JPH05120921A - Transparent conductive film and its manufacture - Google Patents

Transparent conductive film and its manufacture

Info

Publication number
JPH05120921A
JPH05120921A JP30706691A JP30706691A JPH05120921A JP H05120921 A JPH05120921 A JP H05120921A JP 30706691 A JP30706691 A JP 30706691A JP 30706691 A JP30706691 A JP 30706691A JP H05120921 A JPH05120921 A JP H05120921A
Authority
JP
Japan
Prior art keywords
transparent conductive
conductive film
solution
aluminum
liquid
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.)
Withdrawn
Application number
JP30706691A
Other languages
Japanese (ja)
Inventor
Hiroyuki Tomonaga
浩之 朝長
Takeshi Morimoto
剛 森本
Kazuya Hiratsuka
和也 平塚
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.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP30706691A priority Critical patent/JPH05120921A/en
Publication of JPH05120921A publication Critical patent/JPH05120921A/en
Withdrawn legal-status Critical Current

Links

Abstract

PURPOSE:To manufacture a transparent conductive film without needing any complicated device at a comparatively low temperature. CONSTITUTION:Coating liquid, which contains at least one kind of aluminum complexes (aluminum salt, aluminum alkoxide, hydrolyzed stuff of aluminum alkoxide), for instance, Al(C6H9O3) (OR)2 and the ultrafine particles of conductive oxide, is applied onto a substrate, and is cured so as to form a transparent film.

Description

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

【0001】[0001]

【産業上の利用分野】本発明はガラスや透明性プラスチ
ック基体表面に形成される透明導電膜に関するものであ
る。
FIELD OF THE INVENTION The present invention relates to a transparent conductive film formed on the surface of a glass or transparent plastic substrate.

【0002】[0002]

【従来の技術】従来、透明基体上に透明導電膜を形成さ
せるためには、金属塩化物や有機金属化合物を原料とし
たCVD法や熱分解法、またはスパッタリング法や蒸着
法などの物理的な手法が用いられてきた。しかしなが
ら、これらの方法は高温処理が必要なためにプラスチッ
クや寸法精度を必要とするガラス製品には使用できない
という問題があったり、また複雑な装置が必要であると
いう問題点があった。
2. Description of the Related Art Conventionally, in order to form a transparent conductive film on a transparent substrate, a physical process such as a CVD method using a metal chloride or an organometallic compound as a raw material, a thermal decomposition method, a sputtering method or an evaporation method is used. Techniques have been used. However, these methods have problems that they cannot be used for plastics and glass products that require dimensional accuracy because they require high-temperature treatment, and that complicated devices are required.

【0003】[0003]

【発明が解決しようとする課題】本発明は従来技術が有
していた前述の欠点を解消しようとするものであり、複
雑な装置を必要とせず、低温熱処理が可能な透明導電膜
を新規に提供することを目的とするものである。
SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned drawbacks of the prior art, and to newly provide a transparent conductive film which can be heat-treated at a low temperature without requiring a complicated apparatus. It is intended to be provided.

【0004】[0004]

【課題を解決するための手段】本発明は前述の問題点を
解決すべくなされたものであり、キレート配位子がアル
ミニウムに配位したアルミニウム錯体と導電性酸化物の
超微粒子とを含むコーティング液を基体上に塗布し、硬
化させ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。
The present invention has been made to solve the above-mentioned problems, and is a coating containing an aluminum complex having a chelate ligand coordinated to aluminum and ultrafine particles of a conductive oxide. The present invention provides a method for producing a transparent conductive film, which comprises applying a liquid onto a substrate and curing the liquid.

【0005】導電性酸化物の超微粒子としては、Sbや
FをドープしたSnO2 や、導電性酸化チタン、ITO
(SnをドープしたIn23 )、RuO2 、及びSn
2−RuO2 、TiO2 −RuO2 等の複合酸化物が
挙げられる。
Ultrafine particles of conductive oxide include SnO 2 doped with Sb and F, conductive titanium oxide, and ITO.
(Sn-doped In 2 O 3 ), RuO 2 , and Sn
Examples thereof include composite oxides such as O 2 —RuO 2 and TiO 2 —RuO 2 .

