TW200941506A - Transparent electroconductive substrate and method of manufacturing the same - Google Patents

Transparent electroconductive substrate and method of manufacturing the same Download PDF

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Publication number
TW200941506A
TW200941506A TW97141648A TW97141648A TW200941506A TW 200941506 A TW200941506 A TW 200941506A TW 97141648 A TW97141648 A TW 97141648A TW 97141648 A TW97141648 A TW 97141648A TW 200941506 A TW200941506 A TW 200941506A
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Taiwan
Prior art keywords
compound
film
hydrogen peroxide
transparent conductive
reaction product
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TW97141648A
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Chinese (zh)
Inventor
Kunihiko Nakata
Kenichiro Sugawara
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Sumitomo Chemical Co
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Priority claimed from JP2008193871A external-priority patent/JP5255359B2/en
Application filed by Sumitomo Chemical Co filed Critical Sumitomo Chemical Co
Publication of TW200941506A publication Critical patent/TW200941506A/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • C03C17/256—Coating containing TiO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/212—TiO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/218—V2O5, Nb2O5, Ta2O5
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/24—Doped oxides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/32—After-treatment

Abstract

To provide a method of manufacturing a transparent electroconductive substrate capable of developing excellent electroconductive properties by a simple coating method. The manufacturing method includes coating a precursor liquid containing a reaction product (A) between a titanium compound and hydrogen peroxide and a reaction product (B) between a niobium compound or a tantalum compound and hydrogen peroxide onto a transparent base material; firing the coating, heating the fired coating under a reducing atmosphere to perform annealing to form a transparent electroconductive film of niobium- or tantalum-doped titanium oxide having a specific resistance of <=9*10<SP>-3</SP>[Omega] cm on the transparent base material.

Description

200941506 九、發明說明 【發明所屬之技術領域】 本發明係關於一種展現優異導電性之氧化鈦系透明導200941506 IX. Description of the Invention [Technical Field of the Invention] The present invention relates to a titanium oxide transparent guide exhibiting excellent conductivity

I 電性膜之透明導電性基板之製造方法，以及使用於該方法 中之具備良好儲存安定性之膜形成用前驅物液。 ^ 【先前技術】 Φ 迄今爲止，用於太陽能電池或液晶顯示裝置中之透明 導電性基板已廣泛使用設有例如氧化銦錫（ITO)膜或摻雜 A1之氧化鋅（ZnO)膜等之導電性膜者。然而，由於ITO膜 需要稀有金屬銦（Indinm)，故實際上希望能以其他金屬代 替，另外，由於摻雜A1之ZnO膜含有兩性元素故容易吸 濕而有使其用途受限之缺點。因而，近年來積極進行利用 氧化鈦之透明導電性基板之開發（參照專利文獻1、2)。 通常，形成金屬氧化物薄膜之方法大體上爲濺射法或 φ PLD (脈衝雷射沉積）法之真空系成膜方法，及將含有金屬 — 氧化物粒子之漿料或溶液塗佈於基材上後加熱之方法。前 r 者，需要大規模之裝置而使設備成本變高，進而有製品成 本暴增之問題，相對於此，後者之塗佈方法係可使用既有 設備之簡單操作而便宜地實施之方法，適合於工業上大i 生產。然而，目前，於透明導電性膜等之用途中，通常採 用利用前者之真空系之成膜方法。此係由於若爲前者之胃 空系成膜方法，則可形成具有亦比後者塗佈方法高之 性之膜。也就是說，藉由塗佈法所形成之膜，易發生龜# -5- 200941506 難以製作均一薄膜，相較於以真空形成之膜，有膜的緻密 性變差之傾向，由於結晶粒彼此間縮頸（necking)弱，故導 電性易降低。又，塗佈法相較於真空系成膜之方法，自系 外混入雜質之可能性高，於所形成之膜中混入雜質亦成爲 ^ 損及膜緻密性之原因，而有使導電性降低之顧慮。 於使用氧化鈦開發透明導電性基板中，作爲透明導電 . 性膜之成膜方法通常亦採用濺射法或PLD法，例如，藉 由濺射法或PLD法在無鹼玻璃等之透明基材上形成摻雜 _ 鈮之氧化鈦之無定型薄膜，在還原氛圍下進行退火而結晶 化之方法爲已知（非專利文獻1)。然而，即使以例如濺射 法或PLD法成膜的膜，目前現狀爲氧化鈦膜最多仍僅展 現與以往ITO膜或ZnO膜同等的導電性（非專利文獻1)。 由以上可知，氧化鈦系透明導電性基板朝向實用化， 要求有再提高透明導電性膜之導電性，而且，期望建立可 以簡便之塗佈法形成如此透明導電性膜之方法。 不過，已知屬於周期表VA族之5價鈮或钽可作爲用 ❹ 於提高例如氧化鈦系透明導電性膜之導電性之摻雜物。 ' 又，該等金屬氧化物已利用作爲抗反射膜之構成材料。 τ 此種摻雜鈮或钽之氧化鈦系透明導電性膜或由氧化鈮 或氧化鉬所構成之抗反射膜等之金屬氧化物薄膜之形成方 法，亦大致區分爲以如濺射法或PLD(脈衝雷射沉積）法之 真空系成膜方法以及將含有金屬氧化物粒子之漿料或溶液 塗佈於基材上後加熱之方法，但近幾年來，以使用既有設 備可以簡便操作便宜地實施之方面而言，希望有適於工業 -6- 200941506 上大量生產之塗佈法。 以塗佈法形成如摻雜鈮或钽之氧化鈦系薄膜或氧化鈮 或氧化鉅之薄膜之含鈮或鉬之金屬氧化物膜之際，作爲前 驅物，係使用使鈮化合物或鉬化合物與過氧化氫反應之過 氧化之反應產物（亦即過氧化錯合物）。 . 然而，一般，使金屬氧化物與過氧化氫反應產生之過 , 氧化錯合物由於不安定，若放置於室溫以上，則有進行分 Φ 解放出源自過氧基之氧的傾向，其結果，容易產生凝膠化 或白濁化，隨情況而定，有引起膜形成時之塗佈性、膜之 密著性以及透明性等之重大缺點之情況。因此，目前，於 使用使金屬氧化物與過氧化氫反應產生之反應產物（過氧 化錯合物）作爲膜形成前驅物液時，有需於調製後立即使 用，或於保存時冷卻至低於室溫（例如o°c以下）放置等之 種種限制之處理，而期望有能夠消除該等限制而可在室溫 長期保持安定之過氧化錯合物。此不限於金屬種類爲鈮或 〇 鉅之情況，於鈦過氧化錯合物等之情況也相同。 ： 關於鈮或鉬之過氧化錯合物之安定性，迄今幾無報告 Γ 例，關於鈦過氧化錯合物，於以往雖廣泛使用於光觸媒領 域中作爲膜形成材料或黏著性塗料等，但仍進展比較硏 究。鈦過氧化錯合物之安定性，通常隨著固成分濃度而 異，例如，於固成分濃度爲7重量％時安定性約爲15小 時左右，於3.5重量％時約爲2天左右，於1.5重量％時約 爲4天左右，於0.8重量％約爲8天左右，關於提高其溶 液安定性之方法亦有種種報告。 200941506 例如，報告有藉由添加檸檬酸或乙醇酸等之羥基羧酸 可使過氧化鈦錯合物長期安定化（非專利文獻2〜4)，以係 已知之有用安定化方法之一。關於此方法，係使質子自羥 基羧酸之羥基及羧基脫離，以二囈共價鍵結於中心之鈦原 子上，該鈦原子受到保護，作爲OH_攻擊之起點引起之水 解反應可受到抑制。 然而，依據非專利文獻2~4中記載之安定化方法，雖 然以鈦原子爲中心通過共價鍵結以二嚼形成強的鍵，但使 用以該方法安定化之過氧化錯合物形成透明性導電性膜 時，難以藉由加熱處理分解除去有機分子，所得薄膜中殘 存有添加劑（檸檬酸或乙醇酸等之羥基羧酸）等有機成分， 而有損及該膜物性（尤其是導電性及透明性）之問題。 又，獲得安定之鈦過氧化錯合物時之鈦化合物與過氧 化氫之最佳反應比例已知爲1 : 1 (專利文獻3)。亦即，爲 於鈦1原子上鍵結有過氧化離子1原子之構造之鈦過氧化 錯合物可顯示最良好的保存安定性。 然而，即使爲上述最佳反應比例之安定化鈦過氧化錯 合物，現況爲若固成分濃度變高，仍然無法獲得充分之安 定性，例如若固成分濃度成爲2重量％以上，則通常在室 溫於1天以內將凝膠化。使用作爲膜形成材料時，爲了以 一次塗佈獲得充分之膜厚，通常期望將固成分濃度設爲某 高程度，但期望上述鈦過氧化錯合物即使在高濃度仍可爲 在室溫保存數日之程度之安定性提高。 鈦過氧化錯合物之安定性爲如上述之現狀，或即使於 -8- 200941506 鈮或鉅之過氧化錯合物，亦同樣難以確保充分的安定性， 例如上述之鈦化合物與過氧化氫之最佳比例（1 : 1)即使適 用於鈮化合物或鉅化合物與過氧化氫之最佳比例，若固成 分濃度變高’在室溫亦無法安定地保存數曰。 [專利文獻1]特開平10-226598號公報 . [專利文獻2]特開2005-1 1 737號公報 [專利文獻3]特表2007-532469號公報 〇 [非專利文獻1]「最新透明導電性膜大全集〜材料特集 與替代展望/循環·工程別專門技術.應用別要求特性等 〜」，情報機構股份有限公司發行，2007年12月17日， pi87~pl 98 [非專利文獻 2]Μ· Kakihana 等人之 Angew Chem. Int. Ed. 2006, 45, 2378-2381 [非專利文獻3]垣花真人等人之MATERIAL STAGE 第 3 卷，No.1 2 2004，66-72 〇 [非專利文獻4]垣花真人等人之化學與工業 2006，12, 90 1 -907 【發明內容】 本發明之主要目的係提供一種以簡易塗佈方法形成展 現優異導電性之氧化鈦系透明導電性膜之透明導電性基板 之製造方法，及以該方法獲得之透明導電性基板。 本發明之其他目的係提供一種具備良好儲存安定性之 膜形成用前驅物液。 -9- 200941506 本發明者爲解決上述課題而積極檢討。結果，發現下 列（l)~(viii)之見解，而完成本發明。 (i) 獲得含有（A)使鈦化合物與過氧化氫反應而成之 過氧化反應產物與（B)使鈮化合物或鉬化合物與過氧化氫 反應而成之過氧化反應產物之混合物（前驅物液），將該金 屬氧化物之前驅物的前驅物液塗佈於透明基材上，經燒成 ， 後，藉由在還原氣體中加熱進行退火處理，可形成由摻雜 有鈮或钽之氧化鈦構成之透明導電性優異之膜。 q (ii) 將含有（A)使鈦化合物與過氧化氫反應而成之過氧 化反應產物與（B)使鈮化合物或钽化合物與過氧化氫反應 而成之過氧化反應產物之前驅物液塗佈於透明基材上，經 燒成後，藉由在還原氣體中加熱進行退火處理，形成由摻 雜有鈮或钽之氧化鈦構成之透明導電性膜，此時，藉由將 上述前驅物液塗佈於由銳鈦礦結晶相之氧化鈦系薄膜構成 之底層上，可更進而提高所得透明導電性膜之導電性。 (iii) 塗佈含有（A)使鈦化合物與過氧化氫反應而成之 @ 過氧化反應產物與（B)使鈮化合物或鉬化合物與過氧化氫 一 反應而成之過氧化反應產物之前驅物液塗佈，經燒成後， τ 藉由在還原氣體中加熱進行退火處理，形成由摻雜有鈮或 鉅之氧化鈦構成之透明導電性膜，此時在透明導電性膜形 成之前，將使銳鈦礦型氧化鈦系微粒子分散於分散介質中 而成之分散物塗佈於透明基材上後，藉由使分散介質揮發 形成由銳鈦礦結晶相之氧化鈦系薄膜構成之底層，藉由在 該底層上塗佈前驅物液，可更進而提高所得透明導電性膜 -10- 200941506 之導電性。 (iv)預先使（C)銳鈦礦型氧化鈦系微粒子存在於將含有 (A) 使鈦化合物與過氧化氫反應而成之過氧化反應產物與 (B) 使鈮化合物或鉬化合物與過氧化氫反應而成之過氧化 反應產物之前驅物液中，將其塗佈於透明基材上，經燒成 . 後，藉由在還原氣體中加熱進行退火處理之塗佈方法，可 ^ 更進而提高所得透明導電性膜之導電性。 φ (v)使摻雜鈮或鉬之摻雜氧化鈦之無定型薄膜在還原 氣體中藉由退火處理，轉化成銳鈦礦結晶相產生氧缺損時 之結晶化溫度與摻雜氧化鈦之摻雜物含有率成比例。而 且，於透明基材上形成上述摻雜氧化鈦之無定型薄膜，使 之在還原氣體下進行退火處理藉此形成透明導電性膜，且 以在該無定型薄膜與透明基材之間插入摻雜物含有比率不 同之其他氧化鈦系無定型薄膜（第一種膜）之方式，藉由使 與該透明基材鄰接之氧化鈦系無定型薄膜（第一種膜）之摻 φ 雜物含有比例低於構成在其上形成之無定型膜（第二種膜） ·: 之摻雜氧化鈦之摻雜物含有比率之方式形成，於退火處理 : 中溫度上升中，底層（透明基材側之膜）之氧化鈦系無定型 薄膜（第一膜）之銳鈦礦結晶相首先開始變化，此將作爲種 晶之結合核之作用，而促進了在其上所形成之摻雜氧化鈦 之無定型薄膜（第二膜）之結晶化。 (vi)對於含有（A)使鈦化合物與過氧化氫反應而成之反 應產物與（B)使鈮化合物或鉬化合物與過氧化氫反應而成 之反應產物之混合物’藉由使含有具有特定構造之溶劑’ -11 - 200941506 可提高保存安定性且可形成具有優異導電性及透明性之 膜。詳言之’於後述通式（1)〜（3)表示之化合物（溶劑）之情 況，若與上述（A)及（B)之兩種反應產物（過氧化錯合物）共 存，則該溶劑所必須具有之兩個氧原子與過氧化錯合物之 金屬原子之間之二嚙以鍵結力不同之共價鍵產生配位鍵結 而形成安定之6員環或7員環構造，藉由其交聯構造對過 氧基包圍地與以保護，且由於該交聯構造內鍵結力強的共 價鍵只有一個，因此藉由退火處理時之加熱有機分子容易 快速地自金屬原子脫離，而可避免所得膜中殘存有有機成 分。又，於後述通式（4)及（5)表示之化合物（溶劑）之情況 亦同樣’若與上述（A)及（B)之兩種反應產物（過氧化錯合 物）共存，則該溶劑所必須具有之兩個氧原子與過氧化錯 合物之金靥原子之間之二嚙配位，藉由該溶劑所具有之5 員環至8員環之體積高之構造立體性地保護過氧基，且由 於此時之金屬離子與氧原子之鍵結力亦弱，因此藉由退火 處理時之加熱有機分子容易快速地自金屬原子脫離，而可 避免所得膜中殘存有有機成分。 (vii) 若於含有（A)使鈦化合物與過氧化氫反應而成之 反應產物與（B)使鈮化合物或耝化合物與過氧化氫反應而 成之反應產物之混合物中添加硝酸或鹽酸，則可更進而提 高保存安定性’且依據硝酸或鹽酸，不會損及所形成之膜 之物性（尤其是導電性及透明性）。 (viii) 鈮化合物或鉬化合物與過氧化氫反應中，鈮化 合物或鉬化合物與過氧化氫之比例，係設定爲由以往之認 -12- 200941506 知（亦即安定之鈦過氧化錯合物之最佳比例爲1 : 1)爲較好 所推測之比例（亦即與鈦過氧化錯合物同樣爲1 : 1)以外之 j特定範圍，與預測的相反，卻可獲得具有極優異保存安定 性之過氧化錯合物。因此依據具備超過該預測之高的安定 性之過氧化錯合物，固成分濃度可高如8.5重量％。 . 亦即，本發明之透明導電性基板之製造方法顯示如 下。 φ 第一種方法之特徵爲將含有（A)使鈦化合物與過氧化 氫反應而成之反應產物與（B)使鈮化合物或钽化合物與過 氧化氫反應而成之反應產物之前驅物液塗佈於透明基材 上，經燒成後，藉由在還原氣體中加熱進行退火處理，在 透明基材上形成由摻雜有鈮或鉅之氧化鈦構成之透明導電 性膜，獲得比電阻爲9χ1 (Γ3Ω . cm以下之透明導電性基板 (此稱爲第一透明導電性基板之製造方法）。 第二種方法之特徵爲在透明基材上形成由銳鈦礦結晶 ❹ 相之氧化鈦系薄膜構成之底層，在該底層上塗佈含有（A) 使鈦化合物與過氧化氫反應而成之反應產物與（B)使鈮化 ： 合物或钽化合物與過氧化氫反應而成之反應產物之前驅物 液（I)，經燒成後，藉由在還原氣體中力卩熱進行退火處 理，在上述底層上形成由摻雜有鈮或钽之氧化鈦構成之透 明導電性膜，獲得比電阻爲9 X 1 0_3Ω · cm以下之透明導電 性基板（此稱爲第二透明導電性基板之製造方法）。 第三種方法之特徵爲於透明基材上塗佈將銳鈦礦型氧 化鈦系微粒子分散於分散介質中而成之分散體後，藉由使 -13- 200941506 分散介質揮發，形成由銳鈦礦結晶相之氧化鈦系薄膜構成 之底層，在該底層上塗佈含有（A)使鈦化合物與過氧化氫 反應而成之反-應產物與（B)使鈮化合物或鉬化合物與過氧 化氫反應而成之反應產物之前驅物液，經燒成後，藉由在 ’ 還原氣體中加熱進行退火處理，而在上述底層上形成由摻 雜有鈮或鉬之氧化鈦構成之透明導電性膜，獲得比電阻爲 . 9 X 1 (Γ3Ω · cm以下之透明導電性基板（此稱爲第三透明導 電性基板之製造方法）。 @ 第四種方法之特徵爲將含有（A)使鈦化合物與過氧化 氫反應而成之反應產物、（B)使鈮化合物或鉅化合物與過 氧化氫反應而成之反應產物及（C)銳鈦礦型氧化鈦系微粒 子之含有前驅物之分散體塗佈於透明基材上，經燒成後， 藉由在還原氣體中加熱進行退火處理，而在透明基材上形 成由摻雜有鈮或鉬之氧化鈦構成之透明導電性膜，獲得比 電阻爲9χ10_3Ω· cm以下之透明導電性基板（此稱爲第四 透明導電性基板之製造方法）。 © 第五種方法之特徵爲於透明基材上，形成由摻雜有鈮 7 或鉬作爲摻雜物之摻雜氧化鈦之無定型物或氧化鈦之無定 7 型物構成之第一膜上，層合比構成該第一膜之摻雜氧化鈦 或氧化鈦之摻雜物含有比率更高之含有比率之由摻雜有上 述摻雜物之摻雜氧化鈦之無定型物構成之第二膜層合而成 之層合膜之後，藉由在還原氣體中加熱進行退火處理，在 上述透明基材上形成由摻雜有鈮或钽之氧化鈦構成之透明 導電性膜，獲得比電阻爲9χ1 (Γ3Ω · cm以下之透明導電性 -14- 200941506 基板（此稱爲第五透明導電性基板之製造方法）。 本發明之透明導電性基板可藉由上述本發明之導電性 基板;t製造方法獲得。 本發明之膜形成用前驅物液係如下所示。 第一種前驅物液之特徵爲含有（A)使鈦化合物與過氧 化氫反應而成之反應產物與（B)使鈮化合物或钽化合物與 過氧化氫反應而成之反應產物之透明導電性膜形成用前驅 物液，其特徵爲含有以下述通式（1)〜（5)之任一式表示之溶 劑（此稱爲第一膜形成用前驅物液）： 【化1】 R3 R4A method for producing a transparent conductive substrate of an electric film, and a precursor for film formation having good storage stability used in the method. ^ [Prior Art] Φ Heretofore, conductive conductive substrates such as indium tin oxide (ITO) films or A1-doped zinc oxide (ZnO) films have been widely used for transparent conductive substrates used in solar cells or liquid crystal display devices. Sex film. However, since the ITO film requires a rare metal indium (Indinm), it is actually desirable to replace it with another metal. In addition, since the ZnO film doped with A1 contains an amphoteric element, it is easy to absorb moisture and has a disadvantage of being limited in its use. Therefore, in recent years, development of a transparent conductive substrate using titanium oxide has been actively carried out (see Patent Documents 1 and 2). Generally, a method of forming a metal oxide thin film is generally a vacuum film forming method by a sputtering method or a φ PLD (pulse laser deposition) method, and coating a slurry or a solution containing metal-oxide particles on a substrate. The method of heating up and after. In the former case, a large-scale device is required to increase the equipment cost, and there is a problem that the product cost is increased. In contrast, the latter coating method can be implemented inexpensively using a simple operation of the existing device. Suitable for industrial large i production. However, at present, in the use of a transparent conductive film or the like, a film forming method using a vacuum system of the former is generally employed. This is because, in the case of the former gastric empty film forming method, a film having a higher performance than the latter coating method can be formed. That is to say, the film formed by the coating method is prone to the occurrence of a turtle #-5-200941506, and it is difficult to produce a uniform film, and the denseness of the film tends to be inferior to that of the film formed by vacuum, since the crystal grains are mutually inferior The necking is weak, so the conductivity is easily lowered. Further, the coating method is more likely to be mixed with impurities than the vacuum film forming method, and impurities are mixed in the formed film to cause damage and film denseness, and the conductivity is lowered. concern. In the development of a transparent conductive substrate using titanium oxide, a method of forming a transparent conductive film is usually a sputtering method or a PLD method, for example, a transparent substrate such as an alkali-free glass by a sputtering method or a PLD method. A method of forming an amorphous film of doped cerium-doped titanium oxide and annealing it in a reducing atmosphere is known (Non-Patent Document 1). However, even in the case of a film formed by a sputtering method or a PLD method, the titanium oxide film is currently exhibiting only the same conductivity as that of the conventional ITO film or ZnO film (Non-Patent Document 1). As described above, the titanium oxide-based transparent conductive substrate has been put into practical use, and it is required to further improve the conductivity of the transparent conductive film, and it is desired to form a method for forming such a transparent conductive film by a simple coating method. However, it is known that a pentavalent ruthenium or osmium belonging to Group VA of the periodic table can be used as a dopant for improving the conductivity of, for example, a titanium oxide-based transparent conductive film. Further, these metal oxides have been utilized as a constituent material of the antireflection film. τ The method for forming a metal oxide film such as a titanium oxide-based transparent conductive film doped with yttrium or lanthanum or an anti-reflection film composed of yttrium oxide or molybdenum oxide is also roughly classified into, for example, a sputtering method or a PLD. (Pulse laser deposition) method, a vacuum film forming method, and a method of applying a slurry or a solution containing metal oxide particles to a substrate, followed by heating, but in recent years, it is easy to operate with existing equipment. In terms of implementation, it is desirable to have a coating method suitable for mass production in Industry-6-200941506. When a metal oxide film containing ruthenium or molybdenum or a ruthenium oxide or a ruthenium-containing metal oxide film is formed by a coating method, as a precursor, a ruthenium compound or a molybdenum compound is used. The reaction product of peroxidation of hydrogen peroxide reaction (ie, peroxidation complex). However, in general, when a metal oxide is reacted with hydrogen peroxide, the oxidized complex is unstable, and if it is left at or above room temperature, there is a tendency to liberate oxygen derived from peroxy group. As a result, gelation or clouding is likely to occur, and depending on the case, there are cases in which coating properties such as coating properties, film adhesion, and transparency are caused. Therefore, at present, when a reaction product (peroxide complex) produced by reacting a metal oxide with hydrogen peroxide is used as a film forming precursor liquid, it is necessary to use it immediately after preparation, or to cool it below when it is stored. The treatment of various restrictions such as room temperature (for example, below o ° c) is desired, and it is desirable to have a peroxidation complex which can be stabilized at room temperature for a long period of time by eliminating such restrictions. This is not limited to the case where the metal species is ruthenium or ruthenium, and the same is true in the case of titanium peroxidation complexes and the like. : Regarding the stability of a peroxidation complex of ruthenium or molybdenum, there have been few reported examples of titanium peroxide peroxidation, which have been widely used in the field of photocatalyst as a film-forming material or an adhesive coating. Still progress is more research. The stability of the titanium peroxidation complex generally varies depending on the solid content concentration. For example, the stability is about 15 hours at a solid concentration of 7 wt%, and about 2 days at 3.5 wt%. At about 1.5% by weight, it is about 4 days, and about 0.8% by weight is about 8 days. There are various reports on ways to improve the stability of the solution. For example, it is reported that the titanium peroxide complex can be stabilized for a long period of time by adding a hydroxycarboxylic acid such as citric acid or glycolic acid (Non-Patent Documents 2 to 4), and is one of the known useful stabilization methods. In this method, the proton is detached from the hydroxyl group and the carboxyl group of the hydroxycarboxylic acid, and the divalent covalently bonded to the central titanium atom, the titanium atom is protected, and the hydrolysis reaction caused by the OH_ attack can be suppressed. . However, according to the stabilization method described in Non-Patent Documents 2 to 4, a strong bond is formed by covalent bonding by chewing under a titanium atom, but a peroxidation complex stabilized by this method is used to form a transparent bond. In the case of a conductive film, it is difficult to decompose and remove organic molecules by heat treatment, and an organic component such as an additive (hydroxycarboxylic acid such as citric acid or glycolic acid) remains in the obtained film, thereby impairing the physical properties of the film (especially conductivity). And transparency). Further, the optimum reaction ratio of the titanium compound to hydrogen peroxide in obtaining a stable titanium peroxidation complex is known to be 1:1 (Patent Document 3). Namely, a titanium peroxidic complex having a structure in which a peroxygen ion of 1 atom is bonded to the titanium 1 atom can exhibit the best preservation stability. However, even in the case of the above-described optimum reaction ratio of the stabilized titanium peroxidic complex, in the present case, if the solid content concentration is high, sufficient stability cannot be obtained. For example, if the solid content concentration is 2% by weight or more, it is usually The gelation was carried out at room temperature within 1 day. When using as a film forming material, in order to obtain a sufficient film thickness by one application, it is generally desirable to set the solid content concentration to a certain high level, but it is desirable that the above titanium peroxide complex can be stored at room temperature even at a high concentration. The stability of the degree of several days has increased. The stability of the titanium peroxidation complex is as described above, or even in the case of -8-200941506 铌 or the giant peroxidation complex, it is also difficult to ensure sufficient stability, such as the above-mentioned titanium compound and hydrogen peroxide. The optimum ratio (1:1), even if it is applied to the optimum ratio of bismuth compound or giant compound to hydrogen peroxide, if the solid content concentration becomes high, it is impossible to stably store the enthalpy at room temperature. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Complete film of the film~Special material and alternative outlook/cycle, engineering expertise, application, etc. Μ· Kakihana et al., Angew Chem. Int. Ed. 2006, 45, 2378-2381 [Non-Patent Document 3] MATERIAL STAGE, Vol. 3, No. 1 2 2004, 66-72 〇 [Non-patent [4] The main object of the present invention is to provide a titanium oxide-based transparent conductive film which exhibits excellent conductivity by a simple coating method. A method for producing a transparent conductive substrate, and a transparent conductive substrate obtained by the method. Another object of the present invention is to provide a precursor for film formation which has good storage stability. -9- 200941506 The inventors actively reviewed the above issues. As a result, the findings of the following (1) to (viii) were found, and the present invention was completed. (i) obtaining a mixture (precursor) comprising (A) a peroxidation reaction product obtained by reacting a titanium compound with hydrogen peroxide and (B) a peroxidation reaction product obtained by reacting a ruthenium compound or a molybdenum compound with hydrogen peroxide Liquid), the precursor liquid of the metal oxide precursor is coated on a transparent substrate, fired, and then annealed by heating in a reducing gas to form a doped yttrium or yttrium A film made of titanium oxide having excellent transparency and conductivity. q (ii) a peroxidation reaction product containing (A) a reaction product obtained by reacting a titanium compound with hydrogen peroxide and (B) a peroxidation reaction product obtained by reacting a ruthenium compound or a ruthenium compound with hydrogen peroxide After being applied to a transparent substrate, after firing, annealing is performed by heating in a reducing gas to form a transparent conductive film made of titanium oxide doped with cerium or lanthanum. The liquid is applied to the underlayer composed of the titanium oxide thin film of the anatase crystal phase, whereby the conductivity of the obtained transparent conductive film can be further improved. (iii) coating a peroxidation reaction product comprising (A) reacting a titanium compound with hydrogen peroxide and (B) reacting a ruthenium compound or a molybdenum compound with hydrogen peroxide. After the liquid is applied, after calcination, τ is annealed by heating in a reducing gas to form a transparent conductive film made of tantalum or giant titanium oxide. At this time, before the transparent conductive film is formed, After the dispersion obtained by dispersing the anatase-type titanium oxide fine particles in a dispersion medium on a transparent substrate, the dispersion medium is volatilized to form a bottom layer composed of a titanium oxide film having an anatase crystal phase. By coating the precursor liquid on the underlayer, the conductivity of the obtained transparent conductive film-10-200941506 can be further improved. (iv) preliminarily (C) anatase-type titanium oxide-based fine particles present in a product comprising (A) a reaction product of reacting a titanium compound with hydrogen peroxide and (B) a compound of a ruthenium compound or a molybdenum compound The hydrogen peroxide reaction product is formed in a precursor liquid of a peroxidation reaction product, which is coated on a transparent substrate and fired. After the annealing treatment by heating in a reducing gas, the coating method can be further improved. Further, the conductivity of the obtained transparent conductive film is improved. φ (v) an amorphous film doped with lanthanum or molybdenum doped titanium oxide in an reducing gas, which is annealed to convert into an anatase crystal phase to produce an oxygen deficiency and a crystallization temperature and doping of titanium oxide The content of debris is proportional. Further, the amorphous film doped with titanium oxide is formed on the transparent substrate, and is annealed under a reducing gas to form a transparent conductive film, and a blend is interposed between the amorphous film and the transparent substrate. A method of mixing a titanium oxide-based amorphous film (first film) adjacent to the transparent substrate with a different content of the other titanium oxide-based amorphous film (the first film) The ratio is lower than the ratio of the dopant content of the doped titanium oxide formed on the amorphous film (the second film) formed thereon, in the annealing treatment: in the middle temperature rise, the bottom layer (the transparent substrate side) The film of the titanium oxide-based amorphous film (first film) anatase crystal phase first begins to change, which acts as a binding core of the seed crystal, and promotes the doped titanium oxide formed thereon. Crystallization of an amorphous film (second film). (vi) a mixture of a reaction product comprising (A) reacting a titanium compound with hydrogen peroxide and (B) reacting a ruthenium compound or a molybdenum compound with hydrogen peroxide by making the content specific The solvent of the structure ' -11 - 200941506 can improve the preservation stability and form a film with excellent conductivity and transparency. In the case of the compound (solvent) represented by the following general formulae (1) to (3), if it is coexisted with the two reaction products (peroxide complex) of the above (A) and (B), The solvent must have two oxygen atoms and the metal atom of the peroxidation complex to form a 6-membered ring or a 7-membered ring structure by coordinating bonds with different bonding forces to form a coordination bond. By the cross-linking structure, the peroxy group is surrounded and protected, and since there is only one covalent bond in the cross-linking structure, the organic molecule is heated from the metal atom easily by annealing. The detachment prevents the organic component from remaining in the obtained film. Further, in the case of the compound (solvent) represented by the following general formulae (4) and (5), the same applies to the case where the two reaction products (peroxide complex) of the above (A) and (B) coexist. The solvent must have a two-coordination between the two oxygen atoms and the metal ruthenium atom of the peroxidation complex, and the three-membered ring to the 8-membered ring has a three-dimensional structure. Since the peroxy group has a weak bonding force between the metal ion and the oxygen atom at this time, the organic molecule is easily removed from the metal atom by the heating during the annealing treatment, and the organic component remains in the obtained film. (vii) adding nitric acid or hydrochloric acid to a mixture containing (A) a reaction product obtained by reacting a titanium compound with hydrogen peroxide and (B) a reaction product obtained by reacting a ruthenium compound or a ruthenium compound with hydrogen peroxide, Further, the storage stability can be further improved', and depending on nitric acid or hydrochloric acid, the physical properties (especially conductivity and transparency) of the formed film are not impaired. (viii) In the reaction of a ruthenium compound or a molybdenum compound with hydrogen peroxide, the ratio of the ruthenium compound or the molybdenum compound to hydrogen peroxide is set to be known from the prior -12-200941506 (i.e., the stable titanium peroxidation complex) The optimum ratio is 1: 1) is a better range than the presumed ratio (that is, the same as the titanium peroxidation complex is 1:1), contrary to the prediction, it can be obtained with excellent preservation. A stable peroxidation complex. Therefore, the solid content concentration can be as high as 8.5% by weight, based on the peroxidation complex having a stability exceeding the predicted stability. That is, the method of producing the transparent conductive substrate of the present invention is as follows. φ The first method is characterized by containing (A) a reaction product obtained by reacting a titanium compound with hydrogen peroxide and (B) a reaction product of a reaction product obtained by reacting a ruthenium compound or a ruthenium compound with hydrogen peroxide. After being applied to a transparent substrate, after firing, annealing is performed by heating in a reducing gas, and a transparent conductive film made of tantalum or giant titanium oxide is formed on the transparent substrate to obtain a specific resistance. It is 9χ1 (a transparent conductive substrate of Γ3 Ω·cm or less (this is called a manufacturing method of the first transparent conductive substrate). The second method is characterized in that titanium oxide formed by anatase crystal yttrium is formed on a transparent substrate. a bottom layer formed of a film on which a reaction product comprising (A) reacting a titanium compound with hydrogen peroxide and (B) reacting a deuterated compound or a ruthenium compound with hydrogen peroxide is applied to the underlayer. The precursor (I) of the reaction product is formed into a transparent conductive film made of titanium oxide doped with cerium or lanthanum on the underlayer by annealing after being fired in a reducing gas. Obtain a specific resistance of 9 X a transparent conductive substrate of 1 0_3 Ω · cm or less (this is referred to as a method of manufacturing a second transparent conductive substrate). The third method is characterized in that an anatase-type titanium oxide-based fine particle is dispersed on a transparent substrate. After dispersing the dispersion in the medium, the bottom layer composed of the titanium oxide film of the anatase crystal phase is formed by volatilizing the dispersion medium of -13-200941506, and the (A) titanium compound is coated on the bottom layer. a reaction product formed by reacting with hydrogen peroxide and (B) a reaction product obtained by reacting a ruthenium compound or a molybdenum compound with hydrogen peroxide, after being fired, by heating in a reducing gas An annealing treatment is performed to form a transparent conductive film made of titanium oxide doped with lanthanum or molybdenum on the underlayer, and a transparent conductive substrate having a specific resistance of 9×1 (Γ3 Ω·cm or less) is obtained. Method for producing a three-transparent conductive substrate) @ The fourth method is characterized by containing (A) a reaction product obtained by reacting a titanium compound with hydrogen peroxide, and (B) a ruthenium compound or a macro compound and hydrogen peroxide. reaction The reaction product of the reaction product and (C) anatase-type titanium oxide-based fine particles containing a precursor are applied onto a transparent substrate, and after firing, are annealed by heating in a reducing gas, and are transparent. A transparent conductive film made of titanium oxide doped with cerium or molybdenum is formed on the substrate to obtain a transparent conductive substrate having a specific resistance of 9 χ 10 _ 3 Ω·cm or less (this is referred to as a method for producing a fourth transparent conductive substrate). The fifth method is characterized in that on the transparent substrate, an amorphous form of doped titanium oxide doped with yttrium 7 or molybdenum or an amorphous type 7 of titanium oxide is formed on the first film. a second ratio of the composition of the doped titanium oxide or titanium oxide constituting the first film to a higher ratio of the doped titanium oxide doped with the doped titanium oxide doped After laminating the laminated film, the transparent conductive film made of titanium oxide doped with cerium or lanthanum is formed on the transparent substrate by annealing in a reducing gas to obtain a specific resistance. 9χ1 (Γ3Ω · cm or less transparent Electrically -14-200941506 substrate (referred to herein as a fifth method for producing the transparent conductive substrate of). The transparent conductive substrate of the present invention can be obtained by the above-described conductive substrate of the present invention; The precursor liquid for film formation of the present invention is as follows. The first precursor liquid is characterized by containing (A) a reaction product obtained by reacting a titanium compound with hydrogen peroxide and (B) a transparent conductivity of a reaction product obtained by reacting a ruthenium compound or a ruthenium compound with hydrogen peroxide. The precursor liquid for forming a film, which is characterized by containing a solvent represented by any one of the following general formulae (1) to (5) (this is referred to as a precursor liquid for forming a first film): [Chemical Formula 1] R3 R4

(式（1)中，R1〜R6表示Η或烷基，各可相同亦可不同’ X 表示-ΟΗ或-OR(但是，R表示烷基））， 【化2】 R3 R4(In the formula (1), R1 to R6 represent an anthracene or an alkyl group, and each may be the same or different. 'X represents -ΟΗ or -OR (however, R represents an alkyl group)), [Chemical 2] R3 R4

-15- 200941506 (式（2)中，R1〜R5表示Η或烷基，各可相同亦可不同，X 表示-ΟΗ或- OR(但是，R表示烷基））， 【化3】 R3 R4-15- 200941506 (In the formula (2), R1 to R5 represent an anthracene or an alkyl group, and each may be the same or different, and X represents -ΟΗ or -OR (however, R represents an alkyl group)), [Chemical 3] R3 R4

R1R1

X R5 R6X R5 R6

R7 CII 〇R7 CII 〇

⑶(3)

(式（3)中，R1〜R7表示Η或烷基，各可相同亦可不同，X 表示-ΟΗ或- OR(但是，R表示烷基））， 【化4】(In the formula (3), R1 to R7 represent an anthracene or an alkyl group, and each may be the same or different, and X represents -ΟΗ or -OR (however, R represents an alkyl group), [Chemical 4]

(式（4)中，Y表示可具有取代基之碳數3〜6之伸烷基）， 【化5】(In the formula (4), Y represents an alkylene group having 3 to 6 carbon atoms which may have a substituent), [Chemical 5]

