JPH11279437A - Coating solution for forming transparent electroconductive film and formation of transparent electroconductive film - Google Patents
Coating solution for forming transparent electroconductive film and formation of transparent electroconductive filmInfo
- Publication number
- JPH11279437A JPH11279437A JP7969198A JP7969198A JPH11279437A JP H11279437 A JPH11279437 A JP H11279437A JP 7969198 A JP7969198 A JP 7969198A JP 7969198 A JP7969198 A JP 7969198A JP H11279437 A JPH11279437 A JP H11279437A
- Authority
- JP
- Japan
- Prior art keywords
- transparent conductive
- forming
- conductive film
- coating solution
- transparent electroconductive
- 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.)
- Granted
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 34
- 238000000576 coating method Methods 0.000 title claims abstract description 34
- 230000015572 biosynthetic process Effects 0.000 title claims description 3
- 239000012789 electroconductive film Substances 0.000 title abstract 7
- 238000000034 method Methods 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 22
- SBFKENUEAOCRNR-UHFFFAOYSA-K indium(3+);triformate Chemical compound [In+3].[O-]C=O.[O-]C=O.[O-]C=O SBFKENUEAOCRNR-UHFFFAOYSA-K 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 8
- CSQOEEDPEGAXNJ-UHFFFAOYSA-L tin(2+);diformate Chemical compound [Sn+2].[O-]C=O.[O-]C=O CSQOEEDPEGAXNJ-UHFFFAOYSA-L 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- -1 butyltin diformate Chemical compound 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 69
- FQXRKFOIAIEUHB-UHFFFAOYSA-L [dibutyl(formyloxy)stannyl] formate Chemical compound CCCC[Sn](OC=O)(OC=O)CCCC FQXRKFOIAIEUHB-UHFFFAOYSA-L 0.000 abstract description 4
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 abstract 1
- 150000003606 tin compounds Chemical class 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 5
- 229910052738 indium Inorganic materials 0.000 description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 150000002472 indium compounds Chemical class 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- ARHIRDSNQLUBHR-UHFFFAOYSA-K 2-ethylhexanoate;indium(3+) Chemical compound [In+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O ARHIRDSNQLUBHR-UHFFFAOYSA-K 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Manufacturing Of Electric Cables (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Paints Or Removers (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は液晶表示素子やタッ
チパネル等の各種エレクトロニクス素子に好適に用いら
れる透明導電膜形成用塗布液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 coating solution for forming a transparent conductive film and a method for forming a transparent conductive film, which are suitably used for various electronic devices such as a liquid crystal display device and a touch panel.
【０００２】[0002]
【従来の技術】従来より、透明導電膜は液晶表示素子、
タッチパネル、電磁波シールド材、赤外線反射膜等に広
く使用されている。透明導電膜としては錫をドープした
酸化インジウム膜（ＩＴＯ）、アンチモンをドープした
酸化スズ膜（ＡＴＯ）等があり、これらは蒸着法やスパ
ッタ法、焼成法（塗布熱分解法とも言う）等により形成
されていた。2. Description of the Related Art Conventionally, a transparent conductive film has been used for a liquid crystal display element,
Widely used for touch panels, electromagnetic wave shielding materials, infrared reflection films, etc. Examples of the transparent conductive film include a tin-doped indium oxide film (ITO) and an antimony-doped tin oxide film (ATO), which are formed by a vapor deposition method, a sputtering method, a baking method (also referred to as a coating thermal decomposition method), or the like. Had been formed.
