JPH08185797A - Transparent conductive film forming process liquid and manufacture of transparent conductive film using this process liquid - Google Patents
Transparent conductive film forming process liquid and manufacture of transparent conductive film using this process liquidInfo
- Publication number
- JPH08185797A JPH08185797A JP33808094A JP33808094A JPH08185797A JP H08185797 A JPH08185797 A JP H08185797A JP 33808094 A JP33808094 A JP 33808094A JP 33808094 A JP33808094 A JP 33808094A JP H08185797 A JPH08185797 A JP H08185797A
- Authority
- JP
- Japan
- Prior art keywords
- transparent conductive
- conductive film
- forming
- treatment liquid
- silicate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Formation Of Various Coating Films On Cathode Ray Tubes And Lamps (AREA)
- Vessels, Lead-In Wires, Accessory Apparatuses For Cathode-Ray Tubes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ＯＡ機器のディスプレ
イやテレビジョン（ＴＶ）ブラウン管等の陰極線管から
発生する電界をシールドするための透明導電膜の作製方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a transparent conductive film for shielding an electric field generated from a cathode ray tube such as a display of an OA equipment or a television (TV) cathode ray tube.
【０００２】[0002]
【従来の技術】テレビゲーム機やパーソナルコンピュー
ター、ワープロ等の陰極線管（ＣＲＴ）においては、表
示画面が見やすく、視覚疲労を感じさせないことのほか
に、ＣＲＴ表面の帯電によるホコリの付着や手が触れた
時の電撃ショック等がないことが要求される。さらにこ
れに加えて最近では、ＣＲＴから発生する低周波電磁波
の人体に対する悪影響が懸念されており、このような電
磁波が外部に漏洩しないＣＲＴが望まれている。2. Description of the Related Art In a cathode ray tube (CRT) of a video game machine, a personal computer, a word processor, etc., the display screen is easy to see and does not cause visual fatigue. It is required that there is no electric shock when hit. In addition to this, recently, there is a concern that a low-frequency electromagnetic wave generated from a CRT may adversely affect the human body, and a CRT in which such an electromagnetic wave does not leak outside is desired.
【０００３】電磁波は、偏向コイルやフライバックトラ
ンスから発生し、ＴＶの大型化に伴って益々大きな電磁
波が周囲に洩れる傾向にある。磁界の漏洩は、偏向コイ
ルの形状を変える等の工夫で大部分を防止することがで
きる。一方、電界の漏洩に対しては、ＣＲＴ前面ガラス
表面に導電性の透明被膜を形成することにより防止でき
る。この方法は、近年、帯電防止のためにとられてきた
対策と原理的には同一である。ただし、この場合の導電
性被膜の導電性は、帯電防止用に形成されていた導電性
被膜の導電性よりもはるかに高い値が求められ、帯電防
止には表面抵抗で１０８Ω／□程度で十分とされている
が、漏洩電界を防ぐためには少なくとも１０６Ω／□以
下、好ましくは１０２〜１０３Ω／□台の低抵抗の透明
膜を形成する必要がある。Electromagnetic waves are generated from the deflection coil and the flyback transformer, and as the TV becomes larger, an increasingly large electromagnetic wave tends to leak to the surroundings. Most of the magnetic field leakage can be prevented by changing the shape of the deflection coil. On the other hand, leakage of an electric field can be prevented by forming a conductive transparent film on the surface of the CRT front glass. This method is, in principle, the same as the measures taken in recent years to prevent electrification. However, the conductivity of the conductive film in this case is required to be much higher than the conductivity of the conductive film formed for the antistatic purpose, and the surface resistance is about 10 8 Ω / □ for the antistatic property. However, in order to prevent a leakage electric field, it is necessary to form a low resistance transparent film of at least 10 6 Ω / □ or less, preferably 10 2 to 10 3 Ω / □.
【０００４】このような透明膜の形成において、材料的
にはアンチモン含有酸化錫（ＡＴＯ）や錫含有酸化イン
ジウム（ＩＴＯ）が用いられており、また工程的には４
５０℃以下、好ましくは２００℃程度以下の温度での成
膜が求められる。これは温度条件としてはガラス軟化点
近傍の温度以下とする必要があり、かつコストや歩留を
考慮するとフェイスパネルを真空封着後のＣＲＴ完成球
に透明導電膜を形成することが好ましいという事情によ
る。In forming such a transparent film, antimony-containing tin oxide (ATO) or tin-containing indium oxide (ITO) is used as a material, and the process is 4
Film formation is required at a temperature of 50 ° C. or lower, preferably about 200 ° C. or lower. This is because the temperature condition needs to be lower than the temperature near the glass softening point, and in consideration of cost and yield, it is preferable to form the transparent conductive film on the CRT completed sphere after vacuum sealing the face panel. by.
【０００５】上記の要求に対応するため、従来よりスパ
ッタ法や蒸着法によりＡＴＯやＩＴＯの被膜を形成する
ものなどいくつか知られているが、さらに低コストで低
い表面抵抗を実現できるものとして、アルキルシリケー
トの結合剤とＮーメチル・２ーピロリドンを主成分とす
る極性溶媒中に、錫を１〜１０重量％含有した平均粒径
５０ｎｍ以下のＩＴＯ粉末を１〜１５重量％分散させた
電界シールド用処理液が提案されている（特開平６−２
３４５５２号公報参照）。これによれば、前記の処理液
をＣＲＴ前面ガラスに塗布、乾燥後、２００℃以下の温
度で焼成することにより、１０３〜１０６Ω／□の表面
抵抗値が得られる。この処理液には、導電性微粉末とし
てＩＴＯを主成分として用いるが、ＡＴＯやアルミニウ
ム含有酸化亜鉛（ＡＺＯ）で一部を代替または置換する
こともできる。[0005] In order to meet the above requirements, there are some known methods such as a method of forming a film of ATO or ITO by a sputtering method or a vapor deposition method. However, as a method capable of realizing a low surface resistance at a lower cost, 1 to 15% by weight of ITO powder having an average particle size of 50 nm or less containing tin in an amount of 1 to 10% by weight is dispersed in a polar solvent containing an alkyl silicate binder and N-methyl-2-pyrrolidone as main components for an electric field shield A treatment liquid has been proposed (Japanese Patent Laid-Open No. 6-2
34552). According to this, a surface resistance value of 10 3 to 10 6 Ω / □ can be obtained by applying the treatment liquid to a CRT front glass, drying and baking at a temperature of 200 ° C. or lower. In this treatment liquid, ITO is used as a conductive fine powder as a main component, but ATO or aluminum-containing zinc oxide (AZO) may be partially substituted or substituted.
