JPH08143792A - Composition for forming conductive film and formation of conductive film - Google Patents

Composition for forming conductive film and formation of conductive film

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Publication number
JPH08143792A
JPH08143792A JP28375494A JP28375494A JPH08143792A JP H08143792 A JPH08143792 A JP H08143792A JP 28375494 A JP28375494 A JP 28375494A JP 28375494 A JP28375494 A JP 28375494A JP H08143792 A JPH08143792 A JP H08143792A
Authority
JP
Japan
Prior art keywords
organic acid
conductive film
compound
metal salt
forming
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
Application number
JP28375494A
Other languages
Japanese (ja)
Other versions
JP3230395B2 (en
Inventor
Akira Nishihara
明 西原
Toshiharu Hayashi
年治 林
Masaoki Ishihara
真興 石原
Masahito Murouchi
聖人 室内
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dai Nippon Toryo KK
Mitsubishi Materials Corp
Original Assignee
Dai Nippon Toryo KK
Mitsubishi Materials Corp
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Filing date
Publication date
Application filed by Dai Nippon Toryo KK, Mitsubishi Materials Corp filed Critical Dai Nippon Toryo KK
Priority to JP28375494A priority Critical patent/JP3230395B2/en
Publication of JPH08143792A publication Critical patent/JPH08143792A/en
Application granted granted Critical
Publication of JP3230395B2 publication Critical patent/JP3230395B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Abstract

PURPOSE: To obtain a composition for forming conductive film which, when applied and baked, can be formed into a conductive film excellent in haze, conductivity and adhesion, by adding a tin-containing indium oxide powder to a solvent, an organic compound, and an organic acid metal salt compound. CONSTITUTION: This composition for forming a conducive film comprises a thin-containing indium oxide (ITO powder), a solvent, an organic compound (e.g. a 1-18C aliphatic carboxylic acid, a 6-20C aromatic carboxylic acid, and a phosphonic acid having an ethylene oxide chain), and an organic acid metal salt compound (e.g. salt (Co, Ni, Pb, In, Al, Fe, Ti, Sb, and Zn) of an organic acid compound), with the amount of the powder being 100 pts.wt., the amount of the organic compound being 1 to 40 pts.wt., and the amount of the organic acid metal compound being 0.2 to 15 pts.wt. In comparison with a conventional composition for forming a conductive film that uses a binder (conductive coating material), the above coating material can form a transparent conductive film excellent in transparency, conductivity, and adhesion.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、透明電極、帯電防止
膜、熱線反射膜、電磁波シールド膜、面発熱体等の分野
に利用できる導電膜、特に透明導電膜の形成用組成物
と、導電膜、特に透明導電膜の形成方法に関するもので
ある。FIELD OF THE INVENTION The present invention relates to a composition for forming a conductive film, particularly a transparent conductive film, which can be used in the fields of transparent electrodes, antistatic films, heat ray reflection films, electromagnetic wave shield films, surface heating elements, and the like. The present invention relates to a method for forming a film, particularly a transparent conductive film.

【０００２】[0002]

【従来の技術】透明導電膜の形成法は、ＣＶＤ、スパッ
タリング法等を含む気相法と、塗布法とに大別される。
気相法は、従来より最も広く用いられている膜形成方法
であるが、装置が高価であって、生産性や歩留りが悪
く、大面積の成膜には不向きである。2. Description of the Related Art Methods for forming a transparent conductive film are roughly classified into a vapor phase method including a CVD method, a sputtering method and the like, and a coating method.
The vapor phase method is the most widely used film forming method from the past, but the apparatus is expensive, the productivity and the yield are poor, and it is not suitable for forming a large area film.

【０００３】一方、導電性微粒子をバインダー溶液 (バ
インダーと溶媒からなる溶液) 中に分散させて塗料化
し、得られた導電塗料を基板に塗布して乾燥、硬化さ
せ、透明導電膜を形成する塗布法は、導電膜を形成する
基板の寸法や形状の制限が少なく、設備が簡単で、生産
性に優れており、簡便に透明導電膜を形成することがで
きる。ヘーズ（曇度）の低い透明性に優れた導電膜を得
るには、塗料化の段階で、バインダー溶液中に導電性微
粒子を一次粒子に近い状態までほぼ完全に分散させるこ
とが重要である。On the other hand, conductive fine particles are dispersed in a binder solution (solution consisting of a binder and a solvent) to form a coating, and the conductive coating thus obtained is applied to a substrate, dried and cured to form a transparent conductive film. According to the method, the size and shape of the substrate on which the conductive film is formed are small, the facility is simple, the productivity is excellent, and the transparent conductive film can be easily formed. In order to obtain a conductive film with low haze (cloudiness) and excellent transparency, it is important to disperse the conductive fine particles in the binder solution almost completely to a state close to the primary particles at the stage of coating.

【０００４】バインダーとしては、アクリル樹脂、ポリ
エステル樹脂、ポリカーボネート樹脂等の透明性に優れ
た樹脂が一般的であるが、エチルシリケートやその縮合
物などの金属アルコキシドを使用する場合もある。導電
性微粒子としては、ドープ原子としてAlまたは他の金属
を含有する酸化亜鉛、アンチモンを含有する酸化錫など
も使用できるが、代表例は、特に低抵抗の膜を与えるこ
とが知られている、錫を含有する酸化インジウム（以
下、ＩＴＯともいう）である。As the binder, a resin having excellent transparency such as an acrylic resin, a polyester resin or a polycarbonate resin is generally used, but a metal alkoxide such as ethyl silicate or a condensate thereof may be used in some cases. As the conductive fine particles, zinc oxide containing Al or another metal as a doping atom, tin oxide containing antimony, etc. can be used, but a typical example is known to give a film having particularly low resistance, It is indium oxide containing tin (hereinafter, also referred to as ITO).

【０００５】[0005]

【発明が解決しようとする課題】近年、液晶ディスプレ
イ、タッチパネル、プラズマディスプレイ、エレクトロ
ルミネッセンスディスプレイ或いは蛍光ディスプレイ等
の高性能化は目覚ましく、これらに用いられる透明電極
や帯電防止膜は、より一層の光学特性と導電性の向上が
求められるようになってきた。しかし、塗布法により形
成される導電膜はは、導電性微粒子としてＩＴＯ粉末を
使用しても、気相法により得られたものに比べて、ヘー
ズや導電性の点で劣っており、上記の要請には満足に対
応することができなかった。In recent years, the performance of liquid crystal displays, touch panels, plasma displays, electroluminescent displays, fluorescent displays, etc. has been remarkably improved, and transparent electrodes and antistatic films used for them have further improved optical characteristics. Therefore, improvement in conductivity has been demanded. However, the conductive film formed by the coating method is inferior in terms of haze and conductivity even when ITO powder is used as the conductive fine particles, as compared with that obtained by the vapor phase method. We were unable to satisfy the request satisfactorily.

