TWI801340B - 導電性膜 - Google Patents
導電性膜 Download PDFInfo
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- TWI801340B TWI801340B TW106121243A TW106121243A TWI801340B TW I801340 B TWI801340 B TW I801340B TW 106121243 A TW106121243 A TW 106121243A TW 106121243 A TW106121243 A TW 106121243A TW I801340 B TWI801340 B TW I801340B
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- Prior art keywords
- conductive
- resin layer
- layer
- conductive film
- aforementioned
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
一種導電性膜,係包含樹脂層及導電層,在25℃之前述樹脂層的儲存彈性模數為大於10MPa且小於1000MPa,前述導電層的表面電阻值為1000Ω/sq.以下。
Description
本發明係有關於一種導電性膜。
先前,作為透明導電性構件,係已知一種將氧化銦薄膜形成在玻璃板上而成之導電性玻璃。但是,因為導電性玻璃之基材為玻璃,所以可撓性及加工性較差,而有難以依照用途應用之情形。因此,作為具有優異的可撓性及加工性之透明導電性構件,有提案揭示一種利用樹脂之導電性膜(參照專利文獻1及2)。
又,已知如專利文獻3的技術。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特公昭61-026649號公報
[專利文獻2]日本特開2014-168886號公報
[專利文獻3]國際公開第2015/178370號
近年來,具備有機電激發光元件(以下,有適當地稱為「有機EL元件」之情形)的顯示器裝置之研討係進展中。 具備如此的有機EL元件之顯示器裝置,係被期望能夠實現可折疊式(foldable)、可捲曲式(rollable)之新穎的性能。因此,為了實現如此的性能,係被要求開發一種具有較高的導電性,同時具有優異的耐彎曲性之導電性膜。
作為導電性膜,專利文獻1係提案揭示一種由苯乙烯-二烯系嵌段共聚物及噻吩(thiophene)系共聚物所構成之導電性膜。但是,專利文獻1記載的導電性膜係缺乏導電性。
又,作為導電性膜,專利文獻2係提案揭示一種包含透明樹脂膜、及形成在該透明樹脂膜上的導電層之透明導電性膜。但是,專利文獻2記載的透明導電性膜係缺乏耐彎曲性。
而且,專利文獻3係記載一種由預定的嵌段共聚物氫化物所構成之光學用薄膜。又,專利文獻3係記載一種透明導電膜作為該光學用薄膜用途。但是,專利文獻3未記載該透明導電膜的具體結構。
本發明係鑒於前述課題而發明,其目的係提供一種導電性及耐彎曲性的雙方均優異之導電性膜。
本發明者為了解決前述課題而專心研討之結果,發現藉由將在25℃具有預定的儲存彈性模數的樹脂層、與具有預定的表面電阻值的導電層組合,能夠實現導電性及耐彎曲性的雙方均優異之導電性膜,而完成了本發明。亦即,本發明係包含以下項目。
[1]一種導電性膜,係包含樹脂層及導電層,在 25℃之前述樹脂層的儲存彈性模數為大於10MPa且小於1000MPa,前述導電層的表面電阻值為1000Ω/sq.以下。
[2]如[1]所述之導電性膜,其中在25℃之前述樹脂層的彎曲彈性模數為500MPa以下。
[3]如[1]或[2]所述之導電性膜,其中前述樹脂層係含有嵌段共聚物氫化物的烷氧矽烷基改質物[3],前述烷氧矽烷基改質物[3],係將嵌段共聚物[1]的主鏈及側鏈的碳-碳不飽和鍵及芳香環的碳-碳不飽和鍵氫化而成之氫化物[2]的烷氧矽烷基改質物,前述嵌段共聚物[1],係具有:,在每1分子前述嵌段共聚物[1]中為2個以上之含有芳香族乙烯系化合物單元的聚合物嵌段[A];及,在每1分子前述嵌段共聚物[1]中為1個以上之含有鏈狀共軛二烯化合物單元的聚合物嵌段[B],前述聚合物嵌段[A]在前述嵌段共聚物[1]的全體佔有之重量分率wA、與前述聚合物嵌段[B]在前述嵌段共聚物[1]的全體佔有之重量分率wB之比(wA/wB)為20/80~60/40。
[4]如[1]至[3]項中任一項所述之導電性膜,其中前述導電層係包含選自由金屬、導電性奈米線及導電性聚合物所組成群組之至少1種類的導電材料。
依照本發明,能夠提供一種導電性及耐彎曲性的雙方均優異之導電性膜。
10、20、30、40‧‧‧導電性膜
110‧‧‧樹脂層
120、140‧‧‧導電層
130、150‧‧‧支撐體層
第1圖係示意性顯示作為本發明的第一實施形態之導電性膜之剖面圖。
第2圖係示意性顯示作為本發明的第二實施形態之導電性膜之剖面圖。
第3圖係示意性顯示作為本發明的第三實施形態之導電性膜之剖面圖。
第4圖係示意性顯示作為本發明的第四實施形態之導電性膜之剖面圖。
[用以實施發明之形態]
以下,揭示實施形態及例示物而詳細地說明本發明。但是,本發明係不被以下揭示的實施形態及例示物限定,在不脫離本發明的申請專利範圍及其均等範圍的範圍內,能夠任意地變更而實施。
[1.導電性膜的概要]
本發明的導電性膜係包含樹脂層及導電層。又,本發明的導電性膜亦可視需要而包含任意層。但是,通常在導電層與樹脂層之間係不設置任意層,導電層與樹脂層係直接接觸。
[2.樹脂層]
[2.1.在25℃之樹脂層的儲存彈性模數]
樹脂層係由樹脂所構成之層,在25℃具有預定範圍的儲存彈性模數。
在25℃之樹脂層的具體的儲存彈性模數,係通常大於 10MPa,以大於15MPa為佳,以大於30MPa為較佳,而且,通常小於1000MPa,以小於950MPa為佳,以小於900MPa為較佳。
藉由在25℃之樹脂層的儲存彈性模數落入前述範圍內,能夠有效地提高導電性膜的耐彎曲性。在此,所謂導電性膜的耐彎曲性,係意味著即便將該導電性膜彎曲,導電層的導電性亦不容易降低,而且不容易產生白化等的外觀變化之性質。具體而言,藉由在25℃之樹脂層的儲存彈性模數為大於前述範圍的下限值,將導電性膜折彎時,能夠不容易產生外觀變化。又,藉由在25℃之樹脂層的儲存彈性模數為小於前述範圍的上限值,將導電性膜折彎時,能夠抑制導電層的導電性降低。
樹脂層的儲存彈性模數,係能夠使用動態黏彈性裝置,在頻率1Hz的條件下測定。
[2.2.在樹脂層所含有的樹脂]
作為樹脂層所含有的樹脂,通常係使用含有聚合物,視需要而進一步含有任意成分之樹脂。作為如此的聚合物,係以使用特定的烷氧矽烷基(alkoxy silyl)改質物[3]為佳。該烷氧矽烷基改質物[3],係將特定的嵌段共聚物[1]的不飽和鍵氫化而成之氫化物[2]的烷氧矽烷基改質物。
(2.2.1.嵌段共聚物[1])
嵌段共聚物[1],係具有在每1分子嵌段共聚物[1]中為2個以上的聚合物嵌段[A]、及在每1分子嵌段共聚物[1]中為1個以上的聚合物嵌段[B]之嵌段共聚物。
聚合物嵌段[A],係含有芳香族乙烯系化合物 (aromatic vinyl compound)單元之聚合物嵌段。在此,所謂芳香族乙烯系化合物單元,係指具有將芳香族乙烯系化合物聚合而形成的結構之結構單元。
作為對應聚合物嵌段[A]所具有的芳香族乙烯系化合物單元之芳香族乙烯系化合物,可舉出,例如,苯乙烯;α-甲基苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、2,4-二甲基苯乙烯、2,4-二異丙基苯乙烯、4-第三丁基苯乙烯、5-第三丁基-2-甲基苯乙烯等的、具有碳數1~6的烷基作為取代基之苯乙烯類;4-氯苯乙烯、二氯苯乙烯、4-單氟苯乙烯等的、具有鹵素原子作為取代基之苯乙烯類;4-甲氧基苯乙烯等的、具有碳數1~6的烷氧基作為取代基之苯乙烯類;4-苯基苯乙烯等的、具有芳基作為取代基之苯乙烯類;1-乙烯基萘、2-乙烯基萘等的乙烯基萘類等。該等可單獨使用1種類,亦可以任意比率組合2種類以上而使用。該等之中,從能夠降低吸濕性的觀點,以苯乙烯、具有碳數1~6的烷基作為取代基之苯乙烯類等的不含有極性基的芳香族乙烯系化合物為佳,從工業上容易取得的觀點,以苯乙烯為特佳。
在聚合物嵌段[A]之芳香族乙烯系化合物單元的含有率,係以90重量%以上為佳,以95重量%以上為較佳,以99重量%以上為特佳。藉由在聚合物嵌段[A]之芳香族乙烯系化合物單元的量成為如前述之多,能夠提高樹脂層的硬度及耐熱性。
