alcohol, Polyethylene, 315051 12 1284764 Polycarbonate, Polyamide, Polyimide, Poly Duck At least one of them forms a two-axis, a sheet. Among them, the scratch-resistant shore of the transparent film in the biaxially stretched transparent polyester is applied to the right side. ^Mai Jia. In particular, it is mentioned that the step of preventing the bismuth is high. Therefore, for the film, the shrinkage, the wrinkles, etc., the heat-resistant adhesive is also required on the transparent adhesive film κ for the ancient and monthly substrates. The biaxial stretching of the present invention penetrates to 300 "1! 1 is preferable, and it is preferably 1 to 1 〇〇 #瓜, and 6 amine y. Biaxially stretched transparent enamel can be applied to a known surface treatment such as corona discharge treatment. The layer should have excellent adhesion to the soil membrane of the biaxially-pulled polyester film, etc., and the left-side W is not good in the peeling property between the two pieces. If the transparent adhesive film is adhered to the liquid crystal polarizing plate, the tunnel-like peeling will not occur, X, paste:: the other side of the liquid crystal polarizing plate, and then Sticky and cold stay: When the adhesive film is coated and dried, it will also be dried or swallowed. It is characterized by the addition of liquid crystal polarizing, "micro (tetra) and (iv) dissociation properties" and it is necessary to have no residual glue on the surface of the liquid crystal polarizing plate even if it is peeled off again. 〃 The adhesive layer of the present invention is preferably urethane.酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉 酉Polyol, poly(tetra)ol 'polycarbonate SI polyalcohol, polycaprolactone and polyisophthalic acid vinegar cross-linking agent obtained by reacting a catalyst with a molecular weight of 10, _ to -, 000 polyamine: acid polyalcohol Further, a solvent-based one-formate-based binder which is a polyisocyanate-based crosslinking agent is preferably added, and the adhesive is further shaped by a crosslinking reaction of a polyisocyanate 315051 13 1284764 crosslinking agent. Amino formic acid 6 is a layer of adhesive / 4 layer of the present invention, the two-liquid hard such as acrylate main agent / 璟 4 琉 children, and 炙 liquid hardening type adhesive (example has a good separation; Agents, etc., for the combination of the futuristic membranes...isophthalic acid vinegar cross-linking acid vinegar, aliphatic polyisocyanuric acid < square incense... Alicyclic polyisocyanate vinegar.哕六"丨s fat^ isocyanic acid vinegar and fat 曰 曰 又 又 又 联 联 联 联 联 联 联 联 联 联 | | | | | | | | | | | | | | | | | | | | | | | | | | | | | |糸 糸 90 90 ° C > 2 J,; the next day after the polarizing plate heat treatment (for example, 2 '2 hours), when the peeling, the point relay does not change ... can change the eye d The adhesion is good, and for the polarized light micro-adhesiveness and re-peelability f, a good liquid crystal polarizing plate can be used with a transparent adhesive film. In the polyisocyanate-based cross-linking agent, a polyfunctional polyisocyanate compound having a diisocyanate ring which is rapidly reacted by a crosslinking reaction is used as a crosslinking agent, and a urethane-based adhesive is crosslinked to form a cross-linking agent. It is better. It is preferable that the polyisocyanate ring composed of a trimer containing a polyfunctional polyisocyanate compound is a polycyanate type crosslinking agent of J, and the peeling property after heat treatment is almost unchanged. The amount of the polyisocyanate crosslinking agent to be added to the urethane-based adhesive of the present invention is 1.5 to 11 