201106381 六、發明說明 【發明所屬之技術領域】 本發明係關於一種具有氧化鋅系導電層之層合體，層 間密著性優異，且耐濕熱性優異之氧化鋅系導電性層合體 及其製造方法。 【先前技術】 以住’於液晶顯不器或液晶觸控面板等之透明電極， 係可使用ITO(摻雜錫之氧化銦）作爲透明導電性材料，但 近年’就未使用稀少金屬之銦的IT 0替代透明導電性材料 已提出氧化鉢系導電材料，但，氧化鋅系導電材料係相較 於ITO而有缺乏耐濕熱性之問題。 因此，例如於設在塑膠基材上之硬塗層上設有已慘雜 矽之氧化鋅膜的透明導電體已被提出（參照專利文獻υ。 如此之透明導電體係藉由摻雜矽之氧化鋅膜，俾可降低在 高溫高濕下之薄片電阻的隨時間變化，但有結晶性降低而 損及電導電性之問題。 又’於氧化鋅系透明導電膜添加鎵而提昇耐熱性之透 明發熱體已被提出（參照專利文獻2)。但，如此之透明發 熱體必須在特定之條件下含有鎵，有製造條件受到相當限 制之問題。又，於此文獻中亦已揭示設有外覆層之透明發 熱體，但爲免導電性受影響，要設置外覆層係很困難，且 很難使用來作爲透明電極。 [先前技術文獻] -5- 201106381 [專利文獻] [專利文獻1]特開平8-45452號公報 [專利文獻2]特開平6- 1 8 7 8 3 3號公報 【發明內容】 [發明之槪要] [發明欲解決之課題] 因此，本發明之課題在於提供一種具有氧化鋅系導電 層之氧化鋅系導電性層合體，且即使在濕熱環境下電阻率 隨時間變化少，且密著性優異之氧化鋅系導電性層合體及 其製造方法。 [用以解決課題之手段] 解決上述課題之本發明的氧化鋅系導電性層合體，其 特徵在於：於基材之至少單面依序形成含有能量線硬化型 樹脂的硬化物與熱塑性樹脂之底塗層、與由氧化鋅系導電 材料所構成之導電層。 其中，熱塑性樹脂宜爲聚酯系樹脂。 又’相對於能量線硬化型樹脂的硬化物丨〇 〇質量份， 宜含有熱塑性樹脂0.1-20質量份。 又’本發明的氧化鋅系導電性層合體之製造方法，其 特徵在於：於基材之至少單面’塗佈含有能量線硬化型樹 脂1 0 0質量份、熱塑性樹脂〇 · i〜2 〇質量份及溶劑之塗佈 液後’除去溶劑而形成塗膜，對塗膜照射能量線而形成底 -6 - 201106381 塗層，然後，於前述底塗層上形成由氧化鲜系導電材料戶斤 構成的導電層。 [發明之效果] 若依如此之本發明，可提供層間密著性佳且耐濕熱性 高之氧化鋅系導電性層合體。又’如此之氧化鋅系導電性 層合體的導電層係與原本之氧化鉢系導電材料所構成的導 電層同樣地電阻率低者。 【實施方式】 [用以實施發明之形態] 以下依據實施形態而說明本發明之氧化鋅系導電性層 合體及其製造方法。 於圖1中係表示一實施形態之氧化鋅系導電性層合體 的槪略截面圖。如圖示般，氧化鋅系導電性層合體1 0係 於基材11上依序層合底塗層12及氧化鋅系導電體13 者。底塗層12及氧化鋅系導電體13係亦可只設於基材 11之一面，但亦可設於雙面。又，於基材11與底塗層12 之間依需要而亦可設有例如形成底塗層時防止溶劑造成基 材的變質等之阻隔層等其他之層。 另外，於基材之背面側亦可設有保護基材之硬塗層。 如此之氧化鋅系導電性層合體的一例表示於圖2中。如此 之氧化鋅系導電性層合體10A係於一方面具有底塗層I2 及氧化鋅系導電層1 3之基材1 1的相反側，設有底塗層 201106381 14者。又，底塗層14係只要設有自以往公知之底塗層即 可〇 以下，更詳細說明本發明之氧化鋅系導電性層合體之 構成。 在本發明中基材係可使用合成樹脂薄膜、玻璃板、陶 瓷板等，只要依用途而選擇即可。又，基材宜實質上爲透 明，但依用途係未必爲透明。 又，可設於基材上之底塗層係可直接設於基材上者， 亦可介由其他之層而設者，但於其上直接設有由氧化鋅系 導電材料所構成之導電層者。 如此之底塗層係含有能量線硬化型樹脂之硬化物與熱 塑性樹脂者。 此處，能量線硬化型樹脂係指藉由於電磁波或荷電粒 子束之中具有能量量子者，亦即，照射紫外線或電子束 等，俾進行交聯、硬化之聚合性化合物。 如此之能量線硬化型化合物係具有自由基聚合型與陽 離子聚合型，可舉例如光聚合性預聚物及/或光聚合性單 體。 自由基聚合型之光聚合性預聚物可舉例如聚酯丙烯酸 系 '環氧基丙烯酸酯系、胺基甲酸酯丙烯酸酯系、多元醇 丙烯酸酯系等。此處，聚酯丙烯酸酯系預聚物係藉由例如 多價羧酸與多元醇之縮合所得到之兩末端具有羥基之聚酯 寡聚物的羥基以（甲基）丙烯酸進行酯化，或，於多價羧酸 加成環氧烷所得到之寡聚物的末端之羥基以（甲基）丙烯酸 201106381 進行醋化來得到。環氧基丙烯酸酯系預聚物係例如於比較 低分子量的雙酚型環氧樹脂或酚酚醛清漆型環氧樹脂的氧 雜環丙烷環’使（甲基）丙烯酸反應，進行酯化所得到。胺 基甲酸酯丙烯酸酯系預聚物例如藉由聚醚多元醇或聚酯多 兀醇與聚異氰酸酯之反應所得到的聚胺基甲酸酯寡聚物以 (甲基）丙燒酸進行酯化來得到。進一步，多元醇丙稀酸醋 系預聚物係使聚醚多元醇之羥基以（甲基）丙烯酸進行酯化 來得到。此等之光聚合性預聚物係可使用1種，亦可組合 2種以上而使用。 另外’陽離子聚合型之光聚合性預聚物係一般可使用 環氧系樹脂。此環氧系樹脂可舉例如於雙酚樹脂或酚醛清 漆樹脂等之多價酚類以表氯醇等環氧化之化合物、使直鏈 狀烯烴化合物或環狀烯烴化合物以過氧化物等進行氧化所 得到之化合物等。 又’自由基聚合型之光聚合性單體可舉例如1,4 - 丁 二醇二（甲基）丙烯酸酯、1，6_己二醇二（甲基）丙烯酸酯' 新戊二醇二（甲基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸 酯、新戊二醇己二酸酯二（甲基）丙烯酸酯、羥基新戊酸新 戊二醇二（甲基）丙烯酸酯、二環戊基二（甲基）丙烯酸酯、 己內酯改性二環戊烯基二（甲基）丙烯酸酯、環氧乙烷改性 磷酸二（甲基）丙烯酸酯、烯丙基化環己基二（甲基）丙烯酸 酯、三聚異氰酸酯二（甲基）丙烯酸酯、三羥甲基丙烷三 (甲基）丙烯酸酯、二季戊四醇三（甲基）丙烯酸酯、丙酸改 性二季戊四醇三（甲基）丙烯酸酯、五季戊四醇三（甲基）丙 201106381 烯酸酯、環氧丙烷改性三羥甲基丙烷三（甲基）丙烯酸酯、 三（丙烯醯氧乙基）三聚異氰酸酯、丙酸改性二季戊四醇 五（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯、己內 酯改性二季戊四醇六（甲基）丙烯酸酯等之多官能丙烯酸 酯。此等之光聚合性單體可使用1種，亦可組合2種以上 而使用，又亦可與前述自由基聚合型之光聚合性預聚合物 併用。 另外，在本發明所使用之熱塑性樹脂並無特別限制， 可使用各種樹脂。熱塑性樹脂係亦可與能量線硬化型樹脂 相溶，於能量線硬化型樹脂之硬化物中亦可分散成粒子狀 而保持。爲使熱塑性樹脂分散成粒子狀係亦可使用粒子狀 之熱塑性樹脂，亦可使用藉由與能量線硬化型樹脂之相分 離成爲粒子狀之熱塑性樹脂。 底塗層表面亦可形成微細之凹凸構造，從易形成微細 凹凸構造之觀點，宜使用能量線硬化型樹脂與熱塑性樹脂 之相分離而於能量線硬化型樹脂之硬化物中使熱塑性樹脂 分散成粒子狀。 熱塑性樹脂係從與導電層之密著性或耐濕熱性之點 等’適宜爲聚酯系樹脂、聚胺基甲酸酯樹脂、聚酯胺基甲 酸酯系樹脂、丙烯酸系樹脂等。此等係可1種單獨使用， 亦可組合2種以上而使用。 此處’聚酯系樹脂可舉例如乙二醇、丙二醇、1 ,3 -丁二醇、1，4- 丁二醇、二乙二醇、三乙二醇、〗，5 -戊二 醇' 1，6 -己二醇、新戊二酯、環己烷-1;4 —二甲醇、氫 -10- 201106381 化雙酚A、雙酚A之環氧乙烷或環氧丙烷加成物等之醇成 分之中所選出的至少一種’與從對酞酸、異酞酸、萘二羧 酸、環己烷-1，4-二羧酸、己二酸、壬二酸、馬來酸、 富馬酸、衣康酸及其酸酐等之羧酸成分之中所選出的至少 一種縮聚合所得到的聚合物等。 又，聚酯胺基甲酸酯系樹脂，係可舉例如於使前述醇 成分與羧酸成分縮聚合所得到之末端具有羥基之聚酯多元 醇，使各種之聚異氰酸酯化合物反應所得到之聚合物等。 又，聚胺基甲酸酯樹脂係可舉例如含羥基之化合物與 聚異氰酸酯化合物之反應物例如作爲硬節段之短鏈甘醇或 短鏈醚與異氰酸酯化合物之反應所得到的聚胺基甲酸酯、 作爲軟節段之長鏈甘醇或長鏈醚與異氰酸酯化合物之反應 所得到的聚胺基甲酸酯之直鏈狀的複嵌段共聚物。又，亦 可爲胺基甲酸酯預聚物與聚異氰酸酯化合物之反應物（硬 化物）。 進一步’丙嫌酸系樹脂係可舉例如自院基之碳數爲 1〜20的（甲基）丙燦酸院基酯中所選出之至少一種的單體之 聚合物、或前述（甲基）丙烯酸烷酯與其他可共聚合的單體 之共聚物等。 此等之中’尤宜爲聚醋系樹脂及/或聚酯胺基甲酸酯 系樹脂。 在本發明中，底塗層係使能量線硬化型樹脂（（A)成 分）、與熱塑性樹脂（稱爲（B)成分）、與溶劑之底塗層用塗 佈劑塗佈於基材上，藉加熱除去溶劑後，照射能量線而硬 201106381 化，俾形成。 此處，在底塗層用塗佈劑之能量線硬化型樹脂、與熱 塑性樹脂之含有比率較佳係就質量基準以100 :0.1〜100:20 之範圍選定。相對於能量線硬化型樹脂1 00質量份，若熱 塑性樹脂之含量爲〇· 1〜20質量份，層間密著性及導電層 之耐濕熱性會提高，但若超出此範圍，此等之效果有不顯 著之傾向。 在本發明之底塗層用塗佈劑中就溶劑而言，相對於前 述（A)成分與（B)成分之兩者的良溶劑（稱爲（C)成分）、及相 對於前述（A)成分爲良溶劑’但藉由混合相對於前述（…成 分爲弱溶劑之溶劑（稱爲（D)成分）而使用，俾可使（A)成分 與（B)成分相分離。此理由未必明確，但（C)成分之沸點低 於（D)成分之沸點時’若加熱塗佈於基材之塗佈劑，因先 除去（C)成分’故成爲僅（A)成分溶解於（D)成分之狀態， 進一步’藉由持續加熱’亦可除去（D)成分，最後成爲（A) 成分與（B)成分相分離之狀態。此處，良溶劑及弱溶劑指 具有以如下所示之方法測定的溶解性之溶劑。 相當成爲對象之熱塑性樹脂的試料之固形分3g，加 入欲測定溶解性之溶劑以使全量成爲2〇g，在溫度25t：下 攪拌混合時，具有均一透明性，無黏度變化且相溶者，對 於5¾ g式料爲良溶劑，另外’可看出混濁，或可看到增黏、 分離者對於該試料爲弱溶劑。 (B)成分之熱塑性樹脂例如爲聚酯系樹脂或聚酯胺基 甲酸酯系樹脂時，對於前述樹脂之良溶劑係可例示環己 -12- 201106381 酮、丙酮、醋酸乙酯、四氫呋喃'甲乙酮等。另外，弱溶 劑係可例示甲苯、二甲苯、甲基異丁基酮、乙基溶纖劑、 丙二醇單甲基醚、異丁醇'異丙醇、乙醇、甲醇'己烷、 精製水等。 又，（B)成分之熱塑性樹脂爲丙烯酸系樹脂時，良溶 劑係可例示環己酮、丙酮、醋酸乙酯、四氫呋喃、二甲 苯、甲苯、甲乙酮、甲基異丁基酮、乙基溶纖劑、丙二醇 單甲基醚等。另外弱溶劑係可例示異丁醇、異丙醇、乙 醇、甲醇、己烷、精製水等。 又’前述之良溶劑、及除去精製水之弱溶劑任一者相 對於一般所使用之能量線硬化型樹脂爲良溶劑。 在本發明中，前述（C)成分之溶劑係可1種單獨使 用’亦可混合2種以上而使用，前述（D)成分之溶劑係可 1種單獨使用，亦可混合2種以上而使用。 又’底塗層用塗佈劑中之前述（C)成分的溶劑與前述 (D)成分之溶劑的含有比率[(C):(D)]就質量基準，可在 99: 1~1 0:90的範圍選定。若該含有比率在於上述範圍，在 底塗層形成時’在藉加熱除去溶劑之過程產生良好的相分 離，所得到之底塗層係成爲粒子狀之熱塑性樹脂被分散 者。該含有比率就質量基準宜爲97:3〜15:85 ,更宜爲 95:5~40:60 ° 於上述底塗層用塗佈劑中係除了前述（A)〜（D)成分以 外，在無損本發明之效果的範圍，依需要，可含有各種添 加劑例如光聚合起始劑、抗靜電劑、抗氧化劑、紫外線吸 201106381 收劑、光安定劑、消泡劑等。 光聚合起始劑係能量線硬化型化合物爲自由基聚合型 時，可使用例如苯偶因、苯偶因甲基醚、苯偶因乙基醚、 苯偶因異丙基醚、苯偶因-正丁基醚、苯偶因異丁基酸、 乙醯苯、二甲基胺基乙醯苯、2,2-二甲氧基-2-苯基乙 醯苯、2,2 -二乙氧基-2 -苯基乙醯苯、2 -羥基-2-甲 基-1-苯基丙烷-1-嗣、1-羥基環己基苯基酮、2_甲 基-1 - [4 -(甲基硫）苯基]-2 -嗎啉基-丙烷-1 -酮、 4 - (2-羥基乙氧基）苯基-2(羥基-2-丙基）酮、二苯甲 酮、對苯基二苯甲酮、4,4’-二乙基胺基二苯甲酮、二 氯二苯甲酮 、2 -甲基蔥醌、2 -乙基蔥醌、2 -第三丁 基蔥醌、2 -胺基蔥醌、2 -甲基硫雜蔥酮、2 -乙基硫雜 蔥酮、2 -氯硫雜蔥酮、2,4 -二甲基硫雜蔥酮、2,4 -二 乙基硫雜蔥酮、苯甲基二甲基縮酮、乙醢苯二甲基縮酮、 對二甲基胺安息香酸酯等。又，能量線硬化型化合物爲陽 離子聚合型時係可舉例如芳香族硫鑰雜子、芳香族氧鑰雜 子、芳香族碘鏺離子等之鑰、四氟硼酸酯、六氟磷酸酯、 六氟銻酸酯、六氟硒酸酯等之陰離子所構成的化合物。光 聚合起始劑係可1種單獨使用，亦可混合2種以上而使 用。又，其調配量係相對於前述能量線硬化型化合物1 00 質量份，一般在0·2~ 1〇質量份的範圍選擇。 