TWI465495B - 偏光子保護用易接著性聚酯薄膜 - Google Patents
偏光子保護用易接著性聚酯薄膜 Download PDFInfo
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- TWI465495B TWI465495B TW101103262A TW101103262A TWI465495B TW I465495 B TWI465495 B TW I465495B TW 101103262 A TW101103262 A TW 101103262A TW 101103262 A TW101103262 A TW 101103262A TW I465495 B TWI465495 B TW I465495B
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- polyvinyl alcohol
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- polyester
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Classifications
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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
-
- 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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
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Description
本發明係關於一種用於保護偏光子之偏光子保護用易接著性聚酯薄膜。詳而言之,係關於一種與偏光子接著性優異的偏光子保護用易接著性聚酯薄膜。
液晶顯示裝置中,基於其影像形成方式而在形成液晶面板表面的玻璃基板之兩側配置偏光板。偏光板通常係構成為:透過聚乙烯醇系樹脂等的親水性接著劑,在由聚乙烯醇系薄膜與碘等二色性材料所構成的偏光子的兩面上黏合偏光子保護薄膜。做為偏光子保護用之保護薄膜,基於光學特性與透明性的考量,以往係使用三乙醯基纖維素薄膜。
然而,三乙醯基纖維素的耐久性並不充分,若在高溫或高濕下使用以三乙醯基纖維素薄膜做為偏光子保護薄膜的偏光板,會有偏光度、色相等的偏光板性能降低的情形。又,為了因應近年來顯示器的薄型化,也要求偏光板的薄膜化,但基於維持著水分阻絕特性的觀點,三乙醯基纖維素薄膜於薄膜化方面有它的限度。因此,已有提案一種使用聚酯薄膜做為具有耐久性及水分阻絕性的偏光子保護薄膜(參照專利文獻1~5)。
做為偏光子保護薄膜使用的三乙醯基纖維素薄膜,其在表面施行有鹼性處理等,和親水性接著劑有極高的親和性。因此,由三乙醯基纖維素薄膜所構成的保護薄膜和塗布有親水性接著劑的偏光子有極高的接著性。然而,聚酯薄膜和親水性接著劑的接著性不充分,尤其在藉由延伸處理而具有配向性的聚酯薄膜的情況,此傾向更加顯著。因此,於專利文獻1~3及5中,為了提升和偏光子或塗布於偏光子上的親水性接著劑的接著性,而提案在聚酯薄膜上設置易接著層。
[先前技術文獻]
[專利文獻]
專利文獻1:日本特開平8-271733號公報
專利文獻2:日本特開平8-271734號公報
專利文獻3:日本特開2009-157361號公報
專利文獻4:日本特開2010-277028號公報
專利文獻5:日本特開2011-8170號公報
聚酯薄膜對水的親和性低,具有芳香族二羧酸做為二羧酸成分的聚酯薄膜此傾向尤其顯著。又,藉由延伸而具有結晶配向性的聚酯薄膜,和水的親和性更低。另一方面,偏光子或塗布於偏光子上的接著劑係以聚乙烯醇系樹脂為主成分,具有高親水性。由於如此的性質上的差異,聚酯薄膜和偏光子或前述接著劑之間的親和性較低,要使兩者牢固地接著是困難的。因此,即使是專利文獻1~3及5中所揭示的具有易接著層的聚酯薄膜,與三乙醯基纖維素薄膜相較,仍未能得到充分的接著性。因此,用以往的聚酯薄膜做為保護薄膜的偏光板來做為顯示器構件而長期間使用時,在保護薄膜/偏光子間會發生浮泡或剝離,並因偏光子內的水分量之變化而降低偏光特性,而有泛白等辨識性變差的情形。
在這種現狀下,本發明之課題係以提供一種具備能使聚酯薄膜和偏光子、或塗布在偏光子上的接著劑等之聚乙烯醇系樹脂層牢固地接著的手段之聚酯薄膜為目的。
本發明人等為了解決上述課題進行反覆進行專心研究及檢討,而得到了在聚酯薄膜和聚乙烯醇系樹脂層之間設置含有和聚酯薄膜的親和性高的聚酯系樹脂、和聚乙烯醇系樹脂層的親和性高的聚乙烯醇系樹脂、及交聯劑而成的層之構想。然而,本發明人等發現:若僅將該等成分組合,因各成分而無法充分發揮使聚酯薄膜與聚乙烯醇系樹脂層密接的功能。因此,本發明人等反覆日夜研究之結果,發現:於上述構想中,採用具有一定的酸值的聚酯樹脂做為聚酯樹脂,並且,採用具有一定的皂化值的聚乙烯醇系樹脂做為聚乙烯醇系樹脂,藉此可有效發揮各成分分別和其親和性高的樹脂層之接著作用。
本發明人等基於上述發現而進一步反覆研究的結果,發現:藉由採用和氫氧基的反應性高的交聯劑,可使聚酯薄膜和偏光子或接著劑等之聚乙烯醇系樹脂層更牢固地接著。本發明人等基於此等發現,進一步反覆檢討及改良於是達成了本發明。
揭示本發明的代表例如下述。
第1之發明為:一種偏光子保護用易接著性聚酯薄膜,其係在至少一面上具有易接著層;前述易接著層含有聚酯系樹脂(A)、聚乙烯醇系樹脂(B)、與交聯劑(C);前述聚酯系樹脂(A)的酸值為20KOH mg/g以下;前述聚乙烯醇系樹脂(B)的皂化值為60~85莫耳%。
第2之發明為:前述聚酯樹脂(A)於二羧酸成分中含有1~15莫耳%的5-磺酸基間苯二甲酸之偏光子保護用易接著性聚酯薄膜。
第3之發明為:前述交聯劑(C)為異氰酸酯化合物或三聚氰胺化合物之偏光子保護用易接著性聚酯薄膜。