【０００３】[0003]
【発明が解決しようとする課題】透明導電膜の形成方法
の中で蒸着法及びスパッタ法は、気相中で目的物質を基
板に堆積させて膜を成長させるものであり、真空容器を
使用するため装置が大がかりで高価なうえ、生産性が悪
く、又、大面積の成膜が困難なものであった。これに対
し焼成法は、スピンコート法やディップコート法、印刷
法などにより基材に目的物質の前駆物質を塗布し、これ
を焼成（熱分解）することで膜を形成するものであり、
装置が簡単で生産性に優れ、大面積の成膜が容易である
という利点があるが、通常焼成時に４００℃から５００
℃の高温処理を必要とするため基材が限られてしまうと
いう問題点を有していた。Among the methods for forming a transparent conductive film, vapor deposition and sputtering are methods for depositing a target substance on a substrate in a gaseous phase to grow a film, and use a vacuum vessel. Therefore, the apparatus is large and expensive, the productivity is low, and it is difficult to form a large-area film. On the other hand, in the firing method, a precursor of a target substance is applied to a base material by a spin coating method, a dip coating method, a printing method, and the like, and is fired (thermally decomposed) to form a film.
There are advantages that the apparatus is simple, excellent in productivity, and easy to form a large-area film.
There is a problem that the base material is limited due to the necessity of high-temperature treatment at ℃.
【０００４】この問題点を解決するための手段として、
特開平９−８６９６７号公報に開示されたようにＩＴＯ
微粒子がシリケートマトリックス中に分散した膜を２０
０℃以下で成膜している例があるが、これはエッチング
等によるパターンニングが困難であり液晶表示素子等の
用途には適していなかった。As a means for solving this problem,
As disclosed in Japanese Patent Application Laid-Open No. 9-86967, ITO
A film in which fine particles are dispersed in a silicate matrix
Although there is an example in which a film is formed at 0 ° C. or lower, it is difficult to perform patterning by etching or the like, and it is not suitable for applications such as a liquid crystal display device.
【０００５】従って本発明の目的は、以上のような問題
点を解消し、広範な種類の基板を使用可能な２００℃程
度の低温での焼成でも透明導電膜を形成することのでき
る透明導電膜形成用塗布液、及び透明導電膜の形成方法
を提供することにある。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems and to form a transparent conductive film capable of forming a transparent conductive film by firing at a low temperature of about 200 ° C. in which a wide variety of substrates can be used. An object of the present invention is to provide a coating solution for formation and a method for forming a transparent conductive film.
【０００６】[0006]
【課題を解決するための手段】即ち本発明は、蟻酸イン
ジウム及び有機錫化合物を溶媒に溶解してなる透明導電
膜形成用塗布液である。また本発明は、有機錫化合物
が、蟻酸錫（II）、ジｎ−ブチル錫ジ蟻酸塩、テトライ
ソプロポキシ錫及びテトラｔ−ブチル錫からなる群より
選択される１種又は２種以上の有機錫化合物である前記
の透明導電膜形成用塗布液である。さらに本発明は、有
機錫化合物がテトラｔ−ブチル錫である前記の透明導電
膜形成用塗布液である。さらにまた本発明は、溶媒が
Ｎ，Ｎ−ジメチルホルムアミドである前記の透明導電膜
形成用塗布液である。また本発明は、前記の透明導電膜
形成用塗布液を基板上に塗布し、熱処理することにより
透明導電膜を形成することを特徴とする透明導電膜の形
成方法である。さらに本発明は、熱処理が１９０℃〜３
５０℃の温度範囲である前記の透明導電膜の形成方法で
ある。さらにまた本発明は、熱処理の前に、蟻酸インジ
ウム及び有機錫化合物が熱分解しない温度で予備乾燥す
る前記の透明導電膜の形成方法である。That is, the present invention provides a coating solution for forming a transparent conductive film, which is obtained by dissolving indium formate and an organotin compound in a solvent. Further, the present invention provides the organic tin compound, wherein the organic tin compound is one or more organic tin compounds selected from the group consisting of tin (II) formate, di-n-butyltin diformate, tetraisopropoxytin and tetra-t-butyltin. The transparent conductive film forming coating liquid is a tin compound. Furthermore, the present invention is the above-mentioned coating solution for forming a transparent conductive film, wherein the organotin compound is tetra-t-butyltin. Furthermore, the present invention is the above-mentioned coating liquid for forming a transparent conductive film, wherein the solvent is N, N-dimethylformamide. Further, the present invention is a method for forming a transparent conductive film, which comprises applying the above-mentioned coating liquid for forming a transparent conductive film on a substrate and subjecting it to a heat treatment to form the transparent conductive film. Further, the present invention provides that the heat treatment is performed at 190 ° C to 3 ° C.
