JPH11170420A - Transparent conductive film and its production - Google Patents
Transparent conductive film and its productionInfo
- Publication number
- JPH11170420A JPH11170420A JP9348161A JP34816197A JPH11170420A JP H11170420 A JPH11170420 A JP H11170420A JP 9348161 A JP9348161 A JP 9348161A JP 34816197 A JP34816197 A JP 34816197A JP H11170420 A JPH11170420 A JP H11170420A
- Authority
- JP
- Japan
- Prior art keywords
- conductive film
- transparent conductive
- electroless plating
- paste
- pattern
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、各種表示装置の漏
洩電磁波遮蔽膜、各種電子デバイスの透明電極、または
透明面状発熱体等として有用な高い透明性と導電性を兼
ね備えた透明導電膜およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent conductive film having both high transparency and conductivity, which is useful as a leakage electromagnetic wave shielding film for various display devices, a transparent electrode for various electronic devices, or a transparent sheet heating element. It relates to the manufacturing method.
【０００２】[0002]
【従来の技術】従来、ＣＲＴ，ＰＤＰ，液晶ディスプレ
イ等の各種表示装置の漏洩電磁波遮蔽膜、各種電子デバ
イスの透明電極、または透明面状発熱体等として用いら
れる透明導電膜には、導電性メッシュを透明基体に貼り
付けたもの、金属やＩＴＯ等の導電性材料を蒸着やスパ
ッタリングによって透明基体上に形成したもの、および
特開平 5-16281号公報、特開平 5-283889 号公報に開示
されているような透明導電膜があった。2. Description of the Related Art Conventionally, a conductive mesh is used as a transparent conductive film used as a leakage electromagnetic wave shielding film of various display devices such as CRT, PDP, liquid crystal display, etc., a transparent electrode of various electronic devices or a transparent sheet heating element. Is attached to a transparent substrate, a conductive material such as metal or ITO is formed on a transparent substrate by vapor deposition or sputtering, and JP-A-5-16281 and JP-A-5-283889 disclose the method. There was such a transparent conductive film.
【０００３】これらの公報に開示された透明導電膜の概
要は、以下のようにして製造されたものである。 透明基体上に親水性透明樹脂層を形成し、メッキ触
媒を吸着させる。 親水性透明樹脂層上に無電解メッキ層を形成する。 親水性透明樹脂層を黒色にする。 無電解メッキ層上にパターン状のレジスト部を形成
する。 非レジスト部をエッチングにより除去し、パターン
化された透明導電膜を形成する。[0003] The outline of the transparent conductive film disclosed in these publications is manufactured as follows. A hydrophilic transparent resin layer is formed on a transparent substrate, and a plating catalyst is adsorbed. An electroless plating layer is formed on the hydrophilic transparent resin layer. Make the hydrophilic transparent resin layer black. A patterned resist portion is formed on the electroless plating layer. The non-resist part is removed by etching to form a patterned transparent conductive film.
【０００４】〔問題点〕前記従来の透明導電膜では、次
に示すような多様な問題点があった。導電性メッシュを
透明基体に貼り付けた場合には、金属製メッシュや、繊
維の表面を金属でメッキしたメッシュが用いられる。そ
れぞれのメッシュは規格の定まったものが用いられるた
めに、メッシュの線幅やピッチを自由に変更することが
難しく、特に、線幅を小さくするには限界があり、視認
性に劣るものであった。また、視認性を高めるためにメ
ッシュ表面を黒色化し、メッシュ表面の反射を抑えよう
とする場合、工程が煩雑となり、コストが高くなる。[Problems] The conventional transparent conductive film has various problems as described below. When a conductive mesh is attached to a transparent substrate, a metal mesh or a mesh in which the surface of a fiber is plated with a metal is used. Since each mesh uses a standardized mesh, it is difficult to freely change the mesh line width and pitch.Especially, there is a limit in reducing the line width, and visibility is poor. Was. In addition, when the surface of the mesh is blackened to improve the visibility and the reflection of the mesh surface is suppressed, the process becomes complicated and the cost increases.
