[go: up one dir, main page]

TW201122064A - Conductive paste, conductive film, touch panel and method for producing conductive thin film - Google Patents

Conductive paste, conductive film, touch panel and method for producing conductive thin film Download PDF

Info

Publication number
TW201122064A
TW201122064A TW99135044A TW99135044A TW201122064A TW 201122064 A TW201122064 A TW 201122064A TW 99135044 A TW99135044 A TW 99135044A TW 99135044 A TW99135044 A TW 99135044A TW 201122064 A TW201122064 A TW 201122064A
Authority
TW
Taiwan
Prior art keywords
conductive
parts
resin
film
paste
Prior art date
Application number
TW99135044A
Other languages
Chinese (zh)
Other versions
TWI486413B (en
Inventor
Ryo Hamasaki
Original Assignee
Toyo Boseki
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Boseki filed Critical Toyo Boseki
Publication of TW201122064A publication Critical patent/TW201122064A/en
Application granted granted Critical
Publication of TWI486413B publication Critical patent/TWI486413B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • 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
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Dispersion Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Conductive Materials (AREA)
  • Laminated Bodies (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Position Input By Displaying (AREA)
  • Non-Insulated Conductors (AREA)
  • Manufacturing Of Electric Cables (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention provides a conductive paste used to form a conductive thin film which enhances adherability observably and has high confidence degree and high electrical conductivity relative to a substrate having a conductive layer. The conductive paste comprises a compound (A) which is a binder resin made of polyurethane resin having an acid value of 50 to 500 eq/ton and glass transition temperature of 60 to 150 DEG C, a compound (B) which is made of metallic powder and a compound (C) which is made of an organic solvent.

