JPH07242842A - Composition for forming transparent electrically-conductive film and transparent electrically-conductive film - Google Patents
Composition for forming transparent electrically-conductive film and transparent electrically-conductive filmInfo
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- JPH07242842A JPH07242842A JP3475194A JP3475194A JPH07242842A JP H07242842 A JPH07242842 A JP H07242842A JP 3475194 A JP3475194 A JP 3475194A JP 3475194 A JP3475194 A JP 3475194A JP H07242842 A JPH07242842 A JP H07242842A
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- conductive film
- transparent conductive
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、透明性と導電性に優れ
た透明導電膜を形成できる組成物と、この組成物を用い
た透明導電膜の形成方法とに関する。より詳しくは、本
発明は錫ドープ酸化インジウム（以下、ＩＴＯという）
の粉末を導電粉として用いた透明導電膜形成用組成物と
透明導電膜の形成方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition capable of forming a transparent conductive film having excellent transparency and conductivity, and a method for forming a transparent conductive film using this composition. More specifically, the present invention relates to tin-doped indium oxide (hereinafter referred to as ITO).
The present invention relates to a composition for forming a transparent conductive film and a method for forming a transparent conductive film, wherein the powder of 1. is used as a conductive powder.
【０００２】本発明の組成物から形成された透明導電膜
は、各種半導体デバイスの包装材、クリーンルーム内装
材、ブラウン管、電子機器などの帯電防止膜として好適
である。また、この透明導電膜は、従来品に比べて低抵
抗であるため、透明電極、回路等としても利用できる。The transparent conductive film formed from the composition of the present invention is suitable as an antistatic film for various semiconductor device packaging materials, clean room interior materials, cathode ray tubes, electronic equipment and the like. Moreover, since this transparent conductive film has a lower resistance than conventional products, it can be used as a transparent electrode, a circuit, or the like.
【０００３】[0003]
【従来の技術】透明導電膜形成用の導電材料としては、
酸化錫、酸化亜鉛、酸化インジウムなどの金属酸化物が
従来より利用されてきた。中でも、酸化インジウムに少
量の酸化錫をドープした混合酸化物からなるＩＴＯは、
導電性と透明性いずれも良好であることが知られてい
る。2. Description of the Related Art As a conductive material for forming a transparent conductive film,
Metal oxides such as tin oxide, zinc oxide and indium oxide have been conventionally used. Among them, ITO composed of a mixed oxide obtained by doping indium oxide with a small amount of tin oxide is
It is known that both conductivity and transparency are good.
【０００４】ＩＴＯを用いた透明導電膜の形成方法は、
基板上に真空蒸着、スパッタリング、イオンプレーティ
ングなどの手法でＩＴＯを付着させる気相法と、サブミ
クロンの微細なＩＴＯ粉末を結合剤 (例、金属アルコキ
シド又は炭素系有機樹脂) を含有する溶液中に分散させ
て塗料化した分散液を使用して、塗布、印刷などの手法
で基板に適用する塗工法とに大別される。The method of forming a transparent conductive film using ITO is
In a vapor phase method in which ITO is deposited on the substrate by a method such as vacuum deposition, sputtering, or ion plating, and in a solution containing a submicron fine ITO powder as a binder (eg, metal alkoxide or carbon-based organic resin) It is roughly classified into a coating method in which a dispersion liquid obtained by dispersing into a coating material is used to apply it to a substrate by a method such as coating or printing.
【０００５】従来は気相法が広く用いられてきたが、得
られる透明導電膜の面積に制約があり、大面積化が困難
である上、設備費が高価であり、生産性も悪い。また、
成膜時の付着効率が低く、ＩＴＯの有効利用率が40〜50
％と非常に低い。しかも、成膜後にエッチング法により
回路を描く場合には、基板に付着したＩＴＯの大半が取
り除かれるため、さらに材料の無駄が多くなるという短
所があった。Conventionally, the vapor phase method has been widely used, but the area of the transparent conductive film to be obtained is limited and it is difficult to increase the area, and the equipment cost is high and the productivity is poor. Also,
The adhesion efficiency during film formation is low, and the effective utilization rate of ITO is 40-50.
Very low at%. In addition, when the circuit is drawn by the etching method after the film formation, most of the ITO adhering to the substrate is removed, so that there is a disadvantage that the amount of material is further wasted.
【０００６】一方、塗工法は、スクリーン印刷などの手
法により回路を直接描けるので、施工が簡便で、材料の
無駄がないため、低コストで導電膜が得られ、生産性も
高い。しかし、塗工法で形成された膜は、ＩＴＯ粉末が
結合剤で結合された構造の膜となることから、気相法で
得られたＩＴＯ単味からなる膜に比べて、一般に導電性
が劣る。On the other hand, in the coating method, since the circuit can be directly drawn by a method such as screen printing, the construction is simple and the material is not wasted. Therefore, the conductive film can be obtained at a low cost and the productivity is high. However, since the film formed by the coating method is a film having a structure in which ITO powder is bonded with a binder, it is generally inferior in conductivity to a film composed of ITO alone obtained by the vapor phase method. .
【０００７】塗工法における結合剤としては、耐熱性と
硬度の良好な透明導電膜を与えることから、有機樹脂よ
りも金属アルコキシドが多く用いられる。しかし、金属
アルコキシドを用いて塗料化すると、ＩＴＯ粉末の分散
性が低くなる上、塗布後の乾燥、焼成の際に粉末の凝集
が起こり易く、得られた膜の透明性と導電性が低くなる
欠点があった。As the binder in the coating method, a metal alkoxide is used more than an organic resin because it gives a transparent conductive film having good heat resistance and hardness. However, when the metal alkoxide is used as a paint, the dispersibility of the ITO powder is lowered, and the powder is apt to agglomerate during drying and baking after coating, resulting in low transparency and conductivity of the obtained film. There was a flaw.