在本發明中，於基材上使如前述做法所調製之底塗層 用塗佈劑使用以往公知之方法例如棒塗佈法、刮刀塗佈 法、輥塗佈法、刮刀塗佈法 '模縫塗佈法、凹版塗佈法 -14 - 201106381 等，進行塗佈而形成塗膜，乾燥後，再 使該塗膜硬化，以形成底塗層。 又，活性能量線係如上述般，可舉 束等β上述紫外線可以高壓水銀燈、Fu 得到，照射量一般爲100〜500mJ/cm2， 藉電子束加速器等而得到，照射量一般 活性能量線之中尤其適宜爲紫外線。又 係未添加光聚合起始劑，可得到硬化膜 如此做法所形成之底塗層的厚度無 0.5~20/zm 之範圍。 本發明之底塗層係於其表面亦可形 子所產生的微細突起而成爲微細的凹凸 層之表面粗度Ra爲l~l〇〇nm，突起之5 方向的長度之平均）爲0.05~3#m，突 個/100 // m2。具有如此之突起的表面係 法製造。 另外，在本發明中，氧化鋅系導電 電材料所構成之導電層，氧化鋅系導電 爲主體者，較佳係宜含有氧化鋅90質 他之組成無特別限定，例如爲降低電阻 添加元素、添加劑。又，氧化鋅系導電 知之方法形成’例如以濺鍍法、離子鍍 化學氣相成長法等。 又，氧化鋅系導電層之厚度係亦依 照射活性能量線而 例如紫外線或電子 sion Η燈、氙燈等 另外，電子束係可 爲 150〜350kV。此 ’使用電子束時， 〇 特別限定，但宜爲 成以熱塑性樹脂粒 表面。此處，底塗 P均徑（突起之長軸 起之密度爲3〜200 可藉上述之製造方 層係由氧化鋅系導 材料係以氧化鋅作 量％以上，但，其 率’亦可添加各種 層係可從習知以公 法、真空蒸鍍法、 用途而異，例如爲 -15- 201106381 lOnm〜500nm 〇 [實施例] 以下，依據實施例而說明本發明。又，實施例之評估 方法及試驗方法係如以下般。 (試驗1)表面電阻率之測定 製作後之氧化鋅系導電性層合體（濕熱前）、與在溫度 85°C、相對濕度85%之環境下放置72小時後（濕熱後）之 導電性層合體各別的表面電阻率藉4端子法測定。測定係 在25°C、相對濕度50%的環境下進行。 (試驗2)密著性試驗 製作後之氧化鋅系導電性層合體（濕熱前）、與在溫度 85°C、相對濕度85%之環境下放置72小時後（濕熱後）之 導電性層合體各別的導電層之密著性依JIS K5600 - 5 - 6 進行測定，進行評估（分離）。又，JIS K 5 6 0 0 - 5 - 6之分 類係分類〇(無剝離）爲密著性最佳，分類之數字愈大，密 著性愈差，分類5爲密著性最差者。 使用原子間力顯微鏡（SII Nano Technology股份公司 製、型號「SPA 300HV」）而測定底塗層之表面粗度Ra。 測定區域爲25 # mx25 // m。又，從原子間力顯微鏡的觀 察圖像（1〇〇 V m2)，求出突起之平均徑及密度。 -16- 201106381 (實施例1 ) 於作爲能量線硬化型樹脂之能量線硬化型丙烯酸系樹 脂（大日精化工業（股）、Seika beam EXF - 01J、含有光聚 合起始劑）之樹脂成分〗〇 〇質量份，添加作爲熱塑性樹脂 之聚酯樹脂（東洋紡績（股）、Vyl〇ne2〇〇)作爲固形分〇·2質 量份’加入甲苯與甲乙酮之混合溶劑（甲苯：甲乙酮 = 8 0:20、質量比）以使固形分濃度成爲50質量％，進行攪 拌而均一溶解而調製底塗層用塗佈劑（塗佈液）。於作爲基 材之厚度188/^m之聚對苯二甲酸乙二酯薄膜（東洋紡績股 份公司製' 商品名「A43 00」）的易接著處理面使用繞線棒 (Meyer)塗佈此塗佈液以使乾燥後之塗膜的厚度成爲2.5 # m ’以8 0 °C進行乾燥1分鐘後，使用紫外線照射裝置 (Eye Graphics(股）、UB042 - 5AM - W 型）而照射光量 300m J/cm2，得到底塗層。 於所得到之底塗層的表面以D C磁子濺鍍法使用含有 Ga203爲5·7質量％之氧化鋅靶材（使用住友金屬礦山（股） 製）而形成由氧化鋅系導電材料所構成之層，以使膜厚成 爲lOOnm，製作氧化鋅系導電性層合體。 底塗層之表面粗度Ra爲4.3 nm。又，於底塗層表面 形成平均徑〇.4"m、密度4個/100/zm2之突起。將所得 到之氧化鋅系導電性層合體的表面電阻率、密著性之評估 結果表示於表1中。 (實施例2) -17- 201106381 除使聚醋樹脂之量爲0.5質量份以外，其餘係與實施 例1同樣做法而製作氧化鋅系導電性層合體。 底塗層之表面粗度Ra爲5_6nm。又，於底塗層表面 形成平均徑〇.4//m、密度8個/ l〇〇//m2之突起。將所得 到之氧化鋅系導電性層合體的表面電阻率、密著性之評估 結果表示於表1中。 (實施例3) 除使聚酯樹脂之量爲18.0質量份以外，其餘係與實 施例1同樣做法而製作氧化鋅系導電性層合體。 底塗層之表面粗度Ra爲8.2nm。又，於底塗層表面 形成平均徑1·5μηι、密度80個/lOOym2之突起。將所得 到之氧化鉢系導電性層合體的表面電阻率、密著性之評估 結果表示於表1中。 (實施例4) 除使聚醋樹脂改變成V y 1 〇 n 2 2 0 (東洋結績（股））以外， 其餘係與實施例1同樣做法而製作氧化鋅系導電性層合 體。 底塗層之表面粗度Ra爲3.2nm。又，於底塗層表面 係形成平均徑〇.4/zm、密度6個/100/zm2之突起。將所 得到之氧化鋅系導電性層合體的表面電阻率、密著性之評 估結果表示於表1中。 -18- 201106381 (實施例5) 實施例1中於作爲能量線硬化型樹脂之胺基甲酸酯丙 烯酸酯系之光聚合性預聚物（荒川化學工業（股）、Beam set5 75 CB、含有光聚合起始劑）之樹脂成分1〇〇質量份， 添加作爲熱塑性樹脂之聚酯樹脂（東洋紡績（股）、 Vylon20 0)就固形分爲K2質量份，使用作爲溶劑之醋酸 乙酯與甲乙酮的混合溶劑（醋酸乙酯：甲乙酮=50:5〇、質量 比）以外，其餘係與實施例1同樣做法而製作氧化鋅系導 電性層合體。又實施例5之底塗層係胺基甲酸酯丙烯酸酯 系之光聚合性預聚物與聚酯樹脂相溶之狀態進行硬化，於 表面看不到突起。將所得到之氧化鋅系導電性層合體的表 面電阻率、密著性之評估結果表示於表1中。 (實施例6) 在實施例5中，除了使底塗層之厚度爲5/zm以外， 其餘係與實施例5同樣做法而製作氧化鋅系導電性層合 體。實施例6之底塗層係胺基甲酸酯丙烯酸酯系之光聚合 性預聚物與聚酯樹脂相溶之狀態進行硬化，於表面看不到 突起。將所得到之氧化鋅系導電性層合體的表面電阻率、 密著性之評估結果表示於表1中。 (實施例7) 在實施例5中，除使用丙烯酸丁酯的聚合物（重量平 均分子量1 5 0萬）1.2質量份作爲熱塑性樹脂以外’其餘係 -19- 201106381 與實施例5同樣做法而製作氧化鋅系導電性層合體。實施 例7之底塗層係胺基甲酸酯丙烯酸酯系之光聚合性預聚物 與丙烯酸丁酯之聚合物相溶之狀態進行硬化，於表面看不 到突起。將所得到之氧化鋅系導電性層合體的表面電阻 率、密著性之評估結果表示於表1中。 (實施例8) 在實施例5中，除使用丙烯酸丁酯的聚合物（重量平 均分子量1 5 0萬）1 0質量份作爲熱塑性樹脂以外，其餘係 與實施例5同樣做法而製作氧化鋅系導電性層合體。實施 例8之底塗層係胺基甲酸酯丙烯酸酯系之光聚合性預聚物 與丙烯酸丁酯之聚合物相溶之狀態進行硬化，於表面看不 到突起。將所得到之氧化鋅系導電性層合體的表面電阻 率、密著性之評估結果表示於表1中。 (實施例9) 在實施例6中，使用厚200 /zm之聚萘二甲酸乙二酯 薄膜（帝人杜邦股份公司製，商品名「Teonecks Q65FA」） 作爲基材，使底塗層設於聚萘二甲酸乙二酯薄膜之易接著 處理面以外，其餘係與實施例6同樣做法而製作氧化鋅系 導電性層合體。實施例9之底塗層係胺基甲酸酯丙烯酸酯 系之光聚合性預聚物與聚酯樹脂相溶之狀態進行硬化，於 表面看不到突起。將所得到之氧化鋅系導電性層合體的表 面電阻率、密著性之評估結果表示於表1中。 -20- 201106381 (實施例ίο) 於實施例5中添加作爲熱塑性樹脂之聚酯樹脂（東洋 紡績（股）、Vylon 290)就固形分爲1 .2質量份以外，其餘 係與實施例5同樣做法而製作氧化鋅系導電性層合體。又 實施例1 〇之底塗層係胺基甲酸酯丙烯酸酯系之光聚合性 預聚物與聚酯樹脂相溶之狀態進行硬化，於表面看不到突 起。將所得到之氧化鋅系導電性層合體的表面電阻率、密 著性之評估結果表示於表1中。 (實施例1 1) 於實施例5中添加作爲熱塑性樹脂之聚酯胺基甲酸酯 樹脂（東洋紡績（股）、V y 1 ο n U R 1 4 0 0)就固形分爲1.2質量 份以外，其餘係與實施例5同樣做法而製作氧化鋅系導電 性層合體。又實施例1 1之底塗層係胺基甲酸酯丙烯酸酯 系之光聚合性預聚物與聚酯胺基甲酸酯樹脂相溶之狀態進 行硬化，於表面看不到突起。將所得到之氧化鋅系導電性 層合體的表面電阻率、密著性之評估結果表示於表1中。 (實施例12) 於實施例5中添加作爲熱塑性樹脂之聚胺基甲酸酯樹 脂（三洋化成工業（股）、Sunprene ΙΒ802)就固形分爲1.2質 量份以外，其餘係與實施例5同樣做法而製作氧化鋅系導 電性層合體。又實施例1 2之底塗層係胺基甲酸酯丙烯酸 -21 - 201106381 酯系之光聚合性預聚物與聚胺基甲酸酯樹脂相溶之狀態進 行硬化，於表面看不到突起。將所得到之氧化鋅系導電性 層合體的表面電阻率、密著性之評估結果表示於表1中》 (比較例1) 在實施例1之底塗層的形成中，除不使用聚酯樹脂以 外，其餘係與實施例1同樣做法而製作氧化鋅系導電性層 合體。 底塗層之表面粗度Ra爲0.83 nm，又，未觀察到突 起。將所得到之氧化鋅系導電性層合體的表面電阻率、密 著性之評估結果表示於表1中。 (比較例2) 在厚188/z m之聚對酞酸乙二酯薄膜（東洋紡績股份公 司製’商品名「A4300」）之易接著處理面以DC磁子濺鍍 法使用含有Ga203爲5.7質量％之氧化鋅靶材（住友金屬礦 山（股）製）而形成由氧化鋅系導電材料所構成之層，以使 膜厚成爲l〇〇nm，製作氧化辞系導電性層合體。亦即，未 設底塗層，而於聚對酞酸乙二酯薄膜之易接著處理面直接 形成由氧化鋅系導電材料所構成之層。將所得到之氧化鲜 系導電性層合體的表面電阻率、密著性之評估結果表示於 表1中。 -22- 201106381 【表1】 表面電阻率（Ω/口） 密著性 濕熱前 濕熱後 濕熱前 濕纖 實施例1 4. 10X102 9. 20X10* 0 0 實施例2 5.50X102 1. 20X103 0 0 實施例3 4. 50X10* 1. 10X103 0 0 實施例4 4.90X10* 8.90X102 0 0 實施例5 4.80X10* 1. 00X103 0 0 實施例6 5. 00X10* 9. 00X102 0 0 實施例7 5. 20X102 8. 80X102 0 0 實施例8 5. 10X10* 1. 10X103 0 0 實施例9 4. 10X10* 8. 50X 102. 0 0 實施例1 0 5. 20X102 9.80X102 0 0 實施例1 1 5. 00X102 9. 40X102 0 0 實施例1 2 5. 90X102 8.90X10* 0 0 比較例1 4. 60X10* 7. 10X104 0 3 比較例2 '8. 80X102 10ΧΙΟ10 以上* 0 4 本表示測定界限以上 (試驗結果） 從表1所示之結果，可知在實施例1〜1 2之氧化鋅系 導電性層合體中係即使在濕熱後表面電阻率或密著性濕熱 前無很大變化，而密著性、耐濕熱性優異者。 然而，作爲不含有熱塑性樹脂之底塗層的比較例1 中，在濕熱後，表面電阻率變大2次方，密著性亦降低。 又，於PET薄膜上設有導電層之比較例2中，亦在濕熱 後，表面電阻率上昇很大，密著性亦降低。 【圖式簡單說明】 圖1係一實施形態之氧化鋅系導電性層合體的槪略_ 面圖。 圖2係另一實施形態之氧化鋅系導電性層合體的槪略 -23- 201106381 截面圖。 