201238765 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種積層體，其作為電子紙、太 電池、有機EL等電子材料之基板時，能發揮優異的 性及水蒸氣阻隔性，且能提高長期使用時之裝置經 可靠性。 、' 【先前技術】 近年來電子紙或有機EL等顯示裝置、太陽能電 能量裝置急速普及。於該等用途以往係使用玻璃基 但從輕量化、破裂難度、可撓性之觀點，以透明塑 代替玻璃基材的需求正在升高。 然而將玻璃基材取代成透明塑膠膜時，由於水 穿過透明塑膠膜，因而會造成裝置劣化。為了解決 題，已考慮利用在包含透明塑膠膜的基材上，積層 且具氣體阻隔性之無機薄膜層而得的氣體阻隔性膜 此的氣體阻隔性膜’向來已被廣泛使用於以食品包 途為中。的$域。但是向來用於食品包裝用途之氣 隔性膜，其水分阻斷性不足，難以抑制裝置劣化。 而於使用在電子紙或有機EL等顯示裝置或太陽 池等能量裝置為目的，已有提議在高分子膜的至少 设置硬化樹脂層與金屬氧化物層之水蒸氣穿透度 〇.lg/m/day的氣體阻隔性膜（專利文獻υ。但是，如 文獻1記載之於表面姑, 衣面破剝出的為無機薄膜層的金屬 物層：：體阻隔性臈’雖然就膜而言的氣體阻隔性 疋田’·内入裝置時容易發生裂痕，會有不易獲得 陽能 透明 時之 池等 材， 膠膜 分會 此問 透明 。如 裝用 體阻 能電 單面 低於 專利 氧化 優良 充分 .201238765 捏濟2方面，就即使納入裝置也不生裂痕，能充分發 揮氣體阻隔性的目沾 ,,.,, ' 13 ，已有提議在雙軸延伸聚酯膜 上所製作之（I方、、g s主工 I、層表面’隔著黏接層而貼合其他雙軸延 伸聚酯膜而得之裔_ ΒΒ π ω 1 ^ _ 氣體阻隔性支持體（專利文獻2)。但是該 氣體阻隔性支括_彳食^^ # 〜 叉将體儘s係作為顯示器的支持體使用，但 70未考慮透明性。且專利文獻2也沒有呈現具體態樣。 先前技術文獻 專利文獻 專利文獻1日本特開2006-28 1505號公報 專利文獻2 曰本專利第4106677號公報 【發明内容】 [發明所欲解決之課題] 本發明係鑑於該習知技術之問題而獲得者，其目的 在於提供一種透明性優異且水蒸氣Ρ且隔性優異之積層體 [用以解決課題之手段] 可解決上述課題之本發明之積層體，係包含以下之 構成。 (1> 一種積層體，其係於第1透明塑膠膜之單面上積 層包含無機物的無機薄膜層而成的積層膜的無機薄膜層 側的表面上，將第2透明塑膠膜隔著黏著劑層而積層所得 之積層體，其特徵為，前述第1透明塑膠膜之折射率η, 、前述黏著劑層之折射率112及前述無機薄膜層之折射率 η二足下列⑴及⑴)的關係， 201238765 I η3-ηι I ^ 0.2 (i) I n3-n2 I ^ 0.2 (ii)。 (2) 如（1)記載之積層體，其中前述無機薄膜層之膜 為 1 0〜200nm 〇 (3) 如⑴或U)記載之積層體，其中前述無機薄膜 含有AI2O3。 ⑷如⑴〜（3)中任一項記栽之積層體，纟中前述無 薄膜層係藉由反應性藏鍵法所為之阻抗（impedance)控 法而形成。 (5) 如（1)至（4)中任一項記載之積層體其中前述 機薄膜層之折射率h與前述第2透明塑膠膜之折射率 滿足下列（iii)之關係， | n3-n4 | ^ 0.2 (iii)。 (6) 士（1)至（5)中任一項記載之積層體，其中在與 述第2透明塑膠膜之設有黏著劑層之面為相反側之面 ，設置有透明導電性薄膜層。 (7) 如（1)至（6)中任一項記載之積層體，其中在與 述第1透明塑膠膜之設有無機薄膜i❾Φ為相反側之 上’設置有硬塗層。 (8) 如（7)记栽之積層體，其中前述硬塗層經防眩處 〇 [發明之效果] 依據本發明，7 e β 了提供兼具優異透明性與優異水蒸 阻隔性的積層冑°且該積層體作為電子紙、太陽能電 '有機電子材料之基板使用時，可獲得 之裝置之經時可靠性提高的效果。 厚 層 機 制 無 η4 前 上 前 面 理 氣 池 時 201238765 【實施方式】 [用以實施發明之形態] 本發明之積層體，係在第1透明塑膠 、、早面上積層 包含無機物的無機薄膜層所得之積層膜之無機薄膜層側 之面，隔著黏著劑層而積層第2透明塑膠骐所得之芦 〇 層體 枣發明之積層體 -^ , θ 十Α _汉弟2圖所 Μ材！所不之積層體10,係以第1透明塑膠膜1作 為基材，並於其單面依序積層無機薄 4、第2透明塑膠膜5 點者劑層 丹者，於弟1透明塑膠 -面設置有硬化物層2。又，於第2圖所示 = 電性薄獏之積層體丨丨中， 導 m 於第1圖所不之積層體ίο中 的第：透明塑膠膜5上，又積層著透明導電性薄膜層：。 本發明中’前述第！透明塑膠膜之 Γ劑層之折射率…述無機薄膜層之折射率Π 足下列（0及（ii)之關係係屬重要。 3滿 I n3-n, | ^ 0.2 (i) ' n3-n2 I ^ 0.2 (ϋ) 若為上述（i)及（ii)之關係均 透明性優S n1 /兩足的積層體，則會成為 優異、且水蒸氣阻隔性優異之積層 之値，較佳為0.16以下，更佳Λ 〇的 3'ni 1 之値較佳為(M6以下，更佳為〇Λ〇、 1丨 塑勝膜之折射率ηι、黏著劑# · m ’第1透明 之折射率I β之折射率n2及無機薄膜層 丰n3各可以例如於實施例後述方法來測定。 .201238765 ^又，本發明中，前述無機薄膜層之折射率n3與前述 第2透明塑膠膜之折射率n4較佳為滿足下列㈣之關係。 i n3-n4 I ^ 0.2 (iii) 的 若為滿足上述（iii)之關係 透明性及水蒸氣阻隔性。| 的積層體，可展現更優良 n3-n4 |之値較佳為〇·16以 下，更佳為0.09以下。又，第2透明塑膠膜之折射率 例如可以後述實施例方法來測定。 η4 > 又，為了滿足上述⑴及（ii)之關係，且更滿足上述（丨⑴ 之關係，調整構成本發明之積層體的各膜或各層（形成層 之材料）之折射率為宜。 a 以下針對構成本發明之積層體的各膜及層加以説 (第1及第2透明塑膠膜） …第1及第2透明塑膠膜，係將有機高分子以熔融擠 壓或溶液擠壓成膜狀而成形為膜狀，並視需要在長产 方向及寬度方向的其中之一或兩者施予延伸、熱固定^ 熱鬆弛處理的膜。 有機高分子例如：聚乙烯、聚丙烯、聚對笨二甲酸 乙二醇酯、聚2,6-萘二甲酸乙二醇酯、聚對笨二曱酸丙 二醇醋、尼龍6、尼龍4、尼龍66、尼龍12、聚醯亞=丙 聚醯胺醯亞胺、聚醚砜、聚醚醚酮、聚碳酸取— , 來方醋、 纖維素丙酸酯、聚氯乙烯、聚偏二氣乙稀、 甘， . 來乙烯醇、 ♦醚醯亞胺、聚笨硫醚、聚笨氧、聚苯乙烯、對 ^ 乙烯、降莰烯系聚合物（環烯烴系聚合物等）等。其笨 較佳為聚對苯二甲酸乙二醇酯、聚對笨二 中 T k丙二醇 201238765 S旨、聚2,6 -蔡二曱酸乙二醇 水率低之對排聚苯乙烯、降 合物等。又，該等有機高分 體之單體成分少量共聚合者 子0 醋、聚碳酸酯、聚芳酯、吸 获稀系聚合物之環稀煙系聚 子也可各為與其他有機聚合 ’也可混合複數種有機高分 第1及第2透明塑膠膜可為包含【種塑膠的單層型 膜也可為有2種以上塑膠膜積層而得之積層型膜。製 成積層型膜時，積層體之種類 '積層數、積層方法等未 特別限定’可因應目的從習知之方法任意選擇。 第1及苐2透明塑膠膜之厚度，各為10"m以上較 佳’更佳為20 " m以上。透明塑膠膜之厚度小於（〇 " m 時機械的強度不足，電子紙等裝置製作步驟的操作會 有變得困難之虞。又’第！及第2透明塑膠膜之厚度為 200"m以下較佳，更佳為16〇“出以下。透明塑膠膜之 厚度若超過200 " m，則電子紙等裝置之厚度會變得太 厚’有時會不理想。 對於第1及第2透明塑膠膜，在不損及本發明目的 之範圍，可以施以電暈放電處理、輝光放電處理、火燄 處理、紫外線照射處理、電子線照射處理、臭氧處理等 表面活性化處理。 (硬塗層（硬化物層）） 第1透明塑膠膜在其兩面或單面也可以設置1層以 上之以硬化型樹脂作為主要構成成分的硬化物層。第1 透明塑膠膜之無機薄膜層的形成面若設置硬化物層’則 與無機薄臈層的密合性會提高，而且可獲得賦予耐藥品 201238765 性、防止寡聚物等低分子量物析出此類的效果。又，若 在與第1透明塑膠膜之無機薄膜層形成面為相反側之面 設置硬化物層，則可獲得賦予耐藥品性、防止寡聚物等 低分子量物析出此類的效果。本說明書中，有時將在與 第1透明塑膠膜之無機薄膜層形成面為相反側之面所設 置之硬化物層，特別稱為「硬塗層」。 刖述硬化型樹脂只要是藉由以加熱、紫外線照射、 電子線照射等施加能量而硬化之樹脂即可，不特別限 定，例如矽酮樹脂、丙烯酸樹脂、曱基丙烯酸樹脂、環 氧樹脂、二聚氰胺樹脂、聚酯樹脂、胺曱酸酯樹脂等。 k生產性之觀點，較佳為以紫外線硬化型樹脂作為主成 分之硬化型樹脂。 前述紫外線硬化型樹脂，例如：如多元醇之丙烯酸 酯或甲基丙烯酸酯之多官能性丙烯酸酯樹脂；由二異氰 酸醋或多元醇、與丙烯酸或f基丙稀酸之經基烧基醋等 合成之多官能性的胺曱酸酯丙烯酸酯樹脂；等多官能性 的樹脂。該等多官能性之樹脂，視需要也可為使單官能 性單體(例如：乙烯基吡洛。定酮、甲基丙烯酸甲醋、苯乙 烯等）共聚合成者。 前述紫外線硬化型樹脂通常係添加光聚合起始劑後 使用。光聚合起始劑可以無特別限制而使用會吸收紫外 線並產生自由基之習知化合物，<列如：各種苯偶因類、 笨基酮類、二苯基酮類等。光聚合起始劑之添加量。通 常相對於100質量份之紫外線硬化型樹脂，以丨〜5質量 份左右為較佳。 -10- 201238765 設置硬化物層時，例如將含前述硬化型樹脂之塗布 液塗布在第1透明塑膦贈 暴膜上之後’視需要使加熱乾燥， 或使Μ外線硬化型樹脂時照射紫外線即可。塗布方法 未特別限定ϋ用桿塗法、照相凹版塗布法、反相塗 布法等習知的方法。加熱溫度可因應塗布液使用之溶劑 之沸點適當設定，不牲 。 特别限制，但通常為5 01：以上2 5 0 c以下較佳’更佳$ 7〇t以上2〇〇t;以下。，照射紫 外線時之光量，通常為1〇 — 2以上5〇〇mW以下 較佳，更佳為200mJ/cm2以上4〇〇mJ/cm2以下。 含有前述硬化型樹脂之塗布液之濃度，可考慮因應 塗布方法之黏度等適當選擇。例如：塗布液含有紫外線 硬化型樹脂及光聚合起始劑時，紫外線硬化型樹脂及光 聚合起始劑之合計量在塗布液中所占比例通"2〇〜8〇 質量％左右。 又，在塗布液中也可視需要添加例如：石夕酮系界面 活性劑或1系界面活性劑等塗平劑等f知之添加劑。 ^硬化物層之厚度為O·1^以上較佳，更佳為\.5_ :上’尤佳為Um以上。硬化物層之厚度小於〇 _ 時’由於不易形成充分交聯的構造，故 Μ、又+易獲侍耐藥品 ::聚物等低分子量物之抑制不夠’有無法獲得密 〇 1王权咼效果之傾向。又，硬化物層之厚产 物乂二更…—以下’尤佳為8…下。硬化 曰之厚度超過15#爪時，生產性有降低的傾向。 較佳為對於在與前述第i透明塑膠膜之無機薄膜層 4面為相反侧之面設置的硬化物層(即，硬塗層)施以 201238765 防眩處理。若對於成為積層體的最表面的硬塗層施以防 眩處理，則可以理想地使用在電子紙或有機EL·等顯示器 裝置。防眩處理例如可藉由於形成硬化物層之塗布液中 添加二氧化矽粒子來進行。 更化物層中’為了提咼對於無機薄膜層之附著力， 且細*以表面處理。具體方法，例如使用照射輝光放電或 電暈放電的放電處理法而使羰基、羧基、羥基增加之方 法 '使用以酸或處理之化學藥品處理法而使胺基、羥基 、羰基等極性基增加之方法等。 (無機薄膜層） 無機薄膜層係包含金屬或無機氧化物之薄膜。形成 無機薄膜層之材料，例如Si〇2、ALA等金屬氧化物、 SiCVAhh等複合金屬氧化物等。其中，含Ai2〇3之材料 於水蒸氣阻隔性之觀點為較佳。 無機薄膜層之折射率h為145以上較佳，更佳為！ 以上。折射率小於145時，容易變成多孔質的膜，氣 體阻隔性有不易提高的傾向。又，無機薄膜層之折射率 MUO以下較佳’更佳為165以下。折射率〜超過17〇 時，與第1或第2透明塑膠膜、黏著劑層間的折射率差異 會增大，故有積層體之穿透率降低之虞。 無機薄膜層之膜厚為10nm以上較佳，更佳為2〇nm 以上，又更佳為30nm以上。無機薄膜層之獏厚小於！⑽爪 時’不易連續形成薄膜，不易獲得良好的氣體阻隔性。 又，無機薄膜層之膜厚為200nmw下較佳，更佳為Η⑽爪 以下，更佳為160nm以下。無機薄膜層之膜厚超過 -12- 201238765 時，無機薄膜層之應力會增大， 易發生裂痕，水蒸氣阻隔性有降 第1透明塑膠膜薄時容 低之虞。又，若膜厚加 厚，雖然水蒸氣阻隔性良好， 但於積層超過 1 OOnm 時 生產性會降低。所以，最佳* 2 Λ , Λ Λ _ 取住马30〜ΙΟΟηπι之範圍。 無機薄膜層之成膜方法， y戍，已知有真空蒸鍍法、濺鍍 法、CVD法、離子佈植法、喷塗法等 可從該等習知之 方法當中，因應所欲形成之膜厚適當選擇。尤其，從減 少膜厚的不均-性的觀點，w濺鍍法為較佳。以一般濺 鑛法製膜時’可使用反應性Dc< AC濺鍍法。該反應性 濺鍍法之中，為了提高成膜速度，較佳為使dc或AC電 源之電壓値保持固定的方式控制反應性氣體流量之阻抗 控制法、或將特定元素在電漿中之發光強度保持固定之 方式控制反應性氣體流量之電漿發射法。尤其阻抗控制 法不需龐大設備，且製程安定性優異，故為較佳。 阻抗控制&中，當於僅流通Ar等惰性氣體時之金屬 模式的放電電壓…00%，流通Ο〗，等反應性氣體 時之氧化物或氮化物模式之放電電壓定為〇%時，控制使 成為20〜80%之値之放電電壓較佳，尤佳為3〇〜7〇%。低 於20%時，成膜速度之提高效果會有減小的傾向，另二 方面，當超過_，在膜寬方向會有容易發生膜厚分布 之虞。 射 内 μ 、电求汛 離子輔助等方法。又，在it指太路ΒΒ ，、娟桊發明之目的的範圍 也可對於基板施加直流、交流、高頻等偏壓。 -13- 201238765 又，就將無機薄膜層成膜時之水分壓力而言，為2Χ l(T3Pa以下較佳，更佳為5xl(T4Pa以下。水分壓超過2Χ l(T3Pa時，無機薄膜層中會跑入氫，有時網絡（例如：M-0-) 會停止成長，所以無機薄膜層會變得欠缺連續性，氣體 阻隔性有降低之虞。 將無機薄膜層成膜時，可以預先將第1透明塑膠膜 暴露於真空。此時壓力通常定為〇.〇〇1Pa以上〇 〇1Pa以 下的程度。暴露時間通常為5分鐘以上即可。 將無機薄膜層成膜時’為了安定地獲得具有更優良 氣體阻隔性之無機薄膜層’宜在成膜裝置内設置光學特 性（穿透率、彩色）測定裝置。以光學特性之測定，可以 確認無機薄膜層之膜厚、氧化度。又，為了測定膜厚， 使用螢光X射線於線上（line_in)測定亦為有效。 (黏著劑層） 黏著劑層，係於在上述積層膜之無機薄膜層上積層 第2透明塑膠膜時，在無機薄膜層或第2透明塑膠膜炱 少其中之塗布黏著樹脂、或貼合使黏著樹脂成片狀者 而形成。 黏著樹脂無特別限制，例如可使用丙烯酸系樹脂、 石夕系樹脂、橡膠系樹脂等習知之樹脂。尤其，較佳為適 於光學用的丙烯酸系樹脂。 述丙烯&L系树脂，例如可藉由將含（甲基）丙烯酸 叙炫S曰^單體成分予以聚合而冑。就（曱基）丙稀酸酸 烷土 -曰而σ例如可舉例（曱基）丙烯酸曱酯、（曱基）丙烯 酸乙酉曰、（甲基)丙烯酸丙_、（甲基)丙烯酸正丁酯、（甲 -14- 201238765 基）丙烯酸異丁酯、（甲基）丙烯酸第三丁酯、（曱基）丙烯 酸正己酯、（曱基）丙烯酸2_乙基己酯、（曱基）丙烯酸正辛 酯、（甲基）丙烯酸異辛酯、（甲基）丙烯酸月桂酯、（曱基） 丙稀酸硬脂酯等。 亦可以使含前述（甲基）丙烯酸酸烷基酯之單體成分 進一步共聚合具羥基、羧基、醯胺基、胺基等親水性基 之單體。藉由將具親水性基之單體共聚合，可以增加與 被黏著物之密合性。具體而言，例如丙烯酸、曱基丙烯 酸、馬來酸酐、具叛基之苯乙稀、（曱基）丙稀酸2_經基 乙酯、（甲基）丙烯酸2_羥基丙醋、丙烯醯胺、甲基丙烯 醯胺、（甲基）丙烯酸二曱胺基乙酯等。 獲得 合反應之 獲得之丙 存之未反 起始劑會 定性降低 劑之未反 之聚合起 量％以下 反應量可 等控制。 刖现丙稀酸 5^合起始劑 稀酸系樹脂 應之聚合起 影響阻隔性 。所以，理 應量，具體 始劑之量為 ’又更佳為 由聚合時間 系樹脂時，通常會添 而將前述單體成分逐 ’係以維持含有聚合 始劑的狀態使用。然 ’而且有時會使耐濕 想為儘可能減少聚合 而言’丙烯酸系樹脂 0 · 2質量％以下較佳， 〇·〇5質量％以下。聚 、聚合溫度、聚合起 加用於加速聚 次聚合。並且 反應結束後殘 未反應之聚合 熱性等環境安 時之聚合起始 中所含未反應 更佳為0.1質 合起始劑之未 始劑之添加量 就獲得前述丙嫌酸备姓+ 士 而-旨時可以使用之聚合起始劑 …例如可舉例過氧化苯甲 異丙苯過氧化氫、113, w - 丁基過氧化虱、 ，，，3-四甲基丁基過氧化氫、過氧化 -15- 201238765 第二己基、過氧化第二丁基、1，1，3,3-四甲基丁基過氧化 -2-乙基己酸酿、第三己基過氧化_2_乙基己酸酯、第三丁 基過氧化-2-乙基己酸醋、過氧化月桂醯等有機過氧化 物；2,2’-偶氮雙異丁腈、2,2’-偶氮雙（2,4•二甲基戊腈）、 2,2’-偶氮雙（2-曱基丁腈）等偶氮化合物等。 又，前述黏著樹脂中，為了提高作為黏著劑層之保 持力’含有交聯劑較佳。就交聯劑而言，例如：可舉例 異氰酸酯系、環氧系、二聚氰胺系、尿素系、金屬螯合 物系等多官能性化合物。交聯劑之含量，相對於黏著樹 脂之固體成分總量（黏著片成分）定為〇 〇 1質量％以上i 〇 質量％以下較佳。含有交聯劑時。也可於塗布黏著樹脂 後，視需要加熱、或於適當溫度熟化而進一步進行交聯 反應。 前述黏著樹脂之玻璃轉移溫度為_8〇〇C以上yc以下 較佳，-70°c以上-20°c以下則更佳。前述黏著樹脂之分 子量，以重量平均分子量計為10,000〜3,000,000較佳。 5 0,000〜2,000,000又更佳。黏著樹脂之重量平均分子量 若小於1 0，0 0 0，當形成黏著劑層時，由於黏性過低，流 動性會過大，難以片的形式形成均勻的層。又，若超過 3，000,000則黏性會變得過高，不能充分展現勻塗作用， 同樣難以形成均勻的層。 (透明導電性薄膜層） 本發明之積層體，在與設有前述第2透明塑膠膜之 黏著劑層之面為相反侧之面上，可以設置透明導電性薄 膜層。藉此，可以作為透明導電性積層膜而使用在電子 紙、有機EL、太陽能電池等。 -16- 201238765 就形成透明導電性薄膜之材料而言，例如氧化銦、 氧化錫、氧化鋅、銦-錫複合氧化物、錫-銻複合氧化物、 鋅-紹複合氧化物、銦-鋅複合氧化物等無機物；聚苯胺、 聚°比B各、聚乙快、聚D塞吩、p E D Ο T (聚（3，4 -伸乙基二氧基 嗟吩））等導電性高分子；於高分子中分散著極細導電碳 纖維（奈来碳管、奈米碳角、奈米碳線等）的有機物；石 墨稀等。其中，從環境安定性或電路加工性之觀點，銦_ 錫複合氧化物為較佳。 透明導電性薄膜之層構造可為單層構造也可為2層 以上之積層構造。為具2層以上之積層構造的透明導電 性薄膜時，構成各層之材料（金屬氧化物等）可相同也可 不同。 、透明導電性薄膜之成膜方法已知真空蒸鍍法'錢鑛 法、CVD法、離子佈植法、喷塗法等，可從該等習知之 方法當中’因應欲形成之膜厚適當選擇。尤其從減低膜 厚之不均勾的觀點’錢鍍法為較佳。此時反應性氣體可 以導入氧氣、氮氣等’也可併用臭氧添加、電聚照射、 離子輔助等方法。又，在無損本發明之目的的範圍，也 可對於基板施加直流、交流、高頻等偏壓。 透明導電性薄膜之膜厚為4_以上較佳，更佳為 1 Onm以上。透明導電性薄 ·'、、 暝之膜厗小於4nm時，不易成 士連續的缚膜，不易獲得良好導電性。