parts by mass based on the mass of the urethane-based adhesive solids. Preferably, it is preferably 2 to 1 part by mass. When the amount is less than 1.5 parts by mass, the degree of crosslinking is insufficient, the adhesion is enhanced, and particularly, the adhesion after heating is enhanced, and the removability from the liquid crystal polarizing plate may be deteriorated. On the other hand, when it exceeds 11 parts by mass, the degree of crosslinking is too high and the adhesion is lowered by 14 315051 1284764, and the micro-adhesiveness of the polarizing plate is insufficient or saturated, which hinders crosslinking and causes cohesive force to be lowered, and re-peelability may be poor. . The thickness of the adhesive layer is preferably 5 to 5 μm, and more preferably 20 to 30 # m. When the thickness of the adhesive layer is less than 5, the adhesion to the bonded body may be insufficient. Moreover, when it exceeds 5 〇# m, the adhesive force becomes uneconomical due to saturation, and in addition, the adhesive is caused. Escapes, and may be the cause of destruction of cohesion during peeling. The light transmittance of the transparent adhesive film of the present invention is affected by the composition of each layer such as the substrate sheet, the antistatic layer, the scratch resistant layer and the adhesive layer, but the turbidity is preferably 3% or less. In the case of a liquid crystal polarizing plate, the liquid crystal polarizing plate can be directly inspected for defects. A method for forming a transparent adhesive film for protecting a liquid crystal polarizing plate of the present invention, for example, coating an antistatic layer on a surface of a biaxially stretched transparent film of a base sheet, and drying it, applying a scratch-resistant layer, and drying it The inner side of the antistatic biaxially stretched transparent film is coated with a two-liquid hardening type urethane-based adhesive, and then dried to form a bonded county. Then, the adhesive is attached to the peeling sheet. The method, or coating the release sheet with the adhesive layer to form an adhesive layer, and then the layer of the adhesive layer is peeled off from the inner surface side of the electrostatically biaxially stretched transparent film. Can be followed by the early face. For example, reverse roll coater, air knife to coater, reverse/antistatic layer 'and scratch resistance on top of it. Known method is formed on biaxially stretched transparent polyester film misalignment coating machine' lip coating Machine, curtain coater, knife coater, bar coater, slot die coater, 315051 15 1284764: coating of wheel gravure coater, co-rotating gravure coater, micro-rotary gravure spreader, etc. The method of applying the device to the biaxially stretched transparent film is: =: The black coating may be carried out by a double layer of 5 or the like, such as a curtain coater or a slot die coater, or may be carried out successively by any of the above methods. The adhesive layer may be used in the same manner as the above-mentioned antistatic layer or the damage resistant layer: a known method 'directly applied to an antistatic biaxially stretched transparent polyester film=face method' or once applied to a release sheet, and then transcribed A method of using an antistatic biaxially stretched transparent polyester film or the like can be employed. Further, the step of the layer = the electrostatic layer and the damage-resistant layer may be formed by forming the above-mentioned bonding; Sheet peeling sheet, film sheet, (b) Other The peeling sheet of the present invention may be substantially 1 plastic film 2 other peeling sheet. 