Description

.201122064 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種導電性糊及其用途，更詳言之，係 關於一種含有作爲黏結劑樹脂之聚胺甲酸酯樹脂的導電性 糊’使用由該導電性糊所構成的導電性膜及其製造方法， 該導電性薄膜係積層於透明導電性層上之導電性積層體， 及使用它之導電性積層體的觸控面板。 【先前技術】 藉由利用手指或專用筆等接觸畫面而進行操作的透明 觸控面板已用於ATM、汽車衛星定位系統、遊戲機、車站 之車票自動販賣機、複印機、博物館之解說終端、及便利 商店之資訊終端等之廣範圍的用途。 透明觸控面板係使透明之二片導電性薄膜重疊而形成 切換的方式來構成。一般而言，此種透明觸控面板之透明 導電性薄膜係利用蒸鏟法或濺鍍法，藉由使成爲透明電極 材料之氧化銦錫膜（以下，也有簡稱爲ITO膜之情形）附 著於聚酯薄膜、玻璃等之基材而蝕刻該ITO膜，來進行圖 案形成所形成。 觸控面板具有各種方式，電阻膜方式與靜電容量方式 爲其代表。 電阻膜方式之特徵爲利用感測壓力特定所接觸的位置 之簡單構造而製造爲既簡單且低成本地能夠生產，容易進 行詳細之位置檢測，也能夠對應於藉由筆所獲得之文字輸 [S1 -3- 201122064 入。另一方面，缺點可列舉：由於將導電薄膜貼附於液晶 上之構造，使畫面之穿透率變低，難以實現鮮明的畫面之 點。 靜電容量方式之特徵係以藉由利用手指或專用筆接觸 面板而感測所引起的放電現象等來特定位置之方式，能夠 進行多點感測。 若觸控面板欲利用筆或指尖等而輸入時，雖然使其固 定電極側之透明導電性薄膜與可動電極（薄膜電極）側之 透明導電性薄膜的透明導電性薄膜彼此接觸或接近的方式 來形成，但是近年來隨著遊戲機等所觀察到的筆輸入形態 的多樣化、輸入時之荷重，尤其因爲藉由筆輸入所導致的 荷重而於透明導電性薄膜中發生裂痕、剝離等之破壞而成 爲問題。因此，使筆磨擦耐久性提高成爲必須，近年來正 熱衷於進行使透明導電性薄膜之強度提高的嘗試。 爲了提高透明導電性薄膜之強度的嘗試，例如，認爲 使構成薄膜的氧化物結晶化爲有效。爲了使透明導電性薄 膜結晶化，具有下列之手法：在塑膠薄膜基材上長成非結 晶性之透明導電性薄膜後，將所獲得之積層膜加熱至透明 導電性薄膜之結晶化溫度以上（例如，專利文獻1 )。 其他，如專利文獻2所示，使規定比表面積値、平均 粒徑之氧化銦粉末 '及氧化錫粉末予以混合/粉碎，除了規 定氧化錫含量之外’藉由加壓成形，得到成形體而獲得結 晶性ITO薄膜之方法等’各公司爲了提高耐久性，以提高 結晶化率爲目標。 -4- 201122064 另一方面，如上所述，隨著構成透明導電性薄膜的氧 化物之結晶化，確保在透明導電性薄膜上所形成的導電性 塗膜之密著性將變得困難。一般而言，連接電極之導電性 塗膜形成係藉由含有銀等之導電性粉末的導電性糊之網板 印刷塗布所實施，構成透明導電性薄膜的氧化物爲結晶性 之情形，由於藉由結晶化而保持透明導電性薄膜之表面構 造的秩序，具有表面活性低、因凹凸所導致的固定效果將 降低之傾向。再者，由於保持了構造之秩序，存在於導電 性糊中之溶劑向基底層的滲透效果則具有較非晶性透明導 電性薄膜還弱的傾向。根據此等之理由，確保乾燥後之密 著性爲困難的。 基於以上之事實，尤其相對於結晶性透明導電性薄膜 之密著性爲良好，現在正強烈尋求確保導電性之低溫加工 可能的導電性糊，如此之導電性糊之開發現狀尙不充足。 習知之觸控面板用之導電性糊，大多係將作爲習知之 膜切換或感壓感測器等之電極用途所用之導電性糊轉用於 觸控面板使用之情形爲多的。例如，於專利文獻3所示之 導電性糊中，使用玻璃轉移溫度爲80 °C以上之聚酯樹脂， 如此之聚酯樹脂作爲觸控面板用途使用之情形，密著性之 觀點下，與構成透明導電性薄膜的氧化物並無能夠相互作 用之部位，基於密著性之觀點，並不適合。同樣的，於專 利文獻4中，揭示以聚酯樹脂或聚胺甲酸酯樹脂作爲黏結 劑樹脂之導電性糊，對於結晶性透明導電性薄膜之密著性 -5- 201122064 則未必充足。換言之，未導入用以使與構成透明導電性薄 膜的氧化物之密著性提高之樹脂或添加劑的設計思想，根 據氧化物之種類而產生密著性之偏異，尤其針對相對於結 晶性透明導電性薄膜之密著性不得不說極爲缺乏。 另外，於專利文獻5中，揭示玻璃轉移溫度爲50°C以 上之有機樹脂，尤其以聚酯樹脂作爲構造成分之導電性 糊。於專利文獻5之實施例及比較例中所使用的聚酯樹脂 係僅根據玻璃轉移溫度所特定而欠缺具體性，驗證其效果 係困難的，若根據本發明人等之探討，對於結晶性透明導 電性薄膜之密著性未必充足。另外，相同於專利文獻4之 情形，未導入用以使與構成透明導電性薄膜的氧化物之密 著性提高之樹脂或添加劑的設計思想，根據氧化物之種類 而產生密著性之偏異，尤其針對對於結晶性透明導電性薄 膜之密著性不得不說極爲缺乏。 另一方面，如在專利文獻6所用之熱硬化型導電性糊 中，除了構成樹脂與透明導電性薄膜的氧化物並無能夠相 互作用之部位以外，由於爲熱硬化型，1 50°C以上之加工溫 度爲必要，將有引起基底層之熱變形的擔憂及生產性之降 低的問題點。 另一方面，於專利文獻3中，觸控面板用銀糊係藉由 摻合矽烷耦合劑而進行欲確保與ITO之密著性的嘗試。然 而’由於矽烷耦合劑係低分子，藉由可塑劑之效用而僅對 導電性或表面硬度造成影響，在長期信賴性方面也不佳。 [S] -6- 201122064 另外’由於矽烷耦合劑係以少量添加劑的方式所使用，擔 憂容易產生塗膜內之偏異，且因塗膜之長期保管而流出的 可能性。 專利文獻1:特開2005-141981號公報 專利文獻2:特開2004-323877號公報 專利文獻3:特開2003-203523號公報 專利文獻4:特開2〇〇3-223812號公報 專利文獻5:特開2006-059720號公報 專利文獻6 :特開平1 - 1 5 9 9 0 6號公報 【發明內容】 發明所欲解決之技術問題 本發明之目的在於提供一種用以使導電性薄膜形成之 導電性糊，其係對於具有透明導電層等之基材，顯著地使 密著性提高，能夠賦予高信賴性及高導電性。 解決問題之技術手段 爲了解決如此之問題，鑽硏之結果，得到如下之見解： 導電性糊中，黏結劑樹脂係於導電性糊中含有一種具有特 定之數量平均分子量、酸價及玻璃轉移溫度之聚胺甲酸酯 樹脂，作爲形成導電性薄膜之導電性糊係有用的。本發明 係基於如此之見解所完成者。 項1: 一種導電性糊，其係含有： (A)成分，由酸價爲50至500eq/ton、玻璃轉移溫度爲 60至150°C之聚胺甲酸酯樹脂所構成的黏著劑樹脂； 201122064 (B) 成分，由金屬粉末所構成，·及 (C) 成分，由有機溶劑所構成。 項2:揭示於項1之導電性糊，其中（A)成分係由具有 經藉由進行下列（Al)、（A2)與（A3)之加成聚合反應所獲得 結構之聚胺甲酸酯樹脂所構成的黏著劑樹脂： (A1)數量平均分子量爲1，〇〇〇至1 0,000及玻璃轉移溫 度爲3 0至8 0 °C之非晶性性聚醇、 (A2)數量平均分子量低於1，〇〇〇且一分子中具有2個 以上可與異氰酸酯進行反應之官能基的化合物、及 (A3)聚異氰酸酯。 項3:揭示於項1或2之導電性糊，其中（A)成分係由 具有經藉由進行下列（Al)、（A2)、（A3)與（A4)之加成聚合 反應所獲得結構之聚胺甲酸酯樹脂所構成的黏著劑樹脂： (A1)數量平均分子量爲1,000至1〇,〇〇〇及玻璃轉移溫 度爲3 0至8 0 °C之非晶性性聚醇、 (A2)數量平均分子量低於1，000且一分子中具有2個 以上可與異氰酸酯進行反應之官能基的化合物、 (A3)聚異氰酸酯、及 (A4)數量平均分子量爲1,000至1〇,〇〇〇及玻璃轉移溫 度低於3 0 °C之非晶性性聚醇。 項4 :揭示於項2或3之導電性糊，其中該非晶性性 聚醇（A 1)係非晶聚酯聚醇’該非晶聚酯聚醇係將全部聚羧 酸與全部聚醇成分分別設爲莫耳％時，全部聚羧酸成 -8 - 201122064 分之內，芳香族二羧酸爲60莫耳％以上，全部聚醇成分之 內，主鏈之碳數爲4以下之二醇爲60莫耳％以上。 項5.揭示於項2至4中任一項之導電性糊，其中可與 化合物（A2)中之異氰酸酯進行反應之官能基爲羥基或胺 基。 項6 :揭示於項2至5中任一項之導電性糊’其中化 合物（A2)更含有羧基。· 項7 :揭示於項1至6中任一項之導電性糊’其中（B) 成分更含有金屬粉末以外之導電性粉末。 項8:揭示於項1至7中任一項之導電性糊’其中相 對於1〇〇質量份之黏結劑樹脂（A)而言’（B)成分之含量爲 400至1，900質量份。 項9:揭示於項1至8中任一項之導電性糊’其中相 對於100質量份之黏結劑樹脂（A)而言’（C)成分之含量爲 150至500質量份。 項10: —種導電性薄膜，其係由使用揭示於項1至9 中任一項之導電性糊所構成。 項11: 一種導電性積層體，其係在透明導電性層上積 層揭示於項10之導電性薄膜。 項12:揭示於項11之導電性積層體’其中透明導電 性層係由以氧化銦錫作爲主要成分所構成的IT0膜。 項13: —種觸控面板，其係使用揭示於項11或12之 導電性積層體。 -9- 201122064 項14: 一種導電性薄膜之製造方法，其係包括： 揭示於項1至9中任一項之導電性糊塗布或印刷於基 材上的步驟；及 於80至150 °C進行加熱的步驟。 發明之效果 本發明之導電性糊係由於所含有的黏結劑樹脂具有高 的玻璃轉移溫度，於形成薄膜之際’即使於高溫環境下也 能夠維持良好之膜，具有高的信賴性。另外，於黏結劑樹 脂中，由於具有特定之酸價，在基材上形成薄膜之際，因 存在於基材上之吸附水等之附著物所造成的剝離爲少的， 能夠顯著地使與其他材料之密著性提高。 因此，適合於特別良好之密著性與高的信賴性、導電 性所要求的觸控面板等之用途。 【實施方式】 以下，針對本發明之導電性糊之各成分，詳細加以說 明。 (A)成分 聚胺甲酸酯樹脂之黏結劑樹脂（A)具有胺甲酸酯鍵結 成爲必須。 藉由具有胺甲酸酯鍵，於導電性糊的塗布或印刷後之 硬化中，根據起因於分子間氫鍵之高的凝聚力，藉由使塗 膜內部的金屬粉末等之導電性粉末相互的距離接近，能夠 發現高導電性。另外，於低溫乾燥中，例如，殘存溶劑之 201122064 情形下，也根據黏結劑樹脂之高的凝聚力而能夠發現高導 電性與對基材之高密著性。胺甲酸酯鍵係至少依照非晶性 聚醇與聚異氰酸酯之反應所形成，再者，較佳的實施形態 係數量平均分子量低於1，〇〇〇、且含有一分子中具有2個以 上可與異氰酸酯進行反應之官能基的化合物、與聚異氰酸 酯之反應所形成之物。 基於黏結劑樹脂之耐久性之觀點，黏結劑樹脂之數量 平均分子量爲10,000以上，較佳爲20,000以上。若數量平 均分子量低於10, 〇〇〇時，除了長期耐久性發生問題之外， 糊黏度將降低，印刷性將降低。另外，基於糊黏度（網板印 刷適合性）、溶解性之觀點，黏結劑樹脂之數量平均分子量 較佳爲1 00,000以下。 黏結劑樹脂係玻璃轉移溫度爲60°c以上，較佳爲70 t以上。若玻璃轉移溫度較6(TC爲低時，不摻合硬化劑之 情形下，由於高溫時，樹脂將軟化，擔憂作爲糊之信賴性 將降低。另外，誘導表面硬度之降低，另外，由於黏著性， 於製造步驟及/或使用之際，擔憂發生樹脂、摻合物之移向 接觸對方側，信賴性將降低。若考量密著性、溶解性、糊 黏度及印刷性等時，黏結劑樹脂之玻璃轉移溫度較佳爲1 5 0 °C以下，更佳爲120°C以下，進一步更佳爲l〇〇°C以下。黏 結劑樹脂之玻璃轉移溫度係藉由選擇非晶性聚醇 A 1 ,A4， 一分子中具有2個以上可與異氰酸酯進行反應之官能基的 化合物A2，聚異氰酸酯A3之組成比及A1，A2，A3,A4之化 [S] -11- 201122064 學構造而能夠調整。爲了使本發明之申請專利範圍內的玻 璃轉移溫度得以發現，A1之玻璃轉移溫度較佳爲4(TC以 上’聚異氰酸酯較佳爲至少一種具有脂環族骨架及/或芳香 族骨架’其組成比較佳爲質量比A1>A3>A2，另外，較佳 爲質量比A 1 > A4。 黏結劑樹脂係具有特定範圍之酸價。藉由賦予酸價， 根據與存在於透明導電層中之吸附水的化學相互作用而使 密著性顯著提高。 黏結劑樹脂之酸價爲50至500eq/ton，較佳爲100至 350eq/t〇n。若酸價較50eq/ton還低時，所獲得之導電性薄 膜與透明導電性薄膜之密著性提高效將具有變小的傾向。 另一方面，若酸價超過5 00eq/ton時，除了吸水性變高之 外’依照觸媒作用而具有促進黏結劑樹脂水解之可能性， 具有與形成導電性薄膜時之電極的信賴性降低有關之傾 向。 ... 將酸價導入黏結劑樹脂之方法，可列舉下列之方法 等：於黏結劑樹脂之聚胺甲酸酯樹脂的步驟中之聚醇與聚 異氰酸醋的鏈延長步驟中，共聚合二經甲基丁酸、二淫甲 基丙酸等之含有羧基的一分子中含有2個以上官能基的化 合物；或是在偏苯三酸酐、二苯甲酮四羧酸、三羥甲基酸 酐等之多價羧酸酐而將酸價導入分子中或分子末端。本發 明之導入酸價之方法可以使用上述方法中任一種。 [S] -12- 201122064 黏結劑樹脂（A)係較佳爲一種聚酯胺甲酸酯樹脂，至少 (A1)分子量爲1,000至1〇,〇〇〇，較佳爲ι，500至7,000，玻 璃轉移溫度爲3 0至8 0 °C，較佳爲4 5至7 0 T：之非晶性聚 醇；（A2)數量平均分子量低於1,〇〇〇，較佳爲6〇至400, 一分子中具有2個以上可與異氯酸酯進行反應之官能基的 化合物；及（A3)藉由聚異氰酸酯之加成聚合反應所製造❶ 另外，黏結劑樹脂（A)也較佳爲一種聚酯胺甲酸酯樹脂，至 少（A1)分子量爲1，000至10,〇〇〇，較佳爲1，500至7,000, 玻璃轉移溫度爲30至8 0°C，較佳爲45至70 °C之非晶性聚 醇；（A2)數量平均分子量低於1，000，較佳爲60至400, 一分子中具有2個以上可與異氰酸酯進行反應之官能基的 化合物；（A3)聚異氰酸酯；及（A4)分子量爲 1,000至 1 0,000，較佳爲1，5 00至7,〇〇〇，且玻璃轉移溫度低於30 °C之非晶性聚醇之加成聚合反應所製造的較佳之聚酯胺甲 酸酯樹脂。非晶性聚醇可列舉：聚醚聚醇、聚酯聚醇等， 基於分子設計之自由度’較佳爲聚酯聚醇。聚酯聚醇較佳 爲藉由二羧酸與聚醇之縮合所得到者》還有，二羧酸也可 以爲利用碳數1至12之醇所酯化的二羧酸酯。 於該聚酯聚醇之製造中所使用的二羧酸，可列舉：對 苯二酸、間苯二酸、鄰苯二酸、2,6-萘二酸等之芳香族二 酸；琥珀酸、戊二酸、己二酸、癸二酸、十二烷二酸、壬 二酸等之脂肪族二酸；二聚物酸等之碳數12至28之二鹼 式酸；1,4-環己二酸' 1，3-環己二酸、1，2-環己二酸、4-甲 -13- 201122064 基六氫鄰苯二酸酐、3-甲基六氫鄰苯二酸酐、2-甲基六氫 鄰苯二酸酐、二羧基加氫雙酚A、二羧基加氫雙酚S、二聚 物酸、加氫二聚物酸、加氫萘二酸、三環癸二酸等之脂環 族二酸或脂環族二酸酐；羥基安息香酸、乳酸等之羥基羧 酸等。另外，於不損害發明之效果的範圍內，也可以與偏 苯三酸酐、均苯四酸酐等之多價羧酸：反丁烯二酸等之不 飽和二羧酸進行共聚合；再者也可以與5-磺基間苯二酸鈉 鹽等之含有磺酸金屬鹼之二羧酸進行共聚合。 非晶性聚醇（A1)較佳爲聚酯聚醇，基於強度或耐熱 性、耐濕性及耐熱衝擊性等之耐久性之觀點，構成聚酯聚 醇之全部酸成分之中的芳香族二羧酸較佳爲共聚合60莫 耳％以上，更佳爲80莫耳％以上，進一步更佳爲90莫耳 %以上，特別理想爲98莫耳％以上。全部酸成分爲由芳香 族二羧酸所構成係較佳的實施形態。芳香族二羧酸成分較 60莫耳％還少時，擔憂本發明之聚胺甲酸酯樹脂（A)之玻璃 轉移溫度變得較60°C還低，且擔憂耐濕熱性、耐久性將降 低。另一方面，非晶性聚醇（A4)較佳爲聚酯聚醇，構成聚 酯聚醇之全部酸成分之中，芳香族二羧酸較佳爲30莫耳％ 以上，較佳爲50莫耳％以上，進一步更佳爲70莫耳％以 上。 於該聚酯聚醇之製造中所使用的二醇，可列舉：乙二 醇、丙二醇、1，3-丁二醇、1，4-丁二醇、1，5-戊二醇、新戊 二醇、1，6-己二醇、3-甲基·1，5-戊二醇、2-甲基-1,5-戊二 [S] -14- 201122064 醇、2-甲基-1，3-丙二醇' 2,2-二乙基-1，3-丙二醇、2-丁基·2-乙基-1，3-丙二醇、1，9-壬二醇、1，1〇-癸二醇等之脂肪族二 醇、1，4-環己二甲醇、1，3-環己二甲醇、1,2-環己二甲醇、 二聚物二醇等之脂環族二醇。另外，於不損害發明之範圍 內’也可以倂用三羥甲基乙烷、三羥甲基丙烷、甘油 '新 戊二醇、聚甘油等之多元聚醇。 非晶性聚醇（Α1)較佳爲聚酯聚醇，基於強度或耐熱 性、耐濕性及耐熱衝擊性等之耐久性之觀點，構成聚酯聚 醇之全部聚醇成分之內，主鏈之碳數爲4以下之二醇較佳 爲60莫耳％以上’更佳爲80莫耳％以上，進一步更佳爲 95莫耳％以上。全部聚醇成分之內，若主鏈之碳數爲4以 下之二醇變得較60莫耳％還少時，擔憂本發明之聚胺甲酸 酯樹脂Α之玻璃轉移溫度較6〇°C還低，擔憂耐濕熱性、耐 久性將降低。另一方面，非晶性聚醇（A4)較佳爲聚酯聚醇， 構成聚酯聚醇之全部聚醇成分之內，主鏈之碳數4以下之 乙二醇較佳爲80莫耳％以下，更佳爲70莫耳％以下，進 一步更佳爲60莫耳％以下。 本發明使用的黏結劑樹脂（A)能夠藉由至少該非晶性 聚醇（A1)與數量平均分子量低於」，〇〇〇, 一分子中具有2個 以上可與異氰酸酯進行反應之官能基的化合物（A2)、及以 下所示之聚異氰酸酯（A3)之加成聚合反應而製造。另外， 黏結劑樹脂（A)係至少該非晶性聚醇（Al )、（A4)且數量平均 分子量低於1,000,能夠藉由一分子中具有2個以上可與異 -15- 201122064 氰酸酯進行反應之官能基的化合物（A2)與以下所示之聚異 氰酸酯（A3)的加成聚合反應而製造。可與化合物(A2)中之 異氰酸酯進行反應所獲得之官能基較佳爲羥基及胺基，化 合物（A2)也可以爲具有其中任一種或二種。具體之（A2)成 分，如先前敘述作爲酸價導入手法之使用的二羥甲基丁 酸、二羥甲基丙酸之含有羧基的化合物之外，也可列舉： 1，2-丙二醇、1，2-丁 二醇、1，3-丁 二醇、2,3· 丁 二醇、2,2-二甲基-1，3-丙二醇、3-甲基-1，5-戊二醇、2,2,4-三甲基-1，3-戊二醇、2-乙基-1，3-己二醇、2,2-二甲基-3-羥丙基-2’，2’-二甲基-3-羥基丙酸酯、2-正丁基-2-乙基-l，3-丙二醇、3-乙基·l,：5-戊二醇、3-丙基-l，5-己二醇、2,2-二乙基-l，3-丙 二醇、3-辛基-1,5-戊二醇、3-苯基-1,5-戊二醇、2,5-二甲 基 -3-磺基鈉 -2,5-己二醇、二聚物二醇 (PRIPOL-2033(Unichema International 公司製））等之一分 子中具有2個羥基的化合物；三羥甲基乙烷、三羥甲基丙 烷、甘油、新戊二醇、聚甘油等之多元醇；單乙醇胺、二 乙醇胺、三乙醇胺等之一分子中具有1個以上之羥基與胺 基之胺基醇；乙二胺、1,6-己二胺、1,8-辛二胺、1,9-辛二 胺、1，1〇-癸二胺、1,11-十一烷二胺、1,12-十二烷二胺等之 脂肪族二胺或間二甲苯二胺、4,4-二胺基二苯基甲烷、3,4’-二胺基二苯基醚' 4,4，-二胺基二苯基醚等之一分子中具有 2個胺基之芳香族二胺等。上述之數量平均分子量係低於 1，000，一分子中具有2個以上可與異氰酸酯進行反應之官 -16- 201122064 能基的化合物可以單獨使用，也可以倂用數種，無任何問 題。 構成黏結劑樹脂（A)之聚異氰酸酯（A3)，可列舉：2,4-甲苯二異氰酸酯' 2，6 -甲苯二異氰酸酯、對苯二異氰酸酯、 4,4’-二苯甲烷二異氰酸酯、間苯二異氰酸酯、3,3, _二甲氧 基-4,4’-聯苯二異氰酸酯、2，6_萘二異氰酸酯、3，3，·二甲氧 基-4,4’-聯苯二異氰酸酯、4,4’-二苯基二異氰酸酯、4,4，-二異氰酸酯二苯基醚、1，5 -萘二異氰酸酯、間二甲苯二異 氰酸酯、異佛酮二異氰酸酯、伸丁二異氰酸酯、伸己二異 氰酸酯、甲苯二異氰酸醋等。 該聚異氰酸酯（A3)與非晶性聚醇（A1)及數量平均分子 量低於1，000,且藉由使一分子中具有2個以上可與異氰酸 酯進行反應之官能基的化合物（A2)反應，能夠將胺甲酸酯 鍵導入黏結劑樹脂（A)中。另外，該聚異氰酸酯（A3)與非晶 性聚醇（Al)、（A4)及數量平均分子量低於1，〇〇〇，且藉由使 一分子中具有2個以上可與異氰酸酯進行反應之官能基的 化合物（A2)反應，能夠將胺甲酸酯鍵導入黏結劑樹脂（A) 中 〇 黏結劑樹脂（A)能夠於溶劑中進行聚合，其溶劑之沸點 較佳爲8 0 °C以上。若沸點爲8 0 °C以上之溶劑的話，因爲揮 發性爲低的，摻合金屬粉末及所期望的金屬粉末以外之導 電性粉末或其他摻合物之後，利用三輥等使其分散之際， 無進行溶劑置換之必要，能夠有效地進行作業，基於成本 [S] -17- 201122064 之觀點，也形成優點。另一方面，以無溶劑方式聚合黏結 劑樹脂（A)之後，即使溶解於沸點80〇c以上之溶劑中，也無 任何之問題。 該沸點8 0 °C以上之溶劑，能夠使用下列各種之溶劑： 甲苯、一甲本、四甲基本、Solvesso 100、Solvesso 150、 Solvesso 200、四氫化萘等之芳香族烴系；Decaiin等之脂 肪族烴系；萜品醇（terpineol)等之醇系；甲基乙基酮、甲基 異丁基酮、環己酮等之酮系；乙二醇二甲基醚、二乙二醇 二甲基醚、二乙二醇單乙基醚、二丙二醇二乙基醚、二噚 烷、二乙基醚、四氫呋喃等之醚系：纖維素醋酸酯、乙基 纖維素、丁基纖維素等之纖維素系；卡必醇、丁基卡必醇 等之卡必醇類之各種溶劑。聚合中，即使混合2種以上之 該溶劑也無任何之問題。 於製造黏結劑樹脂（A)時的各單體摻合之際，除了該溶 劑之外，只要能夠抑制三輥時之揮發的影響下，添加沸點 較8 0 °C還低的溶劑，並無任何問題。另外，於使用前添加 沸點低於8 0 °C之溶劑，也不設定限制。 於黏結劑樹脂中，於不損害本發明效果之程度下’也 可以摻合可與具有胺甲酸酯鍵之聚胺甲酸酯樹脂進行反應 之硬化劑。藉由摻合硬化劑，具有使硬化溫度變高之可能 性，能夠期待因塗膜物性之提高所導致的信賴性之提高。 能夠與本發明之黏結劑樹脂進行反應所獲得之硬化劑，雖 然種類並不限定，但是基於接著性、耐彎曲性、硬化性等， [S3 201122064 特佳爲異氰酸酯化合物。再者，基於儲藏安定性，此等異 氰酸酯化合物較佳使用嵌段化異氰酸基之物。異氰酸酯化 合物以外之硬化劑，可列舉：甲基化三聚氰胺、丁基化三 聚氰胺、苯并三聚氰二胺、尿素樹脂等之胺基樹脂、酸酐、 咪唑類、環氧樹脂、苯酚樹脂等之習知化合物》 異氰酸酯化合物，可列舉：芳香族或脂肪族之二異氰 酸酯、3價以上之聚異氰酸酯等，低分子化合物、高分子 化合物中任一種皆可，例如，可列舉：伸丁二異氰酸酯、 伸己二異氰酸酯等之脂肪族二異氰酸酯、甲苯二異氰酸 酯、二苯基甲烷二異氰酸酯、二甲苯二異氰酸酯等之芳香 族二異氰酸酯、氫化二苯基甲烷二異氰酸酯、氫化二甲苯 二異氰酸酯、二聚物酸二異氰酸酯、異佛酮二異氰酸酯等 之脂環族二異氰酸酯、或是此等之異氰酸酯化合物之三量 體、及此等之異氰酸酯化合物的過剩量與例如乙二醇、丙 二醇、三羥甲基丙烷、甘油、山梨醇、乙二胺 '單乙醇胺、 二乙醇胺、三乙醇胺等之低分子活性氫化合物或各種聚酯 聚醇類、聚醚聚醇類、聚醯胺類之高分子活性氫化合物等 反應所獲得之含有末端異氰酸酯基之化合物。 異氰酸酯基之嵌段化劑，例如，可列舉：苯酚、苯硫 酚、甲基苯硫酚、乙基苯硫酚、甲酚、二甲苯酚、間苯二 酚、硝基苯酚、氯苯酚等之苯酚類；丙酮肟、甲基乙基酮 肟、環己酮肟等之肟類；甲醇、乙醇、丙醇等之醇類；氯 乙醇、1，3·二氯-2-丙醇等之鹵素取代醇類；三級丁醇、三 -19- 201122064 級戊醇等之二級醇類；ε -己內酯、δ -戊內酯、γ -丁內醋、β- 丙內酯等之內酯類；其他，也可列舉：芳香族胺類、醯亞 胺化類、乙醯丙酮、乙醯醋酸酯、丙二酸乙酯等之活性亞 甲基化合物；硫醇類、亞胺類、咪唑類、尿素類、二芳基 化合物類、亞硫酸氫鹼等。其中，基於硬化性，肟類、咪 唑類、胺類特別理想。 於此等硬化劑中，按照其種類也能夠倂用所選出的習 知觸媒或促進劑。 硬化劑之摻合量，於不損害本發明效果之程度所摻合 的量，並未予以特別限制，相對於1 0 0質量份之黏結劑樹 脂而言，較佳爲0.5至50質量份，更佳爲1至30質量份， 進一步更佳爲2至20質量份。 藉由於導電性糊中含有黏結劑樹脂（Α)，爲了使導電性 薄膜形成，即使實施低溫乾燥（例如，1 3 5 °C以下），對於所 積層的透明電極層也具有極爲優異之密著性，能夠發現高 導電性。 本發明之導電性糊係除了黏結劑樹脂（A)以外，其他之 樹脂也可以併用該特定之聚胺甲酸酯樹脂以外之胺甲酸酯 系樹脂、聚酯樹脂、環氧樹脂、苯酚樹脂、丙烯酸樹脂、 苯乙烯-丙烯酸樹脂、苯乙烯-丁二烯共聚物、聚苯乙烯、 聚醯胺樹脂、聚碳酸酯樹脂、氯乙烯-醋酸乙烯共聚合樹 脂、乙烯-醋酸乙烯共聚合樹脂等，並無任何限制。但是， 於不損害黏結劑樹脂（A)的特徵之程度，相對於黏結劑樹脂 m -20- 201122064 (A) 而言，較佳爲含有30重量％以下 其種類並無限制，基於對基材之密著 溶解性、相溶性之觀點，較佳爲聚酯 以外的胺甲酸酯系樹脂。 (B) 成分 用於本發明之金屬粉末（B)，可歹! 金粉、鈀粉等之貴金屬粉；銅粉、鎳I 銀等之貴金屬電鍍或合金化之賤金屬 末可以單獨使用，或是也可以倂用。 獨之銀粉或以銀粉爲主體之金屬粉末 金屬粉末之形狀，可列舉：習知 球狀、樹枝狀（松林石狀）、在特開平 示的球狀1次粒子爲凝聚成3次元狀 之中，基於導電性·方面，特別理想爲 球狀1次粒子爲凝聚成3次元狀之形 另外，除了該金屬粉末以外，也 以外之導電性粉末。基於得到高的導 100質量份之金屬粉末而言，金屬粉 之含量較佳爲1 1質量份以下，更佳赁 粉末以外之導電性粉末的含量之下| 定，相對於1〇〇質量份之金屬粉末而 份以上，更佳爲1質量份以上。金屬 末也可以添加習知之無機物，例如， 。併用該樹脂之際， 性、耐彎曲性及溶劑 樹脂、黏結劑樹脂（A) J舉：銀粉、金粉、白 分、鋁粉、黃銅粉等； 粉等。此等之金屬粉 此等之中，較佳爲單 〇 丨之薄片狀（鱗片狀）、 9-306240號公報所揭 之形狀等，此等形狀 薄片狀銀粉、上述之 狀銀粉。 可以更含有金屬粉末 電性之觀點，相對於 末以外之導電性粉末 ^ 9質量份以下。金屬 限，並未予以特別限 言，較佳爲0.5質量 粉末以外之導電性粉 能夠使用：碳黑、石 201122064 墨粉等之碳系之塡料；碳化矽、碳化硼、碳化鈦、碳化鉻、 碳化鈴、碳化釩、碳化鉬、碳化鈮、碳化鎢、碳化鉻、碳 化鉬、碳化鈣、鑽石碳內醯胺等之各種碳化物；氮化硼、 氮化鈦、氮化鉻等之各種氮化物；硼化銷等之各種硼化物； 氧化鈦（鈦）、氧化鈣、氧化鎂、氧化鋅、氧化銅、氧化鋁、 二氧化矽、膠體二氧化矽等之各種氧化物；鈦酸鈣、鈦酸 鎂、鈦酸緦等之鈦酸化合物；二硫化鉬等之硫化物；氟化 鎂、氟化碳等之各種氟化物；硬脂酸鋁、硬脂酸鈣、硬脂 酸鋅、硬脂酸鎂等之各種金屬肥皂；其他，滑石、膨土、 碳酸鈣、高嶺土、玻璃纖維、雲母等。藉由添加如上述之 無機物，具有使耐熱性或耐久性提高成爲可能之情形。 另外，基於導電性、耐濕性等之環境特性、成本面之 觀點，較佳爲碳黑、石墨粉。相對於100質量份之金屬粉 末而言，含有碳黑、石墨粉之情形的碳黑及/或石墨粉之含 量較佳爲摻合25質量份以下，更佳爲摻合11質量份以下》 另外，能夠使用搖變性賦予劑、消泡劑、難燃劑、黏 著賦予劑、抗水解劑、平坦劑、可塑劑、抗氧化劑、紫外 線吸收劑、難燃劑、顏料、染料。再者，樹脂分解抑制劑 也可以適宜使用碳化二亞胺、環氧化物等。此等添加劑能 夠單獨使用或是倂用。 基於所形成的導電性薄膜之導電性爲良好之觀點，相 對於100質量份之黏結劑樹脂（A)而言，（B)成分之含量較 佳爲400質量份以上，更佳爲560質量份以上，進一步更 -22- 201122064 佳爲700質量份以上。另外，基於與透明導電性層之密著 性爲良好之觀點，相對於100質量份之黏結劑樹脂（A)而 言’（B)成分之含量較佳爲1,900質量份以下，更佳爲1，230 質量份以下，進一步更佳爲75 0質量份以下。 (C)成分 作爲（C)成分之有機溶劑，其較佳爲（A)成分之黏結劑 樹脂爲可溶，且能夠使（B)成分之導電性粉末良好分散。具 體例可列舉：乙二醇醋酸酯（ECA)、丁二醇醋酸酯（BCA)、 環己酮、甲基乙基酮、甲苯、異佛酮、γ-丁內酯、节醇、 Exxon化學製之Solvesso 100、150、200、丙二醇單甲基酸 醋酸酯、萜品醇等，此等溶劑之中，基於溶解性、網板印 刷性爲良好之觀點，較佳爲乙二醇醋酸酯（ECA)、丁二醇醋 酸酯（BCA)或其混合溶劑。 網板印刷中，基於抑制印刷後的模糊或版阻塞上爲良 好之觀點，相對於100質量份之黏結劑樹脂（A)而言，（C) 成分之含量較佳爲150質量份以上，更佳爲200質量份以 上，進一步更佳爲240質量份以上。另外，基於網板印刷 中之滲出抑制、膜厚均一性方面爲良好之觀點，相對於1 〇〇 質量份之黏結劑樹脂（A)而言’（C)成分之含量較佳爲500 質量份以下’更佳爲400質量份以下’進一步更佳爲300 質量份以下。 本發明之導電性糊適用於作爲觸控面板用，除了觸控 面板以外，用於電磁波屏蔽用途、電子零件之電路形成用 途、端子或導線之導電性接著劑等之用途也爲可能。 -23- 201122064 本發明之導電性糊的F値較佳爲60至95%，更佳爲 75至95%。所謂F値係表示相對於100質量份之糊中所含 之全部固形物的塡料質量份之數値，以F値=(塡料質量份 /固形物質量份）x 1 〇〇所示。於此提到的所謂塡料質量份係 指導電性粉末（B)之質量份，所謂固形物質量份係指溶劑以 外之成分的質量份，包含全部之導電性粉末（B)、黏結劑樹 脂、其他之硬化劑或添加劑。若F値低於60%時，得不到 良好之導電性；若超過95 %時，將有密著性及/或硬度將降 低之傾向。印刷性品質之降低也無可避免。 另外，本發明也關於使用由該導電性糊所構成的導電 性薄膜及其製造方法。 導電性薄膜係將導電性糊塗布或印刷於基材上，其 後，藉由進行加熱而硬化塗布或印刷的導電性糊所得到。 塗布方法可列舉：藉由薄層塗布機、桿式塗布機所進行的 塗布、或旋轉塗布法、浸潰塗布法等之方法。另外，藉由 印刷而形成導電性薄膜之情形的印刷方法，可列舉：網板 印刷法、凹版印刷、可撓印刷、平版印刷等之方法。 基於乾燥後之導電性薄膜的導電性或密著性、表面硬 度上爲良好之觀點，進行塗布或印刷的導電性糊之硬化時 的加熱溫度較佳爲80 °C以上，更佳爲100 °C以上，進一步 更佳爲110 °C以上。另外，基於基底的透明導電性層之耐 熱性、及生產步驟中之省能量上爲良好之觀點，加熱溫度 較佳爲1 5 (TC以下，更佳爲1 3 5 °C以下，進一步更佳爲1 3 0 °C以下。 -24- 201122064 導電性薄膜之厚度係根據所用之用途而有所不同，基 於乾燥後之導電性薄膜導電性上爲良好之觀點，較佳爲 5μιη以上’更佳爲7μιη以上，進一步更佳爲9μιη以上。另 外，基於網板印刷性上爲良好之方面、因糊中之銀含量減 低所導致的成本優點之觀點，導電性薄膜之厚度較佳爲 30μιη以下，更佳爲25μιη以下，進一步更佳爲20μιη以下。 另外，塗布有導電性糊之基材，例如，可列舉：聚碳 酸酯、壓克力、聚醯亞胺、聚酯等，用於觸控面板用途之 情形下，較佳將透明導電性層設置於基材與導電性膜之間 而作成將導電性薄膜積層於透明導電性層上之導電性積層 體。透明導電性層較佳爲由以氧化銦錫爲主成分所構成的 ΙΤΟ膜，由於針對使用習知結晶性ΙΤΟ膜之際形成的導電 性薄膜之密著性也具有極爲優異之密著性，ΙΤΟ膜之表面 形狀不論爲平坦之物或具有凹凸之物等任何表面形狀皆爲 可能適用。 再者，也關於使用該導電性積層體之觸控面板。觸控 面板可列舉：電阻膜方式與靜電容量方式之觸控面板，不 論任一種觸控面板皆適用將成爲可能。 觸控面板之製造方法並未予以特別限定，例如，能夠 在積層ΙΤΟ膜等之透明導電性層的基材上，硬化後，形成 賦予導電性之電路的方式來塗布或印刷導電性糊，藉由加 熱而使塗布或印刷的導電性糊硬化，形成導電性積層體， 藉由使所獲得之導電性積層體貼合於其他之導電性積層體 而能夠製造。 -25- 201122064 [實施例] 以下，顯示實施例及比較例，進—步具體說明本發明。 還有，本發明並不受以下之實施形態所限定，另外，只要 無特別之限制，例中之「份」係表示「質量份」，所謂固 形物濃度係表示使溶劑完全揮發後之不揮發性成分。 以下顯示所後述的製造例中所製造的聚酯樹脂（P)及 聚胺甲酸酯樹脂（U)之物性評估（1.數量平均分子量、2.玻璃 轉移溫度（Tg)、3.酸價、及4.樹脂組成）之測定方法。 另外’以下顯示於製造例中使用所製造的聚酯樹脂（P) 及聚胺甲酸酯樹脂（U)而調製的導電性糊之10.儲藏安定 性、及針對使用導電性糊而形成的試驗片之物性評估（5.密 著性、6.比電阻、7·鉛筆硬度' 8·環境試驗、及9耐結塊性） 之測定方法。 1 ·數量平均分子量 使樹脂濃度成爲約0.5重量％的方式來將試料樹脂溶 解或稀釋於四氫呋喃中，利用孔徑05μιη2聚四氟化乙烯 製爐膜而進行過濾，作成GPC測定試料。將四氫呋喃作爲 移動相’使用島津製作所公司製之凝膠滲透層析儀 (GPC)Pr〇minence ’將微差折射計（IU計）作爲檢測器，管柱 溫度30C、以流量lmi/分鐘而進行樹脂試料之gpc：測定。 使用數量平均分子量已知之單分散聚苯乙烯之GpC測定結 果而求得試料樹脂之聚苯乙烯換算數量平均分子量，將該 數値作爲本發明申請案中之試料樹脂的數量平均分子量。 [S] -26- 201122064 但是，管柱係使用昭和電工（股份）製之Shodex KF-802、 804L ' 806L。 2. 玻璃轉移溫度（Tg) 將試料樹脂5mg置入鋁製試樣盤而密封，使用Seiko Instruments (股）製之微差掃描熱分析計（DSC)DSC-220, 直到200°C爲止，以升溫速度20°C /分鐘進行測定，由玻璃 轉移溫度以下之基線延長線與顯示遷移部中之最大傾斜的 接線之交點溫度而求得。 3. 酸價 精稱試料樹脂〇.2g而溶解於20ml之氯仿中。接著， 利用0.0 1 N之氫氧化鉀（乙醇溶液）進行滴定而求出。於指 示劑中’使用酚酞溶液。酸價之單位係eq/ton，亦即，設 爲試料每1噸之當量。 4. 樹脂組成 將試料樹脂溶解於氯仿-d中，使用 VARIAN製 400MHZ-NMR裝置，藉由 j-NMR而求出樹脂組成比。 5 .密著性 在厚度100 μιη之已進行退火處理之PET薄膜或結晶性 I Τ Ο膜上，藉由網板印刷法，將製得的導電性糊以印刷2 5 x20〇nm之圖案，於150°C乾燥30分鐘，將已硬化之物作成 試驗片。乾燥膜厚係成形處理20至30μηι的方式來調整。 使用此試驗片，依照 JIS Κ-5600-5-6: 1991，使用. 201122064 VI. Description of the Invention: [Technical Field] The present invention relates to a conductive paste and its use, and more particularly to a conductive paste containing a polyurethane resin as a binder resin A conductive film composed of the conductive paste, which is a conductive laminated body laminated on a transparent conductive layer, and a touch panel using the conductive laminate of the conductive film, and a method for producing the same. [Prior Art] A transparent touch panel that operates by touching a screen with a finger or a special pen has been used for an ATM, a car satellite positioning system, a game machine, a ticket vending machine at a station, a copying machine, a commentary terminal of a museum, and A wide range of uses such as information terminals for convenience stores. The transparent touch panel is constructed by overlapping two transparent conductive films to form a switching pattern. In general, the transparent conductive film of such a transparent touch panel is attached to an indium tin oxide film (hereinafter, also referred to simply as an ITO film) which is a transparent electrode material by a steaming method or a sputtering method. The ITO film is etched by a base material such as a polyester film or glass to form a pattern. There are various ways for the touch panel, and the resistive film method and the electrostatic capacity method are representative. The resistive film method is characterized in that it is manufactured in a simple and low-cost manner by a simple configuration in which the pressure is specifically contacted, and it is easy to perform detailed position detection, and can also correspond to a character obtained by a pen. S1 -3- 201122064 In. On the other hand, the disadvantage is that the structure of the conductive film is attached to the liquid crystal, so that the transmittance of the screen is lowered, and it is difficult to achieve a clear picture. The electrostatic capacitance type is characterized in that multi-point sensing can be performed by sensing a predetermined discharge phenomenon or the like by touching a panel with a finger or a dedicated pen. When the touch panel is to be input by a pen or a fingertip or the like, the transparent conductive film on the fixed electrode side and the transparent conductive film on the movable electrode (thin film electrode) side are in contact with or close to each other. In recent years, with the variety of pen input patterns observed in game machines and the like, and the load at the time of input, especially in the transparent conductive film, cracks, peeling, and the like are caused by the load due to the pen input. Destruction becomes a problem. Therefore, it is necessary to improve the durability of the pen friction, and in recent years, attempts have been made to improve the strength of the transparent conductive film. In an attempt to increase the strength of the transparent conductive film, for example, it is considered that the oxide constituting the film is crystallized to be effective. In order to crystallize the transparent conductive film, the obtained laminated film is heated to a temperature higher than the crystallization temperature of the transparent conductive film after the amorphous conductive film is grown on the plastic film substrate. For example, Patent Document 1). In addition, as shown in Patent Document 2, an indium oxide powder having a predetermined specific surface area 値 and an average particle diameter and a tin oxide powder are mixed and pulverized, and a molded body is obtained by press molding in addition to a predetermined tin oxide content. A method of obtaining a crystalline ITO film, etc. 