JPH0687631A - Two-layered electric conductive transparent film - Google Patents

Two-layered electric conductive transparent film

Info

Publication number
JPH0687631A
JPH0687631A JP23610592A JP23610592A JPH0687631A JP H0687631 A JPH0687631 A JP H0687631A JP 23610592 A JP23610592 A JP 23610592A JP 23610592 A JP23610592 A JP 23610592A JP H0687631 A JPH0687631 A JP H0687631A
Authority
JP
Japan
Prior art keywords
layer
film
transparent conductive
conductive
reinforcing
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
Application number
JP23610592A
Other languages
Japanese (ja)
Inventor
Tsuneo Yanagisawa
恒夫 柳澤
Atsumi Wakabayashi
淳美 若林
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.)
Sumitomo Cement Co Ltd
Original Assignee
Sumitomo Cement 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 Sumitomo Cement Co Ltd filed Critical Sumitomo Cement Co Ltd
Priority to JP23610592A priority Critical patent/JPH0687631A/en
Publication of JPH0687631A publication Critical patent/JPH0687631A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/24—Reinforcing the conductive pattern

Abstract

PURPOSE:To provide a two-layered electric conductive transparent film having high electric conductivity and high transparency, also having high film strength and capable of being produced by coating at a low treatment temp. CONSTITUTION:A highly electric conductive layer and a reinforcing layer are successively formed on a substrate to obtain the two-layered electric conductive transparent film. The highly electric conductive layer is formed with an electric conductive coating material contg. 62.5-100wt.% electric conductive transparent filler in the solid matter and the reinforcing layer is formed with a coating material for reinforcement contg. 71.4-100wt.% binder in the solid matter.

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、例えばＣＲＴの前面よ
り発生する電磁波を遮断するための電磁波遮断膜や、窓
ガラス表面に形成されて外部から侵入する不要電磁波を
遮断するための電磁波遮断膜、さらには液晶表示板やタ
ッチスイッチなどの透明電極として用いることのできる
透明導電性膜に係り、詳しくはガラス等の基板の表面上
に形成される高導電性層と、該高導電性層の上に形成さ
れる補強層とからなる２層型透明導電性膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electromagnetic wave shielding film for shielding an electromagnetic wave generated from the front surface of a CRT, or an electromagnetic wave shielding film for shielding an unnecessary electromagnetic wave formed on the surface of a window glass. Further, the present invention relates to a transparent conductive film that can be used as a transparent electrode such as a liquid crystal display panel or a touch switch, and more specifically, a high conductive layer formed on the surface of a substrate such as glass, and a high conductive layer The present invention relates to a two-layer type transparent conductive film including a reinforcing layer formed above.

【０００２】[0002]

【従来の技術】一般にＣＲＴは、その前面より不要電磁
波を発生することが知られている。その不要電磁波を遮
断するためには、高い導電性を有しかつ透明性を有する
透明高導電性膜をＣＲＴ前面に形成することが効果的で
ある。従来、このような透明導電性薄膜をＣＲＴの前面
のような透明基板上に形成するには、酸化スズや、酸化
インジウム等の導電性金属酸化物粉を含む透明導電性コ
ーティング液を塗布するか、もしくは、金属や導電性金
属酸化物の蒸着膜、またはスパッタ膜を成膜するといっ
た方法が採られている。特に、このような高い導電性を
持った透明導電性薄膜の成膜には、後者の蒸着またはス
パッタによる方法が現在のところ有利であるとされ、主
に採用されている。また、これら蒸着法やスパッタ法に
よって得られる透明導電性薄膜は、液晶表示板やタッチ
スイッチなどに用いられる透明電極としても多く用いら
れている。2. Description of the Related Art Generally, a CRT is known to generate unnecessary electromagnetic waves from its front surface. In order to block the unnecessary electromagnetic waves, it is effective to form a transparent and highly conductive film having high conductivity and transparency on the front surface of the CRT. Conventionally, in order to form such a transparent conductive thin film on a transparent substrate such as a front surface of a CRT, a transparent conductive coating liquid containing a conductive metal oxide powder such as tin oxide or indium oxide should be applied. Alternatively, a method of forming a vapor-deposited film of metal or conductive metal oxide or a sputtered film is adopted. In particular, the latter method of vapor deposition or sputtering is said to be advantageous at present and is mainly used for forming a transparent conductive thin film having such high conductivity. Further, the transparent conductive thin film obtained by the vapor deposition method or the sputtering method is often used as a transparent electrode used for a liquid crystal display panel, a touch switch, or the like.

【０００３】しかし、スパッタ法や蒸着法による透明導
電性薄膜の形成法では、成膜コストが高く、しかも成膜
を行うためには真空容器が必要となることから、大面積
基板上への成膜や複雑な形状を持つ物質表面への成膜が
著しく困難となる。これに対し、前述した透明導電性コ
ーティング液による成膜法は、大面積基板上や、複雑な
形状を持つ物質表面上でも低い成膜温度で透明導電性薄
膜を成膜することができる方法であり、その実用化が要
望されている。However, in the method of forming a transparent conductive thin film by the sputtering method or the vapor deposition method, the film forming cost is high, and a vacuum container is required for forming the film, so that it is formed on a large area substrate. It becomes extremely difficult to form a film on a surface of a film or a material having a complicated shape. On the other hand, the above-mentioned film forming method using the transparent conductive coating liquid is a method capable of forming a transparent conductive thin film at a low film forming temperature even on a large-area substrate or on the surface of a substance having a complicated shape. There is a demand for its practical application.

