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(19)【発行国】日本国特許庁(JP)
(12)【公報種別】公開特許公報(A)
(11)【公開番号】特開2015-128066(P2015-128066A)
(43)【公開日】2015年7月9日
(54)【発明の名称】透明導電膜複合材および透明導電膜
(51)【国際特許分類】
H01B 1/22 20060101AFI20150612BHJP
H01B 5/14 20060101ALI20150612BHJP
H01B 1/00 20060101ALI20150612BHJP
B22F 9/00 20060101ALI20150612BHJP
C08L 101/00 20060101ALI20150612BHJP
C08K 7/06 20060101ALI20150612BHJP
【ＦＩ】
H01B1/22 A
H01B5/14 A
H01B1/00 H
B22F9/00 B
C08L101/00
C08K7/06
【審査請求】有
【請求項の数】10
【出願形態】ＯＬ
【外国語出願】
【全頁数】38
(21)【出願番号】特願2014-261734(P2014-261734)
(22)【出願日】2014年12月25日
(31)【優先権主張番号】102148966
(32)【優先日】2013年12月30日
(33)【優先権主張国】TW
(71)【出願人】
【識別番号】390023582
【氏名又は名称】財團法人工業技術研究院
【氏名又は名称原語表記】ＩＮＤＵＳＴＲＩＡＬ ＴＥＣＨＮＯＬＯＧＹ ＲＥＳＥＡＲＣＨ ＩＮＳＴＩＴＵＴＥ
(74)【代理人】
【識別番号】100108833
【弁理士】
【氏名又は名称】早川 裕司
(74)【代理人】
【識別番号】100162156
【弁理士】
【氏名又は名称】村雨 圭介
(72)【発明者】
【氏名】蕭 ▲い▼翰
(72)【発明者】
【氏名】邱 俊毅
(72)【発明者】
【氏名】邱 國展
(72)【発明者】
【氏名】李 宗銘
【テーマコード（参考）】
4J002
4K017
5G301
5G307
【Ｆターム（参考）】
4J002AB021
4J002AB031
4J002BE021
4J002BJ001
4J002DA076
4J002DC006
4J002FD116
4J002GQ02
4J002HA01
4K017AA08
4K017BA02
4K017BA05
4K017BB02
4K017BB05
4K017CA03
4K017CA04
4K017CA07
4K017DA01
5G301DA03
5G301DA05
5G301DA06
5G301DA42
5G301DD02
5G301DE01
5G307FA01
5G307FA02
5G307FB02
5G307FC09
5G307FC10
(57)【要約】
【課題】透明導電膜複合材および透明導電膜を提供する。【解決手段】透明導電膜複合材が提供される。透明導電膜複合材は、（ａ）０．０７−０．２ｗｔ％の金属素材；（ｂ）０．０１−０．５ｗｔ％の分散剤；および、９９．３−９９．９２ｗｔ％の溶剤を含み、金属素材（ａ）は、：（ａ１）８４−９９．９９ｗｔ％の金属ナノワイヤー；および、（ａ２）０．０１−１６ｗｔ％のミクロン金属フレークを含む。透明導電膜複合材から製造される透明導電膜も提供される。
【選択図】図２Ａ
【特許請求の範囲】
【請求項1】
透明導電膜複合材であって、
（ａ）０．０７−０．２ｗｔ％の金属素材と、
（ｂ）０．０１−０．５ｗｔ％の分散剤と、
（ｃ）９９．３−９９．９２ｗｔ％の溶剤と、
を含み、
前記金属素材（ａ）は、
（ａ１）８４−９９．９９ｗｔ％の金属ナノワイヤーと、
（ａ２）０．０１−１６ｗｔ％のミクロン金属フレークと、
を含むことを特徴とする透明導電膜複合材。
（ａ）０．０７−０．２ｗｔ％の金属素材と、
（ｂ）０．０１−０．５ｗｔ％の分散剤と、
（ｃ）９９．３−９９．９２ｗｔ％の溶剤と、
を含み、
前記金属素材（ａ）は、
（ａ１）８４−９９．９９ｗｔ％の金属ナノワイヤーと、
（ａ２）０．０１−１６ｗｔ％のミクロン金属フレークと、
を含むことを特徴とする透明導電膜複合材。
【請求項2】
前記ミクロン金属フレークと前記ナノ金属ワイヤーは、それぞれ独立して、Ａｕ，Ａｇ，Ｃｕ，それらの合金、または、それらの組み合わせを含むことを特徴とする請求項１に記載の透明導電膜複合材。
【請求項3】
前記ミクロン金属フレークの平均フレークサイズ（Ｄ５０）は、０．５μｍ〜１０μｍであることを特徴とする請求項１に記載の透明導電膜複合材。
【請求項4】
前記ナノ金属ワイヤーのアスペクト比は、１００〜１０００であることを特徴とする請求項１に記載の透明導電膜複合材。
【請求項5】
前記分散剤は、メチルセルロース、カルボキシメチルセルロース、エチルセルロース、ヒドロキシプロピルセルロース、ポリビニルピロリドン、ポリビニルアルコール、または、それらの組み合わせを含むことを特徴とする請求項１に記載の透明導電膜複合材。
【請求項6】
透明導電膜であって、
（ａ）金属素材と、
（ｂ）分散剤と、を含み、前記金属素材と前記分散剤の重量比は０．１４：１〜２０：１であり、
前記金属素材（ａ）は、
（ａ１）８４−９９．９９ｗｔ％の金属ナノワイヤー、および、
（ａ２）０．０１−１６ｗｔ％のミクロン金属フレークを含み、
前記透明導電膜のシート抵抗は１００Ω／□以下であり、前記透明導電膜の透明性は９５％以上であることを特徴とする透明導電膜。
（ａ）金属素材と、
（ｂ）分散剤と、を含み、前記金属素材と前記分散剤の重量比は０．１４：１〜２０：１であり、
前記金属素材（ａ）は、
（ａ１）８４−９９．９９ｗｔ％の金属ナノワイヤー、および、
（ａ２）０．０１−１６ｗｔ％のミクロン金属フレークを含み、
前記透明導電膜のシート抵抗は１００Ω／□以下であり、前記透明導電膜の透明性は９５％以上であることを特徴とする透明導電膜。
【請求項7】
前記ミクロン金属フレークおよび前記ナノ金属ワイヤーは、それぞれ、独立して、Ａｕ，Ａｇ，Ｃｕ，それらの合金、または、それらの組み合わせを含むことを特徴とする請求項６に記載の透明導電膜。
【請求項8】
前記ミクロン金属フレークの平均フレークサイズ（Ｄ５０）は、０．５μｍ〜１０μｍであることを特徴とする請求項６に記載の透明導電膜。
【請求項9】
前記ナノ金属ワイヤーのアスペクト比は、１００〜１０００であることを特徴とする請求項６に記載の透明導電膜。
【請求項10】
前記分散剤は、メチルセルロース、カルボキシメチルセルロース、エチルセルロース、ヒドロキシプロピルセルロース、ポリビニルピロリドン、ポリビニルアルコール、または、それらの組み合わせを含むことを特徴とする請求項６に記載の透明導電膜。
【発明の詳細な説明】
【技術分野】
【0001】
本発明は、透明導電膜に関するものであって、特に、透明導電膜複合材と、透明導電膜複合材から製造される透明導電膜とに関するものである。
【背景技術】
【0002】
近年、透明導電膜の応用領域が絶え間なく拡大し、透明導電膜に対する要求が絶え間なく変化している。たとえば、フラットディスプレイパネル中の液晶ディスプレイ、エレクトロルミネッセンスパネル、プラズマディスプレイパネル、電界放出ディスプレイ、タッチパネル、および、太陽電池などの電子製品はどれも、透明導電膜を電極材としている。３Ｃ産業の発展と省エネルギーの世界的傾向により、透明導電膜の技術はますます重要になっている。
【0003】
米国特許第６，１４３，４１８号は、少なくとも二種の金属を含む透明導電層を有する透明導電膜を提供する。少なくとも二種の金属はパラジウムと銀である。
【0004】
米国特許第６，５２４，４９９号は、少なくともルテニウム微粒子、金微粒子と銀微粒子を含む導電層を有する透明導電膜を提供し、導電層中のルテニウム微粒子と金微粒子の重量比は、４０：６０〜９９：１である。
【0005】
米国特許第８，７１５，５３６号は、複数のナノワイヤーと複数のナノコネクターを含む電気的導電材料を提供する。
【先行技術文献】
【特許文献】
【0006】
【特許文献1】米国特許第６，１４３，４１８号
【特許文献2】米国特許第６，５２４，４９９号
【特許文献3】米国特許第８，７１５，５３６号
【発明の概要】
【発明が解決しようとする課題】
【0007】
透明導電膜はまだあらゆる方面で条件を満たしていないので、高導電性、高透明性を有し、且つ、フレキシブル電子製品に応用できる透明導電膜が必要とされる。
【課題を解決するための手段】
【0008】
本発明は、（ａ）０．０７−０．２ｗｔ％の金属素材、（ｂ）０．０１−０．５ｗｔ％の分散剤、および、（ｃ）９９．３−９９．９２ｗｔ％の溶剤を含み、金属素材（ａ）は、（ａ１）８４−９９．９９ｗｔ％の金属ナノワイヤー、および、（ａ２）０．０１−１６ｗｔ％のミクロン金属フレークを含む、透明導電膜複合材を提供する。
【0009】
本発明は、さらに、（ａ）金属素材、および（ｂ）分散剤を含み、金属素材と分散剤の重量比は、約０．１４：１〜２０：１で、金属素材（ａ）は、（ａ１）８４−９９．９９ｗｔ％の金属ナノワイヤー、および、（ａ２）０．０１−１６ｗｔ％のミクロン金属フレークを含み、透明導電膜のシート抵抗は１００Ω／□以下であり、透明導電膜の透明性は９５％以上である、透明導電膜を提供する。
【発明の効果】
【0010】
透明導電膜の導電性と透明性が改善され、透明導電膜がフレキシブル電子製品に応用できる。
【図面の簡単な説明】
【0011】
上記及び他の目的及び本発明の特徴は、添付図面とともに以下の記載を参照することにより明らかとなる。【図1A】ナノ金属ワイヤーだけを含む透明導電膜の概略図である。
【図1B】ナノ金属ワイヤーだけを含む透明導電膜の顕微鏡写真である。
【図2A】金属ナノワイヤーおよびミクロン金属フレークを含む透明導電膜の概略図である。
【図2B】金属ナノワイヤーおよびミクロン金属フレークを含む透明導電膜の顕微鏡写真である。
【発明を実施するための形態】
【0012】
本発明の透明導電膜複合材および透明導電膜が以下の詳細な説明で記述される。以下の詳細な説明においては、本願を説明するためにひとつまたはそれ以上の実施形態が提供されることに注意されるべきである。以下の詳細な説明において記述される特定の要素および構成は、単に、本発明を明確に記述するために用いられ、本願の範囲は、特定の要素および構成に限定することを意図するものではない。このほか、各種実施形態中、重複した参照番号で本発明を説明しているが、重複した参照番号は、各種実施形態と構造間の相互関係を示すものではない。
【0013】
用語“約”および“ほぼ”は、典型的には規定値の＋／−２０％であり、より典型的には規定値の＋／−１０％であり、および、さらに典型的には規定値の＋／−５％である。本発明の規定値は、概略値である。特定の説明がない状況下で、規定値は“約”または“ほぼ”の意味を含む。
【0014】
図１Ａは、ナノ金属ワイヤーだけを含む透明導電膜の概略図であり、図１Ｂは、ナノ金属ワイヤーだけを含む透明導電膜の顕微鏡写真である。図１Ａと図１Ｂによると、金属ナノワイヤー１００だけを含む透明導電膜において、金属ナノワイヤー１００は、接触点１１０だけによって互いに電気的に接続されて、導電性経路を形成する。
【0015】
本発明においては、透明性を維持するとともに、透明導電膜の導電性を増加させるため、微量の金属フレークが透明導電膜に加えられる。図２Ａと図２Ｂを参照すると、図２Ａは、金属ナノワイヤーとミクロン金属フレークとを含む透明導電膜の概略図であり、図２Ｂは、金属ナノワイヤーとミクロン金属フレークとを含む透明導電膜の顕微鏡写真である。二つの図に示されるように、金属ナノワイヤー２００とミクロン金属フレーク２２０とを含む透明導電膜においては、金属ナノワイヤー２００は互いに電気的に接続されて、導電性経路を形成し、接触点２１０だけでなく、金属ナノワイヤー２００とミクロン金属フレーク２２０との接触領域２３０により、導電性を増加する。本発明の実施形態による透明導電膜複合材および透明導電膜の製造方法および使用を、以下の詳細な説明にて記述する。
【0016】
まず、ナノ金属ワイヤーとミクロン金属フレークとを含む金属素材が、分散剤により溶剤中で分散して、透明導電膜複合材を形成する。一実施形態において、３ロールミルの使用により、よい分散が達成され得る。透明導電膜複合材において、ナノ金属ワイヤーおよびミクロン金属フレークの全固形分は、約０．０７−０．２ｗｔ％である。金属素材において、ミクロン金属フレークの重量比は、金属素材の全固形分に基づいて、約０．０１−１６ｗｔ％である。
【0017】
特に、本発明の透明導電膜複合材は、約０．０７−０．２ｗｔ％の金属素材、約０．０１−０．５ｗｔ％の分散剤；および、約９９．３−９９．９２ｗｔ％の溶剤を含み得る。たとえば、一実施形態において、本発明の透明導電膜複合材は、約０．０７−０．１ｗｔ％の金属素材、約０．０３−０．３ｗｔ％の分散剤；および、約９９．６−９９．９０ｗｔ％の溶剤を含み得る。
【0018】
上述の金属素材は、ナノ金属ワイヤーとミクロン金属フレークを含み得る。金属素材は、約８４−９９．９９ｗｔ％のナノ金属ワイヤー、および、約０．０１−１６ｗｔ％のミクロン金属フレークを含む。たとえば、一実施形態において、金属素材は、約９０−９９．９ｗｔ％のナノ金属ワイヤー、および、約０．１−１０ｗｔ％のミクロン金属フレークを含む。別の実施態様において、金属素材は、約９９−９９．９ｗｔ％のナノ金属ワイヤー、および、約０．１−１ｗｔ％のミクロン金属フレークを含む。本発明において、微量の金属フレークが透明導電膜複合材に加えられるので、この透明導電膜複合材により製造される透明導電膜の導電性は、透明性を維持しながらも、増加し得る。
【0019】
また、透明導電膜複合材中の金属素材が多すぎるミクロン金属フレーク、たとえば、１６ｗｔ％を超えるミクロン金属フレークを含む場合、この透明導電膜複合材から製造されるその後の透明導電膜の透明性が減少し得、その応用性に影響することに注意されるべきである。一方、透明導電膜複合材中の金属素材のミクロン金属フレークが少なすぎる、たとえば、ミクロン金属フレークが０．０１ｗｔ％より少ない場合、この透明導電膜複合材から製造されるその後の透明導電膜の導電性は効果的に改善されない。