【主要元件符號說明】 10、10A :氧化鋅系導電性層合體 1 1 :基材 12 :底塗層 1 3 :氧化鋅系導電體 1 4 :硬塗層 -24-[Technical Field] The present invention relates to a zinc oxide-based conductive laminate having a zinc oxide-based conductive layer, which is excellent in interlayer adhesion and excellent in moisture-heat resistance, and a method for producing the same . [Prior Art] ITO (tin-doped indium oxide) can be used as a transparent conductive material for a transparent electrode such as a liquid crystal display or a liquid crystal touch panel, but in recent years, a rare metal indium has not been used. The IT 0 replaces the transparent conductive material and has been proposed to be a lanthanum oxide-based conductive material. However, the zinc oxide-based conductive material has a problem of lack of heat and humidity resistance compared to ITO. Therefore, for example, a transparent conductor having a ruthenium oxide film provided on a hard coat layer provided on a plastic substrate has been proposed (refer to the patent document υ. Such a transparent conductive system is oxidized by doping ruthenium Zinc film, yttrium can reduce the change of sheet resistance under high temperature and high humidity with time, but it has the problem of lowering the crystallinity and damaging the electrical conductivity. Further, adding transparency to the zinc oxide-based transparent conductive film to improve the heat resistance A heating element has been proposed (see Patent Document 2). However, such a transparent heating element must contain gallium under specific conditions, and there are problems in that manufacturing conditions are considerably limited. Further, it has been disclosed in the literature. In the case of the transparent heat-generating body of the layer, it is difficult to provide the outer cover layer, and it is difficult to use it as a transparent electrode. [Prior Art Document] -5-201106381 [Patent Document] [Patent Document 1] [Patent Document 2] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. 8-45. Oxidized A zinc oxide-based conductive laminate of a conductive layer, and a zinc oxide-based conductive laminate having a small change in electrical resistivity with time and a good adhesion even in a hot and humid environment, and a method for producing the same. The zinc oxide-based conductive laminate of the present invention which solves the above-mentioned problems is characterized in that an undercoat layer of a cured product containing an energy ray-curable resin and a thermoplastic resin is formed on at least one side of a substrate, and is oxidized. A conductive layer composed of a zinc-based conductive material. The thermoplastic resin is preferably a polyester resin. Further, it is preferably contained in an amount of 0.1 to 20 parts by mass based on the mass of the cured product of the energy ray-curable resin. The method for producing a zinc oxide-based conductive laminate according to the present invention is characterized in that: at least one side of the substrate is coated with 100 parts by mass of the energy ray-curable resin, and the thermoplastic resin 〇·i 〜2 〇 After the coating liquid of the solvent and the solvent, the solvent is removed to form a coating film, and the coating film is irradiated with an energy ray to form a coating of the bottom -6 - 201106381, and then an oxygen is formed on the undercoat layer. [Effect of the Invention] According to the present invention, a zinc oxide-based conductive laminate having excellent interlayer adhesion and high heat and humidity resistance can be provided. The conductive layer of the conductive laminate is lower in electrical resistivity than the conductive layer composed of the original yttria-based conductive material. [Embodiment] [Mode for Carrying Out the Invention] Hereinafter, the present invention will be described based on the embodiment. A zinc oxide-based conductive laminate and a method for producing the same are shown in Fig. 1. Fig. 1 is a schematic cross-sectional view showing a zinc oxide-based conductive laminate according to an embodiment. The undercoat layer 12 and the zinc oxide-based conductor 13 are sequentially laminated on the substrate 11. The undercoat layer 12 and the zinc oxide-based conductor 13 may be provided only on one side of the substrate 11, but may be provided on Double sided. Further, between the base material 11 and the undercoat layer 12, for example, another layer such as a barrier layer for preventing deterioration of the substrate by a solvent when the undercoat layer is formed may be provided. Further, a hard coat layer for protecting the substrate may be provided on the back side of the substrate. An example of such a zinc oxide-based conductive laminate is shown in Fig. 2 . The zinc oxide-based conductive laminate 10A is provided on the opposite side of the substrate 11 having the undercoat layer I2 and the zinc oxide-based conductive layer 13 on the one hand, and is provided with an undercoat layer 201106381. Further, the undercoat layer 14 is a structure in which the zinc oxide-based conductive laminate of the present invention is described in more detail as long as it is provided with a conventionally known undercoat layer. In the present invention, a synthetic resin film, a glass plate, a ceramic plate or the like can be used as the substrate, and it may be selected according to the use. Further, the substrate should be substantially transparent, but it is not necessarily transparent depending on the application. Further, the undercoat layer which may be provided on the substrate may be directly provided on the substrate, or may be provided through another layer, but the conductive layer composed of the zinc oxide-based conductive material may be directly provided thereon. Layer. Such a primer layer is a cured product containing an energy ray-curable resin and a thermoplastic resin. Here, the energy ray-curable resin refers to a polymerizable compound which is crosslinked and hardened by irradiation of ultraviolet rays or electron beams, etc., among electromagnetic waves or charged particle beams. Such an energy ray-curable compound