【０００６】[0006]
【発明が解決しようとする課題】上記のインク塗布法
は、真空蒸着やスパッタ法等の透明導電膜形成方法に比
べてはるかに簡便であって製造コストも低く、ＣＲＴの
電界シールドへの対応としては極めて有利な方法であ
る。しかしながら、この方法はスパッタ法や蒸着法に比
べると、得られる表面抵抗値においてやや劣ることが欠
点として挙げられる。前記の処理液を用いた場合、膜厚
を厚くすれば１０３Ω／□台の低表面抵抗も可能である
が、膜厚を厚くすると膜に曇り（ヘイズ）が生じてくる
ので好ましくない。したがって、膜厚を増加せずに電界
シールド効果を高めるためには、可及的に比抵抗の小さ
い膜をインク法で形成することが望まれる。The above-mentioned ink coating method is much simpler and has a lower manufacturing cost than transparent conductive film forming methods such as vacuum vapor deposition and sputtering, and is suitable as a CRT electric field shield. Is a very advantageous method. However, this method has a drawback in that the obtained surface resistance value is slightly inferior to the sputtering method or the vapor deposition method. When using the processing liquid, although the thickness can be also thickened them if 10 3 Ω / □ pedestal low surface resistance, since when increasing the thickness cloudy film (haze) is arise unfavorably. Therefore, in order to enhance the electric field shielding effect without increasing the film thickness, it is desired to form a film having a resistivity as small as possible by the ink method.
【０００７】本発明は、従来のこのような実状に鑑みて
なされたもので、低温で焼成可能であり、ＣＲＴの電界
シールド用の高い導電性をもつ膜を形成できる透明導電
膜形成用処理液およびその処理液を用いた透明導電膜の
作製方法を提案しようとするものである。The present invention has been made in view of such a conventional situation, and is a treatment liquid for forming a transparent conductive film which can be fired at a low temperature and can form a film having high conductivity for the electric field shield of a CRT. And a method for producing a transparent conductive film using the treatment liquid.
【０００８】[0008]
【課題を解決するための手段】本発明に係る透明導電膜
形成用処理液は、（１）ＩＴＯとＡＴＯのうちのいずれ
か一方もしくは両方の微粉末、七価のレニウム化合物と
その還元能を有する化合物、および有機溶媒とから実質
的に構成されるもの、（２）ＩＴＯとＡＴＯのうちのい
ずれか一方もしくは両方の微粉末、七価のレニウム化合
物とその還元能を有する化合物、アルキルシリケート部
分加水分解重合物を主成分とするシリケート系バインダ
ー、および有機溶剤とから実質的に構成されるもの、
（３）前記七価のレニウム化合物の還元能を有する化合
物として、水、アルコール、アンモニアのうちの一種も
しくは二種以上を使用すること、（４）前記七価のレニ
ウム化合物は、七酸化二レニウム、過レニウム酸、過レ
ニウム酸アンモニウムのうちの一種以上であること、
（５）前記七価のレニウム化合物の含有量は、三酸化レ
ニウムに換算して、錫含有酸化インジウムまたは／およ
びアンチモン含有酸化錫微粉末の含有量に対して重量比
で０．１％以上２５％未満であることを特徴とする。さ
らに、本発明に係る前記透明導電形成用処理液を用いた
透明導電膜の作製方法は、（６）前記透明導電形成用処
理液を含む塗布液を基体に塗布後、１００℃以上４５０
℃以下の温度で焼成すること、（７）前記透明導電膜形
成用処理液を含む塗布液を基体に塗布後、アルキルシリ
ケート部分加水分解重合物を主成分とするシリケート系
オーバーコート液を塗布し、１００℃以上４５０℃以下
の温度で焼成することを特徴とする。The treatment liquid for forming a transparent conductive film according to the present invention comprises (1) a fine powder of one or both of ITO and ATO, a heptavalent rhenium compound and its reducing ability. (2) Fine powder of either or both of ITO and ATO, a heptavalent rhenium compound and a compound having its reducing ability, and an alkyl silicate moiety. A silicate-based binder whose main component is a hydrolyzed polymer, and what is substantially composed of an organic solvent,
(3) Use of one or more of water, alcohol, and ammonia as the compound having a reducing ability of the heptavalent rhenium compound. (4) The heptavalent rhenium compound is dirhenium heptoxide. , One or more of perrhenic acid and ammonium perrhenate,
(5) The content of the heptavalent rhenium compound is 0.1% or more by weight ratio with respect to the content of tin-containing indium oxide or / and antimony-containing tin oxide fine powder in terms of rhenium trioxide. It is less than%. Further, the method for producing a transparent conductive film using the transparent conductive forming treatment liquid according to the present invention is (6) 100 ° C. or higher 450 ° C. after applying a coating liquid containing the transparent conductive forming treatment liquid onto a substrate.
Baking at a temperature of ℃ or less, (7) After applying a coating liquid containing the transparent conductive film forming treatment liquid to the substrate, apply a silicate-based overcoat liquid containing an alkyl silicate partially hydrolyzed polymer as a main component. The firing is performed at a temperature of 100 ° C. or higher and 450 ° C. or lower.
【０００９】[0009]
【作用】本発明の処理液において、透明導電性を与える
微粒子の主体として用いられるＩＴＯ粉末としては、錫
を１〜１０重量％含有した平均粒径１００ｎｍ以下のも
のを使用することができ、またＡＴＯ粉末としては、ア
ンチモンを１〜２０重量％含有した平均粒径７０ｎｍ以
下のものを使用することができるが、膜にしたときに十
分低いヘイズ値や反射率を得るには、平均粒径は両者と
も５０ｎｍ以下のものがより好ましい。In the treatment liquid of the present invention, the ITO powder used as a main component of the fine particles imparting transparent conductivity may be one having an average particle size of 100 nm or less and containing 1 to 10% by weight of tin. As the ATO powder, one having an average particle size of 70 nm or less containing 1 to 20% by weight of antimony can be used, but in order to obtain a sufficiently low haze value and reflectance when formed into a film, the average particle size is It is more preferable that both are 50 nm or less.
【００１０】ＩＴＯやＡＴＯの酸素の一部をフッ素で置
換すると導電性向上のために効果のあることが知られて
いるが、本発明においてもＩＴＯやＡＴＯの代わりにフ
ッ素添加酸化インジウム（ＦＩＯ）、フッ素添加酸化錫
（ＦＴＯ）、フッ素添加酸化亜鉛（ＦＺＯ）等で一部を
代替してもよい。また、ＩＴＯやＡＴＯの代わりにＡＺ
Ｏ（アルミニウム含有酸化亜鉛）で一部を代替してもよ
い。It is known that substituting a part of oxygen in ITO or ATO with fluorine is effective for improving conductivity, and in the present invention, indium oxide (FIO) containing fluorine is added instead of ITO or ATO. Alternatively, fluorine-added tin oxide (FTO), fluorine-added zinc oxide (FZO) or the like may be partially substituted. Also, instead of ITO or ATO, AZ
O (aluminum-containing zinc oxide) may be partially substituted.
