TW201415496A - 透明導電膜 - Google Patents
透明導電膜 Download PDFInfo
- Publication number
- TW201415496A TW201415496A TW102122431A TW102122431A TW201415496A TW 201415496 A TW201415496 A TW 201415496A TW 102122431 A TW102122431 A TW 102122431A TW 102122431 A TW102122431 A TW 102122431A TW 201415496 A TW201415496 A TW 201415496A
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- Taiwan
- Prior art keywords
- transparent conductive
- conductive film
- polymer
- transparent
- weight
- Prior art date
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- 238000000576 coating method Methods 0.000 claims description 58
- 239000011248 coating agent Substances 0.000 claims description 54
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- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 claims description 5
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- 229920000742 Cotton Polymers 0.000 description 1
- 229920003270 Cymel® Polymers 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
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- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
- HKQOBOMRSSHSTC-UHFFFAOYSA-N cellulose acetate Chemical compound OC1C(O)C(O)C(CO)OC1OC1C(CO)OC(O)C(O)C1O.CC(=O)OCC1OC(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(COC(C)=O)O1.CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 HKQOBOMRSSHSTC-UHFFFAOYSA-N 0.000 description 1
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- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
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- OVPXRLUTUWRYEY-UHFFFAOYSA-N dimethyl naphthalene-1,8-dicarboxylate Chemical compound C1=CC(C(=O)OC)=C2C(C(=O)OC)=CC=CC2=C1 OVPXRLUTUWRYEY-UHFFFAOYSA-N 0.000 description 1
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- UHPJWJRERDJHOJ-UHFFFAOYSA-N ethene;naphthalene-1-carboxylic acid Chemical compound C=C.C1=CC=C2C(C(=O)O)=CC=CC2=C1 UHPJWJRERDJHOJ-UHFFFAOYSA-N 0.000 description 1
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- 125000001072 heteroaryl group Chemical group 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
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- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