又，透明導電性 涛膜之膜厚為200η“下較佳，更佳為"Ο·以下。透 明導電性薄膜之膜厚比2〇〇 發生裂痕之虞。 "厂子時曲時會有容易 201238765 積層透明導電性薄膜 ® t 1¾ Μ A <; 、而仔之本發明之積層體其表 =且値為5〜_Ω/□較佳，更佳為⑽ 面電阻値若為前述 表 使用在雪 作為透明導電性積層膜而 有…太陽能電池等。另-方面，若 表面電阻値脫離前述範 右 虞，為不佳。 $置之回應速度有減慢之 全光線層體其全光線穿透率為87%以上較佳。 時，裝置之透1低於87%,作為電子紙等電極基板使用 使全光線穿读L性會減低，視讀性有變差的傾向。為了 透明%以上’尤其使無機薄膜層與第1 層：二^率差卜…1丨及無機薄膜層與黏著劑 " :差1 η3_η2丨減少為有效，只要滿足上述⑴及 關係即可。不滿足上述⑴及(Π)之關係時(即，丨 或1 ―丨之値超過〇.2時)，難以使穿透率 又’積層體之全光線穿透㈣如可以於實 例中的後述方法測定。 又，本發明之積層體其彩色b値為mo%較 二彩色b値若低於-"%，則裝置的泛藍程度會增強， -方面若超過4.0%，則泛黃程度會增強，戶斤以視讀性 差的傾向。若為滿足上述⑴及(ii)之關係的積層體， 1衫色上値會成為前述範圍。又’積層體之彩色“直例 α可以實施例後述之方法來測定。 本發明之積層體其水蒸氣穿透率低於0.3g/m2/day :佳。若為0.3g/m2/day以上’當裝置長期使用時，水分 會逐漸進入裝置中，容易 201238765 滿足上述⑴及（π)之關係之積層體，則水蒸氣 為前述範圍。又，積層體之水蒸氣穿透率'， 施例後述方法測定。 [實施例] 以下以實施例對於本發明更詳細説明， 限於該等實施例。X，積層體之性能係依下列 <水蒸氣穿透率> 依據JIS-K7129 B法’使用水蒸氣穿透 (MOCON公司製「AQUATRAN」），於溫度 90%RH之氣體環境下測定水蒸氣穿透度。又 體之調濕’係疋為水蒸氣從第1透明塑膠側 透明塑膠側之方向。 <全光線穿透率> 依據JIS-K7136，使用日本電色工 「NDH-1 00 1 DP」測定全光線穿透率（％)。 <彩色b値〉 依據JIS-K7105，使用色差計（日本$ 「ZE-2000」），以標準之光c/2測定彩色b 1 <表面電阻値> 依據JIS - K 7 1 9 4 ’以4端子法測定表面電 使用三菱油化（股）製「Lotest AMCP-T400」。 <無機薄膜層、透明導電性薄膜層之膜厚> 無機薄膜層之膜厚，係將形成有無機薄 的之膜作為試樣片，透明導電性薄膜層之膜 成有透明導電性薄膜層之階段之膜作為試樣 穿透率會成 例如可依實 但本發明不 :方法測定。 度測定裝置 40°C、濕度 ，對於積層 穿透到第2 業（股）製 ^色工業製 ί直。 阻値。測定 膜層之階段 厚，係以形 片，各將膜 -19- 試樣片切成1 mmx 1 〇mm大小，祐幻 巴埋於電 氧樹脂。將其固定在超微切片機的試樣支 埋之試樣片的短邊為平行之剖面薄切片 片之薄膜之無明顯損傷的部位，蚀 1文用穿透 (JEOL 公司製「JEM-2010 w | + 」）以加速電 野，於觀察倍率1萬倍拍攝昭M 哪，尽月，從得 厚。 201238765 <無機薄膜層、透明導電性薄膜層之折制 無機薄膜層之折射率，係藉由在石 施例或比較例為相同成膜條件形成無= 折射率測定用試樣，並針對獲得之試樣 振光譜儀（ellipsometer)(大塚電子（股 :則定於55〇n…斤射率，將獲 ：[Technical Field] The present invention relates to a laminate which exhibits excellent properties and water vapor barrier properties as a substrate of an electronic material such as an electronic paper, a battery or an organic EL. It can improve the reliability of the device during long-term use. [Prior Art] In recent years, display devices such as electronic paper and organic EL, and solar energy devices have rapidly spread. In the past, glass substrates have been used for such applications. However, from the viewpoints of weight reduction, difficulty in cracking, and flexibility, the demand for transparent plastics to replace glass substrates is increasing. However, when a glass substrate is replaced with a transparent plastic film, the device is deteriorated due to water passing through the transparent plastic film. In order to solve the problem, it has been considered that a gas barrier film which is obtained by using a gas barrier film which is laminated and has a gas barrier property on a substrate containing a transparent plastic film has been widely used for food packaging. The way is medium. $domain. However, the gas barrier film which has been used for food packaging purposes has insufficient moisture barrier properties and it is difficult to suppress deterioration of the device. For the purpose of using an energy device such as an electronic paper or an organic EL display device or a solar cell, it has been proposed to provide at least a water vapor permeability of the hardened resin layer and the metal oxide layer in the polymer film 〇.lg/m. /day gas barrier film (Patent Document υ. However, as described in Document 1, the metal layer of the inorganic thin film layer: the body barrier layer 臈', although the film is Gas barrier 疋 ' '····································································································· 201238765 In terms of kneading 2, even if it is incorporated into the device, there is no crack, and the gas barrier property can be fully exerted. ,,, '13 has been proposed to be produced on the biaxially stretched polyester film (I, , gs main work I, layer surface 'adhered to the other biaxially stretched polyester film through the adhesive layer _ ΒΒ π ω 1 ^ _ gas barrier support (Patent Document 2). But the gas barrier Sexual support _ 彳食^^ # 〜 fork will do the body s It is used as a support for a display, but 70 does not consider transparency. Moreover, the patent document 2 does not show a specific aspect. The prior art document patent document patent document 1 Japanese patent publication 2006-281505 patent document 2 曰本 patent 4106677 SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] The present invention has been made in view of the problems of the prior art, and an object of the present invention is to provide a laminate having excellent transparency and excellent water vapor entanglement. Means for Solving the Problem The laminated body of the present invention which solves the above-described problems includes the following constitution: (1) A laminated body obtained by laminating an inorganic thin film layer containing an inorganic material on one surface of a first transparent plastic film. The laminated body obtained by laminating the second transparent plastic film on the surface of the inorganic thin film layer on the surface of the inorganic thin film layer via the adhesive layer is characterized in that the refractive index η of the first transparent plastic film and the adhesive layer are The relationship between the refractive index 112 and the refractive index η of the inorganic thin film layer is the following (1) and (1)), 201238765 I η3-ηι I ^ 0.2 (i) I n3-n2 I ^ 0.2 (ii) (2) 1) In the laminated body, the film of the inorganic thin film layer is 10 to 200 nm, and the inorganic thin film contains AI2O3. (4) As described in any one of (1) to (3), the laminated body described in (1) or (U). In the layered body, the film-free layer is formed by the impedance control method according to any one of (1) to (4), wherein the film-free layer is formed by the reactive bond method. The refractive index h of the machine film layer and the refractive index of the second transparent plastic film satisfy the following relationship (iii), | n3-n4 | ^ 0.2 (iii). (6) The laminated body according to any one of (1) to (5), wherein a transparent conductive film layer is provided on a surface opposite to a surface on which the adhesive layer of the second transparent plastic film is provided. . (7) The layered body according to any one of (1) to (6), wherein a hard coat layer is provided on the side opposite to the side on which the inorganic film i❾Φ is provided on the first transparent plastic film. (8) The laminated body of (7), wherein the hard coat layer is subjected to anti-glare treatment [effect of the invention] According to the present invention, 7 e β provides a laminate having excellent transparency and excellent water vapor barrier properties. When the laminate is used as a substrate for electronic paper or solar electric 'organic electronic material, the effect of improving the reliability of the device with time is obtained. In the thick layer mechanism, there is no η4, and the front and the front of the gas pool are in the form of a liquid crystal cell. [Embodiment] The layered body of the present invention is obtained by laminating an inorganic thin film layer containing an inorganic material on the first transparent plastic or on the early surface. The layer on the side of the inorganic thin film layer of the laminated film, the layer of the reed layer obtained by the second transparent plastic enamel interposed by the adhesive layer -^, θ 十Α _ Handi 2 figure coffin! In the laminated body 10, the first transparent plastic film 1 is used as a substrate, and the inorganic thin 4 and the second transparent plastic film are sequentially laminated on one side thereof. The hardened layer 2 is provided on the surface. Further, in the laminated body of the electric thin film shown in Fig. 2, the transparent plastic film 5 is laminated on the first transparent plastic film 5 in the laminated body ίο of the first drawing. :. In the present invention, the aforementioned The refractive index of the coating layer of the transparent plastic film... The refractive index of the inorganic film layer is as follows: (0 and (ii) are important. 