第4之發明為:偏光子保護用易接著性聚酯薄膜前述易接著層中,聚酯系樹脂(A)、聚乙烯醇系樹脂(B)及交聯劑(C)之質量比係滿足下式之偏光子保護用易接著性聚酯薄膜,0.8≦(A)/(B)≦5
0.2≦((A)+(B))/(C)≦50。
第5之發明為:一種偏光板,其係在偏光子的兩面具有偏光子保護薄膜而成;其至少一面的偏光子保護膜係前述之偏光子保護用易接著性聚酯薄膜。
本發明之偏光子保護用易接著性聚酯薄膜和偏光子、或塗布於其上的做為接著劑的代表性之聚乙烯醇系樹脂層之間的接著性優異。因此,本發明之聚酯薄膜能適宜地做為偏光子的保護薄膜使用。藉由使用此種本發明之聚酯薄膜來做為偏光子的保護薄膜,可更廉價地製造較以往耐久性及水阻絕性優異的偏光板。又,由於本發明之偏光板耐久性優異,故可做成較以往更薄膜化。因而,藉由利用本發明之偏光板,可使液晶顯示器更加薄型化。
[用以實施發明之形態]
(聚酯薄膜)
本發明中做為基材使用的聚酯薄膜,主要是由聚酯樹脂構成的薄膜。此處,所謂「主要是由聚酯樹脂構成的薄膜」,係指由含有聚酯樹脂50質量%以上的樹脂組成物所形成的薄膜,於摻合其他聚合物時,係意味著含有聚酯樹脂50質量%以上,於與其他單體共聚合時,係意味著含有聚酯構造單位50莫耳%以上。較宜為聚酯薄膜含有聚酯樹脂90質量%以上,較佳為95質量%以上,更佳為含有100質量%。
聚酯樹脂的材料並無特別限定,可用二羧酸成分與二醇成分聚縮合所形成的共聚物、或其摻合樹脂。二羧酸成分可列舉例如:對苯二甲酸、間苯二甲酸、鄰苯二甲酸、2,5-萘二羧酸、2,6-萘二羧酸、1,4-萘二羧酸、1,5-萘二羧酸、二苯基羧酸、二苯氧基乙烷二羧酸、二苯基碸羧酸、蒽二羧酸、1,3-環戊烷二羧酸、1,3-環己烷二羧酸、1,4-環己烷二羧酸、六氫對苯二甲酸、六氫間苯二甲酸、丙二酸、二甲基丙二酸、丁二酸、3,3-二乙基丁二酸、戊二酸、2,2-二甲基戊二酸、己二酸、2-甲基己二酸、三甲基己二酸、庚二酸、壬二酸、二聚酸、癸二酸、辛二酸、十二烷二酸等。
構成聚酯樹脂的二醇成分可列舉例如:乙二醇、丙二醇、六亞甲二醇、新戊二醇、1,2-環己烷二甲醇、1,4-環己烷二甲醇、癸二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、2,2-雙(4-羥苯基)丙烷、雙(4-羥苯基)碸等。
構成聚酯樹脂的二羧酸成分與二醇成分可分別使用1種或2種以上。又,亦可適當添加偏苯三甲酸等之其他酸成分或三羥甲基丙烷等之其他氫氧基成分。
具體而言,聚酯樹脂可列舉:聚對苯二甲酸乙二酯、聚對苯二甲酸丙二酯、聚對苯二甲酸丁二酯、聚萘酸乙二酯等,此等之中,就物性與成本的均衡性考量,較佳為對苯二甲酸乙二酯。又,為了控制偏光性等光學特性,較佳樣態為含有其他共聚合成分及/或其他聚合物。就控制聚酯薄膜的光學特性的觀點考量,較佳的共聚合成分可列舉例如:二乙二醇或於側鏈具有降莰烯之共聚合成分等。
本發明之聚酯薄膜係用來做為偏光子用保護薄膜,故以具有高透明性較佳。本發明之偏光子保護用聚酯薄膜的透明性,較佳為其全光線透過率為85%以上、更佳為87%以上、尤佳為88%以上、再更佳為89%以上、特佳為90%以上。又,霧度較佳為3%以下、更佳為2.5%以下、更佳為2%以下、特佳為1.5%以下。聚酯薄膜的全光線透過率可依照例如後述實施例中所記載的方法測定。
為了改善聚酯薄膜的平滑性、捲繞性等之取用性,而有在薄膜中含入惰性粒子的情形,但是為了維持高透明性,則於薄膜中的惰性粒子之含量儘量越少為較佳。因而,較佳為做成僅在薄膜表層含有粒子的多層構成、或在薄膜中實質上不含有粒子,只在積層於聚酯薄膜的至少一面的易接著層中含有微粒子。
又,所謂「實質上不含有粒子」,係指例如:於無機粒子的情況,在以螢光X射線分析來對來自粒子的元素進行定量分析時為50ppm以下,較佳為10ppm以下,最佳為偵測限度以下的含量。其理由在於:即使未積極地將粒子添加到基材薄膜中,也會有來自外來異物的污染成分、或原料樹脂、或薄膜製造步驟的作業線或裝置中所附著的污染物剝離而混入薄膜中的情形。
又,於基材薄膜做成為多層構成時,在內層實質上不含有惰性粒子,僅在最外層含有惰性粒子的二種三層構成,由於可兼顧透明性與加工性而為較佳。
本發明中薄膜的厚度並無特別限定,於為了顯示器的薄型化而使偏光板的厚度薄化時,薄膜的厚度較佳為200μm以下,更佳為100μm以下。另一方面,為了維持做為保護膜的機械強度,薄膜的厚度較佳為10μm以上、更佳為12μm以上、尤佳為20μm以上。
做為基材的聚酯薄膜可為單層,亦可為2種以上的層所積層而成。又,只要是在可達到本發明之效果的範圍內,按照需要可在薄膜中含有各種添加劑。添加劑可列舉例如:抗氧化劑、耐光劑、抗膠凝劑、有機濕潤劑、抗靜電劑、紫外線吸收劑、界面活性劑等。薄膜具有積層構成時,較佳為可按照需要依各層的機能而含有添加劑。例如:為防止偏光子的光劣化,較佳樣態為在內層添加紫外線吸收劑等。
聚酯薄膜可藉由例如將上述聚酯樹脂熔融擠壓成薄膜狀,於鑄造輥(casting drum)使其冷卻固化而形成薄膜的方法等來製得。做為本發明之聚酯薄膜,可用無延伸薄膜、延伸薄膜之任一者,就機械強度、耐藥品性之耐久性觀點考量,較佳為延伸薄膜。於聚酯薄膜為延伸薄膜時,其延伸方法並無特別限定,可採用縱單軸延伸法、橫單軸延伸法、縱橫逐次雙軸延伸法、縱橫同時雙軸延伸法等。
(易接著層)
本發明之聚酯薄膜為了提升和偏光子、及設置在偏光子的一面或兩面之水系接著劑等的聚乙烯醇系樹脂層之間的接著性,在其至少一面上積層有易接著層,該易接著層係由含有酸值為20 KOH mg/g以下的聚酯系樹脂(A)、皂化值為60~85莫耳%的聚乙烯醇系樹脂(B)、以及交聯劑(C)之樹脂組成物所形成。易接著層亦可設置在聚酯薄膜的兩面,亦可僅設置在聚酯薄膜的一面,而另一面則設置他種的樹脂被覆層。
下述的理論並非用來限定者,吾人認為:藉由皂化值為20 KOH mg/g以下的特定聚酯系樹脂(A)、皂化值為60~85莫耳%的特定聚乙烯醇系樹脂(B)與交聯劑(C)之組合,聚酯系樹脂與聚乙烯醇系樹脂在易接著層中分別形成各自的區域(domain)單位,形成一般稱為「海島構造」的相分離構造。藉由做成為此種區域單位的分離構造,由聚酯系樹脂所構成的區域和聚酯薄膜間的接著性及由聚乙烯醇系樹脂所構成的區域和聚乙烯醇系樹脂層間的接著性之兩者的機能得以互不損害而妥當地兼顧。並且認為:交聯劑(C)藉由使聚乙烯醇系樹脂(B)交聯/凝集,而促進並維持該區域構造之形成。