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- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
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- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- 239000011782 vitamin Substances 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0274—Optical details, e.g. printed circuits comprising integral optical means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
- B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B23/042—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
- B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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Abstract
本發明揭示並主張透明導電膜,其顯示高透光率、低表面電阻及卓越的剝去黏著力。該等膜適用於電子應用中。
Description
至少一實施例包括一種透明導電膜,該透明導電膜包括至少一透明基板、設於該至少一透明基板上之至少一透明底漆層(primer layer),其中該至少一透明底漆層係從包含至少一含羥基官能基聚合物及至少一熱可固化單體的至少一透明底漆層塗料混合物形成;及設於該至少一透明底漆層上的至少一透明導電層,其中該至少一透明導電層係由包含至少一第一纖維素酯聚合物及至少一金屬奈米線之至少一透明導電層塗料混合物形成。
在至少一些實施例中,該至少一透明基板包括至少一聚酯。
在至少一些實施例中,該至少一透明基板包括至少一第一聚酯,其包含至少約70重量%之對苯甲酸乙二酯重複單元。
在至少一些該等實施例中,該至少一第一含羥基官能基聚合物包括纖維素酯聚合物、聚醚多元醇、聚酯多元醇或聚乙烯醇。
在至少一些上述實施例中,該至少一第一含羥基官能基聚合物包括乙酸纖維素酯聚合物、乙酸丁酸纖維素酯聚合物、或乙酸丙酸纖維素酯聚合物。
在至少一些上述實施例中,該至少一第一含羥基官能基聚合物包括乙酸丁酸纖維素酯聚合物。
在至少一些上述實施例中,該至少一第一含羥基官能基聚合物包括至少約1重量%、或至少約3重量%、或約4.8重量%(按照ASTM
D817-96測得)之羥基含量。
在至少一些上述實施例中,該至少一熱可固化單體包括至少約三個醚基。
在至少一些上述實施例中,該至少一熱可固化單體包括至少一三聚氰胺單體。
在至少一些上述實施例中,該至少一熱可固化單體包括六甲氧基甲基三聚氰胺。
在至少一些上述實施例中,該至少一第一纖維素酯聚合物包括乙酸纖維素酯聚合物、乙酸丁酸纖維素酯聚合物、或乙酸丙酸纖維素酯聚合物。
在至少一些上述實施例中,該至少一第一纖維素酯聚合物包括乙酸丁酸纖維素酯聚合物。
在至少一些上述實施例中,該至少一金屬奈米線包括至少一銀奈米線。
在至少一些上述實施例中,該透明導電膜顯示小於約100歐姆/平方的四點表面電阻。
在至少一些上述實施例中,該透明導電膜顯示按照ASTM D3359-92A測得為5之剝去黏著力值。
可自以下敘述、示例性實施例、實例及申請專利範圍,更好地理解此等實施例及其他變化及修改。所提供之任何實施例僅以說明性實例之方式給出。固有所達成之其他所需目標及優點可出現或變得為熟習此項技術者所明瞭。
本文件中所引用之所有公開案、專利及專利文件係以全文引用
的方式併入本文中,如同以個別引用的方式併入般。
2012年6月26日申請之美國臨時申請案第61/664,268號(題為TRANSPARENT CONDUCTIVE FILM)係以全文引用的方式併入本文中。
特徵為包括銀奈米線及纖維素酯聚合物之導電層的透明導電膜(TCF)揭示於2012年5月3日公開之美國專利申請公開案2012/0107600,TRANSPARENT CONDUCTIVE FILMS COMPRISING CELLULOSE ESTERS中,其以全文引用的方式併入本文中。該等TCF可顯示高透光率及低表面電阻。然而,一種挑戰係開發保留此等性質同時亦顯示卓越之剝去黏著力的TCF。
透明導電膜
近幾年,透明及導電膜已廣泛用於觸控板顯示器、液晶顯示器、電致發光照明、有機發光二極體裝置、光伏打太陽能電池之應用中。直到最近,基於氧化銦錫(ITO)之透明導電薄膜已成為大多數應用之透明導體之選擇,此係由於其高導電率、透明度及相對良好的穩定性。然而,基於氧化銦錫之透明導電膜由於銦之高成本、需要複雜且昂貴的真空沉積設備及製程及尤其係當在可撓性基板上沉積氧化銦錫時其固有的脆性及易於開裂,故具有局限性。