【０００６】本発明の目的は、導電膜を容易に形成でき
る塗布法を用いて、ヘーズ、導電性および密着性に優れ
た導電膜を形成しうる導電膜形成用組成物と導電膜の形
成方法を提供することである。An object of the present invention is to provide a conductive film forming composition and a conductive film forming method capable of forming a conductive film excellent in haze, conductivity and adhesiveness by using a coating method capable of easily forming a conductive film. Is to provide.

【０００７】[0007]

【課題を解決するための手段】本発明者らは、上記目的
を達成すべく検討を重ねた。その結果、ＩＴＯ粉末、溶
媒およびバインダーからなる、塗布法に用いる従来の導
電塗料では、ヘーズ低下のために行うＩＴＯ粉末の分散
処理工程で、ＩＴＯ粉末の表面が絶縁性のバインダーで
被覆されてしまう。そして、バインダーは乾燥または焼
付後の塗膜中にも残留するため、図１に示すように、塗
膜内のＩＴＯ粉末はバインダーにより被覆されたままで
あり、粉末間の直接接触が必要な電子移動が阻害され
て、導電性の向上 (抵抗値の低下) を妨げることがわか
った。電気伝導には、図示のように、膜を横断してＩＴ
Ｏ粉末が直接接触でつながっている導電部が必要である
が、ＩＴＯ粉末がバインダーで被覆されていると、この
ような導電部が形成されにくくなる。Means for Solving the Problems The present inventors have made extensive studies to achieve the above object. As a result, in the conventional conductive coating material used for the coating method, which is composed of the ITO powder, the solvent and the binder, the surface of the ITO powder is coated with the insulating binder in the dispersion treatment step of the ITO powder performed to reduce the haze. . Then, since the binder remains in the coating film after drying or baking, the ITO powder in the coating film remains covered with the binder as shown in FIG. 1, and electron transfer which requires direct contact between the powder particles. It was found that the above-mentioned phenomenon was hindered to prevent improvement of conductivity (reduction of resistance value). For electrical conduction, as shown,
It is necessary to have a conductive portion in which the O powder is connected by direct contact, but when the ITO powder is coated with a binder, such a conductive portion is less likely to be formed.

【０００８】従って、バインダーを使用した従来の導電
塗料では、ヘーズ低下を優先させるために十分なＩＴＯ
粉末の分散を行うと、膜の抵抗値が増大する。逆に、抵
抗値の低下を優先させると、ＩＴＯ粉末の分散が犠牲に
なり、ヘーズが高くなる。そのため、ヘーズと導電性と
を同時に改善することが困難である。Therefore, in the conventional conductive paint using the binder, sufficient ITO is added to give priority to the haze reduction.
When the powder is dispersed, the resistance value of the film increases. Conversely, if priority is given to the reduction of the resistance value, the dispersion of the ITO powder is sacrificed and the haze becomes high. Therefore, it is difficult to improve haze and conductivity at the same time.

【０００９】このような知見に基づいてさらに研究を続
けた結果、バインダーの代わりに、焼成時に容易に分解
する有機酸化合物および有機酸金属塩化合物を用いて
も、ＩＴＯ粉末を塗料中に十分に分散させ、かつ分解生
成物でＩＴＯ粉末を十分に焼結することができ、しかも
ＩＴＯ粉末表面がバインダーで被覆されないため、ヘー
ズ、導電性、密着性のいずれにも優れた導電膜を形成す
ることができることを見出し、本発明に到達した。As a result of further research based on these findings, it was found that ITO powder can be sufficiently incorporated into a coating even if an organic acid compound and an organic acid metal salt compound which are easily decomposed during firing are used instead of the binder. Since the ITO powder can be dispersed and sufficiently decomposed by the decomposition product and the surface of the ITO powder is not covered with the binder, a conductive film having excellent haze, conductivity, and adhesion can be formed. The present invention has been accomplished and the present invention has been achieved.

【００１０】本発明は、錫を含有する酸化インジウム粉
末 (＝ＩＴＯ粉末) 、溶媒、有機酸化合物、および有機
酸金属塩化合物からなり、前記粉末100 重量部に対し
て、有機酸化合物を１〜20重量部、有機酸金属塩化合物
を 0.2〜15重量部の割合で含有する、導電膜形成用組成
物である。なお、有機酸化合物および有機酸金属塩化合
物の一方または両方の少なくとも一部は、ＩＴＯ粉末の
表面に付着した表面被覆物の状態で存在しうる。The present invention comprises a tin-containing indium oxide powder (= ITO powder), a solvent, an organic acid compound, and an organic acid metal salt compound. A conductive film-forming composition containing 20 parts by weight of an organic acid metal salt compound in a proportion of 0.2 to 15 parts by weight. At least a part of one or both of the organic acid compound and the organic acid metal salt compound may exist in the state of a surface coating attached to the surface of the ITO powder.

【００１１】この組成物を基体に塗布した後、300 ℃以
上の不活性雰囲気中または還元性雰囲気中で焼成するこ
とにより、導電膜を形成することができる。得られた導
電膜は、ＩＴＯ粉末が有機酸金属化合物の熱分解物によ
り焼結された構造をとる。A conductive film can be formed by applying this composition to a substrate and baking it in an inert atmosphere or a reducing atmosphere at 300 ° C. or higher. The obtained conductive film has a structure in which ITO powder is sintered with a thermally decomposed product of an organic acid metal compound.

【００１２】別の手法として、ＩＴＯ粉末、溶媒、およ
び有機酸化合物からなり、前記粉末100 重量部に対して
有機酸化合物を１〜40重量部の割合で含有する導電膜形
成用組成物を基体に塗布し、得られた塗膜に有機酸金属
塩化合物の溶液を含浸させた後、300 ℃以上の非酸化性
雰囲気中で焼成することによっても、同様の構造の導電
膜を形成することができる。As another method, a conductive film-forming composition comprising an ITO powder, a solvent, and an organic acid compound and containing 1 to 40 parts by weight of the organic acid compound per 100 parts by weight of the powder is used as a substrate. It is also possible to form a conductive film having a similar structure by coating the resulting coating film with a solution of an organic acid metal salt compound and baking it in a non-oxidizing atmosphere at 300 ° C or higher. it can.