【0006】導電性酸化物の超微粒子の平均粒径は、1
000Å以下であることが好ましい。より好ましくは5
00Å以下、特に好ましくは200Å以下であることが
望ましい。1000Å以上の粒径を有する粒子を用いる
と透明導電膜の透明性を阻害するおそれがあり、また、
膜強度にも悪影響を与える。
The average particle size of the conductive oxide ultrafine particles is 1
It is preferably 000Å or less. More preferably 5
It is desirable that it is 00 Å or less, and particularly preferably 200 Å or less. The use of particles having a particle size of 1000Å or more may impair the transparency of the transparent conductive film.
It also adversely affects the film strength.

【0007】これらの導電性酸化物の超微粒子は均一に
水に分散させ、水性ゾルとすることが重要である。また
分散する際、溶液と粉末の接触を容易ならしめるため撹
拌を行うことが望ましい。この場合、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
を用いることができる。また分散させる際には、20〜
200℃の範囲で加熱することもできる。溶液の沸点以
上で撹拌する場合には加圧して液層が保持できるように
する。このようにして導電性酸化物がコロイド粒子とし
て分散した水性ゾルが得られる。
It is important that these conductive oxide ultrafine particles are uniformly dispersed in water to form an aqueous sol. When dispersing, it is desirable to stir to facilitate contact between the solution and the powder. In this case, a commercially available crusher such as a colloid mill, a ball mill, a sand mill or a homomixer can be used. Also, when dispersing, 20 to
It is also possible to heat in the range of 200 ° C. When stirring above the boiling point of the solution, pressurize to maintain the liquid layer. Thus, an aqueous sol in which the conductive oxide is dispersed as colloidal particles can be obtained.

【0008】導電性酸化物の超微粒子を分散させた液に
は、微粒子が凝集して沈澱するのを防ぎ、安定したゾル
をつくるために、キレート配位子がアルミニウムに配位
したアルミニウム錯体を添加しておくことが好ましい。
The liquid in which the ultrafine particles of the conductive oxide are dispersed contains an aluminum complex having a chelate ligand coordinated with aluminum in order to prevent the fine particles from aggregating and precipitating and forming a stable sol. It is preferable to add it.

【0009】かかるアルミニウム錯体としては、キレー
ト配位子がアルミニウムに配位と錯体を形成した、アル
ミニウム塩、アルミニウムアルコキシド、アルミニウム
アルコキシドの加水分解物、の中から選ばれる少なくと
も1種が挙げられる。また、キレート配位子としては、
β−ジケトンやβ−ケト酸エステルのエノール型陰イオ
ンが挙げられる。アルミニウム錯体の代表的な例として
は、Al(C693 )(OR)2 (C693
エチルアセトアセテートのエノール型陰イオン、R=C
1 〜C4 のアルキル基)が挙げられる。
Examples of such an aluminum complex include at least one selected from an aluminum salt, an aluminum alkoxide, and a hydrolyzate of an aluminum alkoxide in which a chelate ligand is coordinated with aluminum to form a complex. Further, as the chelate ligand,
Examples thereof include enol type anions of β-diketone and β-keto acid ester. As a typical example of the aluminum complex, Al (C 6 H 9 O 3 ) (OR) 2 (C 6 H 9 O 3 is an enol type anion of ethyl acetoacetate, R = C
1 alkyl group -C 4) can be mentioned.