This is the method for forming a transparent conductive film described above, which has a temperature range of 50 ° C. Still further, the present invention is the above-mentioned method for forming a transparent conductive film, which is preliminarily dried at a temperature at which indium formate and an organotin compound do not thermally decompose before heat treatment.
【０００７】[0007]
【発明の実施の形態】本発明の塗布液に使用する蟻酸イ
ンジウムは、室温空気中で安定であり、２００℃程度に
加熱すると熱分解して結晶性の酸化インジウムとなるの
で、焼成法による塗布液の成分として適している。又、
透明導電膜は膜の特性として硬度の高いものが好ましい
が、蟻酸インジウムを使用して得られる透明導電膜は、
２００℃程度で熱分解する蟻酸インジウム以外のインジ
ウム化合物を使用した場合に比べて硬度の高い良好な透
明導電膜となる。DESCRIPTION OF THE PREFERRED EMBODIMENTS Indium formate used in the coating solution of the present invention is stable in air at room temperature and is thermally decomposed into crystalline indium oxide when heated to about 200 ° C. Suitable as a liquid component. or,
The transparent conductive film preferably has high hardness as a film property, but the transparent conductive film obtained by using indium formate is
A good transparent conductive film having a higher hardness than when using an indium compound other than indium formate that thermally decomposes at about 200 ° C. is used.
【０００８】本発明の塗布液に使用する有機錫化合物と
しては２００℃程度若しくはそれ以下の温度で熱分解し
て結晶性の酸化錫となるものであればどのような化合物
でもよいが、例えば、錫のアルコキシド、錫の有機酸
塩、及び錫の各種有機錯体等を挙げることができる。こ
のような有機錫化合物として特に好ましいのは、例え
ば、蟻酸錫（II）、ジｎ−ブチル錫ジ蟻酸塩、テトライ
ソプロポキシ錫、テトラｔ−ブチル錫を挙げることがで
きる。良好な導電性を得る点で最も好ましいのはテトラ
ｔ−ブチル錫である。The organotin compound used in the coating solution of the present invention may be any compound as long as it can be decomposed into crystalline tin oxide by thermal decomposition at a temperature of about 200 ° C. or lower. Examples thereof include alkoxides of tin, organic acid salts of tin, and various organic complexes of tin. Particularly preferable examples of such an organic tin compound include tin (II) formate, di-n-butyltin diformate, tetraisopropoxytin, and tetra-t-butyltin. Most preferred in terms of obtaining good conductivity is tetra-t-butyltin.
【０００９】本発明の塗布液中のインジウムと錫の元素
数比率は、最終的に形成された透明導電膜中のインジウ
ムと錫の比となるので、透明導電膜を得るに当たって所
望とする透明導電膜中のインジウムと錫の比となるよう
に、塗布液に使用する蟻酸インジウム及び有機錫化合物
の割合を選択すればが良い。Since the element ratio of indium and tin in the coating liquid of the present invention is the ratio of indium to tin in the finally formed transparent conductive film, the desired transparent conductive film is obtained in obtaining the transparent conductive film. What is necessary is just to select the ratio of the indium formate and the organic tin compound used in the coating liquid so that the ratio of indium to tin in the film is obtained.