以下,就易接著層的各組成詳加說明。
(聚酯系樹脂(A))
本發明之易接著層中所用的聚酯系樹脂(A)係由二羧酸成分與二醇成分進行聚縮合而成的共聚物,二羧酸成分及二醇成分可用做為前述基材的聚酯薄膜材料。就提升和聚酯薄膜基材的接著性的觀點考量,較佳為使用具有和做為基材之聚酯薄膜中的二羧酸成分相同或類似的構造/性質的二羧酸成分來做為聚酯系樹脂(A)的二羧酸成分。因而,例如:於採用芳香族二羧酸做為聚酯薄膜的二羧酸成分時,較佳為使用芳香族二羧酸來做為聚酯系樹脂(A)的二羧酸成分。此種芳香族二羧酸成分,最佳為對苯二甲酸及間苯二甲酸。亦可於對全部二羧酸成分為10莫耳%以下之範圍內,加入其他芳香族二羧酸使其共聚合。
又,聚酯系樹脂(A)的二醇成分較佳為以乙二醇與分枝的二醇做為構成成分。吾人認為:藉由具有分枝構造有助於緩和易接著層中的應力,可適宜地發揮密接性。前述分枝的二醇成分可列舉例如:2,2-二甲基-1,3-丙二醇、2-甲基-2-乙基-1,3-丙二醇、2-甲基-2-丁基-1,3-丙二醇、2-甲基-2-丙基-1,3-丙二醇、2-甲基-2-異丙基-1,3-丙二醇、2-甲基-2-正己基-1,3-丙二醇、2,2-二乙基-1,3-丙二醇、2-乙基-2-正丁基-1,3-丙二醇、2-乙基-2-正己基-1,3-丙二醇、2,2-二-正丁基-1,3-丙二醇、2-正丁基-2-丙基-1,3-丙二醇、及2,2-二-正己基-1,3-丙二醇等。
前述分枝的二醇成分的莫耳比,相對於全部二醇成分,下限較佳為10莫耳%、特佳為20莫耳%。另一方面,上限較佳為80莫耳%、更佳為70莫耳%、特佳為60莫耳%。又,按照需要亦可併用二乙二醇、丙二醇、丁二醇、己二醇或1,4-環己烷二甲醇等。
本發明中所用的聚酯系樹脂(A),就與聚乙烯醇系樹脂(B)的相溶性的考量,較佳為使用水溶性或水分散性樹脂。為使聚酯系樹脂水溶性化或水分散化,較佳為使含有磺酸鹽基、羧酸鹽基等親水性基的化合物共聚合。其中,就考量在保持低的聚酯系樹脂(A)的酸值之下,一邊控制與交聯劑的反應性一邊賦予親水性的觀點,較佳為具有磺酸鹽基的二羧酸成分。具有磺酸鹽基的二羧酸成分可列舉例如:磺酸基對苯二甲酸、5-磺酸基間苯二甲酸、4-磺酸基萘間苯二甲酸-2,7-二羧酸及5-(4-磺酸基苯氧基)間苯二甲酸或其鹼金屬鹽,其中較佳為5-磺酸基間苯二甲酸。具有磺酸鹽基的二羧酸成分,較佳為聚酯樹脂(A)的二羧酸成分中1~15莫耳%,更佳為1.5~12莫耳%,尤佳為2~10莫耳%。具有磺酸鹽基的二羧酸成分為上述下限以上時,於聚酯系樹脂之水溶性化或水分散化為較佳。又,具有磺酸鹽基的二羧酸成分為上述上限以下時,於與聚酯薄膜基材的接著性為較佳。
聚酯系樹脂(A)中與交聯劑(C)的反應基之羧酸基較少較佳。吾人認為:藉由減少與交聯劑有反應性的羧基,可降低與交聯劑的反應性,其結果,不會與聚乙烯醇系樹脂完全相混和,而可維持藉由經交聯的聚乙烯醇系樹脂所形成的區域構造。基於此觀點,聚酯系樹脂(A)的酸值宜為20 KOH mg/g,較佳為15 KOH mg/g以下,更佳為10 KOH mg/g以下,尤佳為8 KOH mg/g以下,再更佳為5 KOH mg/g以下。聚酯系樹脂(A)的酸值可由藉由後述滴定法或NMR等之成分分析的結果而理論性地求出。
為了將聚酯系樹脂(A)的酸值控制在上述範圍中,較佳為:減少用以水溶性化或水分散化的羧酸鹽基之導入量、採用羧酸鹽基以外的親水性基、降低聚酯系樹脂的羧酸末端基濃度。降低聚酯系樹脂的羧酸末端基濃度的方法,較佳為:採用對羧酸末端基進行末端基修飾的聚酯系樹脂、採用聚酯系樹脂的數量平均分子量為較大的聚酯系樹脂。因此,聚酯系樹脂(A)的數量平均分子量較佳為5000以上,更佳為6000以上,尤佳為10000以上。又,聚酯系樹脂(A)之構成成分較佳為降低有3個以上羧基的酸成分之含量。
聚酯系樹脂(A)的玻璃轉化溫度並無特別限定,較佳為20~90℃,更佳為30~80℃。若玻璃轉化溫度為上述下限以上,就對於抗黏結性而言為較佳,若玻璃轉化溫度為上述上限以下,對於和聚酯薄膜基材的接著性而言為較佳。
易接著層中之聚酯系樹脂(A)的含量,較佳為40質量%以上90質量%以下,更佳為45質量%以上85%質量%以下,尤佳為50質量%以上80質量%以下。若聚酯系樹脂(A)的含量為上述下限以上,於與聚酯薄膜基材的接著性為較佳,若為上述上限以下,則和偏光子或親水性接著劑等的聚乙烯醇系樹脂間的接著性為較佳。
(聚乙烯醇系樹脂(B))
聚乙烯醇系樹脂並無特別限定,可列舉例如:使聚乙酸乙烯酯皂化而得到的聚乙烯醇;其衍生物;以及與和醋酸乙烯酯具有共聚合性的單體所成共聚物的皂化物;使聚乙烯醇縮醛化、胺基甲酸酯化、醚化、接枝化、磷酸酯化等而成之改質聚乙烯醇等。前述單體可列舉:(無水)順丁烯二酸、反丁烯二酸、丁烯酸、衣康酸、(甲基)丙烯酸等的不飽和羧酸及其酯類;乙烯、丙烯等的α-烯烴、(甲基)烯丙基磺酸(鈉)、磺酸鈉(順丁烯二酸單烷基酯)、二磺酸鈉順丁烯二酸烷基酯、N-羥甲基丙烯醯胺、丙烯醯胺烷基磺酸鹼鹽、N-乙烯基吡咯啶酮、N-乙烯基吡咯啶酮衍生物等。此等聚乙烯醇系樹脂可僅使用1種、亦可併用2種以上。
本發明中使用的聚乙烯醇系樹脂(B)可例示:乙烯醇-醋酸乙烯酯類共聚物、乙烯醇-乙烯基丁縮醛共聚物、乙烯-乙烯醇共聚物,此等之中較佳為乙烯醇-醋酸乙烯酯共聚物、乙烯-乙烯醇共聚物。聚乙烯醇系樹脂(B)的聚合度無特別限定,就塗布液黏性考量較佳聚合度為3000以下。
乙烯醇的共聚合比例可用皂化值表示。本發明之聚乙烯醇系樹脂(B)的皂化值較佳為60莫耳%以上85莫耳%以下,更佳為65莫耳%以上83莫耳%以下,再更佳為68莫耳%以上80莫耳%以下,尤佳為70莫耳%以上80莫耳%以下,尤佳為為71莫耳%以上78莫耳%以下,特佳為73莫耳%以上75莫耳%以下。若聚乙烯醇系樹脂(B)的皂化值為上述下限以上,可與交聯劑(C)更佳地形成交聯構造。又,若聚乙烯醇系樹脂(B)的皂化值為上述上限以下(或未達到),則聚酯系樹脂(A)可更佳地發揮相溶性。乙烯醇系樹脂的皂化值可由醋酸乙烯酯等之共聚合單位水解所需要的鹼消費量、或藉由NMR的組成分析來求得。