(5) -16- 200941506 (式（5)中，Y表示可具有取代基之碳數3〜6之伸烷基）。 第二種前驅物液爲含有（Α)使鈦化合物與過氧化氫反 應而成之民應產物與（Β)使鈮化合物或鉅化合物與過氧化 氫反應而成之反應產物之透明導電性膜形成用前驅物液， 其特徵爲含有硝酸及鹽酸之至少一方（此稱爲第二膜形成 . 用前驅物液）。 _ 第三種前驅物液之特徵爲含有對鈮化合物或鉬化合物 Q 1莫耳反應2.5〜3.5莫耳之過氧化氫而成之反應產物，且 固成分濃度爲8.5重量％以下（此稱爲第三膜形成用前驅物 液）。 依據本發明，可以簡易塗佈方法形成展現優異導電性 之氧化鈦系透明導電性膜，據此，可提供具有良好導電性 之透明導電性基板。詳言之，依據本發明，可在不需真空 設備之簡易操作之下提供低價之透明導電性基板。而且， 依據本發明，由於將加熱處理時之溫度設定在比較低的溫 ❹ 度，因此減低對透明基材選擇之限制，例如，使用具有可 ^ 撓性之耐熱溫度低的樹脂薄膜作爲透明基材，使以所謂的 ： 輥對輥法製造透明導電性基板成爲可能。尤其，在上述第 三種透明導電性基板之製造方法之情況下，底層之形成係 於塗佈將銳鈦礦形氧化鈦微粒子分散於分散介質中而形成 之分散體後，藉由使分散介質揮發進行者，可在常溫下使 底層成膜，而可省略底層形成時之加熱步驟，而且由於藉 由塗佈法成膜，故在不需真空設備之觀點上，可實現步驟 之簡略化。而且，依據上述第二至第五透明導電性基板之 -17- 200941506 製造方法’透明導電性膜之形成過程中，由於可促進結晶 化，因而亦可將加熱溫度設定在比較低之溫度，結果減低 對透明基材選擇之限制乂 另外，依據本發明，在具備有良好儲存安定性之同 ’ 時，亦可提供可藉由塗佈方法形成具有優異導電性及透明 性之氧化鈦系透明導電性膜或者含有鈮或鉬之膜（摻雜鈮 . 或鉬之氧化鈦系薄膜，或氧化鈮或氧化鉅之薄膜等）之膜 形成用前驅物液。亦即，該膜形成用前驅物液由於在室溫 q 下可安定保存而不會產生凝膠化或白濁化，因此可在良好 之塗佈性下形成密著性及透明性優異之膜。尤其，在上述 第一前驅物液之情況下，於形成膜時，藉由退火處理而加 速分解去除有機分子，而不致於因所得膜中殘留有機成分 使導電性降低。另外，上述第二前驅物之情況，儘管含有 無機酸之硝酸或硫酸者，在形成膜時亦不會使膜之導電性 及透明性降低。 如上述，膜形成用前驅物液並無須在調配後立即使用 G 或必須在冷卻至低於室溫（例如〇°C以下）下儲存之特別限 - 制，且可藉由簡易之塗佈方法用於膜形成。而且’上述膜 ： 形成用前驅物液由於在高濃度下且在室溫下均可安定儲 存，因此亦可將濃度提高至以一次塗佈可獲得足夠膜厚之 程度。 【實施方式】 [透明導電性基板之製造方法] -18- 200941506 (第一透明導電性基板之製造方法） 本發明之第一透明導電性基板之製造方法中，首先獲 得作爲膜形成材料之含有（A)使鈦化合物與過氧化氫反應 而成之反應產物及（B)鈮化合物或鉅化合物（以下，將「鈮 化合物或钽化合物」總稱爲「摻雜物化合物」，將「鈮或 • 鉅」總稱爲「摻雜物」）與過氧化氫反應而成之反應產物 _ 之前驅物液。該前驅物液可爲含有（A)使鈦化合物及（B)鈮 ^ 化合物或钽化合物加以過氧化之錯合物（過氧化錯合物） 者，該過氧化錯合物係藉由加熱成爲摻雜鈮或鉅之氧化鈦 之金屬氧化物前驅物。本發明由於係以週期表VA族所屬 之5價鈮或鉬摻雜於氧化鈦而成之金屬氧化物進行膜形 成，因而展現出良好之導電性。 上述前驅物液可爲i)使（A)藉由使鈦化合物與過氧化 氫反應獲得之反應產物之鈦過氧化錯合物，及（B)藉由使 摻雜物化合物與過氧化氫反應獲得之反應產物之摻雜物之 φ 過氧錯合物以適當之比例混合獲得者，亦可爲ii)藉由使 ~ (A)鈦化合物及（B)摻雜化合物以預先期望之比例混合而成 ： 之混合物與過氧化氫反應獲得者。 獲得上述前驅物時，（A)鈦化合物或源自該鈦化合物 之過氧化錯合物，及（B)摻雜物化合物或源自該摻雜物化 合物之過氧化錯合物之混合比例並沒有特別限制，只要是 最後形成之氧化鈦膜中摻雜物（鈮或鉬）之含有比率爲 0.1〜40莫耳％，較好爲5〜30莫耳％即可。上述（B)(摻雜物 化合物或源自該摻雜物化合物之過氧化錯合物）少於上述 -19- 200941506 範圍時，會有摻雜效果不足，導電性降低之狀況，另一方 面，當上述（B)多於上述範圍時，亦有導電性降低且膜之 透明性降低之問題。 &gt; 獲得上述前驅物液時，與過氧化氫之反應（亦即過氧 化反應）可藉由例如使鈦化合物、摻雜化合物或該等之混 合物溶解於適當溶劑中，且依據需要攪拌，添加濃度 . 1〜60重量％左右之過氧化氫水溶液進行。與鈦化合物或摻 雜物化合物反應之過氧化氫之量並無特別限制，但通常對 _ 於鈦化合物爲每一莫耳之鈦化合物與〇.8~20莫耳之過氧 化氫反應，對於摻雜物化合物爲每一莫耳之摻雜物化合物 與0.8~20莫耳之過氧化氫反應較佳。過氧化反應之反應 時間通常爲1秒~60分鐘，較好爲5分鐘~20分鐘左右。 再者，以氧化氫之過氧化反應通常會伴隨著劇烈之發熱， 因此邊冷卻（具體而言，係使內溫維持在-l〇°C以下）邊進行 反應較適當。反應後，亦可進而冷卻至-1(TC以下保持熟 成。 〇 可用於上述以過氧化氫之過氧化反應中之溶劑並無特 別限制，且較好使用水性或醇性等水溶性溶劑。具體而 ： 言，列舉爲例如水、甲醇、乙醇、丙醇、丁醇、二丙酮 醇、乙二醇等。 上述（A)鈦化合物只要是含有Ti原子作爲鈦源者，則 無特別限制，可使用例如氯化鈦（二氯化欽、三氯化鈦、 四氯化鈦等）、烷氧化鈦（甲氧化鈦、乙氧化鈦、異丙氧化 鈦等）、硫酸鈦醯、金屬鈦、氫氧化鈦（原鈦酸）、氧代硫 -20- 200941506 酸鈦等。 上述（B)摻雜物化合物中之鈮化合物只要是含Nb原子 作爲鈮源者’則無特別限制，可使用例如氯化鈮、烷氧化 鈮（甲氧化鈮、乙氧化鈮等）、金屬鈮、氫氧化鈮等。另 外’上述（B)摻雜物化合物中之鉬化合物只要是含有Ta原 - 子作爲钽源者，則無特別限制，可使用例如氯化钽、烷氧 . 化鉬（甲氧化钽、乙氧化鉅）、金屬钽、氫氧化鉅等。 ❹ 另外，上述中，烷氧化鈦、烷氧化鈮、烷氧化鉬由於 爲與水份接觸時會立即反應之不安定物質，因此較好在乾 燥（低濕度）氣體中處理。 至於上述（A)鈦化合物及上述（B)鈮化合物或钽化合物 較好使用氫氧化物。亦即，使用氫氧化鈦作爲上述（A)， 且使用氫氧化鈮或氫氧化鉬作爲上述（B)，或者，使用該 等氫氧化物以外之鈦化合物及摻雜物化合物，在與過氧化 氫反應之前預先加鹼或水等予以氫氧化，且分取、洗淨所 〇 產生之過氧化物沉澱。如此，若爲氫氧化物與過氧化氫反 應獲得過氧化錯合物，則含有碳原子之有機部位完全不存 : 在，由於不需要於高溫加熱使有機部位分解、揮發，因此 可將轉換成氧化物時之加熱溫度設定在比較低之溫度故而 較佳。例如，直接使用氫氧化物以外之鈦化合物及摻雜物 化合物與過氧化氫反應時，變成所得之過氧化錯合物之一 部分存在有有機部位，因此爲了使該有機部位分解、揮發 而需要加熱至至少400°c以上，較好500~600°c左右之溫 度。 -21 - 200941506 上述前驅物液之固成分濃度通常成爲ι〇重量％以下 較佳，尤其，就前驅物液之儲存安定性（使用壽命）之觀點 而言，以2重量％以下更好。當固成i分濃度超過1 0重量％ 時，前驅物液之儲存安定性大幅降低，使塗佈時之黏度上 升，故而有難以均勻塗佈於透明基材上之問題。 另外，此處所謂固成分濃度意指獲得前驅物液時使用 . 之鈦化合物及摻雜物化合物之合計重量佔前驅物液之總重 _ 量之比例（重量％)。 本發明之第一透明導電性基板之製造方法，接著在透 明基材上塗佈上述前驅物液，經燒成後在特定條件下進行 退火處理。 至於上述透明基材只要是在施加熱之各步驟（例如燒 成或退火處理等）中之加熱溫度下可保持形狀且具有透明 性者即可，而無特別限制。例如，各種玻璃等無機材料、 熱可塑性樹脂或熱硬化性樹脂（例如，環氧樹脂、聚甲基 丙烯酸甲酯 '聚碳酸酯、聚苯乙烯、聚乙烯硫醚、聚醚 ❹ 碾、聚烯烴、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、 Λ 三乙醯基纖維素、聚醯亞胺等塑膠類）等高分子材料等形 ： 成之板狀物、片狀物、薄膜狀物等。透明基材之可見光透 光率通常爲90%以上，較好爲95%以上。 在透明基材上塗佈上述前驅物液時之塗佈方法只要是 可均勻地濕塗佈之方法則無特別限制，亦可採用過去習知 之方法。例如可採用毛細塗佈法、旋轉塗佈法、狹長模嘴 塗佈法、噴霧塗佈法、浸漬塗佈法、輥塗佈法、網版印刷 -22- 200941506 法、平版性刷法、桿塗佈法等。而且，前驅物液之塗佈可 以使成爲所需厚度之方式進行一次塗佈作業，亦可重複進 行複數次之塗佈作業。 β 塗佈上述前驅物液時，塗佈量並無特別限制，只要可 使例如最終形成之膜厚度（乾膜厚）成爲10nm〜3 00nm即 . 可。若最終形成之乾膜厚度比上述範圍小，則有在基材上 _ 存在凹凸之情況等之產生難以部份塗佈處或實質上無法塗 φ 佈處之情況，另一方面，若比上述範圍大，會有透明性降 低之問題。又，以成爲該等厚度塗佈前驅物液時，可以進 行一次塗佈作業，亦可重複進行複數次之塗佈作業。 塗佈上述前驅物液後之基板，接著進行燒成。據此， 使基材上之過氧化錯合物（前驅物液）變化成摻雜Nb或Ta 之氧化鈦。此時之結晶狀態通常係由無定型相組成。 燒成時之加熱溫度爲例如 500 °C以下，較好爲 5 0〜4 0 0 °C。當燒成之加熱溫度過高時，安定之結晶相被析 ❹ 出，而有無法看出顯現燒成處理效果之情況。又，燒成時 ^ 間雖係依據加熱溫度適當設定較好，但通常爲1分鐘~1 : 小時，較好爲3分鐘〜30分鐘左右。而且，燒成可在任何 氣體中進行，而無特別限制。例如，在塗佈之前驅物液之 固成分濃度低之情況下，可在燒成之前藉由真空乾燥或減 壓乾燥等方法使溶劑均勻揮發’據此’形成均勻之膜變得 容易。 對於燒成後之基板係在還原氣體中藉由加熱進行退火 處理。據此，形成膜之經Nb或Ta摻雜之氧化鈦由無定 -23- 200941506 型相結經轉化成銳鈦礦相，在結晶相中產生氧缺損，可提 高導電性。而且，通常若導入氧缺損會有容易轉化成電阻 高之金紅石結晶相之傾向，但本發明中，虫於在氧化鈦中 摻雜之鈮或鉬即使導入氧缺損亦具有使銳鈦礦結晶相安定 化之作用，因此可維持展現高導電性之結晶狀態。 上述退火處理時之還原氣體並無特別限制，可爲例如 _ 氮氣、一氧化碳、氬氣電漿、氫電漿、氫氣、真空、氨、 惰性氣體（氬氣等），或者該等之混合氣體之氣體等，但以 $ 一般之還原氣體較佳。較好，採用具有強還原氛圍之氫氣 體（氫氣100%之氣體）。(5) -16- 200941506 (In the formula (5), Y represents an alkylene group having 3 to 6 carbon atoms which may have a substituent). The second precursor liquid is a transparent conductive film containing a reaction product of reacting a titanium compound with hydrogen peroxide and a reaction product of reacting a ruthenium compound or a macro compound with hydrogen peroxide. The precursor liquid for formation is characterized by containing at least one of nitric acid and hydrochloric acid (this is referred to as a second film formation. The precursor liquid is used). _ The third precursor liquid is characterized in that it contains a reaction product of 2.5 to 3.5 moles of hydrogen peroxide by reacting a ruthenium compound or a molybdenum compound Q 1 molar, and the solid content concentration is 8.5 wt% or less (this is called The precursor liquid for forming a third film). According to the present invention, a titanium oxide-based transparent conductive film exhibiting excellent conductivity can be formed by a simple coating method, whereby a transparent conductive substrate having good conductivity can be provided. In particular, according to the present invention, a low-cost transparent conductive substrate can be provided without the simple operation of a vacuum apparatus. Moreover, according to the present invention, since the temperature at the time of heat treatment is set to a relatively low temperature, the restriction on the selection of the transparent substrate is reduced, for example, a resin film having a low heat-resistant temperature which is flexible can be used as the transparent base. The material makes it possible to manufacture a transparent conductive substrate by a so-called roll-to-roll method. In particular, in the case of the above-described third method for producing a transparent conductive substrate, the formation of the underlayer is performed by applying a dispersion in which anatase-type titanium oxide fine particles are dispersed in a dispersion medium, and then dispersing the medium. In the case of volatilization, the underlayer can be formed at a normal temperature, and the heating step in the formation of the underlayer can be omitted, and since the film formation by the coating method is performed, the steps can be simplified from the viewpoint of not requiring a vacuum apparatus. Further, according to the above-described second to fifth transparent conductive substrate -17-200941506 manufacturing method, in the formation process of the transparent conductive film, since the crystallization can be promoted, the heating temperature can be set to a relatively low temperature, and as a result, the heating temperature can be set to a relatively low temperature. In addition, according to the present invention, it is also possible to provide a titanium oxide-based transparent conductive material having excellent conductivity and transparency by a coating method when it has the same good storage stability. A precursor film for film formation of a film or a film containing ruthenium or molybdenum (a titanium oxide film doped with yttrium or molybdenum, or a film of yttrium oxide or oxidized giant, etc.). In other words, since the precursor for film formation can be stably stored at room temperature q without gelation or clouding, a film excellent in adhesion and transparency can be formed with good coatability. In particular, in the case of the above first precursor liquid, when the film is formed, the organic molecules are decomposed and decomposed by annealing treatment, so that the conductivity is lowered by the residual organic component in the obtained film. Further, in the case of the second precursor described above, even if nitric acid or sulfuric acid containing a mineral acid is contained, the conductivity and transparency of the film are not lowered when the film is formed. As described above, the precursor for film formation does not need to be used immediately after the preparation of G or must be stored under cooling to below room temperature (for example, 〇 ° C or less), and can be applied by a simple coating method. Used for film formation. Further, the above-mentioned film: the precursor liquid for formation can be stably stored at a high concentration and at room temperature, so that the concentration can be increased to such an extent that a sufficient film thickness can be obtained by one coating. [Embodiment] [Method for Producing Transparent Conductive Substrate] -18-200941506 (Manufacturing Method of First Transparent Conductive Substrate) In the method for producing a first transparent conductive substrate of the present invention, first, a film forming material is obtained. (A) a reaction product obtained by reacting a titanium compound with hydrogen peroxide and (B) a ruthenium compound or a macro compound (hereinafter, "an oxime compound or a ruthenium compound" is collectively referred to as a "dopant compound", and "铌 or The giant "generally referred to as "dopant") reacts with hydrogen peroxide to form a reaction product _ precursor fluid. The precursor liquid may be a complex (peroxide complex) containing (A) a titanium compound and (B) a compound or a ruthenium compound, which is heated by heating. A metal oxide precursor doped with cerium or giant titanium oxide. The present invention exhibits good electrical conductivity by forming a film by a metal oxide in which pentad quinone of the periodic table VA or molybdenum is doped with titanium oxide. The precursor liquid may be i) a titanium peroxidation complex which (A) is obtained by reacting a titanium compound with hydrogen peroxide, and (B) by reacting a dopant compound with hydrogen peroxide. The φ of the dopant of the obtained reaction product is obtained by mixing the peroxo complex compound in an appropriate ratio, or ii) by mixing the ~(A) titanium compound and the (B) doping compound in a predetermined ratio. It is obtained by reacting a mixture with hydrogen peroxide. When the precursor is obtained, (A) a titanium compound or a peroxidation complex derived from the titanium compound, and (B) a dopant compound or a peroxidation complex derived from the dopant compound, and It is not particularly limited as long as the content ratio of the dopant (cerium or molybdenum) in the finally formed titanium oxide film is 0.1 to 40 mol%, preferably 5 to 30 mol%. When the above (B) (a dopant compound or a peroxidation complex derived from the dopant compound) is less than the above-mentioned range of -19-200941506, the doping effect is insufficient and the conductivity is lowered. When the above (B) is more than the above range, there is also a problem that the conductivity is lowered and the transparency of the film is lowered. &gt; When the precursor liquid is obtained, the reaction with hydrogen peroxide (that is, the peroxidation reaction) can be carried out, for example, by dissolving a titanium compound, a doping compound or a mixture thereof in a suitable solvent, and stirring as needed. The concentration is about 1 to 60% by weight of an aqueous hydrogen peroxide solution. The amount of hydrogen peroxide reacted with the titanium compound or the dopant compound is not particularly limited, but usually, the titanium compound is reacted with each of the molar titanium compounds and 〇8 to 20 moles of hydrogen peroxide. The dopant compound is preferably reacted with 0.8 to 20 moles of hydrogen peroxide per mole of dopant compound. The reaction time of the peroxidation reaction is usually from 1 second to 60 minutes, preferably from about 5 minutes to 20 minutes. Further, since the peroxidation reaction with hydrogen peroxide is usually accompanied by severe heat generation, it is preferable to carry out the reaction while cooling (specifically, maintaining the internal temperature at -10 ° C or lower). After the reaction, the mixture may be further cooled to -1 (the TC or less is kept mature. The solvent which can be used in the above-mentioned peroxidation reaction of hydrogen peroxide is not particularly limited, and a water-soluble solvent such as water or alcohol is preferably used. And, for example, it is exemplified by water, methanol, ethanol, propanol, butanol, diacetone alcohol, ethylene glycol, etc. The above (A) titanium compound is not particularly limited as long as it contains Ti atoms as a titanium source. For example, titanium chloride (dichlorochloride, titanium trichloride, titanium tetrachloride, etc.), titanium alkoxide (titanium oxide, titanium oxide, titanium isopropoxide, etc.), titanium cerium sulfate, titanium metal, hydrogen Titanium oxide (original titanic acid), oxosulfuric acid-20-200941506 Titanic acid, etc. The ruthenium compound in the above (B) dopant compound is not particularly limited as long as it contains a Nb atom as a source, and for example, chlorine can be used. Antimony oxide, antimony alkoxide (ruthenium oxide, antimony ethoxide, etc.), metal antimony, antimony hydroxide, etc. Further, the molybdenum compound in the above (B) dopant compound may contain a Ta pro-sub-substrate as a source. , there is no particular limitation, and for example, barium chloride can be used. Alkyne. Molybdenum (cerium methoxide, ethoxylated giant), metal ruthenium, giant hydroxide, etc. ❹ In addition, in the above, alkoxytitanium oxide, lanthanum alkoxide, molybdenum alkoxide will react immediately when it comes into contact with water. The unstable substance is therefore preferably treated in a dry (low humidity) gas. As for the above (A) titanium compound and the above (B) bismuth compound or bismuth compound, it is preferred to use a hydroxide. In the above (A), using barium hydroxide or molybdenum hydroxide as the above (B), or using a titanium compound other than the hydroxide and a dopant compound, before adding alkali or water before reacting with hydrogen peroxide The hydrogen peroxide is obtained, and the peroxide precipitate produced by the hydrazine is separated and washed. Thus, if the hydroxide is reacted with hydrogen peroxide to obtain a peroxidic complex, the organic moiety containing the carbon atom is completely absent: Since it is not necessary to heat and decompose the organic portion at a high temperature, it is preferable to set the heating temperature at the time of conversion into an oxide to a relatively low temperature. For example, directly using a hydroxide When the titanium compound and the dopant compound are reacted with hydrogen peroxide, an organic portion is present in a part of the obtained peroxidation complex. Therefore, in order to decompose and volatilize the organic site, heating to at least 400 ° C or more is required. A temperature of about 500 to 600 ° C. -21 - 200941506 The solid concentration of the precursor liquid is usually preferably 3% by weight or less, especially in terms of storage stability (life) of the precursor liquid. More preferably, it is 2% by weight or less. When the concentration of the solid component exceeds 10% by weight, the storage stability of the precursor liquid is greatly lowered, and the viscosity at the time of coating is increased, so that it is difficult to uniformly apply to the transparent substrate. Further, the solid content concentration herein means the ratio (% by weight) of the total weight of the titanium compound and the dopant compound used in the precursor liquid to the total weight of the precursor liquid. In the method for producing a first transparent conductive substrate of the present invention, the precursor liquid is applied onto a transparent substrate, and after firing, annealing treatment is performed under specific conditions. The transparent substrate is not particularly limited as long as it can maintain its shape and has transparency at a heating temperature in each step of applying heat (e.g., baking or annealing treatment). For example, various inorganic materials such as glass, thermoplastic resin or thermosetting resin (for example, epoxy resin, polymethyl methacrylate 'polycarbonate, polystyrene, polyethylene sulfide, polyether ram, polyolefin) , polyethylene terephthalate, polyethylene naphthalate, ruthenium triacetate, plastics, etc., and other polymer materials, etc.: into a plate, a sheet , film and the like. The visible light transmittance of the transparent substrate is usually 90% or more, preferably 95% or more. The coating method for applying the precursor liquid on the transparent substrate is not particularly limited as long as it can be uniformly wet-coated, and a conventional method can be employed. For example, a capillary coating method, a spin coating method, an elongated slit coating method, a spray coating method, a dip coating method, a roll coating method, a screen printing method-22-200941506 method, a lithographic brush method, or a rod can be employed. Coating method, etc. Further, the application of the precursor liquid can be carried out once in a desired thickness, and the coating operation can be repeated a plurality of times. When the precursor liquid is applied to the above-mentioned precursor, the coating amount is not particularly limited as long as the film thickness (dry film thickness) finally formed can be, for example, 10 nm to 300 nm. If the thickness of the dry film finally formed is smaller than the above range, there may be cases where it is difficult to partially coat or substantially fail to apply the φ cloth on the substrate. The range is large and there is a problem of reduced transparency. Further, when the precursor liquid is applied to the thicknesses, the coating operation may be performed once, and the coating operation may be repeated a plurality of times. The substrate after the application of the precursor liquid is followed by baking. According to this, the peroxidation complex (precursor liquid) on the substrate is changed to titanium oxide doped with Nb or Ta. The crystalline state at this time usually consists of an amorphous phase. The heating temperature at the time of firing is, for example, 500 ° C or lower, preferably 50 to 400 ° C. When the heating temperature of the firing is too high, the crystal phase of the stability is precipitated, and the effect of the firing treatment cannot be seen. Further, although the heating time is appropriately set depending on the heating temperature, it is usually from 1 minute to 1 hour, preferably from 3 minutes to 30 minutes. Further, the firing can be carried out in any gas without particular limitation. For example, in the case where the solid content concentration of the precursor liquid before application is low, it is possible to uniformly volatilize the solvent by vacuum drying or pressure reduction drying before firing, and it is easy to form a uniform film. The substrate after firing is annealed by heating in a reducing gas. Accordingly, the Nb or Ta doped titanium oxide forming the film is converted into an anatase phase by the amorphous phase -23-200941506 type phase, and an oxygen deficiency is generated in the crystal phase, thereby improving conductivity. Further, in general, if an oxygen deficiency is introduced, there is a tendency that it is easily converted into a rutile crystal phase having a high electric resistance. However, in the present invention, the indole or molybdenum doped with titanium oxide has an anatase crystal even if an oxygen deficiency is introduced. The phase is stabilized and thus maintains a crystalline state exhibiting high conductivity. The reducing gas in the annealing treatment is not particularly limited, and may be, for example, _nitrogen, carbon monoxide, argon plasma, hydrogen plasma, hydrogen, vacuum, ammonia, inert gas (argon gas, etc.), or a mixed gas thereof. Gas, etc., but it is preferred to use a general reducing gas. Preferably, a hydrogen gas having a strong reducing atmosphere (gas of 100% hydrogen) is used.

上述退火處理之加熱溫度較好爲使塗佈於基板上經燒 成而摻雜鈮或鉬之氧化鈦之結晶相轉化成展現高導電性之 銳鈦礦型之溫度，且較好依據摻雜物之含有比率適當的設 定。轉化成銳鈦礦結晶相所需之溫度爲氧化鈦之鈮或鉬摻 雜量愈多則愈高，退火處理之加熱溫度下限通常爲450°c 以上，較好爲500°C以上。另一方面，當加熱溫度太高 U 時，會使銳鈦礦結晶相開始轉化成電阻高之金紅石結晶 二 相，而使導電性下降，且亦會有膜透明性降低之傾向，因 ： 此退火處理之加熱溫度上限通常宜設定在700°C以下，較 好爲600°C以下，更好爲5 50 °C以下之範圍。但是，開始 轉化成金紅石結晶相時之溫度隨摻雜物之含有比率而異， 摻雜物之含有比率較高時，即使退火處理時之加熱溫度高 至一定程度，亦不會使結晶相轉化而使導電性降低。具體 而言，摻雜物之含有比率（形成透明導電性膜中之鈮或鉅 -24- 200941506 之含有比率）超過10莫耳％時，即使上述退火處理之加熱 溫度超過550°C，亦不會使結晶相轉化成金紅石型，而可 獲得良好之導電性。另外，退火處理之加熱溫度之設定除 上述以外，亦考慮所使用之透明基材之耐熱溫度。例如使 用無鹼玻璃作爲透明基材時，通常爲70(TC以下，較好爲 - 600°C以下，更好爲5 50°C以下。退火處理時間（加熱時間） _ 可依加熱溫度等適當設定，但通常爲1分鐘〜1小時，較 φ 好爲3分鐘〜3 0分鐘左右。 如此，可在透明基材上形成由摻雜鈮或鉬之氧化鈦組 成之透明導電性膜。該透明導電性膜具有銳鈦礦型結晶 相，爲由摻雜Nb或Ta之氧化鈦之多結晶體組成之薄 膜，且在具備良好透明性之同時亦展現高的導電性者。 (第二導電性基板之製造方法） 本發明之第二導電性基板之製造方法爲首先在透明基 〇 板上形成由銳鈦礦結晶相之氧化鈦系薄膜組成之底層。藉 ~ 由在塗佈後述前驅物液（I)之前，先在透明基材上形成上 : 述底層，且對塗佈於該底層上之前驅物液（I)進行燒成、 退火處理，可產生摻雜鈮或鉬之氧化鈦結晶，使底層中之 銳鈦礦結晶相發揮作爲晶種之結晶核作用，而促進結晶 化。其結果，形成之透明導電性膜之電阻低，可展現優異 之導電性。 另外，若促進如上述之摻雜鈮或钽之氧化鈦之結晶 化’則與該結晶化有關之加熱處理（亦即，前驅物液（I)塗 -25- 200941506 佈後之燒成及退火處理）之溫度可設定在較低之溫度下亦 可獲得效果。據此，可減低對透明基材選擇之限制，例如 當使用具有可撓性之耐熱溫度低之樹脂薄膜作爲透明基材 時，亦可以所謂的輥對輥法製造透明導電基板。 另外，第二種製造方法中，所謂銳鈦礦結晶相之氧化 鈦系薄膜意指由銳鈦礦結晶相之氧化鈦組成之薄膜，或 . 者，例如由摻雜鈮或鉅等摻雜物金屬而成之銳鈦礦結晶相 之氧化鈦組成之薄膜。又，作爲底層之銳鈦礦結晶相之氧 _ 化鈦系薄膜爲具有不損及最終所得透明導電性基板之透明 性程度之透明性者。 上述底層之形成只要爲可形成銳鈦礦結晶相之氧化鈦 系薄膜之方法，則可以任何方法進行，例如，可以塗佈法 形成，亦可以過去習知之如濺射法或PLD法之在真空系 統中成膜之方法形成。但，本發明由於係藉由塗佈法形成 透明導電性膜者，因此若上述底層的形成亦選擇塗佈法，The heating temperature of the annealing treatment is preferably a temperature at which a crystal phase of the titanium oxide doped with cerium or molybdenum coated on the substrate is converted into an anatase type exhibiting high conductivity, and is preferably doped. The content ratio of the substance is appropriately set. The temperature required for conversion to the anatase crystal phase is the higher the amount of lanthanum or molybdenum doped with titanium oxide, and the lower limit of the heating temperature for the annealing treatment is usually 450 ° C or more, preferably 500 ° C or more. On the other hand, when the heating temperature is too high U, the anatase crystal phase starts to be converted into a rutile crystal two phase having a high electric resistance, and the conductivity is lowered, and the film transparency tends to decrease, because: The upper limit of the heating temperature in the annealing treatment is usually set to 700 ° C or lower, preferably 600 ° C or lower, more preferably 5 50 ° C or lower. However, the temperature at which the rutile crystal phase starts to be converted varies depending on the content ratio of the dopant, and when the content ratio of the dopant is high, the crystal phase is not converted even if the heating temperature during the annealing treatment is high to some extent. The conductivity is lowered. Specifically, when the content ratio of the dopant (the ratio of the ruthenium or the macro-24-200941506 in the transparent conductive film is formed) exceeds 10 mol%, even if the heating temperature of the annealing treatment exceeds 550 ° C, The crystalline phase is converted to a rutile type, and good electrical conductivity is obtained. Further, in addition to the above, the setting of the heating temperature of the annealing treatment also considers the heat-resistant temperature of the transparent substrate to be used. For example, when an alkali-free glass is used as the transparent substrate, it is usually 70 (TC or less, preferably -600 ° C or lower, more preferably 5 50 ° C or lower. Annealing time (heating time) _ can be appropriately determined depending on heating temperature, etc. It is set, but it is usually from 1 minute to 1 hour, preferably from 3 minutes to about 30 minutes. It is possible to form a transparent conductive film composed of titanium oxide doped with cerium or molybdenum on a transparent substrate. The conductive film has an anatase crystal phase and is a film composed of a polycrystal of titanium oxide doped with Nb or Ta, and exhibits high conductivity while exhibiting good transparency. (Second conductive substrate The manufacturing method of the second conductive substrate of the present invention is to first form a bottom layer composed of a titanium oxide-based thin film of an anatase crystal phase on a transparent substrate, by using a precursor liquid (hereinafter referred to as coating). Prior to I), a bottom layer is formed on a transparent substrate, and the precursor liquid (I) is applied to the underlayer to be fired and annealed to produce a titanium oxide crystal doped with cerium or molybdenum. Making the anatase crystal phase in the bottom layer play It is a crystal nucleus of a seed crystal and promotes crystallization. As a result, the transparent conductive film formed has a low electrical resistance and exhibits excellent electrical conductivity. Further, if the crystallization of the titanium oxide doped with cerium or lanthanum is promoted as described above, The temperature of the crystallization is related to the heat treatment (that is, the firing and annealing treatment of the precursor liquid (I) coated -25-200941506) can be set at a lower temperature to obtain an effect. According to this, it is possible to reduce the restriction on the selection of the transparent substrate. For example, when a resin film having a low heat-resistant temperature having flexibility is used as the transparent substrate, a transparent conductive substrate can also be produced by a so-called roll-to-roll method. In the manufacturing method, the titanium oxide-based film of the anatase crystal phase means a film composed of titanium oxide of an anatase crystal phase, or, for example, a doped metal such as lanthanum or giant. A film composed of a titanium oxide having an anatase crystal phase, and an oxygen-titanium-based film as a bottom layer of an anatase crystal phase has transparency which does not impair the transparency of the finally obtained transparent conductive substrate. The formation of the underlayer may be carried out by any method as long as it is a titanium oxide-based thin film capable of forming an anatase crystal phase, and may be formed, for example, by a coating method, or may be conventionally used in a vacuum system such as a sputtering method or a PLD method. The film forming method is formed. However, since the present invention forms a transparent conductive film by a coating method, if the underlayer is formed, a coating method is also selected.

則全部之步驟均以簡易之塗佈法進行，使得在不需真空設 Q 備之簡易操作下提供便宜之透明導電性基板成爲可能。因 ：· 而，上述底層較好以塗佈法形成。 ： 形成上述底層若選擇塗佈法時，例如可藉由至少將含 有（a)鈦化合物與過氧化氫反應而成之反應產物之前驅物 液（II)塗佈於透明基材上之後，藉由加熱形成上述底層。 其中，上述前驅物液（Π)爲至少含有（a)鈦化合物經過氧化 之錯合物（過氧化錯合物）者。例如當上述前驅物液（11)含 有（a)鈦化合物經單獨過氧化而成之過氧化錯合物時，該 -26- 200941506 過氧化錯合物係藉由加熱成爲氧化鈦之金屬氧化物前驅 物，且形成之底層爲由銳鈦礦結晶相之氧化鈦組成之薄 膜。 _ 上述前驅物液（II)較好包含（a)使鈦化合物與過氧化氫 反應而成之反應產物及（b)使鈮化合物或钽化合物（摻雜物 . 化合物）與過氧化氫反應而成之反應產物。該情況下，上 述前驅物液（II)爲包含（a)鈦化合物及（b)摻雜物化合物經過 φ 氧化之錯合物（過氧化錯合物）者。該過氧化錯合物藉由加 熱而成爲摻雜鈮或钽之氧化鈦之金屬氧化物前驅物，所形 成之底層爲由銳鈦礦結晶相之摻雜鈮或鉬之氧化鈦組成之 薄膜。 關於上述前驅物液（II)，於上述第一種透明導電性基 板之製造方法中前驅物液之說明，可分別以「（a)鈦化合 物」交替讀爲「（A)鈦化合物」，且以「（b)摻雜物化合 物」交替讀爲「（B)摻雜物化合物」。 φ 另外，當前驅物液（Π)爲包含（a)使鈦化合物與過氧化 氫反應而成之反應產物及（b)使摻雜物化合物與過氧化氫 ： 反應而成之反應產物時，（a)鈦化合物或源自該鈦化合物 之過氧錯合物及（b)摻雜物化合物或源自該摻合物化合物 之過氧錯合物之混合比例係與使用之前驅物液（I)中之混 合比例相同，或接近之範圍，但使上述前驅物液（I)與上 述前驅物液（II)爲相同之組成或接近之組成爲較佳。另 外，獲得後述前驅物液（I)時使用（A)鈦化合物爲氫氧化 物，以及（B)鈮化合物或鉬化合物爲氫氧化物之情況下， -27- 200941506 獲得前驅物液（π)時較好使用氫氧化物作爲上述（a)鈦化合 物及上述（b)鈮化合物或鉬化合物。據此，可將底層形成 之加熱溫度設定在比較低之溫度，通過全製造過程之加熱 過程可實現爲低溫化。 底層形成所用之前驅物液（Π)以具有與前驅物液（1)之 組成（相對於鈦量之摻雜物量或其種類等）相同之組成者’ ~ 或者具有接近之組成者較佳。通常，未摻雜鈮或鉬之銳鈦 . 礦結晶相之氧化鈦之結晶型爲正方晶，且對應於摻雜於其 © 中之摻雜物量，a軸、b軸、c軸之晶格常數將會改變。 若以前驅物液（Π)形成之膜與以前驅物液（I)形成之膜間之 a軸、b軸、c軸之晶格常數之差異變得很大，則會有以 兩種前驅物液形成之膜彼此之匹配性變差之問題，但若使 兩種前驅物液爲相同組成或接近之組成，則可抑制a軸、 b軸、c軸之晶格常數差異於較小。 將上述前驅物液（II)塗佈於透明基材上之塗佈方法係 與上述第一透明導電性基板之製造方法中之前驅物液之塗 © 佈方法相同。另外，此時之塗佈量較好經適當設定使最終 形成之膜厚度爲後述底層膜厚所需之範圍。 ： 塗佈上述前驅物液（II)後加熱時之加熱溫度及加熱時 間只要是可將基材上之過氧化錯合物（前驅物液（II))改變 成銳鈦礦相之氧化鈦或摻雜之氧化鈦（摻雜有摻雜物之氧 化鈦），則無特別限制。具體而言，加熱溫度雖較好依據 前驅物液（Π)中之摻雜物量適當設定，但通常爲 2 5 0 ~ 5 5 0 °C，較好爲3 0 0〜5 0 0 °C。另外，加熱時間雖較好依 -28- 200941506 加熱溫度等適當設定，但通常爲1分鐘~1小時，較好爲3 分鐘〜30分鐘左右。另外，塗佈上述前驅物液（Π)之後進 行之加熱，可在任何氛圍中進行，但爲了使作爲晶種之結 晶性良好之粒子析出，除於還原氛圍氣體中之外亦較好在 存在氧之氛圍氣體中進行。 . 如此’可藉由塗佈法形成成爲底層之銳鈦礦晶相之氧 . 化鈦系薄膜（氧化鈦膜或摻雜之氧化鈦（摻雜有摻雜物之氧 φ 化鈦）膜）。 本發明之第二透明導電性基板之製造方法中形成之底 層（銳鈦礦結晶相之氧化鈦系薄膜）之膜厚並無特別限制， 但若底層膜厚太小時，作爲種晶作用之銳鈦礦結晶相之結 晶無法充分存在，而有無法獲得因上述之底層形成之效 果’另一方面’當底層膜厚太大時，由於會有透明性降低 之問題’因此通常爲3 nm以上，較好爲5 nm以上，更好 爲10nm以上’爲50nm以下，較好爲30nm以下，更好爲 φ 20nm以下之範圍。 *： 另外，本發明之第二透明導電性基板之製造方法中可 * 使用之透明基板係與上述第一透明導電性基板之製造方法 相同。 本發明之第二透明導電性基板之製造方法中，接著在 上述底層上塗佈包含（A)使鈦化合物與過氧化氫反應而成 之反應產物及（B)使鈮化合物或钽化合物與過氧化氫反應 而成之反應產物之前驅物液（I)。 前驅物液（I)係與上述第一透明導電性基板之製造方 -29- 200941506 法中之前驅物液相同’且可套用第一透明導電性基板之製 造方法中之前驅物液之說明。 將上述前驅物液（I)塗佈於上述底層上時之塗佈方法^ 係與上述第一透明導電性基板之製造方法中之前驅物液之 塗佈方法相同。 塗佈上述前驅物液（I)時之塗佈量並無特別限制，例 . 如較好爲使最終形成之膜之厚度（乾膜厚）成爲 1 Onm〜300nm所需之量。最終形成之乾膜厚度比上述範圍 小時，於基材上存在凹凸之情況下會造成部份塗佈處或實 質上未塗佈處之問題，另一方面，當比上述範圍大時，會 有透明性降低之問題。另外，塗佈成該等厚度之前驅物液 (I)時，可以進行一次塗佈作業，亦可重複進行複數次之 塗佈作業。All of the steps are carried out by a simple coating method, making it possible to provide an inexpensive transparent conductive substrate without the need for a vacuum. The above primer layer is preferably formed by a coating method. When the coating method is selected, the coating solution may be applied, for example, by applying at least a reaction product (II) containing a reaction product of (a) a titanium compound and hydrogen peroxide to a transparent substrate. The above underlayer is formed by heating. Here, the precursor liquid (Π) is a compound containing at least (a) a oxidized complex (peroxide complex) of the titanium compound. For example, when the precursor liquid (11) contains (a) a peroxidation complex formed by peroxidizing a titanium compound alone, the -26-200941506 peroxidation complex is a metal oxide of titanium oxide by heating. The precursor, and the underlayer formed is a film composed of titanium oxide of an anatase crystal phase. The precursor liquid (II) preferably comprises (a) a reaction product obtained by reacting a titanium compound with hydrogen peroxide and (b) reacting a ruthenium compound or a ruthenium compound (dopant. compound) with hydrogen peroxide. The reaction product. In this case, the precursor liquid (II) is a complex (peroxide complex) containing (a) a titanium compound and (b) a dopant compound oxidized by φ. The peroxidation complex is a metal oxide precursor of doped cerium or lanthanum titanium oxide by heating, and the underlayer is a film composed of doped cerium or molybdenum oxide of an anatase crystal phase. In the above precursor liquid (II), in the method for producing the first transparent conductive substrate, the description of the precursor liquid can be alternately read as "(A) titanium compound" by "(a) titanium compound", and The "(b) dopant compound" is alternately read as "(B) dopant compound". φ In addition, the current precursor liquid (Π) is a reaction product comprising (a) a reaction product obtained by reacting a titanium compound with hydrogen peroxide and (b) reacting a dopant compound with hydrogen peroxide: (a) a mixing ratio of a titanium compound or a peroxygen complex derived from the titanium compound and (b) a dopant compound or a peroxy complex derived from the blend compound, and a precursor fluid ( The mixing ratio in I) is the same or close to the range, but it is preferable that the precursor liquid (I) and the precursor liquid (II) have the same composition or close composition. Further, when the precursor liquid (I) to be described later is used, (A) the titanium compound is a hydroxide, and (B) the ruthenium compound or the molybdenum compound is a hydroxide, -27-200941506 obtains a precursor liquid (π) It is preferred to use a hydroxide as the above (a) titanium compound and the above (b) bismuth compound or molybdenum compound. According to this, the heating temperature at which the underlayer is formed can be set to a relatively low temperature, and the temperature can be lowered by the heating process in the entire manufacturing process. The precursor liquid used in the formation of the underlayer is preferably the same as the composition of the precursor liquid (1) (the amount of the dopant relative to the amount of titanium or the kind thereof) or the like. Generally, anatase not doped with yttrium or molybdenum. The crystal form of titanium oxide of the ore crystal phase is tetragonal, and corresponds to the amount of dopant doped in it, the lattice of the a-axis, the b-axis, and the c-axis. The constant will change. If the difference between the lattice constants of the a-axis, b-axis, and c-axis between the film formed by the precursor liquid (Π) and the film formed by the precursor liquid (I) becomes large, there will be two kinds of precursors. The problem that the film formed by the liquid solution deteriorates is poor. However, if the two precursor liquids have the same composition or a close composition, the difference in lattice constant between the a-axis, the b-axis, and the c-axis can be suppressed to be small. The coating method of applying the precursor liquid (II) to a transparent substrate is the same as the coating method of the precursor liquid in the method for producing the first transparent conductive substrate. Further, the coating amount at this time is preferably set as appropriate so that the film thickness finally formed is in the range required for the thickness of the underlying film described later. : heating temperature and heating time when the precursor liquid (II) is applied, and the peroxidation complex (precursor liquid (II)) on the substrate can be changed to titanium oxide of the anatase phase or The doped titanium oxide (titanium doped with dopant) is not particularly limited. Specifically, the heating temperature is preferably set in accordance with the amount of the dopant in the precursor liquid (Π), but it is usually from 2 5 0 to 5 50 ° C, preferably from 3 0 0 to 50 ° C. Further, although the heating time is preferably set as appropriate according to the heating temperature of -28-200941506, it is usually from 1 minute to 1 hour, preferably from 3 minutes to 30 minutes. Further, the heating after the application of the precursor liquid (Π) can be carried out in any atmosphere. However, in order to precipitate particles having good crystallinity as a seed crystal, it is preferably present in addition to the reducing atmosphere gas. It is carried out in an atmosphere of oxygen. Thus, an oxygen-based titanium film (titanium oxide film or doped titanium oxide (doped with oxygen φ titanium) film) can be formed by a coating method to form an underlying anatase crystal phase. . The film thickness of the underlayer (the titanium oxide film of the anatase crystal phase) formed in the method for producing the second transparent conductive substrate of the present invention is not particularly limited, but if the thickness of the underlayer film is too small, it acts as a seed crystal. The crystal of the crystal phase of the titanium ore cannot be sufficiently present, and the effect of the formation of the underlayer described above cannot be obtained. On the other hand, when the thickness of the underlayer is too large, there is a problem that the transparency is lowered, so that it is usually 3 nm or more. It is preferably 5 nm or more, more preferably 10 nm or more, and is 50 nm or less, preferably 30 nm or less, more preferably φ 20 nm or less. *: The transparent substrate which can be used in the method for producing a second transparent conductive substrate of the present invention is the same as the method for producing the first transparent conductive substrate. In the method for producing a second transparent conductive substrate of the present invention, a reaction product comprising (A) reacting a titanium compound with hydrogen peroxide and (B) a ruthenium compound or a ruthenium compound are applied to the underlayer. Hydrogen peroxide reacts to form a reaction product precursor (I). The precursor liquid (I) is the same as the precursor liquid in the above-mentioned first transparent conductive substrate manufacturing method -29-200941506, and the description of the precursor liquid in the manufacturing method of the first transparent conductive substrate can be applied. The coating method when the precursor liquid (I) is applied onto the underlayer is the same as the coating method of the precursor liquid in the method for producing the first transparent conductive substrate. The coating amount in the case of applying the precursor liquid (I) is not particularly limited. For example, it is preferred that the thickness (dry film thickness) of the finally formed film be 1 Onm to 300 nm. When the thickness of the dry film finally formed is smaller than the above range, there may be a problem of partial coating or substantially uncoated in the presence of irregularities on the substrate, and on the other hand, when it is larger than the above range, there will be The problem of reduced transparency. Further, when the precursor liquid (I) of the above thickness is applied, the coating operation may be performed once, and the coating operation may be repeated a plurality of times.

塗佈上述前驅物液（I)後之基板接著進行燒成。藉 此，底層上之過氧化錯合物（前驅物液）變化成摻雜Nb或 Ta之氧化鈦。此時之結晶狀態通常係由無定型相組成。 Q 燒成時之條件（加熱溫度、燒成時間、燒成氛圍氣體等）係 r 與上述第一透明導電性基板之製造方法中之燒成條件相 ： 同。 對於燒成後之基板在還原氛圍氣體下藉由加熱進行退 火處理。藉此，形成膜之摻雜Nb或Ta之氧化鈦由無定 型相結晶轉移成銳鈦礦相，在結晶相中產生氧缺陷，可改 善導電性。然而，通常導入氧缺陷時會有容易變化成電阻 高之金紅石結晶相之傾向，但本發明中摻雜於氧化鈦中鈮 -30- 200941506 或鉅在導入氧缺陷時由於產生使銳鈦礦結晶相安定化之作 用，因而可維持展現高導電性之結晶狀態。退火處理時之 條件（加熱溫度、處理時間、還原氛圍氣體）等係與上述第 一透明導電性基板之製造方法中之退火處理之條件相同。 如此，在上述底層上形成由摻雜鈮或钽之氧化鈦組成 . 之透明導電性膜。該透明導電性膜具有銳鈦礦結晶相，且 爲由摻雜Nb或Ta之氧化鈦之多結晶體組成之薄膜，在 0 具備有良好透明性的同時，亦展現高的導電性者。 又，本發明之第二透明導電性基板之製造方法中亦可 以多段形成由摻雜鈮或钽之氧化鈦組成之膜（透明導電性 膜）。亦即，在上述底層上塗佈前驅物液（I)之一部份，藉 由進行上述之燒成及上述之退火處理形成第一層之透明導 電性膜，接著，在最表面之膜上塗佈前驅物液（I)，經燒 成、進行退火處理，重複操作至目標膜厚爲止。如此般分 多段形成透明導電性膜時，由於各段塗佈之膜之厚度較 〇 薄，因此以燒成及退火處理之結晶化容易進行，結果，經 ^ 層合之透明導電性膜成爲具有良好之結晶性。 (第三種透明導電性基板之製造方法） 本發明之第三種透明導電性基板之製造方法中，首先 係在透明基材上形成由銳鈦礦結晶相之氧化鈦系薄膜組成 之底層。如此般，在後述前驅物液塗佈之前，藉由在透明 基材上形成上述底層，且對塗佈於該底層上之前驅物液進 行燒成、退火處理，可產生摻雜鈮或鉬之氧化鈦結晶，使 -31 - 200941506 底層中之銳鈦礦結晶相發揮作爲晶種之結晶核作用，促進 結晶化。結果，降低形成之透明導電性膜之電阻，可展現 優異之導電性。 又，在促進如上述之摻雜鈮或鉅之氧化鈦之結晶化 時，與該結晶化有關之加熱處理（亦即，前驅物液塗佈後 之燒成及退火處理）之溫度可設定在較低之溫度下亦可獲 得效果。藉此，可減低對透明基材選擇之限制，例如當使 用具有可撓性之耐熱溫度低之樹脂薄膜作爲透明基材時， 以所謂的輥對輥法製造透明導電基板亦成爲可能。 又，第三種製造方法中，所謂成爲底層之銳鈦礦結晶 相之氧化鈦系薄膜意指由銳鈦礦結晶相之氧化鈦組成之薄 膜，或者，例如由摻雜鈮或鉬.等之摻雜物金屬而成之銳鈦 礦結晶相之氧化鈦組成之薄膜，於後述分散體中以銳鈦礦 型氧化鈦系微粒子構成。又，作爲底層之銳鈦礦結晶相之 氧化鈦系薄膜爲具有不損及最終所得透明導電性基板之透 明性程度之透明性者。 本發明之第三透明導電性基板之製造方法中，上述底 層係使銳鈦礦型氧化鈦系微粒子分散於分散介質中而成之 分散體塗佈於透明基材上之後，藉由使分散介質揮發而形 成。如此，以塗佈法形成底層時，由於可以簡易之塗佈法 進行與透明導電性膜之形成相配合之全部步驟，因而使可 在不需要真空設備之簡易操作下提供便宜之透明導電性基 板成爲可能。而且，第三種製造方法中底層之形成由於係 在塗佈使銳鈦礦型氧化鈦系微粒子分散於分散介質中而成 -32- 200941506 之分散體之後，藉由使分散介質揮發而進行者’因此可在 常溫下成膜，可省略底層形成時之加熱步驟而達到步驟簡 略化，亦爲其優點。 - 上述底層形成用之分散體可爲將銳欽礦型氧化鈦系微 粒子分散於分散介質中者。其中’所謂銳鈦礦型氧化鈦系 . 微粒子意指銳鈦礦結晶相之氧化鈦之微粒子’或者爲由例 如摻雜有鈮或鉬等之摻雜物金屬之銳鈦礦結晶相之氧化鈦 Φ 組成之微粒子。 構成上述銳鈦礦型氧化鈦系微粒子之氧化物之組成 (相對於鈦量之摻雜物量或其種類等）並無特別限制，但較 好爲具有與由後述之前驅物液（包含（A)使鈦化合物與過氧 化氫反應而成之反應產物及（B)使鈮化合物或鉬化合物與 過氧化氫反應而成之反應產物之前驅物液）形成之氧化物 相同組成，或者具有相近組成。通常，未摻雜鈮或鉅之銳 鈦礦結晶相之氧化鈦之結晶型爲正方晶，對應於摻雜於其 φ 中之摻雜物量，a軸、b軸、c軸之晶格常數將會變化。 *- 構成成爲結晶核之銳鈦礦型氧化鈦系微粒子之氧化物與由 ： 前驅物液形成之氧化物之間，a軸、b軸、c軸之晶格常 數之差異若變大時，則會有兩結晶之匹配性變差之問題， 但如上述，若使構成銳鈦礦型氧化鈦系微粒子之氧化物與 由前驅物液形成之氧化物爲相同組成或接近組成，則可抑 制a軸、b軸、c軸之晶格常數之差異於較小。 上述銳鈦礦型氧化鈦系微粒子之平均粒徑（一次平均 粒徑），爲了確保底層之透明性，以20nm以下較好，更好 -33- 200941506 爲10nm以下。如此，就底層透明性之觀點而言，銳鈦礦 型氧化鈦系微粒子愈小愈好，但通常其下限爲1 nrn以上 左右。 上述銳鈦礦型氧化欽系微粒子之形狀或尺寸分佈並無 特別限制，但爲了形成表面平滑之膜作爲底層，因此粒子 形狀以球狀或立方體等對稱性良好之形狀較佳。另外，其 . 尺寸分佈以單分散，亦即以大小均等者較佳。 分散上述銳鈦礦型氧化鈦系微粒子之分散介質並特別 0 限制者，就儘可能省略加熱方面而言，較好使用低沸點溶 劑，例如使用水或醇等之有機溶劑等。 上述分散體可藉由例如i)將粉末狀銳鈦礦型氧化鈦系 微粒子添加於分散介質中，使用分散機（例如，珠粒硏磨 機、球磨機、噴射硏磨機等）進行分散處理而獲得，或Π)The substrate after the application of the precursor liquid (I) is subsequently fired. Thereby, the peroxidic complex (precursor liquid) on the underlayer is changed to titanium oxide doped with Nb or Ta. The crystalline state at this time usually consists of an amorphous phase. The conditions at the time of firing (heating temperature, firing time, firing atmosphere, etc.) are the same as the firing conditions in the method for producing the first transparent conductive substrate. The substrate after firing is subjected to annealing treatment by heating under a reducing atmosphere. Thereby, the titanium oxide doped with Nb or Ta formed into a film is crystallized into an anatase phase by an amorphous phase, and oxygen defects are generated in the crystal phase, whereby conductivity can be improved. However, when oxygen defects are introduced, there is a tendency to easily change into a rutile crystal phase having a high electric resistance, but in the present invention, doped in titanium oxide 铌-30-200941506 or giant in the introduction of oxygen defects due to generation of anatase The crystal phase stabilizes and thus maintains a crystalline state exhibiting high conductivity. The conditions (heating temperature, treatment time, reducing atmosphere) in the annealing treatment are the same as those in the annealing method in the method for producing the first transparent conductive substrate. Thus, a transparent conductive film composed of titanium oxide doped with cerium or lanthanum is formed on the underlayer. The transparent conductive film has an anatase crystal phase and is a film composed of a polycrystal of titanium oxide doped with Nb or Ta, and exhibits good transparency and exhibits high conductivity. Further, in the method for producing a second transparent conductive substrate of the present invention, a film (transparent conductive film) composed of titanium oxide doped with cerium or lanthanum may be formed in a plurality of stages. That is, a portion of the precursor liquid (I) is coated on the underlayer, and the first layer of the transparent conductive film is formed by performing the above-described firing and the annealing treatment described above, and then on the film on the outermost surface. The precursor liquid (I) is applied, fired, annealed, and the operation is repeated until the target film thickness is reached. When the transparent conductive film is formed in a plurality of stages in this manner, since the thickness of the film applied in each step is relatively thin, crystallization by firing and annealing is easily performed, and as a result, the transparent conductive film laminated is provided. Good crystallinity. (Method for Producing Third Transparent Conductive Substrate) In the method for producing a third transparent conductive substrate of the present invention, first, a bottom layer composed of a titanium oxide-based thin film of an anatase crystal phase is formed on a transparent substrate. In this manner, before the application of the precursor liquid described later, by forming the underlayer on the transparent substrate and baking and annealing the precursor liquid applied to the underlayer, an antimony or molybdenum can be produced. The crystallization of titanium oxide causes the anatase crystal phase in the underlayer of -31 - 200941506 to function as a crystal nucleus of the seed crystal to promote crystallization. As a result, the electrical resistance of the formed transparent conductive film can be lowered to exhibit excellent electrical conductivity. Further, when the crystallization of the doped cerium or the giant titanium oxide as described above is promoted, the temperature of the heat treatment (that is, the firing and annealing treatment after the application of the precursor liquid) in the crystallization may be set at The effect can also be obtained at lower temperatures. Thereby, the restriction on the selection of the transparent substrate can be reduced. For example, when a resin film having a low heat-resistant temperature which is flexible is used as the transparent substrate, it is also possible to manufacture a transparent conductive substrate by a so-called roll-to-roll method. Further, in the third manufacturing method, the titanium oxide-based film which is the bottom layer of the anatase crystal phase means a film composed of titanium oxide of an anatase crystal phase, or, for example, doped with antimony or molybdenum. A film composed of a titanium oxide having an anatase crystal phase of a dopant metal is composed of anatase-type titanium oxide-based fine particles in a dispersion to be described later. Further, the titanium oxide-based film which is the crystalline phase of the anatase of the bottom layer has transparency which does not impair the transparency of the finally obtained transparent conductive substrate. In the method for producing a third transparent conductive substrate of the present invention, the underlayer is obtained by dispersing an anatase-type titanium oxide fine particle in a dispersion medium on a transparent substrate, and then dispersing the medium. Formed by volatilization. Thus, when the underlayer is formed by the coating method, since all the steps of matching with the formation of the transparent conductive film can be performed by a simple coating method, it is possible to provide an inexpensive transparent conductive substrate without a simple operation of a vacuum apparatus. become possible. Further, in the third manufacturing method, the formation of the underlayer is carried out by dispersing the dispersion medium after the dispersion of the anatase-type titanium oxide-based fine particles is dispersed in the dispersion medium to form a dispersion of -32 to 200941506. 'Therefore, the film can be formed at a normal temperature, and the heating step at the time of forming the underlayer can be omitted to achieve a simplification of the steps, which is also an advantage. - The dispersion for forming the underlayer may be one in which the Ruiqin-type titanium oxide-based fine particles are dispersed in a dispersion medium. Wherein 'the so-called anatase-type titanium oxide system. The micro-particles mean the fine particles of titanium oxide of the anatase crystal phase' or the titanium oxide crystal phase of an anatase crystal doped with, for example, a dopant metal such as ruthenium or molybdenum. Φ composed of microparticles. The composition of the oxide of the anatase-type titanium oxide-based fine particles (the amount of the dopant relative to the amount of titanium, or the kind thereof) is not particularly limited, but preferably has a precursor liquid (including (A) a reaction product obtained by reacting a titanium compound with hydrogen peroxide and (B) an oxide formed by reacting a ruthenium compound or a molybdenum compound with hydrogen peroxide, or having a similar composition . Generally, the crystal form of titanium oxide which is not doped with yttrium or giant anatase crystal phase is tetragonal, corresponding to the amount of dopant doped in φ, the lattice constants of the a-axis, b-axis, and c-axis will Will change. *- When the difference between the crystal constant of the a-axis, the b-axis, and the c-axis is larger between the oxide of the anatase-type titanium oxide-based fine particles that constitute the crystal nucleus and the oxide formed by the precursor liquid, The problem that the matching of the two crystals is deteriorated, but as described above, if the oxide constituting the anatase-type titanium oxide-based fine particles is made of the same composition or close to the composition of the oxide formed from the precursor liquid, it can be suppressed. The difference in lattice constants of the a-axis, b-axis, and c-axis is small. The average particle diameter (primary average particle diameter) of the anatase-type titanium oxide-based fine particles is preferably 20 nm or less, more preferably -33 to 200941506, and 10 nm or less in order to ensure transparency of the underlayer. As described above, the anatase-type titanium oxide-based fine particles are preferably as small as possible from the viewpoint of the transparency of the underlayer, but usually the lower limit is about 1 nrn or more. The shape or size distribution of the anatase-type oxidized fine-particles is not particularly limited. However, in order to form a film having a smooth surface as a bottom layer, the shape of the particles is preferably a shape having a good symmetry such as a sphere or a cube. In addition, the size distribution is preferably monodisperse, that is, it is preferably equal in size. In order to disperse the dispersion medium of the above-described anatase-type titanium oxide-based fine particles, it is preferable to use a low-boiling solvent, for example, an organic solvent such as water or alcohol, or the like. The dispersion may be added to a dispersion medium by, for example, i) powdery anatase-type titanium oxide-based fine particles, and dispersed by a disperser (for example, a bead honing machine, a ball mill, a jet honing machine, or the like). Get, or Π)