【0020】
ミクロン金属フレークの材料は、フレーク状の導電材料であればよい。一次元金属ナノワイヤー間の導電性経路は、ミクロン金属フレークの二次元形状により増加し得る。ミクロン金属フレークの材料は、これに限定されないが、Ａｕ，Ａｇ，Ｃｕ，それらの合金、それらの組み合わせ、または、その他の適切な金属材料を含み得る。ミクロン金属フレークの平均フレークサイズ（Ｄ５０）は、約０．５μｍ〜１０μｍ、たとえば、約１μｍ〜９μｍである。また、ミクロン金属フレークのＤ９０フレークサイズは約４μｍ〜２５μｍである。ミクロン金属フレークのフレークサイズが大きすぎる場合、その後の透明導電膜の透明性が減少し得ることに注意すべきである。しかし、ミクロン金属フレークのフレークサイズが小さすぎる場合、ミクロン金属フレークと金属ナノワイヤーとの接触領域が減少し、その後の透明導電膜の導電性は効果的に改善されない。
【0021】
ナノ金属ワイヤーは、一次元ナノ金属素材であればよい。ナノ金属ワイヤーは、透明導電膜中に導電性経路を形成し、透明導電膜を導電させるために用いられる。また、ナノ金属ワイヤーは、透明導電膜の透明性を維持するため、ナノサイズを有し得る。ナノ金属ワイヤーの材料は、これに限定されないが、Ａｕ，Ａｇ，Ｃｕ、それらの合金、それらの組み合わせ、あるいは、その他の適切な金属材料を含み得る。ナノ金属ワイヤーの直径は、約１５ｎｍ〜１００ｎｍ、たとえば、約２０ｎｍ〜８０ｎｍであり得る。ナノ金属ワイヤーのアスペクト比は、約１００〜１０００、たとえば、約２００〜９００であり得る。ナノ金属ワイヤーのアスペクト比が大きすぎる、たとえば、約１０００より大きい場合、ナノ金属ワイヤーは破損しやすくなることに注意されるべきである。しかし、ナノ金属ワイヤーのアスペクト比が小さ過ぎる、たとえば、約１００より小さい場合、ナノ金属ワイヤーは、不十分な長さのために、導電性経路を効果的に形成することができず、透明導電膜の導電性に影響する。
【0022】
分散剤は、ミクロン金属フレークとナノ金属ワイヤーとを溶剤中に分散するのに用いられる。分散剤は、ミクロン金属フレークとナノ金属ワイヤーを均一に分散させて、ミクロン金属フレークとナノ金属ワイヤーとの間で凝集するのを防止しなければならない。一実施形態において、分散剤は、これに限定されないが、メチルセルロース、カルボキシメチルセルロース、エチルセルロース、ヒドロキシプロピルセルロース、ポリビニルピロリドン、ポリビニルアルコール、それらの組み合わせ、または、その他の適当な分散剤を含み得る。溶剤は、これに限定されないが、水、アルコール（たとえば、メタノール、エタノール、または、ポリオール）、ケトン、エーテル、それらの組み合わせ、または、別の適当な溶剤を含み得る。
【0023】
次に、透明導電膜複合材を基板にコートする。その後、透明導電膜複合材を加熱乾燥させて、透明導電膜を形成する。コーティング方法は、これに限定されないが、線材コーティング、スピンコーティング、プリントコーティング、または、その他の適切なコーティング方法を含み得る。プリントコーティングは、これに限定されないが、インクジェット印刷、レーザー印刷、スロットコーティング、インプリンティング、グラビア印刷、または、スクリーン印刷を含み得る。また、加熱乾燥ステップの加熱期間は約１時間であり得る。加熱乾燥ステップの加熱温度は約５０℃−１５０℃、たとえば、約７０℃−９０℃であり得る。
【0024】
基板の材料は、これに限定されないが、ガラスなどの無機材料、または、プラスチックもしくは合成樹脂等の有機材料を含み得る。プラスチックは、これに限定されないが、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、ポリカーボネート（ＰＣ）、ポリスチレン（ＰＳ）、ポリアクリロニトリル−ブタジエン−スチレン（ＡＢＳ）、または、その他の適切なプラスチックを含み得る。合成樹脂は、これに限定されないが、フェノール樹脂、ユリアホルムアルデヒド樹脂、不飽和ポリエステル樹脂、メラミン樹脂、ウレタン樹脂、アルキド樹脂、エポキシ樹脂、酢酸ビニル樹脂、ポリアクリレート樹脂、ポリビニルアルコール樹脂、石油樹脂、ポリアミド樹脂、フラン樹脂、または、無水マレイン酸樹脂を含み得る。
【0025】
透明導電膜は、約４０−９６ｗｔ％の金属素材、および、４−６０ｗｔ％の分散剤を含む。たとえば、一実施形態において、透明導電膜は、約５０−８０ｗｔ％の金属素材、および、２０−５０ｗｔ％の分散剤を含む。また、金属素材と分散剤との重量比は、約０．１４：１〜２０：１、たとえば、約１：１〜１５：１である。透明導電膜の金属素材において、ナノ金属ワイヤーとミクロン金属フレークとの比率は、透明導電膜複合材とほぼ等しい。つまり、透明導電膜中の金属素材は、８４−９９．９９ｗｔ％のナノ金属ワイヤー、および、０．０１−１６ｗｔ％のミクロン金属フレークを含み得る。たとえば、金属素材は、９０−９９．９ｗｔ％のナノ金属ワイヤー、および、０．１−１０ｗｔ％のミクロン金属フレークを含み得る。
【0026】
本発明の透明導電膜中における微量の金属フレークにより、透明導電膜の導電性は、その透明性を維持されつつ、増加する。たとえば、一実施形態において、導電性は、微量の金属フレークの添加により、約３５％まで改善される。透明導電膜のシート抵抗は１００Ω／□以下、たとえば、８０Ω／□以下であり得る。透明導電膜の透明性は、９５％以上、たとえば、９８％以上であり得る。
【0027】
本発明は、簡単な乾燥ステップを利用して、透明導電膜複合材を乾燥させて、透明導電膜を形成するので、高真空製造装置が必要ない。また、本発明の透明導電膜は、高コストであるインジウムイオン（Ｉｎ）を含まないので、インジウムスズ酸化物（ＩＴＯ）材料により製造される透明導電膜と比較すると、本発明の透明導電膜は低コストである。
【0028】
さらに、本発明の透明導電膜の導電性は１００Ω／□以下であり得るため、透明導電膜は、中型および大型のディスプレイおよびパネルに応用できる。また、本発明の透明導電膜は可撓性材料なので、フレキシブルな電子製品に応用できる。
【0029】
総合すると、本発明の透明導電膜の微量の金属フレークのため、透明導電膜の導電性は、透明性が維持されつつも、増加し得る。このほか、本発明の透明導電膜は費用効率が高く、高い導電性と高い透明度であり、フレキシブルな電子製品に応用される。
【0030】
以下、当業者に本発明をより明確に説明するため、本発明の典型的な実施形態が詳細に記述される。
【実施例】
【0031】
［実施例１］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍ（平均直径は透過型電子顕微鏡により観察される１２のナノシルバーワイヤにより計算され、および、平均ワイヤ長さは光学顕微鏡により観察される３０のナノシルバーワイヤにより計算された）のナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は０．０５ｗｔ％のメチルセルロースを含んでいた。銀フレーク（Ｄ５０＝１．５７μｍ）の固形分が０．２５ｗｔ％である別の水溶液を調製した。別の水溶液は１ｗｔ％のメチルセルロース、１ｗｔ％のヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、２ｗｔ％のポリビニルピロリドン（ＰＶＰＫ１２０，分子量：２，５４０，０００〜３，２２０，０００）を含み、３ロールミルにより分散した。上述の二溶液を混合して、銀の全固形分が７．６８０×１０−２ｗｔ％（９９ｗｔ％のナノシルバーワイヤ、および、１ｗｔ％の銀フレーク（Ｄ５０＝１．５７μｍ））である透明導電膜複合材を調製した。上述の二溶液を一様に混合後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0032】
［実施例２］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は０．０５ｗｔ％のメチルセルロースを含んでいた。銀フレーク（Ｄ５０＝１．５７μｍ）の固形分が０．２５ｗｔ％である別の水溶液を調製した。別の水溶液は１ｗｔ％のメチルセルロース、１ｗｔ％のヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、２ｗｔ％のポリビニルピロリドン（ＰＶＰＫ１２０，分子量：２，５４０，０００〜３，２２０，０００）を含んでいた。上述の二溶液を混合して、銀の全固形分が７．７７９×１０−２ｗｔ％（９７ｗｔ％のナノシルバーワイヤ、および、３ｗｔ％の銀フレーク（Ｄ５０＝１．５７μｍ））である透明導電膜複合材を調製した。上述の二溶液を一様に混合後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0033】
［実施例３］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。銀フレーク（Ｄ５０＝１．５７μｍ）の固形分が０．２５ｗｔ％である別の水溶液を調製した。別の水溶液は１ｗｔ％のメチルセルロース、１ｗｔ％のヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、２ｗｔ％のポリビニルピロリドン（ＰＶＰＫ１２０，分子量：２，５４０，０００〜３，２２０，０００）を含んでいた。上述の二溶液を混合して、銀の全固形分が７．８９４×１０−２ｗｔ％（９５ｗｔ％のナノシルバーワイヤ、および、５ｗｔ％の銀フレーク（Ｄ５０＝１．５７μｍ））である透明導電膜複合材を調製した。上述の二溶液を一様に混合後、洗浄されたガラス板を用意して、９０℃で２分間加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0034】
［実施例４］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。銀フレーク（Ｄ５０＝１．５７μｍ）の固形分が０．２５ｗｔ％である別の水溶液を調製した。別の水溶液は１ｗｔ％のメチルセルロース、１ｗｔ％のヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、２ｗｔ％のポリビニルピロリドン（ＰＶＰＫ１２０，分子量：２，５４０，０００〜３，２２０，０００）を含み、３ロールミルにより分散した。上述の二溶液を混合して、銀の全固形分が７．９９９×１０−２ｗｔ％（９３ｗｔ％のナノシルバーワイヤ、および、７ｗｔ％の銀フレーク（Ｄ５０＝１．５７μｍ））である透明導電膜複合材を調製した。上述の二溶液を一様に混合後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0035】
［実施例５］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。銀フレーク（Ｄ５０＝１．５７μｍ）の固形分が０．２５ｗｔ％である別の水溶液を調製した。別の水溶液は１ｗｔ％のメチルセルロース、１ｗｔ％のヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、２ｗｔ％のポリビニルピロリドン（ＰＶＰＫ１２０，分子量：２，５４０，０００〜３，２２０，０００）を含み、３ロールミルにより分散した。上述の二溶液を混合して、銀の全固形分が８．１７８×１０−２ｗｔ％（９０ｗｔ％のナノシルバーワイヤ、および、１０ｗｔ％の銀フレーク（Ｄ５０＝１．５７μｍ））である透明導電膜複合材を調製した。上述の二溶液を一様に混合後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0036】
［実施例６］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。銀フレーク（Ｄ５０＝１．５７μｍ）の固形分が０．２５ｗｔ％である別の水溶液を調製した。別の水溶液は１ｗｔ％のメチルセルロース、１ｗｔ％のヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、２ｗｔ％のポリビニルピロリドン（ＰＶＰＫ１２０，分子量：２，５４０，０００〜３，２２０，０００）を含み、３ロールミルにより分散した。上述の二溶液を混合して、銀の全固形分が８．４５２×１０−２ｗｔ％（８４ｗｔ％のナノシルバーワイヤ、および、１６ｗｔ％の銀フレーク（Ｄ５０＝１．５７μｍ））である透明導電膜複合材を調製した。上述の二溶液を一様に混合後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0037】
［実施例７］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。銀フレーク（Ｄ５０＝２．５μｍ）の固形分が０．２５ｗｔ％である別の水溶液を調製した。別の水溶液は１ｗｔ％のメチルセルロース、１ｗｔ％のヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、２ｗｔ％のポリビニルピロリドン（ＰＶＰＫ１２０，分子量：２，５４０，０００〜３，２２０，０００）を含んでいた。上述の二溶液を混合して、銀の全固形分が７．６８０×１０−２ｗｔ％（９９ｗｔ％のナノシルバーワイヤ、および、１ｗｔ％の銀フレーク（Ｄ５０＝２．５μｍ））である透明導電膜複合材を調製した。上述の二溶液を一様に混合後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0038】
［実施例８］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。銀フレーク（Ｄ５０＝２．５μｍ）の固形分が０．２５ｗｔ％である別の水溶液を調製した。別の水溶液は１ｗｔ％のメチルセルロース、１ｗｔ％のヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、２ｗｔ％のポリビニルピロリドン（ＰＶＰＫ１２０，分子量：２，５４０，０００〜３，２２０，０００）を含んでいた。上述の二溶液を混合して、銀の全固形分が７．７７９×１０−２ｗｔ％（９７ｗｔ％のナノシルバーワイヤ、および、３ｗｔ％の銀フレーク（Ｄ５０＝２．５μｍ））である透明導電膜複合材を生成した。上述の二溶液を一様に混合後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0039】