聚合物嵌段[A],係除了芳香族乙烯系化合物單元以外,亦可含有任意結構單元。聚合物嵌段[A]可單獨含有1 種類的任意結構單元,亦可以任意比率組合2種類以上而含有。
作為聚合物嵌段[A]能夠含有的任意結構單元,可舉出,例如,鏈狀共軛二烯化合物單元。在此,所謂鏈狀共軛二烯化合物單元,係指具有將鏈狀共軛二烯化合物聚合而形成的結構之結構單元。作為對應鏈狀共軛二烯化合物單元之鏈狀共軛二烯化合物,可舉出,例如,與作為對應聚合物嵌段[B]所具有之鏈狀共軛二烯化合物單元之鏈狀共軛二烯化合物的例子所舉出者相同的例子。
又,作為聚合物嵌段[A]能夠含有的任意結構單元,可舉出,例如,具有將芳香族乙烯系化合物及鏈狀共軛二烯化合物以外的任意不飽和化合物聚合而形成的結構之結構單元。作為任意不飽和化合物,可舉出,例如,鏈狀乙烯系化合物、環狀乙烯系化合物等的乙烯系化合物;不飽和的環狀酸酐;不飽和醯亞胺化合物等。該等化合物亦可具有腈基、烷氧基羰基、羥羰基、或鹵素基等的取代基。該等之中,從吸濕性的觀點而言,係以乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯、1-十二烯、1-二十烯、4-甲基-1-戊烯、4,6-二甲基-1-庚烯等的、每1分子之碳數為2~20的鏈狀烯烴;乙烯基環己烷等的、每1分子之碳數為5~20的環狀烯烴;等的不具有極性基的乙烯系化合物為佳,以每1分子之碳數為2~20的鏈狀烯烴為較佳,以乙烯、丙烯為特佳。
在聚合物嵌段[A]之任意結構單元的含有率,係以10重量%以下為佳,以5重量%以下為較佳、以1重量%以下為特佳。
在1分子的嵌段共聚物[1]中之聚合物嵌段[A]的數目,係以2個以上為佳,以5個以下為佳,以4個以下為較佳,以3個以下為特佳。在1分子中之複數個聚合物嵌段[A]可互相相同,亦可互為不同。
在1分子的嵌段共聚物[1]中存在複數個不同聚合物嵌段[A]時,將在聚合物嵌段[A]之中,重量平均分子量為最大的聚合物嵌段的重量平均分子量設為Mw(A1),重量平均分子量為最小的聚合物嵌段的重量平均分子量設為Mw(A2)。此時,Mw(A1)與Mw(A2)之比「Mw(A1)/Mw(A2)」係以4.0以下為佳,以3.0以下為較佳,以2.0以下為特佳。藉此,能夠將各種物性值的偏差抑制為較小。
聚合物嵌段[B],係含有鏈狀共軛二烯化合物單元之聚合物嵌段。如前述,所謂鏈狀共軛二烯化合物單元,係指具有將鏈狀共軛二烯化合物聚合而形成的結構之結構單元。
作為對應該聚合物嵌段[B]所具有的鏈狀共軛二烯化合物單元之鏈狀共軛二烯化合物,可舉出,例如,1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯、1,3-戊二烯等。該等可單獨使用1種類,亦可以任意比率組合2種類以上而使用。其中,從能夠降低吸濕性的觀點,以不含有極性基的鏈狀共軛二烯化合物為佳,以1,3-丁二烯、異戊二烯為特佳。
在聚合物嵌段[B]之鏈狀共軛二烯化合物單元的含有率,係以70重量%以上為佳,以80重量%以上為較佳,以90重量%以上為特佳。藉由在聚合物嵌段[B]之鏈狀共軛二烯化合物單元的量成為如前述之多,能夠使樹脂層的可撓性提 升。
聚合物嵌段[B],係除了鏈狀共軛二烯化合物單元以外,亦可含有任意結構單元。聚合物嵌段[B]可單獨含有1種類的任意結構單元,亦可以任意比率組合2種類以上而含有。
作為聚合物嵌段[B]能夠含有的任意結構單元,可舉出,例如,具有將芳香族乙烯系化合物單元、以及芳香族乙烯系化合物及鏈狀共軛二烯化合物以外的任意不飽和化合物聚合而形成的結構之結構單元。作為具有將該等芳香族乙烯系化合物單元、以及任意不飽和化合物聚合而形成的結構之結構單元,可舉出,例如,與作為在聚合物嵌段[A]所含有者已例示之物相同的例子。
在聚合物嵌段[B]之任意結構單元的含有率,係以30重量%以下為佳,以20重量%以下為較佳,以10重量%以下為特佳。藉由在聚合物嵌段[B]之任意結構單元的含有率較低,能夠提升樹脂層的可撓性。
在1分子嵌段共聚物[1]中之聚合物嵌段[B]的數目,係通常為1個以上,亦可為2個以上。在嵌段共聚物[1]之聚合物嵌段[B]的數目為2個以上時,該等聚合物嵌段[B]可互相相同,亦可互為不同。
在1分子的嵌段共聚物[1],存在複數個不同的聚合物嵌段[B]時,將在聚合物嵌段[B]之中,重量平均分子量為最大的聚合物嵌段的重量平均分子量設為Mw(B1),重量平均分子量為最小的聚合物嵌段的重量平均分子量設為Mw(B2)。此時,Mw(B1)與Mw(B2)之比「Mw(B1)/Mw(B2)」係以4.0以 下為佳,以3.0以下為較佳,以2.0以下為特佳。藉此,能夠將各種物性值的偏差抑制為較小。
嵌段共聚物[1]的嵌段形態可為鏈狀型嵌段,亦可為徑向型嵌段。其中,鏈狀型嵌段因具有優異的機械強度,乃是較佳。嵌段共聚物[1]係具有鏈狀型嵌段的形態時,嵌段共聚物[1]的分子鏈的兩端為聚合物嵌段[A],能夠將樹脂層的黏性抑制為適當較低的值,因而較佳。
嵌段共聚物[1]之特佳的嵌段形態,係如[A]-[B]-[A]所示、將聚合物嵌段[A]鍵結在聚合物嵌段[B]的兩端而成之三嵌段共聚物;如[A]-[B]-[A]-[B]-[A]所示、將聚合物嵌段[B]鍵結在聚合物嵌段[A]的兩端,進而將聚合物嵌段[A]分別鍵結在該兩聚合物嵌段[B]的另一端而成之五嵌段共聚物。特別是[A]-[B]-[A]的三嵌段共聚物,因為容易製造且能夠使物性容易地落入所需要的範圍內,乃是特佳。
在嵌段共聚物[1],聚合物嵌段[A]在嵌段共聚物[1]的全體佔有之重量分率wA、與聚合物嵌段[B]在嵌段共聚物[1]的全體佔有之重量分率wB之比(wA/wB)係落入特定範圍內。具體而言,前述的比(wA/wB)係通常為20/80以上,以25/75以上為佳,以30/70以上為較佳,以40/60以上為特佳,通常為60/40以下,以55/45以下為佳。藉由前述的比wA/wB為前述範圍的下限值以上,能夠提升樹脂層的硬度及耐熱性,或是減小雙折射。又,藉由前述的比wA/wB為前述範圍的上限值以下,能夠使樹脂層的可撓性提升。在此,聚合物嵌段[A]的重量分率wA係表示聚合物嵌段[A]全體的重量分率,聚合物嵌 段[B]的重量分率wB係表示聚合物嵌段[B]全體的重量分率。
前述的嵌段共聚物[1]的重量平均分子量(Mw),係以40,000以上為佳,以50,000以上為較佳,以60,000以上為特佳,以200,000以下為佳,以150,000以下為較佳,以100,000以下為特佳。
又,嵌段共聚物[1]的分子量分佈(Mw/Mn),係以3以下為佳,以2以下為較佳,以1.5以下為特佳,以1.0以上為佳。在此,Mn係表示數量平均分子量。
前述嵌段共聚物[1]的重量平均分子量(Mw)及分子量分佈(Mw/Mn),係能夠藉由以四氫呋喃(THF)作為溶劑之凝膠滲透層析法(GPC),設為聚苯乙烯換算之值而測定。
作為嵌段共聚物[1]的製造方法,可舉出,例如,使用活性陰離子聚合等的方法,使含有芳香族乙烯系化合物之單體組合物(a)、與含有鏈狀共軛二烯化合物之單體組合物(b)交替地聚合之方法;及使含有芳香族乙烯系化合物之單體組合物(a)、與含有鏈狀共軛二烯化合物之單體組合物(b)依照順序聚合之後,藉由偶合劑使聚合物嵌段[B]的末端彼此偶合之方法。
單體組合物(a)中的芳香族乙烯系化合物的含量,係以90重量%以上為佳,以95重量%以上為較佳,以99重量%以上為特佳。又,單體組合物(a)亦可含有芳香族乙烯系化合物以外的任意單體成分。作為任意單體成分,可舉出,例如,鏈狀共軛二烯化合物、任意不飽和化合物。任意單體成分的量,係相對於單體組合物(a),以10重量%以下為佳,以5重 量%以下為較佳、以1重量%以下為特佳。
單體組合物(b)中的鏈狀共軛二烯化合物的含量,係以70重量%以上為佳,以80重量%以上為較佳,以90重量%以上為特佳。又,單體組合物(b)亦可含有鏈狀共軛二烯化合物以外的任意單體成分。作為任意單體成分,可舉出芳香族乙烯系化合物、任意不飽和化合物。任意單體成分的量,係相對於單體組合物(b),以30重量%以下為佳,以20重量%以下為較佳,以10重量%以下為特佳。
作為將單體組合物聚合而得到各自的聚合物嵌段之方法,能夠使用,例如,自由基聚合、陰離子聚合、陽離子聚合、配位陰離子聚合、配位陽離子聚合等。就使聚合操作及在後續步驟之氫化反應容易進行的觀點而言,係以藉由活性聚合(living polymerization)進行自由基聚合、陰離子聚合及陽離子聚合等的方法為佳,以藉由活性陰離子聚合進行的方法為特佳。
聚合係能夠在聚合起始劑的存在下進行。例如,在活性陰離子聚合時,能夠使用正丁基鋰、第二丁基鋰、第三丁基鋰、己基鋰、苯基鋰等的單有機鋰;二鋰甲烷、1,4-二鋰丁烷、1,4-二鋰-2-乙基環己烷等的多官能性有機鋰化合物等作為聚合起始劑。該等可單獨使用1種類,亦可以任意比率組合2種類以上而使用。
