JPH05151826A - Transparent conductive film and manufacture thereof - Google Patents
Transparent conductive film and manufacture thereofInfo
- Publication number
- JPH05151826A JPH05151826A JP33758791A JP33758791A JPH05151826A JP H05151826 A JPH05151826 A JP H05151826A JP 33758791 A JP33758791 A JP 33758791A JP 33758791 A JP33758791 A JP 33758791A JP H05151826 A JPH05151826 A JP H05151826A
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- Japan
- Prior art keywords
- oxide
- conductive film
- transparent conductive
- coating liquid
- solution
- 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.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はブラウン管用パネル、自
動車用ガラス等に利用できる高い透明性を有する導電膜
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive film having high transparency which can be used for cathode ray tube panels, automobile glass and the like.
【０００２】[0002]
【従来の技術】従来、透明導電膜は錫含有酸化インジウ
ムやフッ素含有酸化錫、アンチモン含有酸化錫といった
ような物質をスパッタリング法、ＣＶＤ法といった乾式
法や、塩化物や有機化合物を加熱した基体上にスプレー
する熱分解法によって得られてきた。しかし、これらの
方法は高温を必要としたり、複雑な装置を必要とすると
いった問題点が存在していた。2. Description of the Related Art Conventionally, a transparent conductive film has been formed on a substrate prepared by subjecting a material such as tin-containing indium oxide, fluorine-containing tin oxide or antimony-containing tin oxide to a dry method such as a sputtering method or a CVD method, or heating a chloride or an organic compound. It has been obtained by a pyrolysis method of spraying on. However, these methods have problems that they require high temperatures and complicated devices.
【０００３】[0003]
【発明が解決しようとする課題】本発明は従来技術の有
する前述の問題点を解消し、複雑な装置を必要とせずに
高硬度、高耐久性を有する透明導電膜を製造する方法を
提供することを目的とするものである。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and provides a method for producing a transparent conductive film having high hardness and high durability without requiring a complicated device. The purpose is that.
【０００４】[0004]
【課題を解決するための手段】即ち、本発明は、導電性
酸化物の超微粒子と、ジルコニウム化合物、ホウ素化合
物とを主成分とするコーティング液を塗布した後、加熱
することによって透明導電膜を製造することを特徴とす
る透明導電膜の製造方法を提供するものである。That is, according to the present invention, a transparent conductive film is formed by applying a coating solution containing ultrafine particles of a conductive oxide, a zirconium compound, and a boron compound as main components, and then heating. The present invention provides a method for manufacturing a transparent conductive film, which is characterized by manufacturing.
【０００５】本発明における導電性酸化物の超微粒子と
しては、アンチモン含有酸化錫（ＡＴＯ）、錫含有酸化
インジウム（ＩＴＯ）等が利用できるが、経済性、化学
的耐久性、再現性等から考えてアンチモン含有酸化錫が
比較的好適に使用できる。As the ultrafine particles of the conductive oxide in the present invention, antimony-containing tin oxide (ATO), tin-containing indium oxide (ITO) and the like can be used, but it is considered from the viewpoint of economical efficiency, chemical durability and reproducibility. Thus, tin oxide containing antimony can be used relatively favorably.
【０００６】導電性酸化物の超微粒子の分散媒、分散法
は特に限定されるものではなく種々使用可能である。例
えば、水あるいはアルコール等の有機溶媒中に導電性酸
化物超微粒子を添加し、酸あるいはアルカリを添加しｐ
Ｈを調整した後、コロイドミル、ボールミル、サンドミ
ル、ホモミキサー等の市販の粉砕器や超音波分散器など
により分散させて得ることできる。The dispersion medium and dispersion method of the ultrafine particles of the conductive oxide are not particularly limited, and various kinds can be used. For example, conductive oxide ultrafine particles may be added to an organic solvent such as water or alcohol, and an acid or alkali may be added to p.
After adjusting H, it can be obtained by dispersing with a commercially available pulverizer such as a colloid mill, a ball mill, a sand mill, a homomixer, or an ultrasonic disperser.