【0010】こうすることにより、β−ジケトン等のキ
レート配位子が微粒子のまわりをおおうことによる立体
障害効果、及びβ−ジケトン等のキレート配位子の最表
面が正に帯電することによって形成される電気2重層に
より、微粒子同志が反発し、安定したゾル液を形成でき
る。この効果を得るためには、かかるアルミニウム錯体
の添加量は、酸化物換算(重量比)で、SnO2 :Al
23=1:0.05〜1.0、好ましくは1:0.1〜
0.3とするのがよい。これを導電性微粒子のゾルに添
加することにより導電性微粒子のゾルを安定化させるこ
とができる。
By doing so, the chelate ligand such as β-diketone wraps around the fine particles, and the steric hindrance effect is formed, and the outermost surface of the chelate ligand such as β-diketone is positively charged. Due to the electric double layer, fine particles repel each other and a stable sol liquid can be formed. In order to obtain this effect, the addition amount of such an aluminum complex is SnO 2 : Al in terms of oxide (weight ratio).
2 O 3 = 1: 0.05 to 1.0, preferably 1: 0.1
It is better to set it to 0.3. By adding this to the sol of conductive fine particles, the sol of conductive fine particles can be stabilized.

【0011】キレート配位子の代表例であるβ−ジケト
ンやβ−ケト酸エステルのエノール型陰イオンとして
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。
The enol type anion of β-diketone or β-keto acid ester, which is a typical example of the chelating ligand, is acetylacetone, trifluoroacetylacetone, benzoylacetone, hexafluoroacetylacetone, benzoyltrifluoroacetylacetone, dibenzoylmethane. And anions such as acetoacetic acid methyl ester, acetoacetic acid ethyl ester, and acetoacetic acid butyl ester.

【0012】本発明における水性ゾルはそのまま用いる
こともできるが基体に対する塗布性を増すために有機溶
媒に分散または置換して用いることも可能である。親水
性有機溶媒としてはメタノール、エタノール、2−プロ
パノール、エチレングリコール等のアルコール類、エチ
ルセロソルブ等のエーテル類が任意に使用できる。
The aqueous sol in the present invention can be used as it is, but it can also be used by dispersing or substituting it in an organic solvent in order to enhance the coating property on the substrate. As the hydrophilic organic solvent, alcohols such as methanol, ethanol, 2-propanol and ethylene glycol, and ethers such as ethyl cellosolve can be arbitrarily used.

【0013】また本発明において用いるコーティング液
には膜の付着強度を及び硬度を向上させるためにバイン
ダーとしてSi(OR)y4-y (y=3または4、
R:アルキル基)等の珪素化合物を添加することも可能
である。更に基体との濡れ性を向上させるために種々の
界面活性剤を添加することもできる。またコーティング
液にTi化合物、Zr化合物等を混合し、高屈折率の膜
を得ることもできる。
The coating solution used in the present invention contains Si (OR) y R 4-y (y = 3 or 4, as a binder to improve the adhesion strength and hardness of the film.
It is also possible to add a silicon compound such as R: alkyl group). Further, various surfactants can be added to improve the wettability with the substrate. It is also possible to obtain a film having a high refractive index by mixing a Ti compound, a Zr compound or the like with the coating liquid.

【0014】このようにして合成したコーティング液の
基体上への塗布法としては従来用いられてきた方法、即
ちスピンコート法、ディップコート法、スプレーコート
法、ロールコート法、メニスカスコート法、スクリーン
印刷法、フレキソ印刷法などが利用できる。
As a coating method of the coating liquid thus synthesized on the substrate, there have been conventionally used methods such as spin coating method, dip coating method, spray coating method, roll coating method, meniscus coating method and screen printing. Method, flexographic printing method, etc. can be used.

【0015】本発明のコーティング液は低沸点の溶媒を
用いた場合、室温での乾燥で均一な膜を得られるが、高
沸点溶媒を用いた場合や膜の強度を向上させたい場合、
塗布した基板を加熱(基板がガラスの場合は、室温〜6
50℃程度)かつ/または紫外線を照射して硬化させる
のが好ましい。加熱温度の上限は基板に用いられるガラ
ス、プラスチック等の軟化点によって決定される。
When the coating liquid of the present invention uses a solvent having a low boiling point, a uniform film can be obtained by drying at room temperature. However, when a solvent having a high boiling point is used or the strength of the film is desired to be improved,
Heat the coated substrate (if the substrate is glass, room temperature to 6
It is preferable to cure by irradiating with ultraviolet rays and / or about 50 ° C.). The upper limit of the heating temperature is determined by the softening point of glass, plastic, etc. used for the substrate.