【０００８】[0008]
【発明が解決しようとする課題】そのため、ＩＴＯ粉末
を用いて塗工法で形成される透明導電膜について、透明
性を改善し、同時に導電性その他の特性も気相法で得ら
れる膜に近づくように改善することが求められている。Therefore, the transparency of a transparent conductive film formed by coating method using ITO powder is improved, and at the same time, the conductivity and other characteristics are close to those obtained by the vapor phase method. Is required to improve.
【０００９】一般に、粉末の分散性を向上させるため
に、界面活性剤やカップリング剤を分散液に添加する
か、或いは分散液の調製前にこれらで粉末を表面処理す
ることが知られている。しかし、粉末が導電粉の場合、
こうして分散性を向上させると、一方では粉末が結合剤
で完全に覆われるようになるので、得られた膜において
粉末同士の接触がなくなり、膜の導電性の低下につなが
る。そのため、膜の導電性と透明性を両立させることは
困難であった。It is generally known to add a surfactant or a coupling agent to the dispersion liquid or to surface-treat the powder with these before the preparation of the dispersion liquid in order to improve the dispersibility of the powder. . However, if the powder is conductive powder,
By improving the dispersibility in this way, on the other hand, the powder is completely covered with the binder, so that the powders are not in contact with each other in the obtained film, and the conductivity of the film is lowered. Therefore, it has been difficult to achieve both conductivity and transparency of the film.
【００１０】ＩＴＯ粉末にカップリング剤を適用した例
として、特開平１−261469号公報に、シランカップリン
グ剤で表面処理された導電性微粒子 (例、ＩＴＯ粉末)
とビヒクル (例、アルコキシシラン) とを主成分とす
る、表面硬度に優れた透明導電膜が提案されている。シ
ランカップリング剤でＩＴＯ粉末を予め表面処理してお
くことで、ビヒクル (結合剤) への粉末の分散性が向上
し、硬度が高くなると説明されている。しかし、上記公
報における実施例と対応する比較例との比較から明らか
なように、シランカップリング剤でＩＴＯ粉末を表面処
理しても、硬度は高くなるものの、透明性は無処理の場
合とほとんど変わらず、導電性はやや低下傾向を示す。As an example of applying a coupling agent to ITO powder, Japanese Patent Laid-Open No. 1-261469 discloses conductive fine particles surface-treated with a silane coupling agent (eg, ITO powder).
A transparent conductive film having excellent surface hardness, which is mainly composed of a resin and a vehicle (eg, alkoxysilane), has been proposed. It is described that by pre-treating the ITO powder with a silane coupling agent, the dispersibility of the powder in the vehicle (binder) is improved and the hardness is increased. However, as is clear from the comparison between the examples and the corresponding comparative examples in the above publication, even if the ITO powder is surface-treated with the silane coupling agent, the hardness is high, but the transparency is almost the same as in the case of no treatment. There is no change, and the conductivity shows a slight decrease.
【００１１】本発明の目的は、透明性と導電性のいずれ
もが改善された透明導電膜をＩＴＯ粉末を用いて塗工法
により形成する方法と、この形成方法に用いる透明導電
膜形成用組成物とを提供することである。An object of the present invention is to provide a method for forming a transparent conductive film having improved transparency and conductivity by using ITO powder by a coating method, and a composition for forming a transparent conductive film used in this forming method. And to provide.
【００１２】[0012]
【課題を解決するための手段】本発明によれば、上記目
的が、ＩＴＯ粉末を分散させた分散液中にリン酸基、亜
リン酸基またはそれらのエステル基を有する金属系カッ
プリング剤を添加することにより達成される。According to the present invention, the above object is to provide a metal-based coupling agent having a phosphoric acid group, a phosphorous acid group or an ester group thereof in a dispersion liquid in which ITO powder is dispersed. It is achieved by adding.
【００１３】ここに、本発明の要旨とするところは、導
電粉としてＩＴＯ粉末、結合剤として金属アルコキシド
および／もしくはその部分加水分解物、ならびに結合助
剤としてリン酸基、亜リン酸基またはそれらのエステル
基を有する金属系カップリング剤を溶媒中に含有する、
透明導電膜形成用組成物である。Here, the gist of the present invention is that ITO powder is used as the conductive powder, metal alkoxide and / or its partial hydrolyzate is used as the binder, and phosphoric acid group, phosphorous acid group or the like as the bonding aid. Containing a metal-based coupling agent having an ester group in a solvent,
It is a composition for forming a transparent conductive film.
【００１４】この透明導電膜形成用組成物を透明基板上
に塗布し、塗膜を200 ℃未満の温度で乾燥させることに
より、表面抵抗値が１×105 Ω／□以下の透明導電膜を
形成することができる。また、上記の透明導電膜形成用
組成物を透明基板上に塗布し、塗膜を200 ℃未満の温度
で乾燥させた後、 200〜900 ℃の温度で焼成することに
より、表面抵抗値が１×104 Ω／□以下の透明導電膜を
形成することができる。The composition for forming a transparent conductive film is applied onto a transparent substrate, and the coating film is dried at a temperature of less than 200 ° C. to obtain a transparent conductive film having a surface resistance value of 1 × 10 5 Ω / □ or less. Can be formed. Further, the above-mentioned composition for forming a transparent conductive film is applied on a transparent substrate, the coating film is dried at a temperature of less than 200 ° C., and then baked at a temperature of 200 to 900 ° C. A transparent conductive film having a density of × 10 4 Ω / □ or less can be formed.