聚合溫度係以0℃以上為佳,以10℃以上為較佳,以20℃以上為特佳,以100℃以下為佳,以80℃以下為較佳、以70℃以下為特佳。
聚合反應形態,能夠使用,例如,溶液聚合及漿料聚合等。其中,若使用溶液聚時,則容易除去反應熱。
進行溶液聚合時,作為溶劑,可使用能夠溶解在各步驟中所得到的聚合物之惰性溶劑。作為惰性溶劑,可舉出,例如,正丁烷、正戊烷、異戊烷、正己烷、正庚烷、異辛烷等的脂肪族烴溶劑;環戊烷、環己烷、甲基環戊烷、甲基環己烷、十氫萘、雙環[4.3.0]壬烷、三環[4.3.0.12,5]癸烷等的脂環式烴溶劑;苯、甲苯等的芳香族烴溶劑等。該等可單獨使用1種類,亦可以任意比率組合2種類以上而使用。其中,若使用脂環式烴溶劑作為溶劑,則在氫化反應中亦能夠直接使用其作為惰性溶劑,且對嵌段共聚物[1]的溶解性亦良好,因而較佳。溶劑的使用量,係相對於全部使用單體100重量份,以200重量份~2000重量份為佳。
各自的單體組合物係含有2種以上的單體時,能夠使用無規化劑(randomizer),以抑制只有某一成分的鏈變長。特別是藉由陰離子聚合進行聚合反應時,例如,以使用路易斯鹼化合物作為無規化劑為佳。作為路易斯鹼化合物,可舉出,例如,二甲醚、二乙醚、二異丙醚、二丁醚、四氫呋喃、二苯基醚、乙二醇二乙醚、乙二醇甲基苯基醚等的醚化合物;四甲基乙二胺、三甲胺、三乙胺、吡啶(pyridine)等的第3級胺化合物;第三戊基氧化鉀、第三丁基氧化鉀等的鹼金屬烷氧化物化合物;三苯基膦等的膦化合物等。該等可單獨使用1種類,亦可以任意比率組合2種類以上而使用。
(2.2.2.氫化物[2])
氫化物[2],係將嵌段共聚物[1]的不飽和鍵氫化而得到之聚合物。在此,被氫化之嵌段共聚物[1]的不飽和鍵,係包含嵌段共聚物[1]的主鏈及側鏈的碳-碳不飽和鍵、以及芳香族性及非芳香族性的碳-碳不飽和鍵之任一者。
氫化率,係以嵌段共聚物[1]的主鏈及側鏈的碳-碳不飽和鍵及芳香環的碳-碳不飽和鍵之90%以上為佳、以97%以上為較佳、以99%以上為特佳。氫化率越高,能夠使樹脂層的透明性、耐熱性及耐候性成為良好,而且容易使樹脂層的雙折射減小。在此,氫化物[2]的氫化率係能夠藉由1H-NMR測定而求取。
特別是,非芳香族性的碳-碳不飽和鍵之氫化率,係以95%以上為佳,以99%以上為較佳。藉由提高非芳香族性的碳-碳不飽和鍵之氫化率,能夠進一步提高樹脂層的耐光性及耐氧化性。
又,芳香族性的碳-碳不飽和鍵之氫化率,係以90%以上為佳,以93%以上為較佳,以95%以上為特佳。藉由提高芳香環的碳-碳不飽和鍵之氫化率,因為將聚合物嵌段[A]氫化而得到的聚合物嵌段之玻璃轉移溫度變高,所以能夠有效地提高樹脂層的耐熱性。而且,能夠降低樹脂層的光彈性係數。
氫化物[2]的重量平均分子量(Mw),係以40,000以上為佳,以50,000以上為較佳,以60,000以上為特佳,以200,000以下為佳,以150,000以下為較佳,以100,000以下為特佳。藉由氫化物[2]的重量平均分子量(Mw)落入前述範圍內,能夠使樹脂層的機械強度及耐熱性提升,而且容易使樹脂 層的雙折射減小。
氫化物[2]的分子量分佈(Mw/Mn),係以3以下為佳,以2以下為較佳,以1.5以下為特佳,以1.0以上為佳。藉由氫化物[2]的分子量分佈(Mw/Mn)落入前述範圍內,能夠使樹脂層的機械強度及耐熱性提升,而且容易使樹脂層的雙折射減小。
氫化物[2]的重量平均分子量(Mw)及分子量分佈(Mw/Mn),係能夠藉由以四氫呋喃作為溶劑之凝膠滲透層析法(GPC),設為聚苯乙烯換算之值而測定。
前述的氫化物[2],係能夠藉由將嵌段共聚物[1]氫化而製造。作為氫化方法,係以能夠提高氫化率、且嵌段共聚物[1]的鏈切斷反應較少的氫化方法為佳。作為如此的氫化方法,可舉出,例如,國際公開第2011/096389號、國際公開第2012/043708號記載之方法。
作為具體的氫化方法之例子,可舉出,例如,使用含有選自由鎳、鈷、鐵、銠、鈀、鉑、釕、及錸所組成群組的至少1種金屬之氫化觸媒而進行氫化之方法。氫化觸媒可單獨使用1種類,亦可以任意比率組合2種類以上而使用。氫化觸媒,係能夠使用不均勻系觸媒、均勻系觸媒的任一種。又,氫化反應係以在有機溶劑中進行為佳。
不均勻系觸媒,例如,可保持原樣而直接使用金屬或金屬化合物,亦可負載在適當的載體而使用。作為載體,可舉出,例如,活性碳、氧化矽、氧化鋁、碳酸鈣、氧化鈦、氧化鎂、氧化鋯、矽藻土、碳化矽、氟化鈣等。相對於觸媒及 載體的合計量,觸媒的負載量係以0.1重量%以上為佳,以1重量%以上為較佳,以60重量%以下為佳,以50重量%以下為較佳。又,負載型觸媒的比表面積,係以100m2/g~500m2/g為佳。而且,負載型觸媒的平均細孔徑,係以100Å以上為佳,以200Å以上為較佳,以1000Å以下為佳,以500Å以下為較佳。在此,比表面積係能夠測定氮吸附量且使用BET式而求取。又,平均細孔徑係能夠藉由水銀壓入法而測定。
作為均勻系觸媒,能夠使用,例如,鎳、鈷或鐵的化合物與有機金屬化合物(例如有機鋁化合物、有機鋰化合物)組合而成之觸媒;及含有銠、鈀、鉑、釕、錸等之有機金屬錯合物觸媒等。
作為鎳、鈷或鐵的化合物,例如能夠使用各種金屬的乙醯丙酮鹽化合物、羧酸鹽、環戊二烯基化合物等。
作為有機鋁化合物,可舉出,例如,三乙基鋁、三異丁基鋁等的烷基鋁;氯化二乙基鋁(diethyl aluminum chloride)、二氯化乙基鋁(ethyl aluminum dichloride)等的鹵化鋁;氫化二異丁基鋁(diisobutylaluminum hydride)等的氫化烷基鋁(alkylaluminum hydride)等。
作為有機金屬錯合物觸媒,可舉出,例如,二氫化物-肆(三苯基膦)釕(dihydrido-tetrakis(triphenylphosphine)ruthenium)、二氫化物-肆(三苯基膦)鐵(dihydrido-tetrakis(triphenylphosphine)iron)、雙(環辛二烯)鎳(bis(cyclooctadiene)nickel)、雙(環戊二烯基)鎳(bis(cyclopentadienyl)nickel)等的過渡金屬錯合物。
相對於嵌段共聚物[1]100重量份,氫化觸媒的使用量係以0.01重量份以上為佳,以0.05重量份以上為較佳,以0.1重量份以上為特佳,以100重量份以下為佳,以50重量份以下為較佳,以30重量份以下為特佳。
氫化反應的溫度係以10℃以上為佳,以50℃以上為較佳,以80℃以上為特佳,以250℃以下為佳,以200℃以下為較佳,以180℃以下為特佳。藉由在如此的溫度範圍進行氫化反應,能夠提高氫化率,而且能夠使嵌段共聚物[1]的分子切斷較少。
氫化反應時的氫壓力係以0.1MPa以上為佳,以1MPa以上為較佳,以2MPa以上為特佳,以30MPa以下為佳,以20MPa以下為較佳,以10MPa以下為特佳。藉由在如此的氫壓力進行氫化反應,能夠提高氫化率,且能夠使嵌段共聚物[1]的分子鏈切斷較少,而使操作性變為良好。
使用上述的方法所得到的氫化物[2],通常是以包含氫化物[2]、氫化觸媒及聚合觸媒的反應液之方式而得到。因此,可藉由,例如,過濾及離心分離等的方法,將氫化觸媒及聚合觸媒從該反應液除去之後,從反應液回收氫化物[2]。作為從反應液將氫化物[2]回收之方法,可舉出,例如,藉由蒸氣氣提(steam stripping)將溶劑從含有氫化物[2]的反應液除去之蒸氣凝固法;在減壓加熱下將溶劑除去之直接脫溶劑法;及將反應液注入氫化物[2]的弱溶劑中而使其析出或凝固之凝固法等。
被回收後的氫化物[2]之形態,係以容易供給至隨後的矽烷基化改質反應(將烷氧矽烷基導入之反應)之方式而製 成丸粒形狀為佳。例如,可將熔融狀態的氫化物[2]從擠壓模擠出成為股線狀,冷卻後,使用製粒機切割為丸粒狀,而供給至各種的成形。又,使用凝固法時,例如,亦可將所得到的凝固物乾燥後,使用擠製機在熔融狀態下擠出,與上述同樣地製成丸粒狀而供給至各種的成形。
(2.2.3.烷氧矽烷基改質物[3])
烷氧矽烷基改質物[3],係將烷氧矽烷基導入至上述嵌段共聚物[1]的氫化物[2]而得到的聚合物。此時,烷氧矽烷基可直接鍵結在上述的氫化物[2],亦可透過,例如,伸烷基(alkylene group)等的二價有機基而間接地鍵結。經導入烷氧矽烷基的烷氧矽烷基改質物[3],與玻璃、金屬等的無機材料的接著性係特別地優異。因此,通常,樹脂層與前述的無機材料的接著性優異。
相對於烷氧矽烷基之導入前的氫化物[2]100重量份,在烷氧矽烷基改質物[3]之烷氧矽烷基的導入量係以0.1重量份以上為佳,以0.2重量份以上為較佳,以0.3重量份以上為特佳,以10重量份以下為佳,以5重量份以下為較佳,以3重量份以下為特佳。烷氧矽烷基的導入量落入前述範圍內時,因為能夠防止被水分等分解後的烷氧矽烷基之間之交聯度變成太高,所以能夠維持較高的樹脂層對無機材料之接著性。