【0016】本発明の透明導電膜を形成する基体として
は、通常の普通板ガラスやフロート板ガラスの他に、ブ
ラウン管パネル、複写機用ガラス板、CRT或はLCD
等の表示装置の前面板等の各種ガラス、そしてプラスチ
ック基板を用いることができる。
As the substrate for forming the transparent conductive film of the present invention, in addition to ordinary ordinary plate glass or float plate glass, a cathode ray tube panel, a glass plate for a copying machine, a CRT or an LCD.
It is possible to use various kinds of glass such as a front plate of a display device such as, and a plastic substrate.

【0017】本発明による透明導電膜は、その導電性を
利用した帯電防止膜としての機能のほかに、導電性酸化
物の超微粒子としてITOやSb−SnO2 などの熱線
反射性能を有する物を用いれば熱線反射膜としての機能
を具備させることができる。さらに、膜中で導電性微粒
子が高度に分散している不連続膜であるので膜厚を制御
して抵抗値等を調整すれば電磁波を透過させることがで
き、室内アンテナや自動車用のガラスアンテナなどとも
併用して用いることができる熱線反射膜として使用する
ことができる。
The transparent conductive film according to the present invention, in addition to its function as an antistatic film utilizing its conductivity, is made of an ultrafine particle of a conductive oxide, such as ITO or Sb-SnO 2, which has a heat ray reflecting property. If used, it can have a function as a heat ray reflective film. Furthermore, since it is a discontinuous film in which conductive particles are highly dispersed in the film, electromagnetic waves can be transmitted by controlling the film thickness and adjusting the resistance value, etc., and it can be used as an indoor antenna or a glass antenna for automobiles. And the like can be used as a heat ray reflective film that can be used in combination.

【0018】また、同様に本発明品の透明導電膜の上
に、MgF2 、SiO2 等の低屈折率の材料を含む液を
適宜の光学膜厚となるようにコートして、多層干渉効果
による低反射の透明導電膜とすることもできる。
Similarly, a liquid containing a material having a low refractive index such as MgF 2 or SiO 2 is coated on the transparent conductive film of the present invention so as to have an appropriate optical film thickness, and a multilayer interference effect is obtained. It is also possible to use a low-reflection transparent conductive film.

【0019】[0019]

【実施例】以下に本発明の実施例を挙げ更に説明を行う
が、本発明はこれらに限定されるものではない。
The present invention will be further described below with reference to examples of the present invention, but the present invention is not limited thereto.

【0020】[実施例1]平均粒径100ÅのSbドー
プSnO2 をサンドミルで粉砕して得たSnO2ゾル液
をエタノールで3重量%に希釈した。(A液) Al(C693 )(OC372 のエタノール溶
液に、Al(C693 )(OC372 5重量部
に対して塩酸水溶液を2重量部添加して30分間撹拌
し、Al23 換算固形分濃度が3重量%となるように
調製した。(B液) A液とB液を、A液:B液=10:1重量比となるよう
に混合した。(C液)
Example 1 A SnO 2 sol liquid obtained by crushing Sb-doped SnO 2 having an average particle size of 100 Å with a sand mill was diluted with ethanol to 3% by weight. In (A solution) Al (C 6 H 9 O 3) (OC 3 H 7) 2 ethanol solution, Al (C 6 H 9 O 3) a (OC 3 H 7) aqueous hydrochloric acid relative to the 2 5 parts by weight 2 parts by weight was added and stirred for 30 minutes to prepare an Al 2 O 3 conversion solid content concentration of 3% by weight. (Solution B) Solution A and Solution B were mixed in a ratio of Solution A: Solution B = 10: 1 by weight. (C liquid)