【００１３】[0013]

【作用】本発明で用いるＩＴＯ粉末は市販品を利用して
もよく、或いは公知の方法 (例えば、錫とインジウムの
塩化物の酸性水溶液をアルカリで中和して、錫／インジ
ウム水酸化物を共沈させ、この共沈物を焼成する）で製
造することもできる。ＩＴＯ粉末としては、 (In＋Sn)
の合計量に対するSnの割合が１〜15原子％の範囲のもの
が、特に低抵抗であるので好ましい。Sn含有量がこの範
囲を外れると、ＩＴＯ粉末自体の抵抗 (体積抵抗率) が
高くなる傾向がある。また、ＩＴＯ粉末の平均一次粒子
径は、形成された膜の透明性を阻害しないように、平均
粒径が0.5μｍ以下、特に0.2 μｍ以下のものが好まし
い。但し、高い透明性を必要としない用途には、0.5 μ
ｍを超える粗大なＩＴＯ粉末を使用することもできる。The ITO powder used in the present invention may be a commercially available product, or a known method (for example, an acidic aqueous solution of tin and indium chloride is neutralized with an alkali to form a tin / indium hydroxide). Coprecipitation, and the coprecipitate is baked). As ITO powder, (In + Sn)
Those having a ratio of Sn to the total amount of 1 to 15 atomic% are preferable because they have particularly low resistance. If the Sn content deviates from this range, the resistance (volume resistivity) of the ITO powder itself tends to increase. The average primary particle diameter of the ITO powder is preferably 0.5 μm or less, particularly 0.2 μm or less so as not to impair the transparency of the formed film. However, for applications that do not require high transparency, 0.5 μ
It is also possible to use coarse ITO powders exceeding m.

【００１４】ＩＴＯ粉末の表面にはＯＨ基や酸素基など
の極性基が存在し、表面活性が高い。そのため、微細な
ＩＴＯ粉末は非常に凝集し易く、溶媒中で分散させるた
めに、分散剤または界面活性剤によるＩＴＯ粉末の表面
処理が行われてきた。しかし、分散剤や界面活性剤では
ＩＴＯ粉末を完全に分散させることは難しく、たとえ分
散できたとしても、焼成時に導電性に悪影響を及ぼす熱
分解物が生ずることが判明した。On the surface of the ITO powder, polar groups such as OH groups and oxygen groups are present, and the surface activity is high. Therefore, the fine ITO powder is very likely to aggregate, and the surface treatment of the ITO powder with a dispersant or a surfactant has been performed in order to disperse it in a solvent. However, it has been found that it is difficult to completely disperse the ITO powder with a dispersant or a surfactant, and even if the ITO powder can be dispersed, a thermal decomposition product that adversely affects the conductivity is generated during firing.

【００１５】本発明では、有機酸化合物を用いてＩＴＯ
粉末を溶媒中に分散させる。有機酸化合物の酸基がＩＴ
Ｏ粉末表面の極性基と結合して、粉末表面に有機酸化合
物が適度に吸着される結果、粉末の凝集が抑制され、Ｉ
ＴＯ粉末の分散性が向上するものと推測される。In the present invention, ITO is prepared by using an organic acid compound.
Disperse the powder in the solvent. The acid group of the organic acid compound is IT
O As a result of the organic acid compound being appropriately adsorbed on the surface of the powder by binding to the polar group on the surface of the powder, aggregation of the powder is suppressed, and I
It is presumed that the dispersibility of TO powder is improved.

【００１６】本発明において使用する有機酸化合物とし
ては、カルボキシル基またはホスホン酸基を有する有機
化合物、即ち、カルボン酸およびホスホン酸が好まし
い。有用なカルボン酸には、プロピオン酸、イソ酪酸、
DL−２−メチル酪酸、イソ吉草酸、オクタン酸等の炭素
数１〜18の脂肪族カルボン酸；ならびに安息香酸等の炭
素数６〜20の芳香族カルボン酸がある。また、有用なホ
スホン酸の例には、オキシエチルホスホン酸、ジオキシ
エチルホスホン酸、ポリオキシエチルホスホン酸等のエ
チレンオキサイド鎖を有するホスホン酸が挙げられる。The organic acid compound used in the present invention is preferably an organic compound having a carboxyl group or a phosphonic acid group, that is, a carboxylic acid and a phosphonic acid. Useful carboxylic acids include propionic acid, isobutyric acid,
DL-2-methylbutyric acid, isovaleric acid, octanoic acid and other aliphatic carboxylic acids having 1 to 18 carbon atoms; and benzoic acid and other aromatic carboxylic acids having 6 to 20 carbon atoms. In addition, examples of useful phosphonic acids include phosphonic acids having an ethylene oxide chain such as oxyethylphosphonic acid, dioxyethylphosphonic acid and polyoxyethylphosphonic acid.

【００１７】有機酸化合物の使用量は、ＩＴＯ粉末100
重量部に対する量で、１〜40重量部、好ましくは５〜30
重量部の範囲である。有機酸化合物の量が１重量部未満
であると、ＩＴＯ粉末の分散が不十分となり、ヘーズな
どの光学特性が低下する。有機酸化合物の量が40重量部
を超えると、塗料としてのバランスが崩れ、適正な塗布
性と安定性を持った塗料が得られない。The amount of the organic acid compound used is 100% ITO powder.
1-40 parts by weight, preferably 5-30 parts by weight
The range is parts by weight. When the amount of the organic acid compound is less than 1 part by weight, the ITO powder is insufficiently dispersed and the optical characteristics such as haze are deteriorated. When the amount of the organic acid compound exceeds 40 parts by weight, the balance as a coating material is lost, and a coating material having proper coating property and stability cannot be obtained.

【００１８】有機酸化合物は、塗布後の焼成工程で熱分
解し、塗膜から除去されてしまうので、ＩＴＯ粉末を結
合する力はない。そのため、本発明の導電膜形成用組成
物には、有機酸化合物に加えて、有機酸金属塩化合物を
配合する。有機酸金属塩化合物は、焼成工程で熱分解し
て、最終的には無機金属化合物 (酸化物、水酸化物、炭
酸塩、炭化物など) になり、この化学変化の過程でＩＴ
Ｏ粉末に融着して結晶成長し、粉末を焼結する作用があ
ることが判明した。即ち、本発明によれば、樹脂などの
バインダーを使用する代わりに、有機酸金属塩化合物に
よってＩＴＯ粉末を結合する。Since the organic acid compound is thermally decomposed in the baking step after coating and is removed from the coating film, it has no force to bond the ITO powder. Therefore, the composition for forming a conductive film of the present invention contains an organic acid metal salt compound in addition to the organic acid compound. The organic acid metal salt compound is thermally decomposed in the firing process to finally become an inorganic metal compound (oxide, hydroxide, carbonate, carbide, etc.).
It was found that there is an action of fusing with the O powder to grow crystals, and sintering the powder. That is, according to the present invention, instead of using a binder such as a resin, the ITO powder is bound by the organic acid metal salt compound.

【００１９】本発明において使用する有機酸金属塩化合
物としては、有機酸化合物、特にカルボン酸の金属塩が
好ましい。塩を形成する金属は、無機化合物に転換した
後の透明性に優れ、膜のヘーズを妨害しない金属が好ま
しい。その意味で好ましい金属は、Co、Ni、Pb、Sn、I
n、Al、Fe、Ti、Sb、およびZnである。有機酸金属塩化
合物の具体例としては、酢酸、プロピオン酸、イソ酪
酸、酪酸、オクタン酸、ナフテン酸、ステアリン酸、安
息香酸等の炭素数１〜20の脂肪族、脂環式または芳香族
カルボン酸と上記から選んだいずれかの金属とのカルボ
ン酸金属塩である。The organic acid metal salt compound used in the present invention is preferably an organic acid compound, particularly a carboxylic acid metal salt. The salt-forming metal is preferably a metal that has excellent transparency after conversion into an inorganic compound and does not interfere with the haze of the film. Preferred metals in that sense are Co, Ni, Pb, Sn, and I.
n, Al, Fe, Ti, Sb, and Zn. Specific examples of the organic acid metal salt compound include acetic acid, propionic acid, isobutyric acid, butyric acid, octanoic acid, naphthenic acid, stearic acid, benzoic acid and the like having 1 to 20 carbon atoms, alicyclic or aromatic carboxylic acid. It is a carboxylic acid metal salt of an acid and one of the above-mentioned metals.