1 plastic film peeling sheet can be divided into (a) polyolefin plastic film. (4) The polyolefin-based film sheet comprises a composite film in which polyethylene, polypropylene, polybutene, polymethylene: pentene, ethylene-propylene copolymer resin, or a resin of two or more kinds thereof is laminated by mixing the resin. Wait. The above film may be coated with a fluorine-containing resin or a polyoxyalkylene resin or may be mixed. However, the polyolefin-based film has the advantage that it can be used without using polysiloxane or the like. (9) Other plastic diaphragms are exemplified by polyethylene terephthalate vinegar, poly brewing, and other plastic membranes. According to the dry mass, the coating is fluorinated resin or poly-dosage in the amount of 0.1 to 3.0 g/m2. A grease or the like may be provided by a method such as thermosetting or ionizing radiation hardening, or a film containing a fluorine-containing resin or a polysiloxane resin may be mixed. 315051 16 1284764 0 Other examples of peeling m are made by laminating the above-mentioned one film on paper or synthetic paper. = Weaving and coating, etc. in. The paper can also be dicentrically formed: the hydrocarbon-based film can be used as a release sheet without using a release agent such as polysulfide, and the release agent does not migrate to the adhesive layer. 2: The material (4), the film (4) carboxylic acid 1_ _ _ the peeling light, no peeling agent migration caused by the advantages of the existence of the advantages. Mu' is inexpensive and has high transparency. Among them, a biaxially-stretched 5^-propyl film with a surface resistance of less than 100 Å is preferable. In the case of peeling off the adhesive film from the release sheet of the present invention, it is preferred that the surface potential of the release sheet is less than 丨〇〇v. Further, in order not to impair the appearance or transparency of the adhesive after peeling, it is in accordance with this financial. The order of the inclusions published by the P Printing Bureau is that the number of fish eyes having a long diameter of 0.05 mm or more contained in the polyene-based film is less than or equal to m2, and the highest surface roughness is specified in accordance with JISI 06G1. A release sheet of m or less is preferred. The transparent adhesive film for protecting the liquid crystal polarizing plate of the present invention was attached to a temperature of 23 ± 2. (:, the adhesion force measured by the 180-degree peeling method specified in JIS-Z-0237 after 24 hours on the 3-hour triacetyl cellulose film in a humidity of 50 ± 3% RH environment (A) It is preferably in the range of 3 to 30 N/m, and more preferably 5 to 20 N/m. Also, when the bonding force is less than 3 N/m, the adhesion is insufficient, and the liquid crystal plate protection for the micro-adhesive property is required. With a transparent adhesive film and Lu's lack of adaptability. Conversely, when the adhesive force exceeds 30 N/m 17 315051 1284764, the defensive force is too strong, and the transparent polarizing of the liquid crystal polarizing plate for re-peelability is required. In the case of the diaphragm, there is also a problem of lack of suitability. Further, the transparent adhesive film for protecting the liquid crystal polarizing plate of the present invention is attached to an environment of a temperature of 23 ± 2 ° C and a humidity of 50 ± 3% RH. On the second acetonitrile cellulose film, after 24 hours, it was heated at a temperature of 90 t: ± five C for 2 hours, and then the adhesion was measured according to the 180-degree peeling method prescribed by jis-Z-0237 (B). ) preferably in the range of 3 