【０００７】分散液中に導入する導電性酸化物超微粒子
の平均粒径は100nm 以下となっていることが好ましい。
好ましくは50nm以下、特に好ましくは20nm以下であるこ
とが望ましい。100nm 以上の粒径を有する粒子を用いる
と形成された透明導電膜の透明性を阻害するおそれがあ
り、また被膜強度にも悪影響を与える。またこの分散液
はアルコール、水などで任意に希釈して用いることがで
きる。The average particle diameter of the conductive oxide ultrafine particles introduced into the dispersion is preferably 100 nm or less.
It is preferably 50 nm or less, particularly preferably 20 nm or less. If particles having a particle size of 100 nm or more are used, the transparency of the formed transparent conductive film may be impaired, and the film strength may be adversely affected. Further, this dispersion can be diluted with alcohol, water or the like.
【０００８】上記の導電性酸化物の超微粒子の分散液に
は、バインダ成分としてのジルコニウム化合物、ホウ素
化合物を添加してコーティング液とする。A zirconium compound and a boron compound as a binder component are added to the dispersion liquid of the ultrafine particles of the conductive oxide to prepare a coating liquid.
【０００９】ジルコニウム化合物としては、特に限定さ
れないが、Ｚｒ（ＯＲ）m Ｌn （ただし、ｍ＋ｎ＝４、
ｍ＝１〜４、ｎ＝０〜３、Ｒ＝Ｃ1 〜Ｃ4 のアルキル
基、Ｌ＝キレート配位子）、その加水分解物または重合
体のうち少なくとも１種が代表的な例として挙げられ
る。かかるキレート配位子としては、β−ジケトンまた
はβ−ケト酸エステルのエノール型陰イオンが挙げら
れ、その具体例としては、アセチルアセトン、トリフル
オロアセチルアセトン、ベンゾイルアセトン、ヘキサフ
ルオロアセチルアセトン、ベンゾイルトリフルオロアセ
チルアセトン、ジベンゾイルメタン、アセト酢酸メチル
エステル、アセト酢酸エチルエステル、アセト酢酸ブチ
ルエステル等の陰イオンが挙げられる。ジルコニウム化
合物としては、これらの他に、ステアリン酸ジルコニウ
ム等の有機酸塩も使用できる。The zirconium compound is not particularly limited, but Zr (OR) m L n (where m + n = 4,
At least one of m = 1 to 4, n = 0 to 3, R = C 1 to C 4 alkyl group, L = chelate ligand), a hydrolyzate or a polymer thereof is a typical example. Be done. Examples of such chelate ligands include enol-type anions of β-diketones or β-keto acid esters, and specific examples thereof include acetylacetone, trifluoroacetylacetone, benzoylacetone, hexafluoroacetylacetone, benzoyltrifluoroacetylacetone, Examples thereof include anions such as dibenzoylmethane, acetoacetic acid methyl ester, acetoacetic acid ethyl ester and acetoacetic acid butyl ester. Other than these, organic acid salts such as zirconium stearate can also be used as the zirconium compound.
【００１０】ホウ素化合物としては、特に限定されない
が、Ｂ（ＯＲ’）3 （ただし、Ｒ’はアルキル基）、そ
の加水分解物または重合体のうち少なくとも１種が好適
に使用できる。The boron compound is not particularly limited, but at least one of B (OR ') 3 (provided that R'is an alkyl group), its hydrolyzate or polymer can be preferably used.
【００１１】ジルコニウム化合物とホウ素化合物の割合
は、酸化物換算で、酸化ジルコニウム：酸化ホウ素＝
１：２から５：１までであることが好ましい。酸化ジル
コニウムがこの割合より少ないと、良好な耐薬品性を具
備させることができず、またこれより多いと、膜の硬度
が低下するので好ましくない。The ratio of the zirconium compound and the boron compound is, in terms of oxide, zirconium oxide: boron oxide =
It is preferably from 1: 2 to 5: 1. If the amount of zirconium oxide is less than this ratio, good chemical resistance cannot be provided, and if it is more than this ratio, the hardness of the film decreases, which is not preferable.
【００１２】また、これらのジルコニウム化合物やホウ
素化合物は、バインダとして働くばかりでなく、コーテ
ィング液中で酸化物超微粒子表面の水酸基と結合して酸
化物粒子のまわりを覆うために、液中での酸化物超微粒
子の分散性を高めるために有効に働く。Further, these zirconium compounds and boron compounds not only act as binders, but also bond with hydroxyl groups on the surface of the ultrafine oxide particles in the coating solution to coat the oxide particles, so Effectively works to enhance the dispersibility of ultrafine oxide particles.