［実施例９］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。銀フレーク（Ｄ５０＝２．５μｍ）の固形分が０．２５ｗｔ％である別の水溶液を調製した。別の水溶液は１ｗｔ％のメチルセルロース、１ｗｔ％のヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、２ｗｔ％のポリビニルピロリドン（ＰＶＰＫ１２０，分子量：２，５４０，０００〜３，２２０，０００）を含んでいた。上述の二溶液を混合して、銀の全固形分が７．８９４×１０−２ｗｔ％（９５ｗｔ％のナノシルバーワイヤ、および、５ｗｔ％の銀フレーク（Ｄ５０＝２．５μｍ））である透明導電膜複合材を調製した。上述の二溶液を一様に混合後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0040】
［実施例１０］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。銀フレーク（Ｄ５０＝２．５μｍ）の固形分が０．２５ｗｔ％である別の水溶液を調製した。別の水溶液は１ｗｔ％のメチルセルロース、１ｗｔ％のヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、２ｗｔ％のポリビニルピロリドン（ＰＶＰＫ１２０，分子量：２，５４０，０００〜３，２２０，０００）を含み、３ロールミルにより分散した。上述の二溶液を混合して、銀の全固形分が７．９９９×１０−２ｗｔ％（９３ｗｔ％のナノシルバーワイヤ、および、７ｗｔ％の銀フレーク（Ｄ５０＝２．５μｍ））である透明導電膜複合材を調製した。上述の二溶液を一様に混合後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0041】
［実施例１１］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。銀フレーク（Ｄ５０＝２．５μｍ）の固形分が０．２５ｗｔ％である別の水溶液を調製した。別の水溶液は１ｗｔ％のメチルセルロース、１ｗｔ％のヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、２ｗｔ％のポリビニルピロリドン（ＰＶＰＫ１２０，分子量：２，５４０，０００〜３，２２０，０００）を含み、３ロールミルにより分散した。上述の二溶液を混合して、銀の全固形分が８．１７８×１０−２ｗｔ％（９０ｗｔ％のナノシルバーワイヤ、および、１０ｗｔ％の銀フレーク（Ｄ５０＝２．５μｍ））である透明導電膜複合材を調製した。上述の二溶液を一様に混合後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0042】
［実施例１２］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。銀フレーク（Ｄ５０＝２．５μｍ）の固形分が０．２５ｗｔ％である別の水溶液を調製した。別の水溶液は１ｗｔ％のメチルセルロース、１ｗｔ％のヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、２ｗｔ％のポリビニルピロリドン（ＰＶＰＫ１２０，分子量：２，５４０，０００〜３，２２０，０００）を含み、３ロールミルにより分散した。上述の二溶液を混合して、銀の全固形分が８．４５２×１０−２ｗｔ％（８４ｗｔ％のナノシルバーワイヤ、および、１６ｗｔ％の銀フレーク（Ｄ５０＝２．５μｍ））である透明導電膜複合材を調製した。上述の二溶液を一様に混合後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0043】
［実施例１３］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。銀フレーク（Ｄ５０＝４．６３μｍ）の固形分が０．２５ｗｔ％である別の水溶液を調製した。別の水溶液は１ｗｔ％のメチルセルロース、１ｗｔ％のヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、２ｗｔ％のポリビニルピロリドン（ＰＶＰＫ１２０，分子量：２，５４０，０００〜３，２２０，０００）を含んでいた。上述の二溶液を混合して、銀の全固形分が７．８９４×１０−２ｗｔ％（９５ｗｔ％のナノシルバーワイヤ、および、５ｗｔ％の銀フレーク（Ｄ５０＝４．６３μｍ））である透明導電膜複合材を調製した。上述の二溶液を一様に混合後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0044】
［実施例１４］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。銀フレーク（Ｄ５０＝４．６３μｍ）の固形分が０．２５ｗｔ％である別の水溶液を調製した。別の水溶液は１ｗｔ％のメチルセルロース、１ｗｔ％のヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、２ｗｔ％のポリビニルピロリドン（ＰＶＰＫ１２０，分子量：２，５４０，０００〜３，２２０，０００）を含み、３ロールミルにより分散した。上述の二溶液を混合して、銀の全固形分が８．１７８×１０−２ｗｔ％（９０ｗｔ％のナノシルバーワイヤ、および、１０ｗｔ％の銀フレーク（Ｄ５０＝４．６３μｍ））である透明導電膜複合材を調製した。上述の二溶液を一様に混合後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0045】
［実施例１５］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。銀フレーク（Ｄ５０＝４．６３μｍ）の固形分が０．２５ｗｔ％である別の水溶液を調製した。別の水溶液は１ｗｔ％のメチルセルロース、１ｗｔ％のヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、２ｗｔ％のポリビニルピロリドン（ＰＶＰＫ１２０，分子量：２，５４０，０００〜３，２２０，０００）を含み、３ロールミルにより分散した。上述の二溶液を混合して、銀の全固形分が８．４５２×１０−２ｗｔ％（８４ｗｔ％のナノシルバーワイヤ、および、１６ｗｔ％の銀フレーク（Ｄ５０＝４．６３μｍ））である透明導電膜複合材を調製した。上述の二溶液を一様に混合後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0046】
［実施例１６］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。銀フレーク（Ｄ５０＝８．３８μｍ）の固形分が０．２５ｗｔ％である別の水溶液を調製した。別の水溶液は１ｗｔ％のメチルセルロース、１ｗｔ％のヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、２ｗｔ％のポリビニルピロリドン（ＰＶＰＫ１２０，分子量：２，５４０，０００〜３，２２０，０００）を含んでいた。上述の二溶液を混合して、銀の全固形分が７．８９４×１０−２ｗｔ％（９５ｗｔ％のナノシルバーワイヤ、および、５ｗｔ％の銀フレーク（Ｄ５０＝８．３８μｍ））である透明導電膜複合材を調製した。上述の二溶液を一様に混合後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0047】
［実施例１７］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。銀フレーク（Ｄ５０＝８．３８μｍ）の固形分が０．２５ｗｔ％である別の水溶液を調製した。別の水溶液は１ｗｔ％のメチルセルロース、１ｗｔ％のヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、２ｗｔ％のポリビニルピロリドン（ＰＶＰＫ１２０，分子量：２，５４０，０００〜３，２２０，０００）を含み、３ロールミルにより分散した。上述の二溶液を混合して、銀の全固形分が８．１７８×１０−２ｗｔ％（９０ｗｔ％のナノシルバーワイヤ、および、１０ｗｔ％の銀フレーク（Ｄ５０＝８．３８μｍ））である透明導電膜複合材を調製した。上述の二溶液を一様に混合後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0048】
［実施例１８］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。銀フレーク（Ｄ５０＝８．３８μｍ）の固形分が０．２５ｗｔ％である別の水溶液を調製した。別の水溶液は１ｗｔ％のメチルセルロース、１ｗｔ％のヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、２ｗｔ％のポリビニルピロリドン（ＰＶＰＫ１２０，分子量：２，５４０，０００〜３，２２０，０００）を含み、３ロールミルにより分散した。上述の二溶液を混合して、銀の全固形分が８．４５２×１０−２ｗｔ％（８４ｗｔ％のナノシルバーワイヤ、および、１６ｗｔ％の銀フレーク（Ｄ５０＝８．３８μｍ））である透明導電膜複合材を調製した。上述の二溶液を一様に混合後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0049】
［比較例１］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。上述の溶液は、銀の全固形分が７．６８０×１０−２ｗｔ％である透明導電膜複合材を調製するのに用いられ、銀は１００ｗｔ％のナノシルバーワイヤを含んでいた。その後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0050】
［比較例２］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。上述の溶液は、銀の全固形分が７．７７９×１０−２ｗｔ％である透明導電膜複合材を調製するのに用いられ、銀は１００ｗｔ％のナノシルバーワイヤを含んでいた。その後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0051】
［比較例３］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。上述の溶液は、銀の全固形分が７．８９４×１０−２ｗｔ％である透明導電膜複合材を調製するのに用いられ、銀は１００ｗｔ％のナノシルバーワイヤを含んでいた。その後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0052】
［比較例４］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。上述の溶液は、銀の全固形分が７．９９９×１０−２ｗｔ％である透明導電膜複合材を調製するのに用いられ、銀は１００ｗｔ％のナノシルバーワイヤを含んでいた。その後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0053】
［比較例５］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。上述の溶液は、銀の全固形分が８．１７８×１０−２ｗｔ％である透明導電膜複合材を調製するのに用いられ、銀は１００ｗｔ％のナノシルバーワイヤを含んでいた。その後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0054】
［比較例６］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。上述の溶液は、銀の全固形分が８．４５２×１０−２ｗｔ％である透明導電膜複合材を調製するのに用いられ、銀は１００ｗｔ％のナノシルバーワイヤを含んでいた。その後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0055】
［比較例７］平均直径が約６０ｎｍ〜７０ｎｍ、平均ワイヤ長さが約３０μｍ〜４０μｍのナノシルバーワイヤから、ナノシルバーワイヤ固形分が０．０７６２５ｗｔ％の水溶液を調製した。水溶液は、０．０５ｗｔ％のメチルセルロースを含んでいた。上述の溶液は、銀の全固形分が７．６２５×１０−２ｗｔ％である透明導電膜複合材を調製するのに用いられ、銀は１００ｗｔ％のナノシルバーワイヤを含んでいた。その後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0056】
［比較例８］３ｗｔ％固形分の銀フレーク（Ｄ５０＝１．５７μｍ）を有する水溶液を調製した。かかる水溶液は１ｗｔ％のメチルセルロース、１ｗｔ％のヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、２ｗｔ％のポリビニルピロリドン（ＰＶＰＫ１２０，分子量：２，５４０，０００〜３，２２０，０００）を含み、３ロールミルにより分散した。上述の溶液は、銀の全固形分が３００×１０−２ｗｔ％の透明導電膜複合材を生成するのに用いられ、銀は１００ｗｔ％の銀フレーク（Ｄ５０＝１．５７μｍ）を含んでいた。溶液を均一に混合した後、洗浄されたガラス板を用意して、９０℃で２分間、加熱器上で予熱した。５００μＬの準備した溶液をマイクロピペットにより採取して、ガラス板に滴下した。その後、溶液を２５μｍの線材でコートして、加熱器で２分間加熱した。この透明導電膜の物理的特性を表１に示す。
【0057】
【表1】
【0058】
