JPH05314820A - Composition for forming transparent conductive film and formation of transparent conductive film - Google Patents
Composition for forming transparent conductive film and formation of transparent conductive filmInfo
- Publication number
- JPH05314820A JPH05314820A JP4115694A JP11569492A JPH05314820A JP H05314820 A JPH05314820 A JP H05314820A JP 4115694 A JP4115694 A JP 4115694A JP 11569492 A JP11569492 A JP 11569492A JP H05314820 A JPH05314820 A JP H05314820A
- Authority
- JP
- Japan
- Prior art keywords
- transparent conductive
- conductive film
- indium
- tin
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はガラス，セラミックス等
の基板上に、透明導電膜を形成するための組成物および
透明導電膜の形成方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for forming a transparent conductive film on a substrate such as glass or ceramics and a method for forming the transparent conductive film.
【０００２】[0002]
【従来の技術】近年、液晶表示素子，エレクトロルミネ
ッセンス（ＥＬ）表示素子などの表示素子類の電極や、
自動車，航空機，建築物などの窓ガラスの防曇または氷
結防止のための発熱抵抗体において、可視光に対して高
透過性を有する電極材料が使用されている。2. Description of the Related Art In recent years, electrodes of display elements such as liquid crystal display elements and electroluminescence (EL) display elements,
2. Description of the Related Art An electrode material having high transparency to visible light is used in a heating resistor for preventing fogging or freezing of window glass of automobiles, aircraft, buildings and the like.
【０００３】従来、このような透明導電性材料として、
酸化スズ・酸化アンチモン系（ＡＴＯ）や酸化インジウ
ム・酸化スズ系（ＩＴＯ）などが知られており、これら
の金属酸化物はガラスまたはセラミック基板上に容易に
被膜を形成し、透明導電膜とすることができる。Conventionally, as such a transparent conductive material,
Known are tin oxide / antimony oxide (ATO) and indium oxide / tin oxide (ITO). These metal oxides easily form a film on a glass or ceramic substrate to form a transparent conductive film. be able to.
【０００４】このような透明導電膜の形成方法として
は、次の方法が知られている。すなわち、（１）真空蒸
着法，（２）スパッタリング法，（３）ＣＶＤ法，
（４）塗布法である。The following methods are known as methods for forming such a transparent conductive film. That is, (1) vacuum deposition method, (2) sputtering method, (3) CVD method,
(4) It is a coating method.
【０００５】[0005]
【発明が解決しようとする課題】しかし、上記の
（１），（２），（３）の方法は、装置が複雑かつ高価
で、コストと量産性に問題がある。また、（４）の方法
は、上記の（１），（２），（３）の方法の問題点を解
決する可能性を有しているものの、実用に耐えうる膜を
形成することが困難であった。However, the methods (1), (2), and (3) described above have problems in cost and mass productivity because the apparatus is complicated and expensive. Further, the method (4) has a possibility of solving the problems of the above methods (1), (2), and (3), but it is difficult to form a practically usable film. Met.
【０００６】例えば、無機スズ塩を内含する無機インジ
ウム塩溶液とイオン交換樹脂とを接触させて生成するイ
ンジウム・スズ・オキサイドゾル組成物より得られた膜
のシート抵抗は大きく、ピンホールを生じ易いなどの欠
点がある。また、硝酸インジウム，塩化インジウム，塩
化第２スズ等の無機化合物の有機溶液を使用した場合
は、形成された膜に白濁を生じたり、得られた膜の機械
的強度が不足で容易に傷がつく等の欠点がある。さら
に、オクチル酸インジウム等のイオン結合性の強い有機
酸インジウムを用いる方法においては、有機酸インジウ
ムが加水分解し易く、比較的容易に化学変化するため
に、塗布液のゲル化が生じる等の欠点がある。For example, the sheet resistance of a film obtained from an indium tin oxide sol composition produced by contacting an inorganic indium salt solution containing an inorganic tin salt with an ion exchange resin is large, and pinholes are generated. There are drawbacks such as being easy. Further, when an organic solution of an inorganic compound such as indium nitrate, indium chloride, or stannic chloride is used, the formed film becomes cloudy, or the mechanical strength of the obtained film is insufficient, so that the film is easily scratched. There are drawbacks such as sticking. Furthermore, in the method of using indium octoate or another organic acid indium having a strong ionic bond, the organic acid indium is easily hydrolyzed and undergoes a chemical change relatively easily. There is.