聚乙烯醇系樹脂(B)的含量,較佳為易接著層中10質量%以上60質量%以下,更佳為15質量%以上55%質量%以下,尤佳為20質量%以上50質量%以下。若聚乙烯醇系樹脂(B)的含量為上述下限以上,於偏光子、接著劑等和聚乙烯醇系樹脂層之間的接著性為較佳,若為上述上限以下,則於和聚酯薄膜基材之間的接著性為較佳。
(交聯劑(C))
交聯劑(C),只要是與氫氧基有交聯性者皆可,並無特別限定,可列舉:三聚氰胺系、異氰酸酯系、甲烷二亞胺(carbodiimide)系、噁唑啉系、環氧系等的化合物。就塗布液的經時安定性考量,較佳為三聚氰胺系、異氰酸酯系、甲烷二亞胺系、噁唑啉系的化合物。再者,交聯劑較佳為與聚乙烯醇系樹脂(B)的氫氧基可較佳地進行交聯反應之三聚氰胺系化合物或異氰酸酯系化合物。其理由,認為係在於:相對於甲烷二亞胺系交聯劑係與羧基反應,三聚氰胺系化合物或異氰酸酯系化合物則係與氫氧基反應,故可與具有氫氧基的官能基之聚乙烯醇系樹脂(B)較佳地形成交聯構造。其中,就與聚乙烯醇系樹脂的氫氧基可較佳地形成交聯反應、且透明性優異的觀點考量,特佳為使用異氰酸酯系化合物。又,為了促進交聯反應,按照需要亦可適當地使用觸媒等。
異氰酸酯化合物可用低分子或高分子的二異氰酸酯或3價以上的聚異氰酸酯。例如,異氰酸酯化合物,可列舉:2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、4,4’-二苯基甲烷二異氰酸酯、2,4’-二苯基甲烷二異氰酸酯、2,2’-二苯基甲烷二異氰酸酯、1,5-萘二異氰酸酯、1,4-萘二異氰酸酯、苯二異氰酸酯、四甲基伸茬基二異氰酸酯、4,4’-二苯基醚二異氰酸酯、2-硝基二苯基-4,4’-二異氰酸酯、2,2’-二苯基丙烷-4,4’-二異氰酸酯、3,3’-二甲基二苯基甲烷-4,4’-二異氰酸酯、4,4’-二苯基丙烷二異氰酸酯、3,3’-二甲氧基二苯基-4,4’-二異氰酸酯等之芳香族二異氰酸酯類;伸茬基二異氰酸酯等之芳香族脂肪族二異氰酸酯類;異佛爾酮二異氰酸酯及4,4-二環己基甲烷二異氰酸酯、1,3-雙(異氰酸酯甲基)環己烷等之脂環式二異氰酸酯類;六亞甲二異氰酸酯、及2,2,4-三甲基六亞甲二異氰酸酯等之脂肪族二異氰酸酯類;及此等之異氰酸酯化合物的量體。再者,可舉出:此等之異氰酸酯化合物的過剰量與乙二醇、丙二醇、三羥甲基丙烷、丙三醇、山梨糖醇、乙二胺、單乙醇胺、二乙醇胺、三乙醇胺等之低分子活性氫化合物、或聚酯多元醇類;聚醚多元醇類;聚醯亞胺類等之高分子活性氫化合物反應所得之高分子末端含有異氰酸酯基之化合物。
三聚氰胺化合物可舉出:以取代基-(CH2)n-O-R(式中,n為1~3的整數,R為碳數1~4的烷基。)取代的三聚氰胺化合物,前述式中之R較佳為甲基。1個三聚氰胺構造所具有的上述取代基數較佳為3~6。三聚氰胺化合物的具體例可列舉:住友化學公司製Sumitex Resin系列的M-3、MK、M-6、M-100、MC等或三和化學品(股)公司製甲基化三聚氰胺樹脂MW-22、MX-706、MX-042等。
本發明中使用的交聯劑(C)較佳為嵌段異氰酸酯系化合物。藉由添加嵌段異氰酸酯系化合物,可更佳地提升塗布液的經時安定性。
嵌段化異氰酸酯系化合物可使上述異氰酸酯化合物與嵌段化劑以習知的方法進行加成反應而調製得到。異氰酸酯嵌段化劑可列舉例如:苯酚、甲酚、二甲苯酚、間苯二酚、硝基酚、氯酚等之酚類;硫酚、甲基硫酚等之硫酚類;乙肟、甲乙酮肟、環己酮肟等之肟類;甲醇、乙醇、丙醇、丁醇等之醇類;氯乙醇、1,3-二氯-2-丙醇等鹵素取代之醇類;三級丁醇、三級庚醇等之第3級醇類;ε-己內醯胺、δ-戊內醯胺、γ-丁內醯胺、β-丙內醯胺等之內醯胺類;芳香族胺類;醯亞胺類;乙醯丙酮、乙醯醋酸酯、丙二酸乙酯等之活性亞甲基化合物;硫醇類;亞胺類;尿素類;二芳基化合物類;亞硫酸氫鈉等。
交聯劑(C)的含量較佳為在易接著層中為2質量%以上50質量%以下,更佳為5質量%以上40%質量%以下,尤佳為8質量%以上30質量%以下。交聯劑(C)的含量若為上述下限以上,對聚乙烯醇系樹脂交聯形成為較佳,若為上述上限以下,則對黏合劑樹脂所產生之接著性效果的發揮為較佳。
聚酯系樹脂(A)與聚乙烯醇系樹脂(B)的調配比(A)/(B)較佳為以質量比計為0.8~5,更佳為1~4,尤佳為2~4,特佳為2.5~3.5。若(A)/(B)為上述下限以上,與聚酯薄膜基材的接著性為較佳,若為上述上限以下,則與偏光子、接著劑等之聚乙烯醇系樹脂層的接著性較佳。
聚酯系樹脂(A)及聚乙烯醇系樹脂(B)對交聯劑(C)的調配比((A)+(B))/(C)較佳為以質量比計為2~50,更佳為5~40,尤佳為8~30。((A)+(B))/(C)若為上述下限以上,黏合劑樹脂成分所產生之接著性效果可較佳地發揮,若為上述上限以下,則於藉由相分離所致之接著性效果較佳。
本發明之易接著層藉由採用上述組成,可顯示出與三乙醯基纖維素同等之對於偏光子或水性接著劑(特別是聚乙烯醇系的偏光子或水性接著劑)的高接著性。具體而言,藉由後述的接著性試驗之對於水系接著劑的1次剝離後之殘存面積較佳為90%以上、更佳為95%以上、尤佳為100%,5次連續剝離後之殘存面積較佳為75%以上、更佳為85%以上、尤佳為95%以上,10次連續剝離後之殘存面積較佳為50%以上、更佳為80%以上、尤佳為90%以上、再更佳為93%以上、特佳為95%以上。
(添加劑)
於本發明之易接著層中,在不妨礙本發明之效果的範圍內,亦可添加公知的添加劑,例如:界面活性劑、抗氧化劑、觸媒、耐熱安定劑、耐候安定劑、紫外線吸收劑、有機易滑劑、顏料、染料、有機或無機粒子、抗靜電劑、核劑等。
本發明中,為了更加提升易接著層的抗黏結性,較佳樣態為在易接著層中添加粒子。本發明中可使含入於易接著層中的粒子可列舉例如:二氧化鈦、硫酸鋇、碳酸鈣、硫酸鈣、氧化矽、氧化鋁、滑石、高嶺土、黏土等或此等之混合物,乃至於和其他一般的無機粒子例如:磷酸鈣、雲母、鋰蒙脫石、鋯、氧化鎢、氟化鋰、氟化鈣併用等之無機粒子,或苯乙烯系、丙烯酸系、三聚氰胺系、苯并鳥糞胺系、矽氧烷系等之有機聚合物系粒子等。