【0021】Si(OC254 のエタノール溶液
に、Si(OC254 5重量部に対して塩酸水溶液
4重量部添加し、SiO2 換算固形分濃度が3重量%と
なるように調製した。(D液) C液とD液を、C液:D液=17:8重量比となるよう
に混合しこの溶液を2mm厚ガラス板表面に750rp
m、5秒間スピンコート法で塗布し、その後200℃で
30分加熱した。
The ethanol solution of Si (OC 2 H 5) 4 , Si (OC 2 H 5) aqueous solution of hydrochloric acid, 4 parts by weight was added with respect to 4 5 parts by weight, SiO 2 in terms of solid concentration of 3 wt% Was prepared as follows. (D liquid) C liquid and D liquid were mixed in a ratio of C liquid: D liquid = 17: 8 weight ratio, and this solution was 750 rp on the surface of a 2 mm thick glass plate.
The coating was performed by a spin coating method for 5 seconds and then heated at 200 ° C. for 30 minutes.

【0022】[実施例2]A液とB液をA液:B液=1
0:2重量比となるように混合し(E液)、C液のかわ
りにE液を用いてE液:D液=3:2重量比となるよう
に混合した以外は実施例1と同様に行った。
[Example 2] Liquid A and liquid B were liquid A: liquid B = 1
Same as Example 1 except that the mixture was mixed at a ratio of 0: 2 (solution E), and the solution E was used instead of the solution C so that the solution E: solution D was mixed at a ratio of 3: 2 by weight. Went to.

【0023】[実施例3]Al(OC493 のエタ
ノール溶液にアセチルアセトンをAl(OC493
に対して1mol比添加し1時間撹拌した後、Al(O
493 5重量部に対して塩酸水溶液を1重量部添
加し、固形分濃度がAl23 換算で3重量%となるよ
うにしてさらに1時間撹拌した。(F液)
[0023] [Example 3] Al (OC 4 H 9 ) 3 in ethanol in acetylacetone Al (OC 4 H 9) 3
After adding 1 mol ratio to and stirring for 1 hour, Al (O
1 part by weight of an aqueous solution of hydrochloric acid was added to 5 parts by weight of C 4 H 9 ) 3 , and the mixture was further stirred for 1 hour so that the solid content concentration became 3% by weight in terms of Al 2 O 3 . (F liquid)

【0024】実施例1に示されるD液とF液を、D液:
F液=8:2重量比となるように混合した。(G液) D液のかわりにG液を用いてE液:G液=3:2となる
ように混合した以外は実施例2と同様に行った。
Solution D and solution F shown in Example 1 were prepared as solution D:
Liquid F was mixed so that the weight ratio was 8: 2. (Solution G) The same operation as in Example 2 was carried out except that instead of the solution D, the solution G was used and mixed so that the solution E: the solution G was 3: 2.

【0025】[実施例4]平均粒径100ÅのSbドー
プSnO2 をサンドミルで粉砕して得たSnO2ゾル液
をエタノールで10重量%に希釈した。(H液) Al(C693 )(OC372 のエタノール溶
液に、Al(C693 )(OC372 5重量部
に対して硝酸水溶液を2重量部添加して30分間撹拌
し、Al23 換算固形分濃度が10重量%となるよう
に調製した。(I液)
Example 4 A SnO 2 sol liquid obtained by crushing Sb-doped SnO 2 having an average particle size of 100Å with a sand mill was diluted with ethanol to 10% by weight. To (H solution) Al (C 6 H 9 O 3) (OC 3 H 7) 2 ethanol solution, Al (C 6 H 9 O 3) a (OC 3 H 7) nitric acid aqueous solution for two 5 parts by weight 2 parts by weight was added and stirred for 30 minutes to prepare an Al 2 O 3 conversion solid content concentration of 10% by weight. (Liquid I)

【0026】H液とI液を、H液:I液=10:3重量
比となるように混合し、この溶液を2mm厚ガラス板表
面に750rpm、5秒間スピンコート法で塗布し、そ
の後600℃で5分加熱した。
Solution H and solution I were mixed so that the ratio of solution H: solution I was 10: 3 by weight, and this solution was applied onto a surface of a 2 mm thick glass plate by a spin coating method at 750 rpm for 5 seconds, and then 600 Heated at 0 ° C for 5 minutes.