【００１０】本発明の塗布液に使用する溶媒としては、
蟻酸インジウムと上記有機錫化合物の両方の化合物を溶
解、好ましくは室温付近で溶解でき、且つ熱処理時に蟻
酸インジウム、上記有機錫化合物と反応しない、若しく
は反応し難い難いものであれば任意に選ぶことができ
る。尚、ここで言う「溶解」とは溶解させようとする温
度における溶解度が概ね５（ｇ／１００ｇ）以上である
ことを意味する。このような溶媒として好ましいものと
しては、例えば、Ｎ，Ｎ−ジメチルホルムアミドを挙げ
ることができる。The solvent used in the coating solution of the present invention includes:
Dissolve both the indium formate and the organotin compound, preferably at room temperature, and can be arbitrarily selected as long as it does not react with the indium formate, the organotin compound during the heat treatment, or hardly reacts. it can. Here, "dissolution" as used herein means that the solubility at the temperature at which the dissolution is to be performed is generally 5 (g / 100 g) or more. Preferred examples of such a solvent include N, N-dimethylformamide.
【００１１】本発明の塗布液における、蟻酸インジウム
と上記有機錫化合物の濃度は、蟻酸インジウムと有機錫
化合物の比率は上記の通りであるので、ここでは蟻酸イ
ンジウムと上記有機錫化合物の合計量の濃度で表すこと
にする。蟻酸インジウムと上記有機錫化合物の合計量の
濃度は、従来の焼成法による透明導電膜形成用塗布液中
のインジウム化合物と錫化合物の濃度と同程度とすれば
支障無いが、例えば、概ね５〜３０重量％であればよ
く、良好な成膜性を得る点で好ましくは５〜１５重量％
とするのが良い。In the coating solution of the present invention, the concentration of indium formate and the above-mentioned organotin compound is the same as that of the total amount of indium formate and the above-mentioned organotin compound because the ratio of indium formate to the organotin compound is as described above. It will be expressed as concentration. The concentration of the total amount of indium formate and the organotin compound is not hindered as long as the concentration of the indium compound and the tin compound in the coating solution for forming a transparent conductive film by a conventional baking method is approximately the same, for example, approximately 5 to 5. The content may be 30% by weight, and preferably 5 to 15% by weight from the viewpoint of obtaining good film forming properties.
Good to be.
【００１２】本発明の透明導電膜の形成方法は、上記塗
布液を基板上に塗布し、熱処理することにより透明導電
膜を形成するものである。In the method of forming a transparent conductive film according to the present invention, the above-mentioned coating solution is applied on a substrate and heat-treated to form a transparent conductive film.
【００１３】ここに使用する基板としては、熱処理温度
に耐え、かつ使用する溶媒に対して耐性のあるもので有
れば任意に選ぶことができ、従来透明導電膜の形成に使
用されている基板を使用することができる。例えば、無
アルカリガラス基板等のガラス基板は透明導電膜の基板
として普及しており、これを使用できる。The substrate used here can be arbitrarily selected as long as it can withstand the heat treatment temperature and is resistant to the solvent to be used. Can be used. For example, a glass substrate such as a non-alkali glass substrate is widely used as a transparent conductive film substrate, and can be used.
【００１４】本発明の透明導電膜の形成方法における熱
処理は、大気中、本発明に使用する上記蟻酸インジウム
と有機錫化合物の有効な熱分解が可能な温度で行えばよ
いが、広範な種類の基板を使用可能であるという本発明
の効果を得るためには、好ましくは大気中１９０℃〜３
５０℃、好ましくは１９０℃〜２５０℃の温度範囲で行
えば良い。このような温度範囲では上記のガラス基板だ
けでなく、ポリイミド、ポリアリレート、ポリアリール
スルホン、ポリアリーレンスルフィド等の材料も基板と
して好ましく使用できる。The heat treatment in the method for forming a transparent conductive film of the present invention may be performed in the atmosphere at a temperature at which the above-mentioned indium formate and organotin compound used in the present invention can be effectively thermally decomposed. In order to obtain the effect of the present invention that the substrate can be used, it is preferable that the temperature is 190 ° C. to 3 ° C.