【０００４】[0004]

【発明が解決しようとする課題】しかしながら、現在知
られている透明導電性コーティング液から得られる透明
導電性膜では、導電性が低く、傷がつき易い等の問題が
ある。そして、このような問題に起因して、該コーティ
ング液から作製される透明導電性薄膜は、例えばＣＲＴ
前面の帯電防止膜として用いるには十分な効果を有する
ものの、ＣＲＴ前面から放射される人体に有害な電磁波
の遮蔽膜として用いるには不十分なものとなっている。
すなわち、電磁波を遮蔽するには、帯電を防止する以上
に高い導電性が要求されるものの、現在知られている透
明導電性コーティング液ではこれを満足させることので
きるものがないからである。However, the transparent conductive film obtained from the currently known transparent conductive coating liquid has problems that it has low conductivity and is easily scratched. Due to such a problem, the transparent conductive thin film produced from the coating liquid is, for example, a CRT.
Although it has a sufficient effect to be used as an antistatic film on the front surface, it is insufficient to be used as a shielding film for electromagnetic waves radiated from the CRT front surface and harmful to the human body.
That is, in order to shield electromagnetic waves, higher conductivity than that required to prevent electrification is required, but none of the currently known transparent conductive coating liquids can satisfy this requirement.

【０００５】また、より高導電性の薄膜を得ることがで
きるように、スズやインジウムの有機塩や硝酸塩を加熱
分解し、これによって導電性金属酸化物薄膜を形成する
タイプの塗布液も知られている。しかし、この塗布液を
用いる場合には、４００〜５００℃といった高温度下で
の処理を行わなければならず、したがって使用可能な基
板がガラスやセラミックスに限定されてしまうといった
欠点がある。In order to obtain a thin film having higher conductivity, a coating liquid of a type in which an organic salt of tin or indium or nitrate is decomposed by heating to form a conductive metal oxide thin film is known. ing. However, when this coating liquid is used, it is necessary to perform the treatment at a high temperature of 400 to 500 ° C., and therefore, there is a disadvantage that usable substrates are limited to glass and ceramics.

【０００６】本発明は前記事情に鑑みてなされたもの
で、その目的とするところは、高導電性、高透明性を有
し、かつ強い膜強度をも併せ持ち、しかも低い処理温度
で塗布法により作製することができる透明導電性膜を提
供することにある。The present invention has been made in view of the above circumstances, and an object thereof is to have high conductivity, high transparency, strong film strength, and a coating method at a low processing temperature. It is to provide a transparent conductive film that can be manufactured.

【０００７】[0007]

【課題を解決するための手段】本発明における請求項１
記載の２層型透明導電性膜では、基材上に形成される高
導電性層と、該高導電性層の上に形成される補強層とか
らなり、前記高導電性層が、固形分中における透明導電
性フィラーの割合が６２.５〜１００重量％である導電
性塗料によって形成され、前記補強層が、固形分中にお
けるバインダー成分の割合が７１.４〜１００重量％で
ある補強用塗料によって形成されてなることを前記課題
の解決手段とした。請求項２の２層型透明導電性膜で
は、前記導電性塗料中の透明導電性フィラーが、その１
次粒子の平均粒径が０.１μｍ以下であることを前記課
題の解決手段とした。[Means for Solving the Problems] Claim 1 in the present invention
In the two-layer type transparent conductive film described, a high conductive layer formed on a base material and a reinforcing layer formed on the high conductive layer, wherein the high conductive layer has a solid content. The reinforcing layer is formed of a conductive coating material having a transparent conductive filler content of 62.5 to 100% by weight, and the reinforcing layer has a binder component content of 71.4 to 100% by weight in solid content. The means for solving the above-mentioned problems was formed by a paint. In the two-layer type transparent conductive film according to claim 2, the transparent conductive filler in the conductive paint is
The average particle size of the secondary particles being 0.1 μm or less was taken as a means for solving the above problems.

【０００８】以下、本発明を詳しく説明する。従来の透
明導電性コーティング組成物は、導電性フィラーと定着
剤としてのバインダーとが一液に混合されて使用され
る。しかし、このように導電性フィラーとバインダーと
が一液に混合されていると、成膜時にバインダー成分が
導電性フィラー粒子を覆うことによって粒子間に入り込
み、その結果、導電性フィラー粒子間の接触が妨げられ
てしまう。そして、用いられる透明バインダー成分が不
導体であることから、前記コーティング組成物から形成
された膜は、そのフィラーの導電性に見合った導電性を
有するものとならないのである。The present invention will be described in detail below. A conventional transparent conductive coating composition is used by mixing a conductive filler and a binder as a fixing agent in one liquid. However, when the conductive filler and the binder are mixed in one liquid in this way, the binder component enters between the particles by covering the conductive filler particles during film formation, and as a result, the contact between the conductive filler particles is caused. Will be hindered. Further, since the transparent binder component used is a non-conductor, the film formed from the coating composition does not have conductivity matching the conductivity of the filler.