【０００５】金属やＩＴＯ等の導電性材料を蒸着やスパ
ッタリングによって透明基体上に形成した場合には、金
属光沢のため視認性が悪く、また、充分な導電性を得る
ために膜厚を厚くすると、光が吸収されるため、著しく
透過性が悪くなる。また、ＩＴＯ等の透明導電性材料の
膜では、導電性が低く、用途が限定され、かつ高価であ
る。When a conductive material such as metal or ITO is formed on a transparent substrate by vapor deposition or sputtering, visibility is poor due to metallic luster, and when the film thickness is increased to obtain sufficient conductivity. Since light is absorbed, the transmissivity is significantly deteriorated. Further, a film made of a transparent conductive material such as ITO has low conductivity, is limited in use, and is expensive.
【０００６】公報記載の透明導電膜の場合には、透明基
体上に親水性透明樹脂層を形成して製造されたものであ
るため、製造工程が複雑となり、コスト的にも高価にな
る。また、黒色化された親水性樹脂層は、無電解メッキ
時に析出した微細金属粒子により遮光されるものである
が、黒色度が充分でなく、金属微粒子による反射があ
り、また、透明導電膜を斜視した場合には金属光沢色が
目立つ。The transparent conductive film described in the publication is manufactured by forming a hydrophilic transparent resin layer on a transparent substrate, so that the manufacturing process is complicated and the cost is high. The blackened hydrophilic resin layer is shielded from light by fine metal particles precipitated during electroless plating.However, the blackness is not sufficient, and there is reflection by metal fine particles. When viewed obliquely, the metallic luster color is conspicuous.
【０００７】[0007]
【発明が解決しようとする課題】本発明は前記課題を解
決するために成されたものであり、そのための課題は、
金属微粒子による反射や金属光沢の程度が少ない透明導
電膜、および、複雑な工程を必要とせず製造が容易で安
価にできる透明導電膜の製造方法を提供することにあ
る。DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems.
It is an object of the present invention to provide a method for producing a transparent conductive film with less reflection by metal fine particles and a low degree of metallic luster, and a method for producing a transparent conductive film which is easy and inexpensive to manufacture without requiring complicated steps.
【０００８】[0008]
【課題を解決するための手段】本発明における請求項１
に係る透明導電膜は、透明基体表面に所定のパターンに
形成された金属超微粒子触媒層と、この金属超微粒子触
媒層上に形成された金属層とからなることを特徴とする
ものである。Means for Solving the Problems Claim 1 of the present invention
The transparent conductive film according to the above is characterized by comprising a metal ultrafine particle catalyst layer formed in a predetermined pattern on the surface of the transparent substrate, and a metal layer formed on the metal ultrafine particle catalyst layer.
【０００９】請求項２に係る透明導電膜は、前記所定の
パターンが格子状あるいは網目状であることを特徴とす
る。A second aspect of the present invention is the transparent conductive film, wherein the predetermined pattern is a lattice or a mesh.
【００１０】請求項３に係る透明導電膜は、前記所定の
パターンの開口率が 60 ％以上であることを特徴とす
る。The transparent conductive film according to claim 3 is characterized in that the predetermined pattern has an aperture ratio of 60% or more.
【００１１】請求項４に係る透明導電膜は、前記金属超
微粒子触媒層が貴金属超微粒子からなることを特徴とす
る。The transparent conductive film according to a fourth aspect is characterized in that the metal ultrafine particle catalyst layer is made of noble metal ultrafine particles.
【００１２】また、請求項５に係る透明導電膜は、前記
金属超微粒子触媒層が貴金属超微粒子と反対の表面電荷
をもった粒子に前記貴金属超微粒子を担持させて作製し
た担持体からなることを特徴とする。Further, in the transparent conductive film according to the present invention, the metal ultrafine particle catalyst layer is formed of a carrier produced by supporting the noble metal ultrafine particles on particles having a surface charge opposite to that of the noble metal ultrafine particles. It is characterized by.