以由下向上自液相合成銳鈦礦型氧化鈦系微粒子所得之反 應溶液依據需要進行分散處理而獲得。又，例如銳鈦礦型 氧化鈦微粒子等由於有市售者作爲分散體，因此可使用該 Q 等市售品毫無問題。 〃 以上述ii)之方法獲得上述分散體時，具體而言，例 ： 如若爲銳鈦礦型氧化鈦微粒子之分散體，則較好僅加熱後 述之（A)使鈦化合物與過氧化氫反應而成之反應產物，若 爲摻雜有鈮或鉬之銳鈦礦型氧化鈦微粒子，則較好加熱後 述之含有（A)使鈦化合物與過氧化氫反應而成之反應產物 及（B)使鈮化合物或钽化合物與過氧化氫反應而成之反應 產物之前驅物液。另外，摻雜鈮或钽之銳鈦礦型氧化鈦微 -34- 200941506 粒子之分散體可藉由特開2003-252624號公報中所記載之 方法調製。 上述分散體只要不損及透明性，亦可含有各種添加 劑’例如當使用玻璃作爲透明基材時，可添加界面活性劑 等以改善對基材之潤濕性。 - 上述分散體中所佔銳鈦礦型氧化鈦系微粒子之含有量 . 並無特別限制，較好以使最終形成之膜厚度成爲後述底層 φ 膜厚範圍之方式適當設定。 將上述分散體塗佈於透明基材上之塗佈方法與上述第 一透明導電性基板之製造方法中之前驅物液之塗佈方法相 同。又，此時之塗佈量，以可使最終形成之膜厚度成爲後 述底層之膜厚範圍之方式適當設定。 塗佈上述分散體後使分散介質揮發時，以在200°C以 下之溫度進行較佳。亦即，第三種製造方法中，由於在塗 佈含有銳鈦礦型氧化鈦系微粒子之上述分散體之時點形成 〇 作爲底層機能之銳鈦礦結晶相之氧化鈦系薄膜，因此並不 需要爲結晶化而加熱。因而，例如在常溫或其附近之溫度 * 放置或者風乾等未經加熱使分散介質揮發，就達到步驟簡 化之觀點而言爲較佳。但是，若考慮形成之膜與透明基材 之密著性時，以達到某種程度之熱較佳。若斟酌該等，則 較好爲在上述溫度範圍使分散介質揮發。 如此，可藉由塗佈法形成成爲底層之銳鈦礦結晶相之 氧化鈦系薄膜（氧化鈦膜或者摻雜氧化鈦（摻雜有摻雜物之 氧化鈦）膜）。 -35- 200941506 本發明之第三種透明導電性基板之製造方法中形成之 底層（銳鈦礦結晶相之氧化鈦系薄膜）之膜厚並無特別限 制’但當底層之膜厚太小時，作爲種晶作用之銳鈦礦結晶 相之結晶無法充分存在’而有無法獲得因上述底層形成之 效果，另一方面’當底層之膜厚太大時，由於會有透明性 降低之問題’因此通常爲3nm以上，較好爲5nm以上， 更好爲10nm以上，爲50nm以下，較好爲30nm以下，更 好爲20nm以下之範圍。 又，本發明之第三種透明導電性基板之製造方法中可 使用之透明基板係與上述第一透明導電性基板之製造方法 相同。 本發明之第三透明導電性基板之製造方法，如下述， 在上述底層上塗佈包含（A)使鈦化合物與過氧化氫反應而 成之反應產物及（B)使鈮化合物或鉬化合物（摻雜物化合物） 與過氧化氫反應而成之反應產物之前驅物液。 該前驅物液係與上述第一透明導電性基板之製造方法 中之前驅物液相同，且可依循第一透明導電性基板之製造 方法中之前驅物液之說明。 將上述前驅物液塗佈於上述底層上時之塗佈方法係與 上述第一透明導電性基板之製造方法中之前驅物液之塗佈 方法相同。 塗佈上述前驅物液時之塗佈量並無特別限制，例如爲 使最終形成之膜之厚度（乾膜厚）成爲l〇nm~300nm即可。 最終形成之乾膜厚度比上述範圍小時，於基材上存在凹凸 -36- 200941506 時會產生部份塗佈處或實質上未塗佈處之問題，另一方 面，當比上述範圍大時，會有透明性降低之問題。另外， 塗佈該等厚度之前驅物液時，可進行一次塗佈作業，亦可 重複進行複數次之塗佈作業。 塗佈上述前驅物液後之基板接著進行燒成。藉此，底 . 層上之過氧化錯合物（前驅物液）變化成摻雜Nb或Ta之氧 _ 化鈦。此時之結晶狀態通常係由無定型相組成。燒成時之 ❹ 條件（加熱溫度、燒成時間、燒成氛圍氣體等）係與上述第 一透明導電性基板之製造方法中之燒成條件相同。 對於燒成後之基板，在還原氛圍氣體中藉由加熱進行 退火處理。藉此，形成膜之摻雜Nb或Ta之氧化鈦由無 定型相結晶轉移成銳鈦礦相，在結晶相中產生氧缺陷，可 改善導電性。然而，通常導入氧缺陷時會有容易改變成電 阻高之金紅石結晶相之傾向，但本發明中摻雜於氧化鈦中 之鈮或鉅在導入氧缺陷時由於產生使銳鈦礦結晶相安定化 φ 之作用，因而可維持展現高的導電性之結晶狀態。退火處 理時之條件（加熱溫度、處理時間、還原氛圍氣體）等係與 ： 上述第一透明導電性基板之製造方法中之退火處理條件相 同。 如此，在上述底層上形成由摻雜鈮或钽之氧化鈦組成 之透明導電性膜。該透明導電性膜具有銳鈦礦結晶相，且 爲由摻雜Nb或Ta之氧化鈦之多結晶體組成之薄膜，在 具備有良好透明性的同時，亦展現高的導電性者。 而且，本發明之第三透明導電性基板之製造方法中亦 -37- 200941506 可im#段形成由摻雜鈮或钽之氧化鈦組成之膜（透明導電 性膜）°亦即，在上述底層上塗佈前驅物液之一部份，藉 由進行上述之燒成及上述之退火處理形成第一層之透明導 電性膜’接著，在最表面之膜上塗佈前驅物液，經燒成、 進行退火處理，重複操作至目標膜厚爲止。如此般分多段 形成透明導電性膜時，由於各段塗佈之膜之厚度薄，因此 _ 以燒成及退火處理之結晶化容易進行，結果，經層合之透 明導電性膜同時具有良好之結晶性。 (第四透明導電性基板之製造方法） 本發明之第四透明導電性基板之製造方法中，係以包 含（A)使鈦化合物與過氧化氫反應而成之反應產物，及（B) 使鈮化合物或钽化合物（摻雜物化合物）與過氧化氫反應而 成之反應產物，及（C)銳鈦礦型氧化鈦系微粒子之含前驅 物之分散體作爲膜形成材料。該含前驅物之分散體爲使（C) 銳鈦礦型氧化鈦系微粒子分散於由（A)使鈦化合物與過氧 〇 化氫反應而成之反應產物及（B)使摻雜物化合物與過氧化 ^ 氫反應而成之反應產物組成之前驅物液中而成者。 ： 上述前驅物液係以上述第一透明導電性基板之製造方 法中之前驅物液相同，爲包含藉由加熱摻雜鈮或鉬之氧化 鈦而成之金屬氧化物前驅物（過氧化錯合物）者。藉由於該 前驅物液之中預先使（C)銳鈦礦型氧化鈦系微粒子分散並 存在，於塗佈該前驅物液後，進行燒成、退火處理，可產 生摻雜鈮或鉬之氧化鈦結晶，該銳鈦礦型氧化鈦系微粒子 -38- 200941506 發揮作爲晶種之結晶核之作用，而促進結晶化。其結果， 使形成之透明導電性膜之電阻降低，可展現更優異之導電 性。 另外，在促進如上述之摻雜鈮或鉬之氧化鈦之結晶化 時，與該結晶化有關之加熱處理（亦即，含前驅物之分散 . 體塗佈後之燒成及退火處理）之溫度可設定在較低之溫度 _ 亦可獲得效果。據此，可減低對透明基材選擇之限制，例 Φ 如當使用具有可撓性之耐熱溫度低之樹脂薄膜作爲透明基 材時，以所謂的輥對輥法製造透明導電基板亦成爲可能。 第四透明導電性基板之製造方法中，所謂（C)銳鈦礦 型氧化鈦系微粒子意指銳鈦礦結晶相之氧化鈦微粒子，或 者，例如由摻雜鈮或鉅等摻雜物金屬而成之銳鈦礦結晶相 之氧化鈦組成之微粒子。 構成上述（C)銳鈦礦型氧化鈦系微粒子之氧化物之組 成（相對於鈦量之摻雜物量或其種類等）以具有與由前驅物 Φ 液形成之氧化物相同之組成或者具有接近之組成者較佳。 通常，未摻雜鈮或钽之銳鈦礦結晶相之氧化鈦之結晶型爲 ： 正方晶，對應於摻雜於其中之摻雜物量，a軸、b軸、c 軸之晶格常數將變化。構成作爲結晶核之（C)銳鈦礦型氧 化鈦系微粒子之氧化物與由前驅物液形成之氧化物之間， a軸、b軸、c軸之晶格常數差異變大時，則會有兩結晶 之匹配性變差之問題，但如上述般’若使構成（C)銳鈦礦 型氧化鈦系微粒子之氧化物與由前驅物液形成之氧化物爲 相同組成或接近之組成，則可抑制a軸、b軸、c軸之晶 -39- 200941506 格常數之差異於較小。 上述（c)銳鈦礦型氧化鈦系微粒子之平均粒徑（一次平 均粒徑）並無特別限制，但當考量該銳鈦礦型氧化鈦系微 粒子徹底作爲結晶核之機能者，而且考慮最終獲得之透明 導電性基板中殘存之銳鈦礦型氧化鈦系微粒子顯示絕緣性 時，其平均粒徑（一次平均粒徑）以l~20nm較佳，更好爲 . 1〜1Onm。 上述（C)銳鈦礦型氧化鈦系微粒子之形狀或尺寸分佈 0 並無特別限制，但爲了形成表面平滑之膜，粒子形狀以球 狀或立方體等對稱性良好之形狀較佳。另外，其尺寸分佈 以單分散，亦即以大小均等者較佳。The reaction solution obtained by synthesizing anatase-type titanium oxide-based fine particles from the liquid phase from the bottom to the top is obtained by dispersion treatment as needed. Further, since an anatase type titanium oxide fine particle or the like is commercially available as a dispersion, it is possible to use a commercially available product such as Q without any problem.获得 When the dispersion is obtained by the method of the above ii), specifically, for example, if it is a dispersion of anatase-type titanium oxide fine particles, it is preferred to heat only the titanium compound to react with hydrogen peroxide (A) described later. When the reaction product is an anatase-type titanium oxide fine particle doped with cerium or molybdenum, it is preferred to heat (A) a reaction product obtained by reacting a titanium compound with hydrogen peroxide and (B) A precursor product of a reaction product obtained by reacting a ruthenium compound or a ruthenium compound with hydrogen peroxide. Further, a dispersion of an anatase-type titanium oxide micro-34-200941506 particle doped with cerium or lanthanum can be prepared by the method described in JP-A-2003-252624. The dispersion may contain various additives as long as the transparency is not impaired. For example, when glass is used as the transparent substrate, a surfactant or the like may be added to improve the wettability to the substrate. The content of the anatase-type titanium oxide-based fine particles in the above-mentioned dispersion is not particularly limited, and is preferably set so that the film thickness finally formed is in the range of the film thickness of the underlayer φ to be described later. The coating method of applying the above dispersion onto a transparent substrate is the same as the method of applying the precursor liquid in the method for producing the first transparent conductive substrate. Further, the coating amount at this time is appropriately set so that the film thickness finally formed becomes the film thickness range of the underlayer described later. When the dispersion is applied and the dispersion medium is volatilized, it is preferably carried out at a temperature of 200 ° C or lower. In the third manufacturing method, since the titanium oxide-based film of the anatase crystal phase of the underlayer function is formed at the point of coating the dispersion containing the anatase-type titanium oxide-based fine particles, it is not necessary. Heated for crystallization. Therefore, for example, it is preferred from the viewpoint of simplification of the steps, such as leaving at room temperature or in the vicinity thereof, such as standing or air drying to volatilize the dispersion medium without heating. However, in consideration of the adhesion between the formed film and the transparent substrate, it is preferred to achieve a certain degree of heat. If these are considered, it is preferred to volatilize the dispersion medium in the above temperature range. Thus, a titanium oxide-based thin film (titanium oxide film or doped titanium oxide (titanium doped with titanium oxide) film) which is an anatase crystal phase of the underlayer can be formed by a coating method. -35- 200941506 The film thickness of the underlayer (the titanium oxide-based film of the anatase crystal phase) formed in the method for producing the third transparent conductive substrate of the present invention is not particularly limited, but when the film thickness of the underlayer is too small, The crystal of the anatase crystal phase, which is a seed crystal, cannot be sufficiently present, and the effect of the formation of the underlayer is not obtained. On the other hand, when the film thickness of the underlayer is too large, there is a problem that transparency is lowered. It is usually 3 nm or more, preferably 5 nm or more, more preferably 10 nm or more, and 50 nm or less, preferably 30 nm or less, more preferably 20 nm or less. Further, the transparent substrate which can be used in the method for producing a third transparent conductive substrate of the present invention is the same as the method for producing the first transparent conductive substrate. In the method for producing a third transparent conductive substrate of the present invention, as described below, (A) a reaction product obtained by reacting a titanium compound with hydrogen peroxide and (B) a ruthenium compound or a molybdenum compound are applied to the underlayer. The dopant compound is a reaction product of a reaction product formed by reacting with hydrogen peroxide. The precursor liquid is the same as the precursor liquid in the method for producing the first transparent conductive substrate, and can follow the description of the precursor liquid in the method of manufacturing the first transparent conductive substrate. The coating method when the precursor liquid is applied onto the underlayer is the same as the coating method of the precursor liquid in the method for producing the first transparent conductive substrate. The coating amount in the case where the precursor liquid is applied is not particularly limited, and for example, the thickness (dry film thickness) of the finally formed film may be from 10 nm to 300 nm. When the thickness of the dry film finally formed is smaller than the above range, there is a problem that a partial coating portion or a substantially uncoated portion occurs when the unevenness is present on the substrate -36-200941506, and on the other hand, when it is larger than the above range, There will be problems with reduced transparency. Further, when the precursor liquid of the above thickness is applied, the coating operation may be performed once, and the coating operation may be repeated a plurality of times. The substrate after the application of the precursor liquid is subsequently fired. Thereby, the peroxidation complex (precursor liquid) on the bottom layer is changed to doped Nb or Ta oxygen-titanium. The crystalline state at this time usually consists of an amorphous phase. The ❹ condition (heating temperature, firing time, firing atmosphere, and the like) at the time of firing is the same as the firing conditions in the method for producing the first transparent conductive substrate. The substrate after firing is annealed by heating in a reducing atmosphere. Thereby, the titanium oxide doped with Nb or Ta formed into a film is crystallized into an anatase phase by an amorphous phase, and oxygen defects are generated in the crystal phase, whereby conductivity can be improved. However, when an oxygen defect is introduced, there is a tendency to easily change into a rutile crystal phase having a high electric resistance, but in the present invention, the antimony doped in the titanium oxide or the anatase crystal phase is stabilized due to generation of an oxygen defect. By the action of φ, it is possible to maintain a crystalline state exhibiting high conductivity. The conditions (heating temperature, treatment time, reducing atmosphere) in the annealing treatment are the same as those in the method for producing the first transparent conductive substrate. Thus, a transparent conductive film composed of titanium oxide doped with cerium or lanthanum is formed on the underlayer. The transparent conductive film has an anatase crystal phase and is a film composed of a polycrystalline body doped with titanium oxide of Nb or Ta, and exhibits high transparency while exhibiting high conductivity. Further, in the method for producing a third transparent conductive substrate of the present invention, a film (transparent conductive film) composed of titanium oxide doped with cerium or lanthanum may be formed in the period of -37-200941506. One part of the precursor liquid is applied, and the first layer of the transparent conductive film is formed by performing the above-mentioned baking and the above annealing treatment. Next, the precursor liquid is applied onto the film on the outermost surface, and is fired. Annealing is performed until the target film thickness is repeated. When the transparent conductive film is formed in a plurality of stages in this manner, since the thickness of the film applied in each step is small, crystallization by firing and annealing is easy, and as a result, the laminated transparent conductive film has good properties at the same time. Crystallinity. (Method for Producing Fourth Transparent Conductive Substrate) The method for producing a fourth transparent conductive substrate of the present invention comprises (A) a reaction product obtained by reacting a titanium compound with hydrogen peroxide, and (B) A reaction product obtained by reacting a ruthenium compound or a ruthenium compound (a dopant compound) with hydrogen peroxide, and (C) a dispersion containing a precursor of an anatase-type titanium oxide-based fine particle as a film formation material. The precursor-containing dispersion is obtained by dispersing (C) anatase-type titanium oxide-based fine particles in a reaction product obtained by reacting a titanium compound with hydrogen peroxide (A) and (B) a dopant compound. The reaction product formed by the reaction with hydrogen peroxide is composed of the precursor liquid. The precursor liquid is the same as the precursor liquid in the method for producing the first transparent conductive substrate, and is a metal oxide precursor containing a titanium oxide doped with cerium or molybdenum by heating (peroxide oxidization) Person). By preliminarily dispersing (C) anatase-type titanium oxide-based fine particles in the precursor liquid, after the application of the precursor liquid, baking or annealing treatment is performed to cause oxidation of doped cerium or molybdenum. Titanium crystal, the anatase-type titanium oxide-based fine particles -38-200941506 functions as a crystal nucleus of a seed crystal to promote crystallization. As a result, the electric resistance of the formed transparent conductive film is lowered, and more excellent electrical conductivity can be exhibited. Further, in the crystallization of the titanium oxide doped with cerium or molybdenum as described above, the crystallization is related to the heat treatment (that is, the dispersion containing the precursor, the firing and annealing after the coating) The temperature can be set at a lower temperature _ and the effect can be obtained. According to this, it is possible to reduce the restriction on the selection of the transparent substrate. For example, when a resin film having a low heat-resistant temperature having flexibility is used as the transparent substrate, it is also possible to manufacture a transparent conductive substrate by a so-called roll-to-roll method. In the method for producing the fourth transparent conductive substrate, the (C) anatase-type titanium oxide-based fine particles mean titanium oxide fine particles of an anatase crystal phase, or, for example, doped with a dopant metal such as ruthenium or giant. A fine particle composed of titanium oxide in the crystalline phase of the anatase. The composition of the oxide of the above (C) anatase-type titanium oxide-based fine particles (the amount of the dopant relative to the amount of titanium or the kind thereof, etc.) has the same composition as that of the oxide formed of the precursor Φ liquid or has a close The constituents are preferred. Generally, the crystal form of titanium oxide which is not doped with yttrium or yttrium anatase crystal phase is: tetragonal crystal, corresponding to the amount of dopant doped therein, the lattice constants of the a-axis, b-axis, and c-axis will change. . When the difference between the lattice constant of the a-axis, the b-axis, and the c-axis is increased between the oxide of the (C) anatase-type titanium oxide-based fine particles as the crystal nucleus and the oxide formed of the precursor liquid, There is a problem that the matching of the two crystals is deteriorated, but as described above, the composition of the (C) anatase-type titanium oxide-based fine particles is the same as or close to the oxide formed of the precursor liquid. Then, the difference between the lattice constants of the a-axis, the b-axis, and the c-axis-39-200941506 can be suppressed to be small. The average particle diameter (primary average particle diameter) of the above-mentioned (c) anatase-type titanium oxide-based fine particles is not particularly limited. However, considering the function of the anatase-type titanium oxide-based fine particles as a crystal nucleus, and considering the final When the anatase-type titanium oxide-based fine particles remaining in the obtained transparent conductive substrate exhibits insulating properties, the average particle diameter (primary average particle diameter) is preferably from 1 to 20 nm, more preferably from 1 to 1 nm. The shape or size distribution 0 of the (C) anatase-type titanium oxide-based fine particles is not particularly limited. However, in order to form a film having a smooth surface, the shape of the particles is preferably a shape having a good symmetry such as a sphere or a cube. Further, the size distribution is preferably monodisperse, that is, it is preferably equal in size.