【００１１】本発明において、上記の透明導電性微粒子
に加えて、七価のレニウム化合物とその還元能を有する
化合物を用いるのは、これらを含む溶液をコートした膜
を焼成すると、膜中に三酸化レニウム（ＲｅＯ３）が析
出するからである。ＲｅＯ３は比抵抗においてＩＴＯや
ＡＴＯよりも２〜４桁小さいため、ＩＴＯやＡＴＯに加
えてＲｅＯ３が膜の中に混合されて導電層を形成するこ
とにより膜の導電性が顕著に増加する。In the present invention, in addition to the above-mentioned transparent conductive fine particles, a heptavalent rhenium compound and a compound having its reducing ability are used because when a film coated with a solution containing them is baked, three This is because rhenium oxide (ReO 3 ) is deposited. Since the specific resistance of ReO 3 is smaller than that of ITO or ATO by 2 to 4 digits, the conductivity of the film is remarkably increased by mixing ReO 3 in addition to ITO or ATO to form a conductive layer. .
【００１２】ＲｅＯ３を析出させる機構の詳細は不明で
あるが、七価のレニウム化合物により溶媒中に供給され
る過レニウム酸イオンＲｅＯ４ ＋が焼成中に還元されて
ＲｅＯ３を生成する過程や、七価のレニウムイオンＲｅ
７＋が六価のレニウムイオンＲｅ６＋に還元された後こ
れがＲｅＯ３となる過程等が考えられる。Although the details of the mechanism for precipitating ReO 3 are unknown, the process of reducing the perrhenate ion ReO 4 + supplied into the solvent by the heptavalent rhenium compound during firing to form ReO 3 and , Heptavalent rhenium ion Re
A process in which 7+ is reduced to hexavalent rhenium ion Re 6+ and then becomes ReO 3 is considered.
【００１３】還元能を有する化合物としては、七価のレ
ニウムイオンＲｅ７＋や過レニウム酸イオンＲｅＯ４ ＋
を焼成中に還元してＲｅＯ３を生成し、しかも適当な揮
発性を有する化合物が使用され、その好ましい例として
は水、アルコール、アンモニア等を挙げることができ
る。還元作用は水とアルコールがアンモニアよりも強
く、また焼成温度が高いほど強まるが、溶媒の還元作用
が強すぎると、ＲｅＯ３やＲｅ２Ｏ３を生成して導電性
が低下する。導電性に重要なＲｅＯ３の生成量や生成状
態は、処理液に含有されるＲｅ７＋イオン、ＲｅＯ４ ＋
イオン、ＩＴＯ／ＡＴＯ微粒子の量や、焼成温度に大き
な影響を受けるので、これらの条件に応じて溶媒中の
水、アルコール、アンモニアの添加量の選択が必要であ
るが、一般的にはメタノール、エタノール等の低級アル
コールを還元溶媒とした時に好ましい結果が得られてい
る。Examples of the compound having a reducing ability include a heptavalent rhenium ion Re 7+ and a perrhenate ion ReO 4 +.
Is used to produce ReO 3 by reduction during firing, and a compound having appropriate volatility is used. Preferred examples thereof include water, alcohol, ammonia and the like. The reducing action is stronger when water and alcohol are stronger than ammonia and the baking temperature is higher, but when the reducing action of the solvent is too strong, ReO 3 or Re 2 O 3 is produced and conductivity is lowered. The production amount and production state of ReO 3 important for conductivity are Re 7 + ion and ReO 4 + contained in the treatment liquid.
Since the amount of ions, the amount of ITO / ATO fine particles, and the firing temperature are greatly affected, it is necessary to select the amount of water, alcohol, and ammonia added in the solvent according to these conditions. Preferable results have been obtained when a lower alcohol such as ethanol is used as the reducing solvent.
【００１４】七価のレニウム化合物としては、溶液中に
七価のレニウムを含むイオンＲｅ７＋やＲｅＯ４を供給
できるものであれば何でもよく、例えば七酸化二レニウ
ム（Ｒｅ２Ｏ７）、過レニウム酸（ＨＲｅＯ４）レニウ
ムオキシ酸塩（ＭＲｅＯ４：Ｍ＝Ｎａ、Ｋ、Ａｇ、Ｃ
ｓ、Ｐｂ、Ｔｌ、Ｒｂ、およびＮ（ＲｅＯ４）２：Ｎ＝
Ｓｒ、Ｍｇ、Ｃａ、Ｃｕ、Ｚｎ、Ｃｂ、Ｐｂ）、過レニ
ウム酸アンモニウム（ＮＨ４ＲｅＯ４）、七硫化二レニ
ウム（Ｒｅ２Ｓ７）、塩化レニウム酸（ＲｅＯ３Ｃｌ）
等を使用可能なものとして挙げることができるが、水や
アルコール等の溶媒への溶解性が高いことや溶液中に不
純物を導入させないことからＲｅ２Ｏ７、ＨＲｅＯ４、
ＮＨ４ＲｅＯ４が最も好ましい。特にＲｅ２Ｏ７は水や
アルコール等の溶媒に極めて容易に溶解し、Ｒｅ２Ｏ７
の水溶液であるＨＲｅＯ４と並んで好ましい効果が得ら
れる。The heptavalent rhenium compound may be any compound as long as it can supply the ions Re 7+ and ReO 4 containing heptavalent rhenium in a solution, for example, dirhenium heptoxide (Re 2 O 7 ), perrhenium. Acid (HReO 4 ), rhenium oxyacid salt (MReO 4 : M = Na, K, Ag, C
s, Pb, Tl, Rb, and N (ReO 4) 2: N =
Sr, Mg, Ca, Cu, Zn, Cb, Pb), ammonium perrhenate (NH 4 ReO 4 ), dirhenium heptasulfide (Re 2 S 7 ), rhenium chloride (ReO 3 Cl)
And the like can be mentioned, but since Re 2 O 7 , HReO 4 and HReO 4 are highly soluble in solvents such as water and alcohol and do not introduce impurities into the solution,
Most preferred is NH 4 ReO 4 . In particular Re 2 O 7 is very readily soluble in solvents such as water and alcohol, Re 2 O 7
Along with HReO 4 which is an aqueous solution of the above, a preferable effect is obtained.
【００１５】七価のレニウム化合物の含有量が増すと、
析出するＲｅＯ３の量は多くなるが、不均一に析出する
傾向があり、ＲｅＯ３換算で約２５重量％以上になると
大きく凝集したＲｅＯ３粒子やデンドライト状のＲｅＯ
３組織になったりするため、導電バスの形成が阻害さ
れ、導電性は無添加の場合よりも悪くなる傾向があり、
また膜のヘイズ値は高くなる傾向がある。逆に七価のレ
ニウム化合物の含有量が０．１％未満ではＲｅＯ３生成
量が不十分で導電性向上の効果が十分に得られない。本
発明における七価のレニウム化合物の含有量を、ＩＴＯ
または／およびＡＴＯの含有量に対してＲｅＯ３換算の
重量比で０．１％以上２５％未満と限定したのはかかる
理由による。As the content of the heptavalent rhenium compound increases,
Although the amount of ReO 3 to be precipitated is large, it tends to be deposited nonuniformly, and when it becomes about 25% by weight or more in terms of ReO 3 , highly aggregated ReO 3 particles or dendrite-like ReO 3
Since the structure becomes three , the formation of the conductive bath is hindered, and the conductivity tends to be worse than in the case of no addition.