測量透明導電膜(TCF)性質之兩個重要參數係總透光率(%T)及膜表面導電率。更高的透光率允許針對顯示器應用之清晰的影片品質,針對照明及太陽能轉換應用之更高的效率。更低的電阻是大多數透明導電膜應用最需要的,其中可使功率消耗最小。
透明基板
一些實施例提供一種TCF,其包括至少一透明基板。該基板可為剛性或可撓性。
適宜的剛性基板包括例如玻璃、聚碳酸酯、丙烯酸樹脂等。
當將該TCF之各個層之塗料混合物塗佈在可撓性基板上時,該基板較佳為具有任何所需厚度且由一或多種聚合物材料構成之可撓性、透明聚合物膜。該基板需要在塗佈及乾燥導電層期間顯示尺寸穩定性且需要具有與上覆層之適宜黏附性質。製造該基板適用的聚合物材料包括聚酯(諸如聚對苯甲酸乙二酯及聚萘二甲酸乙二酯)、乙酸纖維素酯及其他纖維素酯、聚乙烯縮醛、聚烯烴、聚碳酸酯及聚苯乙烯。較佳的基板係由具有良好熱穩定性之聚合物組成,諸如聚酯及聚碳酸酯。支撐件材料亦可經處理或退火以減少收縮性並促進尺寸穩定性。亦可使用透明多層基板。
至少一些實施例提供包括透明基板之透明導電膜,該透明基板包括至少一聚酯。該至少一聚酯可包括例如至少約70重量%之對苯甲酸乙二酯重複單元。或其可包括至少約75重量%、或至少約80重量%、或至少約85重量%、或至少約90重量%或至少約95重量%之對苯甲酸乙二酯重複單元。
該等聚酯可經由一或多種包含酸或酯部分之單體與一或多種包含醇部分之單體之縮聚反應而製成。包含酸或酯部分之單體之非限制性實例包括例如芳族酸或酯、脂族酸或酯、及非芳族環狀酸或酯。示例性包含酸或酯部分之單體包括例如對苯二甲酸、對苯二甲酸二甲酯、間苯二甲酸、間苯二甲酸二甲酯、鄰苯二甲酸、鄰苯二甲酸甲酯、偏苯三酸、偏苯三酸三甲酯、萘二甲酸、萘二甲酸二甲酯、己二酸、己二酸二甲酯、壬二酸、壬二酸二甲酯、癸二酸、癸二酸二甲酯等。示例性包含醇部分之單體包括例如乙二醇、丙二醇、丁二醇、己二醇、新戊二醇、二乙二醇、環己烷二甲醇等。
該等聚酯可包括例如包含經由酯連接基團與來自包含醇部分之單體之第二殘基連接之來自包含酸或酯部分之單體之第一殘基的重複單元。示例性重複單元為例如對苯甲酸乙二酯、間苯二甲酸乙二酯、
萘二甲酸乙二酯、對苯甲酸二乙二酯、間苯二甲酸二乙二酯、萘二甲酸二乙二酯、對苯二甲酸環己二酯、間苯二甲酸環己二酯、萘二甲酸環己二酯等。該等聚酯可包括多於一種類型之重複基團且有時可稱為共聚酯。
透明底漆層
一些實施例提供一種TCF,其包括設於該至少一透明基板上之至少一透明底漆層,其中該至少一透明底漆層係由包含至少一含羥基官能基聚合物及至少一熱可固化單體之透明底漆層塗料混合物形成。該等底漆層在一些情形下可被稱為載體層、中間層、黏附促進劑層、夾層等。該等底漆層有助於促進至少一透明導電層至至少一透明基板之黏附。
含羥基官能基聚合物係包含能夠與熱可固化單體上之反應性基團(諸如,例如醚基)反應以形成共價鍵之羥基之聚合物。含羥基官能基聚合物之實例包括例如纖維素酯聚合物、聚醚多元醇、聚酯多元醇、聚乙烯醇等。
纖維素酯聚合物包括乙酸纖維素酯,諸如例如乙酸纖維素酯、三乙酸纖維素酯、丙酸纖維素酯、乙酸丙酸纖維素酯、乙酸丁酸纖維素酯(CAB)等。
含羥基官能基聚合物可以其羥基含量表徵,表示為如藉由ASTM D817-96測試方法所測定之重量百分比。特別適用之含羥基官能基聚合物包括至少約1重量%、或至少約3重量%、或約4.8重量%之羥基含量。一種示例性含羥基官能基聚合物為CAB 533-0.4乙酸丁酸纖維素酯聚合物,可購自Eastman Chemical Company,Kingsport,TN,基於典型平均大量值,其具有4.8重量%之羥基含量。
熱可固化單體為已知。此等可包括例如具有一或多個醚基團,諸如一個、兩個、三個或更多個醚基團之單體。該等醚基團可包括例
如一或多個甲氧基、乙氧基或其他基團。該等醚基團可與其他官能基諸如例如羥基反應,或其可與其他醚基團反應。該等反應可導致聚合或交聯。具有芳族或雜芳族環之熱可固化單體(諸如例如官能化之三聚氰胺單體)可提供與基板(諸如聚對苯甲酸乙二酯或聚萘二甲酸乙二酯)之改良塗佈相容性。六甲氧基甲基三聚氰胺為一種示例性熱可固化單體。
透明底漆層塗料混合物亦可包括熱引發劑,以促進聚合及交聯反應。一種示例性引發劑為對甲苯磺酸。
透明底漆層塗料混合物一般可包括有機溶劑。此等可出於諸如控制溶液黏度、改良潤濕及基板塗佈等之目的而使用。有機溶劑之實例包括酮、酯及醇,諸如例如甲基乙基酮、乙酸丁酯、乙醇等。
可藉由使用各種塗佈程序,如繞線棒塗佈、浸漬塗佈、氣刀塗佈、簾式塗佈、滑動塗佈、固體模塗、輥塗、凹版塗佈、或擠出塗佈,將透明底漆層塗料混合物塗佈至透明基板上透明底漆層,來形成透明底漆層。該等塗料混合物可具有例如6至20重量%之固體及在室溫下之5至30cps之黏度。
可在施用之後,乾燥該等塗層,以提供具有例如100至500nm之厚度之塗層。例如,在實例中證實係在280℉(138℃)烘箱中乾燥2分鐘。
透明導電層
一些實施例提供一種TCF,其包括設於至少一透明底漆層上之至少一透明導電層,其中該至少一透明導電層係由包含至少一第一纖維素酯聚合物及至少一金屬奈米線之至少一透明導電層塗料混合物形成。