【００２０】有機酸金属塩化合物の使用量は、ＩＴＯ粉
末100 重量部に対する量で、 0.2〜15重量部、好ましく
は 0.5〜10重量部の範囲である。有機酸金属塩化合物の
量が0.2 重量部未満であると、焼成時の粉末の焼結性が
不十分となり、膜の導電性と密着性が低下する。一方、
有機酸金属塩化合物の量が15重量部を超えると、焼成後
の塗膜に金属が出現し、ヘーズが高くなり、密着性が低
下する。The amount of the organic acid metal salt compound used is 0.2 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the ITO powder. If the amount of the organic acid metal salt compound is less than 0.2 parts by weight, the sinterability of the powder during firing becomes insufficient, and the conductivity and adhesion of the film deteriorate. on the other hand,
When the amount of the organic acid metal salt compound exceeds 15 parts by weight, the metal appears in the coating film after baking, the haze increases, and the adhesion decreases.

【００２１】ＩＴＯ粉末を分散させる溶媒としては、Ｉ
ＴＯ粉末以外の成分と相溶性のよいものが好ましい。適
当な溶媒の例としては、メタノール、エタノール、イソ
プロパノール、ブタノール等のアルコール類、アセト
ン、メチルエチルケトン、ジアセトンアルコール、シク
ロヘキサノン、イソホロン等のケトン類、トルエン、キ
シレン、ヘキサン、シクロヘキサン等の炭化水素類、
N,N−ジメチルホルムアミド、 N,N−ジメチルアセトア
ミド等のアミド類、ならびに水などが挙げられる。溶媒
は、これに溶解させる有機酸化合物や有機酸金属塩化合
物などの種類に応じて、１種もしくは２種以上を選択し
て用いる。溶媒の量は特に制限されず、塗布に適した粘
度の組成物が得られるような量であればよい。通常は、
固形分５〜60重量％が適正である。The solvent for dispersing the ITO powder is I
Those having good compatibility with components other than TO powder are preferable. Examples of suitable solvents include alcohols such as methanol, ethanol, isopropanol and butanol, acetone, methyl ethyl ketone, diacetone alcohol, cyclohexanone, ketones such as isophorone, toluene, xylene, hexane and hydrocarbons such as cyclohexane.
Examples thereof include amides such as N, N-dimethylformamide and N, N-dimethylacetamide, and water. As the solvent, one kind or two or more kinds are selected and used according to the kind of the organic acid compound or the organic acid metal salt compound to be dissolved therein. The amount of the solvent is not particularly limited as long as the composition having a viscosity suitable for coating can be obtained. Normally,
A solid content of 5 to 60% by weight is appropriate.

【００２２】本発明の導電膜形成用組成物は、上記の各
成分を混合して、有機酸化合物および有機酸金属塩化合
物が溶解した溶液中にＩＴＯ粉末を分散させることによ
り調製できる。各成分とも１種もしくは２種以上を使用
できる。混合は、従来より塗料の調製に利用されてきた
手段により実施できる。所望により、上記以外の任意添
加成分をこの組成物にさらに含有させることもできる。
このような添加成分の例には、界面活性剤、レベリング
剤、カップリング剤等が挙げられるが、これらを多量に
添加することは好ましくなく、通常は導電膜形成用組成
物の固形分の５重量％以下が望ましい。The conductive film-forming composition of the present invention can be prepared by mixing the above-mentioned components and dispersing ITO powder in a solution in which the organic acid compound and the organic acid metal salt compound are dissolved. Each component may be used alone or in combination of two or more. The mixing can be carried out by means conventionally used for preparing a paint. If desired, optional components other than the above may be further contained in the composition.
Examples of such an additive component include a surfactant, a leveling agent, a coupling agent and the like, but it is not preferable to add a large amount of these, and usually 5% of the solid content of the conductive film forming composition is used. It is preferably less than or equal to wt%.

【００２３】本発明の導電膜形成用組成物は、各成分を
単に混合するのではなく、有機酸化合物と有機酸金属塩
化合物の一方または両方の少なくとも一部をＩＴＯ粉末
の表面に予め被覆しておくことによって調製することも
できる。有機酸化合物と有機酸金属塩化合物の両方を予
めＩＴＯ粉末に被覆しておくと、この表面被覆ＩＴＯ粉
末と溶媒とを混合するだけで本発明の導電膜形成用組成
物を調製することができ、塗料化工程が著しく簡便とな
る。The conductive film forming composition of the present invention does not simply mix the respective components, but at least part of one or both of the organic acid compound and the organic acid metal salt compound is coated on the surface of the ITO powder in advance. It can also be prepared by storing. When both the organic acid compound and the organic acid metal salt compound are coated on the ITO powder in advance, the conductive film-forming composition of the present invention can be prepared only by mixing the surface-coated ITO powder and the solvent. In addition, the coating process becomes extremely simple.

【００２４】ＩＴＯ粉末の表面被覆は、有機酸化合物お
よび／または有機酸金属塩化合物を適当な溶媒（例、上
に列挙した溶媒の１種もしくは２種以上) に溶解させ、
得られた溶液を浸漬、噴霧などの適当な処理法によりＩ
ＴＯ粉末の表面に付着させ、乾燥して溶媒を除去するこ
とにより実施できる。ＩＴＯ粉末は微細であるので、単
に容器内で攪拌するだけで容易に流動状態になる。この
流動状態のＩＴＯ粉末に上記溶液を噴霧することにより
表面被覆を行うのが簡便である。有機酸化合物および／
または有機酸金属塩化合物の付着量は、上記のそれぞれ
の上限を超えない範囲で適当に選択できる。ＩＴＯ粉末
に付着した量だけでは不十分な場合には、塗料化の段階
で不足分の有機酸化合物および／または有機酸金属塩化
合物を別に添加して補えばよい。The surface coating of the ITO powder is carried out by dissolving the organic acid compound and / or the organic acid metal salt compound in a suitable solvent (eg, one or more of the solvents listed above),
The obtained solution is treated by an appropriate treatment method such as dipping or spraying.
It can be carried out by adhering it to the surface of the TO powder and drying it to remove the solvent. Since the ITO powder is fine, it can be easily fluidized by simply stirring it in the container. It is convenient to perform surface coating by spraying the above solution onto the ITO powder in a fluidized state. Organic acid compounds and /
Alternatively, the amount of the organic acid metal salt compound attached can be appropriately selected within a range not exceeding the respective upper limits. If the amount attached to the ITO powder is insufficient, it may be supplemented by separately adding the insufficient amount of the organic acid compound and / or the organic acid metal salt compound at the stage of forming the coating material.