to 30 N/m, wherein 5 to 2 N/m is more preferable, and when the bonding force is less than 3 N/m, the adhesion is insufficient. In the case of a transparent adhesive film for protecting a liquid crystal polarizing plate which requires micro-adhesiveness, there is a disadvantage of lack of suitability. Conversely, when the adhesive force exceeds 3 (^/claw, the adhesive force is too strong, and the peeling is required for the demand. For the transparent adhesive film for liquid crystal polarizer protection, there is also a problem of lack of suitability. In particular, the adhesive force (A) and the adhesive force (B) measured according to the above conditions can satisfy the requirements of the present invention at the same time. Preferably, in the operation step of peeling off the protective adhesive film from the liquid crystal polarizing plate by an automatic or manual method, the liquid crystal polarizing plate is not deformed or the contaminant such as residual glue adheres. 6), when the urethane-based adhesive is composed of a two-liquid hardening type urethane-based adhesive which is crosslinked by a polyisocyanate crosslinking agent, the adhesive force can be satisfied at the same time (A) Conditions and Adhesive Force (B) Conditions 0 y, EXAMPLES The present invention will be described in detail by way of examples. In the following examples and U, unless otherwise specified, the use of "parts" means "quality means "mass % 〇" 315051 18 1284764 Example 1 On a biaxially stretched polyethylene terephthalate (PET) film of a substrate (trade name: T-100 °c, manufactured by Sakamoto Mitsubishi Chemical Polyester Film Co., Ltd., thickness 25/) /m, the total light transmittance is 88%, the turbidity is 30%), and the tin oxide/polyester resin has a mass ratio of 2/1 antistatic agent (trade name is Micro Solba-Rmd 142, Sol Baker's products, the average particle size of tin oxide is 2〇nm 'Fluorine-based additives' can be 〇3g/m2 in dry weight, coated by micro-rotary gravure coater, and then dried at 100°. Seconds to form an antistatic layer. Next, on the antistatic layer, a polyoxyalkylene hard coating agent (trade name: SHC900, a product of the singular Toshiba ketone company, a solid content of 3% by weight) is used as a thermosetting method. Resin, mixed with non-reactive polyoxyalkylene (trade name: BY-24-842 Additive, Toray Dow Corning ketone company product, solid content 50%) 1 part (solid content meter) preparation coating liquid , drying the Berry δ 10 to 〇 · 5g / m2, coated by a micro-rotary gravure coater, and then dried at 12 ° C for 30 seconds to form a scratch-resistant layer, and obtain antistatic biaxial stretching Transparent polyester film. Lili juice, with hexamethylene methyl one, one open milk defeat b day heart two body (trade name "; 2 is pay 2030" 'product of Japan Polyurethane Industry Co., Ltd.);
父聯劑’添加在胺基甲酸酯系黏接劑(商品名&「赛阿拜I SH·101」，日本東洋油墨公司製品”⑼份（固形物計）經六！ 反應而得黏接劑層用塗布液。 人 、將舞接劑層用塗布液藉逗點塗布機以㈣質量 為g/ln皇布在上述防靜電性雙軸拉伸透明聚酯膜片之丨 315051 19 1284764 靜電層為相反面上，妙 然後以1 00°C乾燥1分鐘而形成黏接劑 層，使用表面電位為s 馬5V之雙軸拉伸聚丙烯膜片（商品名為 「E-200」，王子魏】M a A公司製品，厚度為25 μ m)做為剝離薄 片’貼附在黏接劑芦μ ⑷1上而製成液晶偏光板保護用透明黏著 膜片。 