烷氧矽烷基的導入量係能夠藉由1H-NMR光譜而計量。又,計量烷氧矽烷基的導入量時,導入量較少時,能夠增加累計次數而計量。
烷氧矽烷基改質物[3]的重量平均分子量(Mw),因 為被導入的烷氧矽烷基之量為較少,所以通常與導入烷氧矽烷基之前的氫化物[2]的重量平均分子量(Mw)相比變化不大。但是,在導入烷氧矽烷基時,因為通常在過氧化物的存在下使氫化物[2]進行改質反應,所以會進行該氫化物[2]的交聯反應及切斷反應,致使分子量分佈有變大之傾向。烷氧矽烷基改質物[3]的重量平均分子量(Mw)係以40,000以上為佳,以50,000以上為較佳,以60,000以上為特佳,以200,000以下為佳,以150,000以下為較佳,以100,000以下為特佳。又,烷氧矽烷基改質物[3]的分子量分佈(Mw/Mn)係以3.5以下為佳,以2.5以下為較佳,以2.0以下為特佳,以1.0以上為佳。烷氧矽烷基改質物[3]的重量平均分子量(Mw)及分子量分佈(Mw/Mn)為該範圍時,樹脂層能夠維持良好的機械強度及拉伸伸長率。
烷氧矽烷基改質物[3]的重量平均分子量(Mw)及分子量分佈(Mw/Mn),係能夠藉由以四氫呋喃作為溶劑之凝膠滲透層析法(GPC),設為聚苯乙烯換算之值而測定。
烷氧矽烷基改質物[3],係能夠藉由將烷氧矽烷基導入至前述的嵌段共聚物[1]的氫化物[2]而製造。作為將烷氧矽烷基導入至氫化物[2]之方法,可舉出,例如,在過氧化物的存在下使氫化物[2]與乙烯性不飽和矽烷化合物反應之方法。
作為乙烯性不飽和矽烷化合物,可使用能夠與氫化物[2]進行接枝聚合,而將能夠烷氧矽烷基導入至氫化物[2]者。作為此種乙烯性不飽和矽烷化合物的例子,可舉出乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、二甲氧基甲基乙烯基矽烷、二乙氧基甲基乙烯基矽烷等的具有乙烯基之烷氧基矽烷; 烯丙基三甲氧基矽烷、烯丙基三乙氧基矽烷等的具有烯丙基之烷氧基矽烷;對苯乙烯基三甲氧基矽烷、對苯乙烯基三乙氧基矽烷等的具有對苯乙烯基之烷氧基矽烷;3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷等的具有3-甲基丙烯醯氧基丙基之烷氧基矽烷;3-丙烯醯氧基丙基三甲氧基矽烷、3-丙烯醯氧基丙基三乙氧基矽烷等的具有3-丙烯醯氧基丙基之烷氧基矽烷;2-降莰烯-5-基三甲氧基矽烷等的具有2-降莰烯-5-基之烷氧基矽烷等。該等之中,從更容易得到本發明的效果的觀點,以乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、二甲氧基甲基乙烯基矽烷、二乙氧基甲基乙烯基矽烷、烯丙基三甲氧基矽烷、烯丙基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷為佳。又,乙烯性不飽和矽烷化合物可單獨使用1種類,亦可以任意比率組合2種類以上而使用。
相對於導入烷氧矽烷基之前的氫化物[2]100重量份,乙烯性不飽和矽烷化合物的量係以0.1重量份以上為佳,以0.2重量份以上為較佳,以0.3重量份以上為特佳,以10重量份以下為佳,以5重量份以下為較佳,以3重量份以下為特佳。
作為過氧化物,係能夠使用具有作為自由基反應起始劑之功能者。作為如此的過氧化物,通常係使用有機過氧化物。作為有機過氧化物,可舉出,例如,過氧化二苯甲醯、過氧化乙酸第三丁酯、2,2-二-(過氧化第三丁基)丁烷、過氧化 苯甲酸第三丁酯、過氧化第三丁基異丙苯、過氧化二異丙苯、過氧化二第三己基、2,5-二甲基-2,5-二(過氧化第三丁基己烷)、過氧化二-第三丁基、2,5-二甲基-2,5-二(過氧化第三丁基)己烷-3、第三丁基過氧化氫、過氧化異丁酸第三丁酯、過氧化月桂醯基、過氧化二丙醯基、對薄荷烷過氧化氫等。該等之中,以1分鐘半衰期溫度為170℃~190℃者為佳,具體而言,係以過氧化第三丁基異丙苯、過氧化二異丙苯、過氧化二第三己基、2,5-二甲基-2,5-二(過氧化第三丁基己烷)、過氧化二-第三丁基為佳。又,過氧化物可單獨使用1種類,亦可以任意比率組合2種類以上而使用。
相對於導入烷氧矽烷基之前的氫化物[2]100重量份,過氧化物的量係以0.01重量份以上為佳,以0.1重量份以上為較佳,以0.2重量份以上為特佳,以5重量份以下為佳,以3重量份以下為較佳,以2重量份以下為特佳。
在過氧化物的存在下,使嵌段共聚物[1]的氫化物[2]與乙烯性不飽和矽烷化合物反應之方法,係例如,能夠使用加熱混煉機及反應器而進行。舉出具體例時,係能夠將氫化物[2]、乙烯性不飽和矽烷化合物及過氧化物之混合物使用雙軸混煉機,在氫化物[2]的熔融溫度以上使其加熱熔融,混煉所需要的時間,藉此而能夠得到烷氧矽烷基改質物[3]。混煉時具體的溫度,係以180℃以上為佳,以190℃以上為較佳,以200℃以上為特佳,以240℃以下為佳,以230℃以下為較佳,以220℃以下為特佳。又,混煉時間係以0.1分鐘以上為佳,以0.2分鐘以上為較佳,以0.3分鐘以上為特佳,以15分鐘以下為 佳,以10分鐘以下為較佳,以5分鐘以下為特佳。使用雙軸混煉機、單軸擠製機等的連續混煉設備時,係能夠以使滯留時間成為上述範圍之方式而連續地進行混煉及擠製。
在樹脂層所含有的樹脂,烷氧矽烷基改質物[3]等的聚合物的比例,係以80重量%~100重量%為佳,以90重量%~100重量%為較佳,以95重量%~100重量%為特佳。藉由在樹脂之聚合物的比例落入前述範圍內,能夠使樹脂層的儲存彈性模數容易地落入上述範圍內。
(2.2.4.任意成分)
在樹脂層所含有的樹脂,亦可與上述的聚合物組合而進一步含有任意成分。作為任意成分,可舉出,例如,用以調整玻璃轉移溫度及彈性模數之可塑劑;用以使耐候性及耐熱性提升之光安定劑;紫外線吸收劑;抗氧化劑;滑劑;無機填料等。又,任意成分可單獨使用1種類,亦可以任意比率組合2種類以上而使用。
作為將聚合物與任意成分混合之方法的例子,可舉出將任意成分溶解在適當的溶劑且與聚合物溶液混合後,將溶劑除去而將含有任意成分之樹脂回收之方法;使用雙軸混煉機、輥機、布拉本德混合機(Brabender mixer)、擠製機等的混煉機,使聚合物成為熔融狀態而與任意成分混煉之方法等。
[2.3.樹脂層的物性]
在100℃之樹脂層的儲存彈性模數,係以小於10MPa為佳,以小於7.5MPa為較佳,以小於5MPa為特佳。藉由在高溫環境之樹脂層的儲存彈性模數成為如前述之低,能夠將樹脂 層容易地加熱壓黏到任意構件。因此,能夠將樹脂層與導電層加熱壓黏而容易地製造導電性膜。又,能夠藉由加熱壓黏而容易地將導電性膜貼合到任意構件。從使耐熱性提升之觀點而言,在100℃之樹脂層的儲存彈性模數之下限,係以0.1MPa以上為佳,以0.5MPa以上為較佳,以1MPa以上為特佳。
在25℃之樹脂層的彎曲彈性模數,係以1MPa以上為佳,以5MPa以上為較佳,以10MPa以上為特佳,以500MPa以下為佳,以450MPa以下為較佳,以400MPa以下為特佳。藉由在25℃之樹脂層的彎曲彈性模數為前述範圍的下限值以上,能夠提高導電性膜的操作性,而且藉由為前述範圍的上限值以下,能夠提升導電性膜的耐彎曲性。
樹脂層的彎曲彈性模數,係能夠使用萬能試驗機(例如,INSTRON公司製「電氣機械式萬能試驗機5900」),依據JIS K7117而測定。
樹脂層係通常具有高透明性。樹脂層之具體的總光線透射率,係以70%以上為佳,以80%以上為較佳,以90%以上為更佳。總光線透射率,係能夠使用紫外‧可見分光計,在波長400nm~700nm的範圍進行測定。
又,樹脂層的霧度係以5%以下為佳,以3%以下為較佳,以1%以下為特佳,理想為0%。霧度係能夠依據JIS K7361-1997,使用日本電色工業公司製「濁度計NDH-300A」,測定5處,而採用由其所求得的平均值。
[2.4.樹脂層的製造方法]
樹脂層的製造方法係沒有限制。例如,使用包含如上述烷 氧矽烷基改質物[3]的樹脂之熱可塑性樹脂形成樹脂層時,樹脂層係能夠使用熔融成形法、溶液流延法等的成形方法來製造。其中,從能夠抑制溶劑等的揮發性成分殘留在樹脂層的觀點,以熔融成形法為佳。更詳言之,熔融成形法係能夠分類成為擠製成形法、沖壓成形法、膨脹成形法、射出成形法、吹塑成形法、延伸成形法等。該等方法之中,從能夠得到具有優異的機械強度及表面精度之樹脂層的觀點,以擠製成形法、膨脹成形法及沖壓成形法為佳,從能夠效率良好且簡單地製造樹脂層的觀點而言,以擠製成形法為特佳。
[2.5.樹脂層的厚度]