【００２５】上記のように調製した本発明の導電膜形成
用組成物を基体に塗布し、300 ℃以上、好ましくは 350
〜550 ℃の非酸化性雰囲気中で焼成して、透明導電膜を
形成する。非酸化性雰囲気は、不活性ガス (例、Ｎ2 、
Ａｒ、Ｈｅ等）のみからなる不活性雰囲気と、還元性ガ
ス（例、Ｈ2 、ＣＯ）のみか、これと不活性ガスとの混
合ガスからなる還元性雰囲気のいずれでもよい。焼成時
間は特に制限されないが、通常は 0.5〜２時間の範囲で
ある。The conductive film-forming composition of the present invention prepared as described above is applied to a substrate and heated to 300 ° C. or higher, preferably 350 ° C. or higher.
The transparent conductive film is formed by baking in a non-oxidizing atmosphere at ~ 550 ° C. The non-oxidizing atmosphere is an inert gas (eg, N 2 ,
Either an inert atmosphere consisting only of Ar, He, etc., a reducing atmosphere consisting only of a reducing gas (eg H 2 , CO), or a mixed gas of this and an inert gas may be used. The firing time is not particularly limited, but is usually in the range of 0.5 to 2 hours.

【００２６】焼成によって、ＩＴＯ粉末の粒子間に存在
する有機酸化合物と有機酸金属塩化合物のうち、有機酸
化合物は分解して塗膜から溶媒とともに除去される。一
方、有機酸金属塩化合物も分解するが、分解により生成
した金属化合物が結晶成長する際にＩＴＯ粉末に融着
し、ＩＴＯ粉末の焼結が行われる。即ち、分解生成物で
ある金属化合物によりＩＴＯ粉末間およびＩＴＯ粉末と
基体との間が結合することによって、基体に密着し、か
つ一体化した塗膜が形成される。By firing, of the organic acid compound and the organic acid metal salt compound existing between the particles of the ITO powder, the organic acid compound is decomposed and removed from the coating film together with the solvent. On the other hand, although the organic acid metal salt compound is also decomposed, the metal compound produced by the decomposition is fused to the ITO powder during crystal growth, and the ITO powder is sintered. That is, the metal compound, which is a decomposition product, bonds between the ITO powders and between the ITO powders and the substrate to form a coating film that is in close contact with and integrated with the substrate.

【００２７】この様子を図２に示す。焼成前には、有機
酸化合物がＩＴＯ粉末表面に吸着することによって、Ｉ
ＴＯ粉末が低ヘーズ化に十分な程度まで分散し、この分
散したＩＴＯ粉末間の間隙に有機酸金属塩化合物が存在
している。そして、焼成によって、この有機酸金属塩化
合物の分解で生じた無機金属化合物 (有機酸金属化合物
の熱分解物) を介してＩＴＯ粉末どうしが融着し、導電
膜が形成される。This state is shown in FIG. Before firing, the organic acid compound is adsorbed on the surface of the ITO powder to
The TO powder is dispersed to a degree sufficient to reduce the haze, and the organic acid metal salt compound is present in the gaps between the dispersed ITO powders. Then, by firing, the ITO powders are fused to each other through the inorganic metal compound (a thermal decomposition product of the organic acid metal compound) generated by the decomposition of the organic acid metal salt compound, and the conductive film is formed.

【００２８】焼成温度を300 ℃以上とすることにより、
特に粒界における酸素原子の移動拡散が促進され、それ
に伴う結晶成長を利用してＩＴＯ粒子間の結合を強固に
することができる。そのため、ヘーズを低く保ったま
ま、導電性と密着性が著しく向上した透明導電膜が得ら
れる。この透明導電膜は、例えば 0.1〜3.0 μｍの膜厚
で、ヘーズ１％以下、表面抵抗値 101〜103 Ω／□台、
密着性 (１mm/mm 碁盤目クロスカット、セロファンテー
プ剥離) 100/100 という優れた膜特性を示す。By setting the firing temperature to 300 ° C. or higher,
In particular, the migration and diffusion of oxygen atoms at the grain boundaries are promoted, and the crystal growth accompanying it can be utilized to strengthen the bonds between the ITO particles. Therefore, it is possible to obtain a transparent conductive film having significantly improved conductivity and adhesion while keeping the haze low. This transparent conductive film has, for example, a film thickness of 0.1 to 3.0 μm, a haze of 1% or less, a surface resistance value of 10 1 to 10 3 Ω / □,
Adhesiveness (1mm / mm cross-cut cross-cut, cellophane tape peeling) 100/100, showing excellent film characteristics.

【００２９】本発明の別の透明導電膜の形成方法によれ
ば、導電膜形成用組成物から有機酸金属塩化合物の少な
くとも一部を除去しておく。即ち、ＩＴＯ粉末、溶媒、
および有機酸化合物からなる導電膜形成用組成物を用意
する。この組成物を基体に塗布した後、必要により塗膜
を乾燥させる。その後、有機酸金属塩化合物を適当な溶
媒に溶解させた溶液を塗膜に含浸させる。有機酸金属塩
化合物の含浸量は、上記と同様、ＩＴＯ粉末100 重量部
に対して 0.2〜15重量部、好ましくは 0.5〜10重量部の
範囲とする。それにより、図２に示した焼成前の塗膜構
造と同様の塗膜を得ることができる。この含浸した塗膜
を次いで上記と同様に300 ℃以上の非酸化性雰囲気中で
焼成することによっても、上述した導電性、密着性、お
よび透明性を有する透明導電膜を得ることができる。According to another method for forming a transparent conductive film of the present invention, at least a part of the organic acid metal salt compound is removed from the conductive film forming composition. That is, ITO powder, solvent,
Then, a conductive film-forming composition comprising an organic acid compound is prepared. After applying this composition to a substrate, the coating film is dried if necessary. Then, the coating film is impregnated with a solution prepared by dissolving the organic acid metal salt compound in a suitable solvent. Similar to the above, the impregnation amount of the organic acid metal salt compound is 0.2 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the ITO powder. Thereby, a coating film having the same coating structure as that shown in FIG. 2 before firing can be obtained. The impregnated coating film is then fired in a non-oxidizing atmosphere at 300 ° C. or higher in the same manner as above to obtain the transparent conductive film having the above-mentioned conductivity, adhesion and transparency.

【００３０】本発明の導電膜形成用組成物より形成され
た透明導電膜は、透明電極、帯電防止膜、電磁波シール
ド膜、熱線カット膜、面発熱体、タッチパネル等として
利用可能である。The transparent conductive film formed from the conductive film forming composition of the present invention can be used as a transparent electrode, an antistatic film, an electromagnetic wave shielding film, a heat ray cutting film, a surface heating element, a touch panel and the like.