第四透明導電性基板之製造方法中，作爲膜形成材料 之含前驅物分散體中之各成分（亦即，（A)使鈦化合物與過 氧化氫反應而成之反應產物，（B)使摻雜物化合物與過氧 化氫反應而成之反應產物，及（C)銳鈦礦型氧化鈦系微粒 子）之含有比例，以固成分重量比，較好爲[(A) + (B)] : Q (C) = 100: 0.1~10較佳。當（C)銳鈦礦型氧化鈦系微粒子之 · 量比上述範圍少時，有無法期待作爲晶種之充分作用效果 - 之問題，另一方面，當比上述範圍多時，由於顯示絕緣性 之銳鈦礦型氧化鈦系微粒子會大量殘存於透明導電性基板 中，而有損及導電性之問題。另外，[(A) + (B)]相當於由 「前驅物液之固成分濃度」求得之固成分重量。 上述含前驅物之分散體可例如藉由混合上述（A)之反 應產物、上述（B)之反應產物及上述（C)之微粒子獲得，但 -40- 200941506 此時之混合順序等並無特別限制。例如，通常採用調配由 上述（A)之反應產物與上述（B)之反應產物組成之前驅物 液，於其中添加並分散上述（C)之微粒子之方法。以下針 對該方法詳細敘述。 有關由上述（A)之反應產物與上述（B)之反應產物組成 - 之前驅物液係與上述第一透明導電性基板之製造方法中之 _ 前驅物液相同，可套用第一透明導電性基板之製造方法中 φ 之前驅物液之說明。 於上述前驅物液中添加並分散上述（C)銳鈦礦型氧化 鈦系微粒子時，i)係以粉末狀態將（C)銳鈦礦型氧化鈦系微 粒子添加於前驅物液中，隨後使用分散機（例如，珠粒硏 磨機、球磨機、噴射硏磨機等）進行分散處理而獲得，或 Π)亦可藉由將粉體狀之（C)銳鈦礦型氧化鈦系微粒子分散 於分散介質（例如，水、醇等有機溶劑）中，或者以由下向 上自液相合成（C)銳鈦礦型氧化鈦系微粒子所得之反應溶 〇 液依據需要進行分散處理，預先調配（c)銳鈦礦型氧化鈦 系微粒子之分散體且將該分散體添加於前驅物液中亦可。 ： 又，例如銳鈦礦型氧化鈦微粒子等由於有市售者作爲分散 體，因此亦可將如此市售品添加於前驅物液中亦無妨。再 者，如上述ii)般將（C)銳鈦礦型氧化鈦系微粒子作爲預先 分散體添加時，亦較好在分散體添加後以分散機進行分散 處理。 獲得含有上述前驅物之分散體之方法，除上述以外， 亦可採用藉由適度加熱上述前驅物液或上述（A)之反應產 200941506 物，使僅一部份之過氧錯合物轉化成銳鈦礦結晶相之摻雜 鈮或钽之氧化鈦或氧化鈦之方法。但，該方法由於難以控 制生成之（C)銳鈦礦型氧化鈦系微粒子之粒徑或含前驅物 之分散體中之各成分比{[(A) + (B)] : (C)}等，因此有無法 獲得所需之含前驅物之分散體之情況。 另外，上述含有前驅物之分散體中之（C)銳鈦礦型氧 _ 化鈦系微粒子在塗佈於透明基材上時點，較好被均勻的分 散，例如，較好在恰塗佈之前使用分散機進行分散處理， _ 亦可在不損及本發明之效果（特別是透明性及導電性）下使 用以改善分散安定性爲目的之習知分散劑等。 本發明之第四透明導電性基板之製造方法係在透明基 材上塗佈上述含前驅物之分散體，經燒成後，在還原氛圍 氣體中藉由加熱進行退火處理。 上述透明基材係與上述第一透明導電性基板之製造方 法相同。另外，在透明基材上塗佈上述含前驅物之分散體 時之塗佈方法亦與上述第一透明導電性基板之製造方法中 n 之前驅物液塗佈方法相同。但，含前驅物液之分散體以呈 ：· 均勻分散之狀態供應塗佈較佳。 - 塗佈上述含有前驅物之分散體時，塗佈量並無特別限 制，例如可爲使最終形成之膜厚度（乾膜厚）成爲 10nm~3 0 0 nm之量。當最終形成之乾膜厚度比上述範圍小 時’會有在基材上存在凹凸時產生部份塗佈處或實質上未 塗佈處之情況’另一方面，當比上述範圍大時，會有透明 性降低之問題。又’含有前驅物之分散體塗佈成該種厚度 -42- 200941506 時，可以進行一次塗佈作業，亦可重複進行複數次之塗佈 作業。 塗佈上述含有前驅物之分散體後之基板，接著進行燒 成。藉此，使基材上之過氧化錯合物（前驅物液）變化成摻 雜Nb或Ta之氧化鈦。此時之結晶狀態通常係由無定型 . 相組成。燒成時之條件（加熱溫度、燒成時間、燒成氛圍 _ 氣體）等係與上述第一透明導電性基板之製造方法中之燒 ^ 成條件相同。 對於燒成後之基板，在還原氛圍氣體中藉由加熱進行 退火處理。藉此，使形成膜之摻雜Nb或Ta之氧化鈦自 無定型相結晶轉化成銳鈦礦相之同時，在結晶相中產生氧 缺陷，可提升導電性。而且，通常導入氧缺陷會有容易轉 化成電阻高之金紅石結晶相之傾向，但本發明中由於在氧 化鈦中摻雜之鈮或钽對即使導入氧缺陷之銳鈦礦結晶相亦 具有安定化之作用，因此可維持展現高導電性之結晶狀 〇 態。退火處理時之條件（加熱溫度、處理時間、還原氛圍 *' 氣體）等均與上述第一透明導電性基板之製造方法中之退 火處理條件相同。 如此，可在透明基材上形成由摻雜鈮或钽之氧化鈦組 成之透明導電性膜。該透明導電性膜具有銳鈦礦型結晶 相，爲由摻雜Nb或Ta之氧化鈦之多結晶體組成之薄 膜，在具備良好透明性之同時亦展現高的導電性者。 (第五透明導電性基板之製造方法） -43- 200941506 本發明之第五透明導電性基板之製造方法中，係在透 明基材上形成層合膜，該層合膜係在由摻雜作爲摻雜物之 -鈮或钽之摻雜氧化鈦之無定型物或氧化鈦無定型物組成之 第一膜上，層合由以比構成該第一膜之摻雜氧化鈦或氧化 鈦之摻雜物含有比率高之含有比率摻雜上述摻雜物之摻雜 氧化鈦之無定型物組成之第二膜而成者。以下，針對首先 在透明基材上形成第一膜，接著在該第一膜上形成第二膜 之作爲上述層合膜形成之一實施形態之方法加以說明。 上述第一膜之形成只要爲可形成氧化鈦系無定型薄膜 之方法，則可以任何方法進行，例如，可藉以往習知之如 濺射法或PLD法之在真空系統中成膜之方法進行，亦可 將含金屬氧化物粒子之漿料或溶液塗佈於基材上後經加熱 之所謂塗佈法進行。但，以如濺射法或PLD法之真空系 統成膜之方法，由於需要大規模之裝置而導致設備成本 高，進而有使製品成本升高之顧慮，因此工業上大量生產 以可使用既有之設備在簡易操作下便宜的實施之塗佈法較 適當。 以塗佈法形成上述第一膜時，具體而言，較好列舉爲 在透明基材上塗佈包含（A)使鈦化合物與過氧化氫反應而 成之反應產物之前驅物液（以下，第一膜形成用之該前驅 物液稱爲「前驅物液（P1)」），或者含有（A)使鈦化合物與 過氧化氫反應而成之反應產物與（B)使鈮化合物或钽化合 物（摻雜物化合物）與過氧化氫反應而成之反應產物之前驅 物液（以下，第一膜形成用之該前驅物液稱爲「前驅物液 -44- 200941506 (P2)」）並經加熱之方法。 上述前驅物液（P1)爲包含（A)使鈦化合物加以過氧化 之錯合物（過氧化錯合物）者。該過氧化錯合物爲藉由加熱 成爲氧化鈦之金屬氧化物前驅物，藉由前驅物液（P1)形成 之膜係由氧化鈦組成。 - 另一方面，上述前驅物液（P2)爲包含使（A)鈦化合物 _ 及（B)摻雜物化合物加以過氧化之錯合物（過氧化錯合物） 0 者。該過氧化錯合物係藉由加熱成爲摻雜鈮或钽之氧化鈦 之金屬氧化物前驅物，以該前驅物液（P2)形成之膜爲由摻 雜鈮或鉬之摻雜氧化鈦組成。 上述前驅物液（P2)除其組成（亦即，（A)鈦化合物或源 自該鈦化合物之過氧化錯合物與（B)摻雜物化合物或源自 該摻雜物化合物之過氧化錯合物之混合比例）不同以外， 其餘與上述第一透明導電性基板之製造方法中之前驅物液 相同。又，上述前驅物液（P1)爲上述前驅物液（P2)中未使 ❹ 用（B)摻雜物化合物加以過氧化之錯合物，亦即，除使用 (A)鈦化合物加以過氧化之錯合物取代（B)摻雜物化合物加 以過氧化之錯合物以外，其餘與前驅物液（P2)相同。 上述前驅物液（P2)之組成中，（A)鈦化合物或源自該 鈦化合物之過氧錯合物與（B)摻雜物化合物或源自該摻雜 物化合物之過氧錯合物之混合比例，並無特別限制，較好 以使該前驅物液形成之膜中含有所需摻雜物（鈮或钽）含有 比率之方式適當設定。摻雜氧化鈦之摻雜物含有比率通常 設定在0.1〜40莫耳％，較好爲5〜30莫耳％之範圍內。當 -45- 200941506 摻雜物含有比率小於上述範圍時，會有摻雜效果不足，使 導電性降低之問題’另一方面，當摻雜物含有比率比上述 範圍—大時’會有導電性降低，膜之透明性降低之問題。 在透明基材上塗佈上述前驅物液（P1)或前驅物液（P2) 時之塗佈方法係與上述第一透明導電性基板之製造方法中 之前驅物液塗佈方法相同。 塗佈上述前驅物液（P1)或前驅物液（P2)後加熱時之加 熱溫度及加熱時間只要能使過氧錯合物（前驅物液）變化成 _ 氧化鈦或摻雜氧化鈦，則無特別限制。加熱溫度之上限由 於隨著前驅物液組成之結晶化溫度而不同，因此較好爲結 晶化溫度以下之範圍。更具體而言爲500°C以下，較好爲 5 0~40 0°C。又，加熱時間係依據加熱溫度等適當設定，但 通常爲1分鐘〜1小時左右。又，例如在第一膜形成中所 塗佈之前驅物液（P1)或前驅物液（P2)之固成分濃度低之情 況下等之下，在上述加熱之前，可先藉由風乾（自然乾燥） 或真空乾燥或減壓乾燥等程序使溶劑均句揮發，藉此容易 0 地形成均勻膜。 二 上述第一膜之膜厚並無特別限制，但例如當第一膜之 ： 膜厚太小時，無法使退火處理中作爲晶種作用之結晶核充 分存在，而有無法獲得上述結晶化促進效果。另一方面， 當第一膜之膜厚太厚時，由於透明性會降低，因此乾膜厚 通常爲3nm以上，較好爲5nm以上，更好爲l〇nm以上， 爲50nm以下，較好爲30nm以下，更好爲20nm以下之範 圍。 -46- 200941506 另外，本發明之第五透明導電性基板之製造方法中可 使用之透明基板係與上述第一透明導電性基板之製造方法 . 相同。 在上述第一膜上形成第二膜，重要的是由以比構成第 一膜之摻雜氧化鈦或氧化鈦之摻雜物含有比率高之含有比 . 率摻雜上述摻雜物而成之摻雜氧化鈦之無定型物所組成。 藉此，第一膜係在更低溫下先開始變化成銳鈦礦結晶相， ❹ 此作爲晶種發揮結晶核之作用，而促進其上形成之第二膜 之結晶化。 另外，第五製造方法中，所謂摻雜物之含有比率，爲 相對於構成摻雜氧化鈦或氧化鈦之全部金屬之總量，以百 分率表示鈮或鉬所佔比率者。通常，氧化鈦（未摻雜之氧 化鈦）之摻雜物含有比率爲〇莫耳％，摻雜氧化鈦之摻雜物 含有比率爲例如若使用上述前驅物液（P2)形成摻雜氧化 鈦，則以前驅物液（P2)中之（A)鈦化合物或源自該鈦化合 φ 物之過氧錯合物與（B)摻雜物化合物或源自該摻雜物化合 ' 物之過氧錯合物之合計作爲1〇〇莫耳時之摻雜物之莫耳 ： 數，相當於摻雜物之含有比率。 本發明之第五製造方法中，如上述般，上述第—膜中 摻雜物之含有比率比第二膜中之摻雜物含有比率小（換言 之，第二膜中之摻雜物含有比率高於第一膜中之摻雜物含 有比率）。其中，當二者之摻雜物含有比率之差異太小 時，各無定型膜之結晶化溫度幾乎不產生差異，而無法期 待上述結晶化之促進效果，相反的，當二者之摻雜物含有 -47- 200941506 比率之差異過大時，對於第一膜與第二膜匹配方面而言不 利。亦即，通常，未摻雜鈮或钽之銳鈦礦結晶相之氧化鈦 之結晶型爲正方晶，對應於摻雜於其中之摻雜物量，a 軸、b軸、c軸之晶格常數產生改變，當第一膜與第二膜 之間之a軸、b軸、c軸之晶格常數差異變大時，有膜彼 此匹配性變差之問題。因而，爲了儘可能抑制a軸、b . 軸、c軸之晶格常數之差異於較小，因此第一膜與第二膜 _ 較好爲相近組成。當斟酌此等時，「（第二膜中之摻雜物 @ 含有比率）-（第一膜中摻雜物之含有比率）」之値通常以 5〜25左右較佳。 而且，就如上述般之膜彼此匹配性之觀點而言，以構 成第一膜之氧化鈦或摻雜氧化鈦與構成第二膜之摻雜氧化 鈦組成相近者較佳，因此以摻雜氧化鈦形成第一膜時，形 成兩膜之兩種摻雜氧化鈦中之摻雜物種類等較好相同。 上述第二膜之形成較好以塗佈法進行。以塗佈法形成 上述第二膜時，具體而言較好列舉爲在上述第一膜上塗佈 © 含有（A)使鈦化合物與過氧化氫反應而成之反應產物及（B) -‘ 使摻雜物化合物與過氧化氫反應而成之反應產物之前驅物 ： 液（以下第二膜形成用之該前驅物液稱爲「前驅物液 (P3)」）並經加熱之方法。 上述前驅物液（P3)，除其組成（亦即，（A)鈦化合物或 源自該鈦化合物之過氧化錯合物與（B)摻雜物化合物或源 自該摻雜物化合物之過氧錯合物之混合比例）不同以外， 其餘與上述之前驅物液（P2)相同（亦即，與上述第一透明 -48- 200941506 導電性基板之製造方法中之前驅物液相同），第二膜之形 成中可套用針對第一膜形成中所述之上述各說明。 . 上述前驅物液（P3)之組成，以使以該前驅物液（P3)形 成之第二膜中摻雜物含有比率高於第一膜中之摻雜物之含 有比率之方式，適當地設定（A)鈦化合物或源自該鈦化合 ， 物之過氧錯合物及（B)摻雜物化合物或源自該摻雜物化合 , 物之過氧化錯合物之混合比例。但，上述前驅物液（P3)之 n 組成，如上述，就膜彼此之匹配性觀點而言，以形成第一 膜之上述前驅物液（P1)或上述前驅物液（P2)之組成相近者 較佳，因而該摻雜物之含有比率以將第二膜與第一膜之摻 雜物含有比率之差成爲上述範圍內之方式設定較佳，再 者，以含有摻雜物之上述前驅物液（P2)形成第一膜時，形 成兩膜之前驅物液較好不存在不同之摻雜物。又，以前驅 物液（P3)形成之摻雜氧化鈦之摻雜物含有比率通常以設定 在0.1〜40莫耳％，較好在5〜30莫耳％之範圍較佳。 〇 | 在第一膜上塗佈上述前驅物液（P3)形成第二膜時之塗 ' 佈方法係與上述第一透明導電性基板之製造方法中之前驅 -- 物液之塗佈方法相同。 塗佈上述前驅物液（P3)後加熱時之加熱溫度及加熱時 間’只要能使過氧錯合物（前驅物液）變化成氧化鈦或摻雜 之氧化鈦即可，並無特別限制。具體而言，加熱溫度只要 依據前驅物液中摻雜物之量適當設定即可，但由於若加熱 溫度太高，會析出安定之結晶相，而會有退火處理效果之 展現無法被發揮之問題，因此以 5 0 0。(：以下，較好以 -49- 200941506 5 0〜4 0 0 °C較佳。另外，加熱時間係依據加熱溫度等適當設 定，但通常爲1分鐘〜1小時左右。又，例如在第二膜形 成中塗佈之前驅物液（P3)之固成分濃度低之情況等之下， 亦可在上述加熱之前，藉由風乾（自然乾燥）或真空乾燥或 減壓乾燥等程序使溶劑均勻的揮發，據此可容易地形成均 勻之膜。 _ 上述第二膜之膜厚並無特別限制，宜爲例如使最終形 _ 成之層合膜’亦即第一膜及第二膜之合計膜厚（乾膜厚）成 @ 爲lOnm〜3 00nm。當最終形成之層合膜之膜厚度比上述範 圍小時，在基材上存在凹凸時，會產生部份塗佈處或實質 上未塗佈處之情況，另一方面，當比上述範圍大時，會有 透明性降低之情況。 如此，形成在第一膜上層合第二膜之層合膜，但本發 明之第五製造方法中層合膜之形成方法並不受該等之限 制，例如，在透明基材上塗佈上述前驅物液（P1)或前驅物 液（P2)後，藉由加熱使過氧錯合物（前驅物液）變化成氧化 0 鈦或摻雜之氧化鈦後，塗佈前驅物液（P3)，隨後，經由加 熱使各前驅物液集中變化成氧化鈦或摻雜之氧化鈦亦可。 ： 該情況下’亦可依據需要在塗佈前驅物液（P1)或前驅物液 (P2)之後，經風乾（自然乾燥）或真空乾燥或減壓乾燥等程 序使溶劑均勻揮發。 又’本發明之第五透明導電性基板之製造方法中之上 述層合膜亦可爲在上述第二膜上進而層合由摻雜鈮或鉬之 摻雜氧化鈦之無定型物組成之第三膜、第四膜、第五 -50- 200941506 膜、...者。此情況下，層合於第二膜上之各膜分別爲以由 比構成其下層之膜之摻雜氧化鈦之摻雜物含有比率高之含 有比率摻雜上述摻雜物之摻雜氧化鈦之無定型物組成之膜 較佳。藉此，在退火處理時溫度上升之下，自下層（靠近 透明基材邊之膜）依序開始變化成銳鈦礦結晶相，而以該 、 等作爲晶種發揮結晶核作用，可促進於其上形成之摻雜氧 _ 化鈦之無定型薄膜之結晶化。 H 如上述，在第二膜上又形成膜者係成爲層合膜時，層 合在第二膜上之各膜膜厚並無特別限制，但較好爲最終形 成之層合膜，亦即第一膜、第二膜以及層合於其上之全部 膜之合計膜厚（乾膜厚）宜爲l〇nm〜300nm之範圍。因而， 若第二膜上又形成膜者係成爲層合膜，由於各膜之厚度必 定較薄，因此容易以退火處理進行結晶化，結果，使層合 之各膜具有良好之結晶性。 層合於第二膜上之各膜之細節除如上述般設定上述摻 〇 雜物之含有比率以及膜厚以外，基本上宜與第二膜相同， 例如，可使用對應摻雜物之含有比率改變上述前驅物液 ： (P3)中之組成（（A)鈦化合物或源自該鈦化合物之過氧錯合 物與（B)摻雜物化合物或源自該摻雜物化合物之過氧錯合 物之混合比例）之前驅物液而形成。但，該情況下，各前 驅物液每次塗佈時若進行用以使過氧錯合物（前驅物液）變 化成氧化鈦或摻雜之氧化鈦之加熱，由於層合之膜大多在 愈下層之膜所經歷之熱履歷就愈重，因此如上述，可依序 塗佈各前驅物液後，藉由一起加熱變化成氧化鈦或摻雜之 -51 - 200941506 氧化鈦，或者在每次塗佈前驅物液時加熱，可在愈低溫下 進行而較適宜。 本發明之第五透朋導電性基板之製造方法中，在形成 上述層合膜之後，於還原氛圍氣體中藉加熱進行退火處 理。藉此，使形成膜之經Nb或Ta摻雜之氧化鈦自無定 型相結晶轉移成銳鈦礦結晶相，在結晶相中產生氧缺陷， . 可改善導電性。而且，通常導入氧缺陷時會有容易變化成 _In the method for producing a fourth transparent conductive substrate, each component in the precursor-containing dispersion as a film forming material (that is, (A) a reaction product obtained by reacting a titanium compound with hydrogen peroxide, (B) The ratio of the content of the reaction product of the dopant compound to hydrogen peroxide and the (C) anatase-type titanium oxide-based fine particle) is preferably [(A) + (B)] in terms of solid content by weight. : Q (C) = 100: 0.1~10 is preferred. When the amount of the (C) anatase-type titanium oxide-based fine particles is less than the above range, there is a problem that a sufficient effect of the seed crystal cannot be expected. On the other hand, when the amount is larger than the above range, the insulating property is exhibited. The anatase-type titanium oxide-based fine particles remain in a large amount in the transparent conductive substrate, which may impair the conductivity. Further, [(A) + (B)] corresponds to the solid component weight obtained from the "solid content concentration of the precursor liquid". The precursor-containing dispersion can be obtained, for example, by mixing the reaction product of the above (A), the reaction product of the above (B), and the fine particles of the above (C), but the mixing order of the -40-200941506 at this time is not particularly limit. For example, a method of formulating a precursor liquid comprising the reaction product of the above (A) and the reaction product of the above (B), and adding and dispersing the fine particles of the above (C) is usually employed. The method is described in detail below. Regarding the composition of the reaction product of the above (A) and the reaction product of the above (B) - the precursor liquid system is the same as the precursor liquid in the method for producing the first transparent conductive substrate, the first transparent conductivity can be applied. Description of the φ precursor liquid in the method of manufacturing the substrate. When the (C) anatase-type titanium oxide-based fine particles are added and dispersed in the precursor liquid, i) (C) anatase-type titanium oxide-based fine particles are added to the precursor liquid in a powder state, and then used. Dispersing machine (for example, bead honing machine, ball mill, jet honing machine, etc.) is obtained by dispersion treatment, or Π) by dispersing powdery (C) anatase-type titanium oxide-based fine particles in In a dispersion medium (for example, an organic solvent such as water or alcohol) or a reaction solution obtained by synthesizing (C) anatase-type titanium oxide-based fine particles from a liquid phase in the lower direction, dispersion treatment is carried out as needed, and pre-mixed (c) A dispersion of anatase-type titanium oxide-based fine particles may be added to the precursor liquid. Further, for example, an anatase type titanium oxide fine particle or the like is commercially available as a dispersion, and thus it is also possible to add such a commercially available product to the precursor liquid. Further, when (C) anatase-type titanium oxide-based fine particles are added as a pre-dispersion as in the above ii), it is also preferred to carry out dispersion treatment by a disperser after the dispersion is added. A method for obtaining a dispersion containing the above precursor, in addition to the above, may be carried out by appropriately heating the precursor liquid or the reaction (2009) of the above (A) to convert only a part of the peroxygen complex into A method of doping titanium or titanium oxide of ruthenium or iridium in anatase crystal phase. However, this method is difficult to control the particle size of the (C) anatase-type titanium oxide-based fine particles or the ratio of each component in the dispersion containing the precursor {[(A) + (B)] : (C)} Etc. Therefore, there is a case where the desired dispersion containing the precursor is not obtained. Further, the (C) anatase-type oxy-titanium-based fine particles in the dispersion containing the precursor are preferably uniformly dispersed when applied to a transparent substrate, for example, preferably just before coating. Dispersion treatment using a dispersing machine can also use a conventional dispersing agent for the purpose of improving dispersion stability without impairing the effects (especially transparency and conductivity) of the present invention. In the fourth method for producing a transparent conductive substrate of the present invention, the precursor-containing dispersion is applied onto a transparent substrate, and after firing, annealing is performed by heating in a reducing atmosphere. The transparent substrate is the same as the method for producing the first transparent conductive substrate. Further, the coating method for applying the precursor-containing dispersion onto a transparent substrate is also the same as the method for applying the precursor liquid before the method for producing the first transparent conductive substrate. However, it is preferred that the dispersion containing the precursor liquid is supplied in a state of being uniformly dispersed. - When the dispersion containing the precursor described above is applied, the amount of coating is not particularly limited, and for example, the film thickness (dry film thickness) to be finally formed may be 10 nm to 300 nm. When the thickness of the final formed dry film is smaller than the above range, there may be a case where a portion of the coating portion or a substantially uncoated portion is formed when the unevenness is present on the substrate. On the other hand, when it is larger than the above range, there will be The problem of reduced transparency. Further, when the dispersion containing the precursor is applied to the thickness -42 to 200941506, the coating operation can be performed once, and the coating operation can be repeated a plurality of times. The substrate after the dispersion containing the precursor described above is applied, followed by baking. Thereby, the peroxidation complex (precursor liquid) on the substrate is changed to titanium oxide doped with Nb or Ta. The crystalline state at this time usually consists of an amorphous phase. The conditions (heating temperature, firing time, firing atmosphere _ gas) at the time of firing are the same as those in the method for producing the first transparent conductive substrate. The substrate after firing is annealed by heating in a reducing atmosphere. Thereby, the Nb or Ta doped titanium oxide forming the film is converted into an anatase phase from the amorphous phase crystal, and oxygen defects are generated in the crystal phase, whereby conductivity can be improved. Further, in general, introduction of oxygen defects tends to be converted into a rutile crystal phase having a high electric resistance, but in the present invention, niobium or tantalum doped in titanium oxide has stability even if an oxygen-deficient anatase crystal phase is introduced. The role of the chemical, thus maintaining a crystalline state of high conductivity. The conditions (heating temperature, treatment time, reducing atmosphere *' gas) during the annealing treatment are the same as those of the first transparent conductive substrate. Thus, a transparent conductive film composed of titanium oxide doped with cerium or lanthanum can be formed on the transparent substrate. The transparent conductive film has an anatase crystal phase and is a film composed of a polycrystal of titanium oxide doped with Nb or Ta, and exhibits high conductivity while exhibiting high transparency. (Manufacturing Method of Fifth Transparent Conductive Substrate) -43- 200941506 In the method for producing a fifth transparent conductive substrate of the present invention, a laminated film is formed on a transparent substrate, which is doped by doping a first film composed of a doped titanium oxide-doped titanium oxide amorphous or titanium oxide amorphous material, laminated by doping titanium oxide or titanium oxide which constitutes the first film The impurity contains a second film having a high ratio of the amorphous composition of the doped titanium oxide doped with the above dopant. Hereinafter, a method in which a first film is first formed on a transparent substrate, and then a second film is formed on the first film as an embodiment of the above-described laminated film formation will be described. The formation of the first film may be carried out by any method as long as it can form a titanium oxide-based amorphous film. For example, it can be formed by a conventional method such as sputtering or PLD in a vacuum system. The slurry or solution containing the metal oxide particles may be applied to a substrate and then heated by a so-called coating method. However, in the method of forming a film by a vacuum system such as a sputtering method or a PLD method, since a large-scale apparatus is required, the equipment cost is high, and there is a concern that the cost of the product is increased, so that it is industrially mass-produced to be usable. The coating method which is inexpensive to implement under simple operation is more suitable. When the first film is formed by a coating method, specifically, a precursor solution containing (A) a reaction product obtained by reacting a titanium compound with hydrogen peroxide is applied to a transparent substrate (hereinafter, The precursor liquid for forming the first film is referred to as "precursor liquid (P1)"), or contains (A) a reaction product obtained by reacting a titanium compound with hydrogen peroxide and (B) a ruthenium compound or a ruthenium compound. (dopant compound) a reaction product liquid formed by reacting with hydrogen peroxide (hereinafter, the precursor liquid for forming a first film is referred to as "precursor liquid-44-200941506 (P2)")) The method of heating. The precursor liquid (P1) is a compound (peroxide complex) containing (A) a peroxidation of a titanium compound. The peroxidation complex is a metal oxide precursor which is heated to become titanium oxide, and the film formed by the precursor liquid (P1) is composed of titanium oxide. On the other hand, the precursor liquid (P2) is a complex (peroxide complex) containing a peroxide compound of (A) a titanium compound _ and a (B) dopant compound. The peroxidation complex is a metal oxide precursor which is doped with cerium or lanthanum-doped titanium oxide, and the film formed by the precursor liquid (P2) is composed of doped cerium or molybdenum-doped titanium oxide. . The precursor liquid (P2) is in addition to its composition (that is, (A) a titanium compound or a peroxidation complex derived from the titanium compound and (B) a dopant compound or a peroxidation derived from the dopant compound Other than the difference in the mixing ratio of the complex compound, the rest is the same as the precursor liquid in the method for producing the first transparent conductive substrate. Further, the precursor liquid (P1) is a complex in which the (B) dopant compound is not oxidized in the precursor liquid (P2), that is, in addition to the (A) titanium compound for peroxidation. The complex is the same as the precursor liquid (P2) except that the (B) dopant compound is subjected to a peroxidation complex. In the composition of the precursor liquid (P2), (A) a titanium compound or a peroxygen complex derived from the titanium compound and (B) a dopant compound or a peroxygen complex derived from the dopant compound The mixing ratio is not particularly limited, and is preferably set so as to contain a desired dopant (铌 or 钽) content ratio in the film formed of the precursor liquid. The dopant content ratio of the doped titanium oxide is usually set in the range of 0.1 to 40 mol%, preferably 5 to 30 mol%. When the dopant content ratio of -45 to 200941506 is less than the above range, there is a problem that the doping effect is insufficient and the conductivity is lowered. On the other hand, when the dopant content ratio is larger than the above range, there is conductivity. Reduced, the problem of reduced transparency of the film. The coating method in the case where the precursor liquid (P1) or the precursor liquid (P2) is applied onto the transparent substrate is the same as the method of applying the precursor liquid in the method for producing the first transparent conductive substrate. The heating temperature and the heating time when the precursor liquid (P1) or the precursor liquid (P2) is applied and heated may change the peroxygen compound (precursor liquid) to titanium oxide or titanium oxide. There are no special restrictions. The upper limit of the heating temperature is different depending on the crystallization temperature of the precursor liquid composition, and therefore it is preferably in the range of the crystallization temperature or lower. More specifically, it is 500 ° C or less, preferably 50 to 40 ° C. Further, the heating time is appropriately set depending on the heating temperature, etc., but it is usually from about 1 minute to about 1 hour. Further, for example, in the case where the solid content concentration of the precursor liquid (P1) or the precursor liquid (P2) applied in the formation of the first film is low, the air may be dried first (before the heating) Drying or vacuum drying or drying under reduced pressure, etc., so that the solvent is volatilized uniformly, thereby forming a uniform film easily. The film thickness of the first film is not particularly limited. For example, when the film thickness is too small, the crystal nucleus acting as a seed crystal in the annealing treatment cannot be sufficiently present, and the crystallization promoting effect cannot be obtained. . On the other hand, when the film thickness of the first film is too thick, since the transparency is lowered, the dry film thickness is usually 3 nm or more, preferably 5 nm or more, more preferably 10 nm or more, and 50 nm or less. It is 30 nm or less, more preferably 20 nm or less. -46-200941506 The transparent substrate which can be used in the method for producing a fifth transparent conductive substrate of the present invention is the same as the method for producing the first transparent conductive substrate. Forming a second film on the first film, it is important to dope the dopant by a ratio of a higher ratio of a dopant content of the doped titanium oxide or the titanium oxide constituting the first film. It is composed of an amorphous substance doped with titanium oxide. Thereby, the first film system starts to change into an anatase crystal phase at a lower temperature, and functions as a crystal nucleus as a seed crystal to promote crystallization of the second film formed thereon. Further, in the fifth manufacturing method, the content ratio of the dopant is a ratio of bismuth or molybdenum expressed in percentage to the total amount of all the metals constituting the doped titanium oxide or the titanium oxide. Usually, the dopant content ratio of titanium oxide (undoped titanium oxide) is 〇mol%, and the dopant content ratio of the doped titanium oxide is, for example, if the precursor liquid (P2) is used to form a doped titanium oxide. , (A) a titanium compound in the precursor liquid (P2) or a peroxy complex derived from the titanium compound φ and (B) a dopant compound or derived from the dopant compound The total of the oxygen complexes is the number of moles of the dopant at 1 Torr, which corresponds to the content ratio of the dopant. In the fifth manufacturing method of the present invention, as described above, the content ratio of the dopant in the first film is smaller than the content ratio of the dopant in the second film (in other words, the dopant content ratio in the second film is high) The dopant in the first film contains a ratio). Wherein, when the difference in the dopant content ratio between the two is too small, the crystallization temperature of each amorphous film hardly differs, and the promoting effect of the above crystallization cannot be expected, and conversely, when the dopants of the two contain -47- 200941506 When the difference in ratio is too large, it is disadvantageous in terms of the first film and the second film. That is, in general, the crystal form of the titanium oxide of the anatase crystal phase which is not doped with yttrium or lanthanum is tetragonal, corresponding to the amount of dopant doped therein, the lattice constant of the a-axis, the b-axis, and the c-axis. When the difference in lattice constant between the a-axis, the b-axis, and the c-axis between the first film and the second film becomes large, there is a problem that the film matching property is deteriorated. Therefore, in order to suppress as much as possible the difference in the lattice constants of the a-axis, the b-axis, and the c-axis as much as possible, the first film and the second film _ are preferably in close composition. When considering this, "(the dopant content ratio in the second film) - (the ratio of the dopant in the first film)" is usually preferably about 5 to 25. Further, in view of the above-described compatibility of the films, it is preferable that the titanium oxide or the doped titanium oxide constituting the first film is similar to the doped titanium oxide constituting the second film, and thus doping oxidation When the first film is formed of titanium, the types of dopants and the like in the two kinds of doped titanium oxide forming the two films are preferably the same. The formation of the above second film is preferably carried out by a coating method. When the second film is formed by a coating method, specifically, a coating product containing (A) a reaction between a titanium compound and hydrogen peroxide and (B)-' is preferably applied to the first film. A reaction product: a liquid (the precursor liquid for forming a second film is referred to as "precursor liquid (P3)") and heated by a reaction product obtained by reacting a dopant compound with hydrogen peroxide. The precursor liquid (P3), in addition to its composition (that is, (A) a titanium compound or a peroxidation complex derived from the titanium compound and (B) a dopant compound or derived from the dopant compound The mixing ratio of the oxygen complex compound is the same as that of the precursor liquid (P2) described above (that is, the same as the precursor liquid in the manufacturing method of the first transparent -48-200941506 conductive substrate), The above description of the formation of the first film can be applied to the formation of the second film. The composition of the precursor liquid (P3) is such that the dopant content ratio in the second film formed by the precursor liquid (P3) is higher than the content ratio of the dopant in the first film, suitably The mixing ratio of (A) a titanium compound or a peroxygen complex derived from the titanium compound, and (B) a dopant compound or a peroxidation complex derived from the dopant compound is set. However, the n composition of the precursor liquid (P3) is as described above, and the composition of the precursor liquid (P1) or the precursor liquid (P2) forming the first film is similar in terms of the compatibility of the films. Preferably, the content ratio of the dopant is preferably set such that the difference between the dopant ratio of the second film and the first film is within the above range, and further, the precursor containing the dopant When the liquid (P2) forms the first film, it is preferred that the precursor liquid does not have a different dopant before the formation of the two films. Further, the dopant content ratio of the doped titanium oxide formed by the precursor liquid (P3) is usually preferably in the range of 0.1 to 40 mol%, preferably 5 to 30 mol%. 〇| The method of coating the precursor film (P3) on the first film to form the second film is the same as the method of applying the precursor liquid in the method for producing the first transparent conductive substrate . The heating temperature and the heating time in the case where the precursor liquid (P3) is applied and heated are not particularly limited as long as the peroxygen compound (precursor liquid) can be changed to titanium oxide or doped titanium oxide. Specifically, the heating temperature may be appropriately set according to the amount of the dopant in the precursor liquid. However, if the heating temperature is too high, a stable crystal phase is precipitated, and the annealing treatment effect cannot be exhibited. Therefore, it is 5 0 0. (The following is preferably -49-200941506 5 0~4 0 0 ° C. Further, the heating time is appropriately set depending on the heating temperature, etc., but is usually about 1 minute to 1 hour. Further, for example, in the second In the case where the solid content concentration of the precursor liquid (P3) before coating is low during film formation, the solvent may be uniformly dried by air drying (natural drying), vacuum drying or vacuum drying before the heating. Volatilization, whereby a uniform film can be easily formed. _ The film thickness of the second film is not particularly limited, and is preferably, for example, a film of the final shape, that is, a film of the first film and the second film. The thickness (dry film thickness) is @nnm~300 nm. When the film thickness of the finally formed laminate film is smaller than the above range, when there is unevenness on the substrate, a partial coating portion or substantially uncoated may be generated. On the other hand, when it is larger than the above range, the transparency may be lowered. Thus, the laminated film of the second film is laminated on the first film, but the lamination is performed in the fifth manufacturing method of the present invention. The method of forming the film is not limited by the above, for example, After coating the precursor liquid (P1) or the precursor liquid (P2) on the transparent substrate, the peroxide complex (precursor liquid) is changed into oxidized titanium oxide or doped titanium oxide by heating, and then coated. The cloth precursor liquid (P3) may be, after heating, the concentration of each precursor liquid into titanium oxide or doped titanium oxide. In this case, 'the precursor liquid (P1) may be coated as needed or After the precursor liquid (P2), the solvent is uniformly volatilized by air drying (natural drying), vacuum drying or drying under reduced pressure. Further, the laminated film in the fifth transparent conductive substrate manufacturing method of the present invention may be used. A third film, a fourth film, a fifth-50-200941506 film, which is composed of an amorphous material doped with lanthanum or molybdenum doped titanium oxide, is further laminated on the second film. Each of the films laminated on the second film is an amorphous type of doped titanium oxide doped with the dopant by a ratio of a dopant having a higher content ratio of the doped titanium oxide than the film constituting the lower layer. Preferably, the film of the composition is formed, thereby lowering the temperature during the annealing treatment, from the bottom (The film near the side of the transparent substrate) starts to change into an anatase crystal phase, and the crystal nucleus acts as a seed crystal, thereby promoting the amorphous film of the doped oxygen-titanium formed thereon. Crystallization. H As described above, when the film is formed on the second film to form a laminate film, the film thickness of each film laminated on the second film is not particularly limited, but is preferably a final laminate. The total film thickness (dry film thickness) of the film, that is, the first film, the second film, and all of the films laminated thereon is preferably in the range of from 10 nm to 300 nm. Therefore, if the film is formed on the second film, Since it is a laminated film, since the thickness of each film is necessarily thin, it is easy to crystallize by annealing, and as a result, each film laminated has good crystallinity. Details of each film laminated on the second film In addition to setting the content ratio of the above doped dopants and the film thickness as described above, it is basically preferable to use the same as the second film. For example, the composition of the precursor liquid can be changed using the ratio of the corresponding dopant: (P3) ((A) a titanium compound or a peroxygen mismatch derived from the titanium compound The material is formed by a precursor liquid with a mixture ratio of (B) a dopant compound or a peroxygen compound derived from the dopant compound. However, in this case, each of the precursor liquids is heated to change the peroxygen compound (precursor liquid) into titanium oxide or doped titanium oxide each time the coating liquid is applied, since the laminated film is mostly The heat history experienced by the lower layer film is heavier, so as described above, each precursor liquid can be sequentially applied, and then heated together to change into titanium oxide or doped -51 - 200941506 titanium oxide, or in each Heating while applying the precursor liquid is preferably carried out at a lower temperature. In the method for producing a fifth transparent conductive substrate of the present invention, after the laminated film is formed, annealing treatment is performed by heating in a reducing atmosphere. Thereby, the Nb or Ta-doped titanium oxide forming the film is transferred from the amorphous phase crystal to the anatase crystal phase, and oxygen defects are generated in the crystal phase, and the conductivity can be improved. Moreover, it is easy to change when introducing oxygen defects.