【０００９】これに対して本発明の２層型透明導電性膜
では、前述したように基材上に形成される高導電性層
と、該高導電性層の上に形成される補強層との２層構造
とするとともに、前記高導電性層を、固形分中における
透明導電性フィラーの割合が６２.５〜１００重量％で
ある導電性塗料によって形成し、前記補強層を、固形分
中におけるバインダー成分の割合が７１.４〜１００重
量％である補強用塗料によって形成している。ここで、
導電性塗料は、透明導電性フィラー、該透明導電性フィ
ラーを分散させる分散媒のほか、必要に応じバインダー
や各種添加剤が加えられ形成される。On the other hand, in the two-layer type transparent conductive film of the present invention, the high conductive layer formed on the base material and the reinforcing layer formed on the high conductive layer as described above. In addition to the two-layer structure of the above, the high conductive layer is formed by a conductive coating material in which the ratio of the transparent conductive filler in the solid content is 62.5 to 100% by weight, and the reinforcing layer is formed in the solid content. Is formed of a reinforcing coating material having a binder component ratio of 71.4 to 100% by weight. here,
The conductive paint is formed by adding a transparent conductive filler, a dispersion medium in which the transparent conductive filler is dispersed, and, if necessary, a binder and various additives.

【００１０】透明導電性フィラーとしては、透明性のあ
る導電性金属酸化物、すなわち、酸化スズ、酸化インジ
ウム、アンチモン含有酸化スズ、スズ含有酸化インジウ
ム、アルミニウム含有酸化亜鉛等のうちの１種あるいは
複数種が用いられる。また、このような導電性フィラー
としては、生成させる膜の透明性を維持するため、粉体
であることが必要であり、特にその１次粒子の平均粒径
が０.１μｍ以下であることが、より高い透明性を得る
うえで望ましい。なおここで、この導電性フィラー粉体
粒子は必ずしも分散媒中に一次分散する必要はない。The transparent conductive filler is one or more of transparent conductive metal oxides, that is, tin oxide, indium oxide, antimony-containing tin oxide, tin-containing indium oxide, aluminum-containing zinc oxide and the like. Seeds are used. In addition, such a conductive filler needs to be a powder in order to maintain the transparency of the film to be formed, and in particular, the average particle diameter of the primary particles thereof is 0.1 μm or less. , It is desirable to obtain higher transparency. Here, the conductive filler powder particles do not necessarily have to be primarily dispersed in the dispersion medium.

【００１１】分散媒としては、アルコール類、特にエチ
ルアルコールが好適とされるが、導電性塗料の塗布条件
に合わせて、水を分散媒として用いることもできる。ま
た、分散媒を水、またはアルコール以外の有機溶媒、ま
たはそれらの混合物を用いても同様の効果が得られる。
さらに、導電性フィラー粉を分散させる際、界面活性剤
等の分散剤を添加しても、本発明の効果に悪影響を及ぼ
すものではなく、むしろ、導電性金属酸化物粉の分散を
改善することができ、その結果、得られる高導電性層の
透明性をさらに向上せしめることができる。また、この
ような導電性塗料においては、前記導電性フィラー粉が
凝集した状態で分散され塗料化されても、得られた塗料
は本発明の高導電性層として十分その効果を発揮する。
しかし、導電性塗料の作製に際しては、通常の方法に従
い、超音波分散機やサンドミル、ボールミル等のメディ
アミル等を用い、導電性フィラー粉を分散媒中に分散さ
せる操作を行ってもよいのはもちろんである。Alcohols, particularly ethyl alcohol, are suitable as the dispersion medium, but water can also be used as the dispersion medium depending on the coating conditions of the conductive paint. Similar effects can be obtained by using water, an organic solvent other than alcohol, or a mixture thereof as the dispersion medium.
Furthermore, when dispersing the conductive filler powder, adding a dispersant such as a surfactant does not adversely affect the effect of the present invention, but rather improves the dispersion of the conductive metal oxide powder. As a result, the transparency of the obtained highly conductive layer can be further improved. Further, in such a conductive coating, even if the conductive filler powder is dispersed in the state of being aggregated to form a coating, the obtained coating sufficiently exhibits its effect as the highly conductive layer of the present invention.
However, in the production of the conductive coating material, according to a usual method, using an ultrasonic disperser, a sand mill, a media mill such as a ball mill, or the like, the operation of dispersing the conductive filler powder in the dispersion medium may be performed. Of course.

【００１２】このような導電性塗料において、その固形
分中における透明導電性フィラーの割合を６２.５〜１
００重量％としたのは、６２.５重量％未満では得られ
る膜（層）の透明性は高くなるものの、導電性が低下し
て所望する高い導電性が得られなくなるからである。な
お、透明導電性フィラーの量は多ければ多いほど導電性
については有利となることから、バインダー等を加えず
固形分１００重量％を透明導電性フィラーとするのが好
ましいものの、該フィラーの量が多くなるにつれて得ら
れる膜（層）の透明性が低下することから、最終的に得
られる膜（２層型透明導電性膜）に要求される特性に応
じて適宜フィラーの量が決定される。In such a conductive paint, the ratio of the transparent conductive filler in the solid content is 62.5-1.
The reason why the content is set to 00% by weight is that if the content is less than 62.5% by weight, the transparency of the obtained film (layer) will be high, but the conductivity will be lowered and the desired high conductivity cannot be obtained. Since the larger the amount of the transparent conductive filler, the more advantageous the conductivity is, it is preferable to use 100% by weight of the solid content as the transparent conductive filler without adding a binder or the like, but the amount of the filler is Since the transparency of the obtained film (layer) decreases as the number increases, the amount of the filler is appropriately determined according to the properties required for the finally obtained film (two-layer type transparent conductive film).