The heat treatment may be performed at a temperature of 50 ° C, preferably 190 ° C to 250 ° C. In such a temperature range, not only the above-mentioned glass substrate but also materials such as polyimide, polyarylate, polyarylsulfone, and polyarylene sulfide can be preferably used as the substrate.
【００１５】尚、本発明の透明導電膜の形成方法は、従
来より低温で熱処理することができるが、基板材料の選
択に制限が無いなど、高温（例えば、従来使用されてき
た４００〜５００℃等）での熱処理に耐え得る基板が使
用可能であれば、このような高温で熱処理するにあたり
何ら支障はなく、この場合、得られる透明導電膜はより
低い抵抗値が得られるので、上記本発明の塗布液は従来
法のような高温での熱処理での使用に際しても優れた効
果を発揮する。In the method of forming a transparent conductive film of the present invention, the heat treatment can be performed at a lower temperature than in the past, but there is no limitation on the selection of the substrate material. If a substrate that can withstand the heat treatment in (1) can be used, there is no problem in performing the heat treatment at such a high temperature. In this case, the obtained transparent conductive film can obtain a lower resistance value. The coating liquid of the formula (1) exhibits an excellent effect when used in a heat treatment at a high temperature as in the conventional method.
【００１６】また、本発明の透明導電膜の形成方法は、
熱処理の前に１００℃程度の蟻酸インジウム化合物及び
有機錫化合物が熱分解しない温度で予備乾燥した方がよ
り平滑な膜面を得ることができるので好ましい。Further, the method for forming a transparent conductive film of the present invention comprises:
Prior to the heat treatment, predrying at about 100 ° C. at a temperature at which the indium formate compound and the organotin compound do not thermally decompose is preferable because a smoother film surface can be obtained.
【００１７】[0017]
【実施例】以下、実施例および比較例により本発明をさ
らに説明する。 実施例１ 蟻酸インジウム及び蟻酸錫（II）を、合計で１０重量％
となるようにＮ，Ｎ−ジメチルホルムアミドに溶解させ
て塗布液とした。蟻酸インジウムと蟻酸錫（II）の比率
は、インジウムと錫の元素数含有比率が、９０：１０と
なるように調節した。この塗布液を無アルカリガラス基
板上にスピンコート法で塗布し、１００℃で１０分間乾
燥させた後、大気中で２００℃で６０分間熱処理して透
明導電膜を得た。得られた膜の特性を下記表１に示す。The present invention will be further described below with reference to examples and comparative examples. Example 1 A total of 10% by weight of indium formate and tin (II) formate
Was dissolved in N, N-dimethylformamide to give a coating solution. The ratio between indium formate and tin (II) formate was adjusted so that the content ratio of element number between indium and tin was 90:10. This coating solution was applied on a non-alkali glass substrate by spin coating, dried at 100 ° C. for 10 minutes, and then heat-treated at 200 ° C. for 60 minutes in the air to obtain a transparent conductive film. The properties of the obtained film are shown in Table 1 below.
【００１８】実施例２ 有機錫化合物としてジｎ−ブチル錫ジ蟻酸塩を使用した
以外は、実施例１と同様にして透明導電膜を得た。得ら
れた膜の特性を下記表１に示す。Example 2 A transparent conductive film was obtained in the same manner as in Example 1 except that di-n-butyltin diformate was used as the organotin compound. The properties of the obtained film are shown in Table 1 below.
【００１９】実施例３ 有機錫化合物としてテトライソプロポキシ錫を使用した
以外は、実施例１と同様にして透明導電膜を得た。得ら
れた膜の特性を下記表１に示す。Example 3 A transparent conductive film was obtained in the same manner as in Example 1, except that tetraisopropoxytin was used as the organotin compound. The properties of the obtained film are shown in Table 1 below.