表１は、実施例１−１８および比較例１−８の透明導電膜の組成と物理的特性とを示す。表１によると、同一の金属固形分において、銀フレークを含む透明導電膜はよい導電性を有していた。たとえば、実施例１、７および比較例１中の透明導電膜の全銀固形分は７．６８０×１０−２ｗｔ％であり、実施例１，７（８７Ω／□と８２Ω／□）中の微量の銀フレークを含む透明導電膜のシート抵抗は、比較例１（１１４Ω／□）中の銀フレークがない透明導電膜のシート抵抗より明らかに小さい。また、実施例１、７の透明導電膜の透明性（９８．４５２％および９８．３８９％）は、比較例１の透明導電膜の透明性（９８．４７５％）にほぼ等しい。よって、一定量のミクロン金属フレークを透明導電膜に加えると、透明性を犠牲にすることなく、透明導電膜の導電性を大幅に増加させる。たとえば、比較例３中の透明導電膜の導電性は９０Ω／□であり、対応する実施例３中の５ｗｔ％の銀フレークを含む透明導電膜の導電性は５５Ω／□であった。導電性が意外にも３８％増加した。同じ傾向が別の実施例でも示された。
【0059】
また、実施例１−６のミクロン金属フレークのＤ５０フレークサイズは１．５７μｍであった。実施例７−１２のミクロン金属フレークのＤ５０フレークサイズは２．５μｍであった。実施例１３−１５のミクロン金属フレークのＤ５０フレークサイズは４．６３μｍであった。実施例１６−１８のミクロン金属フレークのＤ５０フレークサイズは８．３８μｍであった。表１の実施例１−１８によると、ミクロン金属フレークのＤ５０フレークサイズが増加するにつれて、透明導電膜のシート抵抗が減少する。しかし、大きいＤ５０フレークサイズのミクロン金属フレークは、透明導電膜の透明性も低下させる。たとえば、実施例１，７中の透明導電膜の銀固形分はいずれも７．６８０×１０−２ｗｔ％であり、銀固形分は、９９ｗｔ％のナノシルバーワイヤと１ｗｔ％の銀フレークを含んでいた。実施例１のミクロン金属フレークのＤ５０フレークサイズ（１．５７μｍ）は、実施例７のミクロン金属フレークのＤ５０フレークサイズ（２．５μｍ）より小さいため、実施例１の透明導電膜のシート抵抗（８７Ω／□）は実施例７の透明導電膜のシート抵抗（８２Ω／□）より大きかった。また、実施例１のミクロン金属フレークは小さいＤ５０フレークサイズを有するため、実施例１の透明導電膜の透明性は高かった。特に、実施例１の透明導電膜の透明性（９８．４５２％）は、実施例７の透明導電膜の透明性（９８．３８９％）よりわずかに高かった。このほか、比較例８によると、銀フレークだけを含む透明導電膜は導電性がなく、透明性が低かった（８２．７４９％）。
【0060】
開示された実施形態に様々な修正や変更を行うことができることは、当業者にとって明らかであろう。明細書および実施例は、単に例示的なものとして考えられることが意図されており、本開示の真の範囲は特許請求の範囲およびその均等物により示される。
【符号の説明】
【0061】
１００、２００ 金属ナノワイヤー１１０、２１０ 接触点
２２０ ミクロン金属フレーク
２３０ 接触領域
【外国語明細書】
TITLE
Transparent conductive film composite and transparent conductive film
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority of Taiwan Patent Application No. 102148966, filed on December, 30, 2013, the entirety of which is incorporated by reference herein.
BACKGROUND
Technical Field
[0002] The disclosure relates to a transparent conductive film, and in particular to a transparent conductive film composite and a transparent conductive film manufactured from the transparent conductive film composite.
Description of the Related Art
[0003] In recent years, the applications of the transparent conductive film increase and the demands of the transparent conductive film varied continuously. For example, electronic products such as liquid-crystal displays in flat display panels, electro luminescence panels, plasma display panels, field emission displays, touch panels, and solar cells, all utilize transparent conductive film as an electrode material. With the flourishing development of the 3C industry and the global trend of saving energy, the technology of the transparent conductive film becomes more and more important.
[0004] US Patent No. 6,143,418 provides a transparent conductive film having a transparent conductive layer containing at least two types of metals. The at least two types of the metals are palladium and silver.
[0005] US Patent No. 6,524,499 provides a transparent conductive film having a conductive layer containing at least ruthenium fine particles, gold fine particles and silver fine particles, the weight ratio of ruthenium fine particles and gold fine particles in the conductive layer being within the range of 40:60 to 99:1.
[0006] US Patent No. 8,715,536 provides an electrically conductive material includes a plurality of nanowires and a plurality of nanoconnectors.
[0007] Patent Document 1: US Patent No. 6,143,418
[0008] Patent Document 2: US Patent No. 6,524,499
[0009] Patent Document 3: US Patent No. 8,715,536
SUMMARY
[0010] PROBLEMS TO BE SOLVED BY THE INVENTION
[0011] Since the ansparent conductive film has not been satisfactory in every respect, a transparent conductive film which has high conductivity, high transparency and may be applied in flexible electronic products is needed.
[0012] MEANS FOR SOLVING THE PROBLEMS
[0013] The present disclosure provides a transparent conductive film composite, including: (a) 0.07-0.2 wt% of a metallic material; (b) 0.01-0.5 wt% of a dispersant; and (c) 99.3-99.92 wt% of a solvent, wherein the metallic material (a) includes: (a1) 84-99.99 wt% of metal nanowires; and (a2) 0.01-16 wt% of micron metal flakes.
[0014] The present disclosure also provides a transparent conductive film, including: (a) a metallic material; and (b) a dispersant, wherein a weight ratio of the metallic material to the dispersant ranges from about 0.14:1 to 20:1, wherein the metallic material (a) includes: (a1) 84-99.99 wt% of metal nanowires; and (a2) 0.01-16 wt% of micron metal flakes, wherein a sheet resistance of the transparent conductive film is 100Ω/□ or less, and a transparency of the transparent conductive film is 95% or greater.
[0015] EFFECTS OF THE INVENTION
[0016] The conductivity and transparency of the transparent conductive film are improved, and the transparent conductive film may be applied in flexible electronic products.
[0017] A detailed description is given in the following embodiments with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
The disclosure may be more fully understood by reading the subsequent detailed description and examples with references made to the accompanying drawings, wherein:
[0018] Fig. 1A is a schematic view of a transparent conductive film which only includes nano metal wires;
[0019] Fig. 1B is a microscopy image of a transparent conductive film which only includes nano metal wires;
[0020] Fig. 2A is a schematic view of a transparent conductive film which includes metal nanowires and micron metal flakes; and
[0021] Fig. 2B is a microscopy image of a transparent conductive film which includes metal nanowires and micron metal flakes.
DETAILED DESCRIPTION
[0022] The transparent conductive film composite and the transparent conductive film of the present disclosure are described in the following detailed description. In the following detailed description, it should be noted that one or more embodiments are provided to illustrate the present application. The specific elements and configurations described in the following detailed description are merely used to clearly describe the present disclosure, and the scope of the present application is not intended to be limited by the specific element and configuration. In addition, various embodiments may use like reference numerals to clearly describe the present disclosure. However, the like reference numerals does not indicate a correlation between various embodiments and structures.