【００１３】また、バインダーについては、得られる導
電性塗料を基材に塗布する際の工程上の都合や、該導電
性塗料を塗布することによって得られる高導電性層の強
度を向上させるために、前記透明導電性フィラーの割合
を保持する範囲、すなわち形成される膜（層）の導電性
や透明性を損なわない範囲で添加することができる。そ
して、このような導電性塗料を用いて高導電性層を形成
するには、例えばよく洗浄したガラス等の基材表面に、
該導電性塗料をディップコート法、スピンコート法、ス
プレーコート法などによって塗布し、さらに乾燥するこ
とによって形成することができる。ここで、塗布した膜
を乾燥させる際の加熱温度としては、分散媒が効率よく
揮発する温度でよく、例えば溶媒としてエチルアルコー
ルを用いた場合には、８０℃程度とするのがよい。Regarding the binder, in order to improve the strength of the highly conductive layer obtained by applying the conductive coating material, and the convenience in the process of applying the conductive coating material to the substrate. Can be added within a range that maintains the ratio of the transparent conductive filler, that is, within a range that does not impair the conductivity and transparency of the film (layer) to be formed. Then, in order to form a highly conductive layer using such a conductive coating, for example, on the surface of a base material such as well washed glass,
It can be formed by applying the conductive coating material by a dip coating method, a spin coating method, a spray coating method, or the like, and further drying. Here, the heating temperature for drying the applied film may be a temperature at which the dispersion medium is efficiently volatilized. For example, when ethyl alcohol is used as the solvent, it is preferably about 80 ° C.

【００１４】補強用塗料は、これによって前記高導電性
層の上に補強層を形成することにより、高導電性層の透
明導電性フィラー粒子を基材上に固定するとともに、高
導電性層の導電性を向上させることを目的としたもの
で、バインダー成分をその主な固形成分とし、さらに必
要に応じて透明導電性フィラーや他の添加剤、および溶
媒を加えてなるものである。ここで用いるバインダー成
分としては、通常の技術を使用することにより高導電性
層の上に均一に塗布でき、かつ所望する膜強度が得られ
るものであるならば特に制限はなく、例えばチタンアル
コキシド、シリコンアルコキシド、水ガラスなどの無機
系バインダー、または、ポリエステル、アクリル系樹
脂、エポキシ系樹脂、ＵＶ硬化性樹脂などの有機バイン
ダーが使用される。By forming a reinforcing layer on the highly conductive layer, the reinforcing coating composition fixes the transparent conductive filler particles of the highly conductive layer on the base material, and at the same time, forms the highly conductive layer. The purpose is to improve conductivity, and the binder component is a main solid component of the binder component, and if necessary, a transparent conductive filler, other additives, and a solvent are added. The binder component used here is not particularly limited as long as it can be uniformly applied on the highly conductive layer by using a usual technique, and a desired film strength can be obtained, for example, titanium alkoxide, Inorganic binders such as silicon alkoxide and water glass, or organic binders such as polyester, acrylic resin, epoxy resin, and UV curable resin are used.

【００１５】このような補強用塗料において、その固形
分中におけるバインダー成分の割合を７１.４〜１００
重量％としたのは、７１.４重量％未満では得られる補
強層の強度（膜強度）が低下し、結果として２層型透明
導電性膜の強度が不十分となってしまうからである。な
お、前述したように補強用塗料においてはその固形分を
バインダー成分のみ、すなわちバインダー成分の割合を
１００重量％とするのが、得られる補強層の強度の点で
好ましいものの、２層型透明導電性膜としてさらに高い
導電性を確保するなど、該透明導電性膜に新たな特性を
付与する場合には、導電性フィラーなどの添加物を前記
範囲内にて添加することができる。In such a reinforcing paint, the proportion of the binder component in the solid content is 71.4 to 100.
The reason why the content is 7% by weight is that if the content is less than 71.4% by weight, the strength (film strength) of the obtained reinforcing layer is lowered, and as a result, the strength of the two-layer type transparent conductive film becomes insufficient. As described above, in the reinforcing coating composition, it is preferable that the solid content thereof is only the binder component, that is, the proportion of the binder component is 100% by weight, from the viewpoint of the strength of the reinforcing layer to be obtained. When imparting new properties to the transparent conductive film, such as ensuring high conductivity as the conductive film, an additive such as a conductive filler can be added within the above range.

【００１６】また、補強用塗料中における固形分の割合
としては、塗料の塗布条件によっても異なるものの、
０.５〜３０重量％程度とするのが、塗布操作が容易と
なり好ましい。このような補強用塗料は、前記高導電性
層表面上にスピンコート法、スプレーコート法などによ
って塗布され、硬化することにより、補強層を形成す
る。補強層の厚さとしては、０.２μｍ以下とするの
が、層自体の透明性および導電性を全く損なうことなく
層（膜）のハードコート性を得ることができ、さらに光
学的反射防止性をも得ることができ好ましい。The proportion of the solid content in the reinforcing coating varies depending on the coating conditions of the coating,
The amount of 0.5 to 30% by weight is preferable because the coating operation is easy. Such a reinforcing coating material is applied on the surface of the highly conductive layer by a spin coating method, a spray coating method, or the like, and is cured to form a reinforcing layer. When the thickness of the reinforcing layer is 0.2 μm or less, the hard coat property of the layer (film) can be obtained without impairing the transparency and conductivity of the layer itself, and further, the optical antireflection property can be obtained. Can be obtained, which is preferable.