3 Full I n3-n, | ^ 0.2 (i) ' n3-n2 I ^ 0.2 (ϋ) If the layered body having the relationship of (i) and (ii) is excellent in transparency and S n1 / two feet, it is excellent in lamination with excellent water vapor barrier properties, preferably 0.16 or less, more preferably 3 3 3'ni 1 is preferably (M6 or less, more preferably 〇Λ〇, 1 丨 plastic film refractive index ηι, adhesive # · m '1st transparent refractive index Each of the refractive index n2 of Iβ and the inorganic thin film layer n3 can be measured, for example, by the method described later in the examples. Further, in the present invention, the refractive index n3 of the inorganic thin film layer and the refractive index of the second transparent plastic film are It is preferable that n4 satisfies the relationship of the following (4): i n3-n4 I ^ 0.2 (iii) If the layered body satisfying the relationship transparency (iv) and the water vapor barrier property of the above (iii) can exhibit more excellent n3-n4 Further, it is preferably 〇16 or less, more preferably 0.09 or less. Further, the refractive index of the second transparent plastic film can be measured, for example, by the method of the following examples. In addition, in order to satisfy the relationship between the above (1) and (ii), and to satisfy the above relationship ((1), it is preferable to adjust the refractive index of each film or each layer (material forming the layer) constituting the laminate of the present invention. a Hereinafter, the first and second transparent plastic films are formed for each film and layer constituting the laminate of the present invention. The first and second transparent plastic films are formed by melt extrusion or solution extrusion. The film is formed into a film shape, and if necessary, one or both of the long-term direction and the width direction are applied to the film which is stretched and thermally fixed. The organic polymer is, for example, polyethylene, polypropylene, or poly. For ethylene glycol dicarboxylate, polyethylene glycol 2,6-naphthalate, propylene glycol propylene glycol, nylon 6, nylon 4, nylon 66, nylon 12, polypyrene = propylene Amine phthalimide, polyether sulfone, polyether ether ketone, polycarbonate -, vinegar, cellulose propionate, polyvinyl chloride, polyvinylidene chloride, glycerol, hexane alcohol, ♦ ether oxime Imine, polystyrene sulfide, polyoxyl, polystyrene, p-ethylene, norbornene-based polymer (cycloalkenyl) Polymer, etc.), etc. It is preferably polyethylene terephthalate, poly-p-dioxin T k propylene glycol 201238765 S, poly 2,6-cained diacetate, low water rate Arranging polystyrene, decomposing compounds, etc. In addition, the monomer components of the organic high fractions are copolymerized in a small amount of vinegar, polycarbonate, polyarylate, ring-absorbing system of rare polymer Each of the organic polymerizations can also be mixed with a plurality of organic high-scores. The first and second transparent plastic films can be made of a single-layer film containing plastics or two or more plastic film layers. Laminated film. When the laminated film is produced, the type of the laminated body 'the number of layers, the lamination method, and the like are not particularly limited', and can be arbitrarily selected from the conventional methods in accordance with the purpose. The thickness of the first and second transparent plastic films is preferably 10 "m or more and more preferably 20 " m or more. When the thickness of the transparent plastic film is less than (〇" m, the mechanical strength is insufficient, and the operation of the manufacturing steps of the electronic paper or the like may become difficult. The thickness of the 'the ! and the second transparent plastic film is 200 " m or less Preferably, it is preferably 16" "outer. If the thickness of the transparent plastic film exceeds 200 " m, the thickness of the device such as electronic paper becomes too thick" may be undesirable. For the first and second transparent The plastic film may be subjected to surface activation treatment such as corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, ozone treatment, etc., without impairing the object of the present invention. (1) The first transparent plastic film may be provided with one or more layers of a cured layer containing a curing resin as a main component on both surfaces or on one side. The surface of the inorganic film layer of the first transparent plastic film is provided. The cured layer's adhesion to the inorganic thin layer is improved, and the effect of imparting the drug-resistant 201238765 property and preventing the precipitation of low molecular weight substances such as oligomers can be obtained. When the inorganic thin film layer forming surface of the transparent plastic film is provided with a cured layer on the opposite side, it is possible to impart chemical resistance and prevent precipitation of low molecular weight substances such as oligomers. In the present specification, sometimes The cured film layer provided on the opposite side of the inorganic thin film layer forming surface of the first transparent plastic film is particularly referred to as a "hard coat layer". The hardened resin described above is heated, irradiated with ultraviolet rays, and irradiated with electron beams. The resin which is hardened by application of energy is not particularly limited, and examples thereof include an anthrone resin, an acrylic resin, a mercapto acrylic resin, an epoxy resin, a melamine resin, a polyester resin, an amine phthalate resin, and the like. From the viewpoint of properties, it is preferably a curable resin containing a UV curable resin as a main component. The above ultraviolet curable resin, for example, a polyfunctional acrylate resin such as a acrylate or methacrylate of a polyhydric alcohol; Polyfunctional amine phthalate acrylate resin synthesized by cyanic acid vinegar or polyhydric alcohol, acrylonitrile or acrylic acid or f-based acrylic acid; and polyfunctional tree The polyfunctional resin may be a copolymer of a monofunctional monomer (for example, vinylpyrrolidine, methacrylic acid methyl acetonate, styrene, etc.) as needed. It is usually used after the addition of a photopolymerization initiator, and a photopolymerization initiator can be used without any particular limitation, and a conventional compound which absorbs ultraviolet rays and generates a radical can be used, for example, various benzoin and stupid ketones. The amount of the photopolymerization initiator to be added is preferably from about 5% to about 5 parts by mass per 100 parts by mass of the ultraviolet curable resin. -10- 201238765 When a cured layer is provided, for example After the coating liquid containing the hardening type resin is applied onto the first transparent plastic phosphine film, it may be heated and dried as necessary, or may be irradiated with ultraviolet rays when the externally curable resin is used. The coating method is not particularly limited to a conventional method such as a bar coating method, a gravure coating method, or a reverse phase coating method. The heating temperature can be appropriately set depending on the boiling point of the solvent used in the coating liquid, and it is not. It is particularly limited, but it is usually 5 01: above 2 5 0 c is better than 'better $ 7 〇 t or more 2 〇〇 t; below. The amount of light when the ultraviolet ray is irradiated is usually 1 〇 - 2 or more and 5 〇〇 mW or less, more preferably 200 mJ / cm 2 or more and 4 〇〇 mJ / cm 2 or less. The concentration of the coating liquid containing the above-mentioned curable resin can be appropriately selected in consideration of the viscosity of the coating method and the like. For example, when the coating liquid contains an ultraviolet curable resin and a photopolymerization initiator, the total amount of the ultraviolet curable resin and the photopolymerization initiator is about 2% by mass in the coating liquid. Further, an additive such as a coating agent such as a linaloone-based surfactant or a 1-based surfactant may be added to the coating liquid as needed. The thickness of the hardened layer is preferably O·1 or more, more preferably \.5_ : upper is preferably more than Um. When the thickness of the hardened layer is less than 〇_, it is difficult to form a structure that is sufficiently crosslinked. Therefore, it is easy to obtain a drug that is resistant to the drug:: Low molecular weight substances such as a polymer are not sufficiently inhibited. The tendency. Moreover, the thick product of the hardened layer is more... the following is particularly good for 8.... When the thickness of the hardened