Further, the haze value of the film tends to increase. On the other hand, if the content of the heptavalent rhenium compound is less than 0.1%, the amount of ReO 3 produced is insufficient and the effect of improving conductivity cannot be sufficiently obtained. The content of the heptavalent rhenium compound in the present invention is
And / or to that limit 0.1% or more than 25 percent by weight of the ReO 3 in terms relative to the content of ATO are by this reason.
【００１６】アルキルシリケート部分加水分解重合物と
しては、オルトアルキルシリケートに水や酸触媒を加え
て加水分解と脱水縮重合をある程度進行させた形のも
の、またはすでに４〜５量体まで加水分解縮重合を進ま
せた市販のアルキルシリケート溶液をさらに加水分解脱
水縮重合を進行させた形のもの等を用いることができ
る。この場合のアルキル基としてはメチル、エチル等の
低級アルキル基が好ましい。縮重合が進むと溶液粘度が
上昇し最終的には固化するので、アルキルシリケートの
縮重合の度合いは溶液が基板に塗布できる粘度の範囲内
で用いる。The partially hydrolyzed alkyl silicate polymer is a form in which water and an acid catalyst are added to orthoalkyl silicate to allow hydrolysis and dehydration polycondensation to proceed to a certain extent, or hydrolyzed polycondensation up to a tetramer to a pentamer. It is possible to use a commercially available alkyl silicate solution in which polymerization has been further advanced, which has been further hydrolyzed, dehydrated and polycondensed. In this case, the alkyl group is preferably a lower alkyl group such as methyl and ethyl. As the polycondensation proceeds, the solution viscosity increases and finally solidifies. Therefore, the degree of polycondensation of the alkyl silicate is used within the range of the viscosity at which the solution can be applied to the substrate.
【００１７】このようなアルキルシリケート部分加水分
解重合物は、処理液塗布後の焼成加熱時に縮重合反応が
ほぼ完結して硬いシリケートになる。アルキルシリケー
ト部分加水分解重合物を含むバインダー溶液には、耐水
性向上のためにフルオロアルキルシランが添加されても
問題はない。また、屈折率調整や強度補強のために、ポ
リシロキサン中のＳｉの一部をＴｉ、Ｚｒ、Ａｌ等で置
換することも可能である。In such an alkyl silicate partially hydrolyzed polymer, the polycondensation reaction is almost completed at the time of baking and heating after application of the treatment liquid to form a hard silicate. There is no problem even if a fluoroalkylsilane is added to the binder solution containing the partially hydrolyzed alkyl silicate polymer to improve water resistance. Further, in order to adjust the refractive index and reinforce the strength, it is possible to replace a part of Si in the polysiloxane with Ti, Zr, Al or the like.
【００１８】なお、透明導電膜形成用処理液には、アル
キルシリケート部分加水分解重合物を含むシリケート系
バインダーは含まれなくても使用できるが、この場合膜
強度が格段に落ちるので、後述するオーバーコートを施
した２層膜として使用するのが好ましい。また、基板ガ
ラスとのなじみが悪くなって塗りむら等を生ずることが
あるので、塗布液成分等に工夫を要する。The treatment liquid for forming a transparent conductive film can be used even if it does not contain a silicate-based binder containing a partially hydrolyzed alkyl silicate polymer. It is preferably used as a coated two-layer film. In addition, since it may become unsuitable for the substrate glass and uneven coating may occur, it is necessary to devise the composition of the coating liquid.
【００１９】処理液の塗布方法としては、スピンコート
法が一般的であるが、スプレーコート法やディップコー
ト法等、処理液を平坦にかつ薄く均一に塗布できる方法
であればいかなる方法でもよい。As a coating method of the treatment liquid, a spin coating method is generally used, but any method such as a spray coating method or a dip coating method can be applied as long as the treatment liquid can be applied flatly and thinly and uniformly.
【００２０】本発明において、処理液塗布後の焼成温度
を１００℃以上４５０℃以下の温度に限定したのは、以
下に示す理由による。本発明の処理液は２００℃以下の
低温でも十分に低抵抗の膜を形成できるが、焼成温度は
なるべく高い方が膜が緻密になり抵抗値も下がる傾向が
ある。しかし、焼成温度が４５０℃を超えると、いった
ん還元されて生成したＲｅＯ３が再び酸化が進んでＲｅ
２Ｏ７へ分解傾向を示すために抵抗が増加し、またＩＴ
Ｏ中の欠損酸素が補充されてＩＴＯ自身の抵抗値も上が
るので、膜の抵抗が増加するとともにヘイズも大きくな
る。逆に、焼成温度が１００℃未満ではシリケートの縮
重合反応が未完結で残る場合が多く、また粒子に吸着し
て残留した有機溶媒の影響で極めて脆弱な膜になってし
まう。かかる理由により、本発明では処理液塗布後の焼
成温度を１００℃以上４５０℃以下に限定したのであ
る。ただし、ＣＲＴ完成後の加熱では通常２００℃を超
えることは好ましくない。In the present invention, the firing temperature after coating the treatment liquid is limited to a temperature of 100 ° C. to 450 ° C. for the following reason. The treatment liquid of the present invention can form a film having a sufficiently low resistance even at a low temperature of 200 ° C. or lower, but if the baking temperature is as high as possible, the film tends to be dense and the resistance value tends to decrease. However, when the firing temperature exceeds 450 ° C., the ReO 3 that is once reduced and produced is oxidized again and ReO 3
Resistance increases due to the tendency to decompose into 2 O 7, and IT
Since the oxygen deficiency in O is replenished and the resistance value of ITO itself increases, the resistance of the film increases and the haze also increases. On the other hand, if the baking temperature is lower than 100 ° C., the polycondensation reaction of silicate often remains uncompleted, and the organic solvent adsorbed to the particles and left remains to form an extremely fragile film. For this reason, in the present invention, the firing temperature after coating the treatment liquid is limited to 100 ° C or higher and 450 ° C or lower. However, it is not preferable that the temperature exceeds 200 ° C. in heating after completion of CRT.
【００２１】本発明の処理液による透明導電膜は、膜強
度の補強と低反射効果付与のために、この透明導電膜の
上にシリケート系のオーバーコートガラスを被せた２層
構造で使用することも可能である。この２層膜は、処理
液を塗布、乾燥後、前記のアルキルシリケート部分加水
分解重合物を主成分とするシリケート溶液を塗布し、そ
の後焼成することにより形成することができる。シリケ
ートをオーバーコートとして用いる理由は、強度、耐候
性に優れ、透明度が高くヘイズが低いこと、およびＣＲ
Ｔに適した低温で焼成できることである。また、低反射
効果は、１層目の反射波と２層目の反射波の間に破壊的
干渉が起こることによる。本処理液とシリケート溶液を
用いたこのような２層透明導電膜は、電界シールド効果
に加えて見やすい画面の低反射効果を備えた低コスト高
付加価値のＣＲＴを供給することができる。The transparent conductive film formed by the treatment liquid of the present invention has a two-layer structure in which a silicate-based overcoat glass is covered on the transparent conductive film in order to reinforce the film strength and impart a low reflection effect. Is also possible. This two-layer film can be formed by applying the treatment liquid and drying, then applying the silicate solution containing the above-mentioned alkyl silicate partially hydrolyzed polymer as the main component, and then baking. The reason for using silicate as an overcoat is that it has excellent strength and weather resistance, high transparency and low haze, and CR.