【００２０】実施例４ 有機錫化合物としてテトラｔ−ブチル錫を使用した以外
は、実施例１と同様にして透明導電膜を得た。得られた
膜の特性を下記表１に示す。Example 4 A transparent conductive film was obtained in the same manner as in Example 1, except that tetra-t-butyltin was used as the organotin compound. The properties of the obtained film are shown in Table 1 below.
【００２１】実施例５ 熱処理温度を２３０℃とした以外は、実施例４と同様に
して透明導電膜を得た。得られた膜の特性を下記表１に
示す。Example 5 A transparent conductive film was obtained in the same manner as in Example 4 except that the heat treatment temperature was 230 ° C. The properties of the obtained film are shown in Table 1 below.
【００２２】実施例６ 基板の材質をポリイミドとした以外は、実施例５と同様
にして透明導電膜を得た。得られた膜の特性を下記表１
に示す。Example 6 A transparent conductive film was obtained in the same manner as in Example 5, except that the substrate was made of polyimide. Table 1 below shows the properties of the obtained film.
Shown in
【００２３】実施例７ 熱処理温度を５００℃とした以外は、実施例１と同様に
して透明導電膜を得た。得られた膜の特性を下記表１に
示す。Example 7 A transparent conductive film was obtained in the same manner as in Example 1 except that the heat treatment temperature was changed to 500 ° C. The properties of the obtained film are shown in Table 1 below.
【００２４】比較例１ ２−エチルヘキサン酸インジウム及び２−エチルヘキサ
ン酸錫を、１０重量％となるようにキシレンに溶解させ
て塗布液とした。この塗布液を無アルカリガラス基板上
にスピンコート法で塗布し、１００℃で１０分間乾燥さ
せた後、大気中で２００℃で６０分間熱処理したが、イ
ンジウム及び錫化合物の熱分解が起こらず、透明導電膜
は得られなかった。Comparative Example 1 Indium 2-ethylhexanoate and tin 2-ethylhexanoate were dissolved in xylene so as to be 10% by weight to prepare a coating solution. This coating solution was applied on an alkali-free glass substrate by a spin coating method, dried at 100 ° C. for 10 minutes, and then heat-treated at 200 ° C. for 60 minutes in the air. However, thermal decomposition of indium and tin compounds did not occur. No transparent conductive film was obtained.
【００２５】[0025]
【表１】 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ シート抵抗値 透過率 鉛筆硬度 外観 （Ω／□） （％） ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 実施例１ ４．２×１０5 88.5 ９Ｈ 良好 実施例２ ２．０×１０5 88.7 ９Ｈ 良好 実施例３ ４．８×１０5 88.5 ９Ｈ 良好 実施例４ ７．１×１０4 89.7 ９Ｈ 良好 実施例５ １．０×１０4 88.4 ９Ｈ 良好 実施例６ ４．９×１０4 73.3 ９Ｈ 良好 実施例７ ４．５×１０3 89.9 ９Ｈ 良好 比較例１ 透明導電膜は得られなかった ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ （透過率は基板込みの値である） なお、透過率の測定は、（株）日立製作所製Ｕ−１１０
０形分光光度計を用いて、波長５５０ｎｍにおける透明
導電膜及び基材の透過率を読み取った。[Table 1] 抵抗 Sheet resistance Transmittance Pencil hardness Appearance (Ω / □) (%) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 1 4.2 × 10 5 88.5 9H Good Example 2 2.0 × 10 5 88.7 9H Good Example 3 4.8 × 10 5 88.5 9H Good Example 4 7.1 × 10 4 89.7 9H Good Example 5 1.0 × 10 4 88.4 9H Good Example 6 4.9 × 10 4 73.3 9H good Example 7 4.5 × 10 3 89.9 9H good Comparative Example 1 No transparent conductive film was obtained. (Transmittance is a value including the substrate.) The transmittance was measured by U-110 manufactured by Hitachi, Ltd.