實施例2 按照實施例1所矛士口 ^ +丄 汀不相同方法，但是防靜電劑改用氧化錫 /聚酯樹脂之質脣μμ & β 里比率為1/1之防靜電劑（商品名為「微索爾The parent-linking agent' is added to the urethane-based adhesive (trade name & "Saibai I SH·101", product of Japan Toyo Ink Co., Ltd." (9) (solid matter meter) The coating liquid for the adhesive layer. The person uses the coating liquid to apply the coating liquid to the comma coater to (4) the mass is g/ln imperial cloth in the above antistatic biaxially stretched transparent polyester film 315051 19 1284764 The electrostatic layer is on the opposite side, and then dried at 100 ° C for 1 minute to form an adhesive layer, using a biaxially oriented polypropylene film with a surface potential of 5 V (trade name "E-200", Prince Wei] M a A product, thickness 25 μm) was used as a release sheet attached to the adhesive reed μ (4) 1 to form a transparent adhesive film for liquid crystal polarizer protection. Example 2 According to Example 1 The spears are not the same as the method, but the antistatic agent is changed to an antistatic agent with a ratio of 1/1 in the lip of the tin oxide/polyester resin (the product name is "Micro Sol".
Md 1 1 2」索爾貝克公司製品）而製成液晶偏光板保護用 透明黏著膜片。 實施例3 按知、μ靶例1所不相同方法，但是所使用非反應型聚矽 氧烷（商品名為「BY_24_842 Additive」，東麗.道康寧·矽 酮公司製品，固形物含量為50%)改為以固形物量計4份而 製成液晶偏光板保護用透明黏著膜片。 實施例4 按妝貫施例1所示相同方法，但是所使用非反應型聚矽 氧烷（商品名為「BY_24_842 Additive」，東麗道康寧矽 酮公司製品，固形物含量為50%)改為以固形物量計〇 5份而 製成液晶偏光板保護用透明黏著膜片。 實施例5 按照貫施例1所示相同方法，但是胺基甲酸酯系黏接劑 (商品名為「阿拜因SH-101」，曰本東洋油墨公司製品）1〇〇 負量份（以固形物計）改用六亞曱基二異氰酸酯之三聚體 315051 20 1284764 (商品名為「克羅乃得2030」，曰本聚胺基甲酸酯工業公司 製品）7份做為交聯劑，而製成液晶偏光板保護用透明黏著 膜片。 實施例6 按照實施例1所示相同方法，但是使用紫外光硬化型表 面處理矽膠塗料（商品名為「UVHC 1105」，奇異東芝矽酮 公司製品，固形物含量為1 〇〇%)做為硬化性樹脂跟非反應 型聚石夕氧烧（商品名為「BY-24-842 Additive」，東麗·道康 寧·矽酮公司製品，固形物含量50%)以固形物量比率計成 為98/2混合，再藉微輪轉凹印塗布機以乾燥質量計成為 3.0g/m2塗布後，在120°C下乾燥30秒鐘之後，用紫外光燈 以300mJ/cm2照射而製得耐傷性層，而製成液晶偏光板保護 用透明黏著膜片。 选較例1 除省略形成防靜電層和耐傷性層之外，其他皆按照實 施例1所不相同方法，在雙軸拉伸聚乙烯酞酸酯（pET)膜片 (商品名為「τ-iooc」，三菱化學聚酯膜片公司製品，厚度 為25//m，全光透過率為88%，混濁度為3〇%)之片面形成 黏接劑層，再貼附以剝離薄片而製成液晶偏光板保護用透 明黏著膜片。 达l較例2 按照實施例1所不相同方法，但是防靜電劑改用丙烯銨 鹽(商品名為「高施費瑪C670」，曰本合成化學公司製品) 而‘成液晶偏光板保護用透明黏著膜片。 315051 1284764 評定 按照下述評定方 光板保護用透明勘著 (評定項目） 法，就各實施例和比較例所得液晶偏 膜片進行評估，其結果示於表1。 昜性層率ΓΩΙ 使用，亞電波卫業公司製品之「數位型絕緣儀麵· 」，按照JIS心2318所記載方法，在溫度抑，濕产 :〇/〇RH:條件下設置試料，外加ι〇〇ν電壓，充電例少： 後，測定其表面之表面電阻率（Ω )。 盒^透過率 之 —就剝除剝離薄片之液晶偏光板保護用透明黏著膜片， 精混濁測定儀（日本電色工業公司製品，NDH2〇〇〇型）測定 ΜΑϋ之評定 u使用學振式堅牢度用磨擦試驗儀（福田器械工業公司 製叩），在20mmx 4〇mm之金屬製曲板壓頭上，將纖維素不 織布（商品名為「本可得」，日本旭化成公司製品）捲裝，然 後在荷重500g狀態下來回摩擦1〇次。之後，觀察表面情形， 以耐傷性層幾乎無變化者評為良好，耐傷性層脫落者則評 為不良。 性之評定 使用學振式堅牢度用摩擦試驗儀（福田器械工業公司 衣οσ )，在20mmx 40mm之金屬製平板壓頭上，將纖維素不 織布（商品名為「本可得」，日本旭化成公司製品）捲裝，然 22 315051 1284764 二浸入5(TC之溫水lml中，於荷重5，狀態下來回摩擦μ 2其後，觀察表面，g耐傷性層幾乎無變化，表面電阻 率沒有降低者評為〇，而耐傷性層雖無脫落，但發生白化， 面電阻率降低者評為△，而脫落者則評估X。 U。使用學振式堅牢度用摩擦試驗儀（福田器械工業公司 製品），在2〇mmx 4〇mm之金屬製平板壓頭上，將纖維素不 為商品名為「本可得」，日本旭化成公司製品）捲裝，然 ^入50°C之溫水lml中，於荷重5〇〇以大態下來回摩擦Μ U八後，蜣察表面，以耐傷性層幾乎無變化，表面電阻 率α有降低者評為〇，而耐傷性層雖無脫落，但發生白化， 表面電阻率降低者評為△，而脫落者則評為X。 將丙烯系黏接劑擦拭在耐傷性層表面，評定有益黏接 劑之附著情形。 ’ 板之點接 y? ( a > 將液晶偏光板係藉用透明黏著膜片（大小：25mmx ^〇〇ΙΏηΐ)取為試料，貼附於經溫度23t，濕度為50%RH之環 放置3小日守之液晶偏光板之三乙醯基纖維素膜片（商品 為田士格克」，厚度為38//m，富士軟片公司製品）上， 用2kg之壓輥來回“欠，經過24小時後，按照们π所 規疋之1 80度剝離法，以拉伸速度3〇〇mm/1分鐘剝離時之黏 接力（A) ’藉拉伸試驗儀（歐利恩得科公司製品，rtc_i2i〇 型）測定之。 23 315051 1284764 矣氡之測宗 臭氧氣體之測定係藉耐傷性層塗布中所排廢氣體經採 取後利用臭氧試驗紙之峨化鉀澱粉紙而檢測之。 對於液晶偏光板之黏接力Γηγ 將液晶偏光板保護用透明黏著膜片（大小·· 25rnin X 100mm)取為試料，貼附於溫度為m，濕度為5〇%rH之環 土兄下放置3小時之液晶偏光板之三乙醯基纖維素膜片（商品 名為萄士搭克」’厚度為38// m，富士軟片公司製品）上， 使用2kg之壓輥來回，經過24小時後，再於9(Γ(：下加熱 處理2小時後，按照jis_z_〇237所規定18〇度剝離法，以拉 伸速度30〇mmn分鐘剝離時之黏接力（B)，藉拉伸試驗儀（歐 利恩得科公司製品，測定之。 片之剝錐六 從液晶偏光板保護用透明黏著膜片（大小：25mmx 100mm)取為試料，在膜片之耐傷性面整面上用雙面膠帶黏 接後將兩面膠帶側黏接在不銹鋼板上，按照jm〇237 所規疋180度剝離法，以拉伸速度3〇〇mm/i分鐘，將剝離薄 片剝離時之黏接力，用拉伸試驗儀（歐利恩得科公司製品， RTC-1210型）測定之。 有無抹漿鈿蒗 ^則疋對衣液晶偏光板之黏接力時，由於液晶偏光板保 護=透明黏著膜片和黏接層間之黏附不良，從液晶偏光板 保痩用透明！έ著膜片有無黏接劑剝落之狀態以肉眼評估， ' J不剝落之狀態評為〇，而黏接劑剝落之狀態則評 315051 24 1284764 為X 〇 附荖性 之 評 將澱粉粉末掉落在液晶偏光板保護用透明黏著膜片 耐傷性層之表面，再把膜片倒過來去除過剩之殿粉後， 估有無;殿粉附著。 