【００１５】[0015]
【作用】以下、本発明の構成をその作用とともに詳しく
説明する。The structure of the present invention will be described in detail below together with its operation.
【００１６】本発明で使用するＩＴＯ粉末は、Sn/(Sn+I
n)の原子比が0.01〜0.15の範囲内で、50 kg/cm2 圧粉体
での粉末比抵抗が100 Ω・cm以下のものが好ましい。こ
の原子比が0.01未満または0.15超では粉末比抵抗が高く
なり、高導電性が得られにくい。また、50 kg/cm2 圧粉
体での粉末比抵抗が100 Ω・cm超となった場合にも、透
明導電膜とした際の表面抵抗値が高くなり、高導電性が
得られにくくなる。The ITO powder used in the present invention is Sn / (Sn + I
It is preferable that the atomic ratio of n) is in the range of 0.01 to 0.15 and the powder specific resistance of the powder compact of 50 kg / cm 2 is 100 Ω · cm or less. If this atomic ratio is less than 0.01 or more than 0.15, the powder resistivity becomes high and it is difficult to obtain high conductivity. In addition, even if the powder specific resistance of 50 kg / cm 2 green compact exceeds 100 Ω · cm, the surface resistance of the transparent conductive film becomes high and it becomes difficult to obtain high conductivity. .
【００１７】ＩＴＯ粉末の平均一次粒子径は0.２μｍ以
下、好ましくは0.１μｍ以下とする。この粒子径が0.２
μｍを越えると、可視光による散乱の影響が大きくな
り、得られる透明導電膜の透明性が低下する。The average primary particle diameter of the ITO powder is 0.2 μm or less, preferably 0.1 μm or less. This particle size is 0.2
When it exceeds μm, the influence of scattering by visible light becomes large, and the transparency of the obtained transparent conductive film decreases.
【００１８】上述したＩＴＯ粉末は、例えば、InとSnの
各塩化物を溶解した水溶液とアルカリ水溶液とを反応さ
せてIn−Sn共沈水酸化物を得、これを 350〜1000℃、好
ましくは 400〜800 ℃の範囲内で焼成して酸化物に転換
することにより製造できる。ただし、ＩＴＯ粉末の製造
方法はこれに限定されるものではない。The above-mentioned ITO powder is prepared, for example, by reacting an aqueous solution in which chlorides of In and Sn are dissolved with an alkaline aqueous solution to obtain an In--Sn coprecipitated hydroxide, which is 350 to 1000 ° C., preferably 400 to 1000 ° C. It can be produced by firing in the range of up to 800 ° C to convert it into an oxide. However, the method for producing the ITO powder is not limited to this.
【００１９】本発明で結合剤として使用する金属アルコ
キシドは、Si、Ti、Zr、Alのいずれかの金属の低級アル
コキシドであり、１種もしくは２種以上を使用すること
ができる。低級アルコキシドとは、炭素数１〜４のアル
コールから形成されたアルコキシドを意味し、具体的に
はメトキシド、エトキシド、ｎ−プロポキシド、ｉ−プ
ロポキシド、ｎ−ブトキシド、ｉ−ブトキシド、 sec−
ブトキシド、およびtert−ブトキシドである。The metal alkoxide used as the binder in the present invention is a lower alkoxide of a metal selected from Si, Ti, Zr and Al, and one kind or two or more kinds can be used. The lower alkoxide means an alkoxide formed from an alcohol having 1 to 4 carbon atoms, specifically, methoxide, ethoxide, n-propoxide, i-propoxide, n-butoxide, i-butoxide, sec-
Butoxide and tert-butoxide.
【００２０】金属アルコキシドの具体例としては、シリ
コンテトラエトキシド (慣用名エチルシリケート) 、ア
ルミニウムトリイソプロポキシド、ジルコニウムテトラ
ブトキシド、チタニウムテトライソプロポキシド等が挙
げられる。本発明で使用するのに特に適した金属アルコ
キシドはケイ素アルコキシドであり、特にエチルシリケ
ートの使用が好ましい。Specific examples of the metal alkoxide include silicon tetraethoxide (commonly known as ethyl silicate), aluminum triisopropoxide, zirconium tetrabutoxide, titanium tetraisopropoxide and the like. A particularly suitable metal alkoxide for use in the present invention is a silicon alkoxide, with the use of ethyl silicate being particularly preferred.
【００２１】金属アルコキシドは、基板上に塗布される
と、組成物中或いは空気中の水分により加水分解を受
け、アルコールを遊離する。このアルコールを乾燥によ
り除去すると、金属−酸素架橋結合からなる被膜を基板
上に形成することができるので、金属アルコキシドは結
合剤として機能する。しかも、有機樹脂に比べて、形成
された被膜の硬度および耐熱性が高く、さらに焼成して
完全に金属酸化物の被膜に変換することもできる。When the metal alkoxide is coated on the substrate, it is hydrolyzed by the water in the composition or in the air to release alcohol. When this alcohol is removed by drying, a coating film composed of a metal-oxygen cross-linking bond can be formed on the substrate, so that the metal alkoxide functions as a binder. Moreover, the hardness and heat resistance of the formed film are higher than those of the organic resin, and it is possible to completely convert it into a metal oxide film by firing.