That is, it can be fired at a low temperature suitable for T. The low reflection effect is due to destructive interference between the reflected waves of the first layer and the reflected waves of the second layer. Such a two-layer transparent conductive film using the treatment liquid and the silicate solution can supply a low-cost and high-value-added CRT having an electric field shielding effect and a low reflection effect of an easily visible screen.
【００２２】さらに、このような透明導電膜は、ＣＲＴ
前面ガラスのみでなく、計測器類を覆う窓や、電子顕微
鏡の観察窓、外部電磁場を遮蔽したいＩＣやＬＳＩの透
明容器等を基体として形成することも可能である。Further, such a transparent conductive film is a CRT.
Not only the front glass but also a window covering measuring instruments, an observation window of an electron microscope, a transparent container such as an IC or an LSI for shielding an external electromagnetic field can be formed as a substrate.
【００２３】なお、本発明の透明導電膜形成用処理液や
オーバーコート液に含まれる有機溶媒としては、焼成温
度以下での適度の揮発性をもち、導電性粒子またはシリ
カ微粒子を効率よく分散し得るものとして、例えばエタ
ノール、イソプロピルアルコール、ｎープタノール、ジ
メチルフォルムアミド、ジメチルアセトアミド、メチル
セロソルブ、Ｎーメチルー２ーピロリドン（ＮＭＰ）、
４ーヒドロキシー４ーメチルー２ーペンタノン（ＤＡ
Ａ）、アセトン、テトラヒドロキシフラン（ＴＨＦ）等
を好ましい例として挙げることができる。処理液中の溶
媒としては、基板ガラス上への塗布方法に応じて、適切
な粘度や表面張力を与えるように、上記以外の溶剤も適
宜用いられる。The organic solvent contained in the treatment liquid for forming a transparent conductive film or the overcoat liquid of the present invention has an appropriate volatility at a firing temperature or lower, and disperses conductive particles or silica fine particles efficiently. As a product to be obtained, for example, ethanol, isopropyl alcohol, n-pentanol, dimethylformamide, dimethylacetamide, methylcellosolve, N-methyl-2-pyrrolidone (NMP),
4-hydroxy-4-methyl-2-pentanone (DA
A), acetone, tetrahydroxyfuran (THF) and the like can be mentioned as preferable examples. As the solvent in the treatment liquid, a solvent other than the above may be appropriately used so as to give an appropriate viscosity and surface tension according to the method of coating on the substrate glass.
【００２４】[0024]
実施例１ ＩＴＯ超微粉（錫成分５重量％、平均粒径２０ｎｍ、住
友金属鉱山株式会社製）１５ｇ、ＮＭＰ２０ｇ、ＤＡＡ
５０ｇを混合し、直径５ｍｍのジルコニアボールを用い
て７２時間ボールミル混合してＩＴＯ分散液８５ｇを作
製した。一方、平均重合度で４〜５量体であるエチルシ
リケート４０（多摩化学工業株式会社製）を４ｇ、蒸留
水５ｇ、エタノール２０ｇの混合溶液中にエタノール１
５ｇと５％塩酸水溶液８ｇの混合溶液を滴下して、部分
的に加水分解と重合反応の進行したエチルシリケート溶
液５２ｇを調製した。次に、これらのＩＴＯ分散液とエ
チルシリケート溶液に、Ｒｅ２Ｏ７粉末４ｇをエタノー
ル２３４ｇに溶解したレニウム溶液２３８ｇを加えて混
合し、Ｒｅ２Ｏ７の重量混合比率がＲｅＯ３換算でＩＴ
Ｏ：ＲｅＯ３＝８０：２０である透明導電膜形成用処理
液３７５ｇを得た。この処理液１５ｇを１５０ｒｐｍで
回転する２００×２００×３ｍｍのソーダライム系板ガ
ラス基板上にビーカから滴下し、そのまま３分振切った
後回転を止めた。これを２００℃の電気炉に入れて３０
分焼成して焼成膜を得た。この焼成膜を薄膜ゴニオメー
タ付きＸ線回折装置で分析したところ、ＩＴＯとＲｅＯ
３からの回折パターンのみが固定された。Example 1 ITO ultrafine powder (tin content 5% by weight, average particle size 20 nm, manufactured by Sumitomo Metal Mining Co., Ltd.) 15 g, NMP 20 g, DAA
50 g was mixed, and ball-milled for 72 hours using a zirconia ball having a diameter of 5 mm to prepare 85 g of an ITO dispersion liquid. On the other hand, ethanol 1 in a mixed solution of 4 g of ethyl silicate 40 (manufactured by Tama Chemical Industry Co., Ltd.) having an average degree of polymerization of 4- to 5-mer, 5 g of distilled water, and 20 g of ethanol.
A mixed solution of 5 g and 8 g of a 5% hydrochloric acid aqueous solution was added dropwise to prepare 52 g of an ethyl silicate solution in which the hydrolysis and the polymerization reaction partially proceeded. Next, 238 g of a rhenium solution prepared by dissolving 4 g of Re 2 O 7 powder in 234 g of ethanol was added to and mixed with these ITO dispersion and ethyl silicate solution, and the weight mixing ratio of Re 2 O 7 was calculated as IT in terms of ReO 3.
375 g of a processing liquid for forming a transparent conductive film in which O: ReO 3 = 80: 20 was obtained. 15 g of this treatment liquid was dropped from a beaker onto a 200 × 200 × 3 mm soda lime-based plate glass substrate rotating at 150 rpm, shaken for 3 minutes and then rotation was stopped. Put this in an electric furnace at 200 ° C for 30
Minute baking was performed to obtain a baked film. When this fired film was analyzed by an X-ray diffractometer with a thin film goniometer, it was found that ITO and ReO
Only the diffraction pattern from 3 was fixed.
【００２５】さらに、形成された膜の表面抵抗は三菱油
化株式会社製の表面抵抗計ＭＣＰーＴ２００を用いて、
ヘイズ値は村上色彩技術研究所製ヘイズメーターＨＲー
２００を用いてそれぞれ測定した。測定結果を表１に示
す。ここでは、ＩＴＯやＡＴＯ等の透明導電性微粒子成
分に対するレニウム酸化物の成分比は、添加したレニウ
ムがすべてＲｅＯ３に変化したと仮定した時の比を重量
％で表示した。本実施例においては、ＩＴＯ：ＲｅＯ３
＝８０：２０である。また、表１には以下に示す実施例
２〜１１および比較例１〜３で得られた膜の特性につい
ても併せて示した。Further, the surface resistance of the formed film was measured by using a surface resistance meter MCP-T200 manufactured by Mitsubishi Petrochemical Co., Ltd.