'In order to improve durability, each company aims to increase the crystallization rate. In addition, as described above, as the oxide constituting the transparent conductive film is crystallized, it is difficult to ensure the adhesion of the conductive coating film formed on the transparent conductive film. In general, the conductive coating film forming the connection electrode is formed by screen printing using a conductive paste containing a conductive powder such as silver, and the oxide constituting the transparent conductive film is crystalline. The order of maintaining the surface structure of the transparent conductive film by crystallization tends to be low in surface activity and the fixing effect due to unevenness tends to be lowered. Further, since the order of the structure is maintained, the effect of the solvent present in the conductive paste on the underlying layer tends to be weaker than that of the amorphous transparent conductive film. For these reasons, it is difficult to ensure the adhesion after drying. Based on the above facts, the adhesion to the crystalline transparent conductive film is particularly good, and it is now strongly sought to ensure a conductive paste which is conductive at low temperatures, and the development of such a conductive paste is insufficient. Conventional conductive pastes for touch panels are often used in many cases where conductive pastes used for electrode applications such as film switching or pressure sensors are used for touch panels. For example, in the conductive paste shown in Patent Document 3, a polyester resin having a glass transition temperature of 80 ° C or higher is used, and such a polyester resin is used as a touch panel, and from the viewpoint of adhesion, The oxide constituting the transparent conductive film does not have a site capable of interacting, and is not suitable from the viewpoint of adhesion. Similarly, Patent Document 4 discloses that a conductive paste using a polyester resin or a polyurethane resin as a binder resin is not necessarily sufficient for the adhesion of the crystalline transparent conductive film -5 to 201122064. In other words, the design concept of the resin or the additive for improving the adhesion to the oxide constituting the transparent conductive film is not introduced, and the adhesion is different depending on the type of the oxide, and is particularly transparent with respect to the crystallinity. The adhesion of the conductive film has to be said to be extremely scarce. Further, Patent Document 5 discloses an organic resin having a glass transition temperature of 50 ° C or more, particularly a conductive paste having a polyester resin as a structural component. The polyester resin used in the examples and comparative examples of Patent Document 5 lacks specificity depending on the glass transition temperature, and it is difficult to verify the effect. If it is difficult to crystallize according to the investigation of the present inventors, The adhesion of the conductive film is not necessarily sufficient. Further, similarly to the case of Patent Document 4, the design idea of a resin or an additive for improving the adhesion to the oxide constituting the transparent conductive film is not introduced, and the adhesion is different depending on the type of the oxide. In particular, it has to be said that the adhesion to the crystalline transparent conductive film is extremely lacking. On the other hand, in the thermosetting conductive paste used in Patent Document 6, the thermosetting type is not more than 50 ° C except for the portion where the resin and the transparent conductive film do not interact with each other. If the processing temperature is necessary, there will be a problem of causing thermal deformation of the underlayer and a decrease in productivity. On the other hand, in Patent Document 3, the silver paste for a touch panel is attempted to ensure adhesion to ITO by blending a decane coupling agent. However, due to the low molecular weight of the decane coupling agent, only the electrical conductivity or surface hardness is affected by the effect of the plasticizer, and the long-term reliability is not good. [S] -6- 201122064 In addition, since the decane coupling agent is used as a small amount of additives, it is likely to cause a deviation in the coating film and may flow out due to long-term storage of the coating film. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. JP-A-2006-059720 (Patent Document 6) Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. No. Hei. No. Hei. No. Hei. In the conductive paste, the substrate having a transparent conductive layer or the like is remarkably improved in adhesion, and high reliability and high conductivity can be imparted. Technical means for solving the problem In order to solve such a problem, the result of the drill collar is as follows: In the conductive paste, the binder resin is contained in the conductive paste containing a specific number average molecular weight, acid value, and glass transition temperature. The polyurethane resin is useful as a conductive paste for forming a conductive film. The present invention has been accomplished based on such insights. Item 1: A conductive paste comprising: (A) a component, an adhesive resin comprising a polyurethane resin having an acid value of 50 to 500 eq/ton and a glass transition temperature of 60 to 150 ° C; 201122064 (B) The composition consists of metal powder, and (C) is composed of an organic solvent. Item 2: The conductive paste of Item 1, wherein the component (A) is a polyurethane having a structure obtained by addition polymerization of (A), (A2) and (A3) Adhesive resin composed of resin: (A1) Amorphous polyhydric alcohol having a number average molecular weight of 1, 〇〇〇 to 10,000 and a glass transition temperature of 30 to 80 ° C, (A2) low average molecular weight A compound having two or more functional groups reactive with isocyanate and (A3) polyisocyanate in one molecule. Item 3: The conductive paste of Item 1 or 2, wherein the component (A) is obtained by having a structure obtained by addition polymerization of (A), (A2), (A3) and (A4) An adhesive resin composed of a polyurethane resin: (A1) an amorphous polyalcohol having a number average molecular weight of 1,000 to 1 Å, a glass transition temperature of 30 to 80 ° C, A2) a compound having a number average molecular weight of less than 1,000 and having two or more functional groups reactive with isocyanate in one molecule, (A3) polyisocyanate, and (A4) having a number average molecular weight of 1,000 to 1 Å, 〇〇 An amorphous polyalcohol with a glass transition temperature below 30 °C. Item 4: The conductive paste of Item 2 or 3, wherein the amorphous polyalcohol (A1) is an amorphous polyester polyol. The amorphous polyester polyol is a polycarboxylic acid and all polyalcohol components. When it is set to mol%, the total polycarboxylic acid is within -8 - 201122064, and the aromatic dicarboxylic acid is 60 mol% or more. The total number of carbon atoms in the main chain is 4 or less. The alcohol is 60 mol% or more. Item 5. The conductive paste according to any one of items 2 to 4, wherein the functional group reactive with the isocyanate in the compound (A2) is a hydroxyl group or an amine group. Item 6: The conductive paste of any one of Items 2 to 5 wherein the compound (A2) further contains a carboxyl group. Item 7: The conductive paste according to any one of Items 1 to 6, wherein the component (B) further contains a conductive powder other than the metal powder. Item 8: The conductive paste of any one of Items 1 to 7, wherein the content of the component (B) is from 400 to 1,900 parts by mass relative to 1 part by mass of the binder resin (A) . Item 9: The conductive paste of any one of Items 1 to 8 wherein the content of the component (C) is from 150 to 500 parts by mass relative to 100 parts by mass of the binder resin (A). Item 10: A conductive film comprising the conductive paste disclosed in any one of Items 1 to 9. Item 11: A conductive laminate which is laminated on a transparent conductive layer and which is disclosed in the conductive film of Item 10. Item 12: The conductive laminated body according to Item 11, wherein the transparent conductive layer is an IT0 film composed of indium tin oxide as a main component. Item 13: A touch panel using the conductive laminate disclosed in Item 11 or 12. -9-201122064 Item 14: A method for producing a conductive film, comprising: the step of coating or printing the conductive paste of any one of Items 1 to 9 on a substrate; and 80 to 150 ° C The step of heating. EFFECTS OF THE INVENTION The conductive paste of the present invention has a high glass transition temperature, and can maintain a good film even in a high-temperature environment when a film is formed, and has high reliability. Further, in the binder resin, when a film is formed on a substrate due to a specific acid value, peeling due to adhering substances such as adsorbed water existing on the substrate is small, and the resin can be remarkably The adhesion of other materials is improved. Therefore, it is suitable for use in touch panels and the like which are required for particularly good adhesion, high reliability, and conductivity. [Embodiment] Hereinafter, each component of the conductive paste of the present invention will be described in detail. (A) Component The binder resin (A) of the polyurethane resin has a urethane bond. By having a urethane bond, in the hardening of the conductive paste or the post-printing hardening, the conductive powder such as the metal powder inside the coating film is mutually made according to the high cohesive force due to the intermolecular hydrogen bond. The distance is close and high conductivity can be found. Further, in the case of low-temperature drying, for example, in the case of 201122064, which has a residual solvent, high conductivity and high adhesion to the substrate can be found depending on the high cohesive force of the binder resin. The urethane bond system is formed at least according to the reaction of the amorphous polyalcohol and the polyisocyanate. Further, in a preferred embodiment, the coefficient average molecular weight is less than 1, 〇〇〇, and contains at least two molecules per molecule. A compound formed by reacting a functional group capable of reacting with an isocyanate with a polyisocyanate. The number average molecular weight of the binder resin is 10,000 or more, preferably 20,000 or more, from the viewpoint of durability of the binder resin. When the number average molecular weight is less than 10, in addition to the problem of long-term durability, the paste viscosity will be lowered and the printability will be lowered. Further, the number average molecular weight of the binder resin is preferably not more than 100,000, from the viewpoint of paste viscosity (stencil printing suitability) and solubility. The binder resin-based glass has a glass transition temperature of 60 ° C or more, preferably 70 t or more. If the glass transition temperature is lower than 6 (TC is low, when the hardener is not blended, the resin will soften due to high temperature, and the reliability of the paste will be lowered. In addition, the surface hardness is lowered, and the adhesion is increased. Sexuality, at the time of the manufacturing process and/or use, it is feared that the resin and the blend will move toward the other side, and the reliability will be lowered. If the adhesion, solubility, paste viscosity and printability are considered, the binder is used. The glass transition temperature of the resin is preferably 150 ° C or less, more preferably 120 ° C or less, still more preferably 10 ° C or less. The glass transition temperature of the binder resin is selected by selecting amorphous polyol A 1 , A 4 , a compound A 2 having a functional group capable of reacting with an isocyanate in one molecule, a composition ratio of polyisocyanate A 3 and a composition of A 1 , A 2 , A 3 , A 4 [S] -11 - 201122064 The glass transition temperature of A1 is preferably found to be 4 (TC or more 'polyisocyanate is preferably at least one having an alicyclic skeleton and/or an aromatic skeleton). 'its Preferably, the mass ratio is A1 > A3 > A2, and further preferably, the mass ratio A 1 > A4. The binder resin has a specific range of acid value. By imparting an acid value, according to the presence and absence in the transparent conductive layer The chemical interaction of the adsorbed water significantly increases the adhesion. The acid value of the binder resin is 50 to 500 eq/ton, preferably 100 to 350 eq/t 〇 n. If the acid value is lower than 50 eq/ton, The adhesion improving effect of the obtained conductive film and the transparent conductive film tends to be small. On the other hand, when the acid value exceeds 500 eq/ton, in addition to the high water absorption, 'according to the catalytic action Further, there is a possibility that the hydrolysis of the binder resin is promoted, and there is a tendency that the reliability of the electrode is lowered when the conductive film is formed. . .  The method of introducing the acid value into the binder resin may be exemplified by the following method: in the step of chain extension of the polyol and the polyisocyanate in the step of the polyurethane resin of the binder resin, the copolymerization is carried out. a compound containing two or more functional groups in a molecule containing a carboxyl group such as methyl butyric acid or dimethylene propionate; or a multivalent amount of trimellitic anhydride, benzophenone tetracarboxylic acid, trishydroxymethyl anhydride or the like The carboxylic acid anhydride introduces the acid value into the molecule or at the end of the molecule. The method of introducing an acid value of the present invention may use any of the above methods. [S] -12- 201122064 The binder resin (A) is preferably a polyester urethane resin having a molecular weight of at least (A1) of 1,000 to 1 Torr, preferably ι, 500 to 7,000. The glass transition temperature is from 30 to 80 ° C, preferably from 4 5 to 70 ° C: amorphous polyalcohol; (A2) the number average molecular weight is less than 1, 〇〇〇, preferably from 6 〇 to 400 a compound having two or more functional groups reactive with an isochlorate in one molecule; and (A3) a ruthenium produced by addition polymerization of polyisocyanate. Further, the binder resin (A) is also preferably A polyester urethane resin having a molecular weight of at least (A1) of 1,000 to 10, hydrazine, preferably 1,500 to 7,000, and a glass transition temperature of 30 to 80 ° C, preferably 45 to An amorphous polyalcohol at 70 ° C; (A2) a compound having a number average molecular weight of less than 1,000, preferably 60 to 400, having two or more functional groups reactive with isocyanate in one molecule; (A3) Polyisocyanate; and (A4) addition polymerization of amorphous polyalcohol having a molecular weight of 1,000 to 10,000, preferably 1,500 to 7, 〇〇〇, and a glass transition temperature of less than 30 ° C The reaction is preferably manufactured of the urethane resin is a polyester. The amorphous polyol may, for example, be a polyether polyol, a polyester polyol or the like, and a degree of freedom based on molecular design is preferably a polyester polyol. The polyester polyol is preferably obtained by condensation of a dicarboxylic acid with a polyalcohol. Further, the dicarboxylic acid may also be a dicarboxylic acid ester esterified with an alcohol having 1 to 12 carbon atoms. Examples of the dicarboxylic acid used in the production of the polyester polyol include aromatic diacids such as terephthalic acid, isophthalic acid, phthalic acid, and 2,6-naphthalenedicarboxylic acid; succinic acid; An aliphatic diacid such as glutaric acid, adipic acid, sebacic acid, dodecanedioic acid or sebacic acid; dibasic acid having a carbon number of 12 to 28 such as a dimer acid; Cyclohexanedioic acid '1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-13- 201122064 hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 2 -methylhexahydrophthalic anhydride, dicarboxylated hydrogenated bisphenol A, dicarboxylated hydrogenated bisphenol S, dimer acid, hydrogenated dimer acid, hydrogenated naphthalic acid, tricyclic sebacic acid, etc. An alicyclic diacid or an alicyclic dianhydride; a hydroxybenzoic acid, a hydroxycarboxylic acid such as lactic acid, or the like. Further, in the range which does not impair the effects of the invention, it may be copolymerized with an unsaturated dicarboxylic acid such as a polyvalent carboxylic acid such as trimellitic anhydride or pyromellitic anhydride or fumaric acid; Copolymerization of a sulfonic acid metal base-containing dicarboxylic acid such as a sulfoisophthalate salt. The amorphous polyol (A1) is preferably a polyester polyol, and constitutes an aromatic group among all the acid components of the polyester polyol based on the viewpoints of durability such as strength, heat resistance, moisture resistance and thermal shock resistance. The dicarboxylic acid is preferably copolymerized at 60 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and particularly preferably 98 mol% or more. The entire acid component is preferably a structure composed of an aromatic dicarboxylic acid. When the amount of the aromatic dicarboxylic acid component is less than 60% by mole, the glass transition temperature of the polyurethane resin (A) of the present invention may be lower than 60 ° C, and the heat and humidity resistance and durability may be worried. reduce. On the other hand, the amorphous polyol (A4) is preferably a polyester polyol, and among the entire acid components constituting the polyester polyol, the aromatic dicarboxylic acid is preferably 30 mol% or more, preferably 50. Mole% or more, further preferably 70 mol% or more. Examples of the diol used in the production of the polyester polyol include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,5-pentanediol, and neopentane. Glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,5-pentane[S]-14-201122064 alcohol, 2-methyl-1 , 3-propanediol ' 2,2-diethyl-1,3-propanediol, 2-butyl·2-ethyl-1,3-propanediol, 1,9-nonanediol, 1,1〇-癸2 An alicyclic diol such as an aliphatic diol such as an alcohol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol or a dimer diol. Further, a polyhydric alcohol such as trimethylolethane, trimethylolpropane, glycerol 'neopentyl glycol or polyglycerin may be used without departing from the scope of the invention. The amorphous polyalcohol (Α1) is preferably a polyester polyol which is composed of all the polyol components of the polyester polyol based on the viewpoints of durability such as strength, heat resistance, moisture resistance and thermal shock resistance. The diol having a carbon number of 4 or less is preferably 60 mol% or more, more preferably 80 mol% or more, still more preferably 95 mol% or more. In all the polyol components, if the diol having a carbon number of 4 or less in the main chain becomes less than 60 mol%, it is feared that the glass transition temperature of the polyurethane resin of the present invention is 6 〇 ° C. It is still low, and it is worried about heat and humidity resistance and durability. On the other hand, the amorphous polyol (A4) is preferably a polyester polyol which constitutes all the polyol components of the polyester polyol, and the ethylene glycol having a carbon number of 4 or less in the main chain is preferably 80 moles. % or less, more preferably 70% by mole or less, still more preferably 60% by mole or less. The binder resin (A) used in the present invention can be obtained by at least the amorphous polyalcohol (A1) having a number average molecular weight lower than "," and having two or more functional groups reactive with isocyanate in one molecule. It is produced by addition polymerization of the compound (A2) and the polyisocyanate (A3) shown below. Further, the binder resin (A) is at least the amorphous polyalcohol (Al ), (A4) and has a number average molecular weight of less than 1,000, and can have two or more iso--15-201122064 cyanate esters in one molecule. The compound (A2) which reacts the functional group is produced by the addition polymerization reaction of the polyisocyanate (A3) shown below. The functional group obtainable by the reaction with the isocyanate in the compound (A2) is preferably a hydroxyl group and an amine group, and the compound (A2) may have either or both of them. Specifically, the component (A2) is exemplified as a carboxyl group-containing compound of dimethylol butyric acid or dimethylolpropionic acid used as an acid value introduction method, and 1,2-propanediol, 1 , 2-butanediol, 1,3-butanediol, 2,3·butanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-dimethyl-3-hydroxypropyl-2', 2' - dimethyl-3-hydroxypropionate, 2-n-butyl-2-ethyl-l,3-propanediol, 3-ethyl·l,:5-pentanediol, 3-propyl-l, 5-hexanediol, 2,2-diethyl-1,3-propanediol, 3-octyl-1,5-pentanediol, 3-phenyl-1,5-pentanediol, 2,5- a compound having two hydroxyl groups in one molecule such as dimethyl-3-sulfo sodium-2,5-hexanediol or dimer diol (PRIPOL-2033 (manufactured by Unichema International)); trimethylol a polyol such as ethane, trimethylolpropane, glycerin, neopentyl glycol or polyglycerol; an amino alcohol having one or more hydroxyl groups and an amine group in one molecule such as monoethanolamine, diethanolamine or triethanolamine; Ethylenediamine, 1,6-hexane 1,8-octanediamine, 1,9-octanediamine, 1,1 fluorene-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, etc. a molecule such as amine or m-xylylenediamine, 4,4-diaminodiphenylmethane, 3,4'-diaminodiphenyl ether 4,4,-diaminodiphenyl ether An aromatic diamine having two amine groups or the like. The above-mentioned number average molecular weight is less than 1,000, and two or more compounds which can react with isocyanate in one molecule can be used singly or in combination of several kinds without any problem. Examples of the polyisocyanate (A3) constituting the binder resin (A) include 2,4-toluene diisocyanate 2,6-toluene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and Benzene diisocyanate, 3,3,dimethoxy-4,4'-biphenyl diisocyanate, 2,6-naphthalene diisocyanate, 3,3,dimethoxy-4,4'-biphenyl Isocyanate, 4,4'-diphenyldiisocyanate, 4,4,-diisocyanate diphenyl ether, 1,5-naphthalene diisocyanate, m-xylene