【０００７】本発明は上記課題を解決するもので、低抵
抗で高硬度の透明導電膜を安定して形成することが可能
な透明導電膜形成用組成物と透明導電膜の形成方法を提
供することを目的とする。The present invention solves the above problems, and provides a composition for forming a transparent conductive film and a method for forming a transparent conductive film, which enables a transparent conductive film having low resistance and high hardness to be stably formed. The purpose is to
【０００８】[0008]
【課題を解決するための手段】本発明は、上記目的を達
成するために、加水分解性のインジウム化合物とスズ化
合物と、酸化インジウムおよび酸化スズの微粒子とを含
む構成である。また、加水分解性のインジウム化合物と
スズ化合物を含む溶液に、酸化インジウムおよび酸化ス
ズの微粒子を加え、加熱処理して得たものを基板に塗布
・乾燥した後、焼成する形成方法である。In order to achieve the above object, the present invention comprises a hydrolyzable indium compound, a tin compound, and fine particles of indium oxide and tin oxide. In addition, it is a formation method in which fine particles of indium oxide and tin oxide are added to a solution containing a hydrolyzable indium compound and a tin compound, and a product obtained by heat treatment is applied to a substrate, dried, and then baked.
【０００９】[0009]
【作用】本発明は、上記した構成により加水分解性のイ
ンジウム化合物とスズ化合物を含む溶液に、酸化インジ
ウムおよび酸化スズの微粒子を加えることで、生成する
結晶粒の成長とその結合力向上を促すため、前記組成物
を塗布・乾燥して得られる被膜のシート抵抗の低下並び
に機械的強度を上げることができるものである。According to the present invention, by adding fine particles of indium oxide and tin oxide to a solution containing a hydrolyzable indium compound and tin compound according to the above-mentioned constitution, growth of crystal grains to be produced and improvement of bonding force thereof are promoted. Therefore, it is possible to reduce the sheet resistance and increase the mechanical strength of the coating film obtained by applying and drying the composition.
【００１０】[0010]
【実施例】以下に、本発明の実施例を詳細に説明する。EXAMPLES Examples of the present invention will be described in detail below.
【００１１】本実施例の透明導電膜形成用組成物は以下
のようにして合成される。用いる加水分解性のインジウ
ム化合物は、インジウムやスズと配位可能な有機化合物
と、置換できるような配位子を持つもので、例えば、硝
酸インジウム，塩化インジウム，インジウムエトキシド
等が挙げられ、さらに結晶水を有しているものが好まし
い。次に、このインジウム化合物に対して、インジウム
とスズに一部配位する有機化合物との混合は、それらの
中間化合物の形成を助け、加水分解速度の制御に有効で
ある。この時の有機化合物は、例えば、β−ジケトン
類，α−またはβ−ケトン酸類、前記ケトン酸類のエス
テル類、α−またはβ−アミノアルコール類が挙げられ
る。The transparent conductive film-forming composition of this example is synthesized as follows. The hydrolyzable indium compound used has an organic compound capable of coordinating with indium or tin and a ligand capable of substituting, and examples thereof include indium nitrate, indium chloride and indium ethoxide. Those having water of crystallization are preferable. Next, with respect to this indium compound, mixing of indium and an organic compound partially coordinating with tin assists the formation of an intermediate compound thereof and is effective in controlling the hydrolysis rate. Examples of the organic compound at this time include β-diketones, α- or β-ketone acids, esters of the ketone acids, and α- or β-amino alcohols.