crucible exceeds 15#, the productivity tends to decrease. Preferably, the cured layer (i.e., the hard coat layer) provided on the surface opposite to the surface of the inorganic thin film layer 4 of the ith transparent plastic film is subjected to an antiglare treatment of 201238765. When the anti-glare treatment is applied to the hard coat layer which is the outermost surface of the laminate, it can be preferably used in a display device such as an electronic paper or an organic EL. The antiglare treatment can be carried out, for example, by adding cerium oxide particles to the coating liquid which forms the cured layer. In the resultant layer, in order to improve the adhesion to the inorganic thin film layer, and to be fine* treated with a surface. A specific method, for example, a method of increasing a carbonyl group, a carboxyl group, or a hydroxyl group by a discharge treatment method using a glow discharge or a corona discharge, using a chemical treatment method using an acid or a treatment to increase a polar group such as an amine group, a hydroxyl group, or a carbonyl group Method, etc. (Inorganic Thin Film Layer) The inorganic thin film layer is a film containing a metal or an inorganic oxide. A material for forming an inorganic thin film layer, for example, a metal oxide such as Si〇2 or ALA, or a composite metal oxide such as SiCVAhh. Among them, the material containing Ai2〇3 is preferred from the viewpoint of water vapor barrier properties. The refractive index h of the inorganic thin film layer is preferably 145 or more, more preferably! the above. When the refractive index is less than 145, it tends to be a porous film, and the gas barrier properties tend not to be improved. Further, the refractive index MUO of the inorganic thin film layer is preferably 'more preferably 165 or less. When the refractive index is more than 17 Å, the difference in refractive index between the first or second transparent plastic film and the adhesive layer is increased, so that the transmittance of the laminated body is lowered. The film thickness of the inorganic thin film layer is preferably 10 nm or more, more preferably 2 Å nm or more, still more preferably 30 nm or more. The thickness of the inorganic film layer is less than! (10) When the claw is used, it is difficult to form a film continuously, and it is difficult to obtain good gas barrier properties. Further, the film thickness of the inorganic thin film layer is preferably 200 nmw, more preferably Η10 (10) or less, still more preferably 160 nm or less. When the film thickness of the inorganic thin film layer exceeds -12-201238765, the stress of the inorganic thin film layer increases, cracks are liable to occur, and the water vapor barrier property is lowered. When the first transparent plastic film is thin, the content is low. Further, when the film thickness is increased, the water vapor barrier property is good, but when the buildup exceeds 100 nm, the productivity is lowered. Therefore, the best * 2 Λ , Λ Λ _ take the range of the horse 30 ~ ΙΟΟ ηπι. A film forming method of an inorganic thin film layer, y y, a vacuum vapor deposition method, a sputtering method, a CVD method, an ion implantation method, a spray coating method, and the like are known, and a film formed according to the above-mentioned conventional methods can be used. Thick and appropriate choice. In particular, the w-sputtering method is preferred from the viewpoint of reducing the unevenness of the film thickness. When the film is formed by a general sputtering method, the reactivity Dc < AC sputtering method can be used. In the reactive sputtering method, in order to increase the deposition rate, it is preferable to control the flow rate of the reactive gas such that the voltage of the dc or AC power source is kept constant, or to emit light of a specific element in the plasma. A plasma emission method for controlling the flow rate of a reactive gas in such a manner that the strength is kept constant. In particular, the impedance control method is preferable because it does not require a large amount of equipment and has excellent process stability. In the impedance control &, when the discharge voltage of the metal mode is 00% in the case where only an inert gas such as Ar is circulated, and the discharge voltage of the oxide or nitride mode when the reactive gas is equal to 〇%, It is preferable to control the discharge voltage to be 20 to 80%, and more preferably 3 to 7 %. When the amount is less than 20%, the effect of improving the film formation speed tends to decrease. On the other hand, when it exceeds _, the film thickness distribution tends to occur in the film width direction. Injecting μ, electrolysis, and ion assist. Further, in the range of the purpose of the invention, it is also possible to apply a direct current, an alternating current, a high frequency or the like to the substrate in the range of the purpose of the invention. Further, the water pressure at the time of film formation of the inorganic thin film layer is 2 Χ l (T3Pa or less, more preferably 5x1 (T4Pa or less. The water pressure exceeds 2 Χ l (T3Pa, in the inorganic thin film layer) Will run into hydrogen, sometimes the network (for example: M-0-) will stop growing, so the inorganic thin film layer will become lack of continuity, and the gas barrier properties will be reduced. When the inorganic thin film layer is formed into a film, it can be The first transparent plastic film is exposed to a vacuum, and the pressure is usually set to a degree of 〇1 Pa or more and 〇〇1 Pa or less. The exposure time is usually 5 minutes or more. When the inorganic thin film layer is formed into a film, It is preferable to provide an optical property (transmittance, color) measuring device in the film forming apparatus for the inorganic thin film layer having a higher gas barrier property. The film thickness and the oxidation degree of the inorganic thin film layer can be confirmed by measuring the optical characteristics. In order to measure the film thickness, it is also effective to use a fluorescent X-ray on the line (in line). (Adhesive layer) The adhesive layer is applied to the second transparent plastic film on the inorganic thin film layer of the laminated film. Film layer Or the second transparent plastic film is formed by coating the adhesive resin or laminating the adhesive resin into a sheet. The adhesive resin is not particularly limited, and for example, an acrylic resin, a stone resin, a rubber resin, or the like can be used. In particular, it is preferably an acrylic resin suitable for optics. The propylene & L-based resin can be polymerized by, for example, polymerizing a monomer component containing (meth)acrylic acid. (Mercapto) acrylic acid alkane-曰 and σ, for example, may be exemplified by (fluorenyl) decyl acrylate, (mercapto) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, (A-14-201238765 base) isobutyl acrylate, tert-butyl (meth)acrylate, n-hexyl (decyl) acrylate, 2-ethylhexyl (decyl) acrylate, n-octyl (decyl) acrylate An ester, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl acrylate, etc. The monomer component containing the alkyl (meth) acrylate may further be further Copolymerization with hydroxyl, carboxyl, guanamine, A monomer such as a hydrophilic group, which can increase adhesion to an adherend by copolymerizing a monomer having a hydrophilic group, specifically, for example, acrylic acid, methacrylic acid, maleic anhydride, and rebellion Benzophenone, (mercapto)acrylic acid 2_ mercaptoethyl ester, (meth)acrylic acid 2-hydroxypropyl vinegar, acrylamide, methacrylamide, dimethylamine (meth)acrylate Ethyl ester, etc. The obtained non-reverse starter obtained by the combined reaction will have a qualitative lowering agent, and the amount of the reaction can be controlled as follows. 