樹脂層的厚度係以5μm以上為佳,以10μm以上為較佳,以15μm以上為特佳,以200μm以下為佳,以175μm以下為較佳,以150μm以下為特佳。藉由樹脂層的厚度為前述範圍的下限值以上,能夠提高導電性膜的機械強度,另外,藉由為前述範圍的上限值以下,能夠有效地提高導電性膜的耐彎曲性。
[3.導電層]
[3.1.導電層的表面電阻值]
導電層的表面電阻值,係通常為1000Ω/sq.以下,以900Ω/sq.以下為佳,以800Ω/sq.以下為較佳。藉由使導電層的表面電阻值成為如此之低,能夠得到較高的導電性。導電層的表面電阻值的下限係沒有特別限制,從容易製造的觀點,以1Ω/sq.以上為佳,以2.5Ω/sq.以上為較佳,以5Ω/sq.以上為特佳。
[3.2.導電層的組成]
如前述的導電層,係通常以包含具有導電性的材料(以下,有適當地稱為「導電材料」之情形)的層之方式形成。作為如此的導電材料,可舉出,例如,金屬、導電性金屬氧化物、導電性奈米線、導電性聚合物等。又,導電材料可單獨使用1種類,亦可以任意比率組合2種類以上而使用。尤其是從提高導電性膜的耐彎曲性之觀點而言,導電層係以含有選自由金屬、導電性奈米線及導電性聚合物所組成群組之至少1種類的導電材料為佳。
作為金屬,可舉出,例如,金、鉑、銀及銅。其中,以銀、銅及金為佳,以銀為較佳。該等金屬可單獨使用1種類,亦可以任意比率組合2種類以上而使用。使用該等金屬而形成導電層時,藉由將導電層形成細小的線狀,而能夠得到透明的導電層。例如,以形成格子狀金屬網狀物層之方式而形成導電層,藉此能夠得到透明的導電層。
含有金屬之導電層,係例如能夠藉由塗佈含有金屬粒子的導電層形成用組合物而形成。此時,藉由將前述導電層形成用組合物印刷成為預定的格子圖案,而能夠得到作為金屬網狀物層之導電層。此外,例如,藉由塗佈含有銀鹽之導電層形成用組合物,利用曝光處理及顯影處理而將金屬細線形成預定的格子圖案,能夠將導電層形成作為金屬網狀物層。針對如此的導電層及其形成方法之細節,係能夠參照日本特開2012-18634號公報、日本特開2003-331654號公報。
作為導電性金屬氧化物,可舉出,例如,ITO(氧化銦錫)、IZO(氧化銦鋅)、ZnO(氧化鋅)、IWO(氧化銦鎢)、 ITiO(氧化銦鈦)、AZO(氧化鋁鋅)、GZO(氧化鎵鋅)、XZO(鋅系特殊氧化物)、IGZO(氧化銦鎵鋅)等。該等之中,從光線透射性及耐久性的觀點,係以ITO為特佳。導電性金屬氧化物可單獨使用1種類,亦可以任意比率組合2種類以上而使用。
含有導電性金屬氧化物之導電層,例如,能夠使用蒸鍍法、濺鍍法、離子鍍(ion plating)法、離子束輔助蒸鍍(Ion beam assisted vapor deposition)法、電弧放電電漿蒸鍍法、熱CVD法、電漿CVD法、電鍍法、及該等之組合等的成膜方法而形成。該等之中,以蒸鍍法及濺鍍法為佳,以濺鍍法為特佳。在濺鍍法,因為能夠形成厚度均勻的導電層,所以能夠抑制在導電層局部地產生較薄的部分。
所謂導電性奈米線,係指形狀為針狀或線狀、且直徑為奈米尺寸的導電性物質。導電性奈米線可為直線狀,亦可為曲線狀。如此的導電性奈米線,係藉由導電性奈米線彼此形成間隙而成為網孔狀,即便少量的導電性奈米線亦能夠形成良好的導電路徑,而能夠實現電阻較小的導電層。又,因為導電性線係藉由成為網孔狀而在網孔之間隙形成開口部,所以能夠得到光透射率較高的導電層。
導電性奈米線的粗度d與長度L之比(縱橫比:L/d)係以10~100,000為佳,以50~100,000為較佳,以100~10,000為特佳。使用如此之縱橫比大的導電性奈米線時,導電性奈米線係良好地交叉,而能夠使用少量的導電性奈米線來顯現較高的導電性。其結果,能夠得到具有優異的透明性之導電性膜。在此,所謂「導電性奈米線的粗度」,當導電性奈米線的剖面 為圓狀時,係指其直徑;當導電性奈米線的剖面為橢圓狀時,係指其短徑;當導電性奈米線的剖面為多角形時,係指最長的對角線。導電性奈米線的粗度及長度,係能夠使用掃描型電子顯微鏡或穿透式電子顯微鏡而測定。
導電性奈米線的粗度,係以小於500nm為佳,以小於200nm為較佳,以10nm~100nm為更佳,以10nm~50nm為特佳。藉此,能夠提高導電層的透明性。
導電性奈米線的長度,係以2.5μm~1000μm為佳,以10μm~500μm為較佳,以20μm~100μm為特佳。藉此能夠提高導電層的導電性。
作為導電性奈米線,可舉出,例如,由金屬所構成之金屬奈米線、含有奈米碳管之導電性奈米線等。
作為在金屬奈米線所含有的金屬,係以導電性較高的金屬為佳。作為適合的金屬之例子,可舉出金、鉑、銀及銅,其中,以銀、銅及金為佳,以銀為較佳。又,亦可使用對上述金屬進行鍍敷處理(例如,鍍金處理)之材料。而且,前述的材料可單獨使用1種類,亦可以任意比率組合2種類以上而使用。
作為金屬奈米線的製造方法,能夠採用任意適當的方法。例如,在溶液中使硝酸銀還原之方法;及從探針的前端部對前驅物表面施加電壓或電流使期起作用,在探針前端部將金屬奈米線拉出,而連續地形成該金屬奈米線之方法等。在溶液中使硝酸銀還原之方法,係能夠藉由在乙二醇等多元醇、及聚乙烯吡咯啶酮(polyvinylpyrrolidone)的存在下,將硝酸銀 等的銀鹽進行液相還原,而合成銀奈米線。均勻尺寸的銀奈米線,係能夠依據,例如,Xia,Y.etal.,Chem.Mater.(2002)、14、436-4745,及Xia,Y.etal.,Nano letters(2003)3(7)、955-960所記載的方法而大量生產。
作為奈米碳管,例如,能夠使用直徑為0.3nm~100nm、長度0.1μm~20μm左右之所謂多層奈米碳管、二層奈米碳管、單層奈米碳管等。其中,就導電性高的觀點而言,係以直徑10nm以下、長度1μm~10μm的單層或二層奈米碳管為佳。又,奈米碳管的集合體係以不含有非晶碳及觸媒金屬等的不純物為佳。作為奈米碳管的製造方法,能夠採用任意適當的方法。較佳是使用藉由電弧放電法所製造的奈米碳管。由於藉由電弧放電法所製造的奈米碳管係具有優異的結晶性,因而較佳。
含有導電性奈米線之導電層,係能夠藉由塗佈將導電性奈米線分散在溶劑而得到之導電性奈米線分散液,並進行乾燥而製造。
作為在導電性奈米線分散液所含有的溶劑,可舉出,例如,水、醇系溶劑、酮系溶劑、醚系溶劑、烴系溶劑、芳香族系溶劑等,其中,從減低環境負荷的觀點而言,係以使用水為佳。又,溶劑可單獨使用1種類,亦可以任意比率組合2種類以上而使用。
在導電性奈米線分散液之導電性奈米線的濃度,係以0.1重量%~1重量%為佳,藉此,能夠形成具有優異的導電性及透明性之導電層。
導電性奈米線分散液,係能夠與導電性奈米線及溶劑組合而含有任意成分。作為任意成分,可舉出,例如,抑制導電性奈米線產生腐蝕之腐蝕抑制劑、抑制導電性奈米線產生凝聚之界面活性劑、用以將導電性奈米線保持在導電層之黏結劑聚合物等。又,任意成分可單獨使用1種類,亦可以任意比率組合2種類以上而使用。
作為導電性奈米線分散液的塗佈方法,可舉出,例如,噴霧塗佈法、棒塗佈法、輥塗佈法、模塗佈法、噴墨塗佈法、網篩塗佈法(screen coating)、浸漬塗佈法、狹縫式塗佈法(slot die coating)、凸版印刷法、凹版印刷法、照相凹版印刷法(gravure printing)等。作為乾燥方法,能夠採用任意適當的乾燥方法(例如,自然乾燥、送風乾燥、加熱乾燥)。例如,加熱乾燥時,能夠將乾燥溫度設為100℃~200、乾燥時間設為1分鐘~10分鐘。
相對於導電層的全重量,在導電層之導電性奈米線的比例,係以80重量%~100重量%為佳,以85重量%~99重量%為較佳。藉此,能夠得到具有優異的導電性及光透射性之導電層。
作為導電性聚合物,可舉出,例如,聚噻吩(polythiophene)系聚合物、聚乙炔(polyacetylene)系聚合物、聚對伸苯基(polyparaphenylene)系聚合物、聚苯胺(polyaniline)系聚合物、聚對伸苯基伸乙烯基(polyparaphenylene vinylene)系聚合物、聚吡咯(polypyrrole)系聚合物、聚伸苯基(polyphenylene)系聚合物、藉由丙烯酸系聚合物改質之聚酯系聚合物等。尤其 是以聚噻吩系聚合物、聚乙炔系聚合物、聚對伸苯基系聚合物、聚苯胺系聚合物、聚對伸苯基伸乙烯基系聚合物及聚吡咯系聚合物為佳。
其中,以聚噻吩系聚合物為特佳。藉由使用聚噻吩系聚合物,能夠得到具有優異的透明性及化學安定性之導電層。作為聚噻吩系聚合物的具體例,可舉出聚噻吩;聚(3-己基噻吩)等的聚(3-C1-8烷基-噻吩);聚(3,4-伸乙基二氧基噻吩)、聚(3,4-伸丙基二氧基噻吩)、聚[3,4-(1,2-伸環己基)二氧基噻吩]等的聚(3,4-(環)伸烷基二氧基噻吩);聚伸噻吩基伸乙烯基(poly thienylene vinylene)等。在此,所謂「C1-8烷基」,係表示碳原子數為1~8的烷基。又,前述導電性聚合物可單獨使用1種類,亦可以任意比率組合2種類以上而使用。