【００２２】金属アルコキシドに水あるいは酸を添加し
て加水分解させることにより得た、その部分加水分解物
も、金属アルコキシドの一部または全部に代えて使用す
ることができる。それにより、塗工後の加水分解による
造膜が促進される。従って、本発明の組成物が、加水分
解促進作用のある水または酸を含有しない場合には、結
合剤として金属アルコキシドの部分加水分解物を使用す
ることが好ましい。The partially hydrolyzed product obtained by adding water or acid to the metal alkoxide for hydrolysis can also be used in place of part or all of the metal alkoxide. This promotes film formation by hydrolysis after coating. Therefore, when the composition of the present invention does not contain water or acid having a hydrolysis promoting action, it is preferable to use a partial hydrolyzate of a metal alkoxide as a binder.
【００２３】本発明では、ＩＴＯ粉末の分散を高め、同
時にＩＴＯ粉末と結合剤との結合を助ける結合助剤とし
て、リン酸基、亜リン酸基またはそれらのエステル基を
有する金属系カップリング剤を使用する。なお、リン酸
基とはピロリン酸などの縮合リン酸基をも含む意味であ
る。本発明で使用するのに適した金属系カップリング剤
は、これらの基を含有するアルミニウム系またはチタネ
ート系カップリング剤であり、１種もしくは２種以上を
使用できる。その具体例を次に示す。In the present invention, a metal-based coupling agent having a phosphoric acid group, a phosphorous acid group, or an ester group thereof is used as a bonding aid for enhancing the dispersion of the ITO powder and at the same time assisting the bonding between the ITO powder and the binder. To use. The phosphoric acid group is meant to include a condensed phosphoric acid group such as pyrophosphoric acid. The metal-based coupling agent suitable for use in the present invention is an aluminum-based or titanate-based coupling agent containing these groups, and one type or two or more types can be used. A specific example is shown below.
【００２４】アルミニウム系カップリング剤Aluminum-based coupling agent
【００２５】[0025]
【化１】 [Chemical 1]
【００２６】チタン系カップリング剤Titanium coupling agent
【００２７】[0027]
【化２】 [Chemical 2]
【００２８】この金属系カップリング剤も塗布後に加水
分解を受け、結合剤の金属アルコキシドと一緒に成膜に
関与する。従って、得られた膜は、金属アルコキシドと
金属系カップリング剤の両者の加水分解物が相互に結合
した、１種の共重合構造のものとなる。This metal-based coupling agent also undergoes hydrolysis after coating and participates in film formation together with the metal alkoxide of the binder. Therefore, the obtained film has one kind of copolymer structure in which the hydrolyzates of both the metal alkoxide and the metal-based coupling agent are bonded to each other.
【００２９】ＩＴＯ粉末の分散媒中に、結合剤の金属ア
ルコキシドに加えて、結合助剤として（亜）リン酸基ま
たはそのエステル基を有する金属系カップリング剤を添
加したことによって、ＩＴＯ粉末が適度に分散され、Ｉ
ＴＯ粉末間に鎖状のネットワーク構造が形成される。そ
のため、粉末の分散状態が安定し、塗布後の乾燥、焼成
中も、ＩＴＯ粉末の凝集が避けられ、膜中にＩＴＯ粉末
が均一に分布し、ひび割れや剥離のない透明性に優れた
膜が形成される。しかも、結合助剤中に (亜)リン酸基
またはそのエステル基が存在すると、結合助剤を添加し
なかった場合、或いは慣用のシランカップリング剤
（例、アミノ基、ビニル基、グリシドキシ基などの官能
基を有するシランカップリング剤）を添加した場合に比
べて、得られる膜の導電性が著しく高まることが判明し
た。By adding a metal-based coupling agent having a (phosphite) group or its ester group as a binding aid in addition to the metal alkoxide of the binder to the dispersion medium of the ITO powder, the ITO powder is obtained. Moderately dispersed, I
A chain network structure is formed between the TO powders. Therefore, the dispersion state of the powder is stable, agglomeration of the ITO powder is avoided even during drying and baking after coating, the ITO powder is uniformly distributed in the film, and a film having excellent transparency without cracking or peeling is formed. It is formed. Moreover, if a (phosphite) group or its ester group is present in the binding aid, the addition of the binding aid or a conventional silane coupling agent (eg, amino group, vinyl group, glycidoxy group, etc.) It has been found that the conductivity of the obtained film is remarkably increased as compared with the case where the silane coupling agent having the functional group (1) is added.
【００３０】ＩＴＯ粉末、結合剤および結合助剤を混合
する溶媒 (ＩＴＯ粉末にとっては分散媒) としては、水
またはアルコールを用いることが好ましい。アルコール
としては、メタノール、エタノール、ｎ−プロパノー
ル、 iso−プロパノール、ブタノール、ヘキサノール、
シクロヘキサノールなどの１種または２種以上を用いる
ことができる。アルコールと水との混合溶媒も使用でき
る。好ましい溶媒は、アルコールと少量 (アルコールに
対して20 vol％以下) の水との混合溶媒である。It is preferable to use water or alcohol as a solvent (dispersion medium for ITO powder) in which the ITO powder, the binder and the binding aid are mixed. As alcohol, methanol, ethanol, n-propanol, iso-propanol, butanol, hexanol,
One kind or two or more kinds such as cyclohexanol can be used. A mixed solvent of alcohol and water can also be used. A preferred solvent is a mixed solvent of alcohol and a small amount (20 vol% or less with respect to alcohol) of water.