丙 丙 丙 丙 5 5 5 5 丙 丙The polymerization of the resin should affect the barrier property. Therefore, the amount of the specific initiator is, and it is more preferable that the polymerization time is a resin, and the monomer component is usually added to maintain the polymerization initiator. The state is used. However, it is preferable that the moisture resistance is as small as possible, and the acrylic resin is preferably 0.2% by mass or less, and 5% by mass or less. The polymerization, polymerization temperature, and polymerization are used to accelerate the polymerization. And after the end of the reaction, the polymerization heat of the residual reaction or the like, the unreacted amount of the unreacted agent in the polymerization start of the environment is preferably 0.1, and the above-mentioned acrylic acid is obtained. A polymerization initiator which can be used for the purpose of, for example, benzepoxyperoxyperoxide, 113, w-butylperoxy peroxide, ,, 3-tetramethylbutyl hydroperoxide, peroxidation -15- 201238765 Second hexyl, dibutyl peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, third hexyl peroxide_2_ethyl Organic peroxides such as acid esters, t-butyl peroxy-2-ethylhexanoic acid vinegar, and lauric acid laurate; 2,2'-azobisisobutyronitrile, 2,2'-azobis (2) , 4• dimethyl valeronitrile), azo compounds such as 2,2′-azobis(2-mercaptobutyronitrile). Further, in the above-mentioned adhesive resin, it is preferable to contain a crosslinking agent in order to improve the holding power of the adhesive layer. The crosslinking agent may, for example, be a polyfunctional compound such as an isocyanate-based, epoxy-based, melamine-based, urea-based or metal-chelating system. The content of the crosslinking agent is preferably 〇 〇 1% by mass or more i 〇 by mass% or less based on the total solid content (adhesive sheet component) of the adhesive resin. When containing a crosslinking agent. It is also possible to further carry out the crosslinking reaction after the application of the adhesive resin, if necessary, or by aging at an appropriate temperature. The glass transition temperature of the above-mentioned adhesive resin is preferably _8 〇〇 C or more and yc or less, more preferably -70 ° C or more and -20 ° C or less. The molecular weight of the above-mentioned adhesive resin is preferably 10,000 to 3,000,000 in terms of weight average molecular weight. 5 0,000 to 2,000,000 is even better. When the weight average molecular weight of the adhesive resin is less than 10,0 0 0, when the adhesive layer is formed, since the viscosity is too low, the fluidity is too large, and it is difficult to form a uniform layer in the form of a sheet. Further, if it exceeds 3,000,000, the viscosity becomes too high, and the leveling action cannot be sufficiently exhibited, and it is also difficult to form a uniform layer. (Transparent Conductive Film Layer) The layered body of the present invention may be provided with a transparent conductive film layer on the surface opposite to the surface on which the pressure-sensitive adhesive layer of the second transparent plastic film is provided. Thereby, it can be used as a transparent conductive laminated film in electronic paper, an organic EL, a solar cell, or the like. -16- 201238765 For the material forming a transparent conductive film, for example, indium oxide, tin oxide, zinc oxide, indium-tin composite oxide, tin-bismuth composite oxide, zinc-bis composite oxide, indium-zinc composite An inorganic substance such as an oxide; a conductive polymer such as polyaniline, a polypyramidine ratio B, a polyethylene fast, a poly D plug, and a p ED Ο T (poly(3,4-ethylideneoxy)); The organic matter of the extremely fine conductive carbon fiber (Neilai carbon tube, nano carbon angle, nano carbon wire, etc.) is dispersed in the polymer; the graphite is thin. Among them, indium-tin composite oxide is preferred from the viewpoint of environmental stability or circuit processability. The layer structure of the transparent conductive film may be a single layer structure or a laminated structure of two or more layers. In the case of a transparent conductive film having a laminated structure of two or more layers, the materials (metal oxides, etc.) constituting each layer may be the same or different. The method for forming a transparent conductive film is known as a vacuum deposition method, such as a "nice method, a CVD method, an ion implantation method, a spray method, etc.", and it is possible to appropriately select the film thickness to be formed according to the conventional methods. . In particular, from the viewpoint of reducing the unevenness of the film thickness, the money plating method is preferable. At this time, oxygen, nitrogen, or the like may be introduced into the reactive gas, or a method such as ozone addition, electropolymerization irradiation, or ion assist may be used in combination. Further, in the range which does not impair the object of the present invention, a bias voltage such as direct current, alternating current, or high frequency may be applied to the substrate. The film thickness of the transparent conductive film is preferably 4 or more, more preferably 1 Onm or more. When the film thickness of ', and 暝 is less than 4 nm, it is not easy to form a continuous film, and it is difficult to obtain good conductivity. Further, the film thickness of the transparent conductive film is 200 η "better, more preferably " Ο · below. The film thickness of the transparent conductive film is less than that of 2 虞. Easy 201238765 laminated transparent conductive film® t 13⁄4 Μ A <;, and the laminate of the present invention has a surface = and 値 is 5 _ Ω / □ preferably, more preferably (10) surface resistance 値 if used in the above table In the case of snow, as a transparent conductive laminated film, there is a solar cell, etc. On the other hand, if the surface resistance 値 is deviated from the above-mentioned range, it is not preferable. The response speed of the full-light layer is slowed down. When the transmittance is 87% or more, it is preferable that the transmittance of the device is less than 87%, and the use of an electrode substrate such as an electronic paper tends to reduce the total light reading L property, and the visibility tends to be deteriorated. 'In particular, the inorganic thin film layer and the first layer: the difference between the two layers and the inorganic thin film layer and the adhesive<: difference 1 η3_η2丨 are effective, as long as the above (1) and the relationship are satisfied. And (Π) relationship (ie, 丨 or 1 丨 丨 値 exceed 〇. 2), difficult In order to make the transmittance and the total light penetration of the layered body (4), it can be determined by the method described later in the example. Further, the layered body of the present invention has a color b値 of mo% and a color of less than -2. %, the degree of bluishness of the device will increase, and if it exceeds 4.0%, the degree of yellowing will increase, and the degree of visibility will be poor. If it is a laminate that satisfies the relationship between (1) and (ii) above, 1 The color of the upper layer of the shirt will be in the above range. The 'color of the laminated body' can be measured by the method described later in the embodiment. The laminate of the present invention has a water vapor permeability of less than 0.3 g/m2/day: preferably. If it is used for a long period of time, when the device is used for a long period of time, moisture gradually enters the device, and it is easy for 201238765 to satisfy the above-mentioned (1) and (π) relationship, and the water vapor is in the above range. Further, the water vapor transmission rate of the laminate was measured by the method described later. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, and is limited to the examples. X, the performance of the laminated body is determined according to the following <water vapor transmission rate> According to JIS-K7129 B method 'using water vapor penetration ("AQUATRAN" manufactured by MOCON Corporation), water is measured in a gas atmosphere at a temperature of 90% RH Vapor permeability. In addition, the body is conditioned, and the water vapor is in the direction of the transparent plastic side of the first transparent plastic side. <Total Light Transmittance> The total light transmittance (%) was measured in accordance with JIS-K7136 using Nippon Electric Co., Ltd. "NDH-1 00 1 DP". <Color b値> According to JIS-K7105, a color difference meter (Japan $ "ZE-2000") is used to measure the color b 1 <surface resistance 値> according to JIS - K 7 1 9 4 'Lotest AMCP-T400, manufactured by Mitsubishi Petrochemical Co., Ltd., was measured by the 4-terminal method. <Thickness of Inorganic Thin Film Layer and Transparent Conductive Thin Film Layer> The thickness of the inorganic thin film layer is a film in which an inorganic thin film is formed, and a film of a transparent conductive thin film layer is formed into a transparent conductive film. The film at the stage of the layer as a sample penetration rate can be determined, for example, but not by the method of the present invention. The measuring device is 40 ° C, humidity, and is laminated to the second industry (stock). Blocking. The thickness of the film layer was measured, and the film was cut into pieces of 1 mm x 1 〇 mm each, and the imaginary ray was buried in the epoxy resin. The short side of the sample piece which is fixed to the sample of the ultramicrotome is a portion of the film of the parallel section thin slice which has no obvious damage, and the etch 1 is used for penetration (JEOL company "JEM-2010" w | + ”) In order to accelerate the electric field, take a picture of 10,000 times and take a shot of 10,000 meters. 201238765 <Refractive index of the inorganic thin film layer of the inorganic thin film layer and the transparent conductive thin film layer, the sample for measuring no refractive index is formed by the same film forming conditions in the stone embodiment or the comparative example, and The sample vibrating spectrometer (ellipsometer) (Dayu Electronics (shares: it is set at 55〇n...the rate of shots, will receive:
折射率。 F .目〜\ 双付之設有無相 測疋分光穿透率，對 進行擬合，” C之數據，使 m ,, 汁"'折射率（此時，無機薄 用上述測定方法獲得 層之折射率與石夕“卜）’、、，°果確認計 Μ ^ ,βιΙ ^ a a ®上之無機薄膜層之 射羊：'用試樣測定之折射率)無大差別 上以斑文透明導電性薄膜層之折射率， 上以與各實施例相 以製作折射率 °成膜條件形成透明㊁ 機薄2 定”樣，並針對獲^ 又：之折射率同樣地以分光楕圓偏指 積層祺，：對實施你"獲得之設有透明驾 曰、’與上述同樣地確認算出之透明 子顯微鏡用環 架，製作與包 其次，於該切 型電子顯微鏡 I 200kv、明視 :之照片求出膜 Ψ > 圓上於與各實 膜層，以製作 用分光楕圓偏 製「FE-5000」） 無機薄膜層之 膜層之積層膜 光學模擬軟體 層之獏厚係使 出之無機薄膜 射率（使用折 ^由於矽晶圓 :性薄膜層， 1樣與上述無 谱儀測定。 性薄膜層之 電性薄膜層 -20- 201238765 之折射率與矽晶圓上之透明導電性薄膜層之折射率（使 用折射率測定用試樣測定之折射率）無大差別。 <黏著劑層、透明塑膠膜之折射率> 依JIS-K7 142-1996 5_1(A法），利用以鈉d線作為光 源之阿貝折射計測定折射率。 [實施例1] 作為第一透明塑膠膜，使用厚度125/zm、折射率 l. 65之雙軸配向透明聚對苯二甲酸乙二醇酯（pet)膜，並 於該PET膜之單面積層硬化物層。 積層硬化物層時，係於含光聚合起始劑之紫外線硬 化型丙烯酸系樹脂（大曰精化工業公司製r SEIKABEAM EXF-01J」）100質量份中，添加作為溶劑之曱苯/曱乙酮 (MEK) = 80/20(質量比）之混合溶劑，使固體成分濃度成 為50質量％，並攪拌使均勻溶解，將藉此製備的塗布液 使用梅爾棒（Meyer Bar)塗布在PET膜上使膜厚成為 m。 之後於8〇°C進行1分鐘乾燥後，使用紫外線照射裝 置（Eyegraphics公司製「UB〇42 5AM_w型」）照射紫外線 (光里.300mJ/cm2) ’使塗膜硬化。其次，於18〇。〇施以 1分鐘的加熱處理，使揮發成分減低。 其-人，為了將無機薄膜層成膜，將前述積層有硬化 物層之第1透明塑膠膜進行真空暴露。具體而言，於真 工腔至只轭回捲處理，此時之壓力設定為2x1 0_3pa、暴 路吟】-又疋為20分鐘，中央輥之溫度設定為4〇。。。 於第1透明塑膠膜之未形成硬化物層之面， 以 D C磁控營減•你： 機鍵法’形成包含氧化鋁（Α!2〇3)的無機薄 201238765 膜層。此時係確認濺鍍前之真空腔室之水壓為i i 〇-4pa 後實施。濺鍍時，靶材使用A1 (Tech no fine公司製），並 施加3W/cm2之DC電力。並且’通入Ar氣體，使成為 〇.4Pa之氣體環境下’中央輥溫度定為。又，使用Refractive index. F. Mesh ~ \ double payment with no phase measurement 疋 split light transmittance, for the fit, "C data, make m,, juice &" 'refractive index (at this time, inorganic thin with the above determination method to obtain the layer The refractive index and the stone eve "b" ',,, °, the fruit is confirmed Μ ^, βιΙ ^ aa ® on the inorganic film layer of the sheep: 'refractive index measured with the sample' without significant difference on the spotted transparent The refractive index of the conductive thin film layer is formed by forming a refractive index with each of the examples to form a transparent thin film, and the refractive index of the obtained refractive index is similarly积 祺 祺 : : : : : : : : : : : : : : : : : : : : : : 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明In the photograph, the thickness of the laminated film optical simulation soft layer of the film layer of the film layer formed on the film layer of the "F-5000" is formed on the film layer of each of the solid film layers. Inorganic film rate (use of folding ^ due to 矽 wafer: thin film layer, 1 and above The spectrometer is measured. The refractive index of the thin film layer 20-201238765 and the refractive index of the transparent conductive film layer on the germanium wafer (the refractive index measured by the sample for refractive index measurement) are not large. Difference: <Refractive index of adhesive layer, transparent plastic film> According to JIS-K7 142-1996 5_1 (method A), the refractive index was measured by an Abbe refractometer using sodium d-line as a light source. [Example 1] As the first transparent plastic film, a biaxially oriented transparent polyethylene terephthalate (PET) film having a thickness of 125/zm and a refractive index of 1.56 was used, and a single-layer cured layer of the PET film was used. When the cured layer is laminated, 100 parts by mass of an ultraviolet curable acrylic resin (r SEIKABEAM EXF-01J, manufactured by Otsuka Seiki Co., Ltd.) containing a photopolymerization initiator is added as a solvent. A mixed solvent of ketone (MEK) = 80/20 (mass ratio), the solid content concentration was 50% by mass, and stirred to uniformly dissolve, and the coating liquid prepared thereby was coated on the PET film using a Meyer Bar. The film thickness was made m. After drying at 8 ° C for 1 minute, Ultraviolet irradiation apparatus ("UB〇42 5AM_w type" manufactured by Eyegraphics Co., Ltd.) was irradiated with ultraviolet rays (light: 300 mJ/cm2) to harden the coating film. Secondly, it was heated at 18 Torr for 1 minute to reduce the volatile content. In order to form an inorganic thin film layer, the first transparent plastic film in which the cured layer is laminated is vacuum-exposed. Specifically, the pressure is set in the true working chamber to the yoke rewinding process. For 2x1 0_3pa, violent path 吟 - - 疋 for 20 minutes, the temperature of the center roller is set to 4 〇. . . On the surface of the first transparent plastic film where the hardened layer is not formed, the inorganic thin 201238765 film layer containing alumina (Α! 2〇3) is formed by the D C magnetic control camp. In this case, it is confirmed that the water pressure of the vacuum chamber before the sputtering is i i 〇 -4pa. At the time of sputtering, A1 (manufactured by Techno Fine Co., Ltd.) was used as the target, and DC power of 3 W/cm 2 was applied. Further, the Ar gas was introduced, and the temperature of the center roll was set to be in a gas atmosphere of 〇.4 Pa. Again, use
Gencoa公司製之「Speedflo」，於控制氧氣流量的狀態實 施濺鍍，使濺鍍時之放電電壓成為固定，此值，係#定 為僅通入Ar氣體時之放電電壓定為1〇〇%、通入μ氣體 與〇2氣體5〇Sccm時之放電電壓定為〇%時，成為5〇%之 値之放電電壓。如此形成之無機薄膜層 丸〇 t 61〜狀坪马40nm、 折射率為1.5 9。 头次，在 山必7|夕 、日〜丄，隔著黏荖名 層貼合第2透明塑膠膜，並製作積層冑。具體而古， 無機薄膜層上’以塗布丙烯酸系黏著樹脂(厚：Μ 片狀物)形成折射率丨·52之黏著劑層後，在二二 之上，貼合厚度50ρ、折射率1>65之 針芏-田减， ^ 、又釉配向透明ί 子本甲二㈣旨〇膜作為第2透 針對獲得之積層體，評價水基/膜 透率、夯由iw古 …礼穿透率、全光線； 一手杉色b値，結果如表1所示。 [實施例2 ] 將無機薄膜層製膜時， 機薄膜層之膜厚成為2〇nm 式製作積層體。 除了藉由改變放電電壓使無 外與I施例1以同樣方 獲得之積層體 針對獲得之積層體 彩色b値，結果如 之無機薄犋層之折射 ，評價水蒸氣穿透率、 表1所示。 率如表1。又 全光線穿透率 -22- 201238765 [實施例3 ] 將無機薄膜層製 無機薄膜層之 、i ’除了心改變放電電壓 灯而製作積層體。 ，、霄％例丨同樣進 獲得之積層體之盔 示。又，針對獲得之積：：折射率，如表1所 線穿透率、彩色b値，…：：水蒸氣穿透率、全光 [實施例4] 、、，。果如表1所示。 將無機薄膜層製膜時 + 無機薄膜層之膜厚成Α 、 θ改變放電電壓而使 行而製作積層體。為10°nm以外’與實施例丨同樣進 獲得之積層體之 示。又，針對獲得之热 之折射率，如表1所 線穿透率、彩層體’評價水蒸氣穿透率、全光 [實施例5] ’結果如表1所示。 將無機薄膜層製M^ ^ 無機薄膜層之膜 、夺，* 了精由改變放電電壓而使 行，而製作積層體。為1 5〇ηΐΏ以外’與實施例1同樣進 獲得之積屏# 示。又，# # 無機薄膜層之折射率，如表丨m 又，針對獲得夕蚀Η 卞戈衣1所 線穿透率、彩“積層體’評價水蒸氣穿透率、全光 [實施例6] 値’結果如表1所示。 將無機薄腔^ i命j 使無機薄膜層之二戸祺時，除了藉由改變放電電壓’而 進行而製作二層體^成為200請以外’與實施例1同樣 -23- 201238765 獲得之積層體之無機薄膜層之折射率，如表丨所。 又，針對獲得之積層體，評價水蒸氣穿透 透率、彩色b値，結果如表u示。 ^ [實施例7] 在實施例1製作之積層體之第2透明塑膠膜之上（外 側面）’以DC磁控管濺鍍法形成包含銦錫複合氧化物的 透明導電性薄膜層。此時確認濺鍍前之真空腔室之水壓 為jxl〇-4Pa後實施濺鍍。濺鍍時，靶材使用含氧化錫ι〇 質1 /〇之氡化銦（住友金屬礦山公司製，密度， 並施加2W/cm2之DC電力。並且，通入Ar氣體與〇2氣 體使其以表面電阻値成為最小的流速流通，並成為& 之氣體環境下，中央輥溫度定為〇<t。又，一面隨時以 濺鍍處理監視器（LEYBOLD INFIC〇N公司製「xpR2」） 觀測氣體環境之氧氣分壓，一面對於氧氣之流量計及^ c 電源回饋，使得銦-錫複合氧化物薄膜層中之氧化度成為 固定。如此形成之透明導電性薄膜層之膜厚為2〇nm、折 射率為1.8 5。 針對獲得之積層體，評價水蒸氣穿透率、全光線穿 透率、彩色b値及透明導電性薄膜層側之表面電阻値， 結果如表1所示。 [實施例8 ] 將硬化物層積層時，對於塗布液添加平均粒徑〇 5 // m之一氧化矽粒子丨〇質量份，除此以外，與實施例1 同樣進行而獲得積層體，並且對於該積層體與實施例7 同樣地積層透明導電性薄膜層，而製作積層體。 -24- 201238765 針對獲得之積層體， 透率、势& U °平饧K虱牙透率、全光線穿"Speedflo" manufactured by Gencoa Co., Ltd. performs sputtering in the state of controlling oxygen flow rate, so that the discharge voltage at the time of sputtering becomes fixed. This value is set to be 1%% of the discharge voltage when only Ar gas is introduced. When the discharge voltage when the μ gas and the helium gas are 5 〇 Sccm is set to 〇%, the discharge voltage is 〇5%. The inorganic thin film layer thus formed was 40 nm and had a refractive index of 1.59. For the first time, in the mountain will be 7 | eve, day ~ 丄, the second transparent plastic film is attached through the layer of adhesive, and a layer of enamel is made. Specifically, on the inorganic thin film layer, an adhesive layer of a refractive index 丨·52 is formed by coating an acrylic adhesive resin (thickness: Μ sheet), and a thickness of 50 ρ and a refractive index of 1 are applied on the second and second layers. 