電阻高之金紅石結晶相之傾向，但本發明中由於在氧化鈦 Q 中摻雜之鈮或鉅對導入氧缺陷之銳鈦礦結晶相有安定化之 作用，因此可維持展現高導電性之結晶狀態。退火處理時 之條件（加熱溫度、處理時間、還原氛圍氣體等）係與上述 第一透明導電性基板之製造方法中之退火處理之條件相 同。 如此，形成由摻雜鈮或钽之氧化鈦組成之透明導電性 膜。該透明導電性膜具有銳鈦礦結晶相，爲由屬於週期表 之VA族之5價Nb或Ta摻雜之氧化鈦之多結晶體組成之 0 薄膜，在具備有良好透明性的同時，亦展現高的導電性 者。 : 又，上述之本發明第一至第五製造方法中，在透明基 材上直接塗佈前驅物液或底層形成材料，而形成透明導電 性膜、底層或第一膜，但在例如液晶顯示器裝置等之透明 電極用途中，亦可在透明基材上透過著色膜（彩色濾光片） 等中間膜，於其上直接塗佈前驅物液或底層形成材料，如 此在透明基材及透明導電性膜、底層或第一膜之間透過中 -52- 200941506 間膜而成之樣態亦包含於本發明範圍中。 [透明導霓性基板] 本發明之透明導電性基板爲可藉由如上之本發明透明 導電性基板之製造方法獲得者。本發明之透明導電性基板 - 之透過率在可見光領域通常爲70%以上，較好爲75%以 . 上，更好爲80%以上，在紅外線領域通常爲70%以上，較 φ 好爲75%以上，更好爲80%以上。另外，本發明之透明導 電性基板之比電阻通常爲 9χ1(Γ3Ω · cm以下，較好爲 8 X 1 (Γ3 Ω · cm以下。又，該等之透過率及比電阻可藉由例 如實施例中後述之方法測定。 本發明之透明導電性基板適用於例如觸控面板、液晶 顯示器、LED(發光元件）、有機EL顯示器、可撓性顯示 器、電漿顯示器等顯示器電極，太陽能電池之電極、窗玻 璃之熱線反射膜、抗靜電膜等用途。而且，藉由本發明之 〇 製造方法獲得之透明導電性基板爲可發揮折射率高之優點 '： 且可有效作爲具有抗反射功能之抗靜電膜。 [膜形成用前驅物液] (第一膜形成用前驅物液） 本發明之第一膜形成用前驅物液爲透明導電性膜形成 用前驅物液，且包含（A)使鈦化合物.與過氧化氫反應而成 之反應產物及（B)使鈮化合物或鉅化合物（摻雜物化合物） 與過氧化氫反應而成之反應產物。亦即，本發明之前驅物 -53- 200941506 液爲（A)鈦化合物及（B)鈮化合物或鉬化合物加以過氧化之 錯合物（過氧化錯合物）者，爲藉由加熱成爲摻雜鈮或鉬之 氧化鈦之金屬氧化物前驅物。如此，以屬於週期表VA族 之5價鈮或钽摻雜於氧化鈦中而成之金屬氧化物形成之膜 展現出良好之導電性。 本發明之第一前驅物液中之包含上述（A)使鈦化合物 與過氧化氫反應而成之反應產物，及上述（B)使摻雜物化 合物與過氧化氫反應而成之反應產物之混合物（以下亦稱 爲「（A)及（B)之混合物」）係與上述第一透明導電性基板 之製造方法中之前驅物液相同，可套用第一透明導電性基 板之製造方法中之前驅物液之說明。但，藉由上述過氧化 氫之過氧化反應中可使用之溶劑，除第一透明導電性基板 之製造方法中所例示者以外，使用以後述通式（1)〜（5)之任 一式表示之特定構造之溶劑也無妨。 本發明之第一膜形成用前驅物液中，重要的是，相對 於上述（A)及（B)之混合物，含有上述通式（1)〜（5)之任一式 表示之溶劑（以下亦稱爲「特定溶劑」）。上述特定溶劑爲 使前驅物液中之過氧錯合物起安定化作用且提高該溶液之 儲存安定性，且作爲在將該前驅物液塗佈於基板上進行退 火處理時藉由加熱快速揮發之溶劑之作用，使形成之膜中 不會殘存有機成分而展現良好之導電性。 上述式（1)〜（3)中，作爲R1〜R6、R1〜R5或RLR7之例 之烷基列舉爲例如甲基、乙基、丙基、丁基等。又，上述 式（1)〜（3)中，X之例之- OR中以R表示之烷基亦相同。 200941506 上述式（4)及（5)中，以Y表示之可具有取代基之碳數 3〜6之伸烷基列舉爲例如伸丙基、伸丁基、伸戊基、伸己 基等。 — 以上述式（1)~(3)表示之化合物若與上述（Α)及（Β)之混 合物共存時，形成在該化合物所必需具有之兩個氧原子與 . 過氧錯合物之金屬原子之間以二齒配位產生鍵結力不同之 _ 共價鍵與配位鍵之安定6員環或7員環構造，可藉由該交 φ 聯構造包圍性地保護過氧基。而且，由於以此形成之交聯 構造內鍵結力強的共價鍵僅有一個，因此在退火處理時藉 由加熱使有機分子容易加速自金屬原子釋離，而不會於所 得膜中殘存有機成分而損及導電性。 以上述式（4)及（5)表示之化合物與上述（Α)及（Β)之混 合物共存時，於該化合物所必需具有之兩個氧原子與過氧 錯合物之金屬原子之間以二齒配位，可立體地保護該化合 物所帶有之5員環至8員環之蓬鬆構造之過氧基。而且， φ 由於以此形成之金屬原子與氧原子之鍵結極弱，因此藉由 退火處理之加熱易使有機分子加速自金屬原子釋離，而不 會於所得膜中殘存有機成分而損及導電性。 上述特定溶劑若爲具有以上述通式（1)〜（5)表示之特定 構造，則亦可爲如醇、烷氧基醇、羧酸、酯等有機化合 物，但具體而言，以選自由3-甲氧基-1-丁醇、3-甲氧基- 3- 甲基-卜丁醇、二乙醯基丙酮（4-羥基-4-甲基戊-2-酮）、 4- 羥基-2-丁酮、5-羥基-2-戊酮 '四氫呋喃-2-羧酸、2-甲 基-1，3-丙二醇、γ-丁內酯、δ-戊內酯、ε-己內酯等組成之 -55- 200941506 群組之至少一種較佳。該等之中，3 -甲氧基-1-丁醇由於 可明顯提高前驅物液之儲存安定性之改善效果，且在塗佈 於基板、進行退火處理後亦不^會引起有機成分殘存（碳 化），而獲得透明性高之膜，因此爲最佳。 上述特定溶劑最終較好上述（A)及（B)之反應產物（過 氧錯合物）共存，例如可於以上述過氧化氫進行過氧化反 應中作爲溶劑使用而包含於前驅物液中，亦可爲使上述（A) 及（B)之混合物成爲適於塗佈或退火處理之液體特性（黏度 等）之稀釋目的添加作爲溶劑使用而包含於前驅物液中。 上述特定溶劑之含有量並無特別限制，但相對於前驅 物液中之全部溶劑量較好爲15〜80重量％。 本發明之第一前驅物液之固成分濃度並無特別限制， 例如，以2~20重量％較佳，更好爲4〜15重量％。通常， 由於固成分濃度高會伴隨著前驅物液之儲存安定性降低， 因此迄今爲止，無法設定在超過例如10重量％之高濃 度，但本發明之第一前驅物液中以上述特定溶劑可改善儲 存安定性，因此可設定在如上述較高之濃度範圍，例如， 使例如以一塗佈即形成充分膜厚之膜成爲可能。 又，其中之固成分濃度意指獲得前驅物液時使用之鈦 化合物及摻雜物化合物之合計重量在前驅物液之總重量中 所佔比例（重量％)。 如上述之本發明第一前驅物液可適用作爲上述本發明 之第一至第五透明導電性基板之製造方法中之各前驅物 液。 -56- 200941506 (第二膜形成用前驅物液） 本發明之第二膜形成用前驅物液爲透明導電性模形成 用前驅物液，且包含（A)使鈦化合物與過氧化氫反應而成 之反應產物及（B)使鈮化合物與钽化合物（摻雜物化合物） - 與過氧化氫反應而成之反應產物。亦即，本發明之前驅物 _ 液爲含有使（A)鈦化合物及（B)鈮化合物或鉬化合物經過氧 φ 化之錯合物（過氧化錯合物）者，且爲藉由加熱而成爲摻雜 鈮或钽之氧化鈦之金屬氧化物前驅物。如此般，以週期表 VA族所屬之5價鈮或鉅摻雜於氧化鈦中而成之金屬氧化 物形成之膜展現出良好之導電性。 本發明之第二前驅物液中之上述（A)使鈦化合物與過 氧化氫反應而成之反應產物，及上述（B)使摻雜物化合物 與過氧化氫反應而成之反應產物之混合物（（A)及（B)之混 合物）係與上述第一透明導電性基板之製造方法中之前驅 ❿ 物液相同，可套用第一透明導電性基板之製造方法中之前 *'· 驅物液之說明。但，上述以過氧化氫進行過氧化反應中可 ： 使用之溶劑，除第一透明導電性基板之製造方法中例示者 以外，使用上述第一前驅物液中之特定溶劑亦無妨。 再者，本發明之第二前驅物液中之上述（A)及（B)之混 合物對於與鈦化合物或摻雜物化合物反應之過氧化氫之量 並無特別限制而可適當設定，但就進一步提高儲存安定性 而言，對於鈦化合物較好每1莫耳鈦化合物與〇.8~ 1.2莫 耳之過氧化氫反應，對摻雜物化合物較好每1莫耳摻雜物 -57- 200941506 化合物與2·5〜3.5莫耳過氧化氫反應。例如，使鈦化合物 及摻雜物化合物分別與過氧化氫反應後之兩反應產物混合 時，各反應中使用之過氧化氫之量宜分別設定在上述範 圍，另一方面，於使鈦化合物與摻雜物化合物預先混合之 混合物與過氧化氫反應時，較好爲相對於該混合物中之鈦 化合物量成爲上述範圍之方式設定之量，與相對於該混合 物中之摻雜物化合物量成爲上述範圍之方式設定之量之合 計量作爲反應之過氧化氫量。 本發明之第二透明導電性膜形成用前驅物液中，相對 於上述（Α)及（Β)之混合物，重要的是需含有硝酸及鹽酸之 至少一種（以下亦稱爲「上述特定無機酸」）。藉此，相對 於前驅物液中以陽離子存在之過氧.錯合物，硝酸離子 (νο3_)或氯化物離子（cr)係作爲相對離子之作用，使過氧 錯合物安定化而展現優異之儲存安定性。例如，當前驅物 液置於常溫時，本來通常於約2〜3小時會產生之凝膠化’ 於約4天後仍不會產生白濁或凝膠化。而且，於前驅物液 中添加使用鹽酸或硝酸’由於亦可藉由在膜形成時之燒成 或退火處理而揮發掉’因此不會殘存於最終形成之膜中’ 而不會對導電性或透明性等物性造成影響。 上述特定無機酸之含有量’係依據其種類或後述之前 驅物液之固成分濃度而定’但只要可以獲得充分之安定性 提高效果之方式適當設定’則無特別限制。例如’固成分 濃度爲8重量％以下之前驅物液之情況下’以相對於獲得 上述（A)及（B)之混合物時使用之鈦化合物及慘雜物化合物 200941506 (亦即，固成分）之合計100莫耳，較好硝酸以l~5〇莫 耳’較好爲5~30莫耳，鹽酸以10〜60莫耳，較好爲 30〜50莫耳之量含有較宜。當固成分濃度超過8重量％且 在1 〇重量％以下之前驅物液之情況下，相對於上述固成 分合計100莫耳，以硝酸爲5 0~ 100莫耳，較好爲60〜80 - 莫耳’鹽酸爲70〜1 50莫耳，較好爲90〜120莫耳之量含有 . 較宜。當固成分濃度爲超過10重量％且在20重量％以下 Φ 之前驅物液時，相對於上述固成分合計100莫耳，以硝酸 爲80〜150莫耳，較好100-140莫耳，鹽酸爲120〜170莫 耳，較好130〜160莫耳之量含有較宜。 又，鹽酸由於其揮發性而有難以維持在既定濃度之情 況，於某些情況則推薦使用硝酸。 又，上述特定無機酸只要含於最終前驅物液中，則其 添加時機並無特別限制。例如，在使鈦化合物與摻合物化 合物分別與過氧化氫反應後之兩反應產物混合之情況下， 〇 特定無機酸之添加可針對混合前之二反應產物分別進行， 亦可在二反應產物混合之後進行。 - 本發明之第二透明導電性膜形成用前驅物液較好進而 含有上述第一前驅物液中之特定溶劑。上述特定溶劑在前 驅物液中具有使過氧錯合物安定化之作用，可提高該溶液 之儲存安定性，且在將該前驅物液塗佈於基板上且進行退 火處理時作爲藉由加熱而快速揮發之溶劑之作用’使形成 之膜中不會殘存有機成分而展現良好之導電性。而且，有 關亦含有該特定溶劑時之說明係套用上述第一前驅物液中 -59- 200941506 之說明。 本發明之第二前驅物液之固成分濃度並無特別限制’ 例如以2〜20重量％較佳，更好爲4〜15重量％。通常’由 於固成分濃度高會伴隨著前驅物液之儲存安定性降低’因 此迄今爲止，原本無法設定在例如超過10重量％之高濃 度，但本發明中由上述特定無機酸及依據需要進而含有之 - 上述特定溶劑可提高儲存安定性，因此可設定在上述較高 . 之濃度範圍，使例如以一塗佈亦可形成充分膜厚之膜成爲 © 可能。 又，此處之固成分濃度意指獲得前驅物液時使用之鈦 化合物及摻雜物化合物之合計重量在前驅物液之總重量中 所佔比例（重量°/。）。 如上之本發明第一前驅物液可適用作爲上述本發明之 第一至第五透明導電性基板之製造方法中之各前驅物液。 (第三膜形成用前驅物液） © 本發明之第三膜形成用前驅物液包含使鈮化合物或鉬 化合物與過氧化氫反應而成之反應產物，亦即，含有鈮化 ： 合物或钽化合物加以過氧化之錯合物（過氧錯合物）。該過 氧錯合物可單獨藉由加熱成爲氧化鈮或氧化钽，另一方 面，例如藉由與鈦過氧錯合物同時加熱成爲摻雜鈮或鉬之 氧化鈦之金屬氧化物前驅物液。 本發明之第三膜形成用前驅物液中，上述反應產物係 對1莫耳之鈮化合物或钽化合物反應2.5〜3.5莫耳之過氧 -60- 200941506 化氫而成。較好爲對1莫耳之鈮化合物或鉬化合物反應 2.8〜3.2莫耳之過氧化氫而成。據此，獲得具有優異安定 性之反應產物（過氧錯合物），本發朋之第三前驅物液可在 例如室溫（20±5°C)下長期安定地儲存1〇天以上，較好15 天以上，更好20天以上，又更好30天以上。當與鈮化合 - 物或組化合物反應之過氧化氫之量比上述範圍少時，且比 . 上述範圍多時，過氧錯合物之儲存安定性均會降低，若使 ❹ 前驅物液在室溫下儲存數小時至數天（例如1小時〜4天左 右）時，會產生凝膠化或白濁化。尤其，當過氧化氫之量 比上述範圍多時，由於會過剩之游離過氧化氫分解而發 熱，因而使液體之安定性大幅降低。 本發明之第三膜形成用前驅物液之固成分濃度爲8.5 重量％以下，更好爲8.0重量％以下，又更好爲7.5重量％ 以下，再更好爲7.0重量％以下。由於本發明之第三前驅 物液中所含過氧錯合物爲具有優異之儲存安定性者，因此 〇 即使設定在較高之固成分濃度，亦可在常溫下至少安定地 儲存1 〇天以上而可安定地儲存不會產生膠凝化或白濁 * 化。固成分濃度之下限並無特別限制，但考量例如膜形成 時之塗佈性，則以2重量％以上較佳，更好爲4重量％以 上。又，此處之固成分濃度意指獲得前驅物液時使用之鈮 化合物或钽化合物之重量佔前驅物液之總重量之比例（重 量％)。 使鈮化合物或钽化合物與過氧化氫反應獲得上述反應 產物時，關於藉由過氧化氫反應（亦即，過氧化反應）、使 -61 - 200941506 用之鈮化合物或钽化合物以及過氧化反應中可使用之溶劑 均可套用上述第一透明導電性基板之製造方法中之前驅物 液中之各項說明（該情況下，關於過氧化反應，作爲使用 鈦化合物者實質上可以另一方法表達）。但，上述以過氧 化氫之過氧化反應中可使用之溶劑，除第一種透明導電性 基板之製造方法中例示者之外，使用上述第一前驅物液中 - 之特定溶劑亦無妨。 本發明之第三膜形成用前驅物液較好進而含有上述第 0 —前驅物液中之特定溶劑。上述特定溶劑在前驅物液中作 爲使過氧錯合物安定化之作用而更提高該溶液之儲存安定 性。又，上述特定溶劑爲在膜形成時，將前驅物液塗佈於 基板上藉由加熱可快速揮發者，由於在形成之膜中不會殘 存源自該特定溶劑之有機成分，因此不會有因加熱使殘存 之有機成分碳化使膜之透明性下降，對導電性等之膜功能 幾無影響。又，亦含有該特定溶劑時之說明可套用上述第 一前驅物液中之說明（但，該情況下「（A)及（B)之混合 ❹ 物」另以「反應產物」代替表示）。 ：‘ 使用本發明之第三膜形成用前驅物液之膜形成方法並 二 無特別限制，但較好例如可將本發明之第三膜形成用前驅 物液單獨，或者例如與習知之鈦過氧錯合物（鈦化合物與 過氧化氫反應而成之反應產物）混合，塗佈於基材上，並 經加熱。當單獨塗佈本發明之第三膜形成用前驅物液時， 可形成適用於抗反射膜等之氧化鈮或氧化鉬薄膜，另一方 面，與鈦之過氧錯合物混合塗佈時，可形成適合透明導電 -62- 200941506 性膜等之摻雜鈮或钽之氧化駄系薄膜。具體而言，第三膜 形成用前驅物液之膜形成方法並無特別限制，但可使用例 如上述本發明之第一至第五透明導電性基板之製造方法。 [實施例] . 以下以實施例更詳細說明本發明，但本發明並不受該 _ 等實施例之限制，且在本發明之範圍內所得之任何變化當 0 然均不離本發明之範圍。 又，透明導電性基板之物性係以下列方法測定。 &lt;比電阻 &gt; 比電阻係使用電阻率計（三菱化學（股）製造 之「LORESTA-GP，MCP-T610」），藉由四端子四探針法 測定。詳細而言，係以一直線將四根針狀電極放置於樣品 上，且在外側二探針間通過一定電流，內側二探針間通過 一定電流，而測定內側二探針間產生之電位差，求得電 阻。 〇 &lt;透過率 &gt;透過率係使用紫外光可見近紅外光分光光度 ' 計（日本分光（股）製造之「V-670」），在190nm~2700nm之 ' 範圍內測定。 &lt;結晶性 &gt;使用X射線繞射裝置（理學電機（股）製造之 ^ RINT2000」，且使用薄膜測定用之附件評價結晶性。 &lt;結晶構造&gt;使用能量分散型X射線微型分析儀（TEM-EDX)調查鈮或钽於鈦中之摻雜狀態，且使用電場輻射型 電子顯微鏡（FE-SEM)調查結晶構造。 又，下列實施例及比較例中，將各製造例中獲得之過 -63- 200941506 氧化錯合物混合獲得前驅物液時，若無特別說明則使用脫 水乙醇調整成所需之固成分濃度。 (製造例al) 在氬氣氛圍中將4.0克四異丙氧化鈦溶解於28.5克 脫水乙醇中，攪拌下於所得溶液中緩慢添加8.0克濃度3 0 . 重量％之過氧化氫水溶液，添加結束後，攪拌5分鐘進行 _ 過氧化反應。又，反應於以乾冰在注入有溶液之燒瓶周圍 n 冷卻下進行，以將因添加過氧化氫水溶液引起發熱時之溶 液內溫控制在不超過-10 °C。如此般獲得之反應產物稱爲 駄過氧錯合物（a 1)。 (製造例bl) 在氬氣氛圍中將1.5克五乙氧化鈮溶解於19.2克脫 水乙醇中，攪拌下於所得溶液中緩慢添加1.6克濃度30 重量％之過氧化氫水溶液，添加結束後，攪拌5分鐘進行 ❹ 過氧化反應。又，反應於以乾冰在注入有溶液之燒瓶周圍 冷卻下進行，以將因添加過氧化氫水溶液引起發熱時之溶 二 液內溫控制在不超過-1 o°c。如此般獲得之反應產物稱爲 鈮過氧錯合物（bl)。 (製造例a2) 在氬氣氛圍中將20.0克蒸餾水添加於3.0克四異丙 氧化鈦中並攪拌，且自母液分取所產生之沉澱（氫氧化 -64- 200941506 鈦）。使1.2克該沉澱溶解於2.0克乙醇中’攪拌下於所得 溶液中緩慢添加17克濃度30重量％之過氧化氫水溶液’ 添加結束後，攪拌1〇分鐘進行過氧化反應V又’反應於 以乾冰在注入有溶液之燒瓶周圍冷卻下進行’以將因添加 過氧化氫水溶液引起發熱時之溶液內溫控制在不超過· . 10°C。如此般獲得之反應產物稱爲鈦過氧錯合物U2)。 0 (製造例b2) 在氬氣氛圍中將40.0克蒸餾水添加於5.0克五乙氧 化鈮中並攪拌，自母液分取所產生之沉澱（氫氧化鈮）。使 2.8克該沉澱溶解於2.0克乙醇中，攪拌下於所得溶液中 緩慢添加2 0克濃度3 0重量％之過氧化氫水溶液，添加結 束後，攪拌1 0分鐘進行過氧化反應。又，反應於以乾冰 在注入有溶液之燒瓶周圍冷卻下進行，以將因添加過氧化 氫水溶液引起發熱時之溶液內溫控制在不超過-1 〇°C。如 〇 此般獲得之反應產物稱爲鈮過氧錯合物（b2)。 ' (製造例cl) 在氬氣氛圍中將1.6克五乙氧化鉬溶解於20.4克脫 水乙醇中，攪拌下於所得溶液中緩慢添加1 _ 3 6克濃度3 0 重量％之過氧化氫水溶液，添加結束後，攪拌5分鐘進行 過氧化反應。又，反應於以乾冰在注入溶液之燒瓶周圍冷 卻下進行，以將因添加過氧化氫水溶液引起/發熱時之溶液 內溫控制在不超過-1 〇°C。如此般獲得之反應產物稱爲鉬 -65- 200941506 過氧錯合物（cl)。 (實施例1-1) 以成爲鈦：鈮=93 : 7(莫耳比）之比例混合製造例al 中獲得之鈦過氧錯合物（al)及製造例bl獲得之鈮過氧錯 合物（b 1 )，作成固成分濃度7重量％之前驅物液。以毛細 塗佈器將該前驅物液一次塗佈於透明基材（無鹼玻璃「康 寧公司製造之 1737」，厚度 〇.7mm)上成爲乾膜厚 35.7nm，且在400°C下燒成（預烘烤）1〇分鐘，隨後，在 100%氫氣之還原氣體氛圍中在5 00°C下進行退火處理60 分鐘，獲得透明導電性基板。 所得透明導電性基板之比電阻爲5.2 XI 0_3Ω · cm，透 過率在可見光領域約80%，紅外線領域約80%。 以X射線繞射檢測該透明導電性基板中導電性膜之 結晶相爲銳鈦礦型。另外，以TEM-EDX及FE-SEM觀察 其結晶構造爲摻雜Nb之氧化鈦之多結晶體。 (實施例1-2) 以成爲鈦：鈮=94 : 6(莫耳比）之比例混合製造例a2 中獲得之鈦過氧錯合物（a2)及製造例b2獲得之鈮過氧錯 合物（b2) ’作成固成分濃度6.5重量％之前驅物液。以毛 細塗佈器將該前驅物液一次塗佈於與實施例1_丨相同之透 明基材上成爲乾膜厚26.0nm’且在8〇〇c下燒成（預烘 烤）1〇分鐘，隨後，在100%氫氣之還原氣體氛圍中在 -66- 200941506 500 °C下進行退火處理60分鐘，獲得透明導電性基板。 所得透明導電性基板之比電阻爲7.3 χ1 0·3Ω . cm， 過率在可見光領域約80%，紅外線領域約80%。 — 以X射線繞射檢測該透明導電性基板中導電性膜 結晶相爲銳鈦礦型。又，以TEM-EDX及FE-SEM觀察 . 結晶構造爲摻雜Nb之氧化鈦之多結晶體。 φ (實施例1-3) 以成爲鈦：鈮=92 : 8(莫耳比）之比例混合製造例 中獲得之鈦過氧錯合物U2)及製造例b2獲得之鈮過氧 合物（b2)，作成固成分濃度6.5重量％之前驅物液。以 轉塗佈器將該前驅物液一次塗佈於與實施例1 -1相同之 明基材上成爲乾膜厚55·〇ηπι，且在 80°C下燒成（預 烤）1〇分鐘，隨後，在100%氫氣之還原氣體氛圍中 5 00°C下進行退火處理60分鐘，.獲得透明導電性基板。 Q 所得透明導電性基板之比電阻爲6.5χ10·3Ω · cm， 過率在可見光領域約80%，紅外線領域約80%。 : 以X射線繞射檢測該透明導電性基板中導電性膜 結晶相爲銳鈦礦型。另外，以TEM-EDX及FE-SEM觀 其結晶構造爲摻雜Nb之氧化鈦之多結晶體。 (實施例1-4) 以成爲鈦：鈮=92 : 8(莫耳比）之比例混合製造例 中獲得之鈦過氧錯合物（al)及製造例bl獲得之鈮過氧 透 之 其 a2 錯 旋 透 烘 在 透 之 察 錯 -67- 200941506 合物（bl)，作成固成分濃度9.16重量％之前驅物液。以旋 轉塗佈器將該前驅物液一次塗佈於與實施例1-1相同之透 明基材上成爲乾膜厚71.0nm，且在 80°C下燒成（預烘 . 烤）1〇分鐘，隨後，在100%氫氣之還原氣體氛圍中在 5 00°C下進行退火處理60分鐘，獲得透明導電性基板。 所得透明導電性基板之比電阻爲5.6χ10_3Ω · cm，透 - 過率在可見光領域約80%，紅外線領域約80%。 _ 以X射線繞射檢測該透明導電性基板中導電性膜之 @ 結晶相爲銳鈦礦型。另外，以TEM-EDX及FE-SEM觀察 該結晶構造爲摻雜Nb之氧化鈦之多結晶體。 (實施例1-5) 以成爲鈦：鈮=80 : 20(莫耳比）之比例混合製造例al 中獲得之鈦過氧錯合物（al)及製造例bl獲得之鈮過氧錯 合物（bl)，作成固成分濃度7重量％之前驅物液。以旋轉 塗佈器將該前驅物液一次塗佈於透明基材（無鹼玻璃「康 © 寧公司製造之 1 73 7」，厚度 0.7mm)上成爲乾膜厚 : lOOnm，且在 300°C下燒成（預烘烤）1〇分鐘，隨後，在 : 100%氫氣之還原氣體氛圍中在500°C下進行退火處理60 分鐘，形成成爲透明導電層之薄膜，獲得透明導電性基 板。以X射線繞射檢測其中形成之薄膜之結晶相爲銳鈦 礦結晶相。另外，以TEM-EDX及FE-SEM觀察其結晶構 造爲摻雜Nb之氧化鈦之多結晶體。 所得透明導電性基板之比電阻爲5.〇χ10_3Ω _ cm，透 -68- 200941506 過率在可見光領域約80%，紅外線領域約80%。 (實施例1-6) ^ 以成爲鈦：鈮=7〇 : 30(莫耳比）之比例混合製造例al 中獲得之鈦過氧錯合物（al)及製造例bl獲得之鈮過氧錯 - 合物（bl)，作成固成分濃度7重量％之前驅物液。以旋轉 _ 塗佈器將該前驅物液一次塗佈於與實施例1-1相同之透明 Q 基材上成爲乾膜厚65nm，且在3 00°C下燒成（預烘烤）1〇分 鐘，隨後，在100%氫氣之還原氣體氛圍中在5 00°c下進行 退火處理60分鐘，獲得透明導電性基板。 所得透明導電性基板之比電阻爲4·0χ10_3Ω · cm ’透 過率在可見光領域約80%，紅外線領域約80%。 以X射線繞射檢測該透明導電性基板中導電性膜之 結晶相爲銳鈦礦型。另外，以TEM-EDX及FE-SEM觀察 其結晶構造爲摻雜Nb之氧化鈦之多結晶體。 ❹ (實施例1-7) ' 以成爲鈦：鈮=80 : 20(莫耳比）之比例混合製造例al 中獲得之鈦過氧錯合物（al)及製造例bl獲得之鈮過氧錯 合物（b 1 )，作成固成分濃度7重量％之前驅物液。以旋轉 塗佈器將該前驅物液一次塗佈於與實施例1 -1相同之透明 基材上成爲乾膜厚50nm，且在300°C下燒成（預烘烤）1〇分 鐘，隨後，在100%氫氣之還原氣體氛圍中在5 50°C下進行 退火處理60分鐘，獲得透明導電性基板。 -69- 200941506 所得透明導電性基板之比電阻爲3.7χ10·3Ω·(：ιη，透 過率在可見光領域約80%，紅外線領域約8〇%。 以X射線繞射檢測該透明導電性基板中導電性膜之 結晶相爲銳鈦礦型。另外，以TEM-EDX及FE-SEM観察 其結晶構造爲摻雜Nb之氧化鈦之多結晶體。 (實施例1-8) 以成爲鈦：鈮=80 : 20(莫耳比）之比例混合製造例al 中獲得之鈦過氧錯合物（al)及製造例bl獲得之鈮過氧錯 合物（bl)，作成固成分濃度7重量％之前驅物液。以旋轉 塗佈器將該前驅物液一次塗佈於與實施例1-1相同之透明 基材上成爲乾膜厚60nm，且在300°C下燒成（預烘烤）1〇分 鐘，隨後，在100%氫氣之還原氣體氛圍中在600°c下進行 退火處理60分鐘，獲得透明導電性基板。 所得透明導電性基板之比電阻爲1 .8x1 0_3Ω . cm，透 過率在可見光領域約70%，紅外線領域約70%。 以X射線繞射檢測該透明導電性基板中導電性膜之 結晶相爲銳鈦礦型。另外，以TEM-EDX及FE-SEM觀察 其結晶構造爲摻雜Nb之氧化鈦之多結晶體。 (實施例1-9) 以成爲鈦：鉅=80 : 20(莫耳比）之比例混合製造例al 中獲得之鈦過氧錯合物（al)及製造例cl獲得之鉬過氧錯 合物（cl)，作成固成分濃度7重量％之前驅物液。以毛細 -70- 200941506 塗佈器將該前驅物液一次塗佈於與實施例1-1相同之透明 基材上成爲乾膜厚67.3nm，且在100°C下燒成（預烘烤）30 分鐘，隨後，在1〇〇%氫氣之還原氣體氛圍中在500 °C下進 行退火處理30分鐘，獲得透明導電性基板。 所得透明導電性基板之比電阻爲8.3 χ1 0_3Ω· cm，透 . 過率在可見光領域約80%，紅外線領域約80%。 . 以X射線繞射檢測該透明導電性基板中導電性膜之 H 結晶相爲銳鈦礦型。另外，以TEM-EDX及FE-SEM觀察 其結晶構造爲摻雜Ta之氧化鈦之多結晶體。 (比較例1-1) 單獨使用製造例a2中獲得之鈦過氧錯合物（a2)，作 成固成分濃度9.4重量％之前驅物液。以旋轉塗佈器將該 前驅物液一次塗佈於與實施例1-1相同之透明基材上成爲 乾膜厚102nm，且在80°C下燒成（預烘烤）1〇分鐘，隨後， Ο 在100%氫氣之還原氣體氛圍中在500°c下進行退火處理 '： 60分鐘，獲得透明導電性基板。 ' 所得透明導電性基板由於係未將摻雜物（鈮或钽）摻雜 於氧化鈦中而得者，因此其比電阻無法測定（測定極限； 1〇3Ω. cm以上），且透過率在可見光領域約8 0%，在紅外 線領域約8 0 %。 以X射線繞射檢測該透明導電性基板中導電性膜之 結晶相爲銳鈦礦型。 -71 - 200941506 (比較例1-2) 以成爲鈦：鈮=92 : 8(莫耳比）之比例混合製造例a2 中獲得之鈦過氧錯合物（a2)及製造例b2獲得之鈮過氧錯 合物（b2)，作成固成分濃度6.5重量％之前驅物液。以旋 轉塗佈器將該前驅物液一次塗佈於與實施例1-1相同之透 明基材上成爲乾膜厚55.0nm，且在 80t下燒成（預烘 烤）1〇分鐘，隨後，在一般大氣壓氣體氛圍中在500 °C下 進行退火處理60分鐘，獲得透明導電性基板。 所得透明導電性基板由於在沒有還原氣體氛圍之大氣 壓氣體氛圍中進行退火處理，因此其比電阻無法測定（測 定極限；103Ω · cm以上），且透過率在可見光領域約 8 0 %，在紅外線領域約8 0 %。 以X射線繞射檢測該透明導電性基板中導電性膜之 結晶相爲銳鈦礦型。 (比較例1-3) 以成爲鈦：鈮=92 : 8(莫耳比）之比例混合製造例a2 中獲得之鈦過氧錯合物（a2)及製造例b2獲得之鈮過氧錯 合物（b2)’作成固成分濃度6.5重量％之前驅物液。以旋 轉塗佈器將該前驅物液一次塗佈於與實施例iq相同之透 明基材上成爲乾膜厚55·0ηιη，且在80。(：下燒成（預供 烤）1〇分鐘，隨後，在1〇〇%氫氣之還原氣體氛圍中在 600 °C下進行退火處理60分鐘，獲得透明導電性基板。 所得透明導電性基板之比電阻爲5.4x10·^ cm，透 -72- 200941506 過率在可見光領域約80%，紅外線領域約80%。 以X射線繞射檢測該透明導電性基板中導電性膜之 結晶相認出有一部分生成金紅石型。 (比較例1 - 4) . 以成爲鈦：鈮=85 : 15(莫耳比）之比例混合製造例al . 中獲得之鈦過氧錯合物（al)及製造例bl獲得之鈮過氧錯 0 合物（bl)，作成固成分濃度7重量％之前驅物液。以旋轉 塗佈器將該前驅物液一次塗佈於透明基材（無鹼玻璃「康 寧公司製造之1 737」，厚度〇.7mm)上成爲乾膜厚 10 0nm ’且在300°C下加熱10分鐘，形成由氧化鈦之無定 型物（該無定型物中之鈮含有比率爲15莫耳％)組成之膜。 隨後，在100%氫氣之還原氣體氛圍中在420°c下進行退火 處理60分鐘，獲得透明導電性基板。以X射線繞射檢測 該透明導電性基板中導電性膜之結晶相，如圖2中所示， 〇 雖爲銳鈦礦型但結晶性低。 ' 所得透明導電性基板之比電阻爲5.4 X 1 0·2Ω · cm，透 * 過率在可見光領域約80%，紅外線領域約80%。 (比較例1 - 5) 以成爲鈦：鈮=80: 20(莫耳比）之比例混合製造例al 中獲得之鈦過氧錯合物（al)及製造例bl獲得之鈮過氧錯 合物（b 1 )，作成固成分濃度7重量％之前驅物液。以旋轉 塗佈器將該前驅物液一次塗佈於與實施例1-1相同之透明 -73- 200941506 基材上成爲乾膜厚8 Onm，且經風乾（室溫下60分鐘），隨 後，在1〇〇%氫氣之還原氣體氛圍中在500°C下進行退火處 理60分鐘，獲得透明導電性基板。 所得透明導電性基板之比電阻爲5.8 χ1 (Γ2Ω · cm，透 過率在可見光領域約8 0%，紅外線領域約80%。 以X射線繞射檢測該透明導電性基板中導電性膜之 . 結晶相爲銳鈦礦型。 (實施例2-1) 以成爲鈦：鈮=80 : 20(莫耳比）之比例混合製造例al 中獲得之鈦過氧錯合物（al)及製造例bl獲得之鈮過氧錯 合物（b 1 )，作成固成分濃度7重量％之前驅物液。以旋轉 塗佈器將該前驅物液一次塗佈於透明基材（無鹼玻璃「康 寧公司製造之1 73 7」，厚度0.7mm)上成爲乾膜厚20nm， 且經風乾（自然乾燥），隨後，在空氣中在5 0(TC下進行退 火處理10分鐘，形成成爲底層之薄膜。以X射線繞射檢 @ 測此處形成之薄膜之結晶相爲銳鈦礦結晶相。 接著，以旋轉塗佈器將與上述相同之前驅物液一次塗 ： 佈於上述形成之底層上，成爲乾膜厚lOOnm，且在300°C 下燒成（預烘烤）1〇分鐘，隨後，在100%氫氣之還原氣體 氛圍中在5 00°C下進行退火處理60分鐘，形成透明導電層 之薄膜。以X射線繞射檢測此處形成之薄膜之結晶相爲 銳鈦礦結晶相。另外，以TEM-EDX及FE-SEM觀察其結 晶構造爲摻雜Nb之氧化鈦之多結晶體。 -74- 200941506 如此獲得之透明導電性基板之比電阻爲2.9x1 0·3Ω . cm，透過率在可見光領域約8 0%，紅外線領域約80%。將 該結果與除未形成底層而在透明基材上直接形成透明導電 層以外其餘與上述實施例2-1相同之實施例1-5作比較， 可明瞭比電阻於上述實施例2 -1方面較低。 . (實施例3-1) ❹ 以成爲鈦：鈮=80 : 20(莫耳比）之比例混合製造例al 中獲得之鈦過氧錯合物（al)及製造例bl獲得之鈮過氧錯 合物（b 1 )，作成固成分濃度7重量％之前驅物液。 接著，以旋轉塗佈器將銳鈦礦型氧化鈦微粒子水分散 體（餛（股）公司製造之「TO sol」，氧化鈦之銳鈦礦溶膠， 平均粒徑l〇nm，固成分濃度1.7重量％) —次塗佈於透明 基材（無鹼玻璃「康寧公司製造之1 737」，厚度0.7mm)上 成爲乾膜厚40nm，且經風乾（自然乾燥），形成成爲底層 ❹ 之薄膜。以X射線繞射檢測此處形成之薄膜之結晶相爲 銳鈦礦結晶相。 : 接著，以旋轉塗佈器將上述前驅物液一次塗佈於上述 形成之底層上，成爲乾膜厚l〇〇nm，且在300°C下燒成（預 烘烤）1〇分鐘，隨後，在100%氫氣之還原氣體氛圍中在 500 °C下進行退火處理60分鐘，形成透明導電層之薄膜。 以X射線繞射檢測此處形成之薄膜之結晶相爲高結晶性 銳鈦礦型。另外，以TEM-EDX及FE-SEM觀察其結晶構 造爲摻雜Nb之氧化鈦之多結晶體。 -75- 200941506 如此獲得之透明導電性基板之比電阻爲3 .1 χ 1 0_3Ω · cm，透過率在可見光領域約8 Ο %，紅外線領域約8 Ο %。其 結果與除未形成底層而在透明基材上直接形成透明導電層 以外其餘與上述實施例3-1相同之實施例1-5作比較，可 明瞭比電阻於上述實施例3 -1方面較低。 (實施例4-1) 以成爲鈦：鈮=80 : 20(莫耳比）之比例混合製造例al q 中獲得之鈦過氧錯合物（a 1)及製造例bl獲得之鈮過氧錯 合物（bl)，作成固成分濃度7重量％之前驅物液。於該前 驅物液中添加銳鈦礦型氧化鈦微粒子水分散體（餛（股）公 司製造之「TO sol」，氧化鈦之銳鈦礦溶膠，平均粒徑 10nm，固成分濃度1.7重量％)，且以攪拌器攪拌，獲得 含有銳鈦礦型氧化鈦微粒子之含前驅物之分散體。此時，The tendency of the rutile crystal phase having a high electric resistance, but in the present invention, since the antimony doped in the titanium oxide Q or the giant anion crystal phase which introduces the oxygen defect has a function of stabilization, the display exhibits high conductivity. Crystallized state. The conditions (heating temperature, treatment time, reducing atmosphere, and the like) at the time of the annealing treatment are the same as those of the annealing treatment in the method for producing the first transparent conductive substrate. Thus, a transparent conductive film composed of titanium oxide doped with cerium or lanthanum is formed. The transparent conductive film has an anatase crystal phase and is a 0 film composed of a polycrystalline body of a valence Nb or Ta-doped titanium oxide belonging to the VA group of the periodic table, and exhibits good transparency and also exhibits High conductivity. Further, in the first to fifth manufacturing methods of the present invention described above, the precursor liquid or the underlayer forming material is directly coated on the transparent substrate to form a transparent conductive film, a bottom layer or a first film, but in, for example, a liquid crystal display. In the transparent electrode application such as a device, an intermediate film such as a colored film (color filter) may be passed through the transparent substrate, and the precursor liquid or the underlayer forming material may be directly coated thereon, thus being transparent substrate and transparent conductive. It is also within the scope of the invention to form a film between the film, the bottom layer or the first film through the interlayer of -52-200941506. [Transparent Nematic Substrate] The transparent conductive substrate of the present invention is obtained by the above-described method for producing a transparent conductive substrate of the present invention. The transmittance of the transparent conductive substrate of the present invention is usually 70% or more, preferably 75% or more, more preferably 80% or more in the visible light field, and 70% or more in the infrared field, preferably 75 in terms of φ. More than %, more preferably 80% or more. Further, the specific resistance of the transparent conductive substrate of the present invention is usually 9 χ 1 (Γ 3 Ω · cm or less, preferably 8 X 1 (Γ 3 Ω · cm or less. Further, the transmittance and specific resistance can be, for example, by way of example The transparent conductive substrate of the present invention is applied to, for example, a display panel such as a touch panel, a liquid crystal display, an LED (light emitting element), an organic EL display, a flexible display, or a plasma display, and an electrode of a solar cell. The use of the heat-reflecting film of the window glass, the antistatic film, etc. Moreover, the transparent conductive substrate obtained by the crucible manufacturing method of the present invention has the advantage of exhibiting a high refractive index': and can be effectively used as an antistatic film having an antireflection function. [Precursor liquid for film formation] (Precursor liquid for forming a first film) The precursor liquid for forming a first film of the present invention is a precursor liquid for forming a transparent conductive film, and contains (A) a titanium compound. a reaction product obtained by reacting with hydrogen peroxide and (B) a reaction product obtained by reacting a ruthenium compound or a macro compound (a dopant compound) with hydrogen peroxide. The precursor -53- 200941506 is a complex of (A) titanium compound and (B) a ruthenium compound or a molybdenum compound peroxidized (peroxide complex), which is heated to become doped yttrium or molybdenum. A metal oxide precursor of titanium oxide. Thus, a film formed of a metal oxide which is doped with a pentavalent lanthanum or lanthanum of Group VA of the periodic table in titanium oxide exhibits good electrical conductivity. The precursor solution contains the above (A) reaction product obtained by reacting a titanium compound with hydrogen peroxide, and (B) a mixture of the reaction product obtained by reacting a dopant compound with hydrogen peroxide (hereinafter also referred to as The "mixture of (A) and (B)") is the same as the precursor liquid in the method for producing the first transparent conductive substrate, and the description of the precursor liquid in the method of manufacturing the first transparent conductive substrate can be applied. However, any solvent of the following formula (1) to (5) may be used in addition to those exemplified in the method for producing the first transparent conductive substrate by the solvent which can be used in the peroxidation reaction of hydrogen peroxide. Representing the dissolution of a particular structure In the first film forming precursor liquid of the present invention, it is important that the mixture of the above formulas (1) to (5) is represented by the mixture of the above (A) and (B). a solvent (hereinafter also referred to as "specific solvent"). The specific solvent is used to stabilize the peroxygen complex in the precursor liquid and to improve the storage stability of the solution, and to coat the precursor liquid. When the annealing treatment is performed on the substrate, by heating the solvent which is rapidly volatilized, the formed film does not remain in the organic component and exhibits good conductivity. In the above formulas (1) to (3), R1 to R6, Examples of the alkyl group of R1 to R5 or RLR7 are, for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc. Further, in the above formulas (1) to (3), the example of X is represented by R in OR. The alkyl groups are also the same. In the above formulas (4) and (5), the alkylene group having a carbon number of 3 to 6 which may have a substituent represented by Y is exemplified by a stretching propyl group, a butyl group, a pentyl group, a hexyl group, and the like. - a compound represented by the above formulas (1) to (3), if it is present in a mixture with the above (Α) and (Β), forms a metal which is necessary for the compound to have two oxygen atoms and a peroxy complex The two-tooth coordination between the atoms produces a different 6-membered or 7-membered ring structure in which the bonding force is different from the covalent bond and the coordinate bond, and the peroxy group can be protected by the cross-linking structure. Moreover, since there is only one covalent bond having a strong bonding force in the crosslinked structure formed by this, the organic molecules are easily accelerated from the metal atom by heating during the annealing treatment, and do not remain in the obtained film. Organic components impair electrical conductivity. When a compound represented by the above formulas (4) and (5) is present in a mixture with the above (Α) and (Β), between the two oxygen atoms necessary for the compound and the metal atom of the peroxy complex The bidentate coordination can stereoscopically protect the peroxy group of the fluffy structure of the 5-membered ring to the 8-membered ring of the compound. Moreover, since φ is a weak bond between the metal atom and the oxygen atom formed by the annealing, the heating by the annealing treatment tends to accelerate the release of the organic molecule from the metal atom without damaging the organic component remaining in the obtained film. Electrical conductivity. The specific solvent may have an organic structure such as an alcohol, an alkoxy alcohol, a carboxylic acid or an ester, as long as it has a specific structure represented by the above formulas (1) to (5), but specifically, selected from 3-methoxy-1-butanol, 3-methoxy-3-methyl-butanol, diethylideneacetone (4-hydroxy-4-methylpentan-2-one), 4-hydroxyl 2-butanone, 5-hydroxy-2-pentanone 'tetrahydrofuran-2-carboxylic acid, 2-methyl-1,3-propanediol, γ-butyrolactone, δ-valerolactone, ε-caprolactone At least one of the groups of -55-200941506 is preferred. Among these, 3-methoxy-1-butanol can significantly improve the storage stability of the precursor liquid, and does not cause residual organic components after being applied to the substrate and subjected to annealing treatment ( It is best to obtain a film with high transparency and to obtain a film with high transparency. In the above specific solvent, it is preferred that the reaction product (peroxy complex) of the above (A) and (B) coexist, and for example, it can be used as a solvent in the peroxidation reaction with hydrogen peroxide described above, and is contained in the precursor liquid. It may be added as a solvent for the purpose of diluting the mixture of the above (A) and (B) into a liquid property (viscosity or the like) suitable for coating or annealing treatment, and may be contained in the precursor liquid. The content of the specific solvent is not particularly limited, but is preferably from 15 to 80% by weight based on the total amount of the solvent in the precursor liquid. The solid concentration of the first precursor liquid of the present invention is not particularly limited, and is, for example, 2 to 20% by weight, more preferably 4 to 15% by weight. In general, since the solid content concentration is high, the storage stability of the precursor liquid is lowered. Therefore, it has not been possible to set a high concentration exceeding 10% by weight, but the specific solvent of the first precursor liquid of the present invention can be used. The storage stability can be improved, so that it can be set to a higher concentration range as described above, for example, it is possible to form a film having a sufficient film thickness by, for example, coating. Further, the solid content concentration thereof means the ratio (% by weight) of the total weight of the titanium compound and the dopant compound used in obtaining the precursor liquid to the total weight of the precursor liquid. The first precursor liquid of the present invention as described above can be suitably used as each of the precursor liquids in the method for producing the first to fifth transparent conductive substrates of the present invention. -56-200941506 (Precursor liquid for forming a second film) The precursor liquid for film formation of the present invention is a precursor liquid for forming a transparent conductive mold, and comprises (A) reacting a titanium compound with hydrogen peroxide. The reaction product formed and (B) a reaction product obtained by reacting a ruthenium compound with a ruthenium compound (dopant compound) with hydrogen peroxide. That is, the precursor liquid of the present invention is a compound containing a (A) titanium compound and (B) a ruthenium compound or a molybdenum compound by oxygen oxidization (peroxidation complex), and is heated by heating. It becomes a metal oxide precursor of titanium oxide doped with cerium or lanthanum. In this manner, a film formed of a metal oxide obtained by a valence of VA of the periodic table VA or heavily doped in titanium oxide exhibits good electrical conductivity. In the second precursor liquid of the present invention, the above (A) is a reaction product obtained by reacting a titanium compound with hydrogen peroxide, and (B) a mixture of the reaction product obtained by reacting a dopant compound with hydrogen peroxide. (The mixture of (A) and (B)) is the same as the precursor liquid in the method for producing the first transparent conductive substrate, and can be applied to the method of manufacturing the first transparent conductive substrate. Description. However, in the above-mentioned peroxidation reaction using hydrogen peroxide, the solvent to be used may be a specific solvent in the first precursor liquid, in addition to those exemplified in the method for producing the first transparent conductive substrate. Further, the mixture of the above (A) and (B) in the second precursor liquid of the present invention is not particularly limited as long as the amount of hydrogen peroxide reacted with the titanium compound or the dopant compound, and can be appropriately set, but Further improving the storage stability, the titanium compound preferably reacts with 1 to 8 moles of hydrogen peroxide per 1 mole of titanium compound, and preferably 1 to 3 moles of dopant compound per mole of dopant. 200941506 The compound reacts with 2. 5 to 3.5 moles of hydrogen peroxide. For example, when the titanium compound and the dopant compound are respectively mixed with the two reaction products after the reaction with hydrogen peroxide, the amount of hydrogen peroxide used in each reaction is preferably set to the above range, and on the other hand, the titanium compound is When the premixed mixture of the dopant compound is reacted with hydrogen peroxide, it is preferably set in such a manner that the amount of the titanium compound in the mixture is in the above range, and the amount of the dopant compound in the mixture becomes the above. The total amount of the amount set by the range is the amount of hydrogen peroxide reacted. In the precursor liquid for forming a second transparent conductive film of the present invention, it is important to contain at least one of nitric acid and hydrochloric acid (hereinafter also referred to as "the above specific inorganic acid" with respect to the mixture of the above (Α) and (Β). "). Thereby, the peroxygen complex (νο3_) or the chloride ion (cr) acts as a relative ion with respect to the peroxy-compound which exists as a cation in the precursor liquid, and the peroxygen complex is stabilized and exhibits excellent performance. Storage stability. For example, when the current flooding solution is placed at a normal temperature, the gelation which would normally occur in about 2 to 3 hours does not cause white turbidity or gelation after about 4 days. Moreover, the addition of hydrochloric acid or nitric acid to the precursor liquid can also be volatilized by firing or annealing treatment at the time of film formation, so that it does not remain in the finally formed film' without being conductive or Physical properties such as transparency have an impact. The content of the specific inorganic acid is not particularly limited depending on the type thereof or the solid content concentration of the precursor liquid to be described later, but is appropriately set as long as a sufficient stability improving effect can be obtained. For example, 'the solid content concentration is 8% by weight or less in the case of the precursor liquid', and the titanium compound and the catastrophic compound 200941506 (that is, the solid component) used in the case of obtaining the mixture of the above (A) and (B). The total amount is 100 moles, preferably nitric acid is preferably 1 to 5 moles, preferably 5 to 30 moles, and hydrochloric acid is preferably 10 to 60 moles, preferably 30 to 50 moles. When the solid content concentration exceeds 8% by weight and is less than 1% by weight of the precursor liquid, the total amount of the solid components is 100 moles, and the nitric acid is 50 to 100 moles, preferably 60 to 80 - Moer's hydrochloric acid is 70 to 1 50 m, preferably 90 to 120 m. It is preferred. When the solid content concentration is more than 10% by weight and less than 20% by weight of Φ before the precursor liquid, 100 mol to 100 mol, preferably 100-140 mol, of hydrochloric acid, relative to 100 mol of the above solid content. It is preferably contained in an amount of 120 to 170 m, preferably 130 to 160 m. Further, since hydrochloric acid is difficult to maintain at a predetermined concentration due to its volatility, nitric acid is recommended in some cases. Further, the specific inorganic acid is not particularly limited as long as it is contained in the final precursor liquid. For example, in the case where two reaction products of the titanium compound and the blend compound are reacted with hydrogen peroxide, respectively, the addition of the specific inorganic acid may be carried out separately for the two reaction products before the mixing, or may be carried out in the second reaction product. After mixing. - The precursor liquid for forming a second transparent conductive film of the present invention preferably further contains a specific solvent in the first precursor liquid. The specific solvent has a function of stabilizing the peroxygen complex in the precursor liquid, and can improve the storage stability of the solution, and is heated by applying the precursor liquid to the substrate and performing annealing treatment. The action of the rapidly evaporating solvent 'will leave the organic component in the formed film and exhibit good electrical conductivity. Further, the description relating to the inclusion of the specific solvent is described in the above-mentioned first precursor liquid -59-200941506. The solid concentration of the second precursor liquid of the present invention is not particularly limited, for example, it is preferably 2 to 20% by weight, more preferably 4 to 15% by weight. In general, since the concentration of the solid component is high, the storage stability of the precursor liquid is lowered. Therefore, it has not been possible to set a high concentration of, for example, more than 10% by weight. However, in the present invention, the above specific inorganic acid and, if necessary, further contained. The above-mentioned specific solvent can improve the storage stability, and therefore can be set to the above-mentioned higher concentration range, so that, for example, it is possible to form a film having a sufficient film thickness by one coating. Here, the solid content concentration herein means the ratio of the total weight of the titanium compound and the dopant compound used in obtaining the precursor liquid to the total weight of the precursor liquid (weight % /.). The first precursor liquid of the present invention as described above can be suitably used as each of the precursor liquids in the method for producing the first to fifth transparent conductive substrates of the present invention. (Precursor liquid for forming a third film) The precursor liquid for forming a third film of the present invention contains a reaction product obtained by reacting a ruthenium compound or a molybdenum compound with hydrogen peroxide, that is, containing a ruthenium compound or A complex of peroxidation of a ruthenium compound (peroxy complex). The peroxy complex can be heated to become cerium oxide or cerium oxide alone, and on the other hand, for example, by heating with titanium peroxycompound to form a metal oxide precursor liquid of cerium-doped or molybdenum-doped titanium oxide. . In the precursor film for forming a third film of the present invention, the reaction product is obtained by reacting a hydrogen salt of 1 mole or a ruthenium compound with 2.5 to 3.5 moles of peroxygen-60-200941506. It is preferably obtained by reacting 2.8 to 3.2 moles of hydrogen peroxide with 1 mole of a ruthenium compound or a molybdenum compound. According to this, a reaction product (peroxy complex) having excellent stability is obtained, and the third precursor liquid of the present invention can be stably stored for a long period of time at room temperature (20±5° C.) for more than 1 day. Good for more than 15 days, better for more than 20 days, and better for more than 30 days. When the amount of hydrogen peroxide reacted with the ruthenium compound or group compound is less than the above range, and the ratio is more than the above range, the storage stability of the peroxygen complex is lowered, and if the ruthenium precursor solution is When stored at room temperature for several hours to several days (for example, from about 1 hour to about 4 days), gelation or clouding occurs. In particular, when the amount of hydrogen peroxide is more than the above range, the excess free hydrogen peroxide decomposes and generates heat, so that the stability of the liquid is greatly lowered. The solid content concentration of the precursor film for forming a third film of the present invention is 8.5 wt% or less, more preferably 8.0 wt% or less, still more preferably 7.5% by weight or less, still more preferably 7.0 wt% or less. Since the peroxygen complex contained in the third precursor liquid of the present invention has excellent storage stability, even if it is set at a higher solid concentration, it can be stored at least at a constant temperature for 1 day. The above can be stored stably without gelation or white turbidity. The lower limit of the solid content concentration is not particularly limited. However, the coating property at the time of film formation is preferably 2% by weight or more, more preferably 4% by weight or more. Further, the solid content concentration herein means the ratio (% by weight) of the weight of the ruthenium compound or ruthenium compound used in obtaining the precursor liquid to the total weight of the precursor liquid. When a ruthenium compound or a ruthenium compound is reacted with hydrogen peroxide to obtain the above reaction product, the ruthenium compound or ruthenium compound used in the reaction of hydrogen peroxide (that is, peroxidation), -61 - 200941506, and the peroxidation reaction are used. The solvent which can be used can be applied to each of the precursor liquids in the method for producing the first transparent conductive substrate (in this case, the peroxidation reaction can be expressed by another method as a titanium compound) . However, the solvent which can be used in the peroxidation reaction of hydrogen peroxide described above may be used in addition to the specific solvent in the first precursor liquid, in addition to those exemplified in the method for producing the first transparent conductive substrate. The precursor film for forming a third film of the present invention preferably further contains a specific solvent in the above-mentioned 0th - precursor liquid. The specific solvent described above further enhances the storage stability of the solution by acting as a stabilizer for the peroxygen complex in the precursor solution. Further, in the specific solvent, when the film is formed, the precursor liquid is applied to the substrate and rapidly volatilized by heating, since the organic component derived from the specific solvent does not remain in the formed film, so there is no The carbonization of the remaining organic component by heating causes the transparency of the film to decrease, and has little effect on the film function such as conductivity. Further, when the specific solvent is contained, the description of the first precursor liquid may be applied (however, in this case, "the mixed product of (A) and (B)" is replaced by "reaction product"). The method of forming a film for forming a precursor film for forming a third film of the present invention is not particularly limited, but preferably, for example, the precursor film for forming a third film of the present invention may be used alone or, for example, with a conventional titanium. The oxygen complex (the reaction product of the reaction of the titanium compound with hydrogen peroxide) is mixed, applied to the substrate, and heated. When the third film-forming precursor liquid of the present invention is applied alone, a cerium oxide or molybdenum oxide film suitable for an antireflection film or the like can be formed, and when it is mixed with a titanium peroxy compound, It is possible to form a ruthenium-doped ruthenium-based film which is suitable for a transparent conductive-62-200941506 film or the like. Specifically, the film forming method of the precursor film for forming a third film is not particularly limited, and a method for producing the first to fifth transparent conductive substrates of the present invention, for example, can be used. [Examples] The present invention will now be described in more detail by way of examples, but the present invention is not limited by the examples, and any changes which are made within the scope of the invention are not to be construed as the scope of the invention. Further, the physical properties of the transparent conductive substrate were measured by the following methods. &lt;Specific resistance &gt; The specific resistance was measured by a four-terminal four-probe method using a resistivity meter ("LORESTA-GP, MCP-T610" manufactured by Mitsubishi Chemical Corporation). Specifically, the four needle electrodes are placed on the sample in a straight line, and a certain current is passed between the outer two probes, and a certain current is passed between the inner two probes, thereby measuring the potential difference generated between the inner two probes. Get the resistance. 〇 &lt;Transmittance &gt; Transmittance is measured in the range of 190 nm to 2700 nm using ultraviolet visible near-infrared spectrophotometry ("V-670" manufactured by JASCO Corporation). &lt;Crystallinity&gt; An X-ray diffraction apparatus (RINT2000 manufactured by Rigaku Electric Co., Ltd.) was used, and crystallinity was evaluated using an accessory for film measurement. &lt;Crystal Structure&gt; The state of doping of ruthenium or iridium in titanium was investigated using an energy dispersive X-ray microanalyzer (TEM-EDX), and the crystal structure was examined using an electric field radiation type electron microscope (FE-SEM). Further, in the following examples and comparative examples, when the precursor solution was obtained by mixing the -62-200941506 oxidative complex obtained in each of the production examples, the desired solid content was adjusted using dehydrated ethanol unless otherwise specified. (Production Example a1) 4.0 g of titanium tetraisopropoxide was dissolved in 28.5 g of dehydrated ethanol under an argon atmosphere, and 8.0 g of a 30% by weight aqueous solution of hydrogen peroxide was slowly added to the resulting solution with stirring, and the addition was completed. Thereafter, stirring was carried out for 5 minutes to carry out a _peroxidation reaction. Further, the reaction was carried out under cooling with dry ice around the flask in which the solution was poured, so that the internal temperature of the solution when the heat was caused by the addition of the aqueous hydrogen peroxide solution was not more than -10 °C. The reaction product thus obtained is referred to as a peroxyl complex (a 1). (Production Example bl) 1.5 g of pentoxide was dissolved in 19.2 g of dehydrated ethanol under an argon atmosphere, and 1.6 g of a 30% by weight aqueous solution of hydrogen peroxide was slowly added to the resulting solution with stirring. After the addition, stirring was carried out. The hydrazine reaction was carried out for 5 minutes. Further, the reaction was carried out under cooling with dry ice around the flask in which the solution was poured, so that the internal temperature of the solution when heat generation due to the addition of the aqueous hydrogen peroxide solution was not more than -1 o °c. The reaction product thus obtained is referred to as a peroxyl complex (bl). (Production Example a2) 20.0 g of distilled water was added to 3.0 g of titanium tetraisopropoxide in an argon atmosphere and stirred, and the resulting precipitate (hydrogen hydroxide - 64 - 200941506 titanium) was taken from the mother liquid. 1.2 g of the precipitate was dissolved in 2.0 g of ethanol. Under stirring, 17 g of a 30% by weight aqueous solution of hydrogen peroxide was slowly added. After the addition, the mixture was stirred for 1 Torr to carry out a peroxidation reaction. The dry ice was cooled under the cooling of the flask filled with the solution to control the internal temperature of the solution when the heat was caused by the addition of the aqueous hydrogen peroxide solution to not exceed 10 °C. The reaction product thus obtained is referred to as titanium peroxy complex U2). 0 (Production Example b2) 40.0 g of distilled water was added to 5.0 g of pentoxide hydrate in an argon atmosphere and stirred, and the resulting precipitate (barium hydroxide) was taken from the mother liquid. 2.8 g of this precipitate was dissolved in 2.0 g of ethanol, and 20 g of a 30% by weight aqueous hydrogen peroxide solution was slowly added to the resulting solution with stirring. After the addition was completed, the mixture was stirred for 10 minutes to carry out a peroxidation reaction. Further, the reaction was carried out by cooling the dry ice around the flask in which the solution was poured, so that the internal temperature of the solution when the heat was caused by the addition of the aqueous hydrogen peroxide solution was not more than -1 〇 °C. The reaction product obtained as such is referred to as a peroxyl complex (b2). (Production Example cl) 1.6 g of molybdenum pentoxide was dissolved in 20.4 g of dehydrated ethanol under an argon atmosphere, and 1 - 3 6 g of a 30% by weight aqueous solution of hydrogen peroxide was slowly added to the resulting solution under stirring. After the end of the addition, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction is carried out under cooling with dry ice in the flask for injecting the solution to control the internal temperature of the solution caused by the addition of the aqueous hydrogen peroxide solution/heating to not exceed -1 〇 °C. The reaction product thus obtained is referred to as molybdenum-65-200941506 peroxy complex (cl). (Example 1-1) The titanium peroxygen complex (al) obtained in Production Example a1 and the peracetic acid miscible obtained in Production Example bl were mixed in a ratio of titanium: 铌 = 93:7 (mole ratio). The substance (b 1 ) was prepared as a precursor liquid having a solid concentration of 7 wt%. The precursor liquid was applied to a transparent substrate (1737, manufactured by Corning Co., Ltd., thickness: 77 mm) by a capillary applicator to a dry film thickness of 35.7 nm, and fired at 400 ° C. (prebaking) for 1 minute, and then annealing treatment was performed at 500 ° C for 60 minutes in a reducing gas atmosphere of 100% hydrogen to obtain a transparent conductive substrate. The specific transparent conductive substrate had a specific resistance of 5.2 XI 0_3 Ω · cm, a transmittance of about 80% in the visible light field, and about 80% in the infrared field. The crystal phase of the conductive film in the transparent conductive substrate was detected by X-ray diffraction to be anatase. Further, the crystal structure of the polycrystalline body doped with Nb-doped titanium oxide was observed by TEM-EDX and FE-SEM. (Example 1-2) The titanium peroxygen complex (a2) obtained in Production Example a2 and the peracetic acid miscible obtained in Production Example b2 were mixed at a ratio of titanium: 铌 = 94:6 (mole ratio). The substance (b2) was prepared as a precursor liquid having a solid concentration of 6.5% by weight. The precursor liquid was applied by a capillary coater to the same transparent substrate as in Example 1_丨 to a dry film thickness of 26.0 nm' and fired (prebaked) at 8 ° C for 1 minute. Subsequently, annealing treatment was carried out at -66 to 200941506 500 ° C for 60 minutes in a reducing gas atmosphere of 100% hydrogen to obtain a transparent conductive substrate. The specific resistance of the obtained transparent conductive substrate was 7.3 χ1 0·3 Ω·cm, and the overshoot was about 80% in the visible light field and about 80% in the infrared field. — The X-ray diffraction is used to detect that the crystalline phase of the conductive film in the transparent conductive substrate is anatase. Further, it was observed by TEM-EDX and FE-SEM. The crystal structure was a polycrystalline body of Nb-doped titanium oxide. φ (Example 1-3) The ruthenium peroxy compound obtained by mixing the titanium peroxy complex U2 obtained in the production example and the production example b2 in a ratio of titanium: 铌 = 92:8 (mole ratio) B2), a precursor liquid having a solid concentration of 6.5% by weight. The precursor liquid was applied to the same substrate as that of Example 1-1 by a transfer coater to have a dry film thickness of 55·〇ηπι, and baked (pre-baked) at 80 ° C for 1 minute. Subsequently, annealing treatment was performed at 500 ° C for 60 minutes in a reducing gas atmosphere of 100% hydrogen to obtain a transparent conductive substrate. The specific resistance of the transparent conductive substrate obtained by Q is 6.5 χ 10·3 Ω · cm, the overshoot is about 80% in the visible light field, and about 80% in the infrared field. : The crystalline phase of the conductive film in the transparent conductive substrate is detected by X-ray diffraction to be anatase. Further, the crystal structure of the Nb-doped titanium oxide was observed by TEM-EDX and FE-SEM. (Example 1-4) The titanium peroxygen complex (al) obtained in the production example was mixed in a ratio of titanium: 铌 = 92: 8 (mole ratio), and the peroxyl peroxide obtained in the production example bl was permeated. A2 The wrong spin-drying was observed in the mixture of -67- 200941506 compound (bl), and the precursor liquid was prepared at a solid concentration of 9.16% by weight. The precursor liquid was applied to the same transparent substrate as in Example 1-1 by a spin coater to have a dry film thickness of 71.0 nm, and fired at 80 ° C (prebaked and baked) for 1 minute. Subsequently, annealing treatment was performed at 500 ° C for 60 minutes in a reducing gas atmosphere of 100% hydrogen to obtain a transparent conductive substrate. The specific resistance of the obtained transparent conductive substrate was 5.6 χ 10 _ 3 Ω · cm, the transmittance was about 80% in the visible light field, and about 80% in the infrared field. _ The X-ray diffraction is used to detect that the @crystalline phase of the conductive film in the transparent conductive substrate is anatase. Further, the crystal structure was observed to be a polycrystalline body of Nb-doped titanium oxide by TEM-EDX and FE-SEM. (Example 1-5) The titanium peroxygen complex (al) obtained in Production Example a1 and the hydrazine peroxy compound obtained in Production Example bl were mixed in a ratio of titanium: 铌 = 80: 20 (mole ratio). The substance (bl) was prepared as a precursor liquid having a solid concentration of 7 wt%. The precursor liquid was applied to a transparent substrate (an alkali-free glass "17 7 7", thickness 0.7 mm) by a spin coater to have a dry film thickness: 100 nm, and at 300 ° C. The film was baked (prebaked) for 1 minute, and then annealed at 500 ° C for 60 minutes in a reducing gas atmosphere of 100% hydrogen to form a film which became a transparent conductive layer, thereby obtaining a transparent conductive substrate. The crystal phase of the film formed therein was examined by X-ray diffraction as an anatase crystal phase. Further, the crystal structure was observed to be a polycrystalline body of Nb-doped titanium oxide by TEM-EDX and FE-SEM. The specific resistance of the obtained transparent conductive substrate was 5. 〇χ 10_3 Ω _ cm, and the transmittance of -68-200941506 was about 80% in the visible light field and about 80% in the infrared field. (Example 1-6) ^ The titanium peroxygen complex (al) obtained in Production Example a1 and the peroxyl peroxyl obtained in Production Example bl were mixed at a ratio of titanium: 铌 = 7 〇: 30 (mol ratio). The compound (bl) was prepared as a precursor liquid having a solid concentration of 7 wt%. The precursor liquid was applied once on the same transparent Q substrate as in Example 1-1 by a spin_applicator to have a dry film thickness of 65 nm and baked (prebaked) at 300 ° C. After a minute, annealing treatment was performed at 500 ° C for 60 minutes in a reducing gas atmosphere of 100% hydrogen to obtain a transparent conductive substrate. The specific resistance of the obtained transparent conductive substrate was 4·0 χ 10_3 Ω · cm ′, the transmittance was about 80% in the visible light field, and about 80% in the infrared field. The crystal phase of the conductive film in the transparent conductive substrate was detected by X-ray diffraction to be anatase. Further, the crystal structure of the polycrystalline body doped with Nb-doped titanium oxide was observed by TEM-EDX and FE-SEM. ❹ (Example 1-7) 'The titanium peroxygen complex (al) obtained in the production example a1 was mixed in the ratio of titanium: 铌 = 80: 20 (mole ratio) and the peroxyl peroxyl obtained in the production example bl The complex (b 1 ) was prepared as a precursor liquid having a solid concentration of 7 wt%. The precursor liquid was applied to the same transparent substrate as that of Example 1-1 by a spin coater to have a dry film thickness of 50 nm, and baked (prebaked) at 300 ° C for 1 minute, followed by Annealing was carried out at 550 ° C for 60 minutes in a reducing gas atmosphere of 100% hydrogen to obtain a transparent conductive substrate. -69- 200941506 The specific resistance of the obtained transparent conductive substrate is 3.7 χ10·3 Ω·(: ηη, transmittance is about 80% in the visible light field, and about 8〇% in the infrared field. The transparent conductive substrate is detected by X-ray diffraction. The crystal phase of the conductive film was anatase. The crystal structure of the polycrystalline silicon doped with Nb was observed by TEM-EDX and FE-SEM. (Examples 1-8) To become titanium: 铌 = The proportion of 80:20 (mole ratio) was mixed with the titanium peroxy complex (al) obtained in the example a1 and the peroxy peroxy complex (bl) obtained in the production example bl before the solid concentration of 7 wt%. The precursor liquid was applied to the transparent substrate of the same manner as in Example 1-1 by a spin coater to have a dry film thickness of 60 nm, and baked at 300 ° C (prebaking) 1 Then, annealing treatment was performed at 600 ° C for 60 minutes in a reducing gas atmosphere of 100% hydrogen to obtain a transparent conductive substrate. The specific resistance of the obtained transparent conductive substrate was 1.8 × 1 0 - 3 Ω · cm, and the transmittance was About 70% in the visible light field and about 70% in the infrared field. The transparent conductive substrate is detected by X-ray diffraction. The crystal phase of the intermediate conductive film was anatase. The crystal structure of the nanocrystalline doped Nb was observed by TEM-EDX and FE-SEM. (Examples 1-9) To become titanium: giant a ratio of =80:20 (mole ratio) to the titanium peroxygen complex (al) obtained in the production example a1 and the molybdenum peroxy complex (cl) obtained in the production example cl, to a solid concentration of 7 wt% The precursor liquid was applied to the transparent substrate of the same Example 1-1 as a dry film thickness of 67.3 nm by a capillary-70-200941506 applicator, and fired at 100 ° C. (prebaking) for 30 minutes, followed by annealing treatment at 500 ° C for 30 minutes in a reducing gas atmosphere of 1% by weight of hydrogen to obtain a transparent conductive substrate. The specific resistance of the obtained transparent conductive substrate was 8.3 χ1 0_3 Ω. · cm, penetration rate is about 80% in the visible light field and about 80% in the infrared field. The X-ray diffraction is used to detect the H crystal phase of the conductive film in the transparent conductive substrate as anatase. In addition, TEM -EDX and FE-SEM were used to observe the polycrystal of the titanium structure doped with Ta. (Comparative Example 1-1) The titanium peroxy complex (a2) obtained in Example a2 was produced as a precursor liquid having a solid concentration of 9.4% by weight, and the precursor liquid was applied in the same manner as in Example 1-1 by a spin coater. The transparent substrate has a dry film thickness of 102 nm and is fired (prebaked) at 80 ° C for 1 minute, and then annealed at 500 ° C in a reducing gas atmosphere of 100% hydrogen. In minutes, a transparent conductive substrate was obtained. Since the obtained transparent conductive substrate is not doped with a dopant (yttrium or lanthanum) in titanium oxide, the specific resistance cannot be measured (measurement limit; 1 〇 3 Ω·cm or more), and the transmittance is About 80% in the visible field and about 80% in the infrared field. The crystal phase of the conductive film in the transparent conductive substrate was detected by X-ray diffraction to be anatase. -71 - 200941506 (Comparative Example 1-2) The titanium peroxygen complex (a2) obtained in Production Example a2 and the production example b2 were obtained at a ratio of titanium: 铌 = 92: 8 (mole ratio). The peroxy complex (b2) was prepared as a precursor liquid having a solid concentration of 6.5% by weight. The precursor liquid was applied to the same transparent substrate as in Example 1-1 by a spin coater to have a dry film thickness of 55.0 nm, and baked (prebaked) at 80 t for 1 minute, and then, Annealing treatment was carried out at 500 ° C for 60 minutes in a general atmospheric gas atmosphere to obtain a transparent conductive substrate. Since the obtained transparent conductive substrate is annealed in an atmospheric gas atmosphere without a reducing gas atmosphere, the specific resistance cannot be measured (measurement limit; 103 Ω · cm or more), and the transmittance is about 80% in the visible light field, in the infrared field. About 80%. The crystal phase of the conductive film in the transparent conductive substrate was detected by X-ray diffraction to be anatase. (Comparative Example 1-3) The titanium peroxygen complex (a2) obtained in Production Example a2 and the peracetic acid miscible obtained in Production Example b2 were mixed at a ratio of titanium: 铌 = 92:8 (mole ratio). The substance (b2)' was prepared as a precursor liquid having a solid concentration of 6.5% by weight. The precursor liquid was applied by a spin coater to the same transparent substrate as in Example iq at once to have a dry film thickness of 55 Å ηηη, and was 80. (: The lower firing (pre-bake) was carried out for 1 minute, and then annealed at 600 ° C for 60 minutes in a reducing gas atmosphere of 1% by weight of hydrogen to obtain a transparent conductive substrate. The specific resistance is 5.4x10·^ cm, and the pass-72-200941506 is about 80% in the visible light field and about 80% in the infrared field. The X-ray diffraction is used to detect the crystal phase of the conductive film in the transparent conductive substrate. A part of the rutile type was produced. (Comparative Example 1 - 4) The titanium peroxygen complex (al) obtained in the production example a1 was mixed at a ratio of titanium: 铌 = 85: 15 (mole ratio) and a production example. The peroxygen compound (bl) obtained by bl was prepared as a precursor liquid having a solid concentration of 7 wt%, and the precursor liquid was applied to a transparent substrate by a spin coater (alkali-free glass). Manufactured in 1 737", the thickness of 〇.7mm) became a dry film thickness of 100 nm' and heated at 300 ° C for 10 minutes to form an amorphous material from titanium oxide (the content of bismuth in the amorphous material was 15 moles) Ear %) of the film formed. Subsequently, in a reducing atmosphere of 100% hydrogen at 420 ° c After heat treatment for 60 minutes, a transparent conductive substrate was obtained. The crystal phase of the conductive film in the transparent conductive substrate was detected by X-ray diffraction, and as shown in Fig. 2, the crucible was anatase type but the crystallinity was low. The specific resistance of the obtained transparent conductive substrate was 5.4 X 1 0·2 Ω·cm, and the transmittance was about 80% in the visible light field and about 80% in the infrared field. (Comparative Example 1 - 5) To become titanium: 铌 = 80: The proportion of 20 (mole ratio) was mixed with the titanium peroxy complex (al) obtained in the production example a1 and the peroxy peroxy complex (b 1 ) obtained in the production example bl, and the solid concentration was 7 wt%. The precursor liquid was applied to the same transparent-73-200941506 substrate as that of Example 1-1 by a spin coater to a dry film thickness of 8 Onm, and air-dried (60 minutes at room temperature). Subsequently, annealing treatment was performed at 500 ° C for 60 minutes in a reducing gas atmosphere of 1% by weight of hydrogen to obtain a transparent conductive substrate. The specific resistance of the obtained transparent conductive substrate was 5.8 χ 1 (Γ 2 Ω · cm, and the transmittance was at About 80% in the visible light field and about 80% in the infrared field. The transparent conductive is detected by X-ray diffraction. The crystalline phase of the conductive film in the substrate is anatase. (Example 2-1) The titanium peroxygen miscide obtained in the production example a1 was mixed at a ratio of titanium: 铌 = 80: 20 (mole ratio). The peroxy peroxy compound (b 1 ) obtained in the product (al) and the production example bl was prepared as a precursor liquid having a solid concentration of 7 wt%, and the precursor liquid was applied to the transparent substrate at a time by a spin coater. (The alkali-free glass "1 73 7 made by Corning", thickness 0.7mm) becomes a dry film thickness of 20nm, and is air-dried (naturally dried), and then annealed in air at 50 °C for 10 minutes. A film is formed as a bottom layer. X-ray diffraction inspection @ The crystal phase of the film formed here is an anatase crystal phase. Next, the same precursor liquid as above was applied by a spin coater at one time: on the above-mentioned formed underlayer to have a dry film thickness of 100 nm, and baked (prebaked) at 300 ° C for 1 minute, followed by Annealing was carried out at 500 ° C for 60 minutes in a reducing atmosphere of 100% hydrogen to form a film of a transparent conductive layer. The crystal phase of the film formed here was detected by X-ray diffraction as an anatase crystal phase. Further, a polycrystalline body having a crystal structure of Nb-doped titanium oxide was observed by TEM-EDX and FE-SEM. -74- 200941506 The transparent conductive substrate thus obtained has a specific resistance of 2.9x1 0·3 Ω·cm, a transmittance of about 80% in the visible light field, and about 80% in the infrared field. Comparing this result with Examples 1-5 which were the same as those of the above Example 2-1 except that the transparent conductive layer was formed directly on the transparent substrate except that the underlayer was not formed, it was confirmed that the specific resistance was in the above-mentioned Example 2-1. Lower. (Example 3-1) 钛 The titanium peroxygen complex (al) obtained in the production example a1 was mixed with titanium in the ratio of 铌=80:20 (mole ratio) and the peroxyl peroxyl obtained in the production example bl The complex (b 1 ) was prepared as a precursor liquid having a solid concentration of 7 wt%. Next, an anatase-type titanium oxide fine particle aqueous dispersion ("TO sol" manufactured by Sigma Co., Ltd., an anatase sol of titanium oxide) having an average particle diameter of 10 nm and a solid concentration of 1.7 was prepared by a spin coater. The weight %) was applied to a transparent substrate (an alkali-free glass "1737" manufactured by Corning Co., Ltd., thickness: 0.7 mm) to have a dry film thickness of 40 nm, and air-dried (naturally dried) to form a film which became the underlying crucible. The crystal phase of the film formed here was detected by X-ray diffraction as an anatase crystal phase. Next, the precursor liquid is applied to the formed underlayer at a time by a spin coater to have a dry film thickness of 10 nm, and is fired (prebaked) at 300 ° C for 1 minute, and then Annealing was carried out at 500 ° C for 60 minutes in a reducing gas atmosphere of 100% hydrogen to form a film of a transparent conductive layer. The crystal phase of the film formed here was examined by X-ray diffraction to be a highly crystalline anatase type. Further, the crystal structure was observed to be a polycrystalline body of Nb-doped titanium oxide by TEM-EDX and FE-SEM. -75- 200941506 The transparent conductive substrate thus obtained has a specific resistance of 3.1 χ 1 0_3 Ω · cm, a transmittance of about 8 Ο % in the visible light field, and about 8 Ο % in the infrared field. As a result, in comparison with Examples 1-5 which were the same as those of the above Example 3-1 except that the transparent conductive layer was formed directly on the transparent substrate except that the underlayer was not formed, it was confirmed that the specific resistance was in the above-mentioned Example 3-1. low. (Example 4-1) The titanium peroxygen complex (a 1) obtained in Production Example aq and the ruthenium peroxyl obtained in Production Example bl were mixed at a ratio of titanium: 铌 = 80: 20 (mole ratio). The complex compound (bl) was prepared as a precursor liquid having a solid concentration of 7 wt%. An anatase-type titanium oxide fine particle aqueous dispersion ("TO sol" manufactured by Sigma Co., Ltd., an anatase sol of titanium oxide, an average particle diameter of 10 nm, and a solid content concentration of 1.7% by weight) was added to the precursor liquid. And stirring with a stirrer to obtain a precursor-containing dispersion containing anatase-type titanium oxide fine particles. at this time,