【００１３】請求項６に係る透明導電膜は、前記金属層
がＡｕ，Ａｇ，Ｃｕ，Ｃｒ，Ｎｉ，Ｓｎ，Ｚｎ，Ｃｏの
１種以上を含有することを特徴とするものである。According to a sixth aspect of the present invention, in the transparent conductive film, the metal layer contains at least one of Au, Ag, Cu, Cr, Ni, Sn, Zn, and Co.
【００１４】請求項７に係る透明導電膜の製造方法は、
透明基体表面上に無電解メッキ触媒を含有するペースト
でパターン印刷を行い、このパターン印刷された無電解
メッキ触媒上に無電解メッキ処理を施して、パターン印
刷部のみに透明導電性の金属層を形成させることを特徴
とする。According to a seventh aspect of the present invention, there is provided a method of manufacturing a transparent conductive film.
Pattern printing is performed on the surface of the transparent substrate with a paste containing an electroless plating catalyst, electroless plating is performed on the electroless plating catalyst on which the pattern is printed, and a transparent conductive metal layer is formed only on the pattern printed portion. It is characterized by being formed.
【００１５】請求項８に係る透明導電膜の製造方法は、
前記ペーストが前記無電解メッキ触媒として貴金属超微
粒子を含有することを特徴とする。[0015] The method for producing a transparent conductive film according to claim 8 is characterized in that:
The paste contains precious metal ultrafine particles as the electroless plating catalyst.
【００１６】請求項９に係る透明導電膜の製造方法は、
前記ペーストがチキソトロピー性を有することを特徴と
する。According to a ninth aspect of the present invention, there is provided a method of manufacturing a transparent conductive film.
The paste has a thixotropic property.
【００１７】請求項１０に係る透明導電膜の製造方法
は、前記ペーストが前記無電解メッキ触媒と反対の表面
電荷をもった粒子に前記無電解メッキ触媒を担持させて
作製した担持体を含有することを特徴とする。According to a tenth aspect of the present invention, in the method for manufacturing a transparent conductive film, the paste contains a carrier prepared by supporting the electroless plating catalyst on particles having a surface charge opposite to that of the electroless plating catalyst. It is characterized by the following.
【００１８】請求項１１に係る透明導電膜の製造方法
は、前記ペーストが黒色顔料を含むものであることを特
徴とする。[0018] A method for manufacturing a transparent conductive film according to claim 11 is characterized in that the paste contains a black pigment.
【００１９】請求項１２に係る透明導電膜の製造方法
は、前記パターン印刷がスクリーン印刷であることを特
徴とする。According to a twelfth aspect of the present invention, in the method for manufacturing a transparent conductive film, the pattern printing is screen printing.
【００２０】[0020]
【発明の実施の形態】以下、本発明の実施の形態を具体
的に説明する。ただし、この実施の形態は、発明の趣旨
をより良く理解させるため具体的に説明するものであ
り、特に指定のない限り、発明内容を限定するものでは
ない。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. However, this embodiment is specifically described for better understanding of the gist of the invention, and does not limit the content of the invention unless otherwise specified.
【００２１】〔透明導電膜〕この実施の形態では、スク
リーン印刷によりパターン印刷を行って、ガラスまたは
プラスチック等の透明基板表面に、所定のパターンを有
する無電解メッキ触媒層を形成し、次いで、無電解メッ
キ処理を施すことによって、無電解メッキ触媒層上に金
属層を形成させ、複雑な工程を必要とせずに、容易に、
所定のパターンを形成した金属層を有する透明導電膜を
製造することができ、この方法によって製造された透明
導電膜は、高い導電性と透明性とを兼ね備える。[Transparent conductive film] In this embodiment, pattern printing is performed by screen printing to form an electroless plating catalyst layer having a predetermined pattern on the surface of a transparent substrate such as glass or plastic. By performing the electroplating process, a metal layer is formed on the electroless plating catalyst layer, and without a complicated process,
A transparent conductive film having a metal layer with a predetermined pattern can be manufactured. The transparent conductive film manufactured by this method has both high conductivity and transparency.