diisocyanate, isophorone diisocyanate, butyl diisocyanate, Dihexyl isocyanate, toluene diisocyanate, etc. The polyisocyanate (A3) and the amorphous polyalcohol (A1) have a number average molecular weight of less than 1,000, and are reacted by a compound (A2) having two or more functional groups reactive with isocyanate in one molecule. The urethane bond can be introduced into the binder resin (A). Further, the polyisocyanate (A3) and the amorphous polyalcohol (Al), (A4) and the number average molecular weight are less than 1, 〇〇〇, and by reacting two or more molecules with one isocyanate The functional group compound (A2) is reacted, and the urethane bond can be introduced into the binder resin (A). The binder resin (A) can be polymerized in a solvent, and the boiling point of the solvent is preferably 80 ° C or higher. . When the solvent having a boiling point of 80 ° C or higher is low in volatility, the metal powder and the conductive powder or other blend other than the desired metal powder are blended, and then dispersed by a three-roller or the like. It is necessary to carry out the work efficiently without solvent replacement, and it also has an advantage based on the cost [S] -17- 201122064. On the other hand, after the binder resin (A) is polymerized in a solventless manner, it is not problematic even if it is dissolved in a solvent having a boiling point of 80 〇c or more. For the solvent having a boiling point of 80 ° C or higher, the following various solvents can be used: aromatic hydrocarbons such as toluene, monomethyl, tetramethyl, Solvesso 100, Solvesso 150, Solvesso 200, tetrahydronaphthalene, etc.; fat of Decaiin et al. a hydrocarbon system; an alcohol such as terpineol; a ketone system such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; ethylene glycol dimethyl ether; diethylene glycol dimethyl Ethers such as ethyl ether, diethylene glycol monoethyl ether, dipropylene glycol diethyl ether, dioxane, diethyl ether, tetrahydrofuran, etc.: cellulose acetate, ethyl cellulose, butyl cellulose, etc. Cellulose system; various solvents of carbitol such as carbitol and butyl carbitol. In the polymerization, there is no problem even if two or more kinds of the solvent are mixed. In the case of blending the monomers in the production of the binder resin (A), in addition to the solvent, as long as the influence of the volatilization at the time of the three rolls can be suppressed, a solvent having a boiling point lower than 80 ° C is added, and any problem. In addition, a solvent having a boiling point lower than 80 °C is added before use, and no limitation is imposed. In the binder resin, a hardener which can react with a polyurethane resin having a urethane bond can be blended to the extent that the effects of the present invention are not impaired. By blending the curing agent, there is a possibility that the curing temperature is increased, and improvement in reliability due to improvement in physical properties of the coating film can be expected. Although the type of the hardening agent which can be obtained by the reaction of the binder resin of the present invention is not limited, it is preferably an isocyanate compound based on the adhesiveness, bending resistance, curability, and the like [S3 201122064]. Further, based on the storage stability, it is preferred to use a blocked isocyanate group as the isocyanate compound. Examples of the curing agent other than the isocyanate compound include amine-based resins such as methylated melamine, butylated melamine, benzoguanamine, and urea resins, acid anhydrides, imidazoles, epoxy resins, and phenol resins. The isocyanate compound may, for example, be an aromatic or aliphatic diisocyanate or a trivalent or higher polyisocyanate, and may be any of a low molecular weight compound and a high molecular compound. For example, a dibutyl diisocyanate or a stretch may be mentioned. An aromatic diisocyanate such as an aliphatic diisocyanate such as hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate or xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate or dimer acid An alicyclic diisocyanate such as a diisocyanate or an isophorone diisocyanate, or a trisomer of such an isocyanate compound, and an excess amount of such an isocyanate compound such as ethylene glycol, propylene glycol or trimethylolpropane , glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine The reaction triethanolamine, etc., or a low molecular weight active hydrogen compound, various polyesters polyethylene alcohols, polyether alcohols, polyamide-based polymer of active hydrogen-containing compound obtained by the ester compound of the terminal isocyanate groups. Examples of the isocyanate group blocker include phenol, thiophenol, methyl thiophenol, ethyl thiophenol, cresol, xylenol, resorcin, nitrophenol, chlorophenol, and the like. Phenols; anthraquinones such as acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime; alcohols such as methanol, ethanol, and propanol; chlorohydrin, 1,3-dichloro-2-propanol, etc. Halogen-substituted alcohols; tertiary alcohols such as tertiary butanol, tris-19-201122064 grade pentanol; ε-caprolactone, δ-valerolactone, γ-butyrolactone, β-propiolactone, etc. Lactones; others may also be listed as active methylene compounds such as aromatic amines, quinone imidizations, acetamidineacetone, acetamidine acetate, and ethyl malonate; thiols and imines. , imidazoles, ureas, diaryl compounds, hydrogen sulfite bases, and the like. Among them, based on the curability, hydrazines, imidazoles, and amines are particularly desirable. Among these hardeners, the selected conventional catalyst or accelerator can also be used depending on the type thereof. The blending amount of the hardener is not particularly limited as long as it is not impaired by the effect of the present invention, and is preferably 0% with respect to 100 parts by mass of the binder resin. 5 to 50 parts by mass, more preferably 1 to 30 parts by mass, still more preferably 2 to 20 parts by mass. In order to form a conductive film, the conductive paste contains a binder resin, and even if it is dried at a low temperature (for example, 135 ° C or lower), it has excellent adhesion to the laminated transparent electrode layer. Sex, can find high conductivity. In addition to the binder resin (A), the conductive paste of the present invention may be used in combination with a urethane resin, a polyester resin, an epoxy resin or a phenol resin other than the specific polyurethane resin. , acrylic resin, styrene-acrylic resin, styrene-butadiene copolymer, polystyrene, polyamide resin, polycarbonate resin, vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, etc. There are no restrictions. However, the degree of the characteristics of the binder resin (A) is not impaired, and it is preferably 30% by weight or less with respect to the binder resin m -20- 201122064 (A). From the viewpoint of solubility and compatibility, it is preferably an urethane-based resin other than polyester. (B) The component is used for the metal powder (B) of the present invention, and the precious metal powder such as gold powder or palladium powder; the precious metal of copper powder, nickel I silver or the like which is plated or alloyed may be used alone or It can also be used. The shape of the unique silver powder or the metal powder metal powder mainly composed of silver powder may be exemplified by a conventional spherical shape, a dendritic shape (pine forest stone shape), and a spherical primary particle in a special opening is agglomerated into a three-dimensional shape, based on In terms of conductivity, it is particularly preferable that the spherical primary particles are in a form of agglomerated into a three-dimensional shape, and a conductive powder other than the metal powder. The content of the metal powder is preferably 11 parts by mass or less, more preferably less than the content of the conductive powder other than the powder, based on the metal powder having a high conductivity of 100 parts by mass. The metal powder is at least 1 part by mass, more preferably 1 part by mass or more. It is also possible to add a conventional inorganic substance to the metal, for example, . When using this resin, properties, bending resistance, solvent resin, and binder resin (A) J: silver powder, gold powder, white powder, aluminum powder, brass powder, etc.; Among these, the metal powder is preferably a sheet-like shape (scaly shape) of a single crucible, a shape disclosed in Japanese Laid-Open Patent Publication No. Hei 9-306240, or the like, and a flaky silver powder or a silver powder as described above. It is more than 9 parts by mass or less based on the electrical conductivity of the metal powder. The metal limit is not particularly limited, and is preferably 0. For conductive powders other than 5 mass powders, carbon-based materials such as carbon black and stone 201122064 toner; tantalum carbide, boron carbide, titanium carbide, chromium carbide, carbonized bell, vanadium carbide, molybdenum carbide, tantalum carbide, Various carbides such as tungsten carbide, chromium carbide, molybdenum carbide, calcium carbide, diamond carbon decylamine; various nitrides such as boron nitride, titanium nitride, and chromium nitride; various borides such as boride pins; Various oxides of titanium (titanium), calcium oxide, magnesium oxide, zinc oxide, copper oxide, aluminum oxide, cerium oxide, colloidal cerium oxide, etc.; titanic acid compounds such as calcium titanate, magnesium titanate, barium titanate, etc. Sulfide such as molybdenum disulfide; various fluorides such as magnesium fluoride and carbon fluoride; various metal soaps such as aluminum stearate, calcium stearate, zinc stearate, magnesium stearate, etc.; other, talc , bentonite, calcium carbonate, kaolin, fiberglass, mica, etc. By adding the inorganic substance as described above, it is possible to improve heat resistance or durability. Further, carbon black and graphite powder are preferred from the viewpoints of environmental characteristics such as conductivity and moisture resistance and cost. The content of the carbon black and/or graphite powder in the case of containing carbon black or graphite powder is preferably 25 parts by mass or less, more preferably 11 parts by mass or less with respect to 100 parts by mass of the metal powder. A shake imparting agent, an antifoaming agent, a flame retardant, an adhesion-imparting agent, an anti-hydrolysis agent, a flat agent, a plasticizer, an antioxidant, an ultraviolet absorber, a flame retardant, a pigment, and a dye can be used. Further, as the resin decomposition inhibitor, carbodiimide, epoxide or the like can be suitably used. These additives can be used alone or in combination. The content of the component (B) is preferably 400 parts by mass or more, and more preferably 560 parts by mass, based on 100 parts by mass of the binder resin (A), from the viewpoint that the conductivity of the formed conductive film is good. Above, further more -22- 201122064 is better than 700 parts by mass. In addition, the content of the component (B) is preferably 1,900 parts by mass or less, more preferably 1 or less, based on 100 parts by mass of the binder resin (A), from the viewpoint of the adhesion to the transparent conductive layer. 230 parts by mass or less, further preferably 750 parts by mass or less. (C) Component The organic solvent of the component (C) is preferably a binder of the component (A). The resin is soluble, and the conductive powder of the component (B) can be well dispersed. Specific examples thereof include ethylene glycol acetate (ECA), butanediol acetate (BCA), cyclohexanone, methyl ethyl ketone, toluene, isophorone, γ-butyrolactone, hexanol, and Exxon chemistry. Solveses 100, 150, 200, propylene glycol monomethyl acetate, terpineol, etc. Among these solvents, based on solubility and screen printing properties are good, preferably ethylene glycol acetate ( ECA), butanediol acetate (BCA) or a mixed solvent thereof. In the screen printing, the content of the component (C) is preferably 150 parts by mass or more based on 100 parts by mass of the binder resin (A), based on the viewpoint of suppressing blurring after printing or plate blocking. The amount is preferably 200 parts by mass or more, and more preferably 240 parts by mass or more. In addition, the content of the component (C) is preferably 500 parts by mass based on the viewpoint of suppressing the bleed out in the screen printing and the uniformity of the film thickness, with respect to 1 part by mass of the binder resin (A). The following 'better than 400 parts by mass or less' is further preferably 300 parts by mass or less. The conductive paste of the present invention is suitably used as a touch panel, and can be used for electromagnetic wave shielding applications, circuit formation of electronic parts, conductive adhesives for terminals or wires, and the like as a touch panel. -23- 201122064 The conductive paste of the present invention preferably has a F 60 of 60 to 95%, more preferably 75 to 95%. The F 値 is a number 塡 of the mass fraction of the whole solid matter contained in 100 parts by mass of the paste, and is expressed by F 値 = (塡 mass part / solid part by mass) x 1 〇〇. The so-called dip mass fraction referred to herein refers to the mass fraction of the electroconductive powder (B), and the solid mass fraction refers to the mass fraction of the components other than the solvent, and includes all of the electroconductive powder (B) and the binder resin. , other hardeners or additives. If F値 is less than 60%, good electrical conductivity is not obtained; if it exceeds 95%, there is a tendency that adhesion and/or hardness will be lowered. The reduction in print quality is also inevitable. Further, the present invention relates to the use of a conductive film composed of the conductive paste and a method for producing the same. The conductive film is obtained by applying or printing a conductive paste on a substrate, and then curing or coating the printed conductive paste by heating. The coating method may be, for example, a coating by a thin coater or a bar coater, or a method such as a spin coating method or a dip coating method. Further, examples of the printing method for forming a conductive film by printing include a screen printing method, a gravure printing method, a flexible printing method, and a lithography method. The heating temperature at the time of curing the conductive paste applied or printed is preferably 80 ° C or higher, more preferably 100 °, from the viewpoint of good conductivity, adhesion, and surface hardness of the conductive film after drying. More preferably C or more, and more preferably 110 ° C or more. Further, the heating temperature is preferably 15 (TC or less, more preferably 1 35 ° C or less, further preferably from the viewpoint of heat resistance of the transparent conductive layer of the substrate and energy saving in the production step. The temperature is less than 1 30 ° C. -24- 201122064 The thickness of the conductive film varies depending on the application used, and is preferably 5 μm or more based on the viewpoint that the conductive film after drying is excellent in conductivity. It is 7 μm or more, and more preferably 9 μm or more. Further, the thickness of the conductive film is preferably 30 μm or less from the viewpoint of a good screen printing property and a cost advantage due to a decrease in the silver content in the paste. More preferably, it is 25 μm or less, and more preferably 20 μm or less. Further, the substrate coated with the conductive paste may, for example, be polycarbonate, acrylic, polyimide or polyester, and used for touch. In the case of a panel, it is preferable to provide a transparent conductive layer between a base material and a conductive film to form a conductive laminate in which a conductive thin film is laminated on a transparent conductive layer. It is preferable that the ruthenium film composed of indium tin oxide as a main component has excellent adhesion to the adhesion of the conductive film formed by using the conventional crystalline ruthenium film, and the surface of the ruthenium film is excellent. Any surface shape such as a flat object or a concave-convex object may be applicable. Further, the touch panel using the conductive laminated body may be exemplified by a resistive film method and an electrostatic capacitance method. The touch panel can be applied to any of the touch panels. The method of manufacturing the touch panel is not particularly limited. For example, it can be formed on a substrate of a transparent conductive layer such as a laminate film after hardening. The conductive paste is applied or printed by applying a conductive circuit, and the conductive paste applied or printed is cured by heating to form a conductive laminated body, and the obtained conductive laminated body is bonded to other conductive materials. -25-201122064 [Examples] Hereinafter, the examples and comparative examples will be described, and the present invention will be specifically described in detail. The invention is not limited to the following embodiments, and the "parts" in the examples represent "parts by mass", and the solid content concentration means nonvolatile components after the solvent is completely volatilized. The physical properties of the polyester resin (P) and the polyurethane resin (U) produced in the production examples described later are shown (1. The number average molecular weight, 2. Glass transfer temperature (Tg), 3. Acid price, and 4. Method for measuring resin composition). Further, the following shows a conductive paste prepared by using the produced polyester resin (P) and polyurethane resin (U) in the production example. Storage stability and physical property evaluation of test pieces formed using conductive paste (5. Closeness, 6. Specific resistance, 7·pencil hardness ' 8 · environmental test, and 9 resistance to agglomeration). 1 · The number average molecular weight makes the resin concentration about 0. The sample resin was dissolved or diluted in tetrahydrofuran in a manner of 5% by weight, and filtered by a film of a polytetrafluoroethylene having a pore size of 05 μm 2 to prepare a GPC measurement sample. Using tetrahydrofuran as the mobile phase, a gel permeation chromatograph (GPC) manufactured by Shimadzu Corporation was used as a detector, and a differential refractometer (IU meter) was used as a detector at a column temperature of 30 C at a flow rate of 1 mi/min. Gpc of the resin sample: measurement. The polystyrene-equivalent number average molecular weight of the sample resin was determined using GpC measurement results of monodisperse polystyrene having a known number average molecular weight, and this number was used as the number average molecular weight of the sample resin in the application of the present invention. [S] -26- 201122064 However, the pipe string uses Shodex KF-802 and 804L '806L manufactured by Showa Denko Electric Co., Ltd. 2.  Glass transition temperature (Tg) 5 mg of the sample resin was placed in an aluminum sample pan and sealed, and a differential scanning calorimeter (DSC) DSC-220 manufactured by Seiko Instruments Co., Ltd. was used until 200 ° C at a temperature increase rate. The measurement was carried out at 20 ° C /min, and was determined from the junction extension line below the glass transition temperature and the junction temperature of the maximum inclined wiring in the migration portion. 3.  The acid value is called the resin 〇. 2 g was dissolved in 20 ml of chloroform. Then, use 0. Potassium hydroxide (ethanol solution) of 0 1 N was determined by titration. Use a phenolphthalein solution in the indicator. The unit of acid value is eq/ton, that is, the equivalent of 1 ton of sample. 4.  Resin composition The sample resin was dissolved in chloroform-d, and a resin composition ratio was determined by j-NMR using a 400 MHZ-NMR apparatus manufactured by VARIAN. 5 . Adhesion on a PET film or a crystalline I Ο film which has been annealed to a thickness of 100 μm, the conductive paste prepared by screen printing is printed in a pattern of 25 x 20 〇 nm at 150 After drying at ° C for 30 minutes, the hardened material was made into a test piece. The dry film thickness is formed by a process of 20 to 30 μm. Use this test piece in accordance with JIS Κ-5600-5-6: 1991