【００１３】導電性酸化物超微粒子としてアンチモン含
有酸化錫を用いる場合、高い透明性を具備しながら導電
性を有する膜を形成するための好ましい膜組成比として
は、酸化物換算（重量％）で、アンチモン含有酸化錫：
ＭＯx＝３０：７０〜９０：１０（ＭＯx はＺｒＯ2 、
Ｂ2 Ｏ3 の合計を示す。）である。導電性粒子がこの組
成比より少ないと有効な導電性能を具備することができ
ず、また多いと膜強度が低下するので好ましくない。When antimony-containing tin oxide is used as the conductive oxide ultrafine particles, a preferable film composition ratio for forming a conductive film while having high transparency is in terms of oxide (% by weight). , Tin oxide containing antimony:
MO x = 30: 70 to 90:10 (MO x is ZrO 2 ,
The total of B 2 O 3 is shown. ). When the conductive particles are less than this composition ratio, effective conductive performance cannot be provided, and when the conductive particles are more than this composition ratio, the film strength decreases, which is not preferable.
【００１４】また、透明導電膜形成用のコーティング液
は、総固形分量が溶媒に対して０．３〜１５重量％であ
ることが好ましい。固形分量がこれより多いと、コーテ
ィング液の保存安定性が悪化するために好ましくなく、
これより少ないと１回の塗布で得られる被膜の膜厚が薄
くなり、所望の導電性を得るために塗布操作を繰り返さ
なくてはならなくなるため、実用的でなくなるためであ
る。The coating solution for forming the transparent conductive film preferably has a total solid content of 0.3 to 15% by weight based on the solvent. If the solid content is more than this, the storage stability of the coating liquid deteriorates, which is not preferable,
If it is less than this range, the thickness of the coating film obtained by one-time coating becomes thin, and the coating operation must be repeated to obtain the desired conductivity, which is not practical.
【００１５】本発明における基体ガラスとしては、自動
車用、建築用ガラスとして通常使用されているソーダラ
イムシリケートガラスからなる普通板ガラス、フロート
板ガラスなどが使用でき、またブラウン管用のパネルガ
ラスなどに塗布して帯電防止性能を具備させることもで
きる。As the base glass in the present invention, it is possible to use ordinary plate glass made of soda lime silicate glass, float plate glass, etc., which are usually used as glass for automobiles and construction, and to be applied to panel glass for cathode ray tubes. It can also have antistatic performance.
【００１６】また、本発明において、導電性酸化物とし
て、プラズマ波長を近赤外領域に持つアンチモン含有酸
化錫、フッ素含有酸化錫、錫含有酸化インジウムなどの
超微粒子を用いれば、該透明導電膜は熱線反射膜として
の性能をも具備させることができる。In the present invention, if ultrafine particles of antimony-containing tin oxide, fluorine-containing tin oxide, tin-containing indium oxide having a plasma wavelength in the near infrared region are used as the conductive oxide, the transparent conductive film can be obtained. Can also have the performance as a heat ray reflective film.
【００１７】本発明においては、上述の導電性酸化物の
超微粒子の分散液に、バインダ成分であるジルコニウム
化合物およびホウ素化合物を添加したコーティング液を
塗布した後、加熱することによって高耐久性、高硬度を
有する透明導電膜を形成する。In the present invention, a coating solution containing a zirconium compound and a boron compound, which are binder components, is applied to the above-mentioned dispersion of ultrafine particles of a conductive oxide, and then heated to obtain high durability and high durability. A transparent conductive film having hardness is formed.
【００１８】基体への塗布法は特に限定される物ではな
く、スプレー法、ディップ法、ロールコート法、メニス
カスコート法、スピンコート法、スクリーン印刷法、フ
レキソ印刷法等が利用できる。The method of coating the substrate is not particularly limited, and a spray method, a dip method, a roll coating method, a meniscus coating method, a spin coating method, a screen printing method, a flexographic printing method and the like can be used.