[0023] The terms "about" and "substantially" typically mean +/- 20% of the stated value, more typically +/- 10% of the stated value and even more typically +/- 5% of the stated value. The stated value of the present disclosure is an approximate value. When there is no specific description, the stated value includes the meaning of "about" or "substantially".
[0024] Fig. 1A is a schematic view of a transparent conductive film which only includes nano metal wires, and Fig. 1B is a microscopy image of a transparent conductive film which only includes nano metal wires. According to Figs. 1A and 1B, in the transparent conductive film containing only the metal nanowires 100, the metal nanowires 100 are electrically connected to each other to form conductive paths only through the contact points 110.
[0025] In the present disclosure, trace metal flakes are added into the transparent conductive film to enhance the conductivity of the transparent conductive film while maintaining its transparency. Referring to Figs. 2A and 2B, Fig. 2A is a schematic view of a transparent conductive film which includes metal nanowires and micron metal flakes, and Fig. 2B is a microscopy image of a transparent conductive film which includes metal nanowires and micron metal flakes. As shown in the two figures, in the transparent conductive film containing metal nanowires 200 and micron metal flakes 220, the metal nanowires 200 may be electrically connected to each other to form a conductive path and enhance the conductivity not only through the contact point 210, but also through the contact region 230 of the metal nanowires 200 and the micron metal flakes 220. The manufacturing method and utilization of the transparent conductive film composite and the transparent conductive film in the embodiments of the present disclosure are described in the following detailed description.
[0026] First, a metallic material containing the nano metal wire and the micron metal flake is dispersed in a solvent by a dispersant to form the transparent conductive film composite. In one embodiment, excellent dispersion may be achieved by a three-roll mill. In the transparent conductive film composite, the total solid content of the nano metal wire and the micron metal flake ranges from about 0.07-0.2 wt%. In the metallic material, the weight ratio of the micron metal flake ranges from about 0.01-16 wt% based on the total solid content of the metallic material.
[0027] In particular, the transparent conductive film composite of the present disclosure may include about 0.07-0.2 wt% of the metallic material, about 0.01-0.5 wt% of the dispersant; and about 99.3-99.92 wt% of the solvent. For example, in one embodiment, the transparent conductive film composite of the present disclosure may include about 0.07-0.1 wt% of the metallic material, about 0.03-0.3 wt% of the dispersant; and about 99.6-99.90 wt% of the solvent.
[0028] The above metallic material may include the nano metal wire and the micron metal flake. The metallic material includes about 84-99.99 wt% of the nano metal wire and about 0.01-16 wt% of the micron metal flake. For example, in one embodiment, the metallic material includes about 90-99.9 wt% of the nano metal wire and about 0.1-10 wt% of the micron metal flake. In another embodiment, the metallic material includes about 99-99.9 wt% of the nano metal wire and about 0.1-1 wt% of the micron metal flake. In the present disclosure, since trace metal flakes are added into the transparent conductive film composite, the conductivity of the transparent conductive film manufactured from this transparent conductive film composite may be enhanced while maintaining its transparency.
[0029] In addition, it should be noted that if the metallic material in the transparent conductive film composite includes too many micron metal flakes, for example more than 16 wt% of the micron metal flake, the transparency of the subsequent transparent conductive film manufactured from this transparent conductive film composite may decrease, which in turn affects its applicability. On the other hand, if the metallic material in the transparent conductive film composite includes an insufficient quantity of micron metal flakes, for example less than 0.01 wt% of the micron metal flake, the conductivity of the subsequent transparent conductive film manufactured from this transparent conductive film composite cannot be effectively enhanced.
[0030] The material of the micron metal flake may be any flaky conductive material. The conductive paths between the one-dimensional metal nanowires may be increased through the two-dimensional shape of the micron metal flake. The material of the micron metal flake may include, but is not limited to, Au, Ag, Cu, an alloy thereof, a combination thereof, or any other suitable metal materials. The average flake size (D50) of the micron metal flake ranges from about 0.5 μm to 10 μm, for example from about 1 μm to 9 μm. In addition, the D90 flake size of the micron metal flake ranges from about 4 μm to 25 μm. It should be noted that if the flake size of the micron metal flake is too large, the transparency of the subsequent transparent conductive film may decrease. However, if the flake size of the micron metal flake is too small, the contact region of the micron metal flakes and the metal nanowires may be reduced, and the conductivity of the subsequent transparent conductive film cannot be effectively enhanced.
[0031] The nano metal wire may be any one-dimensional nano metal material. The nano metal wire is used to form the conductive paths in the transparent conductive film to make the transparent conductive film conductive. In addition, the nano metal wire may have nano size to maintain the transparency of the transparent conductive film. The material of the nano metal wire may include, but is not limited to, Au, Ag, Cu, an alloy therof, a combination thereof, or any other suitable metal materials. The diameter of the nano metal wire may range from about 15 nm to 100 nm, for example from about 20 nm to 80 nm. The aspect ratio of the nano metal wire may range from about 100 to 1000, for example from about 200 to 900. It should be noted that if the aspect ratio of the nano metal wire is too large, for example larger than about 1000, the nano metal wire is subject to breakage. However, if the aspect ratio of the nano metal wire is too small, for example smaller than about 100, the nano metal wire cannot effectively form the conductive paths due to its insufficient length, which in turn affects the conductivity of the transparent conductive film.
[0032] The dispersant is used to disperse the micron metal flake and the nano metal wire in the solvent. The dispersant has to disperse the micron metal flake and the nano metal wire uniformly to prevent the aggregation between the micron metal flake and the nano metal wire. In one embodiment, the dispersant may include, but is not limited to, methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol, a combination thereof, or any other suitable dispersant. The solvent may include, but is not limited to, water, alcohol (for example methanol, ethanol, or polyol), ketone, ether, a combination thereof, or any other suitable solvent.
[0033] Next, the transparent conductive film composite is coated on a substrate. Then the transparent conductive film composite is heat dried to form the transparent conductive film. The coating method may include, but is not limited to, wire rods coating, spin coating, print coating, or any other suitable coating methods. The print coating may include, but is not limited to, ink-jet printing, laser printing, slot coating, imprinting, gravure printing or screen printing. In addition, the heating duration of the heat drying step may be about 1 hour. The heating temperature of the heat drying step may be about 50℃-150℃, for example about 70℃-90℃.
[0034] The material of the substrate may include, but is not limited to, inorganic material such as glass or organic material such as plastic or synthetic resin. The plastic may include, but is not limited to, polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polycarbonate (PC), polystyrene (PS), polyacrylonitrile - butadiene - styrene (ABS) or any other suitable plastic. The synthetic resin may include, but is not limited to, phenolic resins, urea-formaldehyde resins, unsaturated polyester resins, melamine resins, urethane resins, alkyd resins, epoxy resins, polyvinyl acetate resins, polyacrylate resins, polyvinyl alcohol resins, petroleum resins, polyamide resins, furan resin, or marin anhydride resin.
[0035] The transparent conductive film includes about 40-96 wt% of the metallic material and 4-60 wt% of the dispersant. For example, in one embodiment, the transparent conductive film includes about 50-80 wt% of the metallic material and 20-50 wt% of the dispersant. In addition, the weight ratio of the metallic material to the dispersant ranges from about 0.14:1 to 20:1, for example from about 1:1 to 15:1. In the metallic material of the transparent conductive film, the ratio of the nano metal wire and the micron metal flake is substantially equal to that in the transparent conductive film composite. In other words, the metallic material in the transparent conductive film may include 84-99.99 wt% of the nano metal wire and 0.01-16 wt% of the micron metal flake. For example, the metallic material may include 90-99.9 wt% of the nano metal wire and 0.1-10 wt% of the micron metal flake.
[0036] Due to the trace of metal flake in the transparent conductive film in the present disclosure, the conductivity of the transparent conductive film may be enhanced while maintaining its transparency. For example, in one embodiment, the conductivity is enhanced by about 35% through the addition of the trace of metal flake. The sheet resistance of the transparent conductive film may be 100Ω/□ or less, for example 80Ω/□ or less. The transparency of the transparent conductive film may be 95% or greater, for example 98% or greater.
[0037] Since the present disclosure utilizes a simple drying step to dry the transparent conductive film composite to form the transparent conductive film, high-vacuum manufacturing equipment is not necessary. In addition, since the transparent conductive film of the present disclosure does not contain indium ion (In) which has a high cost, the transparent conductive film of the present disclosure has a lower cost compared to the transparent conductive film manufactured from the indium tin oxide (ITO) material.
[0038] Furthermore, since the conductivity of the transparent conductive film of the present disclosure may be 100Ω/□ or less, the transparent conductive film may be applied to the medium-size and large-size display and panel. In addition, the transparent conductive film of the present disclosure is a flexible material, therefore it can be applied to flexible electronic products.
[0039] In summary, due to the trace of metal flakes in the transparent conductive film of the present disclosure, the conductivity of the transparent conductive film may be enhanced while maintaining its transparency. In addition, the transparent conductive film of the present disclosure is cost-effective, highly conductive, highly transparent and may be applied in flexible electronic products.
[0040] Below, exemplary embodiments will be described in detail for a more clear illustration of the present disclosure to a person having ordinary knowledge in the art.