The haze value was measured using a haze meter HR-200 manufactured by Murakami Color Research Laboratory. Table 1 shows the measurement results. Here, the component ratio of the rhenium oxide to the transparent conductive fine particle component such as ITO or ATO is shown in weight% when it is assumed that all of the added rhenium is changed to ReO 3 . In this example, ITO: ReO 3
= 80: 20. Table 1 also shows the characteristics of the films obtained in Examples 2 to 11 and Comparative Examples 1 to 3 shown below.
【００２６】実施例２ Ｒｅ２Ｏ７の混合比率を、ＲｅＯ３換算でＩＴＯ：Ｒｅ
Ｏ３＝９５：５とした以外は、実施例１と同様の条件で
焼成膜を得た。Example 2 The mixing ratio of Re 2 O 7 and ITO: Re calculated as ReO 3
A fired film was obtained under the same conditions as in Example 1 except that O 3 = 95: 5 was set.
【００２７】実施例３ Ｒｅ２Ｏ７の混合比率を、ＲｅＯ３換算でＩＴＯ：Ｒｅ
Ｏ３＝９０：１０とした以外は、実施例１と同様の条件
で焼成膜を得た。Example 3 The mixing ratio of Re 2 O 7 was calculated as ITO: Re in terms of ReO 3.
A fired film was obtained under the same conditions as in Example 1 except that O 3 = 90: 10 was set.
【００２８】実施例４ レニウム溶液としてＲｅ成分を５０．８ｗｔ％含有する
過レニウム酸液１．３ｇとエタノール２３６ｇの混合溶
液を用いた以外は、実施例２と同様の条件で焼成膜を得
た。Example 4 A fired film was obtained under the same conditions as in Example 2 except that a mixed solution of 1.3 g of perrhenic acid solution containing 50.8 wt% of Re component and 236 g of ethanol was used as the rhenium solution. .
【００２９】実施例５ レニウム溶液としてＲｅ成分を６９．１ｗｔ％含有する
過レニウム酸アンモニウム０．９ｇと蒸留水３７ｇとエ
タノール２００ｇの混合溶液２３８ｇを用いた以外は、
実施例２と同様の条件で焼成膜を得た。Example 5 As a rhenium solution, 238 g of a mixed solution of 0.9 g of ammonium perrhenate containing 69.1 wt% of Re component, 37 g of distilled water and 200 g of ethanol was used.
A fired film was obtained under the same conditions as in Example 2.
【００３０】実施例６ ＩＴＯ超微粉１５ｇの代りにＡＴＯ超微粉（平均粒径１
４ｎｍ、住友金属鉱山株式会社製）１５ｇを用いた以外
は、実施例１と同様の条件で焼成膜を得た。Example 6 ATO ultrafine powder (average particle size 1
4 nm, Sumitomo Metal Mining Co., Ltd.) 15 g was used to obtain a fired film under the same conditions as in Example 1.
【００３１】実施例７ ＩＴＯ超微粉１５ｇの代りにＩＴＯ超微粉７．５ｇとＡ
ＴＯ超微粉７．５ｇの混合粉１５ｇを用いた以外は、実
施例１と同様の条件で焼成膜を得た。Example 7 Instead of 15 g of ITO ultrafine powder, 7.5 g of ITO ultrafine powder and A
A fired film was obtained under the same conditions as in Example 1 except that 15 g of a mixed powder of 7.5 g of TO ultrafine powder was used.
【００３２】実施例８ 焼成温度を４３０℃とした以外は、実施例３と同様の条
件で焼成膜を得た。Example 8 A fired film was obtained under the same conditions as in Example 3 except that the firing temperature was 430 ° C.
【００３３】実施例９ 焼成温度を１２０℃とした以外は、実施例３と同様の条
件で焼成膜を得た。Example 9 A fired film was obtained under the same conditions as in Example 3 except that the firing temperature was 120 ° C.
【００３４】実施例１０ ＩＴＯ超微粉（平均粒径２０ｎｍ、住友金属鉱山株式会
社製）１５ｇ、ＮＭＰを２０ｇ、ＤＡＡ５０ｇを混合
し、直径５ｍｍのジルコニアボールを用いて１７２時間
ボールミル混合してＩＴＯ分散液８５ｇを作製した。こ
の分散液を、Ｒｅ２Ｏ７粉末４ｇをエタノール２８６ｇ
に溶解したレニウム溶液２９０ｇと共に混合して、シリ
ケート系バインダーを含まない透明導電膜形成用処理液
３７５ｇを得た。一方、平均重合度で４〜５量体である
エチルシリケート４０（多摩化学工業株式会社製）を４
ｇ、蒸留水５ｇ、エタノール２０ｇの混合溶液中にエタ
ノール１５ｇと５％塩酸水溶液８ｇの混合溶液を滴下し
て、部分的に加水分解と重合反応の進行したエチルシリ
ケート溶液５２ｇを調製した。次に、シリケート系バイ
ンダーを含まない透明導電膜形成用処理液１５ｇを１５
０ｒｐｍで回転する板ガラス上に滴下して３分間振切っ
た。続いて、エチルシリケート溶液１５ｇを滴下し、１
分振切った後回転を止めた。これを２００℃の電気炉に
入れて３０分焼成して透明導電膜とオーバーコート膜の
２層からなる焼成膜を得た。Example 10 15 g of ITO ultrafine powder (average particle size 20 nm, manufactured by Sumitomo Metal Mining Co., Ltd.), 20 g of NMP and 50 g of DAA were mixed, and the mixture was ball-milled for 172 hours using zirconia balls having a diameter of 5 mm to form an ITO dispersion liquid. 85 g was made. This dispersion was mixed with 4 g of Re 2 O 7 powder and 286 g of ethanol.
The mixture was mixed with 290 g of the rhenium solution dissolved in to obtain 375 g of a transparent conductive film-forming treatment liquid containing no silicate-based binder. On the other hand, ethyl silicate 40 (manufactured by Tama Chemical Industry Co., Ltd.) having an average degree of polymerization of 4 to 5 is 4
A mixed solution of 15 g of ethanol and 8 g of a 5% hydrochloric acid aqueous solution was added dropwise to a mixed solution of g, 5 g of distilled water, and 20 g of ethanol to prepare 52 g of an ethyl silicate solution in which hydrolysis and polymerization reactions were partially progressed. Next, 15 g of a treatment liquid for forming a transparent conductive film containing no silicate-based binder
It was dropped on a plate glass rotating at 0 rpm and shaken off for 3 minutes. Subsequently, 15 g of ethyl silicate solution was added dropwise, and 1
After shaking off, the rotation was stopped. This was placed in an electric furnace at 200 ° C. and baked for 30 minutes to obtain a baked film composed of two layers of a transparent conductive film and an overcoat film.