【００１９】また、透明導電膜の膜厚は 500Åから１μ
ｍが好ましく、それ以下では導電性能が劣り、それ以上
では被膜の可視光線透過率が減少し、透明性が損なわれ
るので好ましくない。The thickness of the transparent conductive film is from 500Å to 1μ.
m is preferable, and if it is less than m, the electroconductivity is inferior, and if it is more than m, the visible light transmittance of the coating decreases and the transparency is impaired, which is not preferable.
【００２０】[0020]
【実施例】以下に実施例により本発明を具体的に説明す
るが本発明はこれらの実施例に限定されるものではな
い。以下の実施例および比較例において、得られた膜の
評価方法は次の通りである。EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the following examples and comparative examples, the evaluation methods of the obtained films are as follows.
【００２１】１）表面抵抗値 ハイレスタ抵抗測定器（三菱油化製）により膜表面の表
面抵抗値を測定。 ２）可視光線透過率 分光光度計（日立製作所製）により380 〜780nm の透過
率を測定し、ＪＩＳ−Ｒ３１０６に従って可視光線透過
率を算出した。1) Surface resistance value The surface resistance value of the film surface was measured with a Hiresta resistance measuring instrument (manufactured by Mitsubishi Yuka). 2) Visible light transmittance The transmittance at 380 to 780 nm was measured with a spectrophotometer (manufactured by Hitachi Ltd.), and the visible light transmittance was calculated according to JIS-R3106.
【００２２】３）ヘーズ（曇り値） ヘーズコンピューター（スガ試験機製）により測定し
た。 ４）密着性 ＪＩＳ−Ｋ５４００に従って碁盤目剥離試験によって評
価を行った。3) Haze (cloudiness value) It was measured by a haze computer (manufactured by Suga Test Instruments Co., Ltd.). 4) Adhesion Adhesion was evaluated by a cross-cut peeling test according to JIS-K5400.
【００２３】５）鉛筆硬度 ＪＩＳ−Ｋ５４００に従って鉛筆硬度試験によって評価
を行った。 ６）耐薬品性 ５％硫酸、または５％苛性ソーダ液に１２時間浸漬した
後、試験前後の外観、表面抵抗値を調べた。外観につい
ては、全く変化がなかったものを○、部分的に剥離した
ものを△、完全に剥離したものを×とした。5) Pencil Hardness Pencil hardness was evaluated according to JIS-K5400. 6) Chemical resistance After dipping in 5% sulfuric acid or 5% caustic soda solution for 12 hours, the appearance and surface resistance before and after the test were examined. Regarding the external appearance, the one that did not change at all was rated as ◯, the one that was partially peeled was designated as Δ, and the one that was completely peeled was designated as x.
【００２４】[0024]
［実施例１］Ｓｂを９mol ％含有する酸化錫超微粒子
（平均粒径10nm）を水中にサンドミルで４時間撹拌分散
させた後９０℃で１時間加熱解膠し、固形分２０重量％
まで濃縮した。（Ａ液）[Example 1] Ultrafine tin oxide particles (average particle size 10 nm) containing 9 mol% of Sb were dispersed in water by stirring for 4 hours in a sand mill, and then peptized by heating at 90 ° C for 1 hour to give a solid content of 20% by weight.
Concentrated to. (Liquid A)
【００２５】ジルコニウムアセチルアセトンブトキシド
Ｚｒ（ＯＣ4 Ｈ9 ）2 （Ｃ5 Ｈ8 Ｏ2 ）2 210ｇをエタ
ノール（ 358ｇ）に溶解させ、塩酸水溶液（ 121ｇ）で
加水分解し、さらにホウ酸トリエチルＢ（ＯＣ2 Ｈ5 ）
3 を７０ｇ加えてＢ液とした。Zirconium acetylacetone butoxide Zr (OC 4 H 9 ) 2 (C 5 H 8 O 2 ) 2 210 g was dissolved in ethanol (358 g), hydrolyzed with an aqueous hydrochloric acid solution (121 g), and further triethyl borate B (OC). 2 H 5 )
70 g of 3 was added to prepare a solution B.