EXAMPLE
[EXAMPLE 1]
[0041] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm (the average diameter was calculated by 12 nano silver wires observed by a transmission electron microscope and the average wire length was calculated by 30 nano silver wires observed by an optical microscope). The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=1.57 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 7.680 x 10-2 wt% total solid content of silver (99 wt% of the nano silver wire and 1 wt% of a silver flake (D50=1.57 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 2]
[0042] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=1.57 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000). The above two solutions were mixed to prepare a transparent conductive film composite with 7.779 x 10-2 wt% total solid content of silver (97 wt% of the nano silver wire and 3 wt% of a silver flake (D50=1.57 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 3]
[0043] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=1.57 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000). The above two solutions were mixed to prepare a transparent conductive film composite with 7.894 x 10-2 wt% total solid content of silver (95 wt% of the nano silver wire and 5 wt% of a silver flake (D50=1.57 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 4]
[0044] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=1.57 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 7.999 x 10-2 wt% total solid content of silver (93 wt% of the nano silver wire and 7 wt% of a silver flake (D50=1.57 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 5]
[0045] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=1.57 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 8.178 x 10-2 wt% total solid content of silver (90 wt% of the nano silver wire and 10 wt% of a silver flake (D50=1.57 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 6]
[0046] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=1.57 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 8.452 x 10-2 wt% total solid content of silver (84 wt% of the nano silver wire and 16 wt% of a silver flake (D50=1.57 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 7]
[0047] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=2.5 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000). The above two solutions were mixed to prepare a transparent conductive film composite with 7.680 x 10-2 wt% total solid content of silver (99 wt% of the nano silver wire and 1 wt% of a silver flake (D50=2.5 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 8]
[0048] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=2.5 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000). The above two solutions were mixed to prepare a transparent conductive film composite with 7.779 x 10-2 wt% total solid content of silver (97 wt% of the nano silver wire and 3 wt% of a silver flake (D50=2.5 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 9]
[0049] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=2.5 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000). The above two solutions were mixed to prepare a transparent conductive film composite with 7.894 x 10-2 wt% total solid content of silver (95 wt% of the nano silver wire and 5 wt% of a silver flake (D50=2.5 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 10]
[0050] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=2.5 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 7.999 x 10-2 wt% total solid content of silver (93 wt% of the nano silver wire and 7 wt% of a silver flake (D50=2.5 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 11]
[0051] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=2.5 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 8.178 x 10-2 wt% total solid content of silver (90 wt% of the nano silver wire and 10 wt% of a silver flake (D50=2.5 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 12]
[0052] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=2.5 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 8.452 x 10-2 wt% total solid content of silver (84 wt% of the nano silver wire and 16 wt% of a silver flake (D50=2.5 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 13]
[0053] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=4.63 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000). The above two solutions were mixed to prepare a transparent conductive film composite with 7.894 x 10-2 wt% total solid content of silver (95 wt% of the nano silver wire and 5 wt% of a silver flake (D50=4.63 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 14]
[0054] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=4.63 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 8.178 x 10-2 wt% total solid content of silver (90 wt% of the nano silver wire and 10 wt% of a silver flake (D50=4.63 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 15]
[0055] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=4.63 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 8.452 x 10-2 wt% total solid content of silver (84 wt% of the nano silver wire and 16 wt% of a silver flake (D50=4.63 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 16]
[0056] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=8.38 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000). The above two solutions were mixed to prepare a transparent conductive film composite with 7.894 x 10-2 wt% total solid content of silver (95 wt% of the nano silver wire and 5 wt% of a silver flake (D50=8.38 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 17]
[0057] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=8.38 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 8.178 x 10-2 wt% total solid content of silver (90 wt% of the nano silver wire and 10 wt% of a silver flake (D50=8.38 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 18]
[0058] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=8.38 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 8.452 x 10-2 wt% total solid content of silver (84 wt% of the nano silver wire and 16 wt% of a silver flake (D50=8.38 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[COMPARATIVE EXAMPLE 1]
[0059] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. The above solution was used to prepare a transparent conductive film composite with 7.680 x 10-2 wt% total solid content of silver, which contained 100 wt% of the nano silver wire. Then a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[COMPARATIVE EXAMPLE 2]
[0060] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. The above solution was used to prepare a transparent conductive film composite with 7.779 x 10-2 wt% total solid content of silver, which contained 100 wt% of the nano silver wire. Then a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[COMPARATIVE EXAMPLE 3]
[0061] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. The above solution was used to prepare a transparent conductive film composite with 7.894 x 10-2 wt% total solid content of silver, which contained 100 wt% of the nano silver wire. Then a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[COMPARATIVE EXAMPLE 4]
[0062] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. The above solution was used to prepare a transparent conductive film composite with 7.999 x 10-2 wt% total solid content of silver, which contained 100 wt% of the nano silver wire. Then a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[COMPARATIVE EXAMPLE 5]
[0063] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. The above solution was used to prepare a transparent conductive film composite with 8.178 x 10-2 wt% total solid content of silver, which contained 100 wt% of the nano silver wire. Then a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[COMPARATIVE EXAMPLE 6]
[0064] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. The above solution was used to prepare a transparent conductive film composite with 8.452 x 10-2 wt% total solid content of silver, which contained 100 wt% of the nano silver wire. Then a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[COMPARATIVE EXAMPLE 7]
[0065] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. The above solution was used to prepare a transparent conductive film composite with 7.625 x 10-2 wt% total solid content of silver, which contained 100 wt% of the nano silver wire. Then a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[COMPARATIVE EXAMPLE 8]
[0066] A water solution with 3 wt% solid content of a silver flake (D50=1.57 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above solution was used to prepare a transparent conductive film composite with 300 x 10-2 wt% total solid content of silver, which contained 100 wt% of a silver flake (D50=1.57 μm). After the solution was uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
Table 1 Composition and physical characteristics of the transparent conductive films
[0067] Table 1 shows the composition and physical characteristics of the transparent conductive films of examples 1-18 and comparative examples 1-8. According to table 1, for the same metal solid content, the transparent conductive film which contained silver flakes had good conductivity. For example, all of the silver solid content of the transparent conductive films in examples 1, 7 and comparative example 1 were 7.680 x 10-2 wt%, and the sheet resistance of the transparent conductive films containing trace of silver flakes in examples 1, 7 (87Ω/□ and 82Ω/□) was explicitly less than the sheet resistance of the transparent conductive film without the silver flakes in comparative example 1 (114Ω/□). In addition, the transparency of the transparent conductive films in examples 1, 7 (98.452% and 98.389%) was substantially equal to the transparency of the transparent conductive film in comparative example 1 (98.475%). Therefore, adding a specific amount of the micron metal flake into the transparent conductive film could explicitly enhance the conductivity of the transparent conductive film without sacrificing its transparency. For example, the conductivity of the transparent conductive film in comparative example 3 was 90Ω/□, while the conductivity of the transparent conductive film containing 5wt% of the silver flakes in the corresponding example 3 was 55Ω/□. The conductivity was enhanced impressively by 38%. The same trend was shown in other examples.
[0068] In addition, the D50 flake size of the micron metal flakes in examples 1-6 was 1.57 μm. The D50 flake size of the micron metal flakes in examples 7-12 was 2.5 μm. The D50 flake size of the micron metal flakes in examples 13-15 was 4.63 μm. The D50 flake size of the micron metal flakes in examples 16-18 was 8.38 μm. According to examples 1-18 in Table 1, as the D50 flake size of the micron metal flake increased, the sheet resistance of the transparent conductive film decreased. However, the micron metal flake with larger D50 flake size would also decrease the transparency of the transparent conductive film. For example, both of the silver solid contents of the transparent conductive films in examples 1, 7 were 7.680 x 10-2 wt%, and both of the silver solid contents included 99 wt% of the nano silver wire and 1 wt% of the silver flake. Since the D50 flake size of the micron metal flake in example 1 (1.57 μm) was smaller than the D50 flake size of the micron metal flake in example 7 (2.5 μm), the sheet resistance of the transparent conductive film in example 1 (87Ω/□) was greater than the sheet resistance of the transparent conductive film in example 7 (82Ω/□). In addition, since the micron metal flake in example 1 had a smaller D50 flake size, the transparency of the transparent conductive film in example 1 was greater. In particular, the transparency of the transparent conductive film in example 1 (98.452%) was slightly greater than the transparency of the transparent conductive film in example 7 (98.389%). In addition, according to the comparative example 8, the transparent conductive film containing only the silver flake did not have conductivity and had a poor transparency (82.749%).
It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed embodiments. It is intended that the specification and examples be considered as exemplary only, with a true scope of the disclosure being indicated by the following claims and their equivalents.
Transparent conductive film composite and transparent conductive film
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority of Taiwan Patent Application No. 102148966, filed on December, 30, 2013, the entirety of which is incorporated by reference herein.
BACKGROUND
Technical Field
[0002] The disclosure relates to a transparent conductive film, and in particular to a transparent conductive film composite and a transparent conductive film manufactured from the transparent conductive film composite.
Description of the Related Art
[0003] In recent years, the applications of the transparent conductive film increase and the demands of the transparent conductive film varied continuously. For example, electronic products such as liquid-crystal displays in flat display panels, electro luminescence panels, plasma display panels, field emission displays, touch panels, and solar cells, all utilize transparent conductive film as an electrode material. With the flourishing development of the 3C industry and the global trend of saving energy, the technology of the transparent conductive film becomes more and more important.
[0004] US Patent No. 6,143,418 provides a transparent conductive film having a transparent conductive layer containing at least two types of metals. The at least two types of the metals are palladium and silver.
[0005] US Patent No. 6,524,499 provides a transparent conductive film having a conductive layer containing at least ruthenium fine particles, gold fine particles and silver fine particles, the weight ratio of ruthenium fine particles and gold fine particles in the conductive layer being within the range of 40:60 to 99:1.
[0006] US Patent No. 8,715,536 provides an electrically conductive material includes a plurality of nanowires and a plurality of nanoconnectors.
[0007] Patent Document 1: US Patent No. 6,143,418
[0008] Patent Document 2: US Patent No. 6,524,499
[0009] Patent Document 3: US Patent No. 8,715,536
SUMMARY
[0010] PROBLEMS TO BE SOLVED BY THE INVENTION
[0011] Since the ansparent conductive film has not been satisfactory in every respect, a transparent conductive film which has high conductivity, high transparency and may be applied in flexible electronic products is needed.
[0012] MEANS FOR SOLVING THE PROBLEMS
[0013] The present disclosure provides a transparent conductive film composite, including: (a) 0.07-0.2 wt% of a metallic material; (b) 0.01-0.5 wt% of a dispersant; and (c) 99.3-99.92 wt% of a solvent, wherein the metallic material (a) includes: (a1) 84-99.99 wt% of metal nanowires; and (a2) 0.01-16 wt% of micron metal flakes.
[0014] The present disclosure also provides a transparent conductive film, including: (a) a metallic material; and (b) a dispersant, wherein a weight ratio of the metallic material to the dispersant ranges from about 0.14:1 to 20:1, wherein the metallic material (a) includes: (a1) 84-99.99 wt% of metal nanowires; and (a2) 0.01-16 wt% of micron metal flakes, wherein a sheet resistance of the transparent conductive film is 100Ω/□ or less, and a transparency of the transparent conductive film is 95% or greater.
[0015] EFFECTS OF THE INVENTION
[0016] The conductivity and transparency of the transparent conductive film are improved, and the transparent conductive film may be applied in flexible electronic products.
[0017] A detailed description is given in the following embodiments with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
The disclosure may be more fully understood by reading the subsequent detailed description and examples with references made to the accompanying drawings, wherein:
[0018] Fig. 1A is a schematic view of a transparent conductive film which only includes nano metal wires;
[0019] Fig. 1B is a microscopy image of a transparent conductive film which only includes nano metal wires;
[0020] Fig. 2A is a schematic view of a transparent conductive film which includes metal nanowires and micron metal flakes; and
[0021] Fig. 2B is a microscopy image of a transparent conductive film which includes metal nanowires and micron metal flakes.
DETAILED DESCRIPTION
[0022] The transparent conductive film composite and the transparent conductive film of the present disclosure are described in the following detailed description. In the following detailed description, it should be noted that one or more embodiments are provided to illustrate the present application. The specific elements and configurations described in the following detailed description are merely used to clearly describe the present disclosure, and the scope of the present application is not intended to be limited by the specific element and configuration. In addition, various embodiments may use like reference numerals to clearly describe the present disclosure. However, the like reference numerals does not indicate a correlation between various embodiments and structures.
[0023] The terms "about" and "substantially" typically mean +/- 20% of the stated value, more typically +/- 10% of the stated value and even more typically +/- 5% of the stated value. The stated value of the present disclosure is an approximate value. When there is no specific description, the stated value includes the meaning of "about" or "substantially".
[0024] Fig. 1A is a schematic view of a transparent conductive film which only includes nano metal wires, and Fig. 1B is a microscopy image of a transparent conductive film which only includes nano metal wires. According to Figs. 1A and 1B, in the transparent conductive film containing only the metal nanowires 100, the metal nanowires 100 are electrically connected to each other to form conductive paths only through the contact points 110.