適宜的透明導電層塗料混合物係揭示於2012年5月3日申請之美國專利申請公開案2012/0107600,TRANSPARENT CONDUCTIVE
FILMS COMPRISING CELLULOSE ESTERS中,其以全文引用的方式併入本文中。
對於透明導電膜之實際製造製程而言,需要且重要的是在單一塗料溶液中具有導電組分,諸如銀奈米線及聚合物黏合劑。該聚合物黏合劑溶液起雙重作用,作為分散劑以促進銀奈米線之分散及作為增黏劑以使銀奈米線塗料分散液穩定,使得不會在塗佈製程期間的任何時間點發生銀奈米線之沉降。此簡化塗佈製程,且允許一次通過式塗佈,及避免第一次塗佈裸銀奈米線以形成不牢固且脆性膜之處理,隨後在該膜上塗佈聚合物以形成透明導電膜。
為了使透明導電膜適用於各種裝置應用中,亦重要的是該透明導電膜之黏合劑為光學透明且可撓性;而且具有高機械強度、硬度、及良好的熱及光穩定性。亦需要的是用於透明導電膜至聚合物黏合劑包含具有N、O、S或其他含孤對電子元素之官能基,以提供良好的配位鍵結使銀奈米線在銀奈米線及聚合物溶液之分散及塗佈期間穩定。
因此,宜使用具有高氧含量之聚合物黏合劑,諸如羥基己羧酸根基。此等聚合物具有針對銀奈米線表面之強親和力及促進銀奈米線在塗料溶液中之分散及穩定化。大多數富氧聚合物亦具有額外的好處:具有在製備經有機溶劑塗佈之薄膜中通常使用之極性有機溶劑中的良好溶解度。
當用於製備基於銀奈米線之透明導電膜且自有機溶劑,諸如2-丁酮(甲基乙基酮,MEK)、甲基異丁基酮、丙酮、甲醇、乙醇、2-丙醇、乙酸乙酯或其混合物塗佈時,纖維素酯聚合物,諸如乙酸丁酸纖維素酯(CAB)、乙酸纖維素酯(CA)、或乙酸丙酸纖維素酯(CAP)優於其他富氧聚合物黏合劑。其之使用產生經塗佈膜之透光率及導電率均極大改良之透明導電膜。此外,此等纖維素酯聚合物具有至少100℃之玻璃化轉變溫度,可形成具有高機械強度及硬度之透明及可撓性
膜,且具有高熱及光穩定性。相比之下,使用聚胺基甲酸酯或聚乙烯醇縮丁醛聚合物黏合劑以類似方式製得之透明導電膜顯示較不令人合意之透光率及導電率。
纖維素酯聚合物係以約40至約90重量%之乾透明導電膜存在。較佳地,其係以約60至約85重量%之乾膜存在。
在一些構造中,至多50重量%之纖維素酯聚合物可由一或多種其他聚合物代替。此等聚合物應與纖維素聚合物相容。相容意指當乾燥時聚合物形成透明單相混合物。該或該等其他聚合物可提供其他好處,諸如促進黏附至支撐件及改良硬度及耐劃傷性。如上,所有聚合物之總重量%係約50至約90重量%之乾透明導電膜。較佳地,所有聚合物之總重量係約70至約85重量%之乾膜。聚酯及聚丙烯酸系聚合物係適用之其他聚合物之實例。
金屬奈米線諸如例如銀或銅奈米線係用於將導電性賦予給導電膜及賦予給使用導電膜製備之物件之主要組分。透明導電膜之導電率主要受以下控制:a)單一奈米線之導電性,b)在末端之間的奈米線數量,及c)奈米線之間的連通性。在某一奈米線濃度(亦稱為滲流臨限值)以下,末端之間的導電性為零,因為由於奈米線間隔太遠而無法提供連續的電流通路。在此濃度以上,可獲得至少一個電流通路。隨著提供越多電流通路,層之總電阻將下降。然而,隨著提供越多的電流通路,由於奈米線之光吸收及散射,通過導電膜透射之光百分比下降。此外,隨著在導電膜中之金屬奈米線之數量增加,透明膜之濁度由於金屬奈米線之光散射而下降。類似影響將在使用透明膜製備之透明物件中出現。
在一實施例中,該金屬奈米線具有約20至約3300之縱橫比(長度/寬度)。在另一實施例中,該金屬奈米線具有約500至1000之縱橫比(長度/寬度)。具有約5μm至約100μm(微米)之長度及約30nm至約
200nm之寬度之金屬奈米線係適用的。具有約50nm至約120nm之寬度及約15μm至約100μm之長度之金屬奈米線亦適用於構造透明導電網路膜。
可藉由相關技術中已知之方法,來製備金屬奈米線。特定言之,可經由在多元醇(例如乙二醇或丙二醇)及聚(乙烯吡咯啶酮)之存在下銀鹽(例如硝酸銀)之溶液相還原,來合成銀奈米線。可根據在例如Ducamp-Sanguesa, C.等人,J.of Solid State Chemistry,(1992),100,272-280;Sun, Y.等人,Chem.Mater.(2002),14,4736-4745;及Sun, Y.等人,Nanoletters,(2003),3(7),955-960中所述之方法,來製備均一尺寸之銀奈米線之大規模製造。
透明導電層塗料混合物一般可包括有機溶劑。此等可出於諸如控制溶液黏度、改良潤濕及基板塗佈等之目的而使用。有機溶劑之實例包括甲苯、2-丁酮(甲基乙基酮,MEK)、甲基異丁基酮、丙酮、甲醇、乙醇、2-丙醇、乙酸乙酯、乙酸丙酯、乳酸乙酯、或四氫呋喃、或其混合物。甲基乙基酮係特別適用的塗料溶劑。
可藉由使用各種塗佈程序,如繞線棒塗佈、浸漬塗佈、氣刀塗佈、簾式塗佈、滑動塗佈、固體模塗、輥塗、凹版塗佈、或擠出塗佈,將透明導電層塗料混合物塗佈至透明底漆層上,來形成透明導電層。界面活性劑及其他塗料助劑可併入塗料調配物中。該等塗料混合物可具有例如6至20重量%之固體及在室溫下之5至30cps之黏度。