has a radical polymerization type and a cationic polymerization type, and examples thereof include a photopolymerizable prepolymer and/or a photopolymerizable monomer. The photopolymerizable prepolymer of the radical polymerization type may, for example, be a polyester acrylate type epoxy acrylate type, urethane acrylate type or polyhydric alcohol acrylate type. Here, the polyester acrylate-based prepolymer is esterified with (meth)acrylic acid by a hydroxyl group of a polyester oligomer having a hydroxyl group at both terminals obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol, or The hydroxyl group at the terminal of the oligomer obtained by adding a polyvalent carboxylic acid to an alkylene oxide is obtained by acetalizing (meth)acrylic acid 201106381. The epoxy acrylate-based prepolymer is obtained by, for example, reacting a relatively low molecular weight bisphenol epoxy resin or an oxirane ring of a phenol novolak epoxy resin with (meth)acrylic acid to carry out esterification. . A urethane acrylate-based prepolymer, for example, a polyurethane oligomer obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate is carried out with (meth)propionic acid Esterification is obtained. Further, the polyol acrylonitrile-based prepolymer is obtained by esterifying a hydroxyl group of a polyether polyol with (meth)acrylic acid. These photopolymerizable prepolymers may be used alone or in combination of two or more. Further, as the photopolymerizable prepolymer of the cationic polymerization type, an epoxy resin can be generally used. In the epoxy resin, for example, a polyvalent phenol such as a bisphenol resin or a novolak resin is epoxidized with epichlorohydrin or the like, and a linear olefin compound or a cyclic olefin compound is oxidized with a peroxide or the like. The obtained compound and the like. Further, the 'radical polymerization type photopolymerizable monomer may, for example, be 1,4-butanediol di(meth)acrylate or 1,6-hexanediol di(meth)acrylate' neopentyl glycol (Meth) acrylate, polyethylene glycol di(meth) acrylate, neopentyl glycol adipate di(meth) acrylate, hydroxypivalic acid neopentyl glycol di(meth) acrylate , dicyclopentyl bis (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di(meth) acrylate, allylation Cyclohexyl di(meth)acrylate, trimer isocyanate di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid modified dipentaerythritol Tris(meth)acrylate, pentaerythritol tri(methyl)propene 201106381 enoate, propylene oxide modified trimethylolpropane tri(meth)acrylate, tris(propylene oxyethyl)trimeric isocyanate , propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol Meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate functional acrylate much. These photopolymerizable monomers may be used singly or in combination of two or more kinds thereof, or may be used in combination with the above-mentioned radically polymerizable photopolymerizable prepolymer. Further, the thermoplastic resin used in the present invention is not particularly limited, and various resins can be used. The thermoplastic resin may be compatible with the energy ray-curable resin, and may be dispersed in the form of particles in the cured product of the energy ray-curable resin. In order to disperse the thermoplastic resin into a particulate form, a particulate thermoplastic resin may be used, and a thermoplastic resin which is separated into particles by the phase of the energy ray-curable resin may be used. The surface of the undercoat layer may have a fine concavo-convex structure. From the viewpoint of easily forming a fine concavo-convex structure, it is preferable to disperse the thermoplastic resin into the cured product of the energy ray-curable resin by phase separation of the energy ray-curable resin and the thermoplastic resin. Particle-like. The thermoplastic resin is preferably a polyester resin, a polyurethane resin, a polyester urethane resin, an acrylic resin or the like from the viewpoint of adhesion to the conductive layer or heat and humidity resistance. These may be used alone or in combination of two or more. Here, the 'polyester-based resin' may, for example, be ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, or 5-pentanediol. 1,6-hexanediol, neopentyl diester, cyclohexane-1; 4-dimethanol, hydrogen-10-201106381 bisphenol A, ethylene oxide or propylene oxide adduct of bisphenol A, etc. At least one selected from the group consisting of phthalic acid, isodecanoic acid, naphthalene dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, adipic acid, sebacic acid, maleic acid, At least one polymer obtained by polycondensation or the like selected from the carboxylic acid components of fumaric acid, itaconic acid, and an acid anhydride thereof. In addition, the polyester urethane-based resin may be, for example, a polyester polyol having a hydroxyl group at a terminal obtained by polycondensing the alcohol component and the carboxylic acid component, and reacting various polyisocyanate compounds. Things and so on. Further, the polyurethane resin may, for example, be a reaction product of a hydroxyl group-containing compound and a polyisocyanate compound, for example, a polyamino group obtained by reacting a short-chain short-chain glycol or a short-chain ether with an isocyanate compound. A linear, complex block copolymer of a polyurethane obtained by reacting an acid ester, a long chain of a soft segment or a long chain ether with an isocyanate compound. Further, it may be a reactant (hard) of a urethane prepolymer and a