【００２６】Ａ液 200ｇにエタノールを 200ｇ加えた後
Ｂ液を 200ｇ加え、コーティング液とした。このコーテ
ィング液を100mm ×100mm のフロートガラス板に750 回
転でスピンコートし、その後380 ℃で10分間焼付け処理
を行って透明導電膜を得た。この透明導電膜の特性を表
１および表２に示す。After 200 g of ethanol was added to 200 g of solution A, 200 g of solution B was added to obtain a coating solution. A 100 mm × 100 mm float glass plate was spin-coated with this coating solution at 750 rpm, and then baked at 380 ° C. for 10 minutes to obtain a transparent conductive film. The characteristics of this transparent conductive film are shown in Tables 1 and 2.
【００２７】［実施例２］実施例１に示されるＡ液 200
ｇをヘキシレングリコール 200ｇで希釈し、その後Ｂ液
200ｇを加えて粘性コーティング液としてフレキソ印刷
により150mm ×150mm のフロートガラス板に塗布した
後、500 ℃で10分間焼付け処理を行って透明導電膜を得
た。この透明導電膜の特性を表１および表２に示す。Example 2 Solution A shown in Example 1 200
diluted with 200 g of hexylene glycol, and then liquid B
After adding 200 g, a viscous coating liquid was applied by flexographic printing to a 150 mm × 150 mm float glass plate, and then baked at 500 ° C. for 10 minutes to obtain a transparent conductive film. The characteristics of this transparent conductive film are shown in Tables 1 and 2.
【００２８】［実施例３］実施例２で用いた粘性コーテ
ィング液 200ｇに、増粘剤としてエチルセルロースを２
ｇ添加してさらに高粘性のコーティング液とし、これを
200mm ×200 mmのフロートガラス板に 325メッシュのス
クリーンを用いてスクリーン印刷により塗布した後600
℃で５分間焼付け処理を行って透明導電膜を得た。この
透明導電膜の特性を表１および表２に示す。Example 3 200 g of the viscous coating liquid used in Example 2 was mixed with 2 parts of ethyl cellulose as a thickener.
g to make a highly viscous coating liquid.
600 by applying by screen printing to a 200 mm × 200 mm float glass plate using a 325 mesh screen
A transparent conductive film was obtained by baking at 5 ° C. for 5 minutes. The characteristics of this transparent conductive film are shown in Tables 1 and 2.
【００２９】［実施例４］ジルコニウムブトキシドＺｒ
（ＯＣ4 Ｈ9 ）4 ３８ｇをエタノール（ 372ｇ）とアセ
ト酢酸メチル（１２ｇ）の混合溶媒に溶解させ、塩酸水
溶液（１８ｇ）で加水分解し、さらにホウ酸トリエチル
Ｂ（ＯＣ2 Ｈ5 ）3 を２８ｇ加えてＣ液とした。[Example 4] Zirconium butoxide Zr
38 g of (OC 4 H 9 ) 4 was dissolved in a mixed solvent of ethanol (372 g) and methyl acetoacetate (12 g), hydrolyzed with an aqueous hydrochloric acid solution (18 g), and further triethyl borate B (OC 2 H 5 ) 3 was added. 28 g was added to prepare a liquid C.
【００３０】Ａ液３０ｇにエタノールを 170ｇ加えた後
Ｃ液を 200ｇ加え、コーティング液とした。このコーテ
ィング液を100mm ×100mm のフロートガラス板に750 回
転でスピンコートし、その後200 ℃で30分間焼付け処理
を行って透明導電膜を得た。この透明導電膜の特性を表
１および表２に示す。170 g of ethanol was added to 30 g of solution A, and then 200 g of solution C was added to obtain a coating solution. A 100 mm × 100 mm float glass plate was spin-coated with this coating solution at 750 rpm, and then baked at 200 ° C. for 30 minutes to obtain a transparent conductive film. The characteristics of this transparent conductive film are shown in Tables 1 and 2.
【００３１】［実施例５］実施例４において、ホウ酸ト
リエチル２８ｇのかわりにホウ酸トリブチル４４ｇとし
た他は実施例４と同様に行って透明導電膜を得た。この
透明導電膜の特性を表１および表２に示す。[Embodiment 5] A transparent conductive film was obtained in the same manner as in Embodiment 4, except that the amount of tributyl borate was changed to 44 g instead of 28 g of triethyl borate. The characteristics of this transparent conductive film are shown in Tables 1 and 2.