可在施用之後,乾燥該等塗層,以提供具有例如100至500nm之厚度之塗層。例如,在實例中證實係在280℉(138℃)烘箱中乾燥2分鐘。
透明導電膜性質
在塗佈及乾燥之後,該透明導電膜應具有如使用R-CHEK型號RC2175表面電阻測量計(可購自Electronic Design to Market,Inc,
Toledo,OH)所測得之小於1,000歐姆/平方、或小於500歐姆/平方、或小於100歐姆/平方之表面電阻。
在塗佈及乾燥之後,該透明導電膜應具有儘可能高的透光率%。
至少70%之透光率係適用的。至少80%及至少90%之透光率甚至更適用。
在塗佈及乾燥之後,該透明導電膜應顯示超常之剝去黏著力性質,諸如當按照ASTM D3359-92A評估時評定為「5」。該程序係描述於實例1中。
示例性實施例
2012年6月26日申請之美國臨時申請案第61/664,268號,題為TRANSPARENT CONDUCTIVE FILM,其以全文引用的方式併入本文中,揭示以下17項非限制性示例性實施例:
A.一種透明導電膜,其包括:至少一透明基板;設於該至少一透明基板上之至少一透明底漆層,該至少一透明底漆層係由包含至少一含羥基官能基聚合物及至少一熱可固化單體之至少一透明底漆層塗料混合物形成;及設於該至少一透明底漆層上之至少一透明導電層,該至少一透明導電層係由包含至少一第一纖維素酯聚合物及至少一金屬奈米線之至少一透明導電層塗料混合物形成。
B.如實施例A之透明導電膜,其中該至少一透明基板包括至少一聚酯。
C.如實施例A-B中任一項之透明導電膜,其中該至少一透明基板包括包含至少約70重量%之對苯甲酸乙二酯重複單元之至少一第一聚酯。
D.如實施例A-B中任一項之透明導電膜,其中該至少一第一含
羥基官能基聚合物包括纖維素酯聚合物、聚醚多元醇、聚酯多元醇或聚乙烯醇。
E.如實施例A-D中任一項之透明導電膜,其中該至少一第一含羥基官能基聚合物包括乙酸纖維素酯聚合物、乙酸丁酸纖維素酯聚合物、或乙酸丙酸纖維素酯聚合物。
F.如實施例A-E中任一項之透明導電膜,其中該至少一第一含羥基官能基聚合物包括乙酸丁酸纖維素酯聚合物。
G.如實施例A-F中任一項之透明導電膜,其中該至少一第一含羥基官能基聚合物包括按照ASTM D817-96測得之至少約1重量%的羥基含量。
H.如實施例A-G中任一項之透明導電膜,其中該至少一第一含羥基官能基聚合物包括按照ASTM D817-96測得之至少約3重量%的羥基含量。
J.如實施例A-H中任一項之透明導電膜,其中該至少一第一含羥基官能基聚合物包括按照ASTM D817-96測得之約4.8重量%的羥基含量。
K.如實施例A-J中任一項之透明導電膜,其中該至少一熱可固化單體包括至少約三個醚基。
L.如實施例A-K中任一項之透明導電膜,其中該至少一熱可固化單體包括至少一三聚氰胺單體。
M.如實施例A-L中任一項之透明導電膜,其中該至少一熱可固化單體包括六甲氧基甲基三聚氰胺。
N.如實施例A-M中任一項之透明導電膜,其中該至少一第一纖維素酯聚合物包括乙酸纖維素酯聚合物、乙酸丁酸纖維素酯聚合物、或乙酸丙酸纖維素酯聚合物。
P.如實施例A-N中任一項之透明導電膜,其中該至少一第一纖
維素酯聚合物包括乙酸丁酸纖維素酯聚合物。
Q.如實施例A-P中任一項之透明導電膜,其中該至少一金屬奈米線包括至少一銀奈米線。
R.如實施例A-Q中任一項之透明導電膜,其顯示小於約100歐姆/平方之四點表面電阻。
S.如實施例A-R中任一項之透明導電膜,其顯示按照ASTM D3359-92A測得為5之剝去黏著力值。
實例
實例1(比較)
藉由摻合54重量份含於異丙醇中之銀奈米線之1.85重量%分散液、3重量份乙酸丁酸纖維素酯聚合物(CAB 381-20,Eastman Chemical)、33重量份乙酸丙酯及10重量份乳酸乙酯,來製備銀層塗料混合物。該混合物具有3至8重量%固體及在室溫下30至150cps黏度。
然後製備經塗佈之樣品。將幾毫升銀層塗料混合物施覆在鉻凹版印刷板之頂部邊緣,該鉻凹版印刷板經200至500直線篩雕刻。將5-7mil聚對苯甲酸乙二酯(PET)膜包裹在基於乙烯丙烯二烯單體(EPDM)之橡膠加壓輥上,隨後將其從印刷板之頂部邊緣朝底部邊緣軋製,將油墨從凹版深處轉移至PET膜上。然後,將經塗佈之膜置於280℉(138℃)烘箱中持續2分鐘。乾銀層厚度為100至500nm。
待其從烘箱冷卻之後,評估經塗佈膜之表面電阻。使用R-CHEK裝置,測量膜之經塗佈面之四點表面電阻。該樣品顯示48歐姆/平方的表面電阻。
然後,按照ASTM D3359-92A,評估經塗佈膜之剝去黏著力。利用刮鬍刀片對各膜之經塗佈面劃線,且利用無絨棉墊輕柔地除去碎屑。然後,將膠帶(#610半透明感壓型膠帶,購自3M Company,St.