易接著層中之惰性粒子的平均粒徑(依據SEM之個數基準的平均粒徑。以下同)較佳為0.04~2.0μm,更佳為0.1~1.0μm,惰性粒子的平均粒徑若為小於0.04μm,薄膜表面的凹凸形成會不充分,故薄膜平滑性、捲取性等之取用性會降低,且貼合時的加工性會有降低的情形。反之,若超過2.0μm,會溶液發生粒子的脫落故不佳。易接著層中的粒子濃度較佳為固形成分中1~20質量%,更佳為5~15質量%。
本發明中易接著層的厚度可適當地設定在0.001~2.00μm的範圍,為了兼顧加工性與接著性,較佳為0.01~1.00μm的範圍,更佳為0.02~0.80μm,尤佳為0.05~0.50μm。易接著層的厚度若小於0.01μm,接著性會不充分。易接著層的厚度若超過2.00μm,會有發生黏著的情形。
(偏光子保護用易接著性聚酯薄膜的製造)
在本發明之偏光子保護用易接著性聚酯薄膜的製造方法中,雖以聚對苯二甲酸乙二酯(以下簡稱為PET)薄膜為例做說明,當然並非限定於此。
於使PET樹脂充分地真空乾燥之後,供給到擠壓機,自T模將約280℃的熔融PET樹脂熔融擠壓至旋轉冷卻輥做成片狀,藉由施加静電法使其冷卻固化而得到未延伸PET片材。前述未延伸PET片材,可為單層構成,亦可由共擠壓法做成複層構成。
對所得的未延伸PET片材施行單軸延伸、或雙軸延伸使其結晶配向化。例如於雙軸延伸時,係以加熱至80~120℃的輥,於長方向延伸為2.5~5.0倍,得到單軸延伸PET薄膜,然後以夾子夾著薄膜的端部,將其導入到加熱至80~180℃的熱風區域,於寬方向延伸至2.5~5.0倍。又,於單軸延伸時,係於拉幅機內延伸至2.5~5.0倍。延伸後繼續導引至140~240℃的熱處理區域,進行1~60秒的熱處理使其完成結晶配向。
易接著層可於薄膜製造後、或製造步驟中設置。就生產性考量,特佳為在薄膜製造步驟的任意階段,亦即在未延伸或單軸延伸後的PET薄膜之至少一面上塗布塗布液,形成易接著層。
用以將此塗布液塗布於PET薄膜上的方法,可用公知的任意方法。可列舉例如:反向輥塗布法、凹版塗布法、吻合塗布法、模具塗布法、輥刷塗法、噴霧塗布法、刮刀塗布法、線棒塗布法、管刮塗法、浸漬塗布法、簾幕塗布法等。此等之方法可單獨或組合進行塗布。
本發明中,較佳為最終所得到的易接著層的厚度為0.03~0.20 g/m2
。若為0.03 g/m2
以下,接著性會降低,若較0.20 g/m2
更厚,則黏著性、平滑性會降低,故不佳。
(偏光板)
本發明之偏光板為在偏光子的兩面有偏光子保護薄膜而成之偏光板,較佳係至少一面的偏光子保護薄膜為前述偏光子保護用易接著性聚酯薄膜。另一方的偏光子保護薄膜可為本發明之偏光子保護用易接著性聚酯薄膜,較佳可用由三乙醯基纖維素薄膜或丙烯酸樹脂薄膜、降莰烯系薄膜為代表的沒有雙折射的薄膜。
偏光子可列舉例如:在聚乙烯醇系薄膜中含有碘等二色性材料者。偏光子保護薄膜可與偏光子直接貼合或透過接著劑層貼合,就提升接著性之考量,較佳為透過接著劑貼合。此時,本發明之易接著層較佳為配置於偏光子面或接著劑層面。本發明之用來使聚酯薄膜接著的較佳偏光子,可列舉例如:藉由對聚乙烯醇系薄膜以碘或二色性材料進行染色/吸著,於硼酸水溶液中進行單軸延伸,於保持於延伸狀態下進行洗浄/乾燥而得到之偏光子。單軸延伸之倍率,通常為4~8倍左右。聚乙烯醇系薄膜較佳為聚乙烯醇,可使用「Kuraray Vinylon」(Kuraray(股)製)、「TohcelloVinylon」(Tohcello(股)製)、「日合Vinylon」(日本合成化學(股)製)等市售品。做為二色性材料可列舉:碘、雙偶氮化合物、聚氧甲炔(polymethine)等。
塗布於偏光子之接著劑,就使接著劑層薄化之考量,較佳為水系者,即,較佳為將接著劑成分溶解於水中者或或分散於水中者。例如,用聚乙烯醇系樹脂、胺基甲酸酯樹脂等做為主成分,為了提升接著性,按照需要可用調配有異氰酸酯系化合物、環氧化合物等之組成物。接著劑層的厚度較佳為10μm以下,更佳為5μm以下,尤佳為3μm以下。
於用聚乙烯醇系樹脂做為接著劑的主成分時,可用部分皂化聚乙烯醇、完全皂化聚乙烯醇之外,亦可用羧基改質聚乙烯醇、乙醯乙醯基改質聚乙烯醇、羥甲基改質聚乙烯醇、胺基改質聚乙烯醇等之經改質的聚乙烯醇系樹脂。接著劑中的聚乙烯醇系樹脂之濃度較佳為1~10質量%,更佳為2~7質量%。
[實施例]
接著用實施例、比較例及參考例來詳細說明本發明,但本發明當然不限定於以下之實施例。又,本發明中所用之評價方法係如下述。
(1) 玻璃轉化溫度
依據JIS K7121,使用示差掃描熱量計(Seiko Instruments製,DSC6200),使樹脂試樣10mg於25~300℃的溫度範圍以20℃/分鐘昇溫,以由DSC曲線所得之外插玻璃轉化開始溫度做為玻璃轉化溫度。
(2)數量平均分子量
將樹脂0.03g溶解於四氫呋喃10ml中,用GPC-LALLS裝置低角度光散射光度計LS-8000(東曹(股)公司製,四氫呋喃溶劑、參考:聚苯乙烯),塔柱溫度30℃,流量1 ml/分,用塔柱(昭和電工公司製shodex KF-802、804、806),測定數量平均分子量。
(3) 樹脂組成
將樹脂溶解於重氯仿中,用VARIAN公司製核磁共振分析儀(NMR) GEMINI-200,進行1
H-NMR分析由其積分比決定各組成的莫耳%比。
(4) 酸值
將1g(固體成分)的試料溶解於30ml的氯仿或二甲基甲醯胺中,以酚酞做為指示劑,用0.1N的氫氧化鈉乙醇溶液滴定,求出將試料每1g的羧基中和所必要的KOH量(mg)。
(5) 皂化值
依據JIS-K6726,用氫氧化鈉,進行聚乙烯醇樹脂的殘存醋酸基(莫耳%)之定量,以其值做為皂化值(莫耳%)。對同一試樣測定3次,以其平均值做為皂化值(莫耳%)。
(6) 偏光子保護用聚酯薄膜的全光線透過率
偏光子保護用聚酯薄膜的全光線透過率,係依據JIS K 7105,用霧度計(日本電色製,NDH2000)進行測定。