【００２２】所定のパターンとしては、格子状、網目
状、ストライプ状等に形成することができ、特に、格子
状または網目状に形成することが好ましい。このように
して所定のパターンを形成した金属層を有する透明導電
膜では、その開口率を 60 ％以上とすることで、ＣＲ
Ｔ，ＰＤＰ，液晶ディスプレイ等の各種表示装置におけ
る漏洩電磁波遮蔽膜として必要とされる高い透明性を得
ることができる。The predetermined pattern can be formed in a lattice shape, a mesh shape, a stripe shape, or the like, and is particularly preferably formed in a grid shape or a mesh shape. In the case of a transparent conductive film having a metal layer on which a predetermined pattern is formed in this manner, the CR is increased by setting the aperture ratio to 60% or more.
High transparency required as a leakage electromagnetic wave shielding film in various display devices such as T, PDP and liquid crystal display can be obtained.
【００２３】〔無電解メッキ触媒〕使用可能な無電解メ
ッキ触媒としては、Ｐｄ，Ａｕ，Ａｇ，Ｐｔ等の貴金属
超微粒子が挙げられる。[Electroless Plating Catalyst] Examples of usable electroless plating catalysts include ultrafine particles of noble metals such as Pd, Au, Ag, and Pt.
【００２４】〔無電解メッキ触媒担持体〕無電解メッキ
触媒として、Ｐｄ，Ａｕ，Ａｇ，Ｐｔ等の貴金属超微粒
子を用いた場合、無電解メッキ触媒担持体としては、前
記無電解メッキ触媒と反対の表面電荷をもった粒子とし
て微細アルミナゲル、シリカゲル等を用いることが好ま
しい。[Electroless Plating Catalyst Carrier] When noble metal ultrafine particles such as Pd, Au, Ag, and Pt are used as the electroless plating catalyst, the electroless plating catalyst carrier is opposite to the electroless plating catalyst. It is preferable to use fine alumina gel, silica gel, or the like as particles having the above surface charge.
【００２５】〔ペースト〕パターン印刷を行う場合に用
いるペーストは、特に制限はなく、触媒粒子間および触
媒粒子と基材との間をそれぞれ結合させるための接着性
が良いものが望ましく、その中でも粘度が高いものが好
ましい。また、分散剤、消泡脱泡剤、リベリング剤等
を、適宜、添加することができる。ペーストの粘度は 1
0 〜 1000 Ｐａ・ｓｅｃ（10000 〜 1000000ｃＰ）、好
ましくは 50 〜 500Ｐａ・ｓｅｃ（ 50000〜 500000 ｃ
Ｐ）とする。[Paste] The paste used for pattern printing is not particularly limited, and preferably has good adhesiveness for bonding between the catalyst particles and between the catalyst particles and the base material. Is preferable. In addition, a dispersant, a defoaming / defoaming agent, a leveling agent, and the like can be appropriately added. Paste viscosity 1
0 to 1000 Pa · sec (10000 to 100000 cP), preferably 50 to 500 Pa · sec (50,000 to 500,000 cP)
P).
【００２６】溶媒としては、沸点が 200℃前後の比較的
高い沸点を有する溶媒が用いられ、例えば、テルピネオ
ール、ブチルカルビトール、ブチルカルビトールアセテ
ート、エチルカルビトール、エチルカルビトールアセテ
ート等が好適である。この場合、溶媒の沸点が低すぎる
と、ペースト作製時あるいはスクリーン印刷時に溶媒が
揮散して、ペーストの性状が変化、あるいはスクリーン
マスクのメッシュにペーストが目詰まりし、また、溶媒
の沸点が高すぎると、印刷後の乾燥に時間が掛かりすぎ
る。As the solvent, a solvent having a relatively high boiling point of about 200 ° C. is used. For example, terpineol, butyl carbitol, butyl carbitol acetate, ethyl carbitol, ethyl carbitol acetate and the like are suitable. . In this case, if the boiling point of the solvent is too low, the solvent volatilizes during paste production or screen printing, the properties of the paste change, or the paste is clogged on the mesh of the screen mask, and the boiling point of the solvent is too high. And it takes too much time to dry after printing.