【００３２】［実施例６］Ｓｎを５mol ％含有する酸化
インジウム超微粒子（平均粒径20nm）をイオン交換水中
に添加してサンドミルで４時間撹拌分散させた後、水を
添加して固形分８重量％まで希釈した。（Ｄ液） 実施例４に示されるＣ液 100ｇをＤ液37.5ｇに加え、コ
ーティング液とした。[Example 6] Ultrafine indium oxide particles (average particle size 20 nm) containing 5 mol% of Sn were added to ion-exchanged water, and the mixture was stirred and dispersed in a sand mill for 4 hours. Diluted to wt%. (Solution D) 100 g of the solution C shown in Example 4 was added to 37.5 g of the solution D to prepare a coating solution.
【００３３】このコーティング液を100mm ×100mm のフ
ロートガラス板に750 回転でスピンコートし、その後45
0 ℃で10分間焼付け処理を行って透明導電膜を得た。こ
の透明導電膜の特性を表１および表２に示す。A 100 mm × 100 mm float glass plate was spin-coated with this coating solution at 750 rpm and then 45
A transparent conductive film was obtained by performing a baking treatment at 0 ° C. for 10 minutes. The characteristics of this transparent conductive film are shown in Tables 1 and 2.
【００３４】［比較例１］けい酸エチル重合物（コルコ
ート（株）製：エチルシリケート４０） 100ｇにエタノ
ール 600ｇ、塩酸水溶液９０ｇを加え、Ｅ液とした。実
施例１に示されるＡ液１重量部に対して、Ｅ液と水との
１：１混合物（重量比）を３重量部添加してコーティン
グ液とした。[Comparative Example 1] To 100 g of an ethyl silicate polymer (Ethyl silicate 40 manufactured by Colcoat Co., Ltd.), 600 g of ethanol and 90 g of an aqueous hydrochloric acid solution were added to prepare a solution E. A coating solution was prepared by adding 3 parts by weight of a 1: 1 mixture (weight ratio) of solution E and water to 1 part by weight of solution A shown in Example 1.
【００３５】このコーティング液を100mm ×100mm のフ
ロートガラス板に750 回転でスピンコートし、その後45
0 ℃で10分間焼付け処理を行って透明導電膜を得た。こ
の透明導電膜の特性を表１および表２に示す。This coating solution was spin-coated on a 100 mm × 100 mm float glass plate at 750 rotations, and then 45
A transparent conductive film was obtained by performing a baking treatment at 0 ° C. for 10 minutes. The characteristics of this transparent conductive film are shown in Tables 1 and 2.
【００３６】［比較例２］ジルコニウムアセチルアセト
ンブトキシドＺｒ（ＯＣ4 Ｈ9 ）2 （Ｃ5 Ｈ8 Ｏ2 ）2
110 ｇをエタノール（８８ｇ）に溶解させ、塩酸水溶液
（２３ｇ）で加水分解し、Ｆ液とした。Ａ液 200ｇにエ
タノールを 200ｇ加えた後Ｆ液を 200ｇ加え、コーティ
ング液とした。Comparative Example 2 Zirconium acetylacetone butoxide Zr (OC 4 H 9 ) 2 (C 5 H 8 O 2 ) 2
110 g was dissolved in ethanol (88 g) and hydrolyzed with an aqueous hydrochloric acid solution (23 g) to give a liquid F. After 200 g of ethanol was added to 200 g of solution A, 200 g of solution F was added to obtain a coating solution.
【００３７】このコーティング液を100mm ×100mm のフ
ロートガラス板に750 回転でスピンコートし、その後45
0 ℃で10分間焼付け処理を行って透明導電膜を得た。こ
の透明導電膜の特性を表１および表２に示す。This coating solution was spin-coated on a 100 mm × 100 mm float glass plate at 750 rpm, and then 45
A transparent conductive film was obtained by performing a baking treatment at 0 ° C. for 10 minutes. The characteristics of this transparent conductive film are shown in Tables 1 and 2.