[0025] In the present disclosure, trace metal flakes are added into the transparent conductive film to enhance the conductivity of the transparent conductive film while maintaining its transparency. Referring to Figs. 2A and 2B, Fig. 2A is a schematic view of a transparent conductive film which includes metal nanowires and micron metal flakes, and Fig. 2B is a microscopy image of a transparent conductive film which includes metal nanowires and micron metal flakes. As shown in the two figures, in the transparent conductive film containing metal nanowires 200 and micron metal flakes 220, the metal nanowires 200 may be electrically connected to each other to form a conductive path and enhance the conductivity not only through the contact point 210, but also through the contact region 230 of the metal nanowires 200 and the micron metal flakes 220. The manufacturing method and utilization of the transparent conductive film composite and the transparent conductive film in the embodiments of the present disclosure are described in the following detailed description.
[0026] First, a metallic material containing the nano metal wire and the micron metal flake is dispersed in a solvent by a dispersant to form the transparent conductive film composite. In one embodiment, excellent dispersion may be achieved by a three-roll mill. In the transparent conductive film composite, the total solid content of the nano metal wire and the micron metal flake ranges from about 0.07-0.2 wt%. In the metallic material, the weight ratio of the micron metal flake ranges from about 0.01-16 wt% based on the total solid content of the metallic material.
[0027] In particular, the transparent conductive film composite of the present disclosure may include about 0.07-0.2 wt% of the metallic material, about 0.01-0.5 wt% of the dispersant; and about 99.3-99.92 wt% of the solvent. For example, in one embodiment, the transparent conductive film composite of the present disclosure may include about 0.07-0.1 wt% of the metallic material, about 0.03-0.3 wt% of the dispersant; and about 99.6-99.90 wt% of the solvent.
[0028] The above metallic material may include the nano metal wire and the micron metal flake. The metallic material includes about 84-99.99 wt% of the nano metal wire and about 0.01-16 wt% of the micron metal flake. For example, in one embodiment, the metallic material includes about 90-99.9 wt% of the nano metal wire and about 0.1-10 wt% of the micron metal flake. In another embodiment, the metallic material includes about 99-99.9 wt% of the nano metal wire and about 0.1-1 wt% of the micron metal flake. In the present disclosure, since trace metal flakes are added into the transparent conductive film composite, the conductivity of the transparent conductive film manufactured from this transparent conductive film composite may be enhanced while maintaining its transparency.
[0029] In addition, it should be noted that if the metallic material in the transparent conductive film composite includes too many micron metal flakes, for example more than 16 wt% of the micron metal flake, the transparency of the subsequent transparent conductive film manufactured from this transparent conductive film composite may decrease, which in turn affects its applicability. On the other hand, if the metallic material in the transparent conductive film composite includes an insufficient quantity of micron metal flakes, for example less than 0.01 wt% of the micron metal flake, the conductivity of the subsequent transparent conductive film manufactured from this transparent conductive film composite cannot be effectively enhanced.
[0030] The material of the micron metal flake may be any flaky conductive material. The conductive paths between the one-dimensional metal nanowires may be increased through the two-dimensional shape of the micron metal flake. The material of the micron metal flake may include, but is not limited to, Au, Ag, Cu, an alloy thereof, a combination thereof, or any other suitable metal materials. The average flake size (D50) of the micron metal flake ranges from about 0.5 μm to 10 μm, for example from about 1 μm to 9 μm. In addition, the D90 flake size of the micron metal flake ranges from about 4 μm to 25 μm. It should be noted that if the flake size of the micron metal flake is too large, the transparency of the subsequent transparent conductive film may decrease. However, if the flake size of the micron metal flake is too small, the contact region of the micron metal flakes and the metal nanowires may be reduced, and the conductivity of the subsequent transparent conductive film cannot be effectively enhanced.
[0031] The nano metal wire may be any one-dimensional nano metal material. The nano metal wire is used to form the conductive paths in the transparent conductive film to make the transparent conductive film conductive. In addition, the nano metal wire may have nano size to maintain the transparency of the transparent conductive film. The material of the nano metal wire may include, but is not limited to, Au, Ag, Cu, an alloy therof, a combination thereof, or any other suitable metal materials. The diameter of the nano metal wire may range from about 15 nm to 100 nm, for example from about 20 nm to 80 nm. The aspect ratio of the nano metal wire may range from about 100 to 1000, for example from about 200 to 900. It should be noted that if the aspect ratio of the nano metal wire is too large, for example larger than about 1000, the nano metal wire is subject to breakage. However, if the aspect ratio of the nano metal wire is too small, for example smaller than about 100, the nano metal wire cannot effectively form the conductive paths due to its insufficient length, which in turn affects the conductivity of the transparent conductive film.
[0032] The dispersant is used to disperse the micron metal flake and the nano metal wire in the solvent. The dispersant has to disperse the micron metal flake and the nano metal wire uniformly to prevent the aggregation between the micron metal flake and the nano metal wire. In one embodiment, the dispersant may include, but is not limited to, methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol, a combination thereof, or any other suitable dispersant. The solvent may include, but is not limited to, water, alcohol (for example methanol, ethanol, or polyol), ketone, ether, a combination thereof, or any other suitable solvent.
[0033] Next, the transparent conductive film composite is coated on a substrate. Then the transparent conductive film composite is heat dried to form the transparent conductive film. The coating method may include, but is not limited to, wire rods coating, spin coating, print coating, or any other suitable coating methods. The print coating may include, but is not limited to, ink-jet printing, laser printing, slot coating, imprinting, gravure printing or screen printing. In addition, the heating duration of the heat drying step may be about 1 hour. The heating temperature of the heat drying step may be about 50℃-150℃, for example about 70℃-90℃.
[0034] The material of the substrate may include, but is not limited to, inorganic material such as glass or organic material such as plastic or synthetic resin. The plastic may include, but is not limited to, polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polycarbonate (PC), polystyrene (PS), polyacrylonitrile - butadiene - styrene (ABS) or any other suitable plastic. The synthetic resin may include, but is not limited to, phenolic resins, urea-formaldehyde resins, unsaturated polyester resins, melamine resins, urethane resins, alkyd resins, epoxy resins, polyvinyl acetate resins, polyacrylate resins, polyvinyl alcohol resins, petroleum resins, polyamide resins, furan resin, or marin anhydride resin.
[0035] The transparent conductive film includes about 40-96 wt% of the metallic material and 4-60 wt% of the dispersant. For example, in one embodiment, the transparent conductive film includes about 50-80 wt% of the metallic material and 20-50 wt% of the dispersant. In addition, the weight ratio of the metallic material to the dispersant ranges from about 0.14:1 to 20:1, for example from about 1:1 to 15:1. In the metallic material of the transparent conductive film, the ratio of the nano metal wire and the micron metal flake is substantially equal to that in the transparent conductive film composite. In other words, the metallic material in the transparent conductive film may include 84-99.99 wt% of the nano metal wire and 0.01-16 wt% of the micron metal flake. For example, the metallic material may include 90-99.9 wt% of the nano metal wire and 0.1-10 wt% of the micron metal flake.
[0036] Due to the trace of metal flake in the transparent conductive film in the present disclosure, the conductivity of the transparent conductive film may be enhanced while maintaining its transparency. For example, in one embodiment, the conductivity is enhanced by about 35% through the addition of the trace of metal flake. The sheet resistance of the transparent conductive film may be 100Ω/□ or less, for example 80Ω/□ or less. The transparency of the transparent conductive film may be 95% or greater, for example 98% or greater.
[0037] Since the present disclosure utilizes a simple drying step to dry the transparent conductive film composite to form the transparent conductive film, high-vacuum manufacturing equipment is not necessary. In addition, since the transparent conductive film of the present disclosure does not contain indium ion (In) which has a high cost, the transparent conductive film of the present disclosure has a lower cost compared to the transparent conductive film manufactured from the indium tin oxide (ITO) material.
[0038] Furthermore, since the conductivity of the transparent conductive film of the present disclosure may be 100Ω/□ or less, the transparent conductive film may be applied to the medium-size and large-size display and panel. In addition, the transparent conductive film of the present disclosure is a flexible material, therefore it can be applied to flexible electronic products.
[0039] In summary, due to the trace of metal flakes in the transparent conductive film of the present disclosure, the conductivity of the transparent conductive film may be enhanced while maintaining its transparency. In addition, the transparent conductive film of the present disclosure is cost-effective, highly conductive, highly transparent and may be applied in flexible electronic products.
[0040] Below, exemplary embodiments will be described in detail for a more clear illustration of the present disclosure to a person having ordinary knowledge in the art.