【００３１】本発明の透明導電膜形成用組成物の組成
は、ＩＴＯ粉末 100重量部に対して、金属アルコキシド
が酸化物として１〜200 重量部、好ましくは２〜100 重
量部、金属系カップリング剤が酸化物として0.01〜100
重量部、好ましくは 0.1〜10重量部、溶媒が 100〜1000
重量部の範囲内とするのがよい。この範囲外の組成で
は、高い透明性と導電性を併せ持つ透明導電膜を得るこ
とが困難となる。The composition of the transparent conductive film-forming composition of the present invention is 1 to 200 parts by weight, preferably 2 to 100 parts by weight, as a metal alkoxide as an oxide, based on 100 parts by weight of ITO powder. The agent is 0.01 to 100 as an oxide
Parts by weight, preferably 0.1 to 10 parts by weight, the solvent is 100 to 1000
It is preferable that the content is within the range of parts by weight. With a composition outside this range, it becomes difficult to obtain a transparent conductive film having both high transparency and conductivity.
【００３２】本発明の透明導電膜形成用組成物は、上記
の必須成分以外に、さらに、結合剤の金属アルコキシド
の加水分解を促進するために、金属アルコキシド100 重
量部に対して10重量部以下の酸を添加してもよい。特
に、金属酸化物が部分加水分解物ではない場合には、酸
を添加することが好ましい。酸としては、塩酸、硝酸、
リン酸などの無機酸と、酢酸、ギ酸、シュウ酸などのカ
ルボン酸類、スルホン酸類などの有機酸のいずれも使用
できる。In addition to the above essential components, the composition for forming a transparent conductive film of the present invention further comprises 10 parts by weight or less per 100 parts by weight of a metal alkoxide in order to accelerate the hydrolysis of the metal alkoxide of the binder. The acid may be added. Particularly, when the metal oxide is not a partial hydrolyzate, it is preferable to add an acid. Acids include hydrochloric acid, nitric acid,
Any of inorganic acids such as phosphoric acid and carboxylic acids such as acetic acid, formic acid and oxalic acid, and organic acids such as sulfonic acids can be used.
【００３３】本発明の導電膜形成用組成物は、必要に応
じて、さらに別の任意添加剤を含有することもできる。
そのような添加剤の例には、増粘剤 (例えば、ヒドロキ
シプロピルセルロース) 、塗布助剤 (各種の界面活性
剤) などがある。これらの添加剤は、いずれも、得られ
る透明導電膜の透明性、導電性、硬度その他の特性を著
しく阻害しない範囲の量で添加する。The conductive film-forming composition of the present invention may further contain other optional additives, if necessary.
Examples of such additives include thickeners (eg hydroxypropyl cellulose), coating aids (various surfactants) and the like. Each of these additives is added in an amount within a range that does not significantly impair the transparency, conductivity, hardness and other properties of the obtained transparent conductive film.
【００３４】本発明の透明導電膜形成用組成物は、常法
により、ＩＴＯ粉末、結合剤、結合助剤その他添加剤、
溶媒を混合し、液中にＩＴＯ粉末を均一に分散させるこ
とにより調製できる。粉末の分散には、ペイントシェー
カー、ボールミル、セントリミル、サンドグラインドミ
ル、ホモジナイザー等の慣用装置を利用できる。The composition for forming a transparent conductive film of the present invention comprises an ITO powder, a binder, a bonding aid and other additives, according to a conventional method.
It can be prepared by mixing a solvent and uniformly dispersing ITO powder in the liquid. For dispersing the powder, a conventional device such as a paint shaker, a ball mill, a sentry mill, a sand grind mill and a homogenizer can be used.
【００３５】例えば、上記装置のいずれかを用いて、Ｉ
ＴＯ粉末をまず分散媒 (溶媒) のアルコール中に分散さ
せ、表面をアルコールで十分に濡らした後、残りの成分
を加えてさらに混合を続けることにより本発明の組成物
を調製することができる。For example, using any of the above devices, I
The composition of the present invention can be prepared by first dispersing TO powder in alcohol as a dispersion medium (solvent), sufficiently wetting the surface with alcohol, and then adding the remaining components and continuing mixing.
【００３６】透明導電膜形成用組成物の塗布は、ロール
コーター、スピンコーター、浸漬、スプレーなどの慣用
の塗布手段のいずれによって行ってもよい。また、回路
や電極のようにパターンを形成する場合には、スクリー
ン印刷などの印刷手法により本発明の組成物を基板に適
用することもできる。基板材料には制限はないが、通常
は、ガラス、プラスチックスなどの透明材料である。The composition for forming the transparent conductive film may be applied by any of conventional coating means such as a roll coater, a spin coater, dipping and spraying. When forming a pattern such as a circuit or an electrode, the composition of the present invention can be applied to the substrate by a printing technique such as screen printing. The substrate material is not limited, but is usually a transparent material such as glass or plastics.
【００３７】塗布または印刷後、好ましくは加熱して乾
燥を行うと、結合剤の金属アルコキシドおよび結合助剤
の金属系カップリング剤が加水分解し、ＩＴＯ粉末がこ
れらの結合剤および結合助剤の加水分解物で結合されて
なる透明導電膜が得られる。乾燥温度は、使用した溶媒
の種類や基板の耐熱性に応じて適当に決定すればよい
が、例えば、常温ないし200 ℃までの温度が適当であ
る。After coating or printing, preferably by heating and drying, the metal alkoxide of the binder and the metal-based coupling agent of the binding aid are hydrolyzed, and the ITO powder is converted into the binder and the binding aid. A transparent conductive film bonded with a hydrolyzate is obtained. The drying temperature may be appropriately determined depending on the type of solvent used and the heat resistance of the substrate, but, for example, a temperature from room temperature to 200 ° C. is suitable.