於前驅物液中添加之銳鈦礦型氧化鈦微粒子水分散體 (「TO sol」）之添加量爲以該水分散體中之固成分重量相 U 對於前驅物液之固成分（由固成分濃度計算出之固成分重 量）100重量份成爲1重量份（亦即，所得含前驅物分散體 ： 中之各成分之固成分重量比爲[鈦過氧錯合物（a 1) +鈮過氧 錯合物（bl)]:銳鈦礦型氧化鈦微粒子=100: 1)。 接著，以旋轉塗佈器將上述含前驅物之分散體一次塗 佈於透明基材（無鹼玻璃「康寧公司製造之1 737」，厚度 0.7 mm)上成爲乾膜厚100nm，且在 300°C下燒成（預烘 烤）1〇分鐘，隨後，在100%氫氣之還原氣體氛圍中在 -76- 200941506 5 00 °C下進行退火處理60分鐘，獲得透明導電性基板。以 X射線繞射檢測該透明導電性基板中導電性膜之結晶相爲 高結晶性銳鈦礦型。另外，以TEM-EDX及FE-SEM觀察 其結晶構造爲摻雜Nb之氧化鈦之多結晶體。 所得透明導電性基板之比電阻爲2.5χ1(Γ3Ω . cm，透 過率在可見光領域約80%，紅外線領域約80%。其結果與 除未於前驅物液中添加銳鈦礦型氧化鈦微粒子水分散體以 外其餘與上述實施例4-1相同之實施例1 -5作比較，可明 瞭比電阻於以上述實施例4- 1方面較低。 (實施例5-1) 以旋轉塗佈將製造例al中獲得之鈦過氧錯合物（al) 一次塗佈於透明基材（無鹼玻璃「康寧公司製造之 1 737」，厚度〇.7mm)上成爲乾膜厚20nm，且經風乾（自 然乾燥）後，在空氣中在100°C下加熱1〇分鐘，形成由氧 〇 化鈦之無定型物（該無定型物中之鈮與鉬之含有比率爲0 ' 莫耳％)組成之第一膜。 ： 接著，以成爲鈦：鈮=85 : 15(莫耳比）之比例混合製 造例al中獲得之鈦過氧錯合物（al)及製造例bl獲得之鈮 過氧錯合物（bl)，作成固成分濃度7重量％之前驅物液。 以旋轉塗佈器將該前驅物液一次塗佈於上述第一膜上成爲 乾膜厚100nm，且在3 00°C下加熱10分鐘，形成由氧化鈦 之無定型物（該無定型物中之鈮含有比率爲15莫耳％)組成 之第二膜。 -77- 200941506 隨後，在100%氫氣之還原·氣體氛圍中在420°c下進行 退火處理60分鐘，獲得透明導電性基板。以X射線繞射 檢測該透明導電性基板中導電性膜之結晶相，如圖1中所 示，爲高結晶性銳鈦礦型。另外，以TEM-EDX及FE-SEM觀察其結晶構造爲摻雜Nb之氧化鈦之多結晶體。 所得透明導電性基板之比電阻爲3.3 χ1 0_3Ω · cm，透 . 過率在可見光領域約80%，紅外線領域約80%。其結果與 除未形成第一膜而在透明基材上直接形成第二膜以外其餘 @ 與上述實施例5 -1相同之比較例1 -4作比較，可明瞭比電 阻於上述實施例5 -1方面較低。 (實施例6-1~6-10及比較例6-1〜6-7)The addition amount of the anatase-type titanium oxide fine particle aqueous dispersion ("TO sol") added to the precursor liquid is the solid component of the precursor liquid in the aqueous dispersion (the solid content of the precursor liquid) The weight of the solid component calculated by the concentration is 100 parts by weight to 1 part by weight (that is, the solid content ratio of each component in the obtained precursor-containing dispersion: [titanium peroxy complex (a 1) + 铌Oxygen complex (bl)]: anatase type titanium oxide fine particles = 100: 1). Next, the precursor-containing dispersion was applied to a transparent substrate (an alkali-free glass "1 737" manufactured by Corning Incorporated, thickness 0.7 mm) in a spin coater to have a dry film thickness of 100 nm and at 300 °. The film was fired (prebaked) for 1 minute, and then annealed at -76 to 200941506 5 00 ° C for 60 minutes in a reducing gas atmosphere of 100% hydrogen to obtain a transparent conductive substrate. The crystal phase of the conductive film in the transparent conductive substrate was detected by X-ray diffraction to be a highly crystalline anatase type. Further, the crystal structure of the polycrystalline body doped with Nb-doped titanium oxide was observed by TEM-EDX and FE-SEM. The specific conductivity of the obtained transparent conductive substrate was 2.5 χ 1 (Γ 3 Ω·cm, the transmittance was about 80% in the visible light field, and about 80% in the infrared field. The result was that the anatase-type titanium oxide fine particle water was added to the precursor liquid. In comparison with Examples 1 - 5 which are the same as those of the above Example 4-1 except for the dispersion, it is understood that the specific resistance is lower in the above-mentioned Example 4-1. (Example 5-1) Production by spin coating The titanium peroxygen complex (al) obtained in Example a was applied to a transparent substrate (alkali-free glass "1737" manufactured by Corning Co., Ltd., thickness 〇7 mm) to a dry film thickness of 20 nm, and air-dried (al). After naturally drying, it is heated in air at 100 ° C for 1 minute to form an amorphous material of titanium oxytitanium oxide (the content ratio of cerium to molybdenum in the amorphous material is 0 'mol%). First film: Next, the titanium peroxygen complex (al) obtained in the production example a1 and the peracetic acid miscible obtained in the production example bl were mixed in a ratio of titanium: 铌 = 85: 15 (mole ratio). The substance (bl) was prepared as a precursor liquid having a solid concentration of 7 wt%. The precursor liquid was applied once with a spin coater. The film was formed into a dry film thickness of 100 nm on the first film, and heated at 300 ° C for 10 minutes to form an amorphous material of titanium oxide (the content of ruthenium in the amorphous material was 15 mol%). Second film -77- 200941506 Subsequently, annealing treatment was performed at 420 ° C for 60 minutes in a reduction atmosphere of 100% hydrogen to obtain a transparent conductive substrate. Conduction in the transparent conductive substrate was detected by X-ray diffraction. The crystalline phase of the film is a highly crystalline anatase type as shown in Fig. 1. Further, the crystal structure of the film is observed to be a polycrystalline body of Nb-doped titanium oxide by TEM-EDX and FE-SEM. The specific resistance of the substrate is 3.3 χ1 0_3 Ω · cm, and the transmittance is about 80% in the visible light field and about 80% in the infrared field. The result is that the second film is formed directly on the transparent substrate except that the first film is not formed. The remaining @ comparison with Comparative Example 1-4 of the above Example 5-1 shows that the specific resistance is lower in the above-mentioned Example 5-1. (Examples 6-1 to 6-10 and Comparative Example 6-1) ~6-7)

以成爲鈦：鈮=94 : 6(莫耳比）之比例混合製造例al 中獲得之鈦過氧錯合物（al)及製造例bl獲得之鈮過氧錯 合物（bl)’且以表1中所示之溶劑將所得混合物稀釋成兩 倍（重量比），分別獲得固成分濃度爲4.8重量％之前驅物 Q 液。 將所得各前驅物液置於玻璃製細口瓶中，使瓶口呈開 放狀態，以目視觀察在室溫（20±5°C)下放置24小時之狀 態，藉此評價各前驅物液之儲存安定性。其結果，使用以 上述通式（1)〜（5)表示之溶劑之實施例6-1〜6-10之前驅物 液爲具備有良好儲存安定性者，放置一晚後亦呈安定之黃 色溶液狀態，且未發現凝膠化或白濁。相對於此，使用以 上述通式（1)〜（5)表示之溶劑以外之溶劑之比較例6-1〜6-7 -78- 200941506 之前驅物液之儲存安定性惡化，放置一晚後呈白濁之凝膠 化，成爲例如無法適合供給於塗佈者。 [表1] 溶劑 儲存安定性 實施例6-1 3-甲氧基-1-丁醇湘當於式(1)之溶劑） 良好 實施例6-2 3-甲氧基-3-甲基-1-丁醇湘當於式(1)之溶劑） 良好 實施例6-3 二丙酮醇湘當於式(2)之溶劑） 良好 實施例6-4 γ-丁內酯湘當於式(4)之溶劑） 良好 實施例6-5 4-羥基-2-丁酮湘當於式(2)之溶劑） 良好 實施例6-6 5-羥基-2-丁酮湘當於式⑶之溶劑） 良好 實施例6-7 2-甲基-1,3-丙二醇湘當於式(1)之溶劑） 良好 實施例6-8 四氫呋喃-2-羧酸(相當於式(5)之溶劑） 良好 實施例6-9 δ-戊內酯(相當於式(4)之溶劑） 良好 實施例6-10 ε-己內酯湘當於式(4)之溶劑） 良好 比較例6-1 2-丙醇 不良 比較例6-2 1-乙氧基-2-丙醇 不良 比較例6-3 丙二醇 不良 比較例6-4 二乙二醇 不良 比較例6-5 二乙二醇甲基醚 不良 比較例6-6 聚丙二醇二醇型 不良 比較例6-7 甲酸 不良 接著，以毛細塗佈器將實施例6-1 ~6-10中獲得之各 前驅物液一次塗佈於透明基板（無鹼玻璃「康寧公司製造 之1 73 7」，厚度（K7mm)上，分別成爲表2中所式之乾膜 厚，且在150°C下燒成（預烘烤）30分鐘，隨後，在100%氫 氣之還原氣體氛圍中在5 00°C下進行退火處理60分鐘，分 別獲得透明導電性基板，且測定各透明導電性基板之比電 阻及透過率。結果列於表2。 -79- 200941506 [表2] 乾膜厚 (nm) 比電阻(Ω . cm) 透過 .率 可見光領域 紅外線領域 -實施例6-1 50 4.9x1 〇*3 約80% 約80% 實施例6-2 60 4.5X10'3 約80% 約80% 實施例6-3 48 6.4x10'3 約80% 約80% 實施例&quot; 56 7.8χ10'3 約80% 約80% 實施例6,5 60 5.6χ10'3 約80% 約80% 實施例6-6 72 6.3X10&quot;3 約80% 約80% 實施例6-7 70 5.2χ1〇'3 約80% 約80% 實施例6-8 82 6.4x10'3 約80% 約80% 實施例6-9 54 7.5 χΙΟ·3 約80% 約80% 實施例6-10 55 7.9xl〇'3 約80% 約80% (實施例6-11) 首先，於氬氣氛圍中將4.0克四異丙氧化鈦溶解於 28.5克相當於上述通式（1)之溶劑之3-甲氧基-1-丁醇中， 且在攪拌下將8.0克濃度3 0重量％之過氧化氫水溶液緩慢 添加於所得溶液中，添加結束後，攪拌5分鐘進行過氧化 反應。又，反應於以乾冰在注入有溶液之燒瓶周圍冷卻下 進行，以將因添加過氧化氫水溶液引起發熱時之溶液內溫 控制在不超過-10 °C。如此獲得之反應產物稱爲鈦過氧錯 合物（a3)。 另外，於氬氣氛圍中將1.5克五乙氧化鈮溶解於19.2 克相當於上述通式（1)之溶劑之3-甲氧基-卜丁醇中，且在 攪拌下將1.6克濃度30重量％之過氧化氫緩慢添加於所得 溶液中，添加結束後，攪拌5分鐘進行過氧化反應。又， 反應於以乾冰在注入有溶液之燒瓶周圍冷卻下進行，以將 -80- 200941506 因添加過氧化氫水溶液引起發熱時之溶液內溫控制在不超 過-l〇°C。如此獲得之反應產物稱爲鈮過氧錯合物（b3)。 接著，以成爲鈦：鈮=94 : 6(莫耳比）之比例混合上述 鈦過氧錯合物（a3)及上述鈮過氧錯合物（b3)，作成固成分 濃度9.6重量％之前驅物液。如實施例1般在室溫下將該 . 前驅物液放置一晚後，儲存安定性良好，呈安定之黃色溶 _ 液狀態，且未發現凝膠化或白濁。 φ 接著，以毛細塗佈器將所得前驅物液一次塗佈於透明 基材（無鹼玻璃「康寧公司製造之1 73 7」，厚度0.7mm) 上，且在400°C下燒成（預烘烤）30分鐘後，在100%氫氣之 還原氣體氛圍中在5 00 °C下進行退火處理30分鐘，製備透 明導電性基板。如此獲得之透明導電性基板之乾膜厚爲 40nm，比電阻爲7.3x1 0_3Ω . cm，可見光領域之透過率約 8 0%，紅外線領域之透過率約80%。又，以X射線繞射檢 測該透明導電性基板中導電性膜之結晶相爲銳鈦礦型。 Q 又，以TEM-EDX及FE-SEM觀察其結晶構造爲摻雜Nb 之氧化鈦之多結晶體。 (比較例6-1 1) 在氬氣氛圍中將4.0克四異丙氧化鈦溶解於28.5克 脫水乙醇中，且於所得溶液中添加相對於四異丙氧化鈦爲 等莫耳量之乙醯基丙酮。添加結束後，攪拌5分鐘，獲得 乙醯基丙酮鈦錯合物溶液。 以旋轉塗佈器將所得乙醯基丙酮鈦錯合物溶液一次塗 -81 - 200941506 佈於與實施例6-1相同之透明基板上，且在400°C下燒成 (預烘烤）3〇分鐘後’在100%氫氣之還原氣體氛圍中在 5 00 °C下進行退火處理30分鐘。測定所得膜之比電阻並無 法測定（測定極限；1χ1〇3Ω · cm以上）。 (實施例7-1) _ 以成爲鈦：鈮=93 : 7(莫耳比）之比例混合製造例al 中獲得之鈦過氧錯合物U1)及製造例bl中獲得之鈮過氧 @ 錯合物（bl)，且添加以該混合液中之鈦及鈮之合計作爲 100莫耳時相當於35莫耳量之鹽酸（和光純藥公司製造， 試藥特級，濃度35重量％)，獲得固成分濃度6.5重量％ 之前驅物液。 另外，混合之各過氧化錯合物中之鈦或鈮之莫耳量， 係以在獲得各過氧化錯合物時，所得各過氧化錯合物之總 重量中所佔四異丙氧化鈦使用量或五乙氧化鈮使用量之比 例（重量％)而求得，且以該比例計算出者（以下實施例7-2〜 © 7 - 4，比較例7 -1〜7 - 6中亦同）。 r 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 _* 狀態下，以目視觀察在常溫（20±5°C )下放置4天（96小時） 之狀態後，並未產生凝膠化或白濁等而維持透明之溶液狀 態，由此，可明瞭所得前驅物液爲具備良好儲存安定性 者。 另外，以毛細塗佈器將上述獲得之前驅物液一次塗佈 於透明基板（無鹼玻璃「康寧公司製造之1737」，厚度 -82- 200941506 0.7mm)上成爲乾膜厚35.7nm，且在300°C下燒成（預烘 烤）10分鐘後，在100%氫氣之還原氣體氛圍中在500°c下 進行退火處理60分鐘，獲得透明導電性基板。 所得透明導電性基板之比電阻爲5.1χ10·3Ω · cm，透 過率在可見光領域約8 0%，紅外線領域約80%。又，以X 射線繞射檢測該透明導電性基板中導電性膜之結晶相爲銳 鈦礦型。另外，以TEM-EDX及FE-SEM觀察該結晶構造 爲摻雜Nb之氧化鈦之多結晶體。 (實施例7-2) 以成爲鈦：鈮=93 : 7(莫耳比）之比例混合製造例al 中獲得之鈦過氧錯合物（al)及製造例bl中獲得之鈮過氧 錯合物（bl)，且添加以該混合液中之鈦及鈮之合計作爲 1〇〇莫耳時相當於1〇莫耳量之硝酸（和光純藥公司製造， 試藥特級，濃度65重量％)，獲得固成分濃度6.5重量％ ❹ 之前驅物液。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 *. 狀態，以目視觀察在常溫（20±5°C)下放置4天（96小時）之 狀態後，並未產生凝膠化或白濁等而維持透明之溶液狀 態，由此，可明瞭所得前驅物液爲具備良好儲存安定性 者。 又，以毛細塗佈器將上述獲得之前驅物液一次塗佈於 透明基板（無鹼玻璃「康寧公司製造之1737」，厚度 0.7mm)上成爲乾膜厚35.7nm，且在3 00。(：下燒成（預烘 -83 - 200941506 烤）1〇分鐘後，在100°/。氫氣之還原氣體氛圍中在500°C下 進行退火處理60分鐘，獲得透明導電性基板。 所得透月導電性基板之比電阻爲5.2 χ1 0_3Ω. cm，透 過率在可見光領域約80%，紅外線領域約80%。又，以X 射線繞射檢測該透明導電性基板中導電性膜之結晶相爲銳 鈦礦型。另外，以TEM-EDX及FE-SEM觀察其結晶構造 · 爲摻雜Nb之氧化鈦之多結晶體。 _ ❹ (實施例7-3)The titanium peroxygen complex (al) obtained in the example a1 and the peroxy peroxy complex (bl) obtained in the production example bl were mixed in a ratio of titanium: 铌=94:6 (mole ratio) and The solvent shown in Table 1 was diluted to a two-fold (weight ratio) mixture to obtain a precursor Q liquid having a solid concentration of 4.8% by weight. Each of the obtained precursor liquids was placed in a glass-made fine-mouth bottle, and the mouth of the bottle was opened, and the state of each precursor liquid was evaluated by visual observation at room temperature (20±5° C.) for 24 hours. Stability. As a result, the precursor liquids of Examples 6-1 to 6-10 using the solvents represented by the above formulas (1) to (5) are those having good storage stability, and are also stable yellow after being left for one night. In the solution state, no gelation or white turbidity was observed. On the other hand, in Comparative Example 6-1 to 6-7-78-200941506, which is a solvent other than the solvent represented by the above formulas (1) to (5), the storage stability of the precursor liquid deteriorates, and after leaving for one night, The gelation is white and cloudy, and for example, it is not suitable for application to a coater. [Table 1] Solvent Storage Stability Example 6-1 3-methoxy-1-butanol as a solvent of the formula (1) Good Example 6-2 3-methoxy-3-methyl- 1-butanol is a solvent of formula (1). Good example 6-3 diacetone alcohol is used as a solvent of formula (2). Good example 6-4 γ-butyrolactone is used in formula (4) Solvent) Good Example 6-5 4-Hydroxy-2-butanone as solvent of formula (2) Good Example 6-6 5-Hydroxy-2-butanone as solvent of formula (3) Good Example 6-7 2-Methyl-1,3-propanediol as solvent of formula (1) Good Example 6-8 Tetrahydrofuran-2-carboxylic acid (corresponding to solvent of formula (5)) Good implementation Example 6-9 δ-valerolactone (corresponding to the solvent of the formula (4)) Good Example 6-10 ε-Caprolactone xiang as a solvent of the formula (4) Good Comparative Example 6-1 2-propanol Poor Comparative Example 6-2 1-Ethoxy-2-propanol defective Comparative Example 6-3 Propylene glycol poor Comparative Example 6-4 Diethylene glycol defective Comparative Example 6-5 Diethylene glycol methyl ether poor Comparative Example 6 -6 Polypropylene glycol diol type defect Comparative Example 6-7 Formic acid defect Next, in a capillary coater, Examples 6-1 to 6-10 Each of the precursor liquids was applied to a transparent substrate (alkali-free glass "173 7" manufactured by Corning Incorporated, thickness (K7mm), and became the dry film thickness of Table 2, respectively, at 150 ° C. After baking (prebaking) for 30 minutes, annealing treatment was performed at 500 ° C for 60 minutes in a reducing atmosphere of 100% hydrogen to obtain a transparent conductive substrate, and the specific resistance of each transparent conductive substrate was measured. And the transmittance. The results are shown in Table 2. -79- 200941506 [Table 2] Dry film thickness (nm) Specific resistance (Ω. cm) Transmission rate Radiation field in the visible light field - Example 6-1 50 4.9x1 〇*3 About 80% about 80% Example 6-2 60 4.5X10'3 About 80% About 80% Example 6-3 48 6.4x10'3 About 80% About 80% Example &quot; 56 7.8χ10'3 About 80% About 80% Example 6, 5 60 5.6 χ 10'3 About 80% About 80% Example 6-6 72 6.3X10&quot;3 About 80% About 80% Example 6-7 70 5.2χ1〇'3 About 80% About 80% Example 6-8 82 6.4x10'3 About 80% About 80% Example 6-9 54 7.5 χΙΟ·3 About 80% About 80% Example 6-10 55 7.9xl〇'3 About 80% About 80 % (Examples 6-11) First, 4.0 g of four in an argon atmosphere The titanium oxychloride is dissolved in 28.5 g of 3-methoxy-1-butanol corresponding to the solvent of the above formula (1), and 8.0 g of a 30% by weight aqueous solution of hydrogen peroxide is slowly added thereto under stirring. In the obtained solution, after the addition was completed, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction was carried out by cooling the dry ice around the flask to which the solution was poured, so that the internal temperature of the solution when the heat was caused by the addition of the aqueous hydrogen peroxide solution was not more than -10 °C. The reaction product thus obtained is referred to as titanium peroxygen compound (a3). Separately, 1.5 g of pentaethoxy ruthenium oxide was dissolved in 19.2 g of 3-methoxy-butanol corresponding to the solvent of the above formula (1) under an argon atmosphere, and 1.6 g of a concentration of 30 wt. % of hydrogen peroxide was slowly added to the obtained solution, and after completion of the addition, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction was carried out under cooling with dry ice around the flask in which the solution was poured, so that the internal temperature of the solution when -80-200941506 caused by the addition of the aqueous hydrogen peroxide solution was controlled to not exceed -10 °C. The reaction product thus obtained is referred to as a peroxyl complex (b3). Next, the titanium peroxy complex (a3) and the above-mentioned peroxy peroxy complex (b3) were mixed at a ratio of titanium: 铌 = 94:6 (mole ratio) to prepare a solid concentration of 9.6 wt%. Liquid. The precursor liquid was allowed to stand at room temperature for one night as in Example 1, and the storage stability was good, and it was in a stable yellow solution state, and no gelation or white turbidity was observed. φ Next, the obtained precursor liquid was applied to a transparent substrate (alkali-free glass "73 7" manufactured by Corning Incorporated, thickness 0.7 mm) by a capillary coater, and fired at 400 ° C (pre-pre After baking for 30 minutes, annealing treatment was performed at 500 ° C for 30 minutes in a reducing gas atmosphere of 100% hydrogen to prepare a transparent conductive substrate. The transparent conductive substrate thus obtained had a dry film thickness of 40 nm, a specific resistance of 7.3 x 1 0_3 Ω·cm, a transmittance of about 80% in the visible light region, and a transmittance of about 80% in the infrared region. Further, the crystal phase of the conductive film in the transparent conductive substrate was examined by X-ray diffraction to be anatase. Q Further, a polycrystalline body having a crystal structure of Nb-doped titanium oxide was observed by TEM-EDX and FE-SEM. (Comparative Example 6-1 1) 4.0 g of titanium tetraisopropoxide was dissolved in 28.5 g of dehydrated ethanol under an argon atmosphere, and an equivalent amount of acetamidine was added to the obtained solution with respect to titanium tetraisopropoxide. Acetone. After the end of the addition, the mixture was stirred for 5 minutes to obtain a solution of the titanium acetalacetate complex. The obtained solution of titanium acetylacetonate complex was applied to the same transparent substrate as in Example 6-1 by a spin coater at one time, and baked (prebaked) at 400 ° C. After 〇 minute, it was annealed at 500 ° C for 30 minutes in a reducing atmosphere of 100% hydrogen. The specific resistance of the obtained film was measured and measured (measurement limit; 1 χ 1 〇 3 Ω · cm or more). (Example 7-1) _ The titanium peroxygen compound U1 obtained in the production example a1 was mixed in a ratio of titanium: 铌 = 93: 7 (mole ratio) and the ruthenium peroxygen obtained in the production example bl@ a complex compound (bl), and a total of 35 mols of hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd., a reagent grade, a concentration of 35 wt%) in a total of 100 mols of titanium and niobium in the mixture, A precursor liquid having a solid concentration of 6.5% by weight was obtained. In addition, the molar amount of titanium or ruthenium in each of the peroxidized complexes is such that tetraisopropoxide is occupied by the total weight of each of the peroxidized complexes obtained when each peroxidation complex is obtained. The amount of use or the ratio of the amount of pentoxide used (% by weight) was obtained and calculated by the ratio (the following examples 7-2 to © 7 - 4, and the comparative examples 7 -1 to 7 - 6) with). r The obtained precursor liquid was placed in a glass vial, and the mouth of the bottle was opened in a state of _*, and visually observed after being left at room temperature (20 ± 5 ° C) for 4 days (96 hours), It is understood that the obtained precursor liquid is in a state in which it has a good storage stability by causing gelation, turbidity, or the like to maintain a transparent solution state. Further, the above-obtained precursor liquid was applied to a transparent substrate (1737, manufactured by Corning Incorporated, thickness -82 - 200941506 0.7 mm) by a capillary coater to have a dry film thickness of 35.7 nm, and After firing (prebaking) at 300 ° C for 10 minutes, annealing treatment was performed at 500 ° C for 60 minutes in a reducing gas atmosphere of 100% hydrogen to obtain a transparent conductive substrate. The specific resistance of the obtained transparent conductive substrate was 5.1 χ 10·3 Ω · cm, the transmittance was about 80% in the visible light field, and about 80% in the infrared field. Further, the crystal phase of the conductive film in the transparent conductive substrate was detected by X-ray diffraction to be anatase. Further, the crystal structure was observed to be a polycrystalline body of Nb-doped titanium oxide by TEM-EDX and FE-SEM. (Example 7-2) The titanium peroxygen complex (al) obtained in Production Example a1 and the hydrazine peroxygen obtained in Production Example bl were mixed at a ratio of titanium: 铌 = 93:7 (mole ratio). (bl), and the total amount of titanium and lanthanum in the mixture is 1 〇〇 mol, which is equivalent to 1 〇 mol of nitric acid (manufactured by Wako Pure Chemical Industries Co., Ltd., special grade, concentration 65 wt% ), obtaining a solid concentration of 6.5% by weight of 之前 precursor liquid. The obtained precursor liquid was placed in a glass-made fine-mouth bottle, and the mouth of the bottle was opened*. The state was observed by visual observation at a normal temperature (20±5° C.) for 4 days (96 hours), and no coagulation occurred. It is clear that the obtained precursor liquid is in a state in which it has a good storage stability by gelation or turbidity. Further, the precursor liquid obtained above was applied to a transparent substrate (1737, manufactured by Corning Incorporated, thickness: 0.7 mm) by a capillary applicator to have a dry film thickness of 35.7 nm and a thickness of 300 Å. (: Baked (pre-baked -83 - 200941506) After 1 minute, the film was annealed at 500 ° C for 60 minutes in a reducing atmosphere of hydrogen gas of 100 ° C to obtain a transparent conductive substrate. The specific resistance of the conductive substrate is 5.2 χ1 0_3 Ω·cm, the transmittance is about 80% in the visible light field, and about 80% in the infrared field. Further, the crystal phase of the conductive film in the transparent conductive substrate is sharply detected by X-ray diffraction. Titanium ore type. The crystal structure of the titanium oxide doped with Nb was observed by TEM-EDX and FE-SEM. _ ❹ (Example 7-3)