導電性聚合物係以在陰離子性聚合物存在下進行聚合為佳。例如,聚噻吩系聚合物,係以在陰離子性聚合物的存在下使其氧化聚合為佳。作為陰離子性聚合物,可舉出具有羧基、磺酸基、或其鹽之聚合物。較佳是能夠使用聚苯乙烯磺酸等的具有磺酸基之陰離子性聚合物。
含有導電性聚合物之導電層,例如,能夠藉由塗佈含有導電性聚合物之導電層形成用組合物,並進行乾燥而形成。關於包含導電性聚合物之導電層,係能夠參照日本特開2011-175601號公報。
[3.3.導電層的平面形狀]
導電層可形成在樹脂層的一面,亦可形成在兩面。又,導電層可形成在樹脂層面的全體,亦可形成在樹脂層面的一部 分。例如,導電層亦可在樹脂層面的一部分被圖案化成預定的圖案而形成。導電層圖案的形狀,係能夠按照導電性膜的用途而設定。例如,使用導電性膜作為電路基板時,導電層的平面形狀亦可形成對應電路的配線形狀之圖案。又,例如,將導電性膜使用作為觸控面板用的感測膜時,導電層的平面形狀,係以作為觸控面板(例如,電容式觸控面板)可良好地動作之圖案為佳,舉出具體例時,可舉出在日本特表2011-511357號公報、日本特開2010-164938號公報、日本特開2008-310550號公報、日本特表2003-511799號公報、日本特表2010-541109號公報所記載的圖案。
[3.4.導電層的物性]
導電層係通常具有高透明性。因此,可見光線係通常能夠透射該導電層。導電層之具體的透明性,係能夠按照導電性膜的用途而調整。導電層之具體的總光線透射率,係以80%以上為佳,以90%以上為較佳,以95%以上為進一步更佳。
[3.5.導電層的厚度]
導電層的每1層之厚度,係以0.01μm~10μm為佳,以0.05μm~3μm為較佳,以0.1μm~1μm為特佳。導電性膜係具備2層以上的導電層時,該等的導電層的厚度可相同,亦可不同。其中,在樹脂層的兩側具有導電層時,從抑制導電性膜的皺紋及卷曲等的變形的觀點而言,導電層的厚度係以相同為佳。
[4.任意層]
導電性膜係能夠視需要而包含任意層。作為任意層,可舉出,例如,具有比樹脂層更高的儲存彈性模數之支撐體層。在 25℃之支撐體層之具體的儲存彈性模數,係以1000MPa以上為佳,以1500MPa以上為較佳,以2000MPa以上為特佳,以5000MPa以下為佳,以4500MPa以下為較佳,以4000MPa以下為特佳。藉由包含具有如此之大的儲存彈性模數之支撐體層,能夠提高導電性膜的加工、搬運、及裝配時的操作性。
作為支撐體層,可舉出由具有較高的儲存彈性模數之樹脂所構成之層。在支撐體層所含有的樹脂,係能夠含有聚合物、及視需要之任意成分。作為聚合物,可舉出,例如,聚乙烯、聚丙烯等的聚烯烴;聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯等的聚酯;聚伸苯基硫醚(polyphenylene sulfide)等的聚伸芳基硫醚(polyarylene sulfide);聚乙烯醇;聚碳酸酯;聚芳香酯(polyarylate);纖維素酯聚合物、聚醚碸(polyethersulfone);聚碸(polysulfone);聚烯丙基碸(polyallyl sulfone);聚氯乙烯;降莰烯系聚合物等含有脂環式結構之聚合物;棒狀液晶聚合物等。該等聚合物可單獨使用1種類,亦可以任意比率組合2種類以上而使用。又,聚合物可為同元聚合物,亦可為共聚物。該等之中,從機械特性、耐熱性、透明性、低吸濕性、尺寸安定性及輕量性等性質優異的觀點,以含有脂環式結構之聚合物為佳。
支撐體層的厚度係以10μm以上為佳,以13μm以上為較佳,以15μm以上為特佳,以60μm以下為佳,以58μm以下為較佳,以55μm以下為特佳。藉由支撐體層的厚度為前述範圍的下限值以上,能夠提高導電性膜的操作性,另外,藉由為前述範圍的上限值以下,能夠使導電性膜成為較薄。
而且,作為任意層,可舉出,例如,硬塗層、折射率匹配(index matching)層、接著層、相位差層、偏光片層、光學補償層等。
[5.導電性膜的物性及厚度]
導電性膜係具有優異的耐彎曲性。因此,導電性膜即便彎曲,導電層的導電性亦不容易降低。而且,導電性膜即便彎曲,亦不容易產生白化等的外觀變化。能夠得到如此優異的耐彎曲性之結構,係能夠如下述推測。但是,本發明的技術範圍係不被下述說明之結構限制。
因為本發明的導電性膜所具備的樹脂層,係具有適當範圍之儲存彈性模數,所以具有優異的可撓性。因此,將導電性膜彎曲時,容易變形且能夠將彎曲所產生的應力吸收。因此,因彎曲而產生的應力不容易破壞導電層。因此,即便將導電性膜彎曲,導電層的表面電阻值亦不容易上升,因而,能夠抑制導電性降低。
又,因為樹脂層具有適當的範圍的儲存彈性模數,在將導電性膜彎曲時,樹脂層不容易產生破壞,而且,樹脂層與導電層不容易產生剝離。因此,由於不容易因前述的破壞或剝離而產生微小的空隙,所以不容易在折彎部產生霧度上升,因而,能夠抑制白化等的外觀變化。另外,因為樹脂層具有優異的彈性,即便折彎也很容易恢復原來的形狀,所以不容易產生折彎痕跡。
因為導電性膜係具備樹脂層作為用以支撐導電層之層,所以相較於導電性玻璃,通常具有更優異的耐衝擊性及 加工性。而且,通常導電性膜係比導電性玻璃更輕量。
導電性膜的總光線透射率,係以70%以上為佳,以80%以上為較佳,以90%以上為更佳。
又,導電性膜的霧度係以5%以下為佳,以3%以下為較佳,以1%以下為特佳,理想為0%。
導電性膜的厚度係以5μm以上為佳,以7.5μm以上為較佳,以10μm以上為特佳,以200μm以下為佳,以175μm以下為較佳,以150μm以下為特佳。藉由導電性膜的厚度為前述範圍的下限值以上,能夠提高導電性膜的機械強度,另外,藉由為前述範圍的上限值以下,導電性膜能夠薄膜化。
[6.導電性膜的製造方法]
導電性膜,例如,能夠藉由包含製造樹脂層的步驟、及在前述樹脂層上設置導電層的步驟之製造方法而製造。導電層可使用該導電層的材料而形成在樹脂層上;亦可將導電層形成在適當的基材上,將該形成的導電層與樹脂層貼合,藉此而將導電層設置在樹脂層上。例如,藉由使用導電性金屬氧化物之濺鍍法而形成導電層時,樹脂層係有因濺鍍時的成膜條件而受到損傷之可能性。此時,若藉由將導電層形成在能夠經得起濺鍍的基材之後,再將該導電層與樹脂層貼合而製造導電性膜,則能夠在避免對樹脂層產生損傷之同時得到導電性膜。
[7.層結構的例子]
本發明的導電性膜,係在包含樹脂層及導電層之範圍,能夠任意地設定其層結構。以下,揭示圖式而說明導電性膜之適合的層結構之例子。
第1圖係示意性地顯示作為本發明的第一實施形態之導電性膜10之剖面圖。如第1圖所顯示,第一實施形態之導電性膜10,係只有具備樹脂層110及導電層120之二層結構的薄膜。因為該導電性膜10係具有表面電阻值小的導電層120,所以具有優異的導電性。又,因為導電性膜10係具備具有適當範圍的儲存彈性模數之樹脂層110,所以具有優異的耐彎曲性。因此,例如,即便折彎亦不容易產生導電性低落及外觀變化。
第2圖係示意性地顯示作為本發明的第二實施形態之導電性膜20之剖面圖。又,第3圖係示意性地顯示作為本發明的第三實施形態之導電性膜30之剖面圖。如第2圖及第3圖所示,第二及第三實施形態之導電性膜20及30亦可與樹脂層110及導電層120組合而具備支撐體層130。此時,各層的順序為任意,可如第2圖所示之導電性膜20,依照以下的順序設置有樹脂層110、導電層120及支撐體層130,亦可如第3圖所示之導電性膜30,依照以下的順序設置有支撐體層130、樹脂層110及導電層120。如此地具備支撐體層130之導電性膜20及30,係除了與第一實施形態相同的優點以外,能夠進一步提升操作性。
第4圖係示意性地顯示作為本發明的第四實施形態之導電性膜40之剖面圖。導電性膜所含有的層之數目為任意,例如,第4圖所示的第四實施形態之導電性膜40,亦可依照以下的順序設置有支撐體層130、導電層120、樹脂層110、導電層140及支撐層150。此時,導電層120及140的材料、 形狀、厚度,係可相同亦可不同。例如,一方的導電層120之圖案形狀與另一方的導電層140之圖案形狀亦可不同。而且,支撐體層130及150的材料、形狀、厚度,係可相同亦可不同。如此,樹脂層、導電層、及支撐體層等的任意層係各自設置有複數層時,亦能夠得到與第一實施形態~第三實施形態相同的優點。
[8.導電性膜的用途]
導電性膜的用途係沒有限制。舉出導電性膜的適合用途之例子時,可舉出電阻式觸控面板及電容式觸控面板等的觸控面板用感測膜;有機EL元件等的發光元件用電極等。
[實施例]
以下,揭示實施例而具體地說明本發明。但是,本發明係不被以下所揭示的實施例限定,在不脫離本發明的申請專利範圍及其均等範圍之範圍,能夠任意地變更而實施。