【００３８】[0038]
【表１】 [Table 1]
【００３９】[0039]
【表２】 [Table 2]
【００４０】上記試験結果からも明らかなように、本発
明の透明導電膜によれば、透明性を下げることなく導電
性を比較的低温の熱処理で具備させることができる。ま
た、耐薬品性、硬度といった点でも優れた特性を有する
導電膜が得られる。As is clear from the above test results, according to the transparent conductive film of the present invention, conductivity can be provided by heat treatment at a relatively low temperature without lowering transparency. Further, a conductive film having excellent properties in terms of chemical resistance and hardness can be obtained.
【００４１】[0041]
【発明の効果】以上述べたように本発明によれば、真空
を必要とするような複雑な装置を使わず、高い透明性、
耐久性を有する透明導電膜を形成させることができる。As described above, according to the present invention, high transparency, without using a complicated device requiring a vacuum,
A transparent conductive film having durability can be formed.
Claims (6)
化合物と、ホウ素化合物とを含むコーティング液を塗布
した後、加熱することによって透明導電膜を製造するこ
とを特徴とする透明導電膜の製造方法。1. A transparent conductive film is produced by applying a coating liquid containing ultrafine particles of a conductive oxide, a zirconium compound, and a boron compound, and heating the coating liquid. Method.
換算で、導電性酸化物の超微粒子を３０重量％以上、酸
化ジルコニウムと酸化ホウ素の合計を１０重量％以上含
み、また酸化ジルコニウムと酸化ホウ素の重量比が１：
２以上５：１以下であることを特徴とする請求項１の透
明導電膜の製造方法。2. The coating liquid contains 30% by weight or more of ultrafine particles of a conductive oxide, 10% by weight or more of the total amount of zirconium oxide and boron oxide, and zirconium oxide, in terms of oxide, of the solid content in the coating liquid. The weight ratio of boron oxide is 1:
The method for producing a transparent conductive film according to claim 1, wherein the ratio is 2 or more and 5: 1 or less.
（ただし、ｍ＋ｎ＝４、ｍ＝１〜４、ｎ＝０〜３、Ｒ＝
Ｃ1 〜Ｃ4のアルキル基、Ｌ＝キレート配位子）、その
加水分解物または重合体のうち少なくとも１種と、Ｂ
（ＯＲ’）3 （ただし、Ｒ’＝アルキル基）、その加水
分解物または重合体のうち少なくとも１種とを含むこと
を特徴とする請求項１の透明導電膜の製造方法。3. The coating liquid is Zr (OR) m L n
(However, m + n = 4, m = 1 to 4, n = 0 to 3, R =
At least one of a C 1 -C 4 alkyl group, L = chelate ligand), a hydrolyzate or a polymer thereof, and B
(OR ') 3 (however, R' = alkyl group) and its hydrolyzate or at least 1 sort (s) of a polymer are contained, The manufacturing method of the transparent conductive film of Claim 1 characterized by the above-mentioned.
って作成された透明導電膜。4. A transparent conductive film produced by the method according to claim 1.
法によって透明導電膜が施されたガラス物品。5. A glass article whose surface is coated with a transparent conductive film by the method according to claim 1.
ン含有酸化錫、フッ素含有酸化錫、錫含有酸化インジウ
ムのうち少なくとも１種を用いて、請求項１〜３いずれ
か１項の製造方法によって作成された熱線反射膜。6. The method according to claim 1, wherein at least one kind of antimony-containing tin oxide, fluorine-containing tin oxide, and tin-containing indium oxide is used as the ultrafine particles of the conductive oxide. Created heat ray reflection film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33758791A JPH05151826A (en) | 1991-11-27 | 1991-11-27 | Transparent conductive film and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33758791A JPH05151826A (en) | 1991-11-27 | 1991-11-27 | Transparent conductive film and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05151826A true JPH05151826A (en) | 1993-06-18 |
Family
ID=18310055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33758791A Withdrawn JPH05151826A (en) | 1991-11-27 | 1991-11-27 | Transparent conductive film and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05151826A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106782891A (en) * | 2016-12-31 | 2017-05-31 | 浙江大学 | The preparation method of metal oxide compound silver nanometer line transparent conductive film |
-
1991
- 1991-11-27 JP JP33758791A patent/JPH05151826A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106782891A (en) * | 2016-12-31 | 2017-05-31 | 浙江大学 | The preparation method of metal oxide compound silver nanometer line transparent conductive film |
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|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
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