polyisocyanate compound. Further, the 'acrylic acid-based resin' may be, for example, a polymer of a monomer selected from at least one selected from the group consisting of a (meth) propionic acid ester having a carbon number of 1 to 20, or the aforementioned (methyl) a copolymer of an alkyl acrylate and another copolymerizable monomer, and the like. Among these, it is particularly preferably a vinegar-based resin and/or a polyester urethane-based resin. In the present invention, the undercoat layer is applied to the substrate by an energy ray-curable resin (component (A)), a thermoplastic resin (referred to as component (B)), and a coating agent for an undercoat layer of a solvent. After removing the solvent by heating, the energy line is irradiated and hardened 201106381, and hydrazine is formed. Here, the content ratio of the energy ray-curable resin to the thermoplastic resin in the coating agent for an undercoat layer is preferably selected in the range of 100:0.1 to 100:20 on the basis of mass. When the content of the thermoplastic resin is 〇·1 to 20 parts by mass based on 100 parts by mass of the energy ray-curable resin, the interlayer adhesion and the moist heat resistance of the conductive layer are improved, but if it exceeds this range, these effects are obtained. There is an insignificant tendency. In the coating agent for an undercoat layer of the present invention, a solvent (referred to as a component (C)) relative to both of the components (A) and (B), and the above (A) The component is a good solvent, but it is used by mixing the solvent (referred to as a component (D)) as a weak solvent, and the component (A) can be separated from the component (B). This reason may not be necessary. It is clear that when the boiling point of the component (C) is lower than the boiling point of the component (D), when the coating agent applied to the substrate is heated, the component (C) is removed first, so that only the component (A) is dissolved (D). In the state of the component, the component (D) can be removed by continuous heating, and finally the component (A) is separated from the component (B). Here, the good solvent and the weak solvent have the following Solvent solvent measured by the method. The solid content of the sample of the thermoplastic resin to be used is 3 g, and the solvent to be measured is added so that the total amount is 2 〇 g, and the mixture is stirred at a temperature of 25 t: and has uniform transparency. , no viscosity change and compatibility, for the 53⁄4 g formula is a good solvent, another The turbidity can be seen, or the viscosity can be seen, and the separator is a weak solvent for the sample. When the thermoplastic resin of the component (B) is, for example, a polyester resin or a polyester urethane resin, The solvent of the resin may be exemplified by cyclohex-12-201106381 ketone, acetone, ethyl acetate, tetrahydrofuran 'methyl ethyl ketone, etc. Further, the weak solvent may be exemplified by toluene, xylene, methyl isobutyl ketone, and ethyl cellosolve. And propylene glycol monomethyl ether, isobutyl alcohol 'isopropyl alcohol, ethanol, methanol' hexane, purified water, etc. When the thermoplastic resin of the component (B) is an acrylic resin, the good solvent may be cyclohexanone. Acetone, ethyl acetate, tetrahydrofuran, xylene, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl cellosolve, propylene glycol monomethyl ether, etc. The weak solvent may be exemplified by isobutanol, isopropanol, ethanol. And methanol, hexane, purified water, etc. Further, any of the above-mentioned good solvent and the weak solvent from which purified water is removed is a good solvent with respect to the energy ray-curable resin generally used. In the present invention, the above (C) ) The solvent of the component can be 1 kind The solvent can be used alone or in combination of two or more kinds, and the solvent of the component (D) can be used alone or in combination of two or more. The above (C) of the coating agent for the undercoat layer. The content ratio of the solvent of the component to the solvent of the component (D) [(C): (D)] can be selected in the range of 99:1 to 10:90 on the basis of the mass. If the content ratio is in the above range, When the undercoat layer is formed, a good phase separation is produced in the process of removing the solvent by heating, and the obtained undercoat layer is dispersed as a particulate thermoplastic resin. The content ratio is preferably 97:3 to 15 on a mass basis: 85, more preferably 95:5 to 40:60 °, in addition to the components (A) to (D), the coating agent for the undercoat layer may contain the effect of the present invention, and may contain, if necessary, Various additives such as photopolymerization initiator, antistatic agent, antioxidant, ultraviolet absorption 201106381, light stabilizer, defoamer and the like. When the photopolymerization initiator-based energy ray-curable compound is a radical polymerization type, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin can be used. - n-butyl ether, benzoin isobutyl acid, acetophenone, dimethylaminoethyl benzene, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethyl Oxy-2-phenyl phenyl benzene, 2-hydroxy-2-methyl-1-phenylpropan-1-indole, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1 - [4 - ( Methylthio)phenyl]-2-morpholinyl-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2(hydroxy-2-propyl)one, benzophenone, pair Phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methyl onion, 2-ethyl onion, 2-tert-butyl onion Bismuth, 2-amino onion, 2-methylthionone, 2-ethylthioonone, 2-chlorothiarone, 2,4-dimethylthiaxanone, 2,4 - diethyl thiazolone, benzyl dimethyl ketal, acetophenone ketal, p-dimethylamine benzoate, and the like. Further, when the energy ray-curable compound is a cationic polymerization type, for example, a key such as an aromatic sulfodile, an aromatic oxo, or an aromatic iodonium ion, a tetrafluoroborate or a hexafluorophosphate, A compound composed of an anion such as hexafluoroantimonate or hexafluoroselenate. The photopolymerization initiator may be used singly or in combination of two or more. Further, the blending amount is generally selected in the range of from 0. 