第1表Md 1 1 2" Solbeck's product) is made into a transparent adhesive film for liquid crystal polarizer protection. Example 3 According to the method of the known and μ target example 1, the non-reactive polyoxane (trade name "BY_24_842 Additive", product of Toray Dow Corning Acne, 50% solid content) was used. ) A transparent adhesive film for protecting a liquid crystal polarizing plate was prepared by using 4 parts of solid content. Example 4 The same procedure as shown in Example 1 was applied, but the non-reactive polyoxyalkylene (trade name "BY_24_842 Additive", product of Toray Dow Corningone, solid content 50%) was used instead. A transparent adhesive film for protecting a liquid crystal polarizing plate was prepared by 〇5 parts in terms of a solid content. Example 5 The same procedure as in Example 1 was carried out, except that the urethane-based adhesive (trade name "Abein SH-101", manufactured by Sakamoto Toyo Ink Co., Ltd.) was used in a negative amount ( In the case of solids, 7 parts of trimer 315051 20 1284764 (trade name "Clonet 2030", 曰 聚 polyurethane) A transparent adhesive film for protecting a liquid crystal polarizing plate is prepared. Example 6 The same method as in Example 1 was carried out, but using a UV-curable surface-treated silicone coating (trade name "UVHC 1105", a product of the singular Toshiba ketone company, a solid content of 1%) was used as the hardening method. Resin and non-reactive polychlorite (trade name "BY-24-842 Additive", Toray Dow Corning 矽 ketone company product, solid content 50%) in the solid matter ratio to become 98/2 mixed And after drying by a micro-rotary gravure coater to a dry mass of 3.0 g/m2, drying at 120 ° C for 30 seconds, and then irradiating with a UV lamp at 300 mJ/cm 2 to obtain a scratch-resistant layer. A transparent adhesive film for protecting the liquid crystal polarizing plate. Comparative Example 1 A biaxially stretched polyvinyl phthalate (pET) film (trade name "τ-" was used in the same manner as in Example 1 except that the formation of the antistatic layer and the scratch-resistant layer was omitted. Iooc", a product of Mitsubishi Chemical Polyester Film Co., Ltd., having a thickness of 25/m, a total light transmittance of 88%, and a turbidity of 3% by weight, forms a layer of adhesive, and is then attached with a release sheet. A transparent adhesive film for protecting the liquid crystal polarizing plate. Example 1 is different from Example 2, but the antistatic agent is changed to propylene ammonium salt (trade name "Gao Shifeima C670", product of Sakamoto Synthetic Chemical Co., Ltd.) and 'liquid crystal polarizing plate protection' Transparent adhesive film. 315051 1284764 Evaluation The liquid crystal polarizing film obtained in each of the examples and the comparative examples was evaluated in accordance with the following method for evaluating the transparent plate (protection item) for the protection of the light-plate. The results are shown in Table 1.昜 层 Ι Ι Ι Ι Ι Ι Ι 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚〇〇ν voltage, less charge: After that, the surface resistivity (Ω) of the surface was measured. The transmittance of the box is the transparent adhesive film for the protection of the liquid crystal polarizing plate of the peeling sheet. The fine turbidity measuring instrument (product of the Nippon Denshoku Industries Co., Ltd., NDH2 〇〇〇 type) is used to measure the ΜΑϋ u 使用a roll of a non-woven fabric (trade name "Benco", manufactured by Asahi Kasei Corporation of Japan) on a 20 mm x 4 mm metal curved plate indenter using a friction tester (manufactured by Fukuda Industrial Co., Ltd.) Rub back and forth 1 times with a load of 500g. Thereafter, the surface condition was observed, and it was evaluated as good in the case where the scratch-resistant layer was almost unchanged, and as the poor-resisting layer was evaluated as poor. Evaluation of Sexuality Using a friction tester (Fukuda Industrial Co., Ltd., οσ), a non-woven fabric of cellulose on a 20 mm x 40 mm metal plate indenter (trade name "Benco", product of Asahi Kasei Corporation of Japan ) package, then 22 315051 1284764 dip into 5 (TC of warm