【００３５】実施例１１ まず実施例１と同様の手順でシリケート系バインダーを
含む透明導電膜形成用処理液、およびエチルシリケート
溶液を調製した。次に、シリケート系バインダーを含む
透明導電膜形成用処理液１５ｇを１５０ｒｐｍで回転す
る板ガラス上に滴下して３分間振切った。続いて、エチ
ルシリケート溶液１５ｇを滴下し、１分振切った後回転
を止めた。これを２００℃の電気炉に入れて３０分焼成
して透明導電膜とオーバーコート膜の２層からなる焼成
膜を得た。Example 11 First, a treatment liquid for forming a transparent conductive film containing a silicate-based binder and an ethyl silicate solution were prepared by the same procedure as in Example 1. Next, 15 g of a transparent conductive film forming treatment liquid containing a silicate-based binder was dropped on a plate glass rotating at 150 rpm and shaken off for 3 minutes. Subsequently, 15 g of the ethyl silicate solution was added dropwise, shaken for 1 minute, and then stopped rotating. This was placed in an electric furnace at 200 ° C. and baked for 30 minutes to obtain a baked film composed of two layers of a transparent conductive film and an overcoat film.
【００３６】比較例１ ＩＴＯ超微粉（平均粒径２０ｎｍ、住友金属鉱山株式会
社製）１５ｇ、ＮＭＰ２０ｇ、ＤＡＡ５０ｇを混合し、
直径５ｍｍのジルコニアボールを用いて１７２時間ボー
ルミル混合してＩＴＯ分散液８５ｇを作製した。一方、
平均重合度で４〜５量体であるエチルシリケート４０
（多摩化学工業株式会社製）を４ｇ、蒸留水５ｇ、エタ
ノール２０ｇの混合溶液中にエタノール１５ｇと５％塩
酸水溶液８ｇの混合溶液を滴下して、部分的に加水分解
と重合反応の進行したエチルシリケート溶液５２ｇを調
製した。次に、これらのＩＴＯ分散液とエチルシリケー
ト溶液を混合し、透明導電膜形成用処理液１３７ｇを得
た。この処理液１５ｇを、１５０ｒｐｍで回転する２０
０×２００×３ｍｍのソーダライム系板ガラス基板上に
ビーカから滴下し、そのまま３分振切った後回転を止め
た。これを２００℃の電気炉に入れて３０分焼成してＲ
ｅＯ３の存在しない焼成膜を得た。Comparative Example 1 15 g of ITO ultrafine powder (average particle size 20 nm, manufactured by Sumitomo Metal Mining Co., Ltd.), NMP 20 g, and DAA 50 g were mixed,
Using a zirconia ball having a diameter of 5 mm, the mixture was ball-milled for 172 hours to prepare 85 g of an ITO dispersion liquid. on the other hand,
Ethyl silicate 40 having an average degree of polymerization of 4 to 5
(Manufactured by Tama Chemical Industry Co., Ltd.) 4 g, distilled water 5 g, and a mixed solution of ethanol 20 g, a mixed solution of 15 g of ethanol and 8 g of 5% hydrochloric acid aqueous solution was added dropwise to partially hydrolyze and undergo a polymerization reaction. 52 g of silicate solution was prepared. Next, the ITO dispersion liquid and the ethyl silicate solution were mixed to obtain 137 g of a transparent conductive film forming treatment liquid. 15 g of this treatment liquid is rotated at 150 rpm 20
The solution was dropped from a beaker onto a 0 × 200 × 3 mm soda-lime plate glass substrate, shaken for 3 minutes and then stopped rotating. This is put in an electric furnace at 200 ° C and baked for 30 minutes
A fired film free of eO 3 was obtained.
【００３７】比較例２ Ｒｅ２Ｏ７の混合比率を、ＲｅＯ３換算でＩＴＯ：Ｒｅ
Ｏ３＝７０：３０とした以外は、実施例２と同様の条件
で焼成膜を得た。COMPARATIVE EXAMPLE 2 The mixing ratio of Re 2 O 7 was calculated as ReO 3 by using ITO: Re.
A fired film was obtained under the same conditions as in Example 2 except that O 3 = 70: 30 was set.
【００３８】比較例３ 焼成温度を５００℃とした以外は、実施例４と同様の条
件で焼成膜を得た。Comparative Example 3 A fired film was obtained under the same conditions as in Example 4 except that the firing temperature was 500 ° C.
【００３９】以上の実施例１〜１１及び比較例１〜３か
らわかるように、透明導電性粒子に加えて七価のレニウ
ム化合物を添加した場合には、無添加の場合に比べて表
面抵抗が最大１／７程度に低下しており、電界シールド
に必要な高い導電性を得る上で七価のレニウム化合物を
添加する効果は明らかである。また、焼成温度はＣＲＴ
完成球に成膜するのに適した２００℃以下で十分である
が、４００℃を超えるような場合には、抵抗値が急増し
て発明の効果は得られない。As can be seen from the above Examples 1 to 11 and Comparative Examples 1 to 3, when the heptavalent rhenium compound was added in addition to the transparent conductive particles, the surface resistance was higher than that in the case of no addition. The maximum value is reduced to about 1/7, and the effect of adding the heptavalent rhenium compound is clear in obtaining the high conductivity required for the electric field shield. Also, the firing temperature is CRT
A temperature of 200 ° C. or lower, which is suitable for forming a film on a finished sphere, is sufficient. However, when the temperature exceeds 400 ° C., the resistance value sharply increases and the effect of the invention cannot be obtained.
【００４０】[0040]
【表１】 [Table 1]
【００４１】[0041]
【発明の効果】以上説明したごとく、本発明によれば、
従来の電界シールド用処理液による透明導電膜より低い
表面抵抗値が得られるとともに、低温度での焼成が可能
であるから、ＣＲＴの電界シールド用の高い導電性を有
する膜を低コストで作製することができるという優れた
効果を奏する。As described above, according to the present invention,
Since a surface resistance value lower than that of a transparent conductive film using a conventional treatment liquid for electric field shielding is obtained and baking at a low temperature is possible, a highly conductive film for electric field shielding of a CRT can be produced at low cost. It has an excellent effect that it can.
Claims (9)
酸化錫のうちのいずれか一方もしくは両方の微粉末、七
価のレニウム化合物とその還元能を有する化合物、およ
び有機溶媒とから実質的に構成される透明導電膜形成用
処理液。1. Substantially composed of fine powder of one or both of tin-containing indium oxide and antimony-containing tin oxide, a heptavalent rhenium compound and a compound having its reducing ability, and an organic solvent. A treatment liquid for forming a transparent conductive film.
酸化錫のうちのいずれか一方もしくは両方の微粉末、七
価のレニウム化合物とその還元能を有する化合物、アル
キルシリケート部分加水分解重合物を主成分とするシリ
ケート系バインダー、および有機溶剤とから実質的に構
成される透明導電膜形成用処理液。2. A main component comprising fine powder of one or both of tin-containing indium oxide and antimony-containing tin oxide, a heptavalent rhenium compound and a compound having its reducing ability, and an alkylsilicate partially hydrolyzed polymer. A treatment liquid for forming a transparent conductive film, which is substantially composed of a silicate-based binder and an organic solvent.