(7) 偏光子保護用聚酯薄膜的霧度
偏光子保護聚酯薄膜的霧度,係依據JIS K 7136,用霧度計(日本電色製,NDH2000)進行測定。
(8) PVA接著性
將固體成分濃度調整為5質量%的聚乙烯醇水溶液(Kuraray製PVA117),以使乾燥後的聚乙烯醇樹脂層的厚度做成為2μm的方式用線棒塗布在偏光子保護用聚酯薄膜的易接著層表面,於70℃乾燥5分鐘。聚乙烯醇水溶液係使用加入有可容易判定的紅色染料者。將作成的評價對象薄膜,使評價對象的積層薄膜之形成有聚乙烯醇樹脂層的面之相反面貼合到貼合有兩面膠帶的厚度5mm之玻璃板。接著,以間隙間隔為2mm的切割導引器切割成貫穿聚乙烯醇樹脂層到達基材薄膜的100個方格狀切痕。然後,以黏著膠帶(NICHIBAN公司製Cellophane tape(註冊商標)CT-24,24mm寬度)黏貼於方格狀切痕面。將貼合時殘存於界面的空氣以橡皮擦擠壓,使其完全密接後,實施使勁將黏著膠帶垂直拉離的此作業1次、5次、10次。以算出之聚乙烯醇樹脂層未剝離的方格數做為PVA接著性。即,於PVA層完全未剝離時,PVA接著率設為100,PVA層彎全剝離時,PVA接著率設為0。又,於1個方格內部分性剝離者,也算成已剝離的個數。
(聚酯樹脂的聚合)
在具備有攪拌機、溫度計、及部分回流式冷卻器的不銹鋼製高壓釜中,進料194.2質量份的二甲基對苯二甲酸酯、184.5質量份的間苯二甲酸二甲酯、14.8質量份的二甲基-5-鈉磺酸間苯二甲酸酯、233.5質量份二乙二醇、136.6質量份的乙二醇、及0.2質量份的鈦酸四正丁酯,以4小時的時間於160℃至220℃的溫度進行酯交換反應。接著,升溫至255℃,使反應系慢慢減壓之後,在30Pa減壓下使其反應1小時30分,得到共聚合聚酯樹脂(A-1)。得到的共聚合聚酯樹脂(A-1)為淡黃色透明。測定共聚合聚酯樹脂(A-1)的還原黏度,為0.70dl/g。以DSC得到之玻璃轉化溫度為40℃。
用同樣的方法,製得其他組成的共聚合聚酯樹脂(A-2)~(A-5)。對此等共聚合聚酯樹脂,用1
H-NMR測定之組成(莫耳%比)及其他特性示於表1。
(聚酯水分散體調整)
在具備有攪拌機、溫度計與回流裝置的反應器中,進料30質量份的聚酯樹脂(A-1)、15質量份的乙二醇正丁基醚,於110℃加熱、攪拌,將樹脂溶解。於樹脂完全溶解後,在一邊攪拌下將55質量份的水慢慢地添加到聚酯溶液中。添加後,使液體於一邊攪拌下冷卻到室溫,製作得到固體成分30質量%的乳白色聚酯水分散體(Aw-1)。以同樣方法,使用聚酯樹脂(A-2)~(A-5)代替聚酯樹脂(A-1)而製作水分散體,分別做為聚酯水分散體(Aw-2)~(Aw-5)。
(聚乙烯醇水溶液的調整)
在具備有攪拌機與溫度計的容器中,進料90質量份的水,邊攪拌下慢慢地添加10質量份聚合度500的聚乙烯醇樹脂(Kuraray製)(B-1)。添加後,於一邊攪拌、一邊加熱至95℃,使樹脂溶解。溶解後,一邊攪拌、一邊冷卻至室溫,做成固體成分10質量%的聚乙烯醇水溶液(Bw-1)。以同樣的做法,使用聚乙烯醇樹脂(B-2)~(B-7)代替聚乙烯醇樹脂(B-1),做成水溶液,分別做為(Bw-2)~(Bw-7)。聚乙烯醇樹脂(B-1)~(B-7)的皂化值示於表2。
(嵌段聚異氰酸酯交聯劑之聚合)
在具備有攪拌機、溫度計、回流冷卻管的燒瓶中,進料100質量份的以六亞甲二異氰酸酯做為原料之具有異氰酸酯構造的聚異氰酸酯化合物(旭化成化學品公司製,DuranateTPA)、55質量份的丙二醇單甲基醚乙酸酯、30質量份的聚乙二醇單甲基醚(平均分子量750),氮氣環境下、於70℃保持4小時。然後,使反應液溫度降到50℃,滴入47質量份的甲乙酮肟。進行反應液之紅外光譜之測定,確認異氰酸酯基的吸收已消失,得到固體成分75質量%的嵌段聚異氰酸酯水分散液(C-1)。
實施例1
(1)塗布液之調整
混合下述塗劑,做成聚酯系樹脂(A)/聚乙烯醇系樹脂(B)的質量比為70/30的塗布液。聚酯水分散體係使用酸值2KOH mg/g之聚酯樹脂經分散的水分散體(Aw-1),聚乙烯醇水溶液係使用皂化值為74莫耳%之聚乙烯醇經溶解的水溶液(Bw-4)。
水 40.61質量%
異丙醇 30.00質量%
聚酯水分散體(Aw-1) 11.67質量%
聚乙烯醇水溶液(Bw-4) 15.00質量%
嵌段異氰酸酯系交聯劑(C-1) 0.67質量%
粒子 1.25質量%
(平均粒徑100nm的矽石膠體、固體成分濃度40質量%)
觸媒
(有機錫系化合物固體成分濃度14質量%)0.3質量%
界面活性劑 0.5質量%
(矽氧系、固體成分濃度10質量%)
(2) 偏光子保護用聚酯薄膜的製造
將做為薄膜原料聚合物之固有黏度(溶劑:苯酚/四氯乙烷=60/40)為0.62 dl/g且實質上未含有粒子的PET樹脂顆粒,於133 Pa的減壓下,於135℃乾燥6小時。然後,供給至擠壓機中,於約280℃,熔融擠壓成片狀,在表面溫度保持為20℃之旋轉冷卻金屬輥上使其急冷密接固化,得到未延伸PET片。
將此未延伸PET片以經加熱的輥群及紅外線加熱器加熱到100℃,然後以有周速差的輥群沿長的方向延伸為3.5倍,得到單軸延伸PET薄膜。
接著,將前述塗布液以輥塗布法塗布於PET薄膜之一面後,於80℃乾燥15秒。又,調整使最終(雙軸延伸後)的乾燥後之塗布量為0.12g/m2
。接著,用拉幅機,於150℃沿寬方向延伸為4.0倍,於使薄膜寬方向的長度固定之狀態下,於230℃加熱0.5秒,再於230℃進行10秒3%的寬方向之鬆弛處理,得到厚度38μm的偏光子保護聚酯薄膜。評價結果示於表3。
實施例2
除了將聚酯水分散體變更為由酸值為4 KOH mg/g的聚酯樹脂分散所成的水分散體(Aw-2)之外,以與實施例1同樣的做法,製得偏光子保護用聚酯薄膜。
實施例3
除了將聚酯水分散體變更為由酸值為6 KOH mg/g的聚酯樹脂分散所成的水分散體(Aw-3)之外,以與實施例1同樣的做法,製得偏光子保護用聚酯薄膜。
實施例4
除了將聚乙烯醇水溶液變更為聚乙烯醇的皂化值為79莫耳%之聚乙烯醇水溶液(Bw-3)之外,以與實施例1同樣的做法,製得偏光子保護用聚酯薄膜。