2 to 1 part by mass based on 100 parts by mass of the energy ray-curable compound. In the present invention, a coating agent for an undercoat layer prepared as described above is used on a substrate by a conventionally known method such as a bar coating method, a knife coating method, a roll coating method, or a knife coating method. The slit coating method, the gravure coating method-14 - 201106381, etc., apply to form a coating film, and after drying, the coating film is cured to form an undercoat layer. Further, as described above, the active energy ray may be obtained by a beam or the like. The ultraviolet ray may be obtained by a high pressure mercury lamp or a Fu, and the irradiation amount is generally 100 to 500 mJ/cm 2 , which is obtained by an electron beam accelerator or the like, and the irradiation amount is generally in the active energy ray. Especially suitable for ultraviolet light. Further, a photopolymerization initiator is not added, and a cured film can be obtained. The thickness of the undercoat layer formed by this method is not in the range of 0.5 to 20/zm. The undercoat layer of the present invention is formed on the surface of the fine protrusions formed by the shape, and the surface roughness Ra of the fine uneven layer is 1 to 10 nm, and the average length of the protrusions in the 5 direction is 0.05. 3#m, sudden /100 // m2. A surface having such a protrusion is manufactured by a method. Further, in the present invention, the conductive layer composed of the zinc oxide-based conductive material and the zinc oxide-based conductive material are mainly used, and it is preferable that the composition of the zinc oxide-based conductive material is not particularly limited, for example, to reduce resistance addition elements, additive. Further, the zinc oxide-based conductive method is formed by, for example, a sputtering method, an ion plating chemical vapor growth method, or the like. Further, the thickness of the zinc oxide-based conductive layer is also irradiated with an active energy ray such as an ultraviolet ray or an electron sion xenon lamp, a xenon lamp or the like, and the electron beam system may be 150 to 350 kV. When the electron beam is used, 〇 is particularly limited, but it is preferably a surface of a thermoplastic resin granule. Here, the primer P has a uniform diameter (the density of the long axis of the protrusion is from 3 to 200. The above-mentioned layer can be made of a zinc oxide-based conductive material with a zinc oxide content of at least %, but the rate is also The addition of various layers may be carried out by a conventional method, a vacuum evaporation method, or a use, and is, for example, -15 to 201106381 lOnm to 500 nm. [Examples] Hereinafter, the present invention will be described based on examples. Further, evaluation of the examples The method and the test method are as follows. (Test 1) Measurement of surface resistivity After the production of the zinc oxide-based conductive laminate (before moist heat), it was allowed to stand for 72 hours in an environment of a temperature of 85 ° C and a relative humidity of 85%. The surface resistivity of each of the conductive laminates after (wet heat) was measured by a 4-terminal method. The measurement was carried out in an environment of 25 ° C and a relative humidity of 50%. (Test 2) Oxidation after the adhesion test The adhesion of the respective conductive layers of the conductive laminate of the zinc-based conductive laminate (before damp heat) to the environment at a temperature of 85 ° C and a relative humidity of 85% (after moist heat) according to JIS K5600 - 5 - 6 Perform the measurement and evaluate (separate). , JIS K 5 6 0 0 - 5 - 6 classification classification 无 (no peeling) is the best adhesion, the larger the classification number, the worse the adhesion, the classification 5 is the least adhesion. The surface roughness Ra of the undercoat layer was measured by an atomic force microscope (model: "SPA 300HV" manufactured by SII Nano Technology Co., Ltd.). The measurement area was 25 # mx25 // m. Further, an observation image from an atomic force microscope (1〇〇V m2), the average diameter and density of the protrusions are obtained. -16-201106381 (Example 1) An energy ray-curable acrylic resin as an energy ray-curable resin (Dai Ri Jing Chemical Industry Co., Ltd., Seika beam EXF - 01J, a resin component containing a photopolymerization initiator), a mass fraction, and a polyester resin (Toyobo Co., Ltd., Vyl〇ne2〇〇) as a thermoplastic resin is added as a solid bifurcation. a mixture solvent of toluene and methyl ethyl ketone (toluene: methyl ethyl ketone = 80:20, mass ratio) was added to make the solid content concentration 50% by mass, and the mixture was uniformly stirred to prepare a coating agent for the undercoat layer (coating liquid) ) as the thickness of the substrate 188 / ^ m The easy-to-handle surface of the polyethylene terephthalate film (trade name "A43 00" manufactured by Toyobo Co., Ltd.) is coated with a wire bar (Meyer) to make the thickness of the film after drying. After drying for 2.5 minutes at 2.5 °C, the amount of light was 300 m J/cm 2 using an ultraviolet irradiation device (Eye Graphics, UB042 - 5AM - W type) to obtain an undercoat layer. On the surface of the obtained undercoat layer, a zinc oxide target material (manufactured by Sumitomo Metal Mine Co., Ltd.) containing Ga203 of 5.7 mass% was formed by DC magneto-sputtering to form a zinc oxide-based conductive material. The layer was formed to have a film thickness of 100 nm to prepare a zinc oxide-based conductive laminate. The surface roughness Ra of the undercoat layer was 4.3 nm. Further, protrusions having an average diameter of 44. " m and a density of 4/100/zm2 were formed on the surface of the undercoat layer. The results of evaluation of the surface resistivity and the adhesion of the obtained zinc oxide-based conductive laminate are shown in Table 1. (Example 2) -17-201106381 A zinc oxide-based conductive laminate was produced in the same manner as in Example 1 except that the amount of the polyester resin was 0.5 parts by mass. The surface roughness Ra of the undercoat layer was 5-6 nm. Further, protrusions having an average diameter of 44./m and a density of 8 / l 〇〇 / / m2 were formed on the surface of the undercoat layer. The results of evaluation of the surface resistivity and the adhesion of the obtained zinc oxide-based conductive laminate are shown in Table 1. (Example 3) A zinc oxide-based conductive laminate was produced in the same manner as in Example 1 except that the amount of the polyester resin was changed to 18.0 parts by mass. The surface roughness Ra of the undercoat layer was 8.2 nm. Further, protrusions having an average diameter of 1. 5 μm and a density of 80 / 100 μm 2 were formed on the surface of the undercoat layer. The evaluation results of the surface resistivity and the adhesion of the obtained cerium oxide-based conductive laminate are shown in Table 1. (Example 4) A zinc oxide-based conductive laminate was produced in the same manner as in Example 1 except that the polyester resin was changed to V y 1 〇 n 2 2 0 (Toyo's performance). The surface roughness Ra of the undercoat layer was 3.2 nm. Further, on the surface of the undercoat layer, protrusions having an average diameter of .4/zm and a density of 6/100/zm2 were formed. The evaluation results of the surface resistivity and the adhesion of the obtained zinc oxide-based conductive laminate are shown in Table 1. -18-201106381 (Example 5) The urethane acrylate-based photopolymerizable prepolymer (Arakawa Chemical Industry Co., Ltd., Beam set 5 75 CB, contained in the energy ray-curable resin) The resin component of the photopolymerization initiator) is added in an amount of 1 part by mass, and the polyester resin (Toyobo Co., Ltd., Vylon 20 0) added as a thermoplastic resin is divided into K 2 parts by mass, and ethyl acetate and methyl ethyl ketone as a solvent are used. A zinc oxide-based conductive laminate was produced in the same manner as in Example 1 except that a mixed solvent (ethyl acetate: methyl ethyl ketone = 50:5 Torr, mass ratio) was used. Further, the undercoat layer-based urethane acrylate-based photopolymerizable prepolymer was cured in a state of being compatible with the polyester resin, and no protrusion was observed on the surface. The evaluation results of the surface resistivity and the adhesion of the obtained zinc oxide-based conductive laminate are shown in Table 1. (Example 6) A zinc oxide-based conductive laminate was produced in the same manner as in Example 5 except that the thickness of the undercoat layer was 5/zm. The undercoat layer-based urethane acrylate-based photopolymerizable prepolymer of Example 6 was cured in a state of being compatible with the polyester resin, and no protrusion was observed on the surface. The evaluation results of the surface resistivity and the adhesion of the obtained zinc oxide-based conductive laminate are shown in Table 1. (Example 7) In Example 5, except that 1.2 parts by mass of a polymer (weight average molecular weight: 1,500,000) of butyl acrylate was used as a thermoplastic resin, the rest of the system was produced in the same manner as in Example 5. A zinc oxide-based conductive laminate. The undercoat layer-based urethane acrylate-based photopolymerizable prepolymer of Example 7 was cured in a state of being compatible with the polymer of butyl acrylate, and no protrusion was observed on the surface. The evaluation results of the surface resistivity and the adhesion of the obtained zinc oxide-based conductive laminate are shown in Table 1. (Example 8) In Example 5, a zinc oxide system was produced in the same manner as in Example 5 except that 10 parts by mass of a polymer of butyl acrylate (weight average molecular weight: 150,000) was used as the thermoplastic resin. Conductive laminate. The undercoat layer-based urethane acrylate-based photopolymerizable prepolymer of Example 8 was cured in a state of being compatible with the polymer of butyl acrylate, and no protrusion was observed on the surface. The evaluation results of the surface resistivity and the adhesion of the obtained zinc oxide-based conductive laminate are shown in Table 1. (Example 9) In Example 6, a polyethylene naphthalate film (manufactured by Teijin DuPont Co., Ltd., trade name "Teonecks Q65FA") having a thickness of 200 / zm