【００３１】[0031]

【実施例】次に、本発明を実施例により具体的に説明す
る。なお、実施例で使用したＩＴＯ粉末は、いずれも
(In＋Sn) の合計量に対するSn含有量が５原子％、平均
一次粒子径0.05μｍの粉末であった。EXAMPLES Next, the present invention will be specifically described by way of examples. The ITO powders used in the examples are all
The content of Sn based on the total amount of (In + Sn) was 5 atomic%, and the powder had an average primary particle diameter of 0.05 μm.

【００３２】（実施例１）表１に示す種類および割合の
ＩＴＯ粉末、溶媒、有機酸化合物、および有機酸金属塩
化合物 (合計 100ｇ) を250cc の容器に入れ、直径 0.3
〜0.6mm のジルコニアビーズ (ミクロハイカ、昭和シェ
ル石油) 100gを加え、ペイントシェーカーで３時間混合
してＩＴＯ粉末を分散させることにより、導電膜形成用
組成物を得た。この組成物のＩＴＯ粉末の分散状態を目
視観察により評価した。Example 1 ITO powders of the types and proportions shown in Table 1, a solvent, an organic acid compound, and an organic acid metal salt compound (total 100 g) were placed in a 250 cc container and had a diameter of 0.3
A composition for forming a conductive film was obtained by adding 100 g of zirconia beads (Micro-Hika, Showa Shell Sekiyu) having a size of ˜0.6 mm and mixing the mixture with a paint shaker for 3 hours to disperse the ITO powder. The dispersed state of ITO powder of this composition was evaluated by visual observation.

【００３３】こうして調製した各導電膜形成用組成物
を、傾斜させたガラス板 (厚さ２mm、ヘーズ 0.0％) に
フローコートし、表１に記載した温度および雰囲気で１
時間焼成して、ガラス板上に導電膜を形成した。得られ
た導電膜の表面抵抗値を四短針法 (ロレスタＡＰ：三菱
油化）により、ヘーズをヘーズメーター (ＨＧＭ−３
Ｄ：スガ試験機）により測定した。また、膜厚をＳＥＭ
断面写真より、密着性を１mm/mm 碁盤目クロスカット、
セロファンテープ剥離 (枡目数100)により求めた。これ
らの測定結果も表１に示す。Each of the thus-prepared compositions for forming a conductive film was flow-coated on a tilted glass plate (thickness: 2 mm, haze: 0.0%), and the composition was subjected to 1 at the temperature and atmosphere shown in Table 1.
By firing for a period of time, a conductive film was formed on the glass plate. The surface resistance of the obtained conductive film was measured by a four-needle method (Loresta AP: Mitsubishi Yuka) to measure haze (HGM-3).
D: Suga tester). In addition, the film thickness is SEM
From the cross-sectional photograph, the adhesion is 1mm / mm cross-cut cross-cut,
The cellophane tape was peeled off (100 meshes). The results of these measurements are also shown in Table 1.

【００３４】比較のために、導電膜形成用組成物の組成
が本発明の範囲外であるか、焼成条件が本発明の範囲外
である比較例の実験も行った。その試験条件および試験
結果も表１に併せて示す。For comparison, an experiment of a comparative example in which the composition of the conductive film forming composition was outside the scope of the present invention or the firing conditions were outside the scope of the present invention was also conducted. The test conditions and test results are also shown in Table 1.

【００３５】[0035]

【表１】 [Table 1]

【００３６】表１に示すように、本発明により、ヘーズ
１％以下、表面抵抗値 101〜102 Ω／□台 (ほとんどは
101 Ω／□台) 、密着性 100/100という、低ヘーズ、低
抵抗で密着性に優れた透明導電膜を形成することができ
た。これに対し、焼成温度が300 ℃未満であるか、有機
酸金属塩化合物の量が範囲外であると、透明性 (ヘー
ズ) 、導電性、密着性がいずれも低下した。また、有機
酸化合物の量が範囲外であると、ＩＴＯ粉末の分散性が
低下した。また、従来法によりバインダー樹脂を用いて
得た透明導電膜は、ヘーズ、導電性、密着性のいずれも
劣っていた。As shown in Table 1, according to the present invention, the haze is 1% or less and the surface resistance value is in the range of 10 1 to 10 2 Ω / □ (most of them are
It was possible to form a transparent conductive film having a low haze, a low resistance, and an excellent adhesiveness of 10 1 Ω / □) and an adhesiveness of 100/100. On the other hand, when the baking temperature was less than 300 ° C. or the amount of the organic acid metal salt compound was out of the range, the transparency (haze), conductivity and adhesion were all deteriorated. Moreover, when the amount of the organic acid compound was out of the range, the dispersibility of the ITO powder was lowered. Further, the transparent conductive film obtained by using the binder resin by the conventional method was inferior in all of haze, conductivity and adhesion.

【００３７】（実施例２）本実施例では、ＩＴＯ粉末を
予め有機酸化合物および有機酸金属塩化合物で表面被覆
して使用した。表面被覆は、表２の表面処理組成物の欄
に示す種類および割合で有機酸化合物と有機酸金属塩化
合物を溶媒中に溶解させ、得られた溶液を、攪拌により
流動状態にしたＩＴＯ粉末に噴霧した後、攪拌を続けな
がら140 ℃で乾燥することにより行った。こうして得た
表面被覆ＩＴＯ粉末の凝集状態を目視で観察したとこ
ろ、いずれも良好な分散状態を示した。Example 2 In this example, the ITO powder was used after being surface-coated with an organic acid compound and an organic acid metal salt compound in advance. The surface coating was carried out by dissolving the organic acid compound and the organic acid metal salt compound in the solvent in the types and proportions shown in the column of the surface treatment composition in Table 2, and the obtained solution was made into ITO powder which was made into a fluid state by stirring. After spraying, drying was carried out at 140 ° C. with continuous stirring. The agglomerated state of the surface-coated ITO powder thus obtained was visually observed, and all showed a good dispersed state.

【００３８】この表面被覆ＩＴＯ粉末と溶媒 (トルエ
ン) を表２の塗料の欄に示す割合で使用して、実施例１
と同様の方法で分散処理することにより塗料化して、導
電膜形成用組成物を得た。使用する溶媒には、場合によ
り表２に示す種類および割合で有機酸化合物を溶解させ
ておいた。Example 1 was prepared using this surface-coated ITO powder and solvent (toluene) in the proportions shown in the paint column of Table 2.
The dispersion treatment was carried out in the same manner as in the above to make a coating material, thereby obtaining a conductive film-forming composition. In the solvent used, the organic acid compound was dissolved in the types and proportions shown in Table 2 in some cases.