Sellotape(註冊商標）（Nichiban(股）製），經由剝離試驗而進 [S] -27- 201122064 行評估。但是，格子狀圖案之各方向的切割數爲11個、切 割間隔係設爲1mm。1 00/ 1 00係表示無剝離而密著性爲良 好，0/100係表示完全剝離，密著性變差》 6.比電阻 相同於5.的方式來將製得的試驗片切割成25x450mm 寬，測定片電阻與膜厚，算出比電阻。還有，膜厚係使用 Gauge Stand ST-022(小野測器公司製），將PET薄膜之厚度 設爲零點而測定5點之硬化塗膜的厚度，使用其平均値。 片電阻係使用 MILLIOHMMETER4338B(HEWLETT PACKARD公司製），測定4片25x450mm寬之試驗片，利 用其平均値。 7 .鉛筆硬度 將 5.密著性試驗製得的試驗片置於厚度 2mm之 SUS304板上，依照JISK5600-5-4: 1999而測定，依照剝 離之有無而判斷。 8 .環境試驗 將5 .密著性試驗在ITO膜上製得的試驗片進行分別於 8〇°C加熱3 0 0小時的耐熱試驗、及於85°C、85% RH(相對 濕度）加熱3 0 0小時的耐濕熱試驗，加熱結束後，常溫下放 置24小時後，測定電阻値。 環境試驗之良否係進行該耐熱試驗及耐濕熱試驗之實 施前後的導電性塗膜之密著性及鉛筆硬度之評估。 [S] -28- 201122064 9. 耐結塊性 如5.密著性試驗的方式來在ITO膜上製得的 膜，使連接塗膜面的方式來重疊，將500g之載重外 電性塗膜部分，於80 °C放置72小時。接著，除去 常溫下放置1小時後，依照以下之基準’藉由外觀 良否。 〇:不發生對塗膜雙面之轉印，維持原本之塗腹 X:觀察對雙面之轉印，發生剝離。 10. 儲藏安定性 將導電性糊裝入波麗（Poly)容器中，於4〇°C儲 栓物1個月。儲藏後使用黏度與4·同樣製得的試驗 定比電阻、鉛筆硬度、密著性。 〇 :黏度無顯著變化’維持初期之比電阻、鉛筆 密著性。 X :確認黏度大幅上升，且確認比電阻、鉛筆 密著性之降低。 樹脂之製造例 聚酯聚醇（P)之合成 聚酯聚醇（P-1) 於具備攪拌機、冷凝器、及溫度計之反應容器 料700份之對苯二甲酸二甲酯、700份之間苯二甲 酯' 671份之乙二醇、526份之新戊二醇、〇·48份之 丁酯，於1 8 0。(：進行3小時酯交換。接著’慢慢地 2片塗 加於導 載重， 而判定 狀態。 藏該密 片而測 硬度、 硬度、 中，進 酸二甲 鈦酸四 減壓直 -29- 201122064 到ImmHg以下，於240°C進行1_5小時聚合。所獲得之共 聚合聚酯（Ρ-1)之組成係對苯二甲酸/間苯二甲酸//乙二醇/ 新戊二醇=5 0/5 0//5 0/5 0(莫耳比）、數量平均分子量爲 2,000、酸價爲2eq/ton、Tg=58°C。將結果顯示於表1。 聚酯聚醇（P-2)至（P-5)及（P-7) 除了於聚酯聚醇（P-1)中，使用顯示於表1之酸成分及 二醇成分而成爲表1之莫耳比的方式來取代單體以外，利 用與聚酯聚醇（P-1)同樣合成的方法而合成。將聚酯聚醇 (P-1)至（P-5)、及（P-7)之組成及樹脂物性顯示於表1。 聚酯樹脂（P-6)之合成 於具備攪拌機、冷凝器、及溫度計之反應容器中，進 料700份之對苯二甲酸二甲酯、700份之間苯二甲酸二甲 酯、16.9份之偏苯三酸酐、983份之乙二醇、154份之2-甲基-1，3_丙二醇，氮氣環境二大氣壓之加壓下，從160°C 至230 °C爲止花費3小時而進行酯化反應。壓力釋放後， 進料0.92份之鈦酸四丁酯，接著，慢慢地將系統內減壓， 花費20分鐘減壓直到5mmHg以下，進一步直到0.3mmHg 以下之真空下，於260°C進行40分鐘之聚縮合反應。於氮 氣氣流下，冷卻直到220 °C，倒入50.6份之偏苯三酸酐， 進行3 0分鐘之反應而得到聚酯樹脂。所獲得之共聚合聚酯 (P-6)之組成係對苯二甲酸/間苯二甲酸/偏苯三酸//乙二醇 /2-甲基-1,3-丙二醇=48/4 8/4//85/15(莫耳比）、數量平均分 子量爲20,000、酸價爲250eq/ton、玻璃轉移溫度爲62°C。 將結果顯示於表1。 [S] -30- 201122064 [表l] 組成(莫耳比） 聚酯樹脂(P) (P-1) (P-2) (P-3) (P-4) (P-5) (P-6) (P-7) 酸 對苯—甲酸~~~~ 50 100 50 50 48 50 間苯_甲酸 50 — 20 50 — 48 50 成 癸二酸 — — 30 — — 一 — 分 己二酸 — — — — 100 — — 偏苯二酸 — — — 一 — 4 — — 乙_醇 50 — 57 一 — 85 40 醇 成 新戊四醇 50 — 43 50 30 2-甲基-1,3-丙―醇 — — _ 一 — 15 — 分 1，2-丙—醇 — 100 — 一 — — — 1,6-己—醇 — — _ 50 70 — 60 坡瑪轉移溫度(C) 58 63 10 17 -30 62 22 酸價(eq/ton) 2 8 8 6 3 250 12 數量平均分了里 2000 2000 2100 4000 2000 20000 2000 聚胺甲酸酯樹脂之合成 聚胺甲酸酯樹脂（U-1)之合成 於具備攪拌機、冷凝器、溫度計之反應容器中，倒入 合成例的1000份之聚酯聚醇80份之新戊二醇 (NPG)、90份之二羥甲基丁酸（dMBA)後，進料815份之乙 二醇醋酸醋與272份之乙二醇丁酸酯，於85 X：溶解。之後， 添加460份之4,4，-二苯基甲烷二異氰酸酯（MDI)，於85°C 進行2小時反應後，添加作爲觸媒的0.5份之二丁錫二月 桂酸酯’於85 °C進一步使其反應4小時。接著，利用1455 份之乙基卡必醇醋酸酯、485份之丁基溶纖素醋酸酯以稀 釋溶液’得到聚胺甲酸酯樹脂（U-1)。所獲得之聚胺甲酸酯 樹脂溶液之固形物濃度係35 (質量％)。在聚丙烯薄膜上滴 下進行如此方式所獲得之樹脂溶液，使用不銹鋼製之薄層 塗布機而進行展延，得到樹脂溶液之薄膜。將此薄膜靜置 於已調整至120°C之熱風乾燥機內3小時而使溶劑揮發， [S] -3 1- 201122064 接著，從聚丙烯薄膜剝離樹脂薄膜，得到薄膜狀之乾燥樹 脂薄膜。乾燥樹脂薄膜之厚度約爲30μιη。將該乾垛樹脂薄 膜作爲聚胺甲酸酯樹脂（U-1)之試料樹脂，進行各種樹脂物 性之評估’數量平均分子量爲5 5,000、酸價爲3 8 0eq/ton ' Tg爲70°C。將用於製造聚胺甲酸酯樹脂（U-1)之際的各成 分及樹脂物性顯示於表2。 聚胺甲酸酯樹脂（U-2)至（U-6)之合成 聚胺甲酸酯樹脂（U-2)至（U-6)之合成係將具有與聚酯 聚醇、異氰酸酯進行反應之基的化合物及聚異氰酸酯取代 成顯示於表2之物以外，利用與聚胺甲酸酯樹脂（υ_υ之合 成方法同樣的方法而合成。用於製造聚胺甲酸酯樹脂（U-2) 至（U-6)之際的各成分及樹脂物性顯示於表2。還有，聚胺 甲酸酯樹脂溶液（U-2)至（U-6)之固形物濃度爲35±1(質量％) 之範圍。 表2所揭示的簡稱係如下所示： DMBA :二羥甲基丁酸、 DMP A :二羥甲基丙酸、 NPG :新戊二醇、 DMH: 2-丁基-2-乙基-i，3-丙二醇、 MDI: 4,4’-二苯基甲烷二異氰酸酯、 IPID :異佛酮二異氰酸酯。 [S] -32- 201122064 [表2] •4 聚胺甲 酸酯樹脂 U-1 U-2 U-3 U-4 U-5 U-6 聚酯聚醇 P-1 1000 份 P-2 1000 份 P-2 1000 份 P-1 1000 份 Ρ·1 1000 份 Ρ·2 1000 份 — — P_3 50份 P-4 170份 一 一 具有與異氰酸酯進行反應之 基的化合物 DMBA 90份 DMBA 3〇份 DMPA 10份 DMBA 40份 DMBA 20份 DMBA 50份 NPG 80份 — DMH 50份 — DMH 50份 NPG 20份 聚異氰酸酯 MDI 460份 MDI 180份 MDI 230份 MDI 200份 IPDI 140份 IPDI 230份 玻璃轉移纖。C) 70 97 82 71 70 83 酸價（eq/ton) 380 180 60 150 110 260 缝平均分子量 55000 35000 40000 25000 20000 20000 聚胺甲酸酯樹脂（U-7)之合成 於具備攪拌機、冷凝器及溫度計之反應容器中，倒入 合成例的1000份之聚酯聚醇（P-1)、1500份之聚酯聚醇 (P-5)、50份之l，6 -己二醇（1，6HD)、150份之新戊二醇 (NPG)、30份之二羥甲基丁酸（DMBA)後，添力口作爲溶劑的 1730份之乙二醇醋酸酯、577份之丁二醇醋酸酯，於85 °C 溶解。接著添加810份之4,4，-二苯基甲烷二異氰酸酯 (MDI)，進行2小時反應後，添力日〇.8份之二丁錫二月桂酸 酯’於85 °C進一步使其反應4小時。接著，利用3 0 89份 之乙基卡必醇醋酸酯、1030份之丁基溶纖素醋酸酯加以稀 釋’得到聚胺甲酸酯樹脂（U-7)。所獲得之聚胺甲酸酯樹脂 溶液之固形物濃度係35質量％。數量平均分子量爲 40,00〇、酸價爲6〇eq/t〇n、Tg爲-12°C。將用於製造聚胺甲 酸醋樹脂（U-7)之際的各成分及樹脂物性顯示於表3。 [S] -33- 201122064 聚胺甲酸醋樹脂（U-8)至（U-11)之合成 聚胺甲酸酯樹脂（u_8)至（u_u)2合成係除了將具有與 聚酯聚醇'異氰酸酯進行反應之基的化合物及聚異氰酸酯 變更成顯示於表3之物以外，利用與聚胺甲酸酯樹脂（U-7) 之合成方法同樣的方法合成。將用於製造聚胺甲酸酯樹脂 (U-8)至（U-11)之際的各成分及樹脂物性顯示於表3。還 有’聚胺甲酸醋樹脂（U-8)至（U-l 1)之固形物濃度爲35±1(質 量％ )之範圍。 表3中之簡稱係與表2同樣之物，i，6HD係意指1，6-己二醇。 [表3] U-7 U-8 U-9 U-10 U-11 聚酯聚醇 P-1 1000 份 P-2 1000 份 P-1 1000 份 P-1 1000 份 P-2 1000 份 P-5 1500 份 — — — 一 具有與異気酸酯進行反 應之基的化合物 DMBA 30份 — DMBA 170份 DMBA 20份 DMBA 40份 1，6HD 50份 — NPG 10份 — — NPG 150份 — — 一 — 聚異氰酸酯 MDI 810份 MDI 130份 IPDI 430份 MDI 63份 MDI 202份 玻璃轉移溫度(。〇 12 100 72 70 — 酸價（eq/ton) 60 ] 2 700 125 220 數量平均分子量 40000 25000 30000 5200 120000 聚胺甲酸酯樹脂（U-12)之合成 將100份之聚酯樹脂（P-7)、112份之醋酸二乙二醇單 乙基醚、0.1份之二丁基錫二月桂酸酯進料於具備冷卻器之 四口分離式燒瓶中，於8CTC溶解。接著，進料4，4’-二苯基 [S] -34- 201122064 甲烷二異氰酸酯（MDI)12.4份，於氮氧流下、80°C，直到殘 存的異氰酸酯用完爲止進行聚合。反應結束後，利用醋酸 二乙二醇單乙基醚稀釋，使固形物成爲25%的方式來調 整。所獲得之聚胺甲酸酯樹脂之玻璃轉移溫度爲5 8 °C、還 原黏度爲1.8dl/g、數量平均分子量爲58,000、酸價爲 10eq/ton、清漆黏度爲 320dPa· s» 實施例1 摻合2,858份之固形物濃度35質量％之聚胺甲酸酯樹 脂溶液（U-1)(固形物換算1，〇〇〇份）、6,540份之Ferro Japan(股）製之薄片狀銀粉SF70A、作爲碳黑之76份之 Lion(股）製之ECP600JD、76份之中越石墨工業所（股）製之 石墨BF、作爲平坦劑之58份之共榮社化學（股）製之MK Cone、作爲分散劑之16份之BYK Chemie Japan(股）製之 Disperbyk2155'作爲溶劑之640份之乙二醇醋酸酯（ECA)、 2 1 〇份之丁基卡必醇醋酸酯（BCA)，利用冷卻三輥混攪機經 過3次分散。將全部溶液中之各成分的量顯示於表4。將 進行所獲得之銀糊之退火處理的PET薄膜作成基材，利用 5.密著性試驗中所規定的方法而進行印刷後，以120°C x30 分鐘進行乾燥。所獲得之塗膜物性係比電阻爲4.9 χ 1 0 一 5Ω. cm、密著性1〇〇/1〇〇、鉛筆硬度Η爲良好，將結果顯 示於表4。 另一方面’基材係使用結晶性ΙΤΟ薄膜ΚΑ5 00(尾池工 業（股）製），利用於5 .密著性試驗中所上述的方法進行印 [S) -35- 201122064 刷、乾燥、評估。另外，實施環境試驗。將評估結果顯示 於表4。 實施例2至7 藉由顯示於表4之成分及摻合而與實施例1同樣地製 作銀糊，將已進行退火處理之PET薄膜作爲基材而製得塗 膜。將塗膜物性顯示於表4。 另外，與實施例1同樣地使用結晶性ITO薄膜 K A 5 0 0 (尾池工業（股）製），利用於5.密著性試驗中所上述的 方法進行印刷、乾燥、評估。另外’實施環境試驗。將評 估結果顯示於表4。 任一種實施例皆以烘箱120°C X30分鐘之低溫短時間 之條件而得到良好之塗膜物性。另外，對ITO之密著性、 環境試驗後之密著性、耐結塊性等也爲良好。 還有，顯示於表4之導電粉末、添加劑及溶劑係使用 以下之物： 銀粉 1: Ferro Japan(股）製之 SF70A、 銀粉2:福田金屬箔粉工業（股）製之AgC-2011、 碳黑：Lion(股）製之 KetjenECP600JD、 石墨粉：中越石墨工業所（股）製之石墨BF、 硬化劑：旭化成Chemicals(股）製之MF-K60X、 硬化觸媒：共同藥品（股）製之KS 1 260、 平坦劑：共榮社化學（股）之MK Cone、Sellotape (registered trademark) (Nichiban Co., Ltd.), which was evaluated by the stripping test [S] -27- 201122064. However, the number of cuts in each direction of the lattice pattern was 11 and the cutting interval was set to 1 mm. 1 00 / 1 00 means no peeling, and the adhesion is good, 0/100 means complete peeling, and the adhesiveness is deteriorated. 6. The specific test piece is cut into 25x450 mm in the same manner as the electric resistance. The sheet was measured for sheet resistance and film thickness, and the specific resistance was calculated. In addition, the film thickness was measured by using a Gauge Stand ST-022 (manufactured by Ono Co., Ltd.), and the thickness of the PET film was set to zero, and the thickness of the cured coating film at five points was measured, and the average enthalpy was used. For the sheet resistance, four sheets of 25 x 450 mm wide test pieces were measured using MILLIOHMMETER 4338B (manufactured by HEWLETT PACKARD Co., Ltd.), and the average enthalpy was used. 7. Pencil hardness The test piece obtained by the adhesion test was placed on a SUS304 plate having a thickness of 2 mm, and it was measured in accordance with JIS K5600-5-4: 1999, and judged according to the presence or absence of peeling. 8. Environmental test 5. Adhesion test The test piece prepared on the ITO film was heat-treated at 800 ° C for 3 hours, and heated at 85 ° C, 85% RH (relative humidity). The humidity resistance test at 0 0 hours, after the completion of the heating, was allowed to stand at room temperature for 24 hours, and then the resistance enthalpy was measured. Whether the environmental test is good or not is the evaluation of the adhesion of the conductive coating film and the pencil hardness before and after the implementation of the heat resistance test and the damp heat resistance test. [S] -28- 201122064 9. Blocking resistance 5. The film prepared on the ITO film by the method of adhesion test overlaps the way of connecting the coating film surface, and the part of the external coating film of 500 g is applied. , placed at 80 ° C for 72 hours. Then, after leaving it at room temperature for 1 hour, it was judged by the following criteria. 〇: The transfer of both sides of the coating film does not occur, and the original coating is maintained. X: The transfer to both sides is observed, and peeling occurs. 10. Storage stability The conductive paste was placed in a Poly container and stored at 4 °C for 1 month. After storage, the viscosity was the same as that of the test prepared by the test. The specific resistance, pencil hardness, and adhesion were used. 〇 : There is no significant change in viscosity'. Maintain the initial resistance and pencil adhesion. X : It was confirmed that the viscosity was greatly increased, and the decrease in specific resistance and pencil adhesion was confirmed. Production Example of Resin Synthetic Polyester Polyol (P-1) of Polyester Polyol (P) Between 700 parts of dimethyl terephthalate and 700 parts of a reaction vessel containing a stirrer, a condenser, and a thermometer Benzene dicarboxylate '671 parts of ethylene glycol, 526 parts of neopentyl glycol, 〇·48 parts of butyl ester, at 180. (: Perform 3 hours of transesterification. Then 'slowly 2 pieces of the coating are applied to the guide load, and the state is judged. The hardness is measured, the hardness, the hardness, the medium, the dimethic acid, the four decompressions are straight -29- 201122064 to below ImmHg, polymerization for 1 to 5 hours at 240 ° C. The composition of the obtained copolymerized polyester (Ρ-1) is terephthalic acid / isophthalic acid / / ethylene glycol / neopentyl glycol = 5 0/5 0//5 0/5 0 (mol ratio), the number average molecular weight was 2,000, the acid value was 2 eq/ton, and Tg was 58 ° C. The results are shown in Table 1. Polyester polyol (P- 2) to (P-5) and (P-7) In addition to the polyester polyol (P-1), the acid component and the diol component shown in Table 1 were used to form the molar ratio of Table 1. In addition to the monomer, it is synthesized by the same method as the polyester polyol (P-1). The composition of the polyester polyols (P-1) to (P-5), and (P-7) and the resin The physical properties are shown in Table 1. The polyester resin (P-6) was synthesized in a reaction vessel equipped with a stirrer, a condenser, and a thermometer, and fed 700 parts of dimethyl terephthalate and 700 parts of phthalic acid. Dimethyl ester, 16.9 parts of trimellitic anhydride, 983 Ethylene glycol, 154 parts of 2-methyl-1,3-propanediol, and an esterification reaction was carried out for 3 hours from 160 ° C to 230 ° C under a pressure of two atmospheres under a nitrogen atmosphere. After the pressure was released, 0.92 parts of tetrabutyl titanate was fed, and then the pressure in the system was gradually reduced, and the pressure was reduced to 5 mmHg or less for 20 minutes, and further, the condensation was carried out at 260 ° C for 40 minutes under vacuum of 0.3 mmHg or less. The reaction was carried out under a nitrogen gas stream, cooled to 220 ° C, and 50.6 parts of trimellitic anhydride was poured into a reaction for 30 minutes to obtain a polyester resin. The obtained copolymerized polyester (P-6) was obtained by the reaction of p-benzoic acid. Formic acid / isophthalic acid / trimellitic acid / / ethylene glycol / 2 - methyl - 1,3-propanediol = 48 / 4 8 / 4 / / 85 / 15 (mr ratio), the number average molecular weight is 20,000 The acid value was 250 eq/ton, and the glass transition temperature was 62 ° C. The results are shown in Table 1. [S] -30- 201122064 [Table 1] Composition (Mohr ratio) Polyester resin (P) (P-1 ) (P-2) (P-3) (P-4) (P-5) (P-6) (P-7) Acid to Benzene-formic acid ~~~~ 50 100 50 50 48 50 Benzene-formic acid 50 — 20 50 — 48 50 Cheng Cheng Eric Acid — 30 — — One — Adipic acid — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — , 3-propanol-- _ -15 - 1 , 2 - propyl - alcohol - 100 - 1 - - 1,6-hexanol - _ 50 70 - 60 Pomma transfer temperature (C) 58 63 10 17 -30 62 22 Acid value (eq/ton) 2 8 8 6 3 250 12 The average number of points is 2000 2000 2100 4000 2000 20000 2000 Polyurethane resin synthetic polyurethane resin (U- 1) The synthesis is carried out in a reaction vessel equipped with a stirrer, a condenser, and a thermometer, and 1000 parts of polyester polyol of the synthesis example is poured into 80 parts of neopentyl glycol (NPG) and 90 parts of dimethylolbutanoic acid ( After dMBA), 815 parts of ethylene glycol acetate vinegar and 272 parts of ethylene glycol butyrate were fed and dissolved at 85 X:. Thereafter, 460 parts of 4,4,-diphenylmethane diisocyanate (MDI) was added, and after reacting at 85 ° C for 2 hours, 0.5 part of dibutyltin dilaurate was added as a catalyst at 85 °. C was further allowed to react for 4 hours. Next, a polyurethane resin (U-1) was obtained by diluting the solution with 1455 parts of ethyl carbitol acetate and 485 parts of butyl cellosolve acetate. The solid concentration of the obtained polyurethane resin solution was 35 (% by mass). The resin solution obtained in this manner was dropped on a polypropylene film, and stretched using a thin coater made of stainless steel to obtain a film of a resin solution. The film was allowed to stand in a hot air dryer adjusted to 120 ° C for 3 hours to volatilize the solvent, [S] -3 1- 201122064 Next, the resin film was peeled off from the polypropylene film to obtain a film-like dry resin film. The thickness of the dried resin film was about 30 μm. The dried resin film was used as a sample resin of a polyurethane resin (U-1), and various resin physical properties were evaluated. The number average molecular weight was 5 5,000, and the acid value was 380 eq/ton 'Tg was 70 ° C. . The components and resin physical properties at the time of producing the polyurethane resin (U-1) are shown in Table 2. The synthesis of the polyurethane resin (U-2) to (U-6) of the polyurethane resin (U-2) to (U-6) will have a reaction with the polyester polyol and the isocyanate. The compound of the base and the polyisocyanate were substituted and shown in Table 2, and synthesized by the same method as the synthesis method of the polyurethane resin (manufactured by υ_υ). For the production of polyurethane resin (U-2) The physical properties of each component and resin at the time of (U-6) are shown in Table 2. Further, the solid concentration of the polyurethane resin solutions (U-2) to (U-6) was 35 ± 1 (mass The range of %) is as follows: DMBA: dimethylol butyric acid, DMP A: dimethylolpropionic acid, NPG: neopentyl glycol, DMH: 2-butyl-2 -ethyl-i,3-propanediol, MDI: 4,4'-diphenylmethane diisocyanate, IPID: isophorone diisocyanate [S] -32- 201122064 [Table 2] •4 Polyurethane Resin U-1 U-2 U-3 U-4 U-5 U-6 Polyester Polyol P-1 1000 parts P-2 1000 parts P-2 1000 parts P-1 1000 parts Ρ·1 1000 parts Ρ· 2 1000 parts - P_3 50 parts P-4 170 parts - reacted with isocyanate Base compound DMBA 90 parts DMBA 3 parts DMPA 10 parts DMBA 40 parts DMBA 20 parts DMBA 50 parts NPG 80 parts - DMH 50 parts - DMH 50 parts NPG 20 parts polyisocyanate MDI 460 parts MDI 180 parts MDI 230 parts MDI 200 parts IPDI 140 parts IPDI 230 parts glass transfer fiber. C) 70 97 82 71 70 83 acid value (eq/ton) 380 180 60 150 110 260 seam average molecular weight 55000 35000 40000 25000 20000 20000 polyurethane resin (U-7 The synthesis is carried out in a reaction vessel equipped with a stirrer, a condenser and a thermometer, and 1000 parts of the polyester polyol (P-1), 1500 parts of the polyester polyol (P-5), and 50 parts of the synthetic example are poured. 1,6-hexanediol (1,6HD), 150 parts of neopentyl glycol (NPG), 30 parts of dimethylolbutanoic acid (DMBA), and 1730 parts of ethylene glycol as a solvent Acetate and 577 parts of butanediol acetate were dissolved at 85 °C. Then, 810 parts of 4,4,-diphenylmethane diisocyanate (MDI) was added, and after reacting for 2 hours, 8 parts of dibutyltin dilaurate was further reacted at 85 ° C. 4 hours. Next, 300 parts of ethyl carbitol acetate and 1030 parts of butyl cellosolve acetate were used to dilute to obtain a polyurethane resin (U-7). The solid concentration of the obtained polyurethane resin solution was 35 mass%. The number average molecular weight was 40,00 Torr, the acid value was 6 〇 eq/t 〇 n, and the Tg was -12 °C. The respective components and resin physical properties at the time of producing the polyurethane urethane resin (U-7) are shown in Table 3. [S] -33- 201122064 Polyurethane resin (U-8) to (U-11) synthetic polyurethane resin (u_8) to (u_u) 2 synthetic system in addition to having polyester with polyester The compound in which the isocyanate was reacted and the polyisocyanate were changed to those shown in Table 3, and were synthesized in the same manner as in the synthesis method of the polyurethane resin (U-7). Table 3 shows the respective components and resin physical properties at the time of producing the polyurethane resin (U-8) to (U-11). Further, the solid concentration of the polyurethane resin (U-8) to (U-1) is in the range of 35 ± 1 (% by mass). The abbreviation in Table 3 is the same as in Table 2, and i, 6HD means 1,6-hexanediol. [Table 3] U-7 U-8 U-9 U-10 U-11 Polyester Polyol P-1 1000 parts P-2 1000 parts P-1 1000 parts P-1 1000 parts P-2 1000 parts P- 5 1500 parts — — A compound having a reaction with isodecanoate DMBA 30 parts — DMBA 170 parts DMBA 20 parts DMBA 40 parts 1,6HD 50 parts — NPG 10 parts — NPG 150 parts — — — Polyisocyanate MDI 810 parts MDI 130 parts IPDI 430 parts MDI 63 parts MDI 202 parts glass transfer temperature (. 〇12 100 72 70 - acid value (eq/ton) 60 ] 2 700 125 220 number average molecular weight 40000 25000 30000 5200 120000 Synthesis of urethane resin (U-12) 100 parts of polyester resin (P-7), 112 parts of diethylene glycol monoethyl ether acetate, 0.1 part of dibutyltin dilaurate are fed In a four-necked flask equipped with a cooler, it was dissolved at 8 CTC. Next, 4,4'-diphenyl[S]-34-201122064 methane diisocyanate (MDI) was fed in an amount of 12.4 parts under a nitrogen-oxygen stream at 80°. C, the polymerization is carried out until the remaining isocyanate is used up. After the reaction is completed, it is diluted with diethylene glycol monoethyl ether to make the solid matter 25%. To adjust, the obtained polyurethane resin has a glass transition temperature of 58 ° C, a reducing viscosity of 1.8 dl / g, a number average molecular weight of 58,000, an acid value of 10 eq / ton, and a varnish viscosity of 320 dPa · s » Example 1 2,858 parts of a polyurethane resin solution (U-1) having a solid content of 35% by mass (solid content: 1 part) and 6,540 parts of a sheet of Ferro Japan (manufactured) were blended. Silver powder SF70A, ECP600JD manufactured by Lion Co., Ltd., 76 parts of carbon black, 76 parts of graphite BF manufactured by Zhongyue Graphite Industry Co., Ltd., and 58 parts of Kyoeisha Chemical Co., Ltd. as a flattening agent. MK Cone, 16 parts of Disperbyk 2155' made by BYK Chemie Japan as a dispersing agent, 640 parts of ethylene glycol ester (ECA) as solvent, and 2 parts of butyl carbitol acetate (BCA) The dispersion was carried out three times by a three-roller mixer using a cooling. The amounts of the respective components in the entire solution are shown in Table 4. The PET film obtained by annealing the obtained silver paste was used as a substrate, and the adhesion was utilized. After printing by the method specified in the test, it was dried at 120 ° C for 30 minutes. The film properties of the obtained coating film were 4.9 χ 1 0 to 5 Ω·cm, the adhesion was 1 〇〇/1 〇〇, and the pencil hardness Η was good, and the results are shown in Table 4. On the other hand, 'the base material is a crystalline ruthenium film ΚΑ500 (manufactured by Oikei Co., Ltd.), and it is used for printing [S) -35 - 201122064 by the above method in the adhesion test. Evaluation. In addition, environmental tests were carried out. The evaluation results are shown in Table 4. Examples 2 to 7 A silver paste was produced in the same manner as in Example 1 by the components shown in Table 4, and a PET film which had been annealed was used as a substrate to prepare a coating film. The coating film properties are shown in Table 4. Further, in the same manner as in Example 1, a crystalline ITO film K A 500 (manufactured by Oike Industrial Co., Ltd.) was used, and printing, drying, and evaluation were carried out by the above method in the adhesion test. In addition, environmental testing was carried out. The evaluation results are shown in Table 4. In any of the examples, good film properties were obtained under the conditions of an oven at 120 ° C for 30 minutes at a low temperature for a short period of time. In addition, adhesion to ITO, adhesion after environmental test, and blocking resistance are also good. Further, the conductive powder, the additive, and the solvent shown in Table 4 were as follows: Silver powder 1: SF70A manufactured by Ferro Japan Co., Ltd., Silver powder 2: AgC-2011, carbon manufactured by Fukuda Metal Foil Powder Co., Ltd. Black: KetjenECP600JD manufactured by Lion Co., Ltd., graphite powder: Graphite BF made by Sino-Vietnamese Graphite Industry Co., Ltd., hardener: MF-K60X manufactured by Asahi Kasei Chemicals Co., Ltd., hardening catalyst: common drug (share) KS 1 260, flattening agent: MK Cone of Kyoeisha Chemical Co., Ltd.

[SJ -36- 201122064 分散劑 2: BYKChemieJapan(股）製之 Dieperbykl80、 ECA : Daicel化學工業（股）製之乙二醇醋酸酯、 BCA: Daicel化學工業（股）製之丁二醇醋酸酯。 [表4] 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 導 電 性 糊 份 樹脂 υ·1 1000 — — ~ — - 1000 U-2 - 1000 — ~ - - — U-3 — — 1000 — — — - U-4 — — 一 1000 — 一 — U-5 - — 一 - 1000 - - U-6 — — — - — 1000 - 導電粉 銀粉1 6540 — 7517 7517 7517 7517 — 銀粉2 - 7517 — — — 一 7517 UtiEB 販黑 76 87 87 87 87 87 87 石墨 76 87 87 87 87 87 87 添加劑 硬化劑 — — — — — 一 30 硬化觸媒 — — — — — - δ 平坦劑 58 58 58 58 58 58 58 分散劑1 16 — 17 17 17 17 - 分散劑2 — 17 — 一 — — 17 溶劑 ECA 2030 2091 2091 2091 2091 2091 2091 BCA 677 700 700 700 700 700 700 基 材 PET 基材 密著性 100/100 100/100 100/100 100/100 100/100 100/100 100/100 給筆硬度 Η 2Η 2Η Η Η Η 2Η 比電阻値(Ω · cm) 4.9χ10-5 4.3χ10'5 4.6χ10"5 4.8χ1(Γ5 5.8χ10-5 5.5^10-5 3.9χ10'5 ITO (初期） 密著性 100/100 100/100 100/100 100/100 100/100 100/100 100/100 給筆硬度 Η 2Η 2Η Η Η Η 2Η ITO (¾境試 驗後） 密著性 100/100 100/100 100/100 100/100 100/100 100/100 100/100 _硬度 Η 2Η 2Η Η Η Η 2Η 耐結塊性 0 〇 0 0 〇 ο 0 儲藏安定性 0 0 0 0 〇 0 〇 比較例1 摻合2,8 5 8份（固形物換算1，000份）之已將聚酯樹脂 (P-6)調整成固形物濃度35質量％ (乙二醇醋酸酯：丁二醇 醋酸酯=75: 25 (質量比））之溶液、6,540份之Ferro Japan(股） 製之薄片狀銀粉SF70A、作爲碳黑之76份之Lion(股）製之 Ketjen ECP600JD、76份之中越石墨工業所（股）製之石墨 BF、作爲平坦劑之58份之共榮社化學（股）製之MK Cone、 作爲分散劑1之16份之8丫〖（：1^1^6“？&11(股）製之 [S] -37- 201122064[SJ-36- 201122064 Dispersant 2: Dieperbykl80, ECA: manufactured by Daicel Chemical Industry Co., Ltd., ethylene glycol ester manufactured by Daicel Chemical Industry Co., Ltd., BCA: butane glycol acetate manufactured by Daicel Chemical Industry Co., Ltd. [Table 4] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Conductive paste resin υ·1 1000 — — — — — 1000 U-2 - 1000 — ~ - - — U-3 — — 1000 — — — — U-4 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — Silver Powder 2 - 7517 — — — A 7517 UtiEB Black 76 87 87 87 87 87 87 Graphite 76 87 87 87 87 87 87 Additive Hardener — — — — — A 30 Hardening Catalyst — — — — — δ Flat Agent 58 58 58 58 58 58 58 Dispersant 1 16 — 17 17 17 17 - Dispersant 2 — 17 — One — — 17 Solvent ECA 2030 2091 2091 2091 2091 2091 2091 BCA 677 700 700 700 700 700 700 Substrate PET substrate dense Qualitative 100/100 100/100 100/100 100/100 100/100 100/100 100/100 Pen hardness Η 2Η 2Η Η Η Η 2Η Specific resistance 値 (Ω · cm) 4.9χ10-5 4.3χ10'5 4.6 Χ10"5 4.8χ1(Γ5 5.8χ10-5 5.5^10-5 3.9χ10'5 ITO (initial) Adhesion 100/100 100/100 100/100 100/100 100/ 100 100/100 100/100 Pen hardness Η 2Η 2Η Η Η Η 2Η ITO (after 3⁄4 environment test) Adhesive 100/100 100/100 100/100 100/100 100/100 100/100 100/100 _ Hardness Η 2Η 2Η Η Η Η 2Η Blocking resistance 0 〇0 0 〇ο 0 Storage stability 0 0 0 0 〇0 〇Comparative example 1 Blending 2,8 5 8 parts (1,000 parts for solids conversion) The polyester resin (P-6) was adjusted to a solution having a solid concentration of 35 mass% (ethylene glycol acetate: butanediol acetate = 75:25 (mass ratio)), and 6,540 parts of Ferro Japan. The flaky silver powder SF70A, the Ketjen ECP600JD manufactured by Lion Co., Ltd., which is 76 parts of the carbon black, the 76 parts of the graphite BF manufactured by Zhongyue Graphite Industry Co., Ltd., and the 58 parts of the Kyoei Chemical Co., Ltd. ) MK Cone, as a dispersant 1 of 16 parts of 丫 〖(:1^1^6"? &11 (shares) system [S] -37- 201122064

Dieperbyk2155、作爲溶劑之640份之乙二醇醋酸酯、210 份之丁基卡必醇醋酸酯，利用冷卻三輥混攪機經過3次分 散。將全部溶液中之各成分的量顯示於表5。在進行所獲 得之銀糊之退火處理的PET薄膜上，利用5.密著性試驗中 所述之方法進行印刷後，以120°C x30分鐘進行乾燥。所獲 得之塗膜物性係比電阻爲 9.2xl0 5ii.cm、密著性 10 0/100、鉛筆硬度HB爲良好。將結果顯示於表5。 另一方面’基材係使用結晶性IΤ Ο薄膜K A 5 0 0 (尾池工 業（股）製），利用於5 .密著性試驗中所述之方法進行印刷、 乾燥、評估。另外’實施環境試驗。將評估結果顯示於表 比較例2至7 藉由顯示於表5之成分及摻合而與實施例1同樣地製 作銀糊’將已進行退火處理之PET薄膜作爲基材而製得塗 膜。將塗膜物性顯示於表5。 還有，關於比較例6，由於利用高黏度之印刷爲困難， 停止以後之評估。 除了比較例6以外，與比較例1同樣的，使用結晶性 ITO薄膜KA5 00(尾池工業（股）製），利用於5.密著性試驗中 所述之方法進行印刷、乾燥、評估。另外，實施環境試驗。 將評估結果顯示於表5。 任一種之比較例皆以供箱1 2 0 °C X 3 0分鐘之低溫短時 間之條件，以對IΤ Ο基材之密著性爲主的塗膜物性係不 [S1 -38- 201122064 良。另外，環境試驗後之ITO密著性、耐結塊性等也爲不 良。 將評估結果顯示於表5。還有，顯示時表5之導電粉 末、添加劑及溶劑係相同於表4之物。 [表5] 比較例1 比較例2 比較例3 比較例4 比較例5 比較例ό 比較例7 P-6 1000 一 - 一 — — — U-7 一 1000 - — — — — U-8 一 - 1000 — — — — 樹脂 U-9 一 - - 1000 — - - U-10 - - — - 1000 — — 導 電 υ·】ι - - — — - 1000 - U-12 ~ 一 一 一 — — 1000 銀粉1 6540 - 7517 7517 7517 7517 7517 粉 糊 導電粉 銀粉2 - 7517 - — — — - 碳黑 76 87 87 87 87 87 87 份 石墨 76 87 87 87 87 87 87 硬化劑 - — — - - — — 硬化觸媒 一 - 一 — 一 - — 添加劑 平坦劑 58 58 58 58 58 58 58 分散劑1 16 - 17 17 17 17 — 分散劑2 - 16 - — — — 17 溶劑 ECA 2030 2091 2091 2091 2091 — 2091 BCA 677 700 700 700 700 - 700 PET 基材 密著性 100/100 100/100 100/100 100/100 75/100 — 100/100 戀硬度 HB HB 3H Η Β — 2Η 比電阻値(Ω _ cm) 9.2χ10~5 4.6χ10"5 4.36χ10-5 5.2χ10'5 7.3Χ10-5 - 4.3>=1(Γ5 基 材 ITO 密著性 100/100 100/100 0/100 100/100 80/100 — 15/100 (初期） 鉛筆硬度 HB HB 5B 2Η Β — 2Β ITO (環境試 驗後） 密著性 70/100 100/100 0/100 40/100 0/100 - 0/100 給筆硬度 HB 2B 5B 2Η 4Β - 5Β 耐結塊性 X X X X X - X 儲藏安定性 X 〇 〇 X 〇 X 〇 【圖式簡單說明】 〇 【主要元件符號說明】 無。 [S] -39-Dieperbyk 2155, 640 parts of ethylene glycol acetate as a solvent, and 210 parts of butyl carbitol acetate were dispersed three times using a cooling three-roll mixer. The amounts of the respective components in the entire solution are shown in Table 5. The PET film subjected to the annealing treatment of the obtained silver paste was printed by the method described in 5. The adhesion test, and then dried at 120 ° C for 30 minutes. The obtained coating film had a specific resistance of 9.2 x 10 5 ii.cm, a tack of 10 0/100, and a pencil hardness HB. The results are shown in Table 5. On the other hand, the substrate was printed, dried, and evaluated by the method described in the 5. Adhesion test using a crystalline I Ο film K A 500 (manufactured by Oike Industrial Co., Ltd.). In addition, environmental testing was carried out. The evaluation results are shown in the table. Comparative Examples 2 to 7 A silver paste was produced in the same manner as in Example 1 by the components shown in Table 5 and blending. A PET film which had been annealed was used as a substrate to prepare a coating film. The coating film properties are shown in Table 5. Further, regarding Comparative Example 6, since it was difficult to use high-viscosity printing, the evaluation later was stopped. In the same manner as in Comparative Example 1, a crystalline ITO film KA5 00 (manufactured by Oikei Co., Ltd.) was used, and printing, drying, and evaluation were carried out by the method described in 5. Adhesion test. In addition, environmental tests were carried out. The evaluation results are shown in Table 5. In any of the comparative examples, the film properties of the coating of the substrate of the I Τ Ο substrate were not [S1 - 38 - 201122064, which was good for a short period of time of 1 2 0 ° C X 30 minutes. In addition, ITO adhesion and blocking resistance after environmental testing are also poor. The evaluation results are shown in Table 5. Further, the conductive powder, the additive and the solvent of Table 5 were the same as those of Table 4 at the time of display. [Table 5] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example ό Comparative Example 7 P-6 1000 One-one--- U-7 One 1000 - — — — U-8 One- 1000 — — — — Resin U-9 One - - 1000 — - - U-10 - - - - 1000 — — Conductive υ·】ι - - — — - 1000 - U-12 ~ 117 — 1000 Silver 1 6540 - 7517 7517 7517 7517 7517 Paste Conductive Powder Silver Powder 2 - 7517 - — — — - Carbon Black 76 87 87 87 87 87 87 Parts Graphite 76 87 87 87 87 87 87 Hardener - — — — — — — Hardening Catalyst One-one-one--additive flattening agent 58 58 58 58 58 58 58 Dispersing agent 1 16 - 17 17 17 17 — Dispersing agent 2 - 16 - — — 17 Solvent ECA 2030 2091 2091 2091 2091 — 2091 BCA 677 700 700 700 700 - 700 PET substrate adhesion 100/100 100/100 100/100 100/100 75/100 — 100/100 Love hardness HB HB 3H Η Β — 2Η Specific resistance 値 (Ω _ cm) 9.2χ10~5 4.6χ10"5 4.36χ10-5 5.2χ10'5 7.3Χ10-5 - 4.3>=1(Γ5 Substrate ITO Adhesion 100/100 100/100 0/100 1 00/100 80/100 — 15/100 (Initial) Pencil hardness HB HB 5B 2Η Β — 2Β ITO (after environmental test) Adhesion 70/100 100/100 0/100 40/100 0/100 - 0/100 Pen hardness HB 2B 5B 2Η 4Β - 5Β Blocking resistance XXXXX - X Storage stability X 〇〇X 〇X 〇【Simple description of the chart】 〇【Main component symbol description】 None. [S] -39-

Claims (1)

201122064 七、申請專利範圍： 1. 一種導電性糊，其係含有： (a)成分’由酸價爲50至500eq/ton、玻璃轉移溫 度爲60至150°c、聚胺甲酸酯樹脂所構成的黏著劑樹脂； 成分，由金屬粉末所構成；及 (C)成分，由有機溶劑所構成。 2. 如申請專利範圍第1項之導電性糊’其中（A)成分係由 具有經藉由進行下列（A1) 、 （A2)與（A3)之加成聚 合反應所獲得結構之聚胺甲酸酯樹脂所構成的黏著劑樹 脂： (A1)數量平均分子量爲h 000至10，000及玻璃轉 移溫度爲30至80°C之非晶性性聚醇、 (A2)數量平均分子量低於i，000且—分子中具有2 個以上可與異氰酸酯進行反應之官能基的化合物、及 (A 3 )聚異氰酸酯。 3. 如申請專利範圍第1或2項之導電性糊’其中（A)成分 係由具有經藉由進行下列（Al )、（ A2 )、（ A3 )與（A4 ) 之加成聚合反應所獲得結構之聚胺甲酸酯樹脂所構成的 黏著劑樹脂： (A1)數量平均分子量爲1，000至1 0,000及玻璃轉 移溫度爲3 0至8 0 °C之非晶性性聚醇、 (A2)數量平均分子量低於1，〇〇〇且一分子中具有2 個以上可與異氰酸酯進行反應之官能基的化合物、 [S] -40- 201122064 (A3 )聚異氰酸酯、及 (A4)數量平均分子量爲1，0〇〇至1〇,〇〇〇 移溫度低於30°C之非晶性性聚醇。 4. 如申請專利範圍第2或3項之導電性糊，其中 性聚醇（A 1 )係非晶聚酯聚醇，該非晶聚酯聚 部聚羧酸與全部聚醇成分分別設爲100莫耳％ 聚羧酸成分之內，芳香族二羧酸爲60莫耳％以 聚醇成分之內，主鏈之碳數爲4以下之二醇爲 以上。 5. 如申請專利範圍第2至4項中任一項之導電性 可與化合物（A2)中之異氰酸酯進行反應之官 基或胺基。 6. 如申請專利範圍第2至5項中任一項之導電性 化合物（A2)更含有羧基。 7. 如申請專利範圍第1至6項中任一項之導電性 (B)成分更含有金屬粉末以外之導電性粉末。 8. 如申請專利範圍第1至7項中任一項之導電性 相對於1 0 0質量份之黏結劑樹脂（A )而言， 之含量爲400至1,900質量份。 9. 如申請專利範圍第1至8項中任一項之導電性 相對於100質量份之黏結劑樹脂（A)而言，I 之含量爲1 50至500質量份。 及玻璃轉 該非晶性 醇係將全 時，全部 上，全部 60莫耳％ 糊，其中 能基爲羥 糊，其中 糊，其中 糊，其中 (B )成分 糊，其中 C)成分 -41 - * 201122064 10. —種導電性薄膜，其係由使用如申請專利範圍第1至9 項中任一項之導電性糊所構成。 11. 一種導電性積層體，其係在透明導電性層上積層如申請 專利範圍第10項之導電性薄膜。 1 2 .如申請專利範圍第1 1項之導電性積層體，其中透明導 電性層係由以氧化銦錫作爲主要成分所構成的ITO(銦錫 氧化物）膜。 1 3 . —種觸控面板，其係使用如申請專利範圍第1 1或1 2項 之導電性積層體。 14. 一種導電性薄膜之製造方法，其係包括： 將如申請專利範圍第1至9項中任一項之導電性糊 塗布或印刷於基材上的步驟；及 於8 0至1 5 0 °C進行加熱的步驟。 [S] -42- 201122064 四、指定代表圖： (一) 本案指定代表圖為：無。 (二) 本代表圖之元件符號簡單說明： 無0 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： 無0201122064 VII. Patent application scope: 1. A conductive paste containing: (a) the composition 'from acid value of 50 to 500 eq / ton, glass transition temperature of 60 to 150 ° C, polyurethane resin The adhesive resin is composed of a component; the component is composed of a metal powder; and the component (C) is composed of an organic solvent. 2. The conductive paste as described in claim 1 wherein the component (A) is a polyamine having a structure obtained by addition polymerization of (A1), (A2) and (A3) Adhesive resin composed of an acid ester resin: (A1) an amorphous polyalcohol having a number average molecular weight of h 000 to 10,000 and a glass transition temperature of 30 to 80 ° C, (A2) a number average molecular weight lower than i 00 and - a compound having two or more functional groups reactive with isocyanate in the molecule, and (A 3 ) polyisocyanate. 3. The conductive paste of claim 1 or 2 wherein the component (A) has an addition polymerization reaction by (A), (A2), (A3) and (A4) An adhesive resin comprising a structural polyurethane resin: (A1) an amorphous polyalcohol having a number average molecular weight of 1,000 to 10,000 and a glass transition temperature of 30 to 80 ° C, ( A2) a compound having a number average molecular weight of less than 1, and having two or more functional groups reactive with isocyanate in one molecule, [S] -40 - 201122064 (A3 ) polyisocyanate, and (A4) An amorphous polyalcohol having a molecular weight of 1,0 Torr to 1 Torr and a shift temperature of less than 30 °C. 4. The conductive paste according to claim 2 or 3, wherein the neutral polyol (A 1 ) is an amorphous polyester polyol, and the amorphous polyester polycarboxylate and all the polyol components are respectively set to 100. In the mol% polycarboxylic acid component, the aromatic dicarboxylic acid is 60 mol% in the polyalcohol component, and the diol having 4 or less carbon atoms in the main chain is at least the above. 5. The functional group or amine group which can be reacted with the isocyanate in the compound (A2) as disclosed in any one of claims 2 to 4. 6. The conductive compound (A2) according to any one of claims 2 to 5, further contains a carboxyl group. 7. The conductive (B) component according to any one of claims 1 to 6 further contains a conductive powder other than the metal powder. 8. The conductive property according to any one of claims 1 to 7 is from 400 to 1,900 parts by mass relative to 100 parts by mass of the binder resin (A). 9. Conductivity according to any one of claims 1 to 8 The content of I is from 1 50 to 500 parts by mass relative to 100 parts by mass of the binder resin (A). And the glass is transferred to the amorphous alcohol system all the time, all on, all 60 mole% paste, wherein the energy base is a hydroxy paste, wherein the paste, wherein the paste, wherein the (B) component paste, wherein the C) component -41 - * 201122064 10. A conductive film comprising the conductive paste according to any one of claims 1 to 9. A conductive laminate which is laminated on a transparent conductive layer as in the conductive film of claim 10 of the patent application. The conductive laminate of the first aspect of the invention, wherein the transparent conductive layer is an ITO (indium tin oxide) film comprising indium tin oxide as a main component. A touch panel using a conductive laminate as disclosed in claim 11 or 12. A method for producing a conductive film, comprising: a step of coating or printing a conductive paste according to any one of claims 1 to 9 on a substrate; and 80 to 150 °C is the step of heating. [S] -42- 201122064 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 0. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:
TW099135044A 2009-10-15 2010-10-14 Conductive paste, conductive film, touch panel and method for producing conductive thin film TWI486413B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2009238403 2009-10-15

Publications (2)

Publication Number Publication Date
TW201122064A true TW201122064A (en) 2011-07-01
TWI486413B TWI486413B (en) 2015-06-01

Family

ID=43876126

Family Applications (1)

Application Number Title Priority Date Filing Date
TW099135044A TWI486413B (en) 2009-10-15 2010-10-14 Conductive paste, conductive film, touch panel and method for producing conductive thin film

Country Status (5)

Country Link
JP (1) JP4968410B2 (en)
KR (1) KR101223408B1 (en)
CN (1) CN102576581B (en)
TW (1) TWI486413B (en)
WO (1) WO2011046076A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI596172B (en) * 2016-09-02 2017-08-21 Teikoku Printing Inks Mfg Co Ltd Conductive liquid composition
TWI603342B (en) * 2013-03-29 2017-10-21 富士軟片股份有限公司 Composition for forming electroconductive film and method of producing electroconductive film by using the same
US9818498B2 (en) 2011-10-25 2017-11-14 Lg Innotek Co., Ltd. Paste composition for printing and touch panel
TWI802582B (en) * 2017-08-24 2023-05-21 日商東洋紡股份有限公司 Conductive paste, three-dimensional printed circuit, touch sensor, and method for manufacturing the aforementioned objects

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5767498B2 (en) * 2011-03-31 2015-08-19 太陽ホールディングス株式会社 Conductive paste
WO2013084283A1 (en) 2011-12-05 2013-06-13 日立化成株式会社 Method for forming protective film for touch panel electrodes, photosensitive resin composition, and photosensitive element
JP2013200577A (en) * 2011-12-05 2013-10-03 Hitachi Chemical Co Ltd Formation method of cured resin film pattern, photosensitive resin composition, photosensitive element, manufacturing method of touch panel and cured resin film
WO2013084282A1 (en) * 2011-12-05 2013-06-13 日立化成株式会社 Method for forming resin cured film pattern, photosensitive resin composition, and photosensitive element
JP5304971B1 (en) * 2011-12-05 2013-10-02 日立化成株式会社 Protective film for touch panel electrode and touch panel
WO2013084284A1 (en) * 2011-12-05 2013-06-13 日立化成株式会社 Method for forming protective film for touch panel electrodes, photosensitive resin composition, and photosensitive element
JP5773292B2 (en) * 2012-07-20 2015-09-02 東洋紡株式会社 Conductive paste, conductive thin film and conductive laminate for laser etching
JP5751509B2 (en) * 2013-01-18 2015-07-22 東洋紡株式会社 Conductive paste, conductive film, electric circuit and touch panel
JP6233792B2 (en) * 2013-01-28 2017-11-22 国立大学法人群馬大学 Conductive paste
CN103232799B (en) * 2013-05-16 2015-07-15 佩特化工(上海)有限公司 Conductive coating for electrode of capacitive inductor of intelligent touch screen and preparation method
CN103426497B (en) * 2013-08-30 2016-01-06 东莞市平波电子有限公司 A kind of conductive silver paste for touch screens and preparation method thereof
CN105612585B (en) * 2013-09-30 2018-03-16 东洋纺株式会社 Electrocondution slurry, conductive coating, galvanic circle, electric conductivity laminate and touch-screen
CN103605443B (en) * 2013-11-30 2016-05-18 东莞市平波电子有限公司 A kind of manufacture craft of touch-screen of PG structure
CN103593090B (en) * 2013-11-30 2016-08-31 东莞市平波电子有限公司 The two-sided conductive film of a kind of GF2, the touch module processing technology of elargol wire structures
CN103593089B (en) * 2013-11-30 2016-06-29 东莞市平波电子有限公司 A kind of processing technology of the touch screen of GG structure
CN103605444B (en) * 2013-11-30 2016-07-06 东莞市平波电子有限公司 A kind of processing technology of the touch screen of G1F structure
WO2015099049A1 (en) * 2013-12-27 2015-07-02 日本化薬株式会社 Conductive paste and conductive film
CN103713772B (en) * 2013-12-31 2016-08-24 东莞市平波电子有限公司 A kind of processing technology of the touch screen of GF monolayer multipoint configuration
CN105993050B (en) * 2014-01-22 2018-09-25 东洋纺株式会社 Laser-induced thermal etching processing electrocondution slurry, conductive membrane, conductive laminate
KR102324621B1 (en) * 2014-01-22 2021-11-11 도요보 가부시키가이샤 Conductive paste for laser etching, conductive thin film and conductive laminate
WO2016031483A1 (en) 2014-08-29 2016-03-03 富士フイルム株式会社 Touch sensor film manufacturing method, touch sensor film, and touch panel
CN104361922B (en) * 2014-10-26 2017-02-08 余姚市慧点电子科技开发有限公司 Electronic paste for touch screens and preparation method of electronic paste
CN104934098A (en) * 2015-01-05 2015-09-23 深圳市思迈科新材料有限公司 Low temperature curing laser silver paste and preparation method thereof
JP2016173933A (en) * 2015-03-17 2016-09-29 昭和電工株式会社 Conductive paste, conductive pattern, and method of manufacturing conductive pattern
JP6376269B1 (en) * 2017-11-15 2018-08-22 東洋インキＳｃホールディングス株式会社 Gravure ink for surface printing and printed matter
CN109385145A (en) * 2018-10-30 2019-02-26 宁波石墨烯创新中心有限公司 A kind of organic system electrically conductive ink, preparation method and flexible device
CN113039239B (en) * 2018-11-13 2023-04-04 Ppg工业俄亥俄公司 Conductive polymer composition
CN112466508A (en) * 2019-09-06 2021-03-09 臻鼎科技股份有限公司 Conductive composition, conductive film, circuit structure and wearable device

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05299288A (en) * 1992-04-17 1993-11-12 Tokin Corp Manufacture of laminated ceramic capacitor
JPH11320769A (en) * 1998-05-20 1999-11-24 Tomoegawa Paper Co Ltd Transparent infrared cutoff film
JP2003203523A (en) * 2002-01-08 2003-07-18 Fujikura Ltd Conductive paste
JP4396130B2 (en) 2003-04-22 2010-01-13 住友金属鉱山株式会社 Target for producing ITO thin film and manufacturing method thereof
JP2006059720A (en) * 2004-08-20 2006-03-02 Sony Corp Conductive paste and touch panel
JP4841158B2 (en) * 2005-03-31 2011-12-21 大日本印刷株式会社 Conductive paste composition and printed wiring board
JP2007281306A (en) * 2006-04-10 2007-10-25 Sekisui Chem Co Ltd Screen printing paste for multilayer ceramic electronic components
JP5376808B2 (en) * 2008-01-25 2013-12-25 Ｄｉｃ株式会社 Method for producing transparent conductive film, transparent conductive film and touch panel
JP5304152B2 (en) * 2008-09-30 2013-10-02 東洋紡株式会社 RESIN COMPOSITION FOR ADHESIVE, ADHESIVE CONTAINING THE SAME, ADHESIVE SHEET AND PRINTED WIRING BOARD CONTAINING THE SAME AS ADHESIVE LAYER

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9818498B2 (en) 2011-10-25 2017-11-14 Lg Innotek Co., Ltd. Paste composition for printing and touch panel
TWI603342B (en) * 2013-03-29 2017-10-21 富士軟片股份有限公司 Composition for forming electroconductive film and method of producing electroconductive film by using the same
TWI596172B (en) * 2016-09-02 2017-08-21 Teikoku Printing Inks Mfg Co Ltd Conductive liquid composition
TWI802582B (en) * 2017-08-24 2023-05-21 日商東洋紡股份有限公司 Conductive paste, three-dimensional printed circuit, touch sensor, and method for manufacturing the aforementioned objects

Also Published As

Publication number Publication date
JP4968410B2 (en) 2012-07-04
TWI486413B (en) 2015-06-01
CN102576581B (en) 2015-07-22
JPWO2011046076A1 (en) 2013-03-07
KR101223408B1 (en) 2013-01-16
KR20120052408A (en) 2012-05-23
WO2011046076A1 (en) 2011-04-21
CN102576581A (en) 2012-07-11

Similar Documents

Publication Publication Date Title
TWI486413B (en) Conductive paste, conductive film, touch panel and method for producing conductive thin film
TWI648748B (en) Conductive paste, conductive coating film, electrical circuit, conductive laminate, and touch panel
TWI458797B (en) Resin composition for adhesive, adhesive containing it, adhesive sheet and printed wiring board containing it as adhesive layer
TW201141977A (en) Resin composition for adhesive agent, adhesive agent containing thereof, adhesive sheet and printed wire board containing the same as adhesive layer
KR102495564B1 (en) Transparent conductive film laminate and its processing method
TW202108371A (en) Transparent conductive film laminate and processing method thereof
JP6303367B2 (en) Conductive paste, conductive film and touch panel
TW201207059A (en) Resin composition for adhesive agent, adhesive agent containing thereof, adhesive sheet and printed wire board containing the same as adhesive layer
JP2008171828A (en) Conductive paste, and printed circuit using it
CN108026420A (en) Conductive adhesive and screened film
JP6343903B2 (en) Conductive paste and printed circuit using the same
TWI748014B (en) High molecular compound containing carboxylic acid group and adhesive composition containing the high molecular compound
JP4158080B2 (en) Conductive paste
JP2016029638A (en) Conductive paste for laser machining
JP4514390B2 (en) Conductive paste and printed circuit using the same
JP7002122B2 (en) Laminate
JP2005259546A (en) Conductive paste for rotary screen printing apparatus and conductor circuit using the same
JP3790869B2 (en) Conductive paste for metal plating
CN117651747A (en) Adhesive composition, adhesive sheet, laminate and printed wiring board
JP2006059720A (en) Conductive paste and touch panel
JP2002008441A (en) Conductive paste
JP2006260818A (en) Conductive paste and printed circuit using the same
JP2006100081A (en) Conductive paste
JP2005133056A (en) Polymer type conductive paste
JP2006252807A (en) Conductive paste and laminate using this