【００１２】さらに、前記溶液に有機溶剤とスズ化合物
を加える。ここで、スズ化合物としては、空気中では比
較的安定であるが、加熱処理により容易に加水分解し易
いものであればよい。例えば、カルボン酸スズ，ジカル
ボン酸スズ，スズエトキシド等が挙げられるが、ギ酸ス
ズ，酢酸スズ，シュウ酸スズ等の炭素数が小さいものが
好ましい。また、前記有機溶剤としては、本実施例で用
いる有機化合物や無機化合物を溶解するものであればよ
い。例えば、トルエン，キシレン等の芳香族炭化水素，
エタノール，イソプロパノール等のアルコール類、酢酸
エチル，酢酸ブチル等の酢酸エステル類、アセトン，ジ
エチルケトン等のケトン類、メトキシエタノール，エト
キシエタノール等のエーテル類、テトラヒドロフラン等
が挙げられる。Further, an organic solvent and a tin compound are added to the solution. Here, the tin compound may be any compound that is relatively stable in the air but is easily hydrolyzed by heat treatment. Examples thereof include tin carboxylate, tin dicarboxylate, tin ethoxide, and the like, and those having a small carbon number such as tin formate, tin acetate, and tin oxalate are preferable. Further, the organic solvent may be one that dissolves the organic compound or the inorganic compound used in this example. For example, aromatic hydrocarbons such as toluene and xylene,
Examples thereof include alcohols such as ethanol and isopropanol, acetic acid esters such as ethyl acetate and butyl acetate, ketones such as acetone and diethyl ketone, ethers such as methoxyethanol and ethoxyethanol, and tetrahydrofuran.
【００１３】そして、これらの有機溶液に平均粒径が
０．１μｍ以下の酸化インジウムおよび酸化スズの微粒
子を分散させた有機溶液を加え、加熱処理する。この
時、酸化インジウムおよび酸化スズの微粒子の平均粒径
が０．２μｍ以上になると膜に亀裂を生じ易くなる。ま
た、加熱処理の温度としては、インジウム化合物とスズ
化合物と、それらと配位可能な有機化合物とからなる有
機溶液の還流温度もしくは還流温度付近が好ましい。Then, an organic solution in which fine particles of indium oxide and tin oxide having an average particle diameter of 0.1 μm or less are dispersed is added to these organic solutions, and heat treatment is performed. At this time, if the average particle size of the fine particles of indium oxide and tin oxide is 0.2 μm or more, the film is likely to crack. The temperature of the heat treatment is preferably at or near the reflux temperature of an organic solution containing an indium compound, a tin compound, and an organic compound capable of coordinating with them.
【００１４】最後に加熱処理後の有機溶液を室温付近ま
で冷却し、多価アルコール類を加えて、混合した有機溶
液を透明導電膜形成用組成物とする。ここで、多価アル
コール類は、有機溶液の増粘効果と、透明導電膜形成用
組成物を基板に塗布・乾燥して得られる被膜の安定性を
与えるものであり、例えばグリコール類や３価のアルコ
ール類が挙げられるが、炭素数が小さく、熱分解時の炭
素残留の恐れの少ない、エチレングリコールやグリセリ
ンが好ましい。Finally, the organic solution after the heat treatment is cooled to around room temperature, polyhydric alcohols are added, and the mixed organic solution is used as a composition for forming a transparent conductive film. Here, the polyhydric alcohol provides the thickening effect of the organic solution and the stability of the coating film obtained by coating and drying the composition for forming a transparent conductive film on the substrate. Examples of alcohols include ethylene glycol and glycerin, which have a small number of carbon atoms and are less likely to cause carbon residue during thermal decomposition.
【００１５】このようにして、得られた透明導電膜形成
用組成物を基板に塗布・乾燥した後、焼成して、透明導
電膜を形成する。ここで、透明導電膜形成用組成物の塗
布には、スクリーン印刷法，ロールコート法，ディップ
コート法，スピンコート法等を用いることができるが、
ディップコート法，スピンコート法が好ましい。また、
焼成温度としては、透明導電膜形成用組成物が分解する
温度以上で、かつ基板の変形温度以下であればよく、４
００〜７００℃が好ましい。The composition for forming a transparent conductive film thus obtained is applied to a substrate, dried, and then baked to form a transparent conductive film. Here, a screen printing method, a roll coating method, a dip coating method, a spin coating method, or the like can be used to apply the composition for forming the transparent conductive film.
The dip coating method and the spin coating method are preferable. Also,
The firing temperature may be higher than the decomposition temperature of the composition for forming a transparent conductive film and lower than the deformation temperature of the substrate.
The temperature is preferably 00 to 700 ° C.
【００１６】以下、本発明をさらに詳細な実施例によっ
て説明するが、本発明はこれらの実施例によって限定さ
れるものではない。Hereinafter, the present invention will be described with reference to more detailed examples, but the present invention is not limited to these examples.