【００３９】こうして調製した各導電膜形成用組成物
を、傾斜させたガラス板 (厚さ２mm、ヘーズ 0.0％) に
フローコートし、表２に記載した温度および雰囲気で１
時間焼成して、ガラス板上に導電膜を形成した。得られ
た導電膜の表面抵抗値、ヘーズ、膜厚および密着性を実
施例１と同様に測定した結果も表２に併せて示す。Each composition for forming a conductive film thus prepared was flow-coated on a tilted glass plate (thickness: 2 mm, haze: 0.0%), and the composition was subjected to 1 at the temperature and atmosphere shown in Table 2.
By firing for a period of time, a conductive film was formed on the glass plate. Table 2 also shows the results of measuring the surface resistance value, haze, film thickness and adhesion of the obtained conductive film in the same manner as in Example 1.

【００４０】[0040]

【表２】 [Table 2]

【００４１】表２に示したように、有機酸化合物と有機
酸金属塩化合物を予めＩＴＯ粉末に表面被覆しておくこ
とによっても、表面抵抗値 101〜102 Ω／□台の導電性
に優れた透明導電膜を得ることができた。ただし、ヘー
ズと密着性は、これらの化合物を溶媒に溶解させた実施
例１に比べるとやや低下した。比較のために、有機酸化
合物の被覆量が過大である表面被覆ＩＴＯ粉末を調製し
たが、この表面被覆ＩＴＯ粉末は、表２に示すように凝
集体を形成し、容易に分散可能な状態ではなかった。As shown in Table 2, by coating the surface of the ITO powder with the organic acid compound and the organic acid metal salt compound in advance, the surface resistance value becomes 10 1 to 10 2 Ω / □. An excellent transparent conductive film could be obtained. However, the haze and adhesion were slightly lower than those of Example 1 in which these compounds were dissolved in a solvent. For comparison, a surface-coated ITO powder having an excessively large amount of the organic acid compound was prepared. The surface-coated ITO powder formed aggregates as shown in Table 2 and was easily dispersed. There wasn't.

【００４２】（実施例３）本実施例では、有機酸金属塩
化合物を、後からＩＴＯ粉末の塗膜に含浸させる方法で
透明導電膜を形成した。ＩＴＯ粉末を表３のＡ液の欄に
示す種類および割合の溶媒および有機酸化合物(合計100
ｇ) と共に250cc の容器に入れ、直径 0.3〜0.6mm の
ジルコニアビーズ (ミクロハイカ、昭和シェル石油) 10
0gを加え、ペイントシェーカーで３時間混合してＩＴＯ
粉末を分散させることにより、塗布用のＩＴＯ粉末分散
液 (Ａ液とする) を得た。このＡ液のＩＴＯ粉末の分散
状態を目視観察で評価した。(Example 3) In this example, a transparent conductive film was formed by a method of impregnating a coating film of ITO powder with an organic acid metal salt compound later. For the ITO powder, the types and proportions of the solvent and the organic acid compound shown in the column of liquid A in Table 3 (total 100
g) and put it in a 250cc container and zirconia beads with a diameter of 0.3-0.6mm (Micro hika, Showa Shell Sekiyu) 10
Add 0 g, mix with a paint shaker for 3 hours and mix with ITO
By dispersing the powder, an ITO powder dispersion liquid (referred to as liquid A) for coating was obtained. The dispersed state of the ITO powder of this liquid A was evaluated by visual observation.

【００４３】別に、表３のＢ液の欄に示す種類および割
合で有機酸金属塩化合物を溶媒に溶解させて含浸用溶液
(Ｂ液とする) を得た。上記Ａ液を傾斜させたガラス板
(厚さ２mm、ヘーズ 0.0％) にフローコートして塗布
し、風乾により塗膜を乾燥させた後、この塗膜上にＢ液
をフローコート法により塗布して塗膜に含浸させた。Ｂ
液の塗布量は 0.3〜0.7 mg/cm2であった。その後、表３
に記載した温度および雰囲気で１時間焼成して、ガラス
板上に導電膜を形成した。得られた導電膜の表面抵抗
値、ヘーズ、膜厚および密着性を実施例１と同様に測定
した結果も表３に併せて示す。Separately, an organic acid metal salt compound was dissolved in a solvent in the kind and proportion shown in the column of Solution B in Table 3 to prepare a solution for impregnation.
(Solution B) was obtained. A glass plate in which the liquid A is inclined
(Thickness 2 mm, haze 0.0%) was applied by flow coating, and the coating film was dried by air drying, and then liquid B was applied onto this coating film by the flow coating method to impregnate the coating film. B
The coating amount of the liquid was 0.3 to 0.7 mg / cm 2 . After that, Table 3
By firing at the temperature and atmosphere described in 1 hour, a conductive film was formed on the glass plate. Table 3 also shows the results of measuring the surface resistance value, haze, film thickness and adhesion of the obtained conductive film in the same manner as in Example 1.

【００４４】[0044]

【表３】 [Table 3]

【００４５】表３から分かるように、有機酸化合物とＩ
ＴＯ粉末から塗膜を形成し、この塗膜に有機酸金属塩化
合物を含浸させてから焼成することにより、導電性、密
着性、透明性 (低ヘーズ) のいずれにも優れた透明導電
膜を得ることができた。実施例１〜３の３種類の方法の
うち、本実施例の方法で得た塗膜がヘーズと導電性の両
面で最も高い性能を示す傾向があることが判明した。As can be seen from Table 3, organic acid compounds and I
By forming a coating film from TO powder, impregnating this coating film with an organic acid metal salt compound, and then baking it, a transparent conductive film excellent in conductivity, adhesion, and transparency (low haze) can be obtained. I was able to get it. It was found that among the three methods of Examples 1 to 3, the coating film obtained by the method of this example tends to exhibit the highest performance in terms of both haze and conductivity.

【００４６】比較のために、Ａ液における有機酸化合物
の量を範囲外にしてＩＴＯ粉末の分散液を調製したが、
表３に示すように、いずれも分散不良であった。For comparison, an ITO powder dispersion was prepared with the amount of the organic acid compound in the liquid A outside the range.
As shown in Table 3, the dispersion was poor in all cases.

【００４７】[0047]

【発明の効果】本発明の導電膜形成用組成物は、バイン
ダーを用いた従来の導電膜形成用組成物 (導電塗料) に
比べて、透明性、導電性および密着性のいずれにも優れ
た透明導電膜を形成することができる。その結果、塗布
法という簡便かつ効率的な方法で、表面抵抗値 101〜10
2 Ω／□台、ヘーズ２％以下、密着性95／100 以上、好
ましくは表面抵抗値 101Ω／□台、ヘーズ１％以下、密
着性 100／100 という、極めて高性能の透明導電膜を安
価に得ることが可能となり、工業的利用価値は非常に高
い。The conductive film-forming composition of the present invention is superior in transparency, conductivity and adhesion to conventional conductive film-forming compositions using a binder (conductive paint). A transparent conductive film can be formed. As a result, the surface resistance of 10 1 to 10
2 Omega / □ platform, haze of 2% or less, adhesion 95/100 or more, preferably a surface resistance of 10 1 Ω / □ platform, haze of 1% or less, as adhesion 100/100, extremely high performance of the transparent conductive film It can be obtained at low cost and has a very high industrial utility value.