【００３８】乾燥後に得られた本発明の透明導電膜は、
表面抵抗値が１×105 Ω／□以下という特性を示す。ま
た、光透過率90％のガラス基板上に膜厚0.5 μｍで形成
した場合で、得られた膜の光透過率は87％以上である。
これに対し、結合助剤を添加しないか、結合助剤がシラ
ンカップリング剤である場合には、膜の表面抵抗値は１
×106 Ω／□以上となる。即ち、本発明により、透明導
電膜の光透過率を低下させずに、導電性を著しく高める
ことができる。The transparent conductive film of the present invention obtained after drying is
The surface resistance is 1 × 10 5 Ω / □ or less. Further, when the film having a thickness of 0.5 μm is formed on a glass substrate having a light transmittance of 90%, the light transmittance of the obtained film is 87% or more.
On the other hand, when the binding aid is not added or the binding aid is a silane coupling agent, the surface resistance value of the film is 1
× 10 6 Ω / □ or more. That is, according to the present invention, the conductivity can be remarkably enhanced without lowering the light transmittance of the transparent conductive film.
【００３９】基板がガラスのように耐熱性が高い材料で
ある場合には、乾燥後に得られた透明導電膜をさらに大
気中または不活性ガス中で焼成してもよい。この焼成に
より膜中に残留する有機分が除去され、膜が緻密化し、
膜の導電性がさらに向上して、表面抵抗値を１×104 Ω
／□以下とすることができる。焼成条件は、この目的が
達成されるように選択すればよいが、例えば、 200〜90
0 ℃で20分〜10時間程度が適当である。焼成温度が350
℃以上であることが一層好ましい。When the substrate is made of a material having high heat resistance such as glass, the transparent conductive film obtained after drying may be further fired in the air or an inert gas. This baking removes the organic components remaining in the film, densifying the film,
The conductivity of the film is further improved and the surface resistance value is 1 × 10 4 Ω
/ It can be less than or equal to □. The firing conditions may be selected so that this purpose is achieved, and for example, 200 to 90
20 minutes to 10 hours at 0 ° C is suitable. Firing temperature is 350
It is more preferable that the temperature is not lower than 0 ° C.
【００４０】[0040]
【実施例】以下に実施例を示すが、これらは本発明を限
定するものではない。EXAMPLES Examples will be shown below, but these do not limit the present invention.
【００４１】ＩＴＯ粉末の調製 In金属 300ｇを含有するInCl3 水溶液900 mLと55wt％Sn
Cl4 水溶液 130ｇとを混合した後、液温50℃で重炭酸ア
ンモニウム水溶液（1800ｇ／6 L)と反応させ、InとSnの
水酸化物を共沈させた [Sn/(Sn+In)の原子比は1/10] 。
沈殿物をイオン交換水により傾斜洗浄し、濾別乾燥後、
650℃で３時間焼成した後、ＩＴＯ粉末を得た。この粉
末の比表面積はＢＥＴ法による測定で30 m2/g (平均一
次粒子径0.03μｍに相当) 、50 kg/cm2 圧粉体での比抵
抗値は25Ω・cmであった。 Preparation of ITO Powder 900 mL of InCl 3 aqueous solution containing 300 g of In metal and 55 wt% Sn
After mixing with 130 g of Cl 4 aqueous solution, it was reacted with an ammonium bicarbonate aqueous solution (1800 g / 6 L) at a liquid temperature of 50 ° C. to coprecipitate In and Sn hydroxides [Sn / (Sn + In) The atomic ratio is 1/10].
The precipitate is decanted with ion-exchanged water, filtered and dried,
After firing at 650 ° C. for 3 hours, ITO powder was obtained. The specific surface area of this powder was 30 m 2 / g (corresponding to an average primary particle diameter of 0.03 μm) as measured by the BET method, and the specific resistance value of the powder of 50 kg / cm 2 was 25 Ω · cm.
【００４２】以下の実施例および比較例においては、上
記のＩＴＯ粉末を用いて透明導電膜を形成した。また、
膜の光透過率は日本分光（株）製 UBEST55型分光光度計
で、表面抵抗値は三菱油化（株）製ローレスタAP MCP-T
400 でそれぞれ調べた。In the following examples and comparative examples, transparent conductive films were formed using the above ITO powder. Also,
The light transmittance of the film is UBEST55 spectrophotometer manufactured by JASCO Corporation, and the surface resistance value is ROLLESTA AP MCP-T manufactured by Mitsubishi Yuka Co., Ltd.
I checked each with 400.
【００４３】(実施例１)ＩＴＯ粉末10ｇをペイントシェ
イカー (ガラスビーズ25ｇ) を用いて振盪することによ
りエチルアルコール20ｇ中に60分間分散させた。得られ
た分散液に、エチルシリケート1.8 ｇ、ビス (ジオクチ
ルパイロホスフェート) オキシアセテーExample 1 10 g of ITO powder was dispersed in 20 g of ethyl alcohol for 60 minutes by shaking using a paint shaker (25 g of glass beads). 1.8 g of ethyl silicate and bis (dioctyl pyrophosphate) oxyacetate were added to the obtained dispersion.
【００４４】トチタネート (Totitanate (
【化２】のの化合物 ) 0.2ｇ、12Ｎ塩酸0.02ｇ、水２
ｇを加え、さらに30分間振盪した後、ビーズを除去し
て、透明導電膜形成用組成物を調製した。Compound of formula 2) 0.2 g, 12N hydrochloric acid 0.02 g, water 2
After adding g and shaking for 30 minutes, the beads were removed to prepare a composition for forming a transparent conductive film.
【００４５】この透明導電膜形成用組成物をバーコータ
ーを用いて、光透過率90％のガラス板上に乾燥膜厚が0.