【００１７】（実施例１）三角フラスコに、４５ｇの硝
酸インジウム（化１）を秤量し、５０ｇのアセチルアセ
トンを加えて、室温で混合・溶解させた。その溶液に
８．１ｇ［（数２）で３０ｗｔ％］のシュウ酸第１スズ
（化２）とアセトンを加え、さらに、酸化インジウムお
よび酸化スズの微粒子（平均粒径：０．０１μｍ程度）
を２ｇ分散させた有機溶液を加えて還流した。そして、
その還流後の溶液を、室温まで冷却し、１０ｇのグリセ
リンを加えて、撹拌・混合し透明導電膜形成用組成物を
合成した。その透明導電膜形成用組成物に、ＳｉＯ2コ
ート並ガラス基板を６０cm／minの引き上げ速度でディ
ップコートした。その基板を５分間室音で放置し、１０
０℃で５分間乾燥した後、５００℃で１時間焼成した。
得られた膜の厚みは０．０６μｍである。(Example 1) 45 g of indium nitrate (Chemical Formula 1) was weighed in an Erlenmeyer flask, 50 g of acetylacetone was added, and they were mixed and dissolved at room temperature. To the solution was added 8.1 g [(Numerical formula 2) 30 wt%] stannous oxalate (Chemical Formula 2) and acetone, and fine particles of indium oxide and tin oxide (average particle size: about 0.01 μm).
2 g of an organic solution dispersed therein was added and refluxed. And
The solution after the reflux was cooled to room temperature, 10 g of glycerin was added, and the mixture was stirred and mixed to synthesize a composition for forming a transparent conductive film. The transparent conductive film-forming composition was dip-coated with a SiO 2 -coated glass substrate at a pulling rate of 60 cm / min. Leave the substrate in the room sound for 5 minutes, then 10
After drying at 0 ° C. for 5 minutes, it was baked at 500 ° C. for 1 hour.
The thickness of the obtained film is 0.06 μm.
【００１８】表面硬度は表面硬さ試験によって測定し、
用いたダイヤモンドの針は０．０５mmRで荷重を１０ｇ
とした。The surface hardness is measured by a surface hardness test,
The diamond needle used is 0.05 mmR and the load is 10 g.
And
【００１９】[0019]
【数２】 [Equation 2]
【００２０】[0020]
【化１】 [Chemical 1]
【００２１】[0021]
【化２】 [Chemical 2]
【００２２】（実施例２）無機インジウム化合物とし
て、塩化インジウム（化３）を、有機スズ化合物とし
て、シュウ酸第１スズを用い、（数２）で１０ｗｔ％と
なるようにした。他は実施例１と同じ条件である。Example 2 Indium chloride (Chemical Formula 3) was used as the inorganic indium compound, and stannous oxalate was used as the organic tin compound, and the content was set to 10 wt% in (Equation 2). The other conditions are the same as in Example 1.
【００２３】[0023]
【化３】 [Chemical 3]
【００２４】（比較例１）酸化インジウムおよび酸化ス
ズの微粒子を添加しない他は実施例１と同じ条件であ
る。(Comparative Example 1) The conditions are the same as in Example 1 except that fine particles of indium oxide and tin oxide are not added.
【００２５】（比較例２）酸化インジウムおよび酸化ス
ズの微粒子の平均粒径０．２μｍのものを用いた。他は
実施例１と同じ条件である。Comparative Example 2 Indium oxide and tin oxide fine particles having an average particle diameter of 0.2 μm were used. The other conditions are the same as in Example 1.
【００２６】（表１）に実施例１，２、比較例１，２の
結果を示す。Table 1 shows the results of Examples 1 and 2 and Comparative Examples 1 and 2.
【００２７】[0027]
【表１】 [Table 1]
【００２８】[0028]
【発明の効果】以上の説明から明らかなように、本発明
の透明導電膜形成用組成物と透明導電膜の形成方法を用
いることにより、導電性に優れ、表面硬度の高い透明導
電膜を容易にかつ安価で得ることができ、表示素子や発
熱抵抗体等の透明電極等の用途に適するものを提供でき
る。As is apparent from the above description, by using the composition for forming a transparent conductive film of the present invention and the method for forming a transparent conductive film, a transparent conductive film having excellent conductivity and high surface hardness can be easily formed. In addition, it can be obtained at low cost, and it is possible to provide a display element, a transparent electrode such as a heating resistor, or the like suitable for use.
Claims (4)
合物と、スズ化合物と、微粒子である酸化インジウムお
よび酸化スズを含むことを特徴とする透明導電膜形成用
組成物。1. A composition for forming a transparent conductive film comprising at least a hydrolyzable indium compound, a tin compound, and fine particles of indium oxide and tin oxide.