在以下的說明,表示量之「%」及「份」,係只要未特別地預先告知,就是重量基準。又,在以下說明之操作,係只要未特別地預先告知,就是在常溫常壓大氣中進行。
又,在以下的說明,只要未特別地預先告知,所謂「PEDOT」,係表示聚(3,4-伸乙基二氧基噻吩),所謂「PSS」,係表示聚苯乙烯磺酸。
所謂「PEDOT/PSS」,係表示摻雜有聚苯乙烯磺酸之聚(3,4-伸乙基二氧基噻吩)。
[評價方法]
[儲存彈性模數的測定方法]
樹脂層的儲存彈性模數,係使用動態黏彈性裝置(SII公司製「DMS6100」),在頻率1Hz的條件下測定。
[彎曲彈性模數的測定方法]
樹脂層的彎曲彈性模數,係使用電氣機械式萬能試驗機(INSTRON公司製「5900」),依據JIS K 7117而測定。
[表面電阻值的測定方法]
透明導電性膜的導電層之表面電阻值,係使用非接觸電阻測定器(Napson公司製「NC-10」)而測定。
[因折疊試驗而引起之表面電阻值的變化之評價方法]
對透明導電性膜進行折疊試驗。在該折疊試驗,係使用彎曲試驗機(YUASA系統機器公司製「TCDM 111LH」),對透明導電性膜在曲率半徑5mm進行折疊操作1萬次。隨後,測定透明導電性膜的導電層之表面電阻值。而且,從折疊試驗前的表面電阻值Ro及折疊試驗後的表面電阻值Ri,依照下述式(X)計算因折疊試驗而引起之表面電阻值的上升率。
表面電阻值的上升率[%]={(Ri-Ro)/Ro)}×100 (X)
針對如此進行而求得的表面電阻值之上升率,基於下述的基準而進行評價。在此,因折疊試驗而引起之表面電阻值的上升率越小,係表示透明導電性膜的耐彎曲性越優異。
A:表示彎曲性試驗前後的表面電阻值之上升率為小於5%之值。
B:表示彎曲性試驗前後的表面電阻值之上升率為5%以上、小於10%之值。
C:表示彎曲性試驗前後的表面電阻值之上升率為10%以上之值。
[折疊試驗後的外觀之評價方法]
進行前述的折疊試驗之後,係進行目視觀察透明導電性膜,基於下述的基準進行評價。因折疊試驗而引起的外觀變化較小者,係表示透明導電性膜具有優異的耐彎曲性。
A:折彎處的外觀完全沒有變化。
B:在折彎處產生稍微能夠看見之折彎痕跡。
C:折彎處產生白化或產生能夠清楚地看見之折彎痕跡。
D:折彎處產生白化並且產生能夠清楚地看見之折彎痕跡。
[製造例1.樹脂層(1)的製造]
參考在國際公開2014/077267號所記載的方法,將苯乙烯25份、異戊二烯50份及苯乙烯25份依照該順序進行聚合,而製造三嵌段共聚物氫化物(ia1)(重量平均分子量Mw=48,200;分子量分佈Mw/Mn=1.04;主鏈及側鏈的碳-碳不飽和鍵、以及芳香環的碳-碳不飽和鍵之氫化率≒100%)。而且,參考在前述國際公開2014/077267號所記載的方法,使乙烯基三甲氧基矽烷1.8份鍵結在前述三嵌段共聚物氫化物(ia1)100份,而製造三嵌段共聚物氫化物的烷氧矽烷基改質物(ia1-s)之丸粒。
使用具備側給料器(side feeder)及寬度400mm的T型模具之雙軸擠製機(東芝機械公司製「TEM-37B」)、以及鑄造滾筒及脫模膜供給裝置之薄片捲取機,依照下述的方法而製造樹脂層(1)。
將烷氧矽烷基改質物(ia1-s)供給至雙軸擠製機。相 對於該烷氧矽烷基改質物(ia1-s)100份,以氫化聚丁烯(日油公司製「PARLEAM(註冊商標)24」)成為15份的比例之方式,將氫化聚丁烯從側給料器連續地供給,而得到含有前述烷氧矽烷基改質物(ia1-s)及氫化聚丁烯之熔融樹脂。然後,將該熔融樹脂從T型模具擠出至鑄造滾筒上,而成形為膜狀。該擠出係在熔融樹脂溫度180℃、T型模具溫度180℃、鑄造滾筒溫度40℃的成形條件下進行。被擠出的熔融樹脂係被鑄造滾筒冷卻,而得到厚度50μm的樹脂層(1)。
將脫模用PET膜(厚度50μm)供給至被擠出至鑄造滾筒上之樹脂層(1)的一面,將樹脂層(1)與PET膜重疊而捲取成為捲物狀且回收。藉此,得到具備樹脂層(1)及PET膜之複層膜的捲物。
將複層膜從前述的捲物拉出,將PET膜剝離,而得到樹脂層(1)。測定在25℃之樹脂層(1)的儲存彈性模數時為143MPa。又,測定在25℃之樹脂層(1)的彎曲彈性模數時為437MPa。
[製造例2.樹脂層(2)的製造]
參考在國際公開2011/096389號所記載的方法,將苯乙烯25份、異戊二烯50份及苯乙烯25份依照該順序進行聚合,而製造三嵌段共聚物氫化物(ia2)(重量平均分子量Mw=48,200;分子量分佈Mw/Mn=1.04;主鏈及側鏈的碳-碳不飽和鍵、以及芳香環的碳-碳不飽和鍵之氫化率≒100%)之丸粒。
使用具備寬度400mm的T型模具之雙軸擠製機(東芝機械公司製「TEM-37B」)、以及鑄造滾筒及脫模膜供給裝置之薄片捲取機,依照下述的方法而製造樹脂層(2)。
將三嵌段共聚物氫化物(ia2)供給至雙軸擠製機且使其熔融,而得到熔融樹脂。然後,將該熔融樹脂從T型模具擠出至鑄造滾筒上,而成形為膜狀。該擠出係在熔融樹脂溫度180℃、T型模具溫度180℃、鑄造滾筒溫度40℃的成形條件下進行。被擠出的熔融樹脂係被鑄造滾筒冷卻,而得到厚度50μm的樹脂層(2)。
將脫模用PET膜(厚度50μm)供給至被擠出至鑄造滾筒上之樹脂層(2)的一面,將樹脂層(2)與PET膜重疊而捲取成為捲物狀且回收。藉此,得到具備樹脂層(2)及PET膜之複層膜的捲物。
將複層膜從前述的捲物拉出,將PET膜剝離,而得到樹脂層(2)。測定在25℃之樹脂層(2)的儲存彈性模數時為111MPa。又,測定在25℃之樹脂層(2)的彎曲彈性模數時為760MPa。
[製造例3.樹脂層(3)的製造]
參考在國際公開2011/096389號所記載的方法,將苯乙烯30份、異戊二烯40份及苯乙烯30份依照該順序進行聚合,而製造三嵌段共聚物氫化物(ia3)(重量平均分子量Mw=48,200;分子量分佈Mw/Mn=1.04;主鏈及側鏈的碳-碳不飽和鍵、以及芳香環的碳-碳不飽和鍵之氫化率≒100%)之丸粒。
使用具備寬度400mm的T型模具之雙軸擠製機(東芝機械公司製「TEM-37B」)、以及鑄造滾筒及脫模膜供給裝置之薄片捲取機,依照下述的方法而製造樹脂層(3)。
將三嵌段共聚物氫化物(ia3)供給至雙軸擠製機且使其熔融,而得到熔融樹脂。然後,將該熔融樹脂從T型模具擠出至鑄造滾筒上,而成形為膜狀。該擠出係在熔融樹脂溫度180℃、T型模具溫度180℃、鑄造滾筒溫度40℃的成形條件下進行。被擠出的熔融樹脂係被鑄造滾筒冷卻,而得到厚度50μm的樹脂層(3)。
將脫模用PET膜(厚度50μm)供給至被擠出至鑄造滾筒上之樹脂層(3)的一面,將樹脂層(3)與PET膜重疊而捲取成為捲物狀且回收。藉此,得到具備樹脂層(3)及PET膜之複層膜的捲物。
將複層膜從前述的捲物拉出,將PET膜剝離,而得到樹脂層(3)。測定在25℃之樹脂層(3)的儲存彈性模數時為800MPa。又,測定在25℃之樹脂層(2)的彎曲彈性模數時為1260MPa。
[實施例1.使用導電性聚合物之例子]
在工業用改質醇(日本ALCOHOL販售公司製「SOLMIX AP-7」)100g中,添加PEDOT/PSS(Hearaus公司製「Clevios PH1000」)10g、丙烯酸樹脂(東亞合成公司製「JURYMER AT-510」、固體成分30%)0.8g、及乙二醇(和光純藥公司製)3g且攪拌,而製造作為導電層形成用組合物之塗佈組合物。
使用棒塗佈器(安田精機製作所製)將塗佈組合物塗佈在製造例1所製造的樹脂層(1)上,而且使用乾燥器於100℃施行加熱處理1分鐘。藉此,將厚度1μm的導電層形成在樹脂層(1)上,而得到透明導電性膜(a)。
測定所得到的透明導電性膜(a)的導電層之表面電阻值時為450Ω/sq.。使用上述的方法評價該透明導電性膜(a)。
[實施例2.使用銀奈米線之例子]
準備含有銀奈米線之分散液(Cambrios Technologies Corporation公司製「ClearOhm」)作為導電性奈米線分散液。
使用棒塗佈器而將前述分散液塗佈在製造例1所製造的樹脂層(1)上,於80℃使其乾燥。藉此,將厚度1μm的導電層形成在樹脂層(1)上,而得到透明導電性膜(b)。
測定所得到的透明導電性膜(b)的導電層之表面電阻值時為750Ω/sq.。使用上述的方法評價該透明導電性膜(b)。
[實施例3.使用CNT之例子]
(使用超成長法而製造奈米碳管)