５μｍ厚になるように塗布し、100 ℃で２時間乾燥し
て、透明導電膜を形成した。得られた透明導電膜は目視
で観察してひび割れや剥離がなかった。膜特性は、光透
過率が89％、表面抵抗値は 4.2×104 Ω／□であった。This transparent conductive film-forming composition was dried on a glass plate having a light transmittance of 90% with a bar coater to give a dry film thickness of 0.1.
A transparent conductive film was formed by applying the solution to a thickness of 5 μm and drying at 100 ° C. for 2 hours. The transparent conductive film thus obtained was visually observed and found to be free from cracks and peeling. The film characteristics were a light transmittance of 89% and a surface resistance value of 4.2 × 10 4 Ω / □.
【００４６】(実施例２)実施例２で得た透明導電膜を、
さらに大気中にて 400℃で30分間焼成した。焼成後の膜
にもひび割れや剥離は認められなかった。焼成後の膜特
性は、光透過率が89％で変化せず、表面抵抗値は 1.8×
103 Ω／□に低下した。即ち、焼成により導電性がさら
に向上した。Example 2 The transparent conductive film obtained in Example 2 was
Further, it was baked in the air at 400 ° C. for 30 minutes. Neither cracking nor peeling was observed in the film after baking. The film characteristics after baking did not change at a light transmittance of 89%, and the surface resistance value was 1.8 ×
It decreased to 10 3 Ω / □. That is, the conductivity was further improved by firing.
【００４７】(実施例３)結合剤をチタニウムイソプロポ
キシド2.5 ｇ、結合助剤をイソプロポキシジオ(Example 3) 2.5 g of titanium isopropoxide was used as a binder, and isopropoxydio was used as a binding aid.
【００４８】クチルホスフェートアルミニウムエチルア
セトアセテート (Cutyl Phosphate Aluminum Ethyl Acetoacetate (
【化１】の化合物)0.001ｇに変えた以外は、実施例１と
同様にして透明導電膜形成用組成物および透明導電膜を
形成した。膜特性は、光透過率が87％、表面抵抗値が
5.7×104 Ω／□であった。A composition for forming a transparent conductive film and a transparent conductive film were formed in the same manner as in Example 1 except that the compound of [Chemical Formula 1] was changed to 0.001 g. The film characteristics are that the light transmittance is 87% and the surface resistance value is
It was 5.7 × 10 4 Ω / □.
【００４９】（実施例４）結合剤としてエチルシリケー
ト1.2 ｇとジルコニウムｎ−ブトキシド0.6 ｇとの混合
物を、結合助剤としてテトライソプロピル (ジオクチル
ホスファイト) チExample 4 A mixture of 1.2 g of ethyl silicate and 0.6 g of zirconium n-butoxide was used as a binder, and tetraisopropyl (dioctyl phosphite) ti was used as a binder.
【００５０】タネート (Tanate (
【化２】のの化合物) 10ｇを使用した以外は、実施例
１と同様にして透明導電膜形成用組成物および透明導電
膜を形成した。膜特性は、光透過率が87％、表面抵抗値
が 6.2×104 Ω／□であった。A composition for forming a transparent conductive film and a transparent conductive film were formed in the same manner as in Example 1 except that 10 g of the compound of Chemical formula 2 was used. Regarding the film characteristics, the light transmittance was 87% and the surface resistance value was 6.2 × 10 4 Ω / □.
【００５１】(比較例１)結合助剤のビス (ジオクチルパ
イロホスフェート) オキシアセテートチタネートを加え
なかった以外は実施例１と同様にして、透明導電膜形成
用組成物および透明導電膜を形成した。膜特性は、光透
過率が86％、表面抵抗値は 2.6×107 Ω／□であった。Comparative Example 1 A transparent conductive film-forming composition and a transparent conductive film were formed in the same manner as in Example 1 except that bis (dioctylpyrophosphate) oxyacetate titanate as a binding aid was not added. The film characteristics were a light transmittance of 86% and a surface resistance value of 2.6 × 10 7 Ω / □.
【００５２】(比較例２)比較例１で得られた透明導電膜
を、さらに 400℃で30分間焼成した後、透明導電膜特性
を調べた。その結果、光透過率が87％、表面抵抗値が
8.3×105 Ω／□であった。Comparative Example 2 The transparent conductive film obtained in Comparative Example 1 was further baked at 400 ° C. for 30 minutes, and the characteristics of the transparent conductive film were examined. As a result, the light transmittance is 87% and the surface resistance value is
It was 8.3 × 10 5 Ω / □.
【００５３】(比較例３)結合助剤のイソプロポキシジオ
クチルホスフェートアルミニウムエチルアセトアセテー
トを加えなかった以外は実施例３と同様にして透明導電
膜形成用組成物および透明導電膜を形成した。膜特性
は、光透過率が86％、表面抵抗値は 3.3×107 Ω／□で
あった。Comparative Example 3 A transparent conductive film-forming composition and a transparent conductive film were formed in the same manner as in Example 3 except that the binding aid isopropoxydioctyl phosphate aluminum ethyl acetoacetate was not added. The film characteristics were a light transmittance of 86% and a surface resistance value of 3.3 × 10 7 Ω / □.
【００５４】(比較例４)結合助剤のテトライソプロピル
(ジオクチルホスファイト) チタネートを加えなかった
以外は実施例４と同様にして透明導電膜形成用組成物お
よび透明導電膜を形成した。膜特性は、光透過率が84
％、表面抵抗値は 1.1×108 Ω／□であった。(Comparative Example 4) Tetraisopropyl as a binding aid
(Dioctyl phosphite) A transparent conductive film-forming composition and a transparent conductive film were formed in the same manner as in Example 4 except that titanate was not added. The film has a light transmittance of 84.