EXAMPLE
[EXAMPLE 1]
[0041] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm (the average diameter was calculated by 12 nano silver wires observed by a transmission electron microscope and the average wire length was calculated by 30 nano silver wires observed by an optical microscope). The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=1.57 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 7.680 x 10-2 wt% total solid content of silver (99 wt% of the nano silver wire and 1 wt% of a silver flake (D50=1.57 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 2]
[0042] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=1.57 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000). The above two solutions were mixed to prepare a transparent conductive film composite with 7.779 x 10-2 wt% total solid content of silver (97 wt% of the nano silver wire and 3 wt% of a silver flake (D50=1.57 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 3]
[0043] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=1.57 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000). The above two solutions were mixed to prepare a transparent conductive film composite with 7.894 x 10-2 wt% total solid content of silver (95 wt% of the nano silver wire and 5 wt% of a silver flake (D50=1.57 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 4]
[0044] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=1.57 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 7.999 x 10-2 wt% total solid content of silver (93 wt% of the nano silver wire and 7 wt% of a silver flake (D50=1.57 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 5]
[0045] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=1.57 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 8.178 x 10-2 wt% total solid content of silver (90 wt% of the nano silver wire and 10 wt% of a silver flake (D50=1.57 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 6]
[0046] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=1.57 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 8.452 x 10-2 wt% total solid content of silver (84 wt% of the nano silver wire and 16 wt% of a silver flake (D50=1.57 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 7]
[0047] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=2.5 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000). The above two solutions were mixed to prepare a transparent conductive film composite with 7.680 x 10-2 wt% total solid content of silver (99 wt% of the nano silver wire and 1 wt% of a silver flake (D50=2.5 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 8]
[0048] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=2.5 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000). The above two solutions were mixed to prepare a transparent conductive film composite with 7.779 x 10-2 wt% total solid content of silver (97 wt% of the nano silver wire and 3 wt% of a silver flake (D50=2.5 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 9]
[0049] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=2.5 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000). The above two solutions were mixed to prepare a transparent conductive film composite with 7.894 x 10-2 wt% total solid content of silver (95 wt% of the nano silver wire and 5 wt% of a silver flake (D50=2.5 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 10]
[0050] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=2.5 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 7.999 x 10-2 wt% total solid content of silver (93 wt% of the nano silver wire and 7 wt% of a silver flake (D50=2.5 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 11]
[0051] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=2.5 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 8.178 x 10-2 wt% total solid content of silver (90 wt% of the nano silver wire and 10 wt% of a silver flake (D50=2.5 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 12]
[0052] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=2.5 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 8.452 x 10-2 wt% total solid content of silver (84 wt% of the nano silver wire and 16 wt% of a silver flake (D50=2.5 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 13]
[0053] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=4.63 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000). The above two solutions were mixed to prepare a transparent conductive film composite with 7.894 x 10-2 wt% total solid content of silver (95 wt% of the nano silver wire and 5 wt% of a silver flake (D50=4.63 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 14]
[0054] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=4.63 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 8.178 x 10-2 wt% total solid content of silver (90 wt% of the nano silver wire and 10 wt% of a silver flake (D50=4.63 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 15]
[0055] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=4.63 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 8.452 x 10-2 wt% total solid content of silver (84 wt% of the nano silver wire and 16 wt% of a silver flake (D50=4.63 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 16]
[0056] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=8.38 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000). The above two solutions were mixed to prepare a transparent conductive film composite with 7.894 x 10-2 wt% total solid content of silver (95 wt% of the nano silver wire and 5 wt% of a silver flake (D50=8.38 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 17]
[0057] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=8.38 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 8.178 x 10-2 wt% total solid content of silver (90 wt% of the nano silver wire and 10 wt% of a silver flake (D50=8.38 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[EXAMPLE 18]
[0058] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. Another water solution with 0.25 wt% solid content of a silver flake (D50=8.38 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above two solutions were mixed to prepare a transparent conductive film composite with 8.452 x 10-2 wt% total solid content of silver (84 wt% of the nano silver wire and 16 wt% of a silver flake (D50=8.38 μm)). After the above two solutions were uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[COMPARATIVE EXAMPLE 1]
[0059] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. The above solution was used to prepare a transparent conductive film composite with 7.680 x 10-2 wt% total solid content of silver, which contained 100 wt% of the nano silver wire. Then a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[COMPARATIVE EXAMPLE 2]
[0060] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. The above solution was used to prepare a transparent conductive film composite with 7.779 x 10-2 wt% total solid content of silver, which contained 100 wt% of the nano silver wire. Then a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[COMPARATIVE EXAMPLE 3]
[0061] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. The above solution was used to prepare a transparent conductive film composite with 7.894 x 10-2 wt% total solid content of silver, which contained 100 wt% of the nano silver wire. Then a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[COMPARATIVE EXAMPLE 4]
[0062] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. The above solution was used to prepare a transparent conductive film composite with 7.999 x 10-2 wt% total solid content of silver, which contained 100 wt% of the nano silver wire. Then a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[COMPARATIVE EXAMPLE 5]
[0063] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. The above solution was used to prepare a transparent conductive film composite with 8.178 x 10-2 wt% total solid content of silver, which contained 100 wt% of the nano silver wire. Then a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[COMPARATIVE EXAMPLE 6]
[0064] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. The above solution was used to prepare a transparent conductive film composite with 8.452 x 10-2 wt% total solid content of silver, which contained 100 wt% of the nano silver wire. Then a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[COMPARATIVE EXAMPLE 7]
[0065] A water solution with 0.07625 wt% solid content of a nano silver wire was prepared from the nano silver wire with an average diameter ranging from about 60 nm to 70 nm and an average wire length ranging from about 30 μm to 40 μm. The water solution contained 0.05 wt% of methyl cellulose. The above solution was used to prepare a transparent conductive film composite with 7.625 x 10-2 wt% total solid content of silver, which contained 100 wt% of the nano silver wire. Then a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
[COMPARATIVE EXAMPLE 8]
[0066] A water solution with 3 wt% solid content of a silver flake (D50=1.57 μm) was prepared, which contained 1 wt% of methyl cellulose, 1 wt% of hydroxypropyl methylcellulose (HPMC), 2 wt% of polyvinylpyrrolidone (PVPK120, molecular weight: 2,540,000 to 3,220,000) and was dispersed by a three-roll mill. The above solution was used to prepare a transparent conductive film composite with 300 x 10-2 wt% total solid content of silver, which contained 100 wt% of a silver flake (D50=1.57 μm). After the solution was uniformly mixed, a washed glass sheet was prepared and preheated on a heater at 90℃ for 2 minutes. 500 μL of the prepared solution was pipetted by a micropipette and dropped onto the glass sheet. Subsequently, the solution was coated by a 25 μm wire rod and heated for 2 minutes on the heater. The physical characteristics of this transparent conductive film are shown in Table 1.
Table 1 Composition and physical characteristics of the transparent conductive films
[0067] Table 1 shows the composition and physical characteristics of the transparent conductive films of examples 1-18 and comparative examples 1-8. According to table 1, for the same metal solid content, the transparent conductive film which contained silver flakes had good conductivity. For example, all of the silver solid content of the transparent conductive films in examples 1, 7 and comparative example 1 were 7.680 x 10-2 wt%, and the sheet resistance of the transparent conductive films containing trace of silver flakes in examples 1, 7 (87Ω/□ and 82Ω/□) was explicitly less than the sheet resistance of the transparent conductive film without the silver flakes in comparative example 1 (114Ω/□). In addition, the transparency of the transparent conductive films in examples 1, 7 (98.452% and 98.389%) was substantially equal to the transparency of the transparent conductive film in comparative example 1 (98.475%). Therefore, adding a specific amount of the micron metal flake into the transparent conductive film could explicitly enhance the conductivity of the transparent conductive film without sacrificing its transparency. For example, the conductivity of the transparent conductive film in comparative example 3 was 90Ω/□, while the conductivity of the transparent conductive film containing 5wt% of the silver flakes in the corresponding example 3 was 55Ω/□. The conductivity was enhanced impressively by 38%. The same trend was shown in other examples.
[0068] In addition, the D50 flake size of the micron metal flakes in examples 1-6 was 1.57 μm. The D50 flake size of the micron metal flakes in examples 7-12 was 2.5 μm. The D50 flake size of the micron metal flakes in examples 13-15 was 4.63 μm. The D50 flake size of the micron metal flakes in examples 16-18 was 8.38 μm. According to examples 1-18 in Table 1, as the D50 flake size of the micron metal flake increased, the sheet resistance of the transparent conductive film decreased. However, the micron metal flake with larger D50 flake size would also decrease the transparency of the transparent conductive film. For example, both of the silver solid contents of the transparent conductive films in examples 1, 7 were 7.680 x 10-2 wt%, and both of the silver solid contents included 99 wt% of the nano silver wire and 1 wt% of the silver flake. Since the D50 flake size of the micron metal flake in example 1 (1.57 μm) was smaller than the D50 flake size of the micron metal flake in example 7 (2.5 μm), the sheet resistance of the transparent conductive film in example 1 (87Ω/□) was greater than the sheet resistance of the transparent conductive film in example 7 (82Ω/□). In addition, since the micron metal flake in example 1 had a smaller D50 flake size, the transparency of the transparent conductive film in example 1 was greater. In particular, the transparency of the transparent conductive film in example 1 (98.452%) was slightly greater than the transparency of the transparent conductive film in example 7 (98.389%). In addition, according to the comparative example 8, the transparent conductive film containing only the silver flake did not have conductivity and had a poor transparency (82.749%).
It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed embodiments. It is intended that the specification and examples be considered as exemplary only, with a true scope of the disclosure being indicated by the following claims and their equivalents.
1. A transparent conductive film composite, comprising:
(a) 0.07-0.2 wt% of a metallic material;
(b) 0.01-0.5 wt% of a dispersant; and
(c) 99.3-99.92 wt% of a solvent,
wherein the metallic material (a) comprises:
(a1) 84-99.99 wt% of metal nanowires; and
(a2) 0.01-16 wt% of micron metal flakes.
2. The transparent conductive film composite as claimed in claim 1, wherein the micron metal flake and the nano metal wire each independently comprises: Au, Ag, Cu, an alloy thereof, or a combination thereof.
3. The transparent conductive film composite as claimed in claim 1, wherein an average flake size (D50) of the micron metal flake ranges from 0.5 μm to 10 μm.
4. The transparent conductive film composite as claimed in claim 1, wherein an aspect ratio of the nano metal wire ranges from 100 to 1000.
5. The transparent conductive film composite as claimed in claim 1, wherein the dispersant comprises methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol, or a combination thereof.
6. A transparent conductive film, comprising:
(a) a metallic material; and
(b) a dispersant, wherein a weight ratio of the metallic material to the dispersant ranges from 0.14:1 to 20:1,
wherein the metallic material (a) comprises:
(a1) 84-99.99 wt% of metal nanowires; and
(a2) 0.01-16 wt% of micron metal flakes,
wherein a sheet resistance of the transparent conductive film is 100Ω/□ or less, and a transparency of the transparent conductive film is 95% or greater.
7. The transparent conductive film as claimed in claim 6, wherein the micron metal flake and the nano metal wire each independently comprises: Au, Ag, Cu, an alloy therof, or a combination thereof.
8. The transparent conductive film as claimed in claim 6, wherein an average flake size (D50) of the micron metal flake ranges from 0.5 μm to 10 μm.
9. The transparent conductive film as claimed in claim 6, wherein an aspect ratio of the nano metal wire ranges from 100 to 1000.
10. The transparent conductive film as claimed in claim 6, wherein the dispersant comprises methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol, or a combination thereof.
(a) 0.07-0.2 wt% of a metallic material;
(b) 0.01-0.5 wt% of a dispersant; and
(c) 99.3-99.92 wt% of a solvent,
wherein the metallic material (a) comprises:
(a1) 84-99.99 wt% of metal nanowires; and
(a2) 0.01-16 wt% of micron metal flakes.
2. The transparent conductive film composite as claimed in claim 1, wherein the micron metal flake and the nano metal wire each independently comprises: Au, Ag, Cu, an alloy thereof, or a combination thereof.
3. The transparent conductive film composite as claimed in claim 1, wherein an average flake size (D50) of the micron metal flake ranges from 0.5 μm to 10 μm.
4. The transparent conductive film composite as claimed in claim 1, wherein an aspect ratio of the nano metal wire ranges from 100 to 1000.
5. The transparent conductive film composite as claimed in claim 1, wherein the dispersant comprises methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol, or a combination thereof.
6. A transparent conductive film, comprising:
(a) a metallic material; and
(b) a dispersant, wherein a weight ratio of the metallic material to the dispersant ranges from 0.14:1 to 20:1,
wherein the metallic material (a) comprises:
(a1) 84-99.99 wt% of metal nanowires; and
(a2) 0.01-16 wt% of micron metal flakes,
wherein a sheet resistance of the transparent conductive film is 100Ω/□ or less, and a transparency of the transparent conductive film is 95% or greater.
7. The transparent conductive film as claimed in claim 6, wherein the micron metal flake and the nano metal wire each independently comprises: Au, Ag, Cu, an alloy therof, or a combination thereof.
8. The transparent conductive film as claimed in claim 6, wherein an average flake size (D50) of the micron metal flake ranges from 0.5 μm to 10 μm.
9. The transparent conductive film as claimed in claim 6, wherein an aspect ratio of the nano metal wire ranges from 100 to 1000.
10. The transparent conductive film as claimed in claim 6, wherein the dispersant comprises methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol, or a combination thereof.
1. Abstract
A transparent conductive film composite is provided. The transparent conductive film composite includes (a) 0.07-0.2 wt% of a metallic material; (b) 0.01-0.5 wt% of a dispersant; and 99.3-99.92 wt% of a solvent, wherein the metallic material (a) includes: (a1) 84-99.99 wt% of metal nanowires; and (a2) 0.01-16 wt% of micron metal flakes. A transparent conductive film manufactured from the transparent conductive film composite is also provided.
2. Representative Drawing
Fig. 2A
A transparent conductive film composite is provided. The transparent conductive film composite includes (a) 0.07-0.2 wt% of a metallic material; (b) 0.01-0.5 wt% of a dispersant; and 99.3-99.92 wt% of a solvent, wherein the metallic material (a) includes: (a1) 84-99.99 wt% of metal nanowires; and (a2) 0.01-16 wt% of micron metal flakes. A transparent conductive film manufactured from the transparent conductive film composite is also provided.
2. Representative Drawing
Fig. 2A
Fig. 1A
Fig. 1B
Fig. 2A
Fig. 2B
Fig. 1B
Fig. 2A
Fig. 2B