【0027】[実施例5]Al(OC493 のイソ
プロピルアルコール溶液にアセチルアセトンをAl(O
493 に対して1mol比添加し30分撹拌した
後、Al(OC493 5重量部に対して塩酸水溶液
を2重量部添加してさらに1時間撹拌し、Al23
算固形分濃度が10重量%となるように調製した。(J
液) 実施例4に示されるH液とJ液を、H液:J液=10:
1重量比となるように混合した。(K液)
[Example 5] Acetylacetone was added to Al (O) in an isopropyl alcohol solution of Al (OC 4 H 9 ) 3.
After adding 1 mol ratio to C 4 H 9 ) 3 and stirring for 30 minutes, 2 parts by weight of hydrochloric acid aqueous solution was added to 5 parts by weight of Al (OC 4 H 9 ) 3 and further stirred for 1 hour, and Al 2 It was prepared so that the solid content concentration in terms of O 3 would be 10% by weight. (J
Solution) Solution H and Solution J shown in Example 4 were prepared as Solution H: Solution J = 10:
It mixed so that it might become 1 weight ratio. (K liquid)

【0028】珪酸エチル重合物(SiO2 換算固形分4
0重量%)のエタノール溶液に、珪酸エチル重合物5重
量部に対して塩酸水溶液を4重量部添加し、SiO2
算固形分濃度が10重量%となるように調製した。(L
液) L液とK液を、L液:K液=11:4重量比となるよう
に混合してコーティング液とし、実施例4と同様にして
透明導電性膜を得た。
Ethyl silicate polymer (solid content of SiO 2 4
0% by weight) of ethanol solution was added with 4 parts by weight of hydrochloric acid aqueous solution to 5 parts by weight of ethyl silicate polymer to prepare a solid content concentration of 10% by weight in terms of SiO 2 . (L
Liquid) The L liquid and the K liquid were mixed so as to have a L liquid: K liquid = 11: 4 weight ratio to form a coating liquid, and a transparent conductive film was obtained in the same manner as in Example 4.

【0029】[実施例6]J液の代わりにI液を用いた
以外は実施例5と同様に行った。
[Example 6] The same procedure as in Example 5 was repeated except that the solution I was used instead of the solution J.

【0030】[実施例7]実施例3で用いたコーティン
グ液を、35℃の恒温乾燥器中で2週間保存した後、実
施例3と同様にしてコーティングを行った。
Example 7 The coating solution used in Example 3 was stored in a thermostatic oven at 35 ° C. for 2 weeks and then coated in the same manner as in Example 3.

【0031】[比較例1]C液のかわりにA液を用いた
以外は実施例1と同様に行った。
[Comparative Example 1] The same procedure as in Example 1 was carried out except that the liquid A was used instead of the liquid C.

【0032】[比較例2]K液のかわりにH液を用いた
以外は実施例5と同様に行った。
[Comparative Example 2] The same operation as in Example 5 was carried out except that the H solution was used instead of the K solution.

【0033】以上の実施例及び比較例において得られた
膜の評価は膜表面の表面抵抗値、可視光線透過率、ヘー
ズ(曇り値)について行った。実施例及び比較例の結果
を表1に示す。また、実施例5については、300nm
〜2600nmの分光透過率を測定し、熱線反射性能に
ついて評価を行った。その結果を図1に示す。膜を形成
する前のガラスの分光透過率と比べて、実施例5の膜を
形成した後の分光透過率は、近赤外から赤外領域におい
てかなり低くなっており、実施例5の膜の熱線反射性能
が高いことがわかる。
The films obtained in the above Examples and Comparative Examples were evaluated for the surface resistance value of the film surface, visible light transmittance, and haze. The results of Examples and Comparative Examples are shown in Table 1. Also, for Example 5, 300 nm
The spectral transmittance of ˜2600 nm was measured, and the heat ray reflection performance was evaluated. The result is shown in FIG. Compared with the spectral transmittance of the glass before forming the film, the spectral transmittance after forming the film of Example 5 is considerably low in the near infrared to infrared region. It can be seen that the heat ray reflection performance is high.