water lml, under the load 5, rubbing μ 2 back and forth, observe the surface, g damage layer is almost unchanged, surface resistivity is not reduced For the flaw, although the scratch-resistant layer does not fall off, it is whitened, the surface resistivity is lowered as △, and the shedding is evaluated as X. U. Using the vibration-fastness tester (Fukuda Instrument Industrial Co., Ltd.) On the metal plate indenter of 2〇mmx 4〇mm, the cellulose is not sold under the trade name “本可得”, Japan Asahi Kasei Co., Ltd.), and then into the warm water lml of 50 °C, The load is 5 〇〇 rubbing back and forth in a large state Μ U eight, after observing the surface, the scratch-resistant layer has almost no change, the surface resistivity α is reduced as the 〇, while the damage-resistant layer is not shed, but whitening occurs. Surface resistivity reduction It is △, and the person who falls off is rated as X. The propylene-based adhesive was wiped on the surface of the scratch-resistant layer to evaluate the adhesion of the adhesive. 'The point of the board is connected to y? ( a > The liquid crystal polarizing plate is made of a transparent adhesive film (size: 25mmx ^〇〇ΙΏηΐ) as a sample, attached to a ring with a temperature of 23t and a humidity of 50% RH. 3 Xiaoshou's liquid crystal polarizing plate of triacetyl cellulose film (commercially known as Tianshigeke), thickness of 38 / / m, Fujifilm company products), with 2kg of pressure roller back and forth "owed, after 24 After an hour, according to the 280 degree peeling method prescribed by π, the adhesion force at the stretching speed of 3〇〇mm/1 minute peeling (A) 'Browth tensile tester (Olien Deco products, rtc_i2i〇) 23) 315051 1284764 The measurement of the ozone gas in the test is carried out by using the ozone-degraded potassium starch paper of the ozone test paper after the exhaust gas in the coating of the damage-resistant layer is taken. Adhesive force Γγγ A transparent adhesive film (size · 25rnin X 100mm) for liquid crystal polarizer protection is taken as a sample, and is attached to a liquid crystal polarizing plate which is placed under a temperature of m and a humidity of 5〇% rH for 3 hours. Triacetyl cellulose membrane (trade name: 士士克) "thick The degree is 38 / / m, Fujifilm company products), using a 2kg pressure roller back and forth, after 24 hours, and then 9 (Γ (: 2 hours after the heat treatment, according to jis_z_〇237 specified 18 degrees Peeling method, the adhesion force (B) at a peeling speed of 30 〇 mmn minutes, by a tensile tester (Olympus Co., Ltd., the measurement. The peeling cone of the film from the transparent polarizing film for liquid crystal polarizing plate protection) (Size: 25mmx 100mm) Take the sample as a sample. After bonding the double-sided tape on the whole surface of the film's scratch-resistant surface, bond the two sides of the tape to the stainless steel plate, according to the 180 degree peeling method according to jm〇237. The adhesive force at the time of peeling the peeled sheet at a stretching speed of 3 〇〇mm/i minutes was measured by a tensile tester (Olympus Co., product, RTC-1210 type). When the adhesion of the liquid crystal polarizing plate is changed, due to the protection of the liquid crystal polarizing plate = the adhesion between the transparent adhesive film and the adhesive layer, the transparency is ensured from the liquid crystal polarizing plate; the film is peeled off without any adhesive peeling off to the naked eye. , 'J does not peel off the state as 〇, and the adhesive peeling In the state of 315051 24 1284764, the starch powder is dropped on the surface of the scratch-resistant layer of the transparent adhesive film for liquid crystal polarizing plate protection, and then the film is reversed to remove the excess powder. There is no; the temple powder is attached. The first table