The transmittance of the transparent conductive film and the substrate at a wavelength of 550 nm was read using a 0-type spectrophotometer.
【００２６】[0026]
【発明の効果】本発明の効果は、従来の方法の問題とな
っている真空容器を使用せず大面積の成膜が容易に行
え、広範な種類の基板に対し使用可能な２００℃程度の
低温での焼成でも透明導電膜を形成することのできる透
明導電膜形成用塗布液、及び透明導電膜の形成方法を提
供したことにある。また、本発明によれば、膜特性の良
好な透明導電膜を簡便にしかも低温で得られるという効
果がある。The effect of the present invention is that a large-area film can be easily formed without using a vacuum vessel, which is a problem of the conventional method, and a temperature of about 200 ° C. which can be used for a wide variety of substrates. It is an object of the present invention to provide a transparent conductive film forming coating solution capable of forming a transparent conductive film even by firing at a low temperature, and a method for forming a transparent conductive film. Further, according to the present invention, there is an effect that a transparent conductive film having good film properties can be easily obtained at a low temperature.
Claims (7)
に溶解してなる透明導電膜形成用塗布液。1. A coating liquid for forming a transparent conductive film, comprising indium formate and an organotin compound dissolved in a solvent.
ブチル錫ジ蟻酸塩、テトライソプロポキシ錫及びテトラ
ｔ−ブチル錫からなる群より選択される１種又は２種以
上の有機錫化合物である請求項１に記載の透明導電膜形
成用塗布液。2. The method according to claim 1, wherein the organotin compound is tin (II) formate, di-n-
The coating liquid for forming a transparent conductive film according to claim 1, wherein the coating liquid is one or more kinds of organotin compounds selected from the group consisting of butyltin diformate, tetraisopropoxytin and tetra-t-butyltin.
る請求項２に記載の透明導電膜形成用塗布液。3. The coating solution for forming a transparent conductive film according to claim 2, wherein the organotin compound is tetra-t-butyltin.
ある請求項１ないし３のいずれか１項に記載の透明導電
膜形成用塗布液。4. The coating solution for forming a transparent conductive film according to claim 1, wherein the solvent is N, N-dimethylformamide.
明導電膜形成用塗布液を基板上に塗布し、熱処理するこ
とにより透明導電膜を形成することを特徴とする透明導
電膜の形成方法。5. A transparent conductive film formed by applying the coating liquid for forming a transparent conductive film according to any one of claims 1 to 4 on a substrate and performing heat treatment. Formation method.
である請求項５に記載の透明導電膜の形成方法。6. The method for forming a transparent conductive film according to claim 5, wherein the heat treatment is performed in a temperature range of 190 ° C. to 350 ° C.
錫化合物が熱分解しない温度で予備乾燥する請求項５ま
たは６に記載の透明導電膜の形成方法。7. The method for forming a transparent conductive film according to claim 5, wherein before the heat treatment, preliminary drying is performed at a temperature at which the indium formate and the organotin compound do not thermally decompose.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7969198A JP4161086B2 (en) | 1998-03-26 | 1998-03-26 | Transparent conductive film forming coating liquid and transparent conductive film forming method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7969198A JP4161086B2 (en) | 1998-03-26 | 1998-03-26 | Transparent conductive film forming coating liquid and transparent conductive film forming method |
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| Publication Number | Publication Date |
|---|---|
| JPH11279437A true JPH11279437A (en) | 1999-10-12 |
| JP4161086B2 JP4161086B2 (en) | 2008-10-08 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7416695B2 (en) | 2001-06-15 | 2008-08-26 | Kaneka Corporation | Semiconductive polymide film and process for production thereof |
-
1998
- 1998-03-26 JP JP7969198A patent/JP4161086B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7416695B2 (en) | 2001-06-15 | 2008-08-26 | Kaneka Corporation | Semiconductive polymide film and process for production thereof |
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| Publication number | Publication date |
|---|---|
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