Paul,MN)應用至陰影線區域,並用橡膠輥弄平滑,直到膠帶與經塗佈膜之間無氣泡。然後,迅速地剝去膠帶。對經塗佈膜之外觀以0至5等級打分:5=劃線切口之邊緣完全光滑;4=塗層薄片在劃線之一些相交處分離,其中小於約5%之測試區域受影響;3=塗層薄片沿著一些邊緣及在劃線之一些相交處分離,其中約5至15%之測試區域受影響;2=塗層薄片沿著劃線之一些邊緣及在方形之部分處分離,其中約15至35%之測試區域受影響;1=塗層沿著劃線的邊緣呈大型帶狀分離,其中超過約35%之測試區域受影響;0=塗層完全除去。獲得5分之膜給予「合格」之評定,而獲得小於5分之膜給予「不合格」之評定。該樣品之外觀被評定為「不合格」。
實例2(比較)
藉由摻合12重量份直鏈飽和熱塑性聚酯聚合物(VITEL® 2200,Bostik)及88重量份甲基乙基酮,來製備底漆層塗料混合物。該混合物具有6至20重量%之固體及在室溫下5至30cps之黏度。
藉由摻合54重量份含於異丙醇中之銀奈米線之1.85重量%分散液、3重量份乙酸丁酸纖維素酯聚合物(CAB 381-20,Eastman Chemical)、33重量份乙酸丙酯及10重量份乳酸乙酯,來製備銀層塗料混合物。該混合物具有3至8重量%之固體及在室溫下30至150cps之黏度。
然後製備經塗佈之樣品。使用凹版臺式檢驗臺,將底漆層塗料混合物施覆至5-7mil PET膜。然後,將經塗佈之膜置於280℉(138℃)烘箱中持續2分鐘。乾底漆層厚度為10至500nm。
然後,使用實例1之方法,將銀層塗料混合物施用至經塗佈之PET膜之底漆層。乾銀層厚度為100至500nm。
待其從烘箱冷卻之後,評估經塗佈膜之表面電阻。使用R-CHEK裝置,測量膜之經塗佈面之四點表面電阻。該樣品顯示無限的表面電
阻。
然後,使用實例1之方法,評估經塗佈膜之剝去黏著力。該樣品之外觀被評定為「合格」。
實例3(本發明)
藉由摻合6重量份乙酸丁酸纖維素酯聚合物(CAB 553-0.4,Eastman Chemical)、6重量份六甲氧基甲基三聚氰胺(CYMEL® 303,Cytec)、77.4重量份甲基乙基酮、10重量份丁醇及0.6重量份對甲苯磺酸。來製備底漆層塗料混合物。該混合物具有6至20重量%之固體及在室溫下5至30cps之黏度。
藉由摻合54重量份含於異丙醇中之銀奈米線之1.85重量%分散液、3重量份乙酸丁酸纖維素酯聚合物(CAB 381-20,Eastman Chemical)、33重量份乙酸丙酯及10重量份乳酸乙酯,來製備銀層塗料混合物。該混合物具有3至8重量%之固體及在室溫下30至150cps之黏度。
然後製備經塗佈之樣品。使用凹版臺式檢驗臺,將底漆層塗料混合物施用至5-7mil PET膜。然後,將經塗佈之膜置於280℉(138℃)烘箱中持續2分鐘。乾底漆層厚度為100至500nm。
然後,使用實例1之方法,將銀層塗料混合物施用至經塗佈之PET膜之底漆層。乾銀層厚度為100至500nm。
待其從烘箱冷卻之後,評估經塗佈膜之表面電阻。使用R-CHEK裝置,測量膜之經塗佈面之四點表面電阻。該樣品顯示48歐姆/平方的表面電阻。該樣品顯示48歐姆/平方之表面電阻。
然後,使用實例1之方法,評估經塗佈膜之剝去黏著力。該樣品之外觀被評定為「合格」。
已參考特定實施例詳細描述本發明,但是應瞭解,可在本發明之精神及範圍內實現變化及修改。因此,目前揭示之實施例在所有態
樣中僅視為說明性而非限制性。本發明之範圍係由隨附申請專利範圍表明,且在其等效物之含義及範圍內之所有改變意欲涵蓋於其中。
Claims (10)
- 一種透明導電膜,其包括:至少一透明基板;設於該至少一透明基板上的至少一透明底漆層(primer layer),該至少一透明底漆層係由包含至少一含羥基官能基聚合物及至少一熱可固化單體之至少一透明底漆層塗料混合物形成;及設於該至少一透明底漆層上之至少一透明導電層,該至少一透明導電層係由包含至少一第一纖維素酯聚合物及至少一金屬奈米線之至少一透明導電層塗料混合物形成。
- 如請求項1之透明導電膜,其中該至少一透明基板包括包含至少約70重量%之對苯甲酸乙二酯重複單元之至少一聚酯。
- 如請求項1之透明導電膜,其中該至少一第一含羥基官能基聚合物包括乙酸纖維素酯聚合物、乙酸丁酸纖維素酯聚合物、或乙酸丙酸纖維素酯聚合物。
- 如請求項1之透明導電膜,其中該至少一含羥基官能基聚合物包括至少約3重量%(按照ASTM D817-96測得)之羥基含量。
- 如請求項1之透明導電膜,其中該至少一第一含羥基官能基聚合物包括約4.8重量%(按照ASTM D817-96測得)之羥基含量。
- 如請求項1之透明導電膜,其中該至少一熱可固化單體包括至少約三個醚基團。
- 如請求項1之透明導電膜,其中該至少一熱可固化單體包括至少一三聚氰胺單體。
- 如請求項1之透明導電膜,其中該至少一熱可固化單體包括六甲氧基甲基三聚氰胺。
- 如請求項1之透明導電膜,其中該至少一第一纖維素酯聚合物包 括乙酸纖維素酯聚合物、乙酸丁酸纖維素酯聚合物、或乙酸丙酸纖維素酯聚合物。
- 如請求項1之透明導電膜,其中該至少一金屬奈米線包括至少一銀奈米線。
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US201261664268P | 2012-06-26 | 2012-06-26 | |
US13/905,380 US20130341071A1 (en) | 2012-06-26 | 2013-05-30 | Transparent conductive film |