65 needle acupuncture - field reduction, ^, and glaze alignment transparent 子 本 甲 ( ( ( ( ( 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为 作为, full light; one hand cedar b値, the results are shown in Table 1. [Example 2] When the inorganic thin film layer was formed into a film, the film thickness of the organic film layer was 2 nm to form a laminate. In addition to changing the discharge voltage, the laminate obtained in the same manner as in Example 1 was obtained for the obtained color of the laminate, and as a result, the refractive index of the inorganic thin layer was evaluated, and the water vapor transmission rate was evaluated. Show. The rate is shown in Table 1. Further, the total light transmittance is -22-201238765. [Example 3] An inorganic thin film layer was formed into an inorganic thin film layer, and i' was made to have a laminate by changing the discharge voltage lamp. , 霄% of the cases are also obtained by the helmet of the laminated body. Further, for the obtained product:: refractive index, as shown in Table 1, the line transmittance, color b, ...:: water vapor transmission rate, total light [Example 4], . The results are shown in Table 1. When the inorganic thin film layer is formed into a film, the thickness of the inorganic thin film layer is Α, and θ is changed by a discharge voltage to form a laminated body. The layered body obtained in the same manner as in Example 为 except for 10 ° nm is shown. Further, the refractive index of the obtained heat was as shown in Table 1 as shown in Table 1 for the line penetration rate, the evaluation of the water vapor transmission rate of the color layer body, and the total light [Example 5]. The inorganic thin film layer is formed into a film of the M^^ inorganic thin film layer, and the fine film is formed by changing the discharge voltage to form a laminate. It is shown in Fig. 1 which is obtained in the same manner as in the first embodiment except for 1 5〇ηΐΏ. Moreover, the refractive index of the ## inorganic thin film layer, as shown in Table 又m, is obtained for the line penetration rate of the eclipse 卞 卞 衣 1 、 、 、 、 、 、 、 、 、 、 、 、 评价 评价 评价 评价 评价 评价 评价 评价 评价 评价 评价 评价 评价 评价 评价 评价The results are shown in Table 1. When the inorganic thin film layer was used to make the inorganic thin film layer two turns, the second layer was formed by changing the discharge voltage, and the second layer was formed to be 200. 1 Similarly -23- 201238765 The refractive index of the inorganic thin film layer obtained by the laminated body is as shown in Table 又. Further, for the obtained laminated body, the water vapor transmission rate and the color b 评价 are evaluated, and the results are shown in Table u. [Example 7] A transparent conductive thin film layer containing an indium tin composite oxide was formed on the second transparent plastic film (outer side surface) of the laminate produced in Example 1 by DC magnetron sputtering. It is confirmed that the water pressure of the vacuum chamber before the sputtering is jxl 〇 -4 Pa, and the sputtering is performed. When the sputtering is performed, the target is made of indium antimonide containing tin oxide ITO 1 / ( (manufactured by Sumitomo Metal Mining Co., Ltd., density, And apply 2W/cm2 of DC power. And, Ar gas and helium 2 gas are introduced to make the surface resistance The minimum flow rate is circulated, and the temperature of the center roll is set to 〇<t. In the gas environment of the &, the oxygen of the gas environment is observed by a sputter treatment monitor ("xpR2" manufactured by LEYBOLD INFIC〇N). The partial pressure, the oxygen flow meter and the ^ c power feedback, make the degree of oxidation in the indium-tin composite oxide film layer fixed. The transparent conductive film layer thus formed has a film thickness of 2 〇 nm and a refractive index of 1.8. The water vapor permeability, the total light transmittance, the color b値, and the surface resistance 侧 on the transparent conductive film layer side were evaluated for the obtained laminate, and the results are shown in Table 1. [Example 8] In the case of the layered layer of the hardened material, a layered body was obtained in the same manner as in Example 1 except that the amount of the cerium oxide particles was 5% by mass or less, and the layered body was obtained. Example 7 A transparent conductive thin film layer was laminated in the same manner to form a laminated body. -24- 201238765 For the obtained laminated body, permeability, potential & U ° flat K 虱 tooth permeability, total light wear
y 値及透明導電性薄膜層側之矣& f K 結果如表丨所示。等罨性/專膜層側之表面電阻値’The 矣& f K results on the side of the y 値 and the transparent conductive film layer are shown in Table 。. The surface resistance of the isotropic/adhesive layer side
[實施例9J 就無機薄膜厚而 Α1 〇 ς.〇膜層而& ，係以DC磁控管濺鍍法將包含 AI2〇3-S1〇2的無機薄膜 同樣進行而製作積層體二Q除此卜與實施例1 詩〜W 2 3_siG2膜之相，係確認 ’又刖λ空腔室之水壓為lxl0-4pa後實施。濺鍍時， 靶材使用A“Si(組成比A1: Si=5: 5,高純度化學製卜 並施加3WW之DC電力。並且，通人^氣體，使成 為0.4Pa之氣體環境下，中央輥溫度設定為^又，使 用Gencoa公司製「Speedfl0」於控制氧氣流量的狀態進 行濺鍍，使得濺鍍時之放電電壓成為固定，此時，設定 為僅通入Ar氣體時之放電電壓定為1 〇〇%、流通Ar氣體 與〇2氣體50sccm時之放電電壓定為0%時，使得成為 50%之値之放電電壓。如此形成之無機薄膜層之膜厚為 40 nm、折射率為1.52° 針對獲得之積層體’評價水蒸氣穿透率、全光線穿 透率、彩色b値及透明導電性薄膜層側之表面電阻値， 結果如表1所示。 [實施例10] 就第1透明塑膠膜而言’除了使用厚度100/zm、折 射率1.53之環烯烴系膜（日本ZE〇N公司製r ZF_14」）， 且不積層硬化物層以外’與實施例1同樣進行而製作積 層體。 -25- 201238765 透率、全光線穿透 針對獲得之積層體評價水蒸 率、彩色b値’結果如表1所示。 [實施例1 1 j (外側面Γ:νο製作之積層體之第2透明塑膠膜之上 物的透日7同樣進行，將包含銦.錫複合氣化 透月導電性薄膜層成膜而製作積層體。 針對獲得之積層體，評價皮Υ 、 透率、彩色b値及透明導電性薄膜：透率、全光線穿 結果如表丨所示。導…膜層側之表面電阻値’[Example 9J] Inorganic film was thick and Α1 〇ς. 〇 film layer and &, the inorganic film containing AI2〇3-S1〇2 was similarly subjected to DC magnetron sputtering to form a laminate 2 Q addition This is the same as the phase of the poem ~ W 2 3_siG2 film of Example 1 and was confirmed to be carried out after the water pressure of the chamber of the 刖λ chamber was lxl0-4pa. When sputtering, the target uses A "Si (composition ratio A1: Si = 5: 5, high-purity chemical preparation and application of 3WW of DC power. And, through the gas, to become a 0.4Pa gas environment, the central The roll temperature was set to ^, and the "Speedfl0" manufactured by Gencoa Co., Ltd. was used to perform sputtering at a state in which the oxygen flow rate was controlled, so that the discharge voltage at the time of sputtering was fixed. At this time, the discharge voltage when only Ar gas was introduced was set as When 放电%, the discharge voltage of the Ar gas and the 〇2 gas at 50 sccm is set to 0%, the discharge voltage is 50%. The inorganic thin film layer thus formed has a film thickness of 40 nm and a refractive index of 1.52. ° The water vapor permeability, the total light transmittance, the color b値, and the surface resistance 侧 on the side of the transparent conductive film layer were evaluated for the obtained laminated body. The results are shown in Table 1. [Example 10] In the transparent plastic film, a layered layer was produced in the same manner as in Example 1 except that a cycloolefin film (r ZF_14 manufactured by ZE〇N Co., Ltd.) having a thickness of 100/zm and a refractive index of 1.53 was used, and the layer of the cured layer was not laminated. -25- 201238765 Transmittance, full light penetration needle The results of the evaluation of the water vaporization rate and the color b 値 of the obtained laminate were as shown in Table 1. [Example 1 1 j (outer side Γ: νο The second transparent plastic film of the laminated body produced by the same material A laminate comprising an indium-tin composite vaporized vapor-permeable conductive film layer was formed to form a laminate. The obtained laminate was evaluated for skin flaw, transmittance, color b値, and transparent conductive film: transmittance, total light. The results of the wear are shown in the table. The surface resistance of the film side is...