ウムおよび酸化スズの微粒子であることを特徴とする請
求項１記載の透明導電膜形成用組成物。2. The composition for forming a transparent conductive film according to claim 1, which is fine particles of indium oxide and tin oxide having an average particle diameter of 0.1 μm or less.
（数１）で５〜２０ｗｔ％の範囲にあることを特徴とす
る請求項１記載の透明導電膜形成用組成物。 【数１】 3. The compounding ratio of tin to indium is
The composition for forming a transparent conductive film according to claim 1, which is in the range of 5 to 20 wt% in (Equation 1). [Equation 1]
合物とスズ化合物を含む溶液に、酸化インジウムおよび
酸化スズの微粒子を含む溶液を加え、加熱処理して得ら
れる透明導電膜形成用組成物を、基板に塗布・乾燥した
後、焼成することを特徴とする透明導電膜の形成方法。4. A transparent conductive film forming composition obtained by adding a solution containing fine particles of indium oxide and tin oxide to a solution containing at least a hydrolyzable indium compound and a tin compound and subjecting the solution to heat treatment. A method for forming a transparent conductive film, which comprises coating, drying, and baking.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4115694A JPH05314820A (en) | 1992-05-08 | 1992-05-08 | Composition for forming transparent conductive film and formation of transparent conductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4115694A JPH05314820A (en) | 1992-05-08 | 1992-05-08 | Composition for forming transparent conductive film and formation of transparent conductive film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05314820A true JPH05314820A (en) | 1993-11-26 |
Family
ID=14668930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4115694A Pending JPH05314820A (en) | 1992-05-08 | 1992-05-08 | Composition for forming transparent conductive film and formation of transparent conductive film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05314820A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4142867A1 (en) * | 1990-12-28 | 1992-07-02 | Shimano Kk | CLOSED DEVICE WITH SEVERAL SPEED LEVELS WITH PLANETARY GEARBOX FOR BICYCLES |
| DE4143603C2 (en) * | 1990-12-28 | 1998-08-27 | Shimano Kk | Planetary change speed bicycle hub gearing |
| EP1031642A1 (en) * | 1999-02-26 | 2000-08-30 | Agfa-Gevaert N.V. | Conductive metal oxide based layer |
| DE202008005553U1 (en) | 2008-04-22 | 2008-08-14 | Evonik Degussa Gmbh | Highly conductive, transparent metal oxide layers by plasma immersion |
| DE102007013181A1 (en) | 2007-03-20 | 2008-09-25 | Evonik Degussa Gmbh | Transparent, electrically conductive layer, a process for the preparation of the layer and the use |
| JP2011216319A (en) * | 2010-03-31 | 2011-10-27 | Teijin Ltd | Transparent conductive laminate and method for manufacturing the same |
-
1992
- 1992-05-08 JP JP4115694A patent/JPH05314820A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4142867A1 (en) * | 1990-12-28 | 1992-07-02 | Shimano Kk | CLOSED DEVICE WITH SEVERAL SPEED LEVELS WITH PLANETARY GEARBOX FOR BICYCLES |
| DE4143603C2 (en) * | 1990-12-28 | 1998-08-27 | Shimano Kk | Planetary change speed bicycle hub gearing |
| EP1031642A1 (en) * | 1999-02-26 | 2000-08-30 | Agfa-Gevaert N.V. | Conductive metal oxide based layer |
| DE102007013181A1 (en) | 2007-03-20 | 2008-09-25 | Evonik Degussa Gmbh | Transparent, electrically conductive layer, a process for the preparation of the layer and the use |
| US7867606B2 (en) | 2007-03-20 | 2011-01-11 | Evonik Degussa Gmbh | Transparent, electrically conductive layer, a process for producing the layer and its use |
| US8137794B2 (en) | 2007-03-20 | 2012-03-20 | Evonik Degussa Gmbh | Transparent electrically conductive layer, a process for producing the layer and its use |
| DE202008005553U1 (en) | 2008-04-22 | 2008-08-14 | Evonik Degussa Gmbh | Highly conductive, transparent metal oxide layers by plasma immersion |
| JP2011216319A (en) * | 2010-03-31 | 2011-10-27 | Teijin Ltd | Transparent conductive laminate and method for manufacturing the same |
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