【0034】[0034]

【表1】 [Table 1]

【0035】[0035]

【発明の効果】本発明によればスプレーまたはスピンコ
ートあるいは溶液中に基体を浸漬するなどの簡便な方法
により効率よく優れた透明導電膜を提供することが可能
となる。本発明は生産性に優れ、かつ真空を必要としな
いので装置も比較的安価なものでよい。特に建築、ビル
用板ガラスや自動車用ガラス、CRTのパネルフェイス
面等の大面積の基体にも充分適用でき、量産も可能であ
るため工業的価値は非常に高い。
According to the present invention, an excellent transparent conductive film can be efficiently provided by a simple method such as spraying, spin coating or immersing a substrate in a solution. Since the present invention is excellent in productivity and does not require a vacuum, the device may be relatively inexpensive. In particular, it has a very high industrial value because it can be sufficiently applied to large-area substrates such as plate glass for buildings and buildings, glass for automobiles, and panel face surfaces of CRTs, and mass production is possible.

【0036】またキレート配位子がアルミニウムに配位
したアルミニウム錯体を加えることによりSnO2 等の
導電性粒子がコーティング液中で安定に分散し、ヘーズ
が少なく高性能な膜が得られる。
By adding an aluminum complex in which a chelate ligand is coordinated to aluminum, conductive particles such as SnO 2 are stably dispersed in the coating liquid, and a high performance film with less haze can be obtained.

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

【図1】実施例5で得られた膜の分光透過率を示すグラ
FIG. 1 is a graph showing the spectral transmittance of the film obtained in Example 5.

Claims (8)

【特許請求の範囲】[Claims] 【請求項1】キレート配位子がアルミニウムに配位した
アルミニウム錯体と導電性酸化物の超微粒子とを含むコ
ーティング液を基体上に塗布し、硬化させることを特徴
とする透明導電膜の製造方法。
1. A method for producing a transparent conductive film, which comprises applying a coating solution containing an aluminum complex having a chelate ligand coordinated to aluminum and ultrafine particles of a conductive oxide to a substrate and curing the coating solution. ..
【請求項2】アルミニウム錯体は、キレート配位子がア
ルミニウムに配位した、アルミニウム塩、アルミニウム
アルコキシド、アルミニウムアルコキシドの加水分解
物、の中から選ばれる少なくとも1種であることを特徴
とする請求項1の透明導電膜の製造方法。
2. The aluminum complex is at least one selected from an aluminum salt, an aluminum alkoxide, and a hydrolyzate of an aluminum alkoxide in which a chelate ligand is coordinated with aluminum. 1. The method for producing a transparent conductive film of 1.
【請求項3】キレート配位子が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であることを特徴
とする請求項1または2の透明導電膜の製造方法。
3. The chelate ligand is β-diketone or β-
3. The method for producing a transparent conductive film according to claim 1, which is an enol type anion of keto acid ester.
【請求項4】コーティング液が珪素化合物を含むことを
特徴とする請求項1〜3いずれか1項の透明導電膜の製
造方法。
4. The method for producing a transparent conductive film according to claim 1, wherein the coating liquid contains a silicon compound.
【請求項5】請求項1〜4いずれか1項の製造方法によ
って得られた透明導電膜。
5. A transparent conductive film obtained by the manufacturing method according to claim 1.
【請求項6】請求項1〜4いずれか1項の製造方法によ
ってガラス基体上に透明導電膜を形成したガラス物品。
6. A glass article having a transparent conductive film formed on a glass substrate by the manufacturing method according to claim 1.
【請求項7】請求項1〜4いずれか1項の製造方法によ
って表面に透明導電膜を形成し、それによって熱線反射
性能を具備させたガラス。
7. A glass comprising a transparent conductive film formed on the surface by the manufacturing method according to any one of claims 1 to 4 and having heat ray reflection performance thereby.
【請求項8】請求項1〜4いずれか1項の製造方法によ
って表面に透明導電膜を形成し、それによって帯電防止
性能を具備させたブラウン管。
8. A CRT having a transparent conductive film formed on its surface by the manufacturing method according to any one of claims 1 to 4, thereby providing antistatic performance.
JP30706691A 1991-10-25 1991-10-25 Transparent conductive film and its manufacture Withdrawn JPH05120921A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP30706691A JPH05120921A (en) 1991-10-25 1991-10-25 Transparent conductive film and its manufacture