依照國際公開第2006/011655號的記載,使用超成長法(Super-Growth method)而製造奈米碳管。以下,有將該奈米碳管適當地稱為「SGCNT」之情形。所得到的SGCNT係藉由氮吸附之BET比表面積為804m2/g,藉由水蒸氣吸附之BET比表面積為2.4m2/g,質量密度為0.03g/cm3,微孔容積為0.44mL/g。又,使用穿透式電子顯微鏡,隨意地測定100支SGCNT的直徑之結果,平均直徑(Av)為3.3nm,將直徑的標本標準偏差(σ)乘以3而得到的值(3σ)為1.9nm,(3σ/Av)為0.58,平均長度為500μm。又,所得到的SGCNT,係主要含有單層奈米碳管(單層CNT)。
(導電性膜的製造)
在容量30mL的試樣瓶,量取0.015g的SGCNT,及作為 分散劑之苯乙烯磺酸鈉/順丁烯二酸二鈉的共聚物(單體的莫耳比1/1、平均聚合度2萬)0.030g,添加離子交換水8g及乙醇2g後,使用硝酸而將pH調整成為2.5。隨後,藉由使用槽浴型超音波分散機處理2小時,而得到CNT分散液作為導電性奈米線分散液。
使用棒塗佈器將前述CNT分散液塗佈在製造例1所製造的樹脂層(1)上,使其乾燥。藉此,將厚度1.5μm的導電層形成在樹脂層(1)上,而得到透明導電性膜(c)。
測定所得到的透明導電性膜(c)的導電層之表面電阻值時為1000Ω/sq.。使用上述的方法評價該透明導電性膜(c)。
[實施例4.使用銀粒子之例子]
準備銀墨(Sigma-Aldrich Japan製「Silver Nanoparticle Ink」)作為包含以銀奈米粒子作為金屬粒子之導電層形成用組合物。
使用棒塗佈器將前述銀墨塗佈在製造例1所製造的樹脂層(1)上,在120℃使其乾燥60秒鐘。藉此,將厚度0.7μm的導電層形成在樹脂層(1)上,而得到透明導電性膜(d)。
測定所得到的透明導電性膜(d)的導電層之表面電阻值時為300Ω/sq.。使用上述的方法評價該透明導電性膜(d)。
[實施例5.使用導電性金屬氧化物之例子]
作為基材,係準備厚度50μm的環烯烴聚合物膜(日本ZEON公司製「ZEONORFILM ZF16-50」。以下,有稱為「COP膜」之情形)。使用薄膜捲取式磁控濺鍍(magnetron sputtering)裝置進行濺鍍,而在前述COP膜上形成ITO層作為導電層, 以得到含有COP膜及ITO層之複層膜。前述濺鍍係使用將氧化錫及氧化銦煅燒而成之物作為靶材,且在氬(Ar)流量150sccm、氧(O2)流量10sccm、輸出功率4.0kW、真空度0.3Pa、薄膜搬運速度0.5m/min的條件下進行。在此,「sccm」係氣體流量的單位,將每1分鐘流動氣體的量,以該氣體在25℃、1atm時的體積(cm3)表示。
藉由熱貼合法(溫度100℃、搬運速度1m/min、壓力0.4MPa)將所得到的複層膜之ITO層側的面、與製造例1所製造的樹脂層(1)貼合。隨後,將COP膜剝離,而得到具備樹脂層(1)及厚度30nm的ITO層之透明導電性膜(e)。
測定所得到的透明導電性膜(e)的ITO層之表面電阻值時為150Ω/sq.。使用上述的方法評價該透明導電性膜(e)。
[實施例6]
使用製造例2所製造的樹脂層(2)代替樹脂層(1),除此之外,係與實施例1進行相同的操作,而製造透明導電性膜(f)。
測定所得到的透明導電性膜(f)的導電層之表面電阻值時為450Ω/sq.。使用上述的方法評價該透明導電性膜(f)。
[實施例7]
使用製造例3所製造的樹脂層(3)代替樹脂層(1),除此之外,係與實施例5進行相同的操作,而製造透明導電性膜(g)。
測定所得到的透明導電性膜(g)的導電層之表面電阻值時為150Ω/sq.。使用上述的方法評價該透明導電性膜(g)。
而且,使用霧度計量器(日本電色股份公司製「NDH-4000」)測定所得到的透明導電性膜(g)之霧度,基於JIS K 7136之測定結果為0.5%。
[比較例1]
使用聚對苯二甲酸乙二酯膜(TORAY公司製「U-34」、厚度50μm、在25℃之儲存彈性模數4000MPa)代替樹脂層(1),除此之外,係與實施例1進行相同的操作,而製造透明導電性膜。
測定所得到的透明導電性膜的導電層之表面電阻值時為450Ω/sq.。使用上述的方法評價該透明導電性膜。
[比較例2]
使用聚萘二甲酸乙二酯膜(帝人DuPont公司製「Q65HA」、厚度50μm、在25℃之儲存彈性模數5000MPa)代替樹脂層(1),除此之外,係與實施例1進行相同的操作,而製造透明導電性膜。
測定所得到的透明導電性膜的導電層之表面電阻值時為450Ω/sq.。使用上述的方法評價該透明導電性膜。
[比較例3]
使用聚碳酸酯膜(帝人DuPont公司製「PURE-ACE」、厚度50μm、在25℃之儲存彈性模數1300MPa)代替樹脂層(1),除此之外,係與實施例1進行相同的操作,而製造透明導電性膜。
測定所得到的透明導電性膜的導電層之表面電阻值時為450Ω/sq.。使用上述的方法評價該透明導電性膜。
[比較例4]
準備具備脫模基材、及設置在該脫模基材上的感壓性黏著
劑(日東電工公司製「CS9621」)之層之黏著膜(日東電工公司製、黏著劑之層的厚度20μm、黏著劑之層在25℃之儲存彈性模數1Mpa、剝離基材的厚度50μm)。
使用棒塗佈器(安田精機製作所製)而將實施例1所製造的塗佈組合物塗佈在前述黏著膜的黏著劑之層上,使用乾燥器於100℃施行加熱處理1分鐘。藉此,將導電層形成在黏著劑之層上。隨後,將剝離基材剝離而得到具備黏著劑之層及導電層之透明導電性膜。
測定所得到的透明導電性膜的導電層之表面電阻值時為450Ω/sq.。使用上述的方法評價該透明導電性膜。
[結果]
將前述的實施例及比較例之結果顯示在下述的表。在下述的表之簡稱的意思係如下述。
PET:聚對苯二甲酸乙二酯膜。
PEN:聚萘二甲酸乙二酯膜。
PC:聚碳酸酯膜。
PSA:感壓性黏著劑之層。
儲存彈性模數:在25℃之樹脂層的儲存彈性模數。
彎曲彈性模數:在25℃之樹脂層的彎曲彈性模數。
CNT:奈米碳管
[研討]
如前述實施例及比較例所揭示,將在25℃具有預定範圍的儲存彈性模數之樹脂層、及具有預定範圍的表面電阻值之導電層組合而成之導電性膜,係即便將該導電性膜彎曲,導電層的表面電阻值亦不容易上升,而且不容易產生白化等的外觀變化。因而,從前述的實施例及比較例之結果,能夠確認依照本發明,能夠實現導電性及耐彎曲性的雙方均優異之導電性膜。
[參考例1]
(樹脂層A的製造)
將製造例1所得到的三嵌段共聚物氫化物的烷氧矽烷基改質物(ia1-s)之丸粒46.15g、及氫化聚丁烯(日油股份公司製「10SH」)13.85g溶解在環己烷140g中,而得到樹脂溶液。
將所得到的樹脂溶液,使用狹縫塗佈器而塗佈在厚度50μm的脫模PET膜(三菱樹脂股份公司製「MRV38」)上, 於120℃使其乾燥3分鐘,而將厚度20μm的樹脂層A形成在脫模PET膜上。隨後,將脫模PET膜剝離,而得到厚度20μm的樹脂層A作為單體的薄膜。
(因折疊試驗而引起之樹脂層A的耐折彎性變化之評價1)
使用彎曲性試驗機(YUASA系統機器公司製「TCDM 111LHA」)對樹脂層A在曲率半徑2.5mm進行折疊操作20萬次。
隨後,進行樹脂層A的目視觀察。觀察結果,確認折彎處的外觀完全沒有變化。
(因折疊試驗而引起之樹脂層A的耐折彎性變化之評價2)
使用彎曲性試驗機(YUASA系統機器公司製「DLDM 111LHA」)對樹脂層A在間隙4mm進行折疊操作20萬次。
隨後,進行樹脂層A的目視觀察。觀察結果,確認折彎處的外觀完全沒有變化。
10‧‧‧導電性膜
110‧‧‧樹脂層
120‧‧‧導電層
Claims (4)
- 一種導電性膜,係包含樹脂層及導電層,在25℃之前述樹脂層的儲存彈性模數為大於10MPa且小於1000MPa,前述導電層的表面電阻值為1000Ω/sq.以下,其中前述導電層係選自由導電性奈米線及導電性聚合物所組成群組之至少1種類的導電材料,前述樹脂層包含嵌段共聚物[1]的主鏈及側鏈的碳-碳不飽和鍵及芳香環的碳-碳不飽和鍵氫化而成之氫化物[2],以及,前述氫化物[2]的烷氧矽烷基改質物[3]所組成的群組中的至少一種,前述嵌段共聚物[1],係具有:在每1分子前述嵌段共聚物[1]中為2個以上之含有芳香族乙烯系化合物單元的聚合物嵌段[A]、及在每1分子前述嵌段共聚物[1]中為1個以上之含有鏈狀共軛二烯化合物單元的聚合物嵌段[B],前述聚合物嵌段[A]在前述嵌段共聚物[1]的全體佔有之重量分率wA、與前述聚合物嵌段[B]在前述嵌段共聚物[1]的全體佔有之重量分率wB之比(wA/wB)為20/80~60/40。
- 如申請專利範圍第1項所述之導電性膜,其中在25℃之前述樹脂層的彎曲彈性模數為500MPa以下。
- 如申請專利範圍第1或2項所述之導電性膜,其中前述樹脂層係含有前述烷氧矽烷基改質物[3]。
- 如申請專利範圍第1項所述之導電性膜,其中前述樹脂層與前述導電層直接接觸,其中前述導電性膜的總光線透過率為70%以上。
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