實施例5
除了變更為聚乙烯醇的皂化值為83莫耳%之聚乙烯醇水溶液(Bw-2)之外,以與實施例1同樣的做法,製得偏光子保護用聚酯薄膜。
實施例6
混合下述塗劑,除了使聚酯系樹脂(A)/聚乙烯醇系樹脂(B)的質量比變更為60/40之外,以與實施例1同樣的做法,製得偏光子保護用聚酯薄膜。
水 37.28質量%
異丙醇 30.00質量%
聚酯水分散體(Aw-1) 10.00質量%
聚乙烯醇水溶液(Bw-4) 20.00質量%
嵌段異氰酸酯系交聯劑(C-1) 0.67質量%
粒子 1.25質量%
(平均粒徑100nm的矽石膠體、固體成分濃度40質量%)
觸媒
(有機錫系化合物固體成分濃度14質量%)0.3質量%
界面活性劑 0.5質量%
(矽氧系、固體成分濃度10質量%)
實施例7
混合下述塗劑,除了使聚酯系樹脂(A)/聚乙烯醇系樹脂(B)的質量比變更為80/20之外,以與實施例1同樣的做法,製得偏光子保護用聚酯薄膜。
水 43.95質量%
異丙醇 30.00質量%
聚酯水分散體(Aw-1) 13.33質量%
聚乙烯醇水溶液(Bw-4) 10.00質量%
嵌段異氰酸酯系交聯劑(C-1) 0.67質量%
粒子 1.25質量%
(平均粒徑100nm的矽石膠體、固體成分濃度40質量%)
觸媒
(有機錫系化合物固體成分濃度14質量%)0.3質量%
界面活性劑 0.5質量%
(矽氧系、固體成分濃度10質量%)
實施例8
混合下述塗劑,除了使聚酯系樹脂(A)/聚乙烯醇系樹脂(B)的質量比變更為50/50之外,以與實施例1同樣的做法,製得偏光子保護用聚酯薄膜。
水 33.95質量%
異丙醇 30.00質量%
聚酯水分散體(Aw-1) 8.33質量%
聚乙烯醇水溶液(Bw-4) 25.00質量%
嵌段異氰酸酯系交聯劑(C-1) 0.67質量%
粒子 1.25質量%
(平均粒徑100nm的矽石膠體、固體成分濃度40質量%)
觸媒
(有機錫系化合物固體成分濃度14質量%)0.3質量%
界面活性劑 0.5質量%
(矽氧系、固體成分濃度10質量%)
實施例9
除了將塗布液的組成變更如下述之外,係以與實施例1同樣的做法,製得偏光子保護用聚酯薄膜。
水 40.87質量%
異丙醇 30.00質量%
聚酯水分散體(Aw-1) 11.67質量%
聚乙烯醇水溶液(Bw-4) 15.00質量%
三聚氰胺系交聯劑(C-2) 0.71質量%
(Nikalac MX-042,三和Chemical製固體成分濃度70%)
粒子 1.25質量%
(平均粒徑100nm的矽石膠體、固體成分濃度40質量%)
界面活性劑 0.5質量%
(矽氧系、固體成分濃度10質量%)
實施例10
除了將聚乙烯醇水溶液變更為使聚乙烯醇的皂化值為70莫耳%之聚乙烯醇溶解而成的水溶液(Bw-5)之外,以與實施例1同樣的做法,製得偏光子保護用聚酯薄膜。
實施例11
除了將聚乙烯醇水溶液變更為使聚乙烯醇的皂化值為67莫耳%之聚乙烯醇溶解而成的水溶液(Bw-6)之外,以與實施例1同樣的做法,製得偏光子保護用聚酯薄膜。
實施例12
除了將塗布液的組成變更如下述之外,以與實施例1同樣的做法,製得偏光子保護用聚酯薄膜。
水 40.33質量%
異丙醇 30.00質量%
聚酯水分散體(Aw-1) 11.67質量%
聚乙烯醇水溶液(Bw-2) 15.00質量%
噁唑啉系交聯劑(C-3) 1.25質量%
(EpocrosWS-500、日本觸媒製,固體成分濃度40質量%)
粒子 1.25質量%
(平均粒徑100nm的矽石膠體、固體成分濃度40質量%)
界面活性劑 0.5質量%
(矽氧系、固體成分濃度10質量%)
實施例13
除了將聚酯水分散體變更為使由酸值為10 KOH mg/g的聚酯樹脂分散而成的水分散體(Aw-5)之外,以與實施例1同樣的做法,製得偏光子保護用聚酯薄膜。
比較例1
混合下述塗劑,除了使聚酯系樹脂(A)/聚乙烯醇系樹脂(B)的質量比變更為100/0之外,以與實施例1同樣的做法,製得偏光子保護用聚酯薄膜。
水 50.62質量%
異丙醇 30.00質量%
聚酯水分散體(Aw-1) 16.66質量%
嵌段異氰酸酯系交聯劑(C-1) 0.67質量%
粒子 1.25質量%
(平均粒徑100nm的矽石膠體、固體成分濃度40質量%)
觸媒
(有機錫系化合物固體成分濃度14質量%)0.3質量%
界面活性劑 0.5質量%
(矽氧系、固體成分濃度10質量%)
比較例2
混合下述塗劑,除了使聚酯系樹脂(A)/聚乙烯醇系樹脂(B)的質量比變更為0/100之外,以與實施例1同樣的做法,製得偏光子保護用聚酯薄膜。
水 17.28質量%
異丙醇 30.00質量%
聚乙烯醇水溶液(Bw-4) 50.00質量%
嵌段異氰酸酯系交聯劑(C-1) 0.67質量%
粒子 1.25質量%
(平均粒徑100nm的矽石膠體、固體成分濃度40質量%)
觸媒
(有機錫系化合物固體成分濃度14質量%)0.3質量%
界面活性劑 0.5質量%
(矽氧系、固體成分濃度10質量%)
比較例3
除了將聚酯水分散體變更為由酸值為25KOH mg/g的聚酯樹脂分散所成的水分散體(Aw-3)之外,以與實施例1同樣的做法,製得偏光子保護用聚酯薄膜。
比較例4
除了將聚乙烯醇水溶液變更為使皂化值為88莫耳%溶解而成之聚乙烯醇水溶液(Bw-1)之外,以與實施例1同樣的做法,製得偏光子保護用聚酯薄膜。
比較例5
除了將聚乙烯醇水溶液變更為使聚乙烯醇的皂化值為40莫耳%之聚乙烯醇溶解而成的水溶液(Bw-7)之外,以與實施例1同樣的做法,製得偏光子保護用聚酯薄膜。
比較例6
混合下述塗劑,除了變更為不混合交聯劑之外,以與實施例1同樣的做法,製得偏光子保護用聚酯薄膜。
水 41.58質量%
異丙醇 30.00質量%
聚酯水分散體(Aw-1) 11.67質量%
聚乙烯醇水溶液(Bw-4) 15.00質量%
粒子 1.25質量%
(平均粒徑100nm的矽石膠體、固體成分濃度40質量%)
界面活性劑 0.5質量%
(矽氧系、固體成分濃度10質量%)
參考例1
使用TAC薄膜(富士軟片(股)公司製,厚度80μm、經皂化處理)做為偏光子保護用薄膜,進行前述接著性試驗的結果表示如下。