謨用、$ 1表所示結果可知實施例1至6所得液晶偏光板保 日月黏著膜片，其表面電阻率、混濁度都非常低，耐 埃耐溫水、耐藥品性皆良好，對於表面無黏接劑或塵 、、者’和液晶偏光板間之黏接力則為適度，也不會從防 315051 25 1284764The results shown in the table of $1 show that the liquid crystal polarizing plates obtained in Examples 1 to 6 have a very low surface resistivity and turbidity, and are excellent in heat resistance and chemical resistance. No adhesion or dust on the surface, and the adhesion between the liquid crystal polarizer and the liquid crystal polarizer is moderate, and it will not be prevented from 315051 25 1284764.
十每 A» I 又釉拉伸透明聚酯膜片有黏接劑之剝落，從韌離薄 片之剝離力A 4«人:k - 乜十刀輕。又，實施例1至5中製造防靜電性雙 軸拉伸透明聚自旨膜片之際，亦無臭氧發生。實施例6中塗布 才傷1^層’以紫外光照射安^化處理之際，亦無臭氧氣體 發生。 相對地，比較例丨所得透明黏著膜片由於沒有耐傷性 曰Z、表面之耐傷性、耐溫水性或耐藥品性不良，防靜電 ^也不佳，更可看到塵埃之附著。又，比較例2所得透明黏 著膜片，其耐溫水性或耐藥品性降低，防靜電性不良， 看到塵埃之附著。 主發 本發明之液晶偏光板保護用透明黏著膜片纟其表面形 成含有氧化錫之防靜電層，在其上，因應必要設置含有非 反應尘♦矽氧烷之硬化樹脂層(以聚矽氧烷硬塗布層為 :)、’可得良好之表面電阻率和透明性，且兼備優良之耐傷 以及耐溫水、耐藥品性之防靜電性雙軸拉伸透明聚酯膜 更藉D周配以胺基甲酸醋系黏接劑添加聚異氛酸醋化合 2為交聯劑之黏接劑層以及聚魏絲行較少之歸 ^ ^ 了付黏接劑層和防靜電性雙軸拉伸透明 ♦ S日膜片間之黏附性 ^ 且貼附在液晶偏光板前之捲裝 广通過程中一般容易發生之隨道狀剝離現象也不會 。又，貼附本發明之透明黏著膜片之液晶偏光板之另 ，再塗布以黏接劑使乾燥之際，也不會產生随道狀剝 315051 26 1284764 離或膨脹。並且，本發明之透明黏著膜片也幾乎不會由於 靜電而塵埃附著，黏接劑所造成之不良現象也很少，所以 具有容易實施液晶偏光板之透視檢查之優異功效。 27 315051Ten per A» I glazed stretched transparent polyester film with peeling of the adhesive, peeling force from the tough film A 4 «人: k - 乜 ten knife light. Further, in the examples 1 to 5, when the antistatic biaxially stretched transparent polycrystalline film was produced, no ozone occurred. In the case of the coating of Example 6, the layer was damaged, and no ozone gas occurred when the ultraviolet light was irradiated. In contrast, the transparent adhesive film obtained in the comparative example has no scratch resistance, 表面Z, surface scratch resistance, temperature resistance, or chemical resistance, and the antistatic property is not good, and the adhesion of dust can be seen. Further, the transparent adhesive film obtained in Comparative Example 2 was lowered in temperature resistance and chemical resistance, and was inferior in antistatic property, and adhesion of dust was observed. The transparent adhesive film for protecting a liquid crystal polarizing plate of the present invention mainly forms an antistatic layer containing tin oxide on the surface thereof, and a hardened resin layer containing non-reactive dust oxime is provided thereon The hard coating layer of the alkane is:), which can provide good surface resistivity and transparency, and has excellent anti-injury and anti-static properties, and anti-static biaxially-stretched transparent polyester film which is resistant to warm water and chemical resistance. Adhesive layer with polyisoic acid vinegar compound 2 as cross-linking agent and a small amount of poly-wei wire with a urethane-based adhesive to the adhesive layer and antistatic biaxial pull The transparency is ♦ the adhesion between the S-day film and the tape-like peeling phenomenon which is generally prone to occur in the process of wrapping the film in front of the liquid crystal polarizing plate. Further, the liquid crystal polarizing plate to which the transparent adhesive film of the present invention is attached is coated with an adhesive to dry or not, and does not peel or swell with the peeling 315051 26 1284764. Further, since the transparent adhesive film of the present invention hardly adheres to dust due to static electricity, and the adhesive agent has few defects, it has an excellent effect of facilitating the fluoroscopy of the liquid crystal polarizing plate. 27 315051