was used as a substrate, and the undercoat layer was set on the poly layer. A zinc oxide-based conductive laminate was produced in the same manner as in Example 6 except that the film of the naphthalenedicarboxylate was easily treated. The undercoat layer-based urethane acrylate-based photopolymerizable prepolymer of Example 9 was cured in a state of being compatible with the polyester resin, and no protrusion was observed on the surface. The evaluation results of the surface resistivity and the adhesion of the obtained zinc oxide-based conductive laminate are shown in Table 1. -20-201106381 (Example ίο) The polyester resin (Toyobo Co., Ltd., Vylon 290) as a thermoplastic resin was added in the same manner as in Example 5 except that the solid content was 1.2 parts by mass. A zinc oxide-based conductive laminate was produced by the method. Further, in Example 1, the undercoat layer-based urethane acrylate-based photopolymerizable prepolymer was cured in a state of being compatible with the polyester resin, and no protrusion was observed on the surface. The evaluation results of the surface resistivity and the adhesion of the obtained zinc oxide-based conductive laminate are shown in Table 1. (Example 1 1) A polyester urethane resin (Toyobo Co., Ltd., V y 1 ο n UR 1 4 0 0) as a thermoplastic resin was added in the same manner as in Example 5, and the solid content was 1.2 parts by mass. In the same manner as in Example 5, a zinc oxide-based conductive laminate was produced. Further, the undercoat layer-based urethane acrylate-based photopolymerizable prepolymer was cured in a state of being compatible with the polyester urethane resin, and no protrusion was observed on the surface. The evaluation results of the surface resistivity and the adhesion of the obtained zinc oxide-based conductive laminate are shown in Table 1. (Example 12) A polyurethane resin (Sanyo Chemical Industries Co., Ltd., Sunprene 802) was added as a thermoplastic resin in the same manner as in Example 5 except that the solid content was 1.2 parts by mass. Further, a zinc oxide-based conductive laminate was produced. Further, the undercoat layer of the embodiment 1 is urethane acrylate-21 - 201106381 The photopolymerizable prepolymer of the ester type is hardened in a state of being compatible with the polyurethane resin, and no protrusion is observed on the surface. . The evaluation results of the surface resistivity and the adhesion of the obtained zinc oxide-based conductive laminate are shown in Table 1 (Comparative Example 1) In the formation of the undercoat layer of Example 1, except that no polyester was used. A zinc oxide-based conductive laminate was produced in the same manner as in Example 1 except for the resin. The surface roughness Ra of the undercoat layer was 0.83 nm, and no protrusion was observed. The evaluation results of the surface resistivity and the adhesion of the obtained zinc oxide-based conductive laminate are shown in Table 1. (Comparative Example 2) The easy-to-handle surface of a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., trade name "A4300") having a thickness of 188/zm was used in the DC magnetron sputtering method to contain Ga203 of 5.7 mass. A zinc oxide target (manufactured by Sumitomo Metal Mine Co., Ltd.) was used to form a layer made of a zinc oxide-based conductive material so that the film thickness became 10 nm, and an oxidized-type conductive laminate was produced. Namely, the undercoat layer is not provided, and a layer composed of a zinc oxide-based conductive material is directly formed on the easily-treated surface of the polyethylene terephthalate film. The evaluation results of the surface resistivity and the adhesion of the obtained oxidized fresh-layer conductive laminate are shown in Table 1. -22- 201106381 [Table 1] Surface resistivity (Ω/port) Adhesive wet heat before damp heat wet heat before wet fiber Example 1 4. 10X102 9. 20X10* 0 0 Example 2 5.50X102 1. 20X103 0 0 Implementation Example 3 4. 50X10* 1. 10X103 0 0 Embodiment 4 4.90X10* 8.90X102 0 0 Embodiment 5 4.80X10* 1. 00X103 0 0 Embodiment 6 5. 00X10* 9. 00X102 0 0 Embodiment 7 5. 20X102 8. 80X102 0 0 Embodiment 8 5. 10X10* 1. 10X103 0 0 Embodiment 9 4. 10X10* 8. 50X 102. 0 0 Embodiment 1 0 5. 20X102 9.80X102 0 0 Embodiment 1 1 5. 00X102 9 40X102 0 0 Example 1 2 5. 90X102 8.90X10* 0 0 Comparative Example 1 4. 60X10* 7. 10X104 0 3 Comparative Example 2 '8. 80X102 10ΧΙΟ10 or more* 0 4 This indicates the measurement limit or more (test result) from As a result of the results shown in Table 1, it is understood that the zinc oxide-based conductive laminates of Examples 1 to 12 have no significant change in surface resistivity or adhesive wet heat after moist heat, and adhesion, heat and humidity resistance. Excellent sex. However, in Comparative Example 1 which does not contain the undercoat layer of the thermoplastic resin, the surface resistivity became larger after the moist heat, and the adhesion was also lowered. Further, in Comparative Example 2 in which a conductive layer was provided on the PET film, the surface resistivity was greatly increased after moist heat, and the adhesion was also lowered. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a zinc oxide-based conductive laminate of an embodiment. Fig. 2 is a cross-sectional view showing a zinc oxide-based conductive laminate of another embodiment, -23-201106381. [Main component symbol description] 10, 10A: Zinc oxide conductive laminate 1 1 : Substrate 12 : Undercoat 1 3 : Zinc oxide conductor 1 4 : Hard coat -24-