化合物として、水、アルコール、アンモニアのうちの一
種もしくは二種以上を使用することを特徴とする請求項
１または２に記載の透明導電膜形成用処理液。3. The transparent conductive film according to claim 1, wherein one or more kinds of water, alcohol and ammonia are used as the compound having a reducing ability of a heptavalent rhenium compound. Forming treatment liquid.
ウム、過レニウム酸、過レニウム酸アンモニウムのうち
の一種以上であることを特徴とする請求項１または２に
記載の透明導電膜形成用処理液。4. The treatment for forming a transparent conductive film according to claim 1, wherein the heptavalent rhenium compound is one or more of nirenium heptaoxide, perrhenic acid, and ammonium perrhenate. liquid.
化レニウムに換算して、錫含有酸化インジウムまたは／
およびアンチモン含有酸化錫微粉末の含有量に対して重
量比で０．１％以上２５％未満であることを特徴とする
請求項１、２または４に記載の透明導電膜形成用処理
液。5. The content of the heptavalent rhenium compound is converted to rhenium trioxide and the tin-containing indium oxide or /
And the content of the antimony-containing tin oxide fine powder is 0.1% or more and less than 25% by weight, and the treatment liquid for forming a transparent conductive film according to claim 1, 2 or 4.
透明導電膜形成用処理液を含む塗布液を基体に塗布後、
１００℃以上４５０℃以下の温度で焼成することを特徴
とする透明導電膜の作製方法。6. A coating liquid containing the treatment liquid for forming a transparent conductive film according to claim 1, 2, 3, 4 or 5 is applied to a substrate,
A method for producing a transparent conductive film, which comprises firing at a temperature of 100 ° C. or higher and 450 ° C. or lower.
透明導電膜形成用処理液を含む塗布液を基体に塗布後、
アルキルシリケート部分加水分解重合物を主成分とする
シリケート系オーバーコート液を塗布し、１００℃以上
４５０℃以下の温度で焼成することを特徴とする透明導
電膜の作製方法。7. After applying a coating liquid containing the treatment liquid for forming a transparent conductive film according to claim 1, 2, 3, 4 or 5 to a substrate,
A method for producing a transparent conductive film, which comprises applying a silicate-based overcoat liquid containing an alkyl silicate partially hydrolyzed polymer as a main component and firing the applied solution at a temperature of 100 ° C. or higher and 450 ° C. or lower.
透明導電膜形成用処理液を含む塗布液を基体に塗布後、
１００℃以上４５０℃以下の温度で焼成することにより
得られた透明導電膜。8. A coating liquid containing the treatment liquid for forming a transparent conductive film according to claim 1, 2, 3, 4 or 5 is applied to a substrate,
A transparent conductive film obtained by firing at a temperature of 100 ° C. or higher and 450 ° C. or lower.
透明導電膜形成用処理液を含む塗布液を基体に塗布後、
アルキルシリケート部分加水分解重合物を主成分とする
シリケート系オーバーコート液を塗布し、１００℃以上
４５０℃以下の温度で焼成することにより得られた透明
導電膜。9. After applying a coating liquid containing the treatment liquid for forming a transparent conductive film according to claim 1, 2, 3, 4 or 5 onto a substrate,
A transparent conductive film obtained by applying a silicate-based overcoat liquid containing an alkyl silicate partially hydrolyzed polymer as a main component, and baking the silicate-based overcoat liquid at a temperature of 100 ° C. or higher and 450 ° C. or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33808094A JPH08185797A (en) | 1994-12-27 | 1994-12-27 | Transparent conductive film forming process liquid and manufacture of transparent conductive film using this process liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33808094A JPH08185797A (en) | 1994-12-27 | 1994-12-27 | Transparent conductive film forming process liquid and manufacture of transparent conductive film using this process liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08185797A true JPH08185797A (en) | 1996-07-16 |
Family
ID=18314722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33808094A Pending JPH08185797A (en) | 1994-12-27 | 1994-12-27 | Transparent conductive film forming process liquid and manufacture of transparent conductive film using this process liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08185797A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1033355A1 (en) * | 1998-08-31 | 2000-09-06 | Idemitsu Kosan Company Limited | Target for transparent electroconductive film, transparent electroconductive material, transparent electroconductive glass and transparent electroconductive film |
| KR100348702B1 (en) * | 1999-12-28 | 2002-08-13 | 주식회사 루밴틱스 | A method for preparation of transparent conductive thin-film by Rapid Thermal Annealing Method and a transparent conductive thin-film prepared by the method |
| JP2003302543A (en) * | 2002-04-10 | 2003-10-24 | Matsushita Electric Ind Co Ltd | Opto-electric circuit and opto-electric wiring board |
| JP2007154152A (en) * | 2005-11-11 | 2007-06-21 | Mitsubishi Materials Corp | Heat ray screening composition and application thereof |
| US7586572B2 (en) | 2001-03-29 | 2009-09-08 | Nec Lcd Technologies, Ltd. | Liquid crystal display having transparent conductive film on interlayer insulating film formed by coating |
| CN103855374A (en) * | 2012-12-03 | 2014-06-11 | 丰田自动车株式会社 | Negative electrode active substance and lithium battery |
-
1994
- 1994-12-27 JP JP33808094A patent/JPH08185797A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1033355A1 (en) * | 1998-08-31 | 2000-09-06 | Idemitsu Kosan Company Limited | Target for transparent electroconductive film, transparent electroconductive material, transparent electroconductive glass and transparent electroconductive film |
| EP1033355A4 (en) * | 1998-08-31 | 2010-12-01 | Idemitsu Kosan Co | Target for transparent electroconductive film, transparent electroconductive material, transparent electroconductive glass and transparent electroconductive film |
| KR100348702B1 (en) * | 1999-12-28 | 2002-08-13 | 주식회사 루밴틱스 | A method for preparation of transparent conductive thin-film by Rapid Thermal Annealing Method and a transparent conductive thin-film prepared by the method |
| US7586572B2 (en) | 2001-03-29 | 2009-09-08 | Nec Lcd Technologies, Ltd. | Liquid crystal display having transparent conductive film on interlayer insulating film formed by coating |
| US8610857B2 (en) | 2001-03-29 | 2013-12-17 | Nlt Technologies, Ltd. | Liquid crystal display having transparent conductive film on interlayer insulating film formed by coating |
| JP2003302543A (en) * | 2002-04-10 | 2003-10-24 | Matsushita Electric Ind Co Ltd | Opto-electric circuit and opto-electric wiring board |
| JP2007154152A (en) * | 2005-11-11 | 2007-06-21 | Mitsubishi Materials Corp | Heat ray screening composition and application thereof |
| CN103855374A (en) * | 2012-12-03 | 2014-06-11 | 丰田自动车株式会社 | Negative electrode active substance and lithium battery |
| JP2014110166A (en) * | 2012-12-03 | 2014-06-12 | Toyota Motor Corp | Negative electrode active material and lithium battery |
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