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TW201415496A true TW201415496A (zh) | 2014-04-16 |
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TW102122431A TW201415496A (zh) | 2012-06-26 | 2013-06-24 | 透明導電膜 |
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US (1) | US20130341071A1 (zh) |
EP (1) | EP2864116A2 (zh) |
JP (1) | JP2015530279A (zh) |
KR (1) | KR20150052811A (zh) |
CN (1) | CN104640696A (zh) |
TW (1) | TW201415496A (zh) |
WO (1) | WO2014004194A2 (zh) |
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US9175183B2 (en) * | 2011-05-23 | 2015-11-03 | Carestream Health, Inc. | Transparent conductive films, methods, and articles |
US8974900B2 (en) * | 2011-05-23 | 2015-03-10 | Carestream Health, Inc. | Transparent conductive film with hardcoat layer |
JP2015133250A (ja) * | 2014-01-14 | 2015-07-23 | デクセリアルズ株式会社 | 分散液、透明導電膜、情報入力装置、電子機器、及び透明導電膜の製造方法 |
EP3187322A1 (en) | 2015-12-31 | 2017-07-05 | Arjo Wiggins Fine Papers Limited | Use of printed electronics on paper to embed a circuit into plastic moulded objects |
US20170233541A1 (en) * | 2016-02-12 | 2017-08-17 | Tyco Electronics Corporation | Method of Enhancing Adhesion of Silver Nanoparticle Inks on Plastic Substrates Using a Crosslinked Poly(vinyl butyral) Primer Layer |
JP6859083B2 (ja) * | 2016-11-28 | 2021-04-14 | 昭和電工株式会社 | 導電性フィルム、及び導電性フィルムの製造方法 |
CN107154283B (zh) * | 2017-04-11 | 2020-10-16 | 复旦大学 | 耐电迁移银纳米线复合薄膜及其制备方法 |
KR102393615B1 (ko) * | 2017-08-02 | 2022-05-03 | 쇼와 덴코 가부시키가이샤 | 도전 필름의 제조 방법, 도전 필름, 및 금속 나노 와이어 잉크 |
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DE2555783C3 (de) * | 1975-12-11 | 1979-05-31 | Hoechst Ag, 6000 Frankfurt | Haftmasse |
US4417025A (en) * | 1981-01-13 | 1983-11-22 | Daicel Chemical Industries, Ltd. | Resin composition emulsion |
US4977013A (en) * | 1988-06-03 | 1990-12-11 | Andus Corporation | Tranparent conductive coatings |
US5774164A (en) * | 1994-10-27 | 1998-06-30 | Dai Nippon Printing Co., Ltd. | Thermal transfer image-receiving sheet |
US5610233A (en) * | 1995-08-03 | 1997-03-11 | Eastman Chemical Company | Aqueous coating compositions containing cellulose esters |
KR100223888B1 (ko) * | 1996-11-20 | 1999-10-15 | 구본준 | 정전기 보호회로 |