【００１７】このようにして得られた高導電性層と補強
層とからなる本発明の２層型透明導電性膜にあっては、
高い導電性と、強い膜強度、高い透明性を兼ね備えた透
明導電性薄膜となる。また、導電性塗料中の透明導電性
フィラーとして、十分粒径が小さく、したがって透明性
が高いものを用い、さらに補強層のバインダー成分にも
十分に透明性が高いものを用いれば、本発明の２層型透
明導電性膜を成膜した後のガラス基板等の基材の持つ外
観、透明性を損なうことがない。なお、補強層形成に用
いる補強用塗料に、成膜後の膜強度や透明度を著しく損
なわない程度に染料、顔料を添加し、本発明の２層型透
明導電性膜を任意の色に染色することにより、カラーフ
ィルタとしての性能を持たせることもできる。In the two-layer type transparent conductive film of the present invention comprising the highly conductive layer and the reinforcing layer thus obtained,
The transparent conductive thin film has high conductivity, strong film strength, and high transparency. Further, as the transparent conductive filler in the conductive coating, one having a sufficiently small particle size and therefore high transparency is used, and further, one having sufficiently high transparency as the binder component of the reinforcing layer is also used. The appearance and transparency of a base material such as a glass substrate after forming a two-layer type transparent conductive film is not impaired. A dye or pigment is added to the reinforcing coating material used for forming the reinforcing layer to the extent that the film strength or transparency after film formation is not significantly impaired, and the two-layer transparent conductive film of the present invention is dyed in any color. As a result, the performance as a color filter can be provided.

【００１８】[0018]

【作用】本発明の２層型透明導電性膜によれば、基材上
に高導電性層が形成されていることから、基材上に透明
導電性フィラーが均一に塗布されたものとなり、これに
よって十分な導電性が発揮される。また、該高導電性層
はバインダー成分をほとんど含んでいないため、導電性
フィラー−ガラス基板間、およびフィラー間が固定され
ておらず、したがってこの高導電性層のみではガラス基
板より剥がれ易く、また導電性フィラーの持つ導電性に
見合った高導電性を得ることはできないものの、補強層
が高導電性膜の上に形成されているため、以下のような
作用が得られる。According to the two-layer type transparent conductive film of the present invention, since the highly conductive layer is formed on the base material, the transparent conductive filler is uniformly applied on the base material, As a result, sufficient conductivity is exhibited. In addition, since the highly conductive layer contains almost no binder component, the conductive filler-glass substrate and the filler are not fixed, and therefore the high conductive layer alone is more likely to peel off from the glass substrate, and Although it is not possible to obtain high conductivity matching the conductivity of the conductive filler, the following action is obtained because the reinforcing layer is formed on the high conductivity film.

【００１９】第１に、バインダー成分を主とする補強層
が高導電性層の上にコートされ、硬化せしめられている
ため、高導電性層中の透明導電性フィラーが補強層によ
り糊付けされてガラス基板上に強固に固定、定着されて
いる。第２に、高導電性層のみからなる膜に比べ、本発
明の２層型透明導電性膜では、補強層を形成する補強用
塗料の表面張力、およびそれに続くバインダー成分の硬
化に伴う収縮によって高導電性層中の透明導電性フィラ
ー粒子間の引き締めが行われ、これにより粒子間の接触
の度合いが増加するため、透明導電性フィラー粒子間の
接触面積が増加して該フィラー層の抵抗が引き下げら
れ、結果としてより高い導電性が得られる。First, the transparent conductive filler in the high conductive layer is glued by the reinforcing layer because the reinforcing layer mainly containing the binder component is coated and cured on the high conductive layer. It is firmly fixed and fixed on the glass substrate. Secondly, in the two-layer type transparent conductive film of the present invention, as compared with a film composed of only a highly conductive layer, the surface tension of the reinforcing coating material forming the reinforcing layer and the subsequent shrinkage accompanying curing of the binder component Tightening between the transparent conductive filler particles in the high conductive layer is performed, thereby increasing the degree of contact between the particles, the contact area between the transparent conductive filler particles is increased to increase the resistance of the filler layer. Pulled down, resulting in higher conductivity.

【００２０】なお、バインダー成分として無機バインダ
ーを用い、ガラス基板など耐熱性基板上に成膜するとと
もに、硬化温度を例えば５００℃といった高温に設定す
れば、バインダー成分のさらなる収縮と、透明導電性フ
ィラー間の焼結がおき、前記の作用がさらに増強され
る。第３に、高導電性層の表面が補強層で覆われること
により、全体の膜の強度、すなわち耐擦傷性などが向上
する。If an inorganic binder is used as a binder component and a film is formed on a heat-resistant substrate such as a glass substrate and the curing temperature is set to a high temperature such as 500 ° C., further shrinkage of the binder component and a transparent conductive filler are achieved. Sintering takes place between them, and the above-mentioned effect is further enhanced. Thirdly, by covering the surface of the highly conductive layer with the reinforcing layer, the strength of the entire film, that is, scratch resistance and the like is improved.