首先，於氬氣中將4.0克四異丙氧化鈦溶解於50.5 克3-甲氧基-1-丁醇中，且在攪拌下將1.6克濃度30重量 %之過氧化氫水溶液緩慢添加於所得溶液中，添加結束 後，攪拌5分鐘進行過氧化反應。又，反應於以乾冰在注 入有溶液之燒瓶周圍冷卻下進行，以將因添加過氧化氫水 溶液引起發熱時之溶液內溫控制在不超過-1 〇°C。如此獲 得之反應產物稱爲鈦過氧錯合物（a4)。 Q 另外，於氬氣中將1.5克五乙氧化鈮溶解於7.1克脫 ， 水乙醇及12克3 -甲氧基-1-丁醇之混合溶劑中，且在攪拌 ： 下將1.6克濃度30重量％之過氧化氫緩慢添加於所得溶液 中，添加結束後，攪拌5分鐘進行過氧化反應。又’反應 於以乾冰在注入有溶液之燒瓶周圍冷卻下進行，以將因添 加過氧化氫水溶液引起發熱時之溶液內溫控制在不超過_ l〇°C。如此獲得之反應產物稱爲鈮過氧錯合物（b4)。 以成爲鈦：鈮= 80: 20(莫耳比）之比例混合上述鈦過 -84- 200941506 氧錯合物（a4)及上述鈮過氧錯合物（b4)，且添加以該混合 液中之鈦及鈮之合計作爲1〇〇莫耳時相當於100莫耳量之 硝酸（和光純藥公司製造，試藥特級，濃度65重量％)，獲 得固成分濃度1 5重量％之前驅物液。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 - 狀態，以目視觀察在常溫（20±5°C)下放置4天（96小時）之 . 狀態後，並未產生凝膠或白濁等而維持透明之溶液狀態。 φ 由此，可明瞭所得前驅物液爲具備良好儲存安定性者。 另外，以旋轉塗佈器將上述獲得之前驅物液一次塗佈 於透明基板（無鹼玻璃「康寧公司製造之1737」，厚度 0.7mm)上成爲乾膜厚60nm，且在300 °C下燒成（預烘烤）1〇 分鐘後，在100%氫氣之還原氣體氛圍中在500°C下進行退 火處理60分鐘，獲得透明導電性基板。 所得透明導電性基板之比電阻爲5.0χ10_3Ω · cm，透 過率在可見光領域約8 0%，紅外線領域約80%。又，以X φ 射線繞射檢測該透明導電性基板中導電性膜之結晶相爲銳 鈦礦型。另外，以TEM-EDX及FE-SEM觀察其結晶構造 ' 爲摻雜Nb之氧化鈦之多結晶體。 (實施例7-4) 以成爲鈦：鈮=80 : 20(莫耳比）之比例混合與實施例 7-3同樣獲得之鈦過氧錯合物（a4)及與實施例7-3同樣獲 得之鈮過氧錯合物（b4)，且添加以該混合液中之鈦及鈮之 合計作爲100莫耳時相當於25莫耳量之硝酸（和光純藥公 -85- 200941506 司製造，試藥特級’濃度65重量％)，獲得固成分濃度 7.0 5重量％之前驅物液。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態，以目視觀察在常溫（2〇±5°C)下放置14天之狀態 後，並未產生凝膠化或白濁等而維持透明之溶液狀態。由 此，可明瞭所得前驅物液爲具備良好儲存安定性者。 · 另外，以旋轉塗佈器將上述獲得之前驅物液一次塗佈 . 於透明基板（無鹼玻璃「康寧公司製造之1 73 7」，厚度 0 0.7mm)上成爲乾膜厚50nm，且在300°C下燒成（預烘烤）1〇 分鐘後，在1〇〇%氫氣之還原氣體氛圍中在500°C下進行退 火處理60分鐘，獲得透明導電性基板。 所得透明導電性基板之比電阻爲5.〇xlO_3n.Cm，透 過率在可見光領域約80%，紅外線領域約80%。又，以X 射線繞射檢測該透明導電性基板中導電性膜之結晶相爲銳 鈦礦型。另外，以TEM-EDX及FE-SEM觀察其結晶構造 爲摻雜Nb之氧化鈦之多結晶體。 ◎ (參考例7-1) ； 以成爲鈦：鈮=93 : 7(莫耳比）之比例混合製造例al 中獲得之鈦過氧錯合物（al)及製造例bl中獲得之鈮過氧 錯合物（bl)’獲得固成分濃度7.0重量％之前驅物液。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態’且在常溫（20±5°C)下放置，約4小時後以目視觀察 到凝膠化。亦即’所得前驅物液可於常溫下使用時間（可 -86- 200941506 使用時間）約爲4小時。 (比較例7-1) 以成爲鈦：鈮=93 : 7(莫耳比）之比例混合製造例al 中獲得之鈦過氧錯合物（al)及製造例bl中獲得之鈮過氧 . 錯合物（bl)，且添加以該混合液中之鈦及鈮之合計作爲 . 1〇〇莫耳時相當於20莫耳量之硫酸（和光純藥公司製造， φ 試藥特級，濃度96重量％)，獲得固成分濃度6.5重量％ 之前驅物液。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態，以目視觀察在常溫（20±5°C)下放置4天（96小時）時 之狀態後，未產生凝膠化或白濁等而維持透明溶液狀態。 又’以毛細塗佈器將上述獲得之前驅物液一次塗佈於 透明基板（無鹼玻璃「康寧公司製造之1737」，厚度 0.7mm)上成爲乾膜厚35.7nm，且在300°C下燒成（預烘 Q 烤分鐘後，在100%氫氣之還原氣體氛圍中在50(TC下 進行退火處理6 0分鐘，獲得透明導電性基板。 - 所得透明導電性基板之比電阻爲測定極限（1 X 1 03Ω · cm以上），透過率在可見光領域約80%，紅外線領域約 8 0%。又，以X射線繞射檢測該透明導電性基板中導電性 膜之結晶相爲銳鈦礦型。 (比較例7 - 2) 以成爲鈦：鈮=93 : 7(莫耳比）之比例混合製造例al -87- 200941506 中獲得之鈦過氧錯合物（al)及製造例bl中獲得之鈮過氧 錯合物（bl)，且添加以該混合液中之鈦及鈮之合計作爲 1〇〇莫耳時相當於莫耳量之檸檬酸（和光純藥公司製 造’試藥特級，濃度98重量％)，獲得固成分濃度6.5重 量％之前驅物液。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 . 狀態，以目視觀察在常溫（20±5°C)下放置4天（96小時）時 之狀態後，未產生凝膠化或白濁等而維持透明溶液狀態》 @ 又，以毛細塗佈器將上述獲得之前驅物液一次塗佈於 透明基板（無鹼玻璃「康寧公司製造之1737」，厚度 0.7mm)上成爲乾膜厚 35.7nm，且在30(TC下燒成（預烘 烤）1〇分鐘後，在100%氫氣之還原氣體氛圍中在500°C下 進行退火處理60分鐘，獲得透明導電性基板。 所得透明導電性基板之比電阻爲測定極限（1 X 1 〇3 Ω · cm以上），透過率在可見光領域約70%，紅外線領域約 70%。又，以X射線繞射檢測該透明導電性基板中導電性 @ 膜之結晶相爲銳鈦礦型。 y (比較例7-3) 以成爲鈦：鈮=93:7(莫耳比）之比例混合製造例al 中獲得之鈦過氧錯合物（al)及製造例bl中獲得之鈮過氧 錯合物（bl)，且添加以該混合液中之鈦及鈮之合計作爲 100莫耳時相當於20莫耳量之草酸（和光純藥公司製造， 試藥特級，濃度98重量％)，獲得固成分濃度6.5重量％ -88- 200941506 之前驅物液。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態，以目視觀察在常溫（2〇±5°C)下放置4天（96小時）時 之狀態後，未產生凝膠化或白濁等而維持透明之溶液狀 態。 . 又，以毛細塗佈器將上述獲得之前驅物液一次塗佈於 透明基板（無鹼玻璃「康寧公司製造之1737」，厚度 0 〇.7mm)上成爲乾膜厚35.7nm，且在3 00。(：下燒成（預烘 烤）1〇分鐘後，在100%氫氣之還原氣體氛圍中在500°c下 進行退火處理60分鐘，獲得透明導電性基板。 所得透明導電性基板之比電阻爲測定極限（1 X 1 〇3 Ω · cm以上），透過率在可見光領域約7〇%，紅外線領域約 70%。又’以X射線繞射檢測該透明導電性基板中導電性 膜之結晶相爲銳鈦礦型。 0 (比較例7 - 4) ' 以成爲欽：鈮=93 : 7(莫耳比）之比例混合製造例al ' 中獲得之欽過氧錯合物（a 1)及製造例bl中獲得之鈮過氧 錯合物（b 1)’且添加以該混合液中之鈦及鈮之合計作爲 1〇〇莫耳時相當於25莫耳量之乳酸（和光純藥公司製造， 試藥特級’濃度85〜92重量％)，獲得固成分濃度6.5重量 %之前驅物液。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態，以目視觀察在常溫（2〇±5。〇下放置丨天（24小時）時 -89- 200941506 之狀態後，未產生凝膠化或白濁等而維持透明溶液狀態。 又，以毛細塗佈器將上述獲得之前驅物液一次塗佈於 透明基板（無鹼玻璃「康寧公司製造之 1737」，厚度 0.7mm)上成爲乾膜厚 35.7nm，且在 3 00°C下燒成（預烘 烤）1〇分鐘後，在100%氫氣之還原氣體氛圍中在500°C下 進行退火處理60分鐘，獲得透明導電性基板。 所得透明導電性基板之比電阻爲測定極限（1 X 1 Ο3 Ω . cm以上），透過率在可見光領域約70%，紅外線領域約 7 0 %。又，以X射線繞射檢測該透明導電性基板中導電性 膜之結晶相爲銳鈦礦型。 (比較例7-5) 以成爲鈦：鈮=93 : 7(莫耳比）之比例混合製造例ai 中獲得之鈦過氧錯合物（al)及製造例bl中獲得之鈮過氧 錯合物（bl)’且添加以該混合液中之鈦及鈮之合計作爲 100莫耳時相當於20莫耳量之乙酸（和光純藥公司製造， 試藥特級，濃度9 9 · 9重量％)，獲得固成分濃度6.5重量％ 之前驅物液。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態’以目視觀察在常溫（2 0 ± 5。(：）下放置1天（2 4小時）時 之狀態後’未產生凝膠化或白濁等而維持透明溶液狀態。 另外’以毛細塗佈器將上述獲得之前驅物液一次塗佈 於透明基板（無驗玻璃「康寧公司製造之1737」，厚度 0.7mm)上成爲乾膜厚35.7nm，且在300。(：下燒成（預烘 -90- 200941506 烤）1〇分鐘後，在100%氫氣之還原氣體氛圍中在500°C下 進行退火處理60分鐘，獲得透明導電性基板。 所得透明導電性基板之比電阻爲測定極限（1x1 03Ω · cm以上），透過率在可見光領域約70%，紅外線領域約 7 0%。又，以X射線繞射檢測該透明導電性基板中導電性 膜之結晶相爲銳鈦礦型。 φ (實施例8-1) 於氬氣氛圍中將0.75克五乙氧化鈮溶解於9.56克脫 水乙醇中，攪拌下將0.8克濃度30重量％之過氧化氫水溶 液（相對於五乙氧化鈮1莫耳相當於3.0莫耳之過氧化氫） 緩慢添加於所得溶液中，添加結束後，攪拌5分鐘進行過 氧化反應。又，反應於以乾冰在注入有溶液之燒瓶周圍冷 卻下進行，以將因添加過氧化氫水溶液引起發熱時之溶液 內溫控制在不超過-l〇°C。如此獲得之固成分濃度6.75重 ❹ 量％之反應產物稱爲膜形成用前驅物液（1)。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 ' 狀態，以目視觀察在常溫（20±5°C)下放置15天時之狀態 後，並未產生凝膠化或白濁等而維持透明之溶液狀態。 (實施例8-2) 與實施例8 · 1相同除以固成分濃度改變相對於鈮化合 物之過氧化氫之量以外，其餘如實施例8-1般製造膜形成 用前驅物液。 -91 - 200941506 亦即，於氬氣中將0.75克五乙氧化鈮溶解於9.69克 脫水乙醇中，攪拌下將0.67克濃度30重量％之過氧化氫 水溶液（相對於五乙氧化鈮1莫耳相當於2.5莫耳之過氧 化氫）緩慢添加於所得溶液中，添加結束後，攪拌5分鐘 進行過氧化反應。又，反應係如實施例8· 1般以乾冰在注 入有溶液之燒瓶周圍冷卻下進行，以將因添加過氧化氫水 溶液引起發熱時之溶液內溫控制在不超過-1 〇°C。如此獲 得之固成分濃度6.75重量％之反應產物稱爲膜形成用前驅 物液（2)。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態，以目視觀察在常溫（20±5°C)下放置15天時之狀態 後，並未產生凝膠化或白濁等而維持透明溶液狀態。 (實施例8-3) 與實施例8-1相同除以固成分濃度改變相對於鈮化合 物之過氧化氫之量以外，其餘如實施例8-1般製造膜形成 用前驅物液。 亦即，於氬氣氛圍中將0.75克五乙氧化鈮溶解於 9.43克脫水乙醇中，攪拌下將0.93克濃度30重量％之過 氧化氫水溶液（相對於五乙氧化鈮1莫耳相當於3.5莫耳 之過氧化氫）緩慢添加於所得溶液中，添加結束後，攪拌 5分鐘進行過氧化反應。又，反應係如實施例8-1般以乾 冰在注入有溶液之燒瓶周圍冷卻下進行，以將因添加過氧 化氫水溶液引起發熱時之溶液內溫控制在不超過-10°C。 200941506 如此獲得之固成分濃度6.75重量％之反應產物稱爲膜形成 用前驅物液（3 )。 將所得前驅物液置於^玻璃製細口瓶中，使瓶口呈開放 狀態’以目視觀察在常溫（20±5。〇下放置15天時之狀態 後’並未產生凝膠化或白濁等而維持透明之溶液狀態。 (比較例8 -1) ❻ 與實施例8-1相同除以固成分濃度改變相對於鈮化合 物之過氧化氫量於本發明範圍外之量以外，其餘如實施例 8-1般製造膜形成用前驅物液。 亦即’於氬氣中將0.75克五乙氧化鈮溶解於9.82克 脫水乙醇中’攪拌下將0.54克濃度30重量％之過氧化氫 水溶液（相對於五乙氧化鈮1莫耳相當於2.0莫耳之過氧 化氫）緩慢添加於所得溶液中，添加結束後，攪拌5分鐘 進行過氧化反應。又，反應係如實施例8 · 1般以乾冰在注 ❹ 入有溶液之燒瓶周圍冷卻下進行，以將因添加過氧化氫水 ： 溶液引起發熱時之溶液內溫控制在不超過-10 °c。如此獲 ' 得之固成分濃度6.75重量％之反應產物稱爲膜形成用前驅 物液（C1)。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態’在常溫（2〇±5°C)下放置，4天後以目視觀察到凝膠 化。亦即，所得前驅物液之常溫下可使用時間（可利用時 間）未達4天。 -93- 200941506 (比較例8-2) 與實施例8 -1相同除以固成分濃度改變相對於鈮化合 物之過氧化氫量於本發明範圍外之量以~外，其餘如實施例 8-1般製造膜形成用前驅物液。 亦即，於氬氣氛圍中將 0.7 5克五乙氧化鈮溶解於 1.35克脫水乙醇中，攪拌下將9.01克濃度30重量％之過 市 氧化氫水溶液（相對於五乙氧化鈮1莫耳相當於5.0莫耳 之過氧化氫）緩慢添加於所得溶液中，添加結束後，攪拌 0 5分鐘進行過氧化反應。又，反應係如實施例8-1般以乾 冰在注入有溶液之燒瓶周圍冷卻下進行，以將因添加過氧 化氫水溶液引起發熱時之溶液內溫控制在不超過-1 〇 °C。 如此獲得之固成分濃度6.75重量％之反應產物稱爲膜形成 用前驅物液（C2)。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態，在常溫（20±5°C)下放置，6小時後以目視觀察到凝 膠化。亦即，所得前驅物液之常溫下可使用時間（可利用 © 時間）未達6小時。 ， (實施例8-4) 與實施例8-1相同除以固成分濃度及相對於鈮化合物 之過氧化氫量，改變溶劑組成以外，其餘如實施例8 -1般 製造膜形成用前驅物液。 亦即，於氬氣中將〇·75克五乙氧化鈮溶解於7.56克 脫水乙醇及2克3-甲氧基-1-丁醇之混合溶劑中，且在攪 -94- 200941506 拌下將0.8克濃度30重量％之過氧化氫水溶液（相對於五 乙氧化鈮1莫耳相當於3.0莫耳之過氧化氫）緩慢添加於 所得溶液中，添加結束後，攪挫5分鐘進行過氧化反應。 又，反應係如實施例8-1般以乾冰在注入有溶液之燒瓶周 圍冷卻下進行，以將因添加過氧化氫水溶液引起發熱時之 - 溶液內溫控制在不超過-l〇t。如此獲得之固成分濃度 • 6.75重量％之反應產物作爲膜形成用前驅物液（4)。 φ 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態，以目視觀察在常溫（20±5°C)下放置20天時之狀 態，未產生凝膠化或白濁等而維持透明溶液狀態。 (實施例8 - 5) 與實施例8-1相同除以固成分濃度及相對於鈮化合物 之過氧化氫量下，改變溶劑組成以外，其餘如實施例8-1 般製造膜形成用前驅物液。 φ 亦即，於氬氣中將0.75克五乙氧化鈮溶解於5.56克 脫水乙醇及4克3-甲氧基-1-丁醇之混合溶劑中，且在攪 拌下將〇.8克濃度30重量％之過氧化氫水溶液（相對於五 乙氧化鈮1莫耳相當於3.0莫耳之過氧化氫）緩慢添加於 所得溶液中，添加結束後，攪拌5分鐘進行過氧化反應。 又，反應係如實施例8-1般以乾冰在注入有溶液之燒瓶周 圍冷卻下進行，以將因添加過氧化氫水溶液引起發熱時之 溶液內溫控制在不超過-10°C。如此獲得之固成分濃度 6.75重量％之反應產物稱爲膜形成用前驅物液（5)。 -95- 200941506 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態，以目視觀察在常溫（20±5°C)下放置30天時之狀 態，未產生凝膠化或白濁等而維持透明溶液狀態。 (實施例8-6) 與實施例8-1相同除以固成分濃度及相對於鈮化合物 . 之過氧化氫量下，改變溶劑組成以外，其餘如實施例8-1 般製造膜形成用前驅物液。 @ 亦即，於氬氣中將0.75克五乙氧化鈮溶解於3.56克 脫水乙醇及6克3 -甲氧基-1-丁醇之混合溶劑中，在攪拌 下將〇·8克濃度30重量。/。之過氧化氫水溶液（相對於五乙 氧化鈮1莫耳相當於3.0莫耳之過氧化氫）緩慢添加於所 得溶液中’添加結束後，攪拌5分鐘進行過氧化反應。 又，反應係如實施例8-1般以乾冰在注入有溶液之燒瓶周 圍冷卻下進行’以將因添加過氧化氫水溶液引起發熱時之 溶液內溫控制在不超過-1 0 °C。如此獲得之固成分濃度 0 6.75重量％之反應產物作爲膜形成用前驅物液（6)。 〃 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 ： 狀態’以目視觀察在常溫（20±5。〇下放置30天時之狀 態’未產生凝膠化或白濁等而維持透明之溶液狀態。 (實施例8 - 7) 與實施例8-1相同除以固成分濃度及相對於鈮化合物 之過氧化氫量下，改變溶劑組成以外，其餘如實施例8 -1 -96- 200941506 般製造膜形成用前驅物液。 亦即，於氬氣氛圍中將0.75克五乙氧化鈮溶解於 2.56克脫水乙醇及7克3 -甲氧基-1-丁醇之混合溶劑中， 攪拌下將0.8克濃度30重量％之過氧化氫水溶液（相對於 五乙氧化鈮1莫耳相當於3.0莫耳之過氧化氫）緩慢添加 . 於所得溶液中’添加結束後，攪拌5分鐘進行過氧化反 . 應。又，反應係如實施例8-1般以乾冰在注入有溶液之燒 ❹ 瓶周圍冷卻下進行’以將因添加過氧化氫水溶液引起發熱 時之溶液內溫控制在不超過-1 0°C。如此獲得之固成分濃 度6.75重量％之反應產物作爲膜形成用前驅物液（7)。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態，以目視觀察在常溫（2 0±5°C)下放置30天時之狀 態，未產生凝膠化或白濁等而維持透明之溶液狀態。 (實施例8-8) 〇 與實施例8 -1相同除以固成分濃度及相對於鈮化合物 ' 之過氧化氫量下，改變溶劑組成以外，其餘如實施例8-1 般製造膜形成用前驅物液。 亦即，於氬氣中將0.75克五乙氧化鈮溶解於9.56克 3-甲氧基-1-丁醇中，攪拌下將0.8克濃度30重量％之過 氧化氫水溶液（相對於五乙氧化鈮1莫耳相當於3.0莫耳 之過氧化氫）緩慢添加於所得溶液中，添加結束後，攪拌 5分鐘進行過氧化反應。又，反應係如實施例8-1般以乾 冰在注入有溶液之燒瓶周圍冷卻下進行，以將因添加過氧 -97- 200941506 化氫水溶液引起發熱時之溶液內溫控制在不超過-1 〇 °c。 如此獲得之固成分濃度6.75重量％之反應產物稱爲膜形成 用前驅物液（8)。 . 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態，以目視觀察在常溫（20±5°C)下放置30天時之狀 態，未產生凝膠化或白濁等而維持透明之溶液狀態。 (實施例8-9) 與實施例8-1相同除以相對於鈮化合物之過氧化氫 量，改變溶劑組成及量且提高固成分濃度以外，其餘如實 施例8 -1般製造膜形成用前驅物液。 亦即，於氬氣氛圍中將0.75克五乙氧化鈮溶解於 2.56克脫水乙醇及6克3-甲氧基-1-丁醇之混合溶劑中， 攪拌下將0.8克濃度30重量％之過氧化氫水溶液（相對於 五乙氧化鈮1莫耳相當於3.0莫耳之過氧化氫）緩慢添加 於所得溶液中，添加結束後，攪拌5分鐘進行過氧化反 應。又，反應係如實施例8_ 1般以乾冰在注入有溶液之燒 瓶周圍冷卻下進行，以將因添加過氧化氫水溶液引起發熱 時之溶液內溫控制在不超過_ 1 〇 °C。如此獲得之固成分濃 度7.41重量％之反應產物稱爲膜形成用前驅物液（9)。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態，以目視觀察在常溫（2 0±5t)下放置30天時之狀 態，未產生凝膠化或白濁等而維持透明之溶液狀態。 -98- 200941506 (實施例8-10) 與實施例8-1相同除以相對於鈮化合物之過氧化氫 量，改變溶劑組成及量且提高固成分濃度以外，其餘如實 施例8-1般製造膜形成用前驅物液。 亦即，於氬氣氛圍中將0.75克五乙氧化鈮溶解於8 克3-甲氧基-1·丁醇中，攪拌下將0.8克濃度30重量％之 ， 過氧化氫水溶液（相對於五乙氧化鈮1莫耳相當於3.0莫 0 耳之過氧化氫）緩慢添加於所得溶液中，添加結束後，攪 拌5分鐘進行過氧化反應。又，反應係如實施例8-1般以 乾冰在注入溶液之燒瓶周圍冷卻下進行，以將因添加過氧 化氫水溶液引起發熱時之溶液內溫控制在不超過-1 0°C。 如此獲得之固成分濃度7.85重量％之反應產物稱爲膜形成 用前驅物液（1 0)。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態，以目視觀察在常溫（2 0± 5 °C)下放置15天時之狀 Q 態，未產生凝膠化或白濁等而維持透明之溶液狀態。 (比較例8 - 3 ) 與實施例8-1相同除以相對於鈮化合物之過氧化氫 量，改變溶劑組成及量使固成分濃度在本發明範圍外以 外，其餘如實施例8-1般製造膜形成用前驅物液。 亦即，於氬氣氛圍中將0.75克五乙氧化鈮溶解於7 克3-甲氧基-1-丁醇中，攪拌下將0.8克濃度30重量％之 過氧化氫水溶液（相對於五乙氧化鈮1莫耳相當於3.0莫 -99- 200941506 耳之過氧化氫）緩慢添加於所得溶液中，添加結束後，攪 拌5分鐘進行過氧化反應。而且，反應係如實施例8-1般 以乾冰在注入有溶液之燒瓶周圍冷卻下進行，以將因添加 過氧化氫水溶液引起發熱時之溶液內溫控制在不超過-10 °C。如此獲得之固成分濃度8.77重量％之反應產物稱爲 膜形成用前驅物液（C3)。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態，在常溫（20±5°C)下放置，一天（24小時）後以目視觀 察到凝膠化。亦即，所得前驅物液之常溫可使用時間（可 利用時間）未達一天。 (實施例8-1 1) 於氬氣氛圍中將0.4克五乙氧化鉬溶解於3.1克脫水 乙醇及2克3 -甲氧基-1· 丁醇之混合溶劑中，攪拌下將 0.34克濃度30重量％之過氧化氫水溶液（相對於五乙氧化 钽1莫耳相當於3.0莫耳之過氧化氫）緩慢添加於所得溶 液中，添加結束後，攪拌5分鐘進行過氧化反應。又，反 應係以乾冰在注入有溶液之燒瓶周圍冷卻下進行，以將因 添加過氧化氫水溶液引起發熱時之溶液內溫控制在不超 過-1 〇 °C。如此獲得之固成分濃度6.7 5重量％之反應產物 稱爲膜形成用前驅物液（11)。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態，以目視觀察在常溫（2 0±5°C)下放置20天時之狀 態’未產生凝膠化或白濁等而維持透明之溶液狀態。 -100- 200941506 (實施例8-12) 與實施例8-1 1相同除以固成分濃度改變相對於钽化 合物之過氧化氫量以外，其餘如實施例8-11般製造膜形 成用前驅物液。 . 亦即，於氬氣氛圍中將0.4克五乙氧化鉬溶解於3.17 ， 克脫水乙醇及2.0克3-甲氧基-1-丁醇之混合溶劑中，攪 0 拌下將〇·27克濃度30重量％之過氧化氫水溶液（相對於五 乙氧化鉬1莫耳相當於2.5莫耳之過氧化氫）緩慢添加於 所得溶液中，添加結束後，攪拌5分鐘進行過氧化反應。 又，反應係以乾冰在注入有溶液之燒瓶周圍冷卻下進行， 以將因添加過氧化氫水溶液引起發熱時之溶液內溫控制在 不超過-10°C。如此獲得之固成分濃度6.75重量％之反應 產物稱爲膜形成用前驅物液（12)。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 Q 狀態，以目視觀察在常溫（20±5t)下放置10天時之狀 ' 態，未產生凝膠化或白濁等而維持透明之溶液狀態。 (實施例8-13) 與實施例8 -1 1相同除以固成分濃度改變相對於鉬化 合物之過氧化氫量以外，其餘如實施例8_n般製造膜形 成用前驅物液。 亦即，於氬氣氛圍中將〇.4克五乙氧化鉅溶解於2.94 克脫水乙醇及2.0克3 -甲氧基-1-丁醇之混合溶劑中’攪 -101 - 200941506 拌下將0.5克濃度30重量％之過氧化氫水溶液（相對於五 乙氧化鉅1莫耳相當於3.5莫耳之過氧化氫）緩慢添加於 所得溶液中，添加結束後，攪拌5分鐘進行過氧化反應。 又，反應係以乾冰在注入有溶液之燒瓶周圍冷卻下進行， 以將因添加過氧化氫水溶液引起發熱時之溶液內溫控制在 不超過-10°C。如此獲得之固成分濃度6.75重量％之反應 產物稱爲膜形成用前驅物液（13)。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態，以目視觀察在常溫（2 0±5°C)下放置10天時之狀 態，未產生凝膠化或白濁等而維持透明之溶液狀態。 (比較例8-4) 與實施例8- 1 1相同除以固成分濃度改變相對於鉬化 合物之過氧化氫量於本發明範圍外以外，其餘如實施例 8-11般製造膜形成用前驅物液。 亦即，於氬氣氛圍中將〇·4克五乙氧化鉅溶解於2.2 克脫水乙醇及3.1克3 -甲氧基-1-丁醇之混合溶劑中，攪 拌下將0.1 4克濃度3 0重量％之過氧化氫水溶液（相對於五 乙氧化鉅1莫耳相當於1.25莫耳之過氧化氫）緩慢添加於 所得溶液中，添加結束後，攪拌5分鐘進行過氧化反應。 又，反應係以乾冰在注入有溶液之燒瓶周圍冷卻下進行’ 以將因添加過氧化氫水溶液引起發熱時之溶液內溫控制在 不超過-10°C。如此獲得之固成分濃度6.75重量％之反應 產物稱爲膜形成用前驅物液（C4) ° -102- 200941506 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態，在常溫（20±5°C)下放置，2天後以目視觀察到凝膠 化。亦即，所得前驅物液之常溫可使用時間（可利用時間） 未達2天。 . (比較例8 - 5) _ 與實施例8-1 1相同除以固成分濃度改變相對於鉅化 φ 合物之過氧化氫量於本發明範圍外以外，其餘如實施例 8-11般製造膜形成用前驅物液。 亦即，於氬氣氛圍中將0.4克五乙氧化鉬溶解於1.8 克脫水乙醇及2.52克3-甲氧基-1-丁醇之混合溶劑中，攪 拌下將0.14克濃度30重量％之過氧化氫水溶液（相對於五 乙氧化鉬1莫耳相當於1.0莫耳之過氧化氫）緩慢添加於 所得溶液中，添加結束後，攪拌5分鐘進行過氧化反應。 又，反應係以乾冰在注入有溶液之燒瓶周圍冷卻下進行， Q 以將因添加過氧化氫水溶液引起發熱時之溶液內溫控制在 ' 不超過-l〇°C。如此獲得之固成分濃度6.75重量％之反應 ; 產物稱爲膜形成用前驅物液（C5)。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態，在常溫（20±5°C)下放置，3小時後以目視觀察到凝 膠化。亦即，所得前驅物液之常溫可使用時間（可利用時 間）未達3小時。 (實施例8-14) -103- 200941506 與實施例8-1 1相同除以固成分濃度及相對於鉬化合 物之過氧化氫量改變溶劑之組成以外，其餘如實施例8 -11般製造膜形成用前驅物液。 亦即，於氬氣氛圍中將0.4克五乙氧化鉅溶解於5.1 克脫水乙醇中，攪拌下將0.34克濃度30重量％之過氧化 氫水溶液（相對於五乙氧化钽1莫耳相當於3.0莫耳之過 氧化氫）緩慢添加於所得溶液中，添加結束後，攪拌5分 鐘進行過氧化反應。又，反應係以乾冰在注入有溶液之燒 瓶周圍冷卻下進行，以將因添加過氧化氫水溶液引起發熱 時之溶液內溫控制在不超過-1 0 °C。如此獲得之固成分濃 度6.75重量％之反應產物稱爲膜形成用前驅物液（14)。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態，以目視觀察在常溫（20±5°C)下放置10天時之狀 態，未產生凝膠化或白濁等而維持透明之溶液狀態。 (比較例8-6) 與實施例8-1 1相同除以相對於鉬化合物之過氧化氫 量改變溶劑之組成及量使固成分濃度在本發明範圍外以 外，其餘如實施例8 -1 1般製造膜形成用前驅物液。 亦即，於氬氣氛圍中將0.4克五乙氧化钽溶解於1.53 克脫水乙醇及2.29克3-甲氧基-1-丁醇之混合溶劑中，攪 拌下將0.34克濃度30重量％之過氧化氫水溶液（相對於五 乙氧化鉬1莫耳相當於3.0莫耳之過氧化氫）緩慢添加於 所得溶液中，添加結束後，攪拌5分鐘進行過氧化反應。 -104- 200941506 又，反應係以乾冰在注入有溶液之燒瓶周圍冷卻下進行’ 以將因添加過氧化氫水溶液引起發熱時之溶液內溫控制在 不超過-l〇°C。如此獲得之固成分濃度8.77重量％之反應 產物稱爲膜形成用前驅物液（C6)。 將所得前驅物液置於玻璃製細口瓶中，使瓶口呈開放 狀態，在常溫（20±5°C)下放置，1天（24小時）後以目視觀 察到凝膠化。亦即，所得前驅物液之常溫可使用時間（可 利用時間）未達1天。 以上，就本發明之透明導電性基板及其製造方法以及 膜形成用前驅物液加以詳細說明，但本發明之範圍並不侷 限於該等說明中，且可在不損及本發明主旨之範圍內進行 適度的變更或改善。 【圖式簡單說明】 圖1顯示實施例5-1獲得之透明導電性基板之導電性 膜之X射線繞射峰之圖。 圖2顯示比較例1-4獲得之透明導電性基板之導電性 膜之X射線繞射峰之圖。 -105-First, it will be 4. 0 g of tetraisopropyl titanium oxide dissolved in 50. 5 g of 3-methoxy-1-butanol, and 1. 6 g of a 30% by weight aqueous solution of hydrogen peroxide was slowly added to the obtained solution, and after completion of the addition, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction is carried out by cooling with dry ice around the flask to which the solution is injected, so that the internal temperature of the solution when the heat is caused by the addition of the hydrogen peroxide solution is not more than -1 〇 °C. The reaction product thus obtained is referred to as titanium peroxy complex (a4). Q In addition, it will be 1. 5 grams of pentoxide oxide dissolved in 7. 1 gram of water, ethanol and 12 grams of 3-methoxy-1-butanol in a mixed solvent, and under stirring: 1. 6 g of a 30% by weight hydrogen peroxide was slowly added to the obtained solution, and after completion of the addition, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction is carried out by cooling with dry ice around the flask in which the solution is poured, so that the internal temperature of the solution when heat is generated by the addition of the aqueous hydrogen peroxide solution is not more than _ l 〇 °C. The reaction product thus obtained is referred to as a peroxyl complex (b4). Mixing the above titanium-84-200941506 oxygen complex (a4) and the above-mentioned ruthenium peroxy complex (b4) in a ratio of titanium: 铌 = 80: 20 (mole ratio), and adding the mixture The total amount of titanium and niobium is equivalent to 100 mol of nitric acid (manufactured by Wako Pure Chemical Industries Co., Ltd., special grade of reagent, concentration: 65% by weight), and the concentration of the solid component is 15% by weight. . The obtained precursor liquid was placed in a glass-made fine-mouth bottle, and the mouth of the bottle was opened-state, and it was visually observed to stand at normal temperature (20±5 ° C) for 4 days (96 hours).  After the state, no gel or turbidity or the like was formed to maintain a transparent solution state. φ Thus, it can be understood that the obtained precursor liquid is a person having good storage stability. In addition, the above-prepared precursor liquid was applied to a transparent substrate (an alkali-free glass "1737" manufactured by Corning Co., Ltd.) with a thickness of 0. 7mm) is a dry film thickness of 60nm, and is fired (prebaked) at 300 °C for 1 minute, and then annealed at 500 ° C for 60 minutes in a reducing atmosphere of 100% hydrogen to obtain transparent conductive Substrate. The specific resistance of the obtained transparent conductive substrate is 5. 0χ10_3Ω · cm, the transmittance is about 80% in the visible light field, and about 80% in the infrared field. Further, the crystal phase of the conductive film in the transparent conductive substrate was detected by X φ ray diffraction to be anatase. Further, the crystal structure ' of the Nb-doped titanium oxide was observed by TEM-EDX and FE-SEM. (Example 7-4) The titanium peroxy complex (a4) obtained in the same manner as in Example 7-3 was mixed in a ratio of titanium: 铌 = 80: 20 (mole ratio) and the same as in Example 7-3. Obtaining the peroxygen complex (b4), and adding the total amount of titanium and strontium in the mixture to a total of 25 moles of nitric acid at 100 mol (manufactured by Wako Pure Chemical Industries, Ltd. - 85-200941506, The test drug grade 'concentration of 65% by weight), to obtain a solid concentration of 7. 0 5 wt% of the precursor fluid. The obtained precursor liquid was placed in a glass-made fine-mouth bottle, and the mouth of the bottle was opened, and it was visually observed to be gelled or turbid after being left at a normal temperature (2 〇 ± 5 ° C) for 14 days. Maintain a transparent solution state. Therefore, it can be understood that the obtained precursor liquid is a person having good storage stability. In addition, the above-obtained precursor liquid was applied once by a spin coater.  On a transparent substrate (alkali-free glass "1 73 7 made by Corning", thickness 0 0. 7mm) is a dry film thickness of 50nm, and is fired (prebaked) at 300 ° C for 1 minute, and then annealed at 500 ° C for 60 minutes in a reducing gas atmosphere of 1% hydrogen. A transparent conductive substrate. The specific resistance of the obtained transparent conductive substrate is 5. 〇xlO_3n. Cm, the transmittance is about 80% in the visible light field and about 80% in the infrared field. Further, the crystal phase of the conductive film in the transparent conductive substrate was detected by X-ray diffraction to be anatase. Further, the crystal structure of the polycrystalline body doped with Nb-doped titanium oxide was observed by TEM-EDX and FE-SEM. ◎ (Reference Example 7-1); The titanium peroxygen complex (al) obtained in the production example a1 was mixed in a ratio of titanium: 铌 = 93: 7 (mole ratio) and obtained in the production example bl The oxygen complex (bl)' obtained a solid concentration of 7. 0% by weight of the precursor fluid. The obtained precursor liquid was placed in a glass spar bottle, and the mouth of the bottle was opened and placed at normal temperature (20 ± 5 ° C). After about 4 hours, gelation was visually observed. That is, the resulting precursor liquid can be used at room temperature for a period of time (may be -86 - 200941506) for about 4 hours. (Comparative Example 7-1) The titanium peroxygen complex (al) obtained in Production Example a1 and the hydrazine peroxygen obtained in Production Example bl were mixed at a ratio of titanium: 铌 = 93:7 (mole ratio).  The complex (bl) is added as a total of titanium and bismuth in the mixture.  1 〇〇 mol is equivalent to 20 moles of sulfuric acid (made by Wako Pure Chemical Industries, φ test drug grade, concentration 96% by weight), to obtain a solid concentration of 6. 5% by weight of the precursor fluid. The obtained precursor liquid was placed in a glass spar bottle, and the mouth of the bottle was opened, and no gelation occurred after visual observation of the state at room temperature (20 ± 5 ° C) for 4 days (96 hours). Or it is cloudy or the like to maintain the state of the transparent solution. Further, the above-prepared precursor liquid was applied to a transparent substrate by a capillary coater (an alkali-free glass "1737" manufactured by Corning Co., Ltd., thickness 0. 7mm) becomes dry film thickness 35. 7 nm, and calcined at 300 ° C (after pre-baking Q baking, the annealing treatment was performed at 50 ° C for 60 minutes in a reducing atmosphere of 100% hydrogen to obtain a transparent conductive substrate. - The resulting transparent conductivity The specific resistance of the substrate is the measurement limit (1 X 1 03 Ω · cm or more), the transmittance is about 80% in the visible light field, and about 80% in the infrared field. Further, the conductive film in the transparent conductive substrate is detected by X-ray diffraction. The crystal phase is anatase. (Comparative Example 7 - 2) The titanium peroxy complex obtained in Production Example al-87-200941506 was mixed at a ratio of titanium: 铌 = 93:7 (mole ratio). Al) and the hydrazine peroxy complex (bl) obtained in the production example bl, and adding citric acid equivalent to the molar amount in the total amount of titanium and strontium in the mixed solution (and pure light) The pharmaceutical company manufactures a 'special drug grade, concentration 98% by weight, and obtains a solid concentration of 6. 5 weight% of the precursor fluid. The resulting precursor liquid was placed in a glass vial to open the mouth of the bottle.  The state was observed by visual observation at a normal temperature (20 ± 5 ° C) for 4 days (96 hours), and no gelation or turbidity was observed to maintain the state of the transparent solution. @ Further, with a capillary applicator The above-mentioned precursor liquid was once applied to a transparent substrate (alkali-free glass "1737" manufactured by Corning Incorporated, thickness 0. 7mm) becomes dry film thickness 35. 7 nm, and after firing at 30 (prebaking) for 1 minute, annealing treatment was performed at 500 ° C for 60 minutes in a reducing gas atmosphere of 100% hydrogen to obtain a transparent conductive substrate. The specific resistance of the substrate is the measurement limit (1 X 1 〇3 Ω · cm or more), the transmittance is about 70% in the visible light field, and about 70% in the infrared field. Further, the conductivity in the transparent conductive substrate is detected by X-ray diffraction. @ The crystalline phase of the film is anatase. y (Comparative Example 7-3) The titanium peroxygen complex (al) obtained in the production example a1 was mixed at a ratio of titanium: 铌 = 93:7 (mole ratio). And the oxalic acid complex (bl) obtained in the production example bl, and the total amount of titanium and lanthanum in the mixed liquid is equivalent to 20 moles of oxalic acid at 100 moles (made by Wako Pure Chemical Industries, Ltd.) , the test drug grade, concentration 98% by weight), obtained a solid concentration of 6. 5% by weight -88- 200941506 before the fluid. The obtained precursor liquid was placed in a glass-made fine-mouthed bottle, and the mouth of the bottle was opened, and no gel was produced after visual observation of the state at room temperature (2 〇 ± 5 ° C) for 4 days (96 hours). Maintaining a transparent solution state by turbidity or turbidity. .  Further, the precursor liquid obtained above was applied to a transparent substrate by a capillary applicator (1737, manufactured by Corning Incorporated, having a thickness of 0 〇. 7mm) becomes dry film thickness 35. 7nm, and at 300. (: After firing (prebaking) for 1 minute, annealing treatment was performed at 500 ° C for 60 minutes in a reducing gas atmosphere of 100% hydrogen to obtain a transparent conductive substrate. The specific resistance of the obtained transparent conductive substrate was The measurement limit (1 X 1 〇3 Ω · cm or more), the transmittance is about 7〇% in the visible light field, and about 70% in the infrared field. The X-ray diffraction is used to detect the crystal phase of the conductive film in the transparent conductive substrate. It is anatase type. 0 (Comparative Example 7 - 4) 'In the ratio of chin: 铌 = 93: 7 (mole ratio), the peroxyl complex (a 1) obtained in the production example a' is mixed. The ruthenium peroxygen complex (b 1)' obtained in the production example bl is added to the total amount of titanium and lanthanum in the mixture as a lactic acid equivalent to 25 moles per 1 Torr (Wako Pure Chemical Co., Ltd.) Manufacture, test special grade 'concentration 85~92% by weight), to obtain a solid concentration of 6. 5 wt% of the precursor fluid. The obtained precursor liquid was placed in a glass-made fine-mouth bottle, and the mouth of the bottle was opened, and visually observed at a normal temperature (2 〇 ± 5 丨 under the 丨 ( (24 hours) when the state of -89- 200941506 was not observed. The gelation, white turbidity, etc. were generated to maintain the state of the transparent solution. Further, the obtained precursor liquid was applied to the transparent substrate by a capillary coater at once (the alkali-free glass "1737" manufactured by Corning Co., Ltd., thickness 0. 7mm) becomes dry film thickness 35. After 7 minutes, it was baked (prebaked) at 300 ° C for 1 minute, and then annealed at 500 ° C for 60 minutes in a reducing gas atmosphere of 100% hydrogen to obtain a transparent conductive substrate. The specific resistance of the obtained transparent conductive substrate was the measurement limit (1 X 1 Ο 3 Ω .  Above cm), the transmittance is about 70% in the visible light field and about 70% in the infrared field. Further, the crystal phase of the conductive film in the transparent conductive substrate was detected by X-ray diffraction to be anatase. (Comparative Example 7-5) The titanium peroxygen complex (al) obtained in the production example ai was mixed at a ratio of titanium: 铌 = 93:7 (mole ratio) and the hydrazine peroxygen obtained in Production Example bl Compound (bl)' and the addition of titanium and strontium in the mixture as a total of 20 moles of acetic acid at 100 moles (manufactured by Wako Pure Chemical Industries, Ltd., special grade, concentration 9 9 · 9 wt% ), obtaining a solid concentration of 6. 5% by weight of the precursor fluid. The obtained precursor liquid was placed in a glass-made fine-mouthed bottle, and the mouth of the bottle was opened. It was visually observed after being left at room temperature (2 0 ± 5 (()) for 1 day (24 hours). The state of the transparent solution is maintained by gelation or turbidity, etc. In addition, the above-prepared precursor liquid is applied to the transparent substrate by a capillary applicator (there is no glass 1" manufactured by Corning Incorporated, thickness 0. 7mm) becomes dry film thickness 35. 7nm, and at 300. (: under firing (pre-baking - 90-200941506 baking) After 1 minute, annealing treatment was performed at 500 ° C for 60 minutes in a reducing atmosphere of 100% hydrogen to obtain a transparent conductive substrate. The specific resistance is the measurement limit (1x1 03 Ω · cm or more), the transmittance is about 70% in the visible light field, and about 70% in the infrared field. Further, the crystal phase of the conductive film in the transparent conductive substrate is detected by X-ray diffraction. It is anatase type. φ (Example 8-1) will be 0 in an argon atmosphere. 75 grams of pentoxide oxide was dissolved in 9. 56 grams of dehydrated ethanol, 0. 8 g of a 30% by weight aqueous solution of hydrogen peroxide (equivalent to 3. 0 molar hydrogen peroxide) was slowly added to the obtained solution, and after completion of the addition, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction is carried out by cooling the dry ice around the flask in which the solution is poured, so that the internal temperature of the solution when the heat is caused by the addition of the aqueous hydrogen peroxide solution is not more than -10 °C. The solid concentration of the component thus obtained is 6. The reaction product of 75 wt% is referred to as a precursor liquid for film formation (1). The obtained precursor liquid was placed in a glass-made fine-mouthed bottle, and the mouth of the bottle was opened, and it was visually observed to be gelled or turbid after being left at a normal temperature (20 ± 5 ° C) for 15 days. Wait until the state of the solution is transparent. (Example 8-2) A precursor for film formation was produced in the same manner as in Example 8-1 except that the amount of the hydrogen peroxide relative to the ruthenium compound was changed in the same manner as in Example 8.1. -91 - 200941506 That is, it will be 0 in argon. 75 grams of pentoxide oxide was dissolved in 9. In 69 g of dehydrated ethanol, it will be 0. 67 g of a 30% by weight aqueous solution of hydrogen peroxide (equivalent to 2. 5 mol of hydrogen peroxide was slowly added to the obtained solution, and after the end of the addition, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction was carried out under the cooling of dry ice in a flask filled with a solution as in Example 8.1 to control the internal temperature of the solution when the heat of the hydrogen peroxide solution was added was not more than -1 〇 °C. The solid concentration obtained in this way is 6. The reaction product of 75 wt% is referred to as a precursor liquid for film formation (2). The obtained precursor liquid was placed in a glass-made fine-mouthed bottle, and the mouth of the bottle was opened, and the state of being left at room temperature (20±5° C.) for 15 days was visually observed, and gelation or white turbidity did not occur. The state of the transparent solution is maintained. (Example 8-3) A precursor for film formation was produced in the same manner as in Example 8-1 except that the amount of the hydrogen peroxide relative to the ruthenium compound was changed in the same manner as in Example 8-1. That is, it will be 0 in an argon atmosphere. 75 grams of pentoxide oxide dissolved in 9. 43 grams of dehydrated ethanol, 0. 93 g of a 30% by weight aqueous solution of hydrogen peroxide (equivalent to 3. 5 mol of hydrogen peroxide was slowly added to the obtained solution, and after completion of the addition, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction was carried out by cooling dry ice around the flask in which the solution was poured as in Example 8-1 to control the internal temperature of the solution when the heat generation by the addition of the aqueous hydrogen peroxide solution was not more than -10 °C. 200941506 The solid concentration obtained in this way is 6. The reaction product of 75 wt% is referred to as a precursor liquid for film formation (3). The obtained precursor liquid was placed in a glass-made fine-mouthed bottle, and the mouth of the bottle was opened. It was visually observed at room temperature (20±5. After being placed under the condition of 15 days under the armpits), no gelation or white turbidity was generated. While maintaining a transparent solution state (Comparative Example 8-1), ❻ was the same as Example 8-1 except that the solid content concentration was changed outside the range of the present invention with respect to the amount of hydrogen peroxide of the hydrazine compound. A precursor liquid for film formation is produced in the same manner as in 8-1. That is, '0% in argon gas. 75 grams of pentoxide oxide was dissolved in 9. 82 grams of dehydrated ethanol will be stirred under 0. 54 g of a 30% by weight aqueous solution of hydrogen peroxide (equivalent to 2. 0 mole of hydrogen peroxide was slowly added to the obtained solution, and after completion of the addition, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction was carried out as in Example 8.1, with dry ice being cooled under the flask filled with the solution to control the internal temperature of the solution to be not more than -10 ° due to the addition of hydrogen peroxide water: the solution caused by heat generation. c. So obtained the solid concentration of 6. The reaction product of 75 wt% is referred to as a precursor liquid for film formation (C1). The obtained precursor liquid was placed in a glass spar bottle, and the mouth of the bottle was opened. It was left at room temperature (2 〇 ± 5 ° C), and gelation was visually observed after 4 days. That is, the usable precursor liquid has a usable time (available time) at room temperature for less than 4 days. -93-200941506 (Comparative Example 8-2) The same as Example 8.1 except that the solid content concentration was changed by the amount of hydrogen peroxide relative to the hydrazine compound outside the range of the present invention, and the rest was as in Example 8 - A precursor liquid for film formation is generally produced. That is, it will be 0 in an argon atmosphere. 7 5 grams of pentoxide oxide dissolved in 1. In 35 g of dehydrated ethanol, it will be stirred under 9. 01 grams of concentration of 30% by weight of the aqueous solution of hydrogen peroxide (relative to the five ethoxylated cerium oxide 1 molar equivalent to 5. 0 mole of hydrogen peroxide was slowly added to the obtained solution, and after completion of the addition, the mixture was stirred for 0.5 minutes to carry out a peroxidation reaction. Further, the reaction was carried out by cooling dry ice around the flask in which the solution was poured as in Example 8-1 to control the internal temperature of the solution when the heat generation due to the addition of the aqueous hydrogen peroxide solution was not more than -1 〇 °C. The solid concentration of the component thus obtained is 6. The reaction product of 75 wt% is referred to as a precursor liquid for film formation (C2). The obtained precursor liquid was placed in a glass vial, and the mouth of the bottle was opened, and it was allowed to stand at normal temperature (20 ± 5 ° C), and gelation was visually observed after 6 hours. That is, the usable precursor liquid can be used at room temperature (usable time) for less than 6 hours. (Example 8-4) The film formation precursor was produced as in Example 8.1 except that the solid content concentration and the amount of hydrogen peroxide relative to the hydrazine compound were changed in the same manner as in Example 8-1. liquid. That is, 〇·75 g of pentaethoxy ruthenium oxide was dissolved in 7. 56 g of dehydrated ethanol and 2 g of 3-methoxy-1-butanol in a mixed solvent, and mixed with -94-200941506 will be 0. 8 g of a 30% by weight aqueous solution of hydrogen peroxide (corresponding to pentoxide hydrate 1 mol equivalent to 3. 0 mol of hydrogen peroxide was slowly added to the obtained solution, and after the end of the addition, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction was carried out in the same manner as in Example 8-1 except that the dry ice was cooled under the flask in which the solution was poured, so that the internal temperature of the solution was controlled to not exceed -10 Torr when the heat was caused by the addition of the aqueous hydrogen peroxide solution. The solid concentration obtained in this way • 6. 75 wt% of the reaction product was used as a precursor liquid for film formation (4). φ The obtained precursor liquid was placed in a glass bottle, and the mouth of the bottle was opened, and the state of being placed at room temperature (20 ± 5 ° C) for 20 days was visually observed, and no gelation or white turbidity was observed. Maintain a clear solution state. (Examples 8 - 5) The film formation precursor was produced in the same manner as in Example 8-1 except that the solvent concentration was changed and the solvent composition was changed with respect to the amount of hydrogen peroxide of the ruthenium compound. liquid. φ, that is, 0 in argon. 75 g of pentaethoxy ruthenium oxide was dissolved in 5. 56 g of dehydrated ethanol and 4 g of 3-methoxy-1-butanol in a mixed solvent, and stirred under stirring. 8 g of a 30% by weight aqueous solution of hydrogen peroxide (corresponding to pentoxide hydrate 1 mol equivalent to 3. 0 mole of hydrogen peroxide was slowly added to the obtained solution, and after the addition was completed, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction was carried out under the cooling of the dry ice in the flask in which the solution was poured as in Example 8-1 to control the internal temperature of the solution when the heat generation by the addition of the aqueous hydrogen peroxide solution was not more than -10 °C. The solid concentration obtained in this way is 6. The reaction product of 75 wt% is referred to as a precursor liquid for film formation (5). -95- 200941506 The precursor liquid was placed in a glass vial to open the bottle, and visually observed at room temperature (20 ± 5 ° C) for 30 days without gelation or The turbidity and the like maintain the state of the transparent solution. (Example 8-6) The same as Example 8-1 except the solid concentration and relative to the ruthenium compound.  A precursor for film formation was produced as in Example 8-1 except that the solvent composition was changed under the amount of hydrogen peroxide. @ That is, it will be 0 in argon. 75 g of pentaethoxy ruthenium oxide was dissolved in 3. In a mixed solvent of 56 g of dehydrated ethanol and 6 g of 3-methoxy-1-butanol, a concentration of 30 g of 〇·8 g was stirred under stirring. /. The aqueous hydrogen peroxide solution (relative to the pentoxide of pentoxide is equivalent to 3. 0 mole of hydrogen peroxide was slowly added to the obtained solution. After the addition was completed, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction was carried out in the same manner as in Example 8-1, except that the dry ice was cooled under the flask in which the solution was poured, to control the internal temperature of the solution when the heat generation due to the addition of the aqueous hydrogen peroxide solution was not more than -10 °C. The solid concentration obtained in this way is 0. 6. 75 wt% of the reaction product was used as a precursor liquid for film formation (6). 〃 The obtained precursor liquid is placed in a glass vial to open the bottle mouth: State 'visually observed at room temperature (20±5. The state when placed under the armpit for 30 days' does not cause gelation or turbidity, etc. The state of the solution was maintained in a transparent manner. (Examples 8 - 7) The same as Example 8-1 except that the solid content concentration and the amount of hydrogen peroxide relative to the hydrazine compound were changed, the solvent composition was changed, and the rest was as in Example 8.1. 96- 200941506 A precursor liquid for film formation is produced. That is, it is 0 in an argon atmosphere. 75 grams of pentoxide oxide is dissolved in 2. In a mixed solvent of 56 g of dehydrated ethanol and 7 g of 3-methoxy-1-butanol, 0. 8 g of a 30% by weight aqueous solution of hydrogen peroxide (equivalent to 3. 0 mole of hydrogen peroxide) added slowly.  After the end of the addition in the obtained solution, the mixture was stirred for 5 minutes for the reverse oxidation.  should. Further, the reaction was carried out in the same manner as in Example 8-1, except that the dry ice was cooled under the boiling of the flask filled with the solution to control the internal temperature of the solution when the heat was caused by the addition of the aqueous hydrogen peroxide solution to not exceed -10 °C. . The solid concentration obtained in this way is 6. 75 wt% of the reaction product was used as a precursor liquid for film formation (7). The obtained precursor liquid was placed in a glass-made fine-mouth bottle, and the mouth of the bottle was opened, and the state of being placed at room temperature (20 ± 5 ° C) for 30 days was visually observed, and no gelation or white turbidity was observed. Maintain a clear solution state. (Example 8-8) The same procedure as in Example 8.1 was carried out except that the solid content concentration and the amount of hydrogen peroxide relative to the hydrazine compound were changed, and the solvent composition was changed, and the film formation was carried out as in Example 8-1. Precursor liquid. That is, it will be 0 in argon. 75 grams of pentoxide oxide was dissolved in 9. 56 g of 3-methoxy-1-butanol, 0. 8 g of a 30% by weight aqueous solution of hydrogen peroxide (equivalent to 3. 0 mol of hydrogen peroxide was slowly added to the obtained solution, and after completion of the addition, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction was carried out as in Example 8-1 under the cooling of dry ice in a flask filled with a solution to control the internal temperature of the solution when the heat generation by the addition of peroxy-97-200941506 hydrogenation solution was not more than -1. 〇°c. The solid concentration of the component thus obtained is 6. The reaction product of 75 wt% is referred to as a precursor liquid for film formation (8). .  The obtained precursor liquid was placed in a glass-made fine-mouthed bottle, and the mouth of the bottle was opened, and it was visually observed at a normal temperature (20±5° C.) for 30 days, and gelation or white turbidity was not maintained. Transparent solution state. (Example 8-9) The film formation was carried out in the same manner as in Example 8-1 except that the amount and amount of the solvent were changed with respect to the amount of hydrogen peroxide of the ruthenium compound, and the solid content concentration was increased. Precursor liquid. That is, it will be 0 in an argon atmosphere. 75 grams of pentoxide oxide is dissolved in 2. In a mixed solvent of 56 g of dehydrated ethanol and 6 g of 3-methoxy-1-butanol, 0. 8 g of a 30% by weight aqueous solution of hydrogen peroxide (equivalent to 3. 0 mol of hydrogen peroxide was slowly added to the obtained solution, and after completion of the addition, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction was carried out under the cooling of a dry ice in a flask filled with a solution as in Example 8.1 to control the internal temperature of the solution when heat generation due to the addition of the aqueous hydrogen peroxide solution was not more than _ 1 〇 ° C. The solid concentration obtained in this way is 7. 41% by weight of the reaction product is referred to as a precursor for film formation (9). The obtained precursor liquid was placed in a glass-made fine-mouth bottle, and the mouth of the bottle was opened, and it was visually observed at a normal temperature (20 ± 5 t) for 30 days, and gelation or white turbidity was not observed to maintain transparency. The state of the solution. -98-200941506 (Examples 8-10) The same as Example 8-1 except that the amount of hydrogen peroxide relative to the hydrazine compound was changed, the solvent composition and amount were changed, and the solid content concentration was increased. A precursor liquid for film formation is produced. That is, it will be 0 in an argon atmosphere. 75 g of pentaethoxy ruthenium oxide was dissolved in 8 g of 3-methoxy-1·butanol and stirred under agitation. 8 g of a concentration of 30% by weight of an aqueous hydrogen peroxide solution (relative to 5 ethoxylated ruthenium oxide equivalent to 3. 0 mol of hydrogen peroxide was slowly added to the obtained solution, and after the end of the addition, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction was carried out under the cooling of the dry ice in the flask around the solution as in Example 8-1 to control the internal temperature of the solution when the heat generation by the addition of the aqueous hydrogen peroxide solution was not more than -10 °C. The solid concentration obtained in this way is 7. The reaction product of 85 wt% is referred to as a precursor liquid for film formation (10). The obtained precursor liquid was placed in a glass-made fine-mouth bottle, and the mouth of the bottle was opened, and the Q state at the normal temperature (20 ± 5 ° C) for 15 days was visually observed, and no gelation or white turbidity was produced. Wait until the state of the solution is transparent. (Comparative Example 8 - 3) The same as Example 8-1, except that the amount of hydrogen peroxide relative to the hydrazine compound was changed, and the solvent composition and amount were changed so that the solid content concentration was outside the range of the present invention, and the rest was as in Example 8-1. A precursor liquid for film formation is produced. That is, it will be 0 in an argon atmosphere. 75 g of pentaethoxy ruthenium oxide was dissolved in 7 g of 3-methoxy-1-butanol and stirred under agitation. 8 g of a 30% by weight aqueous solution of hydrogen peroxide (equivalent to 3. 0 Mo -99- 200941506 Hydrogen peroxide in the ear was slowly added to the obtained solution, and after the end of the addition, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction was carried out as in Example 8-1 under cooling of dry ice in a flask filled with a solution to control the internal temperature of the solution at a temperature of not more than -10 °C when heat generation due to the addition of an aqueous hydrogen peroxide solution. The solid concentration obtained in this way is 8. The reaction product of 77% by weight is referred to as a precursor liquid for film formation (C3). The obtained precursor liquid was placed in a glass vial, and the mouth of the bottle was opened, and it was allowed to stand at normal temperature (20 ± 5 ° C), and gelation was visually observed after one day (24 hours). That is, the normal temperature available time (available time) of the obtained precursor liquid is less than one day. (Example 8-1 1) 0 in an argon atmosphere. 4 grams of penta-oxide molybdenum dissolved in 3. 1 g of dehydrated ethanol and 2 g of 3-methoxy-1·butanol in a mixed solvent, stirring under 0. 34 g of a 30% by weight aqueous solution of hydrogen peroxide (equivalent to 3. 0 mol of hydrogen peroxide was slowly added to the obtained solution, and after completion of the addition, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction was carried out by cooling the dry ice around the flask to which the solution was poured, so that the internal temperature of the solution when the heat was caused by the addition of the aqueous hydrogen peroxide solution was not more than -1 〇 °C. The solid concentration of the component thus obtained is 6. 75% by weight of the reaction product is referred to as a precursor for film formation (11). The obtained precursor liquid was placed in a glass-made fine-mouthed bottle, and the mouth of the bottle was opened, and the state of being left at room temperature (20 ± 5 ° C) for 20 days was visually observed, and no gelation or white turbidity was observed. Maintain a clear solution state. -100-200941506 (Examples 8-12) The film formation precursors were produced as in Examples 8-11 except that the solid content concentration was changed with respect to the amount of hydrogen peroxide of the ruthenium compound. liquid. .  That is, it will be 0 in an argon atmosphere. 4 grams of penta-oxide molybdenum dissolved in 3. 17 , grams of dehydrated ethanol and 2. In a mixed solvent of 0 g of 3-methoxy-1-butanol, a solution of 30% by weight of hydrogen peroxide in a concentration of 30 g of hydrazine was added with stirring (corresponding to molybdenum pentoxide 1 mol equivalent to 2. 5 mol of hydrogen peroxide was slowly added to the obtained solution, and after completion of the addition, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction was carried out by cooling the dry ice around the flask to which the solution was poured, so that the internal temperature of the solution when the heat was caused by the addition of the aqueous hydrogen peroxide solution was not more than -10 °C. The solid concentration of the component thus obtained is 6. 75 wt% of the reaction product is referred to as a precursor for film formation (12). The obtained precursor liquid was placed in a glass-made fine-mouth bottle, and the mouth of the bottle was in an open Q state, and visually observed at a normal temperature (20±5 t) for 10 days, and no gelation or white turbidity was observed. Maintain a clear solution state. (Examples 8 to 13) A precursor for film formation was produced in the same manner as in Example 8_n except that the solid content concentration was changed with respect to the amount of hydrogen peroxide of the molybdenum compound. That is, it will be in an argon atmosphere. 4 grams of five ethyl oxidized giant dissolved in 2. 94 grams of dehydrated ethanol and 2. 0 g of 3-methoxy-1-butanol in a mixed solvent 'stirded-101 - 200941506 mixed with 0. 5 g of a 30% by weight aqueous solution of hydrogen peroxide (equivalent to 3. 5 mol of hydrogen peroxide was slowly added to the obtained solution, and after completion of the addition, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction was carried out by cooling the dry ice around the flask to which the solution was poured, so that the internal temperature of the solution when the heat was caused by the addition of the aqueous hydrogen peroxide solution was not more than -10 °C. The solid concentration of the component thus obtained is 6. 75 wt% of the reaction product is referred to as a precursor for film formation (13). The obtained precursor liquid was placed in a glass-made fine-mouth bottle, and the mouth of the bottle was opened, and the state of being placed at room temperature (20 ± 5 ° C) for 10 days was visually observed, and no gelation or white turbidity was observed. Maintain a clear solution state. (Comparative Example 8-4) A precursor for film formation was produced as in Example 8-11 except that the amount of hydrogen peroxide relative to the molybdenum compound was changed outside the range of the present invention except that the solid content concentration was changed outside the range of the present invention. Liquid. That is, in an argon atmosphere, 〇·4 g of pentoxide is dissolved in 2. 2 grams of dehydrated ethanol and 3. 1 g of 3-methoxy-1-butanol in a mixed solvent, 0. 1 4 g of a concentration of 30% by weight of an aqueous hydrogen peroxide solution (relative to the five ethoxylated giant 1 molar equivalent to 1. 25 mol of hydrogen peroxide was slowly added to the obtained solution, and after completion of the addition, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction was carried out by cooling the dry ice around the flask in which the solution was poured. The internal temperature of the solution when the heat was caused by the addition of the aqueous hydrogen peroxide solution was controlled to not exceed -10 °C. The solid concentration of the component thus obtained is 6. 75 wt% of the reaction product is referred to as a precursor for film formation (C4) ° -102- 200941506 The obtained precursor liquid is placed in a glass vial to open the mouth of the bottle at room temperature (20 ± 5 ° C). The cells were placed under the gel, and gelation was visually observed after 2 days. That is, the available temperature of the precursor liquid obtained at room temperature (available time) is less than 2 days. .  (Comparative Example 8 - 5) _ The same as Example 8-1 1 except that the solid content concentration was changed outside the range of the present invention with respect to the amount of hydrogen peroxide of the giantated φ compound, and the others were produced as in Examples 8-11. A precursor liquid for film formation. That is, it will be 0 in an argon atmosphere. 4 grams of penta-oxide molybdenum dissolved in 1. 8 grams of dehydrated ethanol and 2. In a mixed solvent of 52 g of 3-methoxy-1-butanol, 0. 14 g of a 30% by weight aqueous solution of hydrogen peroxide (corresponding to 1 mol of molybdenum pentoxide equivalent to 1. 0 mole of hydrogen peroxide was slowly added to the obtained solution, and after the addition was completed, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction was carried out by cooling the dry ice around the flask in which the solution was poured, and Q was controlled so that the internal temperature of the solution caused by the addition of the aqueous hydrogen peroxide solution did not exceed -10 °C. The solid concentration of the component thus obtained is 6. 75 wt% of the reaction; the product is referred to as a precursor for film formation (C5). The obtained precursor liquid was placed in a glass vial, and the mouth of the bottle was opened, and it was left at room temperature (20 ± 5 ° C), and gelation was visually observed after 3 hours. That is, the usable precursor liquid has a normal temperature usable time (available time) of less than 3 hours. (Examples 8 to 14) -103-200941506 A film was produced as in Example 8-11 except that the composition of the solvent was changed with respect to the solid content concentration and the amount of hydrogen peroxide relative to the molybdenum compound. A precursor liquid is formed. That is, it will be 0 in an argon atmosphere. 4 grams of five ethyl oxidized giant dissolved in 5. 1 g of dehydrated ethanol, 0. 34 g of a 30% by weight aqueous solution of hydrogen peroxide (equivalent to 3. 0 moles of hydrogen peroxide were slowly added to the obtained solution, and after the addition was completed, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction was carried out by cooling the dry ice around the flask into which the solution was poured, so that the internal temperature of the solution when the heat was caused by the addition of the aqueous hydrogen peroxide solution was not more than -1 0 °C. The solid concentration obtained in this way is 6. The reaction product of 75 wt% is referred to as a precursor liquid for film formation (14). The obtained precursor liquid was placed in a glass-made fine-mouthed bottle, and the mouth of the bottle was opened, and it was visually observed at a normal temperature (20±5° C.) for 10 days, and gelation or white turbidity was not maintained. Transparent solution state. (Comparative Example 8-6) The same as Example 8-1 1 except that the composition and amount of the solvent were changed with respect to the amount of hydrogen peroxide of the molybdenum compound so that the solid content concentration was outside the range of the present invention, and the rest was as in Example 8.1. A precursor liquid for film formation is generally produced. That is, it will be 0 in an argon atmosphere. 4 grams of pentoxide oxide dissolved in 1. 53 grams of dehydrated ethanol and 2. In a mixed solvent of 29 g of 3-methoxy-1-butanol, 0. 34 g of a 30% by weight aqueous solution of hydrogen peroxide (relative to molybdenum pentoxide 1 mol equivalent to 3. 0 mole of hydrogen peroxide was slowly added to the obtained solution, and after the addition was completed, the mixture was stirred for 5 minutes to carry out a peroxidation reaction. Further, the reaction was carried out by cooling the dry ice around the flask in which the solution was poured. The internal temperature of the solution when the heat was caused by the addition of the aqueous hydrogen peroxide solution was controlled to not exceed -10 °C. The solid concentration obtained in this way is 8. The 77% by weight reaction product is referred to as a precursor for film formation (C6). The obtained precursor liquid was placed in a glass spar bottle, and the mouth of the bottle was opened, and it was left at room temperature (20 ± 5 ° C), and gelation was visually observed after 1 day (24 hours). That is, the normal temperature available time (available time) of the obtained precursor liquid is less than one day. The transparent conductive substrate, the method for producing the same, and the precursor for film formation of the present invention are described in detail above, but the scope of the present invention is not limited to the above description, and may be within the scope of the gist of the present invention. Moderate changes or improvements are made within. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an X-ray diffraction peak of a conductive film of a transparent conductive substrate obtained in Example 5-1. Fig. 2 is a view showing the X-ray diffraction peak of the electroconductive film of the transparent conductive substrate obtained in Comparative Example 1-4. -105-