[實施例12J 將無機薄膜層成膜時’除了與實施例9同樣將包含 的無機薄膜層成膜以外，與實施 <列記載同 樣進行而製作積層體。 針對獲侍之積層體’評價水蒸氣穿透率、全光線穿 透率、彩色b値，結果如表1。 [比較例1 ] 就無機薄膜層而言，係除了以DC磁控管錢鍍法將 包含氮化鋁的無機薄膜層成膜以外，與實施例1同樣進 打而製作積層體。氮化鋁膜之成膜，係確認濺鍍前之真 二腔至之水壓為lxl〇4pa後實施。賤鑛時，乾材使用[Example 12J When the inorganic thin film layer was formed into a film] A laminate was produced in the same manner as in the description of the column except that the inorganic thin film layer was formed in the same manner as in Example 9. The water vapor transmission rate, the total light transmittance, and the color b 评价 were evaluated for the obtained laminate body. The results are shown in Table 1. [Comparative Example 1] A laminate was produced in the same manner as in Example 1 except that the inorganic thin film layer containing aluminum nitride was formed by DC magnetron plating. The film formation of the aluminum nitride film is carried out after confirming that the true two chambers before the sputtering have a water pressure of lxl 〇 4 Pa. Dry metal use
Al(Technofine公司製）’並施加2w/cm2之dc電力。並 且’通入Ar氣體，使成為〇4pa之氣體環境下，且中央 報溫度定為（TC。又，使用Gencoa公司製「Speedflo」 於控制氮氣流量的狀態使得濺鍍時之放電電壓成為固 疋 此時’设疋為僅通入Ar氣體時之放電電壓定為 -26- 201238765 100%、通入Ar氣體與n2氣體50sccm時之放電電壓定 = 成為50%之値之放電電壓。如此形成之無機薄 膜廣之膜厚為40nm、折射率為2 12。 針對獲得之積層冑’評價水蒸氣穿 透率、彩色b値，結果如表卜 +王先線穿 [比較例2] 就無機薄膜層而言’係除了以Dc磁控管濺鍍法將 包含氧化*-石夕複合氧化物（Zr〇2_Si〇2)的無機薄膜層成 膜以外，與實施例1同樣進行而製作積層體。氧化鈣-矽複合氧化物膜之成膜，係確認濺鍍前之真空腔室之^ 壓為lxl〇-4Pa後實施。濺鍍時，靶材使用zrsi =三井^ 屬製），並施加2W/cm2之DC電力。並且通入&氣體、， 使成為〇.4Pa之氣體環境下’且中央輕溫度定為代。 又’使用Gencoa公司製「Speedfl〇j於控制氧氣流量之 狀態使濺鍍時之放電電壓成為固定，此時，設定為僅通 入Ar氣體時之放電電壓為100%、通入Ar氣體與〇2氣 體5〇Sccm時之放電電壓為0%時，成為5〇%之値之放電 電壓。如此形成之無機薄膜層之膜厚為4〇nm、折射率為 1.80。 針對獲得之積層體，評價水蒸氣穿透率、全光線穿 透率、彩色b値，結果如表1。 [比較例3 ] 就第1透明塑膠膜而言，除了使用厚度100/zm、折 射率1.34之六氟丙烯之共聚物膜（Daikin化學工業製 「Neoflon FEP膜NF-0 100」）以外，與實施例1同樣進 行而製作積層體。 -27- 201238765 針對獲得之積層體評價水蒸氣穿 率、彩色b値，結果如表i。 干、王光線穿透 表1Al (manufactured by Technofine Co., Ltd.) and applied dc power of 2 w/cm 2 . In addition, the Ar gas is introduced into a gas atmosphere of 〇4pa, and the central temperature is set to (TC. In addition, the "Speedflo" manufactured by Gencoa Co., Ltd. is used to control the flow rate of nitrogen gas so that the discharge voltage at the time of sputtering becomes solid. When the current is set to only Ar gas, the discharge voltage is set to -26-201238765 100%, and the discharge voltage when the Ar gas and the n2 gas are 50 sccm are set = the discharge voltage becomes 50%. The inorganic thus formed The film has a film thickness of 40 nm and a refractive index of 2 12. The evaluation of the water vapor transmission rate and the color b 针对 of the obtained laminated layer 値, the results are as shown in the table + Wang Xianxian [Comparative Example 2] on the inorganic thin film layer In other words, a layered body was produced in the same manner as in Example 1 except that an inorganic thin film layer containing an oxidized *-stone compound oxide (Zr〇2_Si〇2) was formed by a Dc magnetron sputtering method. - The film formation of the composite oxide film was carried out after confirming that the pressure of the vacuum chamber before the sputtering was lxl 〇 -4 Pa. When the sputtering was performed, the target was made of zrsi = Mitsui Co., and 2 W/cm 2 was applied. DC power. And the gas is introduced into the gas atmosphere of 〇.4Pa and the central light temperature is determined as a generation. Further, 'the speed of the oxygen flow rate was controlled by the Gencoa company's "Speedfl〇j", and the discharge voltage at the time of sputtering was fixed. At this time, the discharge voltage was set to 100% when only Ar gas was introduced, and Ar gas and helium were introduced. When the discharge voltage of the gas at 5 〇Sccm is 0%, the discharge voltage is 〇5%. The film thickness of the inorganic thin film layer thus formed is 4 〇 nm, and the refractive index is 1.80. Evaluation of the obtained laminate The water vapor transmission rate, the total light transmittance, and the color b 値 are shown in Table 1. [Comparative Example 3] For the first transparent plastic film, except that a hexafluoropropylene having a thickness of 100/zm and a refractive index of 1.34 was used. A laminate was produced in the same manner as in Example 1 except that the copolymer film ("Neoflon FEP film NF-0 100" manufactured by Daikin Chemical Industry Co., Ltd.) was used. -27- 201238765 The water vapor transmission rate and color b値 were evaluated for the obtained laminate. The results are shown in Table i. Dry, king light penetration Table 1
從表1之結果可知，丨無機薄膜展^ 透明塑膠膜之抽M i , 、9之折射率ns-第1 錢膜之折射率〜i之値、 率n3-黏著劑層之折射率:機薄膜層之折射 圍内的實施例丨〜12之積層體得善者落於本發明之範 水蒸氣阻隔性者。 兼具優異透明性與優異 膜之I:::此，1 I機薄膜層之折射率¥第1透明塑膠 甽 · ：； &丨之値、與丨無機薄膜層之折射率ιι3-黏著 二B之折射率112丨之値兩者落於本發明之範圍外的比較 之積層體，或僅有丨無機薄膜層之折射率黏著劑 之折射率112丨之値落於本發明之範圍外的比較例2的 積層體’全光線穿透率為8 2%至Μ%，均為透明性不足 者。又，僅有I無機薄膜層之折射率n3_第丨透明塑膠膜 斤射率η! |之値落於本發明之範圍外之比較例3之積 -28- 201238765 層體’具有足夠之無機薄膜層之厚度（40nm)，但水蒸氣 穿透率而’為〇.25g/m2/day，為水蒸氣阻隔性差者。 [產業上之可利用性] 本發明之積層體，由於透明性及水蒸氣阻隔性優異 故特別適用於作為電子紙、太陽能電池、有機EL等電 子材料之基板。 【圖式簡單說明】 第 面圖。 圖顯示本發明之積層體之一 實施形態之概略剖 第2圖顯示本發明之積 V咐有透 明導電性薄膜之積層體)之J之另貫 Γ ^ Φ 槓層之概略剖面圖。 L主要兀件符號說明】 1 第1透明塑膠膜 2 硬化物層 3 無機薄膜層 4 黏著劑層 5 第2透明塑膠膜 6 透明導電性薄膜層 1Q積層體 11 附有透明導電性 薄膜之積層體From the results of Table 1, it can be seen that the refractive index of the 丨-inorganic film is transparent, and the refractive index of the ns-first film is i, the ratio of the n-adhesive layer is: The laminate of the examples 丨~12 in the refractive area of the film layer is good in the water vapor barrier property of the present invention. I::: This, the refractive index of the 1 I machine film layer: 1st transparent plastic 甽·:; & 丨 丨, and 丨 inorganic film layer refractive index ιι3-adhesive The refractive index of B, which is outside the range of the present invention, or the refractive index of the refractive index adhesive of only the inorganic inorganic thin film layer, is less than the range of the present invention. The laminated body of Comparative Example 2 had a total light transmittance of 82% to Μ%, and all of them were insufficient in transparency. Further, only the refractive index n3 of the I inorganic thin film layer 丨 丨 丨 丨 丨 丨 -28 -28 比较 比较 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 The thickness of the film layer (40 nm), but the water vapor transmission rate is '25 g/m2/day, which is poor in water vapor barrier property. [Industrial Applicability] The laminate of the present invention is particularly suitable for use as a substrate for an electronic material such as an electronic paper, a solar cell, or an organic EL because of its excellent transparency and water vapor barrier properties. [Simple description of the diagram] The first picture. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 2 is a schematic cross-sectional view showing an embodiment of the present invention. Fig. 2 is a schematic cross-sectional view showing a further Γ Φ bar layer of J of a laminate of a transparent conductive film of the present invention. L main component symbol description] 1 first transparent plastic film 2 hardened layer 3 inorganic thin film layer 4 adhesive layer 5 second transparent plastic film 6 transparent conductive film layer 1Q laminated body 11 laminated body with transparent conductive film
S -29.S -29.