【００２１】[0021]

【実施例】以下、本発明の２層型透明導電性膜を実施例
によりさらに具体的に説明する。 （実施例１）エチルアルコールを溶媒とし、これにスズ
含有酸化インジウム微粉末が３ｗｔ％、界面活性剤が
０.０３ｗｔ％となるよう配合混合して混合液を作製
し、さらにこの混合液を超音波分散機（BRANSON社 SON
IFIER ４５０）で１０分間分散処理して導電性塗料を作
製した。次に、この導電性塗料を、よく洗浄したガラス
板上にスピンコート法によって塗布し、さらに空気中に
て８０℃で２５分間加熱処理を行い、乾燥して高導電性
層を形成した。また、エチルアルコールを溶媒とし、こ
れにシリカバインダー液（シリカ固形分３ｗｔ％）を加
えて補強用塗料を作製した。次いで、これを前記高導電
性層の上にスピンコート法によって塗布し、さらに空気
中にて１８０℃で３０分間加熱処理を行い、塗布膜を硬
化せしめて補強層を形成し、２層型透明導電性膜を得
た。EXAMPLES Hereinafter, the two-layer type transparent conductive film of the present invention will be described more specifically by way of examples. (Example 1) Using ethyl alcohol as a solvent, a tin-containing indium oxide fine powder was mixed and mixed in such an amount that the tin-containing indium oxide fine powder was 3 wt% and the surfactant was 0.03 wt% to prepare a mixed liquid. Sonic Disperser (BRANSON SON
IFIER 450) was dispersed for 10 minutes to prepare a conductive paint. Next, this conductive coating material was applied onto a well-washed glass plate by a spin coating method, further heat-treated in air at 80 ° C. for 25 minutes, and dried to form a highly conductive layer. In addition, ethyl alcohol was used as a solvent, and a silica binder liquid (silica solid content: 3 wt%) was added thereto to prepare a reinforcing coating material. Then, this is applied onto the above-mentioned highly conductive layer by a spin coating method, and further subjected to heat treatment in air at 180 ° C. for 30 minutes to cure the applied film to form a reinforcing layer, thereby forming a two-layer type transparent layer. A conductive film was obtained.

【００２２】（比較例１）エチルアルコールを溶媒と
し、これにスズ含有酸化インジウム微粉末が３ｗｔ％、
シリカバインダーがシリカ固形分にして３ｗｔ％となる
よう混合して混合液を作製し、さらにこの混合液を超音
波分散機（BRANSON社 SONIFIER ４５０）で１０分間分
散処理して透明導電性塗料を作製した。次いで、この透
明導電性塗料を、よく洗浄したガラス板上にスピンコー
ト法によって塗布し、さらに空気中にて１８０℃で３０
分間加熱処理を行い、透明導電性膜を作製した。 （比較例２）実施例１で用いた導電性塗料のみを、実施
例１に述べた方法と同様の方法により塗布、熱処理を行
い、ガラス板上に透明導電性膜を形成した。Comparative Example 1 Ethyl alcohol was used as a solvent, and 3 wt% of tin-containing indium oxide fine powder was added thereto,
A silica binder is mixed so that the solid content of silica is 3% by weight to prepare a mixed solution, and the mixed solution is subjected to a dispersion treatment with an ultrasonic disperser (SONIFIER 450 manufactured by BRANSON) for 10 minutes to prepare a transparent conductive paint. did. Then, this transparent conductive paint was applied onto a well-washed glass plate by a spin coating method, and further in air at 180 ° C. for 30 minutes.
Heat treatment was performed for a minute to produce a transparent conductive film. (Comparative Example 2) Only the conductive paint used in Example 1 was applied and heat-treated in the same manner as in Example 1 to form a transparent conductive film on the glass plate.

【００２３】実施例１で得られた２層型透明導電性膜、
および比較例１、比較例２で得られた透明導電性膜につ
いてそれぞれ表面抵抗値、全光透過率、ヘーズ値、膜強
度試験（鉛筆強度試験）を調べ、その結果を表１に示
す。なお、表面抵抗値については三菱油化株式会社製の
「ロレスタＡＰ」を用いて４探針法により測定した。ま
た、ヘーズ値については東京電色株式会社製の「Automa
tic Haze Meter ＴＣ−ＨIIIＤＰ」を用いて測定した。
さらに、鉛筆強度については太平理化株式会社製の鉛筆
強度試験器を用いて測定した。A two-layer type transparent conductive film obtained in Example 1,
The surface resistance value, total light transmittance, haze value, and film strength test (pencil strength test) of the transparent conductive films obtained in Comparative Example 1 and Comparative Example 2 were examined, and the results are shown in Table 1. The surface resistance value was measured by the four-point probe method using "Loresta AP" manufactured by Mitsubishi Petrochemical Co., Ltd. For the haze value, see “Automa” manufactured by Tokyo Denshoku Co., Ltd.
tic Haze Meter TC-HIIIDP ".
Further, the pencil strength was measured using a pencil strength tester manufactured by Taihei Rika Co., Ltd.

【表１】 表１より、本発明の２層型透明導電性膜は、比較例１、
比較例２の透明導電性膜に比べ、表面抵抗値、全光透過
率、ヘーズ値、膜強度（鉛筆強度）の全てにおいて優れ
ていることが確認された。[Table 1] From Table 1, the two-layer type transparent conductive film of the present invention, Comparative Example 1,
It was confirmed that the transparent conductive film of Comparative Example 2 was superior in all of the surface resistance value, the total light transmittance, the haze value, and the film strength (pencil strength).