〔產業上之可利用性〕
本發明之偏光子保護用易接著性聚酯薄膜具有和偏光子、水系接著劑之間的高接著性。因此,可適宜做為偏光子保護構件使用。
Claims (5)
- 一種偏光子保護用易接著性聚酯薄膜,其係在至少一面上具有易接著層;前述易接著層含有聚酯系樹脂(A)、聚乙烯醇系樹脂(B)、及交聯劑(C);前述聚酯系樹脂(A)的酸值為20KOH mg/g以下;前述聚乙烯醇系樹脂(B)的皂化值為60~85莫耳%。
- 如申請專利範圍第1項之偏光子保護用易接著性聚酯薄膜,其中前述聚酯樹脂(A)於二羧酸成分中含有1~15莫耳%的5-磺酸基間苯二甲酸。
- 如申請專利範圍第1或2項之偏光子保護用易接著性聚酯薄膜,其中前述交聯劑(C)為異氰酸酯化合物或三聚氰胺化合物。
- 如申請專利範圍第1或2項之偏光子保護用易接著性聚酯薄膜,其中前述易接著層中,聚酯系樹脂(A)、聚乙烯醇系樹脂(B)及交聯劑(C)之質量比係滿足下式:0.8≦(A)/(B)≦5 0.2≦((A)+(B))/(C)≦50。
- 一種偏光板,其係在偏光子的兩面具有偏光子保護薄膜而成;其至少一面的偏光子保護膜係如申請專利範圍第1至4項中任一項之偏光子保護用易接著性聚酯薄膜。
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| JP6024271B2 (ja) * | 2012-08-08 | 2016-11-16 | 東洋紡株式会社 | 偏光子保護用アクリル系フィルム、偏光板および液晶表示装置 |
| JP6094865B2 (ja) * | 2013-01-10 | 2017-03-15 | Dic株式会社 | 易接着剤組成物、積層ポリエステル樹脂フィルム及び太陽電池バックシート |
| JP5878158B2 (ja) * | 2013-04-05 | 2016-03-08 | 三菱樹脂株式会社 | 積層ポリエステルフィルム |
| KR20150145548A (ko) * | 2014-06-20 | 2015-12-30 | 동우 화인켐 주식회사 | 접착제 조성물 및 이를 포함하는 편광판 |
| JP6261469B2 (ja) * | 2014-07-25 | 2018-01-17 | 富士フイルム株式会社 | 積層フィルム、光学フィルム、偏光子保護フィルム、偏光板、画像表示装置及び積層フィルムの製造方法 |
| EP3026469B1 (en) * | 2014-11-27 | 2023-01-11 | Canon Kabushiki Kaisha | Optical element and method for producing optical element |
| CN110402405B (zh) * | 2017-03-15 | 2022-02-11 | 日东电工株式会社 | 光学层叠体及光学层叠体的制造方法 |
| KR102438334B1 (ko) * | 2018-01-19 | 2022-08-31 | 도요보 가부시키가이샤 | 이접착성 폴리에스테르 필름 |
| TWI763976B (zh) * | 2018-07-25 | 2022-05-11 | 日商日東電工股份有限公司 | 易接著薄膜及其製造方法、偏光板、以及影像顯示裝置 |
| KR102052843B1 (ko) * | 2019-01-07 | 2019-12-06 | 도레이첨단소재 주식회사 | 편광자 보호용 폴리에스테르 필름과 그 제조방법 및 이를 구비하는 편광판 |
| JP7605110B2 (ja) * | 2019-07-23 | 2024-12-24 | 東洋紡株式会社 | 易接着性ポリエステルフィルム |
| CN113773546B (zh) * | 2021-09-10 | 2022-12-06 | 中国科学技术大学先进技术研究院 | 一种亲水性聚酯薄膜及其制备方法、以及显示装置 |
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- 2012-02-01 KR KR1020137022462A patent/KR101577513B1/ko active Active
- 2012-02-01 TW TW101103262A patent/TWI465495B/zh active
- 2012-02-01 WO PCT/JP2012/052279 patent/WO2012105607A1/ja not_active Ceased
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| TW201043675A (en) * | 2009-04-30 | 2010-12-16 | Nitto Denko Corp | Adhesive composition for optical film, adhesive layer for optical film, and adhesive optical film, and image display device |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012105607A1 (ja) | 2012-08-09 |
| KR101577513B1 (ko) | 2015-12-21 |
| CN103339538A (zh) | 2013-10-02 |
| KR20140015346A (ko) | 2014-02-06 |
| TW201233716A (en) | 2012-08-16 |
| JP5109094B2 (ja) | 2012-12-26 |
| JP2012159753A (ja) | 2012-08-23 |
| CN103339538B (zh) | 2015-06-10 |
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