【図面の簡単な説明】[Brief description of drawings]

【図１】バインダーを用いた従来の導電塗料の塗膜の模
式図である。FIG. 1 is a schematic view of a coating film of a conventional conductive paint using a binder.

【図２】本発明の導電膜形成用組成物の塗膜の焼成前後
の模式図である。FIG. 2 is a schematic diagram before and after firing of a coating film of the conductive film-forming composition of the present invention.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 林 年治 埼玉県大宮市北袋町１丁目297番地 三菱 マテリアル株式会社中央研究所内 (72)発明者 石原 真興 栃木県宇都宮市山本町134−163 (72)発明者 室内 聖人 東京都田無市芝久保町３−18−８ ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Toshiharu Hayashi 1-297 Kitabukuro-cho, Omiya City, Saitama Prefecture Central Research Laboratory, Mitsubishi Materials Corporation (72) Inventor Maoki Ishihara 134-163 Yamamotocho, Utsunomiya City, Tochigi Prefecture (72) ) Inventor Chamber Saint 3-18-8 Shibakubocho, Tanashi City, Tokyo

Claims (10)

【特許請求の範囲】[Claims] 【請求項１】 錫を含有する酸化インジウム粉末、溶
媒、有機酸化合物、および有機酸金属塩化合物からな
り、前記粉末100 重量部に対して、有機酸化合物を１〜
40重量部、有機酸金属塩化合物を 0.2〜15重量部の割合
で含有する、導電膜形成用組成物。1. An indium oxide powder containing tin, a solvent, an organic acid compound, and an organic acid metal salt compound, wherein 1 to 100 parts by weight of the powder contains 1 to 1 parts of the organic acid compound.
A conductive film-forming composition containing 40 parts by weight of an organic acid metal salt compound in a proportion of 0.2 to 15 parts by weight. 【請求項２】 前記有機酸化合物が炭素数１〜18の脂肪
族カルボン酸、炭素数６〜20の芳香族カルボン酸、およ
びエチレンオキサイド鎖を有するホスホン酸よりなる群
から選ばれた１種もしくは２種以上である、請求項１記
載の導電膜形成用組成物。2. The organic acid compound is one selected from the group consisting of an aliphatic carboxylic acid having 1 to 18 carbon atoms, an aromatic carboxylic acid having 6 to 20 carbon atoms, and a phosphonic acid having an ethylene oxide chain, or The composition for forming a conductive film according to claim 1, which is two or more kinds. 【請求項３】 前記有機酸金属塩化合物が有機酸化合物
のCo、Ni、Pb、Sn、In、Al、Fe、Ti、Sb、およびZn塩よ
りなる群から選ばれた１種もしくは２種以上である、請
求項１または２記載の導電膜形成用組成物。3. The organic acid metal salt compound is one or more selected from the group consisting of Co, Ni, Pb, Sn, In, Al, Fe, Ti, Sb, and Zn salts of organic acid compounds. The composition for forming a conductive film according to claim 1 or 2. 【請求項４】 前記有機酸化合物および有機酸金属塩化
合物の一方または両方の少なくとも一部が、前記酸化イ
ンジウム粉末の表面に付着した表面被覆物の状態で存在
する、請求項１ないし３のいずれかに記載の導電膜形成
用組成物。4. The method according to claim 1, wherein at least a part of one or both of the organic acid compound and the organic acid metal salt compound is present in the form of a surface coating adhered to the surface of the indium oxide powder. The composition for forming a conductive film as described in 1. 【請求項５】 請求項１ないし４のいずれか１項に記載
の透明導電膜形成用組成物を基体に塗布した後、300 ℃
以上の非酸化性雰囲気中で焼成することを特徴とする、
導電膜の形成方法。5. After applying the composition for forming a transparent conductive film according to any one of claims 1 to 4 to a substrate, 300 ° C.
Characterized by firing in the above non-oxidizing atmosphere,
Method for forming conductive film. 【請求項６】 錫を含有する酸化インジウム粉末、溶
媒、および有機酸化合物からなり、前記粉末100 重量部
に対して有機酸化合物を１〜40重量部の割合で含有する
導電膜形成用組成物を基体に塗布し、得られた塗膜に有
機酸金属塩化合物の溶液を含浸させた後、300 ℃以上の
非酸化性雰囲気中で焼成することを特徴とする、導電膜
の形成方法。6. A composition for forming a conductive film, which comprises an indium oxide powder containing tin, a solvent, and an organic acid compound, and contains 1 to 40 parts by weight of the organic acid compound with respect to 100 parts by weight of the powder. Is applied to a substrate, the resulting coating film is impregnated with a solution of an organic acid metal salt compound, and then baked in a non-oxidizing atmosphere at 300 ° C. or higher. 【請求項７】 前記有機酸化合物が炭素数１〜18の脂肪
族カルボン酸、炭素数６〜20の芳香族カルボン酸、およ
びエチレンオキサイド鎖を有するホスホン酸よりなる群
から選ばれた１種もしくは２種以上である、請求項６記
載の導電膜の形成方法。7. The organic acid compound is one selected from the group consisting of an aliphatic carboxylic acid having 1 to 18 carbon atoms, an aromatic carboxylic acid having 6 to 20 carbon atoms, and a phosphonic acid having an ethylene oxide chain, or The method for forming a conductive film according to claim 6, wherein there are two or more kinds. 【請求項８】 前記有機酸金属塩化合物が有機酸化合物
のCo、Ni、Pb、Sn、In、Al、Fe、Ti、Sb、およびZn塩よ
りなる群から選ばれた１種もしくは２種以上である、請
求項６または７記載の導電膜の形成方法。8. The organic acid metal salt compound is one or more selected from the group consisting of Co, Ni, Pb, Sn, In, Al, Fe, Ti, Sb, and Zn salts of organic acid compounds. The method for forming a conductive film according to claim 6, which is 【請求項９】 錫を含有する酸化インジウム粉末が有機
酸金属塩化合物の熱分解物により融着された構造を有す
る、透明導電膜。9. A transparent conductive film having a structure in which tin-containing indium oxide powder is fused by a thermal decomposition product of an organic acid metal salt compound. 【請求項１０】 前記有機酸金属塩化合物が有機酸化合
物のCo、Ni、Pb、Sn、In、Al、Fe、Ti、Sb、およびZn塩
よりなる群から選ばれた１種もしくは２種以上である、
請求項９記載の透明導電膜。10. The organic acid metal salt compound is one or more selected from the group consisting of Co, Ni, Pb, Sn, In, Al, Fe, Ti, Sb, and Zn salts of organic acid compounds. Is,
The transparent conductive film according to claim 9.
JP28375494A 1994-11-17 1994-11-17 Composition for forming conductive film and method for forming conductive film Expired - Lifetime JP3230395B2 (en)

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