【００２４】（実施例２）アンチモン含有酸化スズ超微
粉末１.５重量部に水３９.４重量部、エチルアルコール
５９.１重量部を加えて混合液を作製し、さらにこの混
合液を超音波分散機（BRANSON社 SONIFIER ４５０）で
１０分間分散処理して導電性塗料を作製した。次に、こ
の導電性塗料を、よく洗浄したガラス板上にスプレー法
によって塗布し、さらに空気中にて８０℃で２５分間加
熱処理を行い、乾燥して高導電性層を形成した。また、
エチルアルコール６４.８２重量部、ブチルアルコール
３３.６８重量部の割合で混合した溶液を溶媒とし、こ
れにシリカバインダー液（シリカ固形分３ｗｔ％）を加
えて補強用塗料を作製した。次いで、これを前記高導電
性層の上にスプレー法によって塗布し、さらに空気中に
て１７５℃で３０分間加熱処理を行い、塗布膜を硬化せ
しめて補強層を形成し、２層型透明導電性膜を得た。(Example 2) 39.4 parts by weight of water and 59.1 parts by weight of ethyl alcohol were added to 1.5 parts by weight of antimony-containing tin oxide ultrafine powder to prepare a mixed solution. A conductive coating material was prepared by dispersing for 10 minutes with a sonic disperser (SONIFIER 450, manufactured by BRANSON). Next, this conductive coating material was applied onto a well-washed glass plate by a spray method, and then heat-treated in air at 80 ° C. for 25 minutes, and dried to form a highly conductive layer. Also,
A solution prepared by mixing 64.82 parts by weight of ethyl alcohol and 33.68 parts by weight of butyl alcohol was used as a solvent, and a silica binder solution (silica solid content: 3 wt%) was added thereto to prepare a reinforcing coating material. Then, this is applied onto the above-mentioned highly conductive layer by a spray method, and further subjected to heat treatment in air at 175 ° C. for 30 minutes to cure the applied film to form a reinforcing layer, thereby forming a two-layer type transparent conductive film. A film was obtained.

【００２５】（比較例３）水３９.４重量部、エチルア
ルコール１２３.９２重量部、ブチルアルコール３３.６
８重量部の割合で混合した溶液を溶媒とし、これにアン
チモン含有酸化スズ超微粉末を１.５ｗｔ％、シリカバ
インダーをシリカ固形分換算で１.５ｗｔ％となるよう
に加えて混合し塗布液とした。次に、この塗布液を、よ
く洗浄したガラス板上に実施例２と同じ条件でスプレー
法にて塗布し、さらに空気中にて１７５℃で３０分加熱
処理を行い、透明導電性膜を作製した。(Comparative Example 3) 39.4 parts by weight of water, 123.92 parts by weight of ethyl alcohol, 33.6 parts of butyl alcohol.
A solution mixed at a ratio of 8 parts by weight was used as a solvent, and antimony-containing tin oxide ultrafine powder was added to this in an amount of 1.5 wt% and a silica binder was added so as to be 1.5 wt% in terms of silica solid content and mixed to obtain a coating liquid. And Next, this coating solution was applied onto a well-washed glass plate by a spray method under the same conditions as in Example 2, and further heat-treated in air at 175 ° C. for 30 minutes to prepare a transparent conductive film. did.

【００２６】実施例２で得られた２層型透明導電性膜、
および比較例３で得られた透明導電性膜についてそれぞ
れ表面抵抗値、全光透過率、ヘーズ値、膜強度試験（鉛
筆強度試験）を調べ、その結果を表２に示す。なお、各
測定については先の例と同様にして行った。A two-layer type transparent conductive film obtained in Example 2,
The surface resistance value, total light transmittance, haze value, and film strength test (pencil strength test) of the transparent conductive film obtained in Comparative Example 3 were examined, and the results are shown in Table 2. Note that each measurement was performed in the same manner as the above example.

【表２】 表２より、本発明の２層型透明導電性膜は、比較例３の
透明導電性膜に比べ、全光透過率、ヘーズ値、膜強度
（鉛筆強度）等膜の性質を低下させずに表面抵抗率を低
下させ得ることができることが確認された。[Table 2] From Table 2, the two-layer type transparent conductive film of the present invention does not deteriorate the properties of the film such as total light transmittance, haze value, film strength (pencil strength) as compared with the transparent conductive film of Comparative Example 3. It was confirmed that the surface resistivity can be lowered.

【００２７】[0027]

【発明の効果】以上説明したように本発明の２層型透明
導電性膜は、バインダー成分を主とする補強層が高導電
性層の上にコートされ、硬化せしめられてなるものであ
るから、高導電性層中の透明導電性フィラーが補強層に
より基材上に糊付けされたものとなり、よって該透明導
電性膜の基材への固定・定着が強固なものとなる。ま
た、高導電性層のみからなる膜に比べ、本発明の２層型
透明導電性膜では、補強層を形成する補強用塗料の表面
張力、およびそれに続くバインダー成分の硬化に伴う収
縮によって高導電性層中の透明導電性フィラー粒子間の
引き締めがなされることから、フィラー粒子間の接触の
度合いが増加して導電性フィラー粒子間の接触面積が増
加し、導電性フィラー層の抵抗が引き下げられたため、
高導電性層がより高い導電性を有するものとなる。さら
に、高導電性層の表面が補強層で覆われることから、耐
擦傷性など膜強度が高いものとなる。As described above, in the two-layer type transparent conductive film of the present invention, a reinforcing layer mainly containing a binder component is coated on the high conductive layer and cured. The transparent conductive filler in the highly conductive layer is glued on the base material by the reinforcing layer, and thus the fixing and fixing of the transparent conductive film on the base material becomes strong. Further, in the two-layer type transparent conductive film of the present invention, as compared with a film composed of only a highly conductive layer, the two-layer type transparent conductive film has a high conductivity due to the surface tension of the reinforcing coating material forming the reinforcing layer and the subsequent contraction due to curing of the binder component. Since the transparent conductive filler particles in the conductive layer are tightened, the degree of contact between the filler particles is increased to increase the contact area between the conductive filler particles and the resistance of the conductive filler layer is lowered. Because
The highly conductive layer has higher conductivity. Furthermore, since the surface of the highly conductive layer is covered with the reinforcing layer, the film strength such as scratch resistance is high.