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP30706691A JPH05120921A (en) 1991-10-25 1991-10-25 Transparent conductive film and its manufacture

Publications (1)

Publication Number Publication Date
JPH05120921A true JPH05120921A (en) 1993-05-18

Family

ID=17964637

Family Applications (1)

Application Number Title Priority Date Filing Date
JP30706691A Withdrawn JPH05120921A (en) 1991-10-25 1991-10-25 Transparent conductive film and its manufacture

Country Status (1)

Country Link
JP (1) JPH05120921A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09302284A (en) * 1996-05-14 1997-11-25 Sumitomo Metal Mining Co Ltd Coating fluid for sunlight-screening film and sunlight-screening film made by using the same
JP2016126921A (en) * 2014-12-29 2016-07-11 小林 博 Transparent conductive film and method for producing the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09302284A (en) * 1996-05-14 1997-11-25 Sumitomo Metal Mining Co Ltd Coating fluid for sunlight-screening film and sunlight-screening film made by using the same
JP2016126921A (en) * 2014-12-29 2016-07-11 小林 博 Transparent conductive film and method for producing the same

Similar Documents

Publication Publication Date Title
JP3302186B2 (en) Substrate with transparent conductive film, method for producing the same, and display device provided with the substrate
JP3973330B2 (en) Substrate with transparent coating, coating liquid for forming transparent coating, and display device
JP3262098B2 (en) Heat ray shielding material, heat ray shielding equipment using the same, coating liquid and heat ray shielding film
JP3473272B2 (en) Coating liquid for conductive film formation and conductive film
JP3219450B2 (en) Method for producing conductive film, low reflection conductive film and method for producing the same
JPH09263716A (en) Overcoat composition for transparent electrically conductive film excellent in electical conductivity
JPH05107403A (en) High refractivity conductive film or low reflective anti-static film and manufacture thereof
JPH0570178A (en) Heat ray-reflecting film and its production
JPH09115438A (en) Conductive film, low-reflection conductive film and its forming method
JP3367241B2 (en) Low reflective / electromagnetic shielding transparent conductive film and paint for its formation
JP2001187864A (en) Transparent coating film-forming coating fluid, substrate with transparent coating film and display
US7625635B2 (en) Transparent film-forming coating liquid, substrate with transparent film, and display device
JPH05120921A (en) Transparent conductive film and its manufacture
JPH06144874A (en) Heat ray reflective film and its production
US5578377A (en) Colored thin film-forming coating solution and colored thin film obtained by such coating solution
JP3288417B2 (en) CRT panel having low reflection conductive film formed thereon and method of manufacturing the same
JPH0534507A (en) Antistatic film and production thereof
JPH0953030A (en) Clear conductive coating material and clear conductive film
KR100420049B1 (en) A composition for a protective layer of a transparent conductive layer and a method of preparing a protective layer using the same
JPH09156963A (en) Coating liquid for heat ray-screening film and heat ray-screening film using the liquid
JPH05186246A (en) Transparent conductive film and its production
JPH10212138A (en) Display device
JPH03167739A (en) Antistatic film
JP3315673B2 (en) CRT with conductive film
JPH06228500A (en) Antistatic and antireflecting film and coating for forming thereof

Legal Events

Date Code Title Description
A300 Withdrawal of application because of no request for examination

Free format text: JAPANESE INTERMEDIATE CODE: A300

Effective date: 19990107