【００２７】ペースト中に添加する結合剤（バインダ
ー）としては，特に制限はなく、エチルセルロース、ニ
トロセルロース等のセルロース誘導体系、アクリル系、
酢酸ビニル系、ＰＶＡ系等を用いることができる。The binder to be added to the paste is not particularly limited. Cellulose derivatives such as ethylcellulose and nitrocellulose, acrylics,
Vinyl acetate type, PVA type and the like can be used.
【００２８】結合剤の量は、多いと基材との密着性は増
大するが、無電解メッキ触媒が、結合剤中に埋没し、後
工程の無電解メッキにおいて金属が析出しなくなる。ま
た、少なすぎると、ペーストと基材との密着が不充分と
なり好ましくない。したがって、結合剤の量はペースト
印刷、乾燥後、無電解メッキ触媒あるいは同触媒の担持
体が皮膜の表面に露出する程度が好ましい。When the amount of the binder is large, the adhesion to the base material is increased, but the electroless plating catalyst is buried in the binder, and no metal is deposited in the subsequent electroless plating. On the other hand, if the amount is too small, the adhesion between the paste and the base material becomes insufficient, which is not preferable. Therefore, the amount of the binder is preferably such that the electroless plating catalyst or the carrier of the catalyst is exposed on the surface of the film after paste printing and drying.
【００２９】ペーストへの要求特性のうち、微細なパタ
ーン印刷を行うためのペーストには、チキソトロピー性
（揺変性）が必要であり、微細アルミナゲル、シリカゲ
ル等の添加はペーストにその特性を付与することが可能
であるため、好ましい。Among the required properties of the paste, the paste for performing fine pattern printing needs thixotropy (thixotropic), and the addition of fine alumina gel, silica gel, etc. imparts the properties to the paste. It is preferable because it is possible.
【００３０】ペーストには、無電解メッキ触媒微粒子を
無電解メッキ触媒と反対の表面電荷をもった粒子に担持
させて作製した担持体を含有させることにより、無電解
メッキ触媒を含有するペーストにチキソトロピー性（揺
変性）を付与することができ、スクリーン印刷時におい
て、精度の高いパターン形成が可能となる。The paste contains a carrier prepared by supporting fine particles of an electroless plating catalyst on particles having a surface charge opposite to that of the electroless plating catalyst, whereby the paste containing the electroless plating catalyst is thixotropic. Properties (thixotropic) can be imparted, and a high-precision pattern can be formed during screen printing.
【００３１】したがって、無電解メッキ触媒のペースト
への添加方法としては、ペーストへ直接添加しても構わ
ないが、貴金属超微粒子と反対の表面電荷をもった粒子
に貴金属超微粒子を担持させた担持体を、ペースト中に
均一に混合し、分散させることが望ましい。Therefore, as a method of adding the electroless plating catalyst to the paste, the catalyst may be directly added to the paste. However, the catalyst having a surface charge opposite to that of the noble metal ultra-fine particles carries the noble metal ultra-fine particles. It is desirable for the body to be uniformly mixed and dispersed in the paste.
【００３２】例えば、クエン酸で安定化された貴金属コ
ロイド粒子は、表面負電荷を有しているので、表面正荷
電のアルミナ微粒子（アルミナゲル）に吸着担持させた
ものを用い、これをペースト中に混練し、均一に分散さ
せる。For example, the noble metal colloid particles stabilized with citric acid have a negative surface charge, and are used by adsorbing and supporting fine alumina particles (alumina gel) having a positive surface charge. And uniformly dispersed.
【００３３】〔黒色顔料〕無電解メッキ触媒を含有する
ペーストは、メッキ皮膜の金属光沢による透明基板裏面
の反射防止および色ムラや金属色の抑制のため、黒色顔
料を含有させることが望ましい。この場合の黒色顔料と
しては、ペースト中に分散容易な粒子径 0.1μｍ以下の
着色力の大きな黒色顔料が好ましい。例えば、カーボン
ブラック、Ｆｅ3 Ｏ4 ，ＣｕＯ−