【００２８】このように本発明の２層型透明導電性膜
は、従来の透明導電性コーティング組成物より得られる
透明導電性膜と比較して、高導電性でありながら強い膜
強度と高い透明性とを兼ね備えた高性能の透明導電性膜
となることから、従来の透明導電性膜が十分高い導電性
が得られないため帯電防止的な用途にしか用いられてい
なかったのに比べ、ＣＲＴや窓ガラス用の電磁波遮断
膜、さらには液晶表示板やタッチスイッチなどの透明電
極など広範囲のものに適用することができる。As described above, the two-layer type transparent conductive film of the present invention has high conductivity and high film strength and high transparency as compared with the transparent conductive film obtained from the conventional transparent conductive coating composition. Since it becomes a high-performance transparent conductive film having both properties, the conventional transparent conductive film cannot be obtained with sufficiently high conductivity, so that it is used only for the antistatic purpose. It can be applied to a wide range of materials such as an electromagnetic wave blocking film for window glass and transparent electrodes such as a liquid crystal display panel and a touch switch.

【００２９】また、このような高性能の透明導電性膜を
塗布法で得るためには、従来ではゾル−ゲル法や熱分解
法などのように高熱での熱処理が必要であったが、本発
明では低温での乾燥・硬化が可能な導電性塗料および補
強用塗料を用いているため、成膜プロセス過程で必要な
熱処理温度を大幅に下げることができ、したがって用い
る基材の選択自由度を大幅に高めることができる。さら
に、スパッタ法や蒸着法によって得られる膜に比べ、簡
便に得られることから、汎用性が高く工業的利用価値が
多大になる。Further, in order to obtain such a high-performance transparent conductive film by a coating method, conventionally, a high heat treatment such as a sol-gel method or a thermal decomposition method was required. Since the invention uses conductive paints and reinforcing paints that can be dried and cured at low temperatures, the heat treatment temperature required in the film formation process can be significantly reduced, and therefore the degree of freedom in selecting the substrate to be used is increased. Can be greatly increased. Further, since it is more easily obtained than a film obtained by a sputtering method or a vapor deposition method, it is highly versatile and has a great industrial utility value.

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】 基材上に形成される高導電性層と、該高
導電性層の上に形成される補強層とからなる２層型透明
導電性膜であって、前記高導電性層が、固形分中におけ
る透明導電性フィラーの割合が６２.５〜１００重量％
である導電性塗料によって形成されてなり、前記補強層
が、固形分中におけるバインダー成分の割合が７１.４
〜１００重量％である補強用塗料によって形成されてな
ることを特徴とする２層型透明導電性膜。1. A two-layer type transparent conductive film comprising a highly conductive layer formed on a base material and a reinforcing layer formed on the highly conductive layer, wherein the highly conductive layer. However, the ratio of the transparent conductive filler in the solid content is 62.5 to 100% by weight.
The reinforcing layer has a binder component ratio of 71.4 in the solid content.
A two-layer type transparent conductive film, which is formed of a reinforcing coating material of 100 wt%. 【請求項２】 請求項１記載の２層型透明導電性膜にお
いて、前記導電性塗料中の透明導電性フィラーが、その
１次粒子の平均粒径が０.１μｍ以下であることを特徴
とする２層型透明導電性膜。2. The two-layer type transparent conductive film according to claim 1, wherein the transparent conductive filler in the conductive paint has an average primary particle size of 0.1 μm or less. A two-layer transparent conductive film.
JP23610592A 1992-09-03 1992-09-03 Two-layered electric conductive transparent film Pending JPH0687631A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP23610592A JPH0687631A (en) 1992-09-03 1992-09-03 Two-layered electric conductive transparent film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP23610592A JPH0687631A (en) 1992-09-03 1992-09-03 Two-layered electric conductive transparent film

Publications (1)

Publication Number Publication Date
JPH0687631A true JPH0687631A (en) 1994-03-29

Family

ID=16995812

Family Applications (1)

Application Number Title Priority Date Filing Date
JP23610592A Pending JPH0687631A (en) 1992-09-03 1992-09-03 Two-layered electric conductive transparent film

Country Status (1)

Country Link
JP (1) JPH0687631A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5853869A (en) * 1995-08-23 1998-12-29 Sumitomo Metal Mining Co., Ltd. Transparent conductor film for electric field shielding

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5853869A (en) * 1995-08-23 1998-12-29 Sumitomo Metal Mining Co., Ltd. Transparent conductor film for electric field shielding

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