Claims (1)

200941506 十、申請專利範圍 1. —種比電阻爲9χ10_3Ω· cm以下之透明導電性基 板之製造方法，其特徵爲將含有（A)使鈦化合物與過氧化 氫反應而成之反應產物與（B)使鈮化合物或鉬化合物與過 氧化氫反應而成之反應產物之前驅物液，塗佈於透明基材 上，經燒成後，藉由在還原氣體中加熱進行退火處理，在 透明基材上形成由摻雜有鈮或组之氧化鈦構成之透明導電 性膜。 2. —種比電阻爲9χ1(Γ3Ω· cm以下之透明導電性基 板之製造方法，其特徵爲在透明基材上形成由銳鈦礦結晶 相之氧化鈦系薄膜構成之底層，且在該底層上塗佈含有（A) 使鈦化合物與過氧化氫反應而成之反應產物與（B)使鈮化 合物或鉬化合物與使過氧化氫反應而成之反應產物之前驅 物液（I)，經燒成後，藉由在還原氣體中加熱進行退火處 理，在上述底層上形成由摻雜有鈮或鉬之氧化鈦構成之透 明導電性膜。 3 ·如申請專利範圍第2項之透明導電性基板之製造 方法，其中上述底層係在塗佈至少含有（a)使鈦化合物與 過氧化氫反應而成之反應產物之前驅物液（Π)後，藉由加 熱而形成。 4 ·如申請專利範圍第3項之透明導電性基板之製造 方法，其中上述前驅物液（II)含有（a)使鈦化合物與過氧化 氫反應而成之反應產物及（b)使鈮化合物或鉬化合物與過 氧化氫反應而成之反應產物。 -106- 200941506 5.—種比電阻爲9xl0_3n.cm以下之透明導電性基 板之製造方法，其特徵爲於透明基材上塗佈將銳鈦礦型氧 化鈦系微粒子分散於分散介質中而成之分散體後，藉由使 分散介質揮發，形成由銳鈦礦結晶相之氧化鈦系薄膜構成 之底層，在該底層上塗佈含有（A)使鈦化合物與過氧化氫 反應而成之反應產物與（B)使鈮化合物或鉬化合物與過氧 化氫反應而成之反應產物之前驅物液，經燒成後，藉由在 還原氣體中加熱進行退火處理，而在上述底層上形成由摻 雜有鈮或钽之氧化鈦構成之透明導電性膜。 6 .如申請專利範圍第5項之透明導電性基板之製造 方法，其中上述分散介質之揮發係在200°C以下之溫度進 行。 7. 如申請專利範圍第5或6項之透明導電性基板之 製造方法，其中上述銳鈦礦型氧化鈦系微粒子之平均粒徑 爲20nm以下。 8. —種比電阻爲9χ1 0_3Ω· cm以下之透明導電性基 板之製造方法，其特徵爲將含有（A)使鈦化合物與過氧化 氫反應而成之反應產物、（B)使鈮化合物或钽化合物與過 氧化氫反應而成之反應產物及（C)銳鈦礦型氧化鈦系微粒 子之含有前驅物之分散體塗佈於透明基材上，經燒成後， 藉由在還原氣體中加熱進行退火處理，而在透明基材上形 成由摻雜有鈮或鉬之氧化鈦構成之透明導電性膜。 9. 如申請專利範圍第8項之透明導電性基板之製造 方法，其中上述（C)銳鈦礦型氧化鈦系微粒子之平均粒徑 -107- 200941506 爲 1~2 Onm ° 1 〇.如申請專利範圍第8或9項之透明導電性基板之 製造方法，其中上述含有前驅物之分散體中之（A)使鈦化 合物與過氧化氫反應而成之反應產物、（B)使鈮化合物或 钽化合物與過氧化氫反應而成之反應產物、及（C)銳鈦礦 型氧化鈦系微粒子之含有比例，以固成分重量比計，爲 [(A)+(B)]: (C)=100: 0·1〜10。 1 1 .如申請專利範圍第1、2、5或8項之透明導電性 基板之製造方法，其中上述（Α)鈦化合物及上述（Β)鈮化合 物或钽化合物爲使用氫氧化物。 12.如申請專利範圍第3及4項之透明導電性基板之 製造方法，其中上述（a)鈦化合物及上述（b)鈮化合物或鉬 化合物爲使用氫氧化物。 1 3 ·如申請專利範圍第1、2、5或8項之透明導電性 基板之製造方法，其中含有上述（A)使鈦化合物與過氧化 氫反應而成之反應產物與（B)使鈮化合物或鉅化合物與過 氧化氫反應而成之反應產物之前驅物液係含有以下述通式 (1)〜（5)之任一式表示之溶劑， 【化1】200941506 X. Patent Application No. 1. A method for producing a transparent conductive substrate having a specific resistance of 9 χ 10 _ 3 Ω·cm or less, which comprises (A) a reaction product obtained by reacting a titanium compound with hydrogen peroxide and (B) a precursor product of a reaction product obtained by reacting a ruthenium compound or a molybdenum compound with hydrogen peroxide, coated on a transparent substrate, and after firing, is annealed by heating in a reducing gas, on a transparent substrate A transparent conductive film made of titanium oxide doped with antimony or a group is formed thereon. 2. A method for producing a transparent conductive substrate having a specific resistance of 9 χ 1 (Γ3 Ω·cm or less), characterized in that a bottom layer composed of a titanium oxide film having an anatase crystal phase is formed on a transparent substrate, and the underlayer is formed on the underlayer The coating product (I) containing (A) a reaction product obtained by reacting a titanium compound with hydrogen peroxide and (B) a reaction product (I) obtained by reacting a ruthenium compound or a molybdenum compound with hydrogen peroxide is applied. After the firing, an annealing treatment is performed by heating in a reducing gas to form a transparent conductive film made of titanium oxide doped with antimony or molybdenum on the underlayer. 3 · Transparent conductivity as in claim 2 In the method of producing a substrate, the underlayer is formed by heating after coating a precursor solution containing at least (a) a reaction product obtained by reacting a titanium compound with hydrogen peroxide. The method for producing a transparent conductive substrate according to the third aspect, wherein the precursor liquid (II) contains (a) a reaction product obtained by reacting a titanium compound with hydrogen peroxide and (b) a ruthenium compound or a molybdenum compound Oxidation a reaction product obtained by the reaction. -106- 200941506 5. A method for producing a transparent conductive substrate having a specific resistance of 9x10_3n.cm or less, characterized in that an anatase-type titanium oxide-based fine particle is coated on a transparent substrate After dispersing the dispersion in a dispersion medium, the dispersion medium is volatilized to form a bottom layer composed of a titanium oxide film of an anatase crystal phase, and the base layer is coated with (A) a titanium compound. a reaction product obtained by reacting hydrogen peroxide with (B) a precursor product of a reaction product obtained by reacting a ruthenium compound or a molybdenum compound with hydrogen peroxide, after being fired, is annealed by heating in a reducing gas, and A transparent conductive film comprising a ruthenium or ruthenium-doped titanium oxide is formed on the underlayer. The method for producing a transparent conductive substrate according to claim 5, wherein the dispersion medium is volatilized at 200°. 7. The method of producing a transparent conductive substrate according to the fifth or sixth aspect of the invention, wherein the anatase-type titanium oxide-based fine particles have an average particle diameter of 20 nm or less. 8. A method for producing a transparent conductive substrate having a specific resistance of 9 χ 1 0_3 Ω·cm or less, which comprises (A) a reaction product obtained by reacting a titanium compound with hydrogen peroxide, and (B) a ruthenium compound or A reaction product obtained by reacting a ruthenium compound with hydrogen peroxide and (C) a precursor containing a precursor of an anatase-type titanium oxide-based fine particle are coated on a transparent substrate, and after firing, in a reducing gas A transparent conductive film made of titanium oxide doped with antimony or molybdenum is formed on the transparent substrate by heat treatment. The method for producing a transparent conductive substrate according to claim 8 of the above-mentioned patent, wherein C) The average particle diameter of the anatase-type titanium oxide-based fine particles -107-200941506 is 1 to 2 Onm ° 1 〇. The method for producing a transparent conductive substrate according to claim 8 or 9, wherein the above-mentioned precursor is contained (A) a reaction product obtained by reacting a titanium compound with hydrogen peroxide, (B) a reaction product obtained by reacting a ruthenium compound or a ruthenium compound with hydrogen peroxide, and (C) anatase type in the dispersion Titanium oxide particles The content ratio as solid content weight ratio of [(A) + (B)]: (C) = 100: 0 · 1~10. The method for producing a transparent conductive substrate according to claim 1, 2, 5 or 8 wherein the (Α) titanium compound and the above (Β) bismuth compound or bismuth compound are hydroxides. 12. The method for producing a transparent conductive substrate according to claims 3 and 4, wherein the (a) titanium compound and the (b) bismuth compound or the molybdenum compound are hydroxides. A method for producing a transparent conductive substrate according to the first, second, fifth or eighth aspect of the invention, comprising the above (A) a reaction product obtained by reacting a titanium compound with hydrogen peroxide and (B) a ruthenium The reaction product obtained by reacting a compound or a macro compound with hydrogen peroxide contains a solvent represented by any one of the following formulas (1) to (5), [Chemical Formula 1] (式（1)中，R1〜R6表示Η或烷基，各可相同亦可不 同’ X表示-0Η或-〇R(但是，R表示烷基））， -108- (2) 200941506(In the formula (1), R1 to R6 represent an anthracene or an alkyl group, and each may be the same or different. 'X represents -0Η or -〇R (however, R represents an alkyl group)), -108- (2) 200941506 (式（2)中，R1〜R5表示Η或烷基，各可相同亦可不 同，X表示-ΟΗ或-OR(但是，R表示烷基））， 【化3】(In the formula (2), R1 to R5 represent an anthracene or an alkyl group, and each may be the same or different, and X represents -ΟΗ or -OR (however, R represents an alkyl group), [Chemical 3] R3 R4R3 R4 X R5 R6X R5 R6 R7 C 〇R7 C 〇 (3) (式（3)中，R1〜R7表示Η或烷基，各可相同亦可不同，X 表示-ΟΗ或- OR(但是，R表示烷基））， 【化4】(3) (In the formula (3), R1 to R7 represent an anthracene or an alkyl group, and each may be the same or different, and X represents -ΟΗ or -OR (however, R represents an alkyl group), [Chemical 4] ⑷ (式（4)中，Y表示可具有取代基之碳數3 ~6之伸烷基）， I化5】(4) (In the formula (4), Y represents an alkyl group having a carbon number of 3 to 6 which may have a substituent), and I is 5] (5) -109- 200941506 (式（5)中，Y表示可具有取代基之碳數3~6之伸烷 基）。 14·如申請專利範圍第13項之透明導電性基板之製 造方法’其中上述溶劑係選自由3 -甲氧基-1-丁醇、3 -甲 氧基-3-甲基-1-丁醇、二丙酮醇、4-羥基-2-丁酮、5-羥基-2-戊酮、四氫呋喃-2-羧酸、2-甲基-1，3-丙二醇、γ-丁內 酯、δ -戊內酯、ε -己內酯組成之群組之至少一種。 1 5 .如申請專利範圍第1、2、5或8項之透明導電性 基板之製造方法，其中含有（Α)使鈦化合物與過氧化氫反 應而成之反應產物與（Β)使鈮化合物或鉅化合物與過氧化 氫反應而成之反應產物之前驅物液係含有硝酸及鹽酸中之 至少一者。 16.如申請專利範圍第1、2、5或8項之透明導電性 基板之製造方法，其中含有（Α)使鈦化合物與過氧化氫反 應而成之反應產物與（Β)使鈮化合物或钽化合物與過氧化 氫反應而成之反應產物之前驅物液，含有對鈮化合物或鉅 化合物1莫耳反應2.5〜3.5莫耳之過氧化氫而成之反應產 物，且固成分濃度在8.5重量％以下。 1 7.如申請專利範圍第1 6項之透明導電性基板之製 造方法，其中上述（Α)使鈦化合物與過氧化氫反應而成之 反應產物係對鈦化合物1莫耳反應〇.8~ 1.2莫耳之過氧化 氫而成者。 18.—種比電阻爲9x1 (Γ3Ω · cm以下之透明導電性基 板之製造方法，其特徵爲於透明基材上，形成由作爲摻雜 -110- 200941506 物之摻雜有鈮或鉬之摻雜氧化鈦之無定型物或氧化鈦之無 定型物構成之第一膜上，在比構成該第一膜之摻雜氧化鈦 或氧化鈦之摻雜物含有比率更高之含有比率下，使由上述 摻雜有摻雜物之摻雜氧化鈦之無定型物構成之第二膜層合 而成之層合膜之後，藉由在還原氣體中加熱進行退火處 理，在上述透明基材上形成由摻雜有鈮或鉬之氧化鈦構成 之透明導電性膜。 Q 19.如申請專利範圍第18項之透明導電性基板之製 造方法，其中上述層合膜係藉由塗佈含有（A)使鈦化合物 與過氧化氫反應而成之反應產物之前驅物液，或含有（A) 使鈦化合物與過氧化氫反應之反應產物與（B)使鈮化合物 或钽化合物與過氧化氫反應而成之反應產物之前驅物液並 經加熱而形成。 20.如申請專利範圍第1 9項之透明導電性基板之製 造方法，其中上述（A)鈦化合物及上述（B)鈮化合物或鉬化 〇 合物係使用氫氧化物。 ' 2 1 ·如申請專利範圍第1 9項之透明導電性基板之製 二 造方法，其中含有上述（A)使鈦化合物與過氧化氫反應而 成之反應產物與（B)使鈮化合物或鉬化合物與過氧化氫反 應而成之反應產物之前驅物液係含有以下述通式（1)~(5)之 任一式表示之溶劑： -111 - 200941506 【化1】(5) -109- 200941506 (In the formula (5), Y represents an alkylene group having 3 to 6 carbon atoms which may have a substituent). 14. The method for producing a transparent conductive substrate according to claim 13 wherein the solvent is selected from the group consisting of 3-methoxy-1-butanol and 3-methoxy-3-methyl-1-butanol. , diacetone alcohol, 4-hydroxy-2-butanone, 5-hydroxy-2-pentanone, tetrahydrofuran-2-carboxylic acid, 2-methyl-1,3-propanediol, γ-butyrolactone, δ-pentyl At least one of the group consisting of lactone and ε-caprolactone. A method for producing a transparent conductive substrate according to claim 1, 2, 5 or 8 which contains a reaction product obtained by reacting a titanium compound with hydrogen peroxide and a ruthenium compound Or the reaction product obtained by reacting a giant compound with hydrogen peroxide, the precursor liquid containing at least one of nitric acid and hydrochloric acid. 16. The method for producing a transparent conductive substrate according to claim 1, 2, 5 or 8 which contains (Α) a reaction product obtained by reacting a titanium compound with hydrogen peroxide and a ruthenium compound or a reaction product of a reaction product of a ruthenium compound and hydrogen peroxide, which comprises a reaction product of 2.5 to 3.5 moles of hydrogen peroxide by reacting a ruthenium compound or a giant compound 1 with a solid concentration of 8.5 by weight. %the following. 1 . The method for producing a transparent conductive substrate according to claim 16 , wherein the reaction product obtained by reacting the titanium compound with hydrogen peroxide is a molar reaction of the titanium compound 1 . 1.2 Moer's hydrogen peroxide. 18. A method for producing a transparent conductive substrate having a specific resistance of 9x1 (Γ3 Ω·cm or less), characterized in that a doping of germanium or molybdenum doped with doping-110-200941506 is formed on a transparent substrate. a first film composed of an amorphous form of titanium oxide or an amorphous form of titanium oxide at a content ratio higher than a content ratio of a dopant of titanium oxide or titanium oxide constituting the first film a laminated film formed by laminating a second film composed of the amorphous material of the doped titanium oxide doped with the dopant, and then annealed by heating in a reducing gas to form on the transparent substrate A transparent conductive film comprising a titanium oxide doped with cerium or molybdenum. The method for producing a transparent conductive substrate according to claim 18, wherein the laminated film is coated with (A) a precursor product of a reaction product obtained by reacting a titanium compound with hydrogen peroxide, or (A) a reaction product of reacting a titanium compound with hydrogen peroxide and (B) reacting a ruthenium compound or a ruthenium compound with hydrogen peroxide. Precursor The method for producing a transparent conductive substrate according to claim 19, wherein the (A) titanium compound and the (B) bismuth compound or the molybdenum compound are hydroxides. ' 2 1 · A method for producing a transparent conductive substrate according to claim 19, which comprises the above (A) reaction product obtained by reacting a titanium compound with hydrogen peroxide and (B) a ruthenium compound Or a reaction product obtained by reacting a molybdenum compound with hydrogen peroxide, the precursor liquid system contains a solvent represented by any one of the following formulas (1) to (5): -111 - 200941506 [Chemical 1] (式（1)中，rLr 表示Η或院基’各可相同亦可不同， 表示-ΟΗ或-OR(但是，R表示烷基））， 【化2】 R3 R4(In the formula (1), rLr represents a fluorene or a primordium, and each may be the same or different, and represents -ΟΗ or -OR (however, R represents an alkyl group)), [Chemical 2] R3 R4 X Ο (式（2)中，R1〜R5表示Η或烷基，各可相同亦可不同’ 表示-ΟΗ或-OR(但是，R表示烷基））， 【化3】X Ο (In the formula (2), R1 to R5 represent an anthracene or an alkyl group, each of which may be the same or different, and represents -ΟΗ or -OR (however, R represents an alkyl group)), [Chemical 3] R7 (式（3)中，R1〜R7表示Η或烷基，各可相同亦可不同’ 表示-ΟΗ或-OR(但是，R表示烷基））， 【化4】 (4) (式（4)中，Y表示可具有取代基之碳數3~6之伸烷基）， X ο-R7 (In the formula (3), R1 to R7 represent an anthracene or an alkyl group, each of which may be the same or different, and represents -ΟΗ or -OR (however, R represents an alkyl group), (4) (4) In 4), Y represents an alkyl group having a carbon number of 3 to 6 which may have a substituent, and X ο- 〇〇 -112 - (5) 200941506 【化5】 Ο C-OH I ◦ Y. . (式（5)中，Y表示可具有取代基之碳數3~6之伸烷基）。 ^ 22.如申請專利範圍第21項之透明導電性基板之製造 ❹ 方法，其中上述溶劑係選自由3 -甲氧基-1-丁醇、3 -甲氧 基-3-甲基-1-丁醇、二丙酮醇、4-羥基-2-丁酮、5-羥基-2-戊酮、四氫呋喃_2 -羧酸、2_甲基-1，3 -丙二醇、γ -丁內酯、 δ -戊內酯、ε_己內醋組成之群組之至少一種。 23 .如申請專利範圍第1 9項之透明導電性基板之製 造方法，其中含有（Α)使鈦化合物與過氧化氫反應而成之 反應產物與（Β)使鈮化合物或鉅化合物與過氧化氫反應而 成之反應產物之前驅物液係含有硝酸及鹽酸中之至少一 〇 者。 '* 24.如申請專利範圍第1 9項之透明導電性基板之製 '‘ 造方法，其中含有（Α)使鈦化合物與過氧化氫反應而成之 反應產物與（Β)使鈮化合物或钽化合物與過氧化氫反應而 成之反應產物之前驅物液係含有對鈮化合物或鉅化合物1 莫耳反應2.5~3.5莫耳之過氧化氫而成之反應產物，且固 成分濃度在8.5重量％以下。 25 ·如申請專利範圍第24項之透明導電性基板之製 造方法，其中上述（Α)使鈦化合物與過氧化氫反應而成之 -113- 200941506 反應產物爲對鈦化合物1莫耳反應0.8〜1.2莫耳之過氧化 氫而成者。 26. 如申請專利範圍第1、2、5、8或18項之透明導 電性基板之製造方法，其中在還原氣體中之退火處理之加 熱溫度爲450〜5 5 0°C。 27. 如申請專利範圍第1、2、5、8或18項之透明導 電性基板之製造方法，其中在還原氣體中之退火處理之加 熱溫度超過5 5 0°C，形成之透明導電性膜中之鈮或钽之含 有比率超過1 0莫耳％。 2 8.如申請專利範圍第1、2、5、8或1 8項之透明導 電性基板之製造方法，其中形成具有銳鈦礦型結晶相之透 明導電性膜。 2 9. —種透明導電性基板，其特徵爲係藉由申請專利 範圍第1、2、5、8或18項之方法獲得。 30. —種膜形成用前驅物液’其係含有（A)使欽化合 物與過氧化氫反應而成之反應產物及（B)使鈮化合物或鉬 化合物與過氧化氫反應而成之反應產物之透明導電性膜形 成用前驅物液，其特徵爲含有以下述通式（1)〜（5)之任一式 表示之溶劑= 【化1】 R3 R4-112 - (5) 200941506 化 C-OH I ◦ Y. (In the formula (5), Y represents an alkylene group having 3 to 6 carbon atoms which may have a substituent). The method of producing a transparent conductive substrate according to claim 21, wherein the solvent is selected from the group consisting of 3-methoxy-1-butanol and 3-methoxy-3-methyl-1- Butanol, diacetone alcohol, 4-hydroxy-2-butanone, 5-hydroxy-2-pentanone, tetrahydrofuran-2-carboxylic acid, 2-methyl-1,3-propanediol, γ-butyrolactone, δ - at least one of the group consisting of valerolactone and ε-caprolactone. A method for producing a transparent conductive substrate according to claim 19, which comprises a reaction product obtained by reacting a titanium compound with hydrogen peroxide and (铌) a ruthenium compound or a macro compound and peroxidation. The precursor of the reaction product formed by hydrogen reaction contains at least one of nitric acid and hydrochloric acid. '* 24. The method for producing a transparent conductive substrate according to claim 19, which comprises a reaction product obtained by reacting a titanium compound with hydrogen peroxide and a ruthenium compound or The reaction product of the reaction product of the ruthenium compound and hydrogen peroxide contains a reaction product of 2.5 to 3.5 moles of hydrogen peroxide by reacting the ruthenium compound or the macro compound 1 with a molar concentration of 8.5 by weight. %the following. [25] The method for producing a transparent conductive substrate according to claim 24, wherein the reaction product of the titanium compound and the hydrogen peroxide is -113-200941506, and the reaction product is a molar reaction of the titanium compound 1 to 0.8. 1.2 Moer's hydrogen peroxide. 26. The method of producing a transparent conductive substrate according to claim 1, 2, 5, 8 or 18, wherein the annealing temperature in the reducing gas is 450 to 550 °C. 27. The method for producing a transparent conductive substrate according to claim 1, 2, 5, 8 or 18, wherein the annealing temperature in the reducing gas is higher than 550 ° C, and the transparent conductive film is formed. The content ratio of 中 or 钽 is more than 10% by mole. 2. A method of producing a transparent conductive substrate according to claim 1, 2, 5, 8 or 18, wherein a transparent conductive film having an anatase crystal phase is formed. 2. A transparent conductive substrate obtained by the method of claim 1, 2, 5, 8 or 18. 30. A precursor film for forming a film, which comprises (A) a reaction product obtained by reacting a compound with hydrogen peroxide and (B) a reaction product obtained by reacting a ruthenium compound or a molybdenum compound with hydrogen peroxide. The precursor liquid for forming a transparent conductive film, which is characterized by containing a solvent represented by any one of the following formulas (1) to (5) = [Chemical Formula 1] R3 R4 X OH (式（1)中，RLR6表示Η或烷基，各可相同亦可不同，X -114- 200941506 表示-OH或-OR(但是，R表示烷基））， 【化2】X OH (In the formula (1), RLR6 represents hydrazine or an alkyl group, and each may be the same or different, and X-114-200941506 represents -OH or -OR (however, R represents an alkyl group), [Chemical 2] (2) . (式（2)中，RLR5表示Η或烷基，各可相同亦可不同， . 表示-ΟΗ或-OR(但是，R表示烷基））， 【化3 I 〇 R3 R4 R5 R6 :γ 丫⑶ X Ο (式（3)中，R1〜R7表示Η或烷基，各可相同亦可不同， 表示-ΟΗ或- OR(但是，R表示烷基））， 【化4】(2) (In the formula (2), RLR5 represents an anthracene or an alkyl group, and each may be the same or different, and represents -ΟΗ or -OR (however, R represents an alkyl group), [Chemical 3 I 〇R3 R4 R5 R6 : γ 丫 (3) X Ο (In the formula (3), R1 to R7 represent an anthracene or an alkyl group, and each may be the same or different, and represents -ΟΗ or -OR (however, R represents an alkyl group), [Chemical 4] (4) (式（4)中，Y表示可具有取代基之碳數3〜6之伸烷基）， 【化5】(4) (In the formula (4), Y represents an alkyl group having 3 to 6 carbon atoms which may have a substituent), [Chemical 5] ⑶ -115- 200941506 (式（5)中’ Y表示可具有取代基之碳數3~6之伸烷基）。 31·如申請專利範圍第3〇項之膜形成用前驅物液， 其中上述溶廁係選自由3 -甲氧基-ΐ_丁醇、3 -甲氧基_3_甲 基-1-丁醇、二丙酮醇、4-羥基-2_ 丁酮、5_羥基-2-戊酮、 四氫呋喃-2-羧酸、2 -甲基-丨，3_丙二醇、^丁內酯、δ -戊內 醋、ε -己內酯組成之群組之至少一種。 32. —種膜形成用前驅物液，其係含有（Α)使鈦化合 物與過氧化氫反應而成之反應產物及（Β)使鈮化合物或鉅 化合物與過氧化氫反應而成之反應產物之透明導電性膜形 成用前驅物液，其特徵爲含有硝酸及鹽酸中之至少一者。 33. —種膜形成用前驅物液，其特徵爲含有對鈮化合 物或鉅化合物1莫耳反應2.5 ~3.5莫耳之過氧化氫而成之 反應產物，且固成分濃度在8.5重量％以下。 34. 如申請專利範圍第32或33項之膜形成用前驅物 液，其中含有以下述通式（1)~(5)之任一式表示之溶劑： 【化1】 R3 R4(3) -115- 200941506 (wherein Y in the formula (5) represents an alkylene group having 3 to 6 carbon atoms which may have a substituent). The precursor liquid for film formation according to the third aspect of the invention, wherein the above-mentioned toilet is selected from the group consisting of 3-methoxy-indolebutanol and 3-methoxy-3-methyl-1-butanol Alcohol, diacetone alcohol, 4-hydroxy-2-butanone, 5-hydroxy-2-pentanone, tetrahydrofuran-2-carboxylic acid, 2-methyl-indole, 3-propanediol, butyrolactone, δ-pentene At least one of the group consisting of vinegar and ε-caprolactone. 32. A precursor liquid for film formation, which comprises (Α) a reaction product obtained by reacting a titanium compound with hydrogen peroxide and a reaction product obtained by reacting a ruthenium compound or a giant compound with hydrogen peroxide. The precursor liquid for forming a transparent conductive film is characterized by containing at least one of nitric acid and hydrochloric acid. 33. A precursor liquid for forming a film, which comprises a reaction product of reacting 2.5 to 3.5 moles of hydrogen peroxide with a ruthenium compound or a macromolecule, and having a solid concentration of 8.5% by weight or less. 34. A precursor for film formation according to claim 32 or 33, which comprises a solvent represented by any one of the following formulas (1) to (5): [Chemical Formula 1] R3 R4 (式（1)中，R1〜R6表示Η或烷基’各可相同亦可不同，X 表不-ΟΗ或- OR(但是，R表不院基））’ -116 - 200941506 【化2】 R1· R4 V • R5 、(Τ (2) X 0 (式（2)中，R1〜R5表示Η或烷基’各可相同亦可不同’ χ 表示-ΟΗ或- OR(但是’ R表示院基））’ 【化3】(In the formula (1), R1 to R6 represent an anthracene or an alkyl group, each of which may be the same or different, and X is not -ΟΗ or -OR (however, R is not a hospital base)) -116 - 200941506 [Chemical 2] R1· R4 V • R5 , (Τ (2) X 0 (in the formula (2), R1 to R5 represent Η or alkyl group 'each may be the same or different' χ denotes -ΟΗ or -OR (but 'R represents the hospital Base))' 【化3】 (式（3)中，RLR7表示Η或烷基’各可相同亦可不同 表示-ΟΗ或- 〇R(但是，R表示烷基））， 【化4】 X ❹ η 0-C ⑷ 0 (式（4)中，Υ表示可具有取代基之碳數 【化5】 6之伸烷基） Ο C-ΟΗ Υ· ⑶ (式（5)中，Υ表示可具有取代基之碳數3〜6之伸院基）° 35.如申請專利範圍第34項之膜形成用前驅物液 -117- 200941506 其中上述溶劑係選自由3 -甲氧基-1-丁醇、3 基·1· 丁醇、二丙酮醇、4-羥基-2-丁酮、5-趕 四氫呋喃-2-羧酸、2-甲基-1，3-丙二醇、γ-丁 酯、ε -己內酯組成之群組之至少一種。 36.如申請專利範圍第32項之膜形成J 其中上述（Α)使鈦化合物與過氧化氫反應而β 係對鈦化合物1莫耳反應0.8〜1.2莫耳之i 者，且上述（B)使鈮化合物或鉅化合物與過讀 成之反應產物係對鈮化合物或鉅化合物 2.5〜3.5莫耳過氧化氫成者。 -甲氧基-3-甲 :基-2-戊酮、 习酯、δ-戊內 百前驅物液， 之之反應產物 I氧化氫而成 民化氫反應而 1莫耳反應 -118- 200941506 七、指定代表圖： (一） 、本案指定代表圖為：無 (二） 、本代表圖之元件代表符號簡單說明：無(In the formula (3), RLR7 represents a hydrazine or an alkyl group, each of which may be the same or different - ΟΗ or - 〇R (however, R represents an alkyl group), [Chemical 4] X ❹ η 0-C (4) 0 ( In the formula (4), Υ represents a carbon number which may have a substituent, and a C. Ο ( (3) (in the formula (5), Υ represents a carbon number which may have a substituent 3~ Precursor solution for film formation according to claim 34 of the invention, wherein the solvent is selected from the group consisting of 3-methoxy-1-butanol and 3 base·1· Group of alcohol, diacetone alcohol, 4-hydroxy-2-butanone, 5- catching tetrahydrofuran-2-carboxylic acid, 2-methyl-1,3-propanediol, γ-butyl ester, ε-caprolactone At least one of them. 36. The film formation of claim 32, wherein the above (Α) reacts the titanium compound with hydrogen peroxide and the β system reacts with the titanium compound 1 with a molar response of 0.8 to 1.2 m, and the above (B) The reaction product of the ruthenium compound or the macro compound with the over-reading is a ruthenium compound or a giant compound of 2.5 to 3.5 mol hydrogen peroxide. -Methoxy-3-methyl-2-pentanone, benzyl ester, δ-pentane 100 precursor liquid, the reaction product I hydrogen peroxide to form a hydrogen reaction and 1 molar reaction -118- 200941506 VII. Designated representative map: (1) The representative representative of the case is: (2), the representative symbol of the representative figure is simple: no 八、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none -4--4-
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