%, And the surface resistance value was 1.1 × 10 8 Ω / □.
【００５５】(比較例５)結合助剤をイソプロピルトリイ
ソステアロイルチタネート0.２ｇに変えた以外は、実施
例１と同様にして透明導電膜形成用組成物および透明導
電膜を形成した。膜特性は、光透過率が89％、表面抵抗
値が 8.7×106 Ω／□であった。Comparative Example 5 A composition for forming a transparent conductive film and a transparent conductive film were formed in the same manner as in Example 1 except that 0.2 g of isopropyltriisostearoyl titanate was used as the binding aid. As for the film characteristics, the light transmittance was 89% and the surface resistance value was 8.7 × 10 6 Ω / □.
【００５６】(比較例６)結合剤としてエチルシリケート
1.2ｇとジルコニウムｎ−ブトキシド 0.6ｇとの混合物
を、結合助剤としてＮ−β (アミノエチル) γ−アミノ
プロピルトリエトキシシラン10ｇを使用した以外は、実
施例１と同様にして透明導電膜形成用組成物および透明
導電膜を形成した。膜特性は光透過率が87％、表面抵抗
値は 1.2×106 Ω／□であった。Comparative Example 6 Ethyl silicate as a binder
A transparent conductive film was formed in the same manner as in Example 1 except that a mixture of 1.2 g and zirconium n-butoxide (0.6 g) was used as a binding aid, and 10 g of N-β (aminoethyl) γ-aminopropyltriethoxysilane was used. And a transparent conductive film were formed. As for the film characteristics, the light transmittance was 87% and the surface resistance value was 1.2 × 10 6 Ω / □.
【００５７】[0057]
【発明の効果】以上に説明したように、本発明の透明導
電膜形成用組成物から塗工法により形成された透明導電
膜は、高い光透過率を保持したまま、表面抵抗値が乾燥
したままで１×105 Ω／□以下、乾燥後に焼成を行うと
１×104 Ω／□以下という、著しく改善された導電性
(低抵抗) を示す。即ち、導電性と透明性を両立させる
ことができる。従って、本発明により形成された透明導
電膜は、高導電性と優れた透明性を併せ持つ高性能の帯
電防止材として有用であり、特に焼成により一層低抵抗
化した透明導電膜は回路や電極といった用途にも使用で
きる。As described above, the transparent conductive film formed from the composition for forming a transparent conductive film of the present invention by the coating method has a high light transmittance and a dry surface resistance value. 1 × 10 5 Ω / □ or less, and when fired after drying, it is 1 × 10 4 Ω / □ or less, significantly improved conductivity.
(Low resistance) That is, both conductivity and transparency can be compatible. Therefore, the transparent conductive film formed according to the present invention is useful as a high-performance antistatic material having both high conductivity and excellent transparency, and a transparent conductive film whose resistance is further reduced by firing is particularly suitable for circuits and electrodes. It can also be used for purposes.
Claims (3)
下の錫ドープ酸化インジウム粉末、結合剤として金属ア
ルコキシドおよび／もしくはその部分加水分解物、なら
びに結合助剤としてリン酸基、亜リン酸基またはそれら
のエステル基を有する金属系カップリング剤を溶媒中に
含有する、透明導電膜形成用組成物。1. A tin-doped indium oxide powder having an average primary particle diameter of 0.2 μm or less as a conductive powder, a metal alkoxide and / or a partial hydrolyzate thereof as a binder, and a phosphate group, a phosphite group or a binding aid. A composition for forming a transparent conductive film, which comprises a metal-based coupling agent having such an ester group in a solvent.
を透明基板上に塗布し、塗膜を200 ℃未満の温度で乾燥
させることからなる、表面抵抗値が１×105Ω／□以下
の透明導電膜の形成方法。2. The composition for forming a transparent conductive film according to claim 1 is applied onto a transparent substrate, and the coating film is dried at a temperature of less than 200 ° C. and has a surface resistance value of 1 × 10 5 Ω / □ The following method for forming a transparent conductive film.
を透明基板上に塗布し、塗膜を200 ℃未満の温度で乾燥
させた後、 200〜900 ℃の温度で焼成することからな
る、表面抵抗値が１×104 Ω／□以下の透明導電膜の形
成方法。3. The composition for forming a transparent conductive film according to claim 1 is applied on a transparent substrate, the coating film is dried at a temperature of less than 200 ° C., and then baked at a temperature of 200 to 900 ° C. And a method for forming a transparent conductive film having a surface resistance value of 1 × 10 4 Ω / □ or less.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03475194A JP3147644B2 (en) | 1994-03-04 | 1994-03-04 | Composition for forming transparent conductive film and transparent conductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03475194A JP3147644B2 (en) | 1994-03-04 | 1994-03-04 | Composition for forming transparent conductive film and transparent conductive film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07242842A true JPH07242842A (en) | 1995-09-19 |
| JP3147644B2 JP3147644B2 (en) | 2001-03-19 |
Family
ID=12423035
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03475194A Expired - Lifetime JP3147644B2 (en) | 1994-03-04 | 1994-03-04 | Composition for forming transparent conductive film and transparent conductive film |
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| Country | Link |
|---|---|
| JP (1) | JP3147644B2 (en) |
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| WO2001036544A1 (en) * | 1999-11-17 | 2001-05-25 | Toyo Gosei Kogyo Co., Ltd. | Coating solution for forming transparent and conductive tin oxide film and method for preparing transparent and conductive tin oxide film, and transparent and conductive tin oxide film |
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