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EP2122638B1 (en) * | 2006-12-19 | 2012-11-07 | Dow Global Technologies LLC | Improved composites and methods for conductive transparent substrates |
US7727578B2 (en) * | 2007-12-27 | 2010-06-01 | Honeywell International Inc. | Transparent conductors and methods for fabricating transparent conductors |
US7642463B2 (en) * | 2008-01-28 | 2010-01-05 | Honeywell International Inc. | Transparent conductors and methods for fabricating transparent conductors |
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JP5599461B2 (ja) * | 2009-07-17 | 2014-10-01 | ケアストリーム ヘルス インク | セルロースエスエルを含む透明導電物品 |
JP2011090878A (ja) * | 2009-10-22 | 2011-05-06 | Fujifilm Corp | 透明導電体の製造方法 |
US8974900B2 (en) * | 2011-05-23 | 2015-03-10 | Carestream Health, Inc. | Transparent conductive film with hardcoat layer |
US9175183B2 (en) * | 2011-05-23 | 2015-11-03 | Carestream Health, Inc. | Transparent conductive films, methods, and articles |
WO2014008003A2 (en) * | 2012-07-02 | 2014-01-09 | Carestream Health, Inc. | Transparent conductive film |
US20140255707A1 (en) * | 2013-03-06 | 2014-09-11 | Carestream Health, Inc. | Stabilization agents for silver nanowire based transparent conductive films |
-
2013
- 2013-05-30 US US13/905,380 patent/US20130341071A1/en not_active Abandoned
- 2013-06-19 CN CN201380032172.0A patent/CN104640696A/zh active Pending
- 2013-06-19 KR KR1020147035734A patent/KR20150052811A/ko not_active Application Discontinuation
- 2013-06-19 EP EP13737009.4A patent/EP2864116A2/en not_active Withdrawn
- 2013-06-19 JP JP2015520291A patent/JP2015530279A/ja active Pending
- 2013-06-19 WO PCT/US2013/046490 patent/WO2014004194A2/en active Application Filing
- 2013-06-24 TW TW102122431A patent/TW201415496A/zh unknown
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JP2015530279A (ja) | 2015-10-15 |
WO2014004194A8 (en) | 2015-01-08 |
KR20150052811A (ko) | 2015-05-14 |
WO2014004194A2 (en) | 2014-01-03 |
CN104640696A (zh) | 2015-05-20 |
WO2014004194A3 (en) | 2014-03-06 |
US20130341071A1 (en) | 2013-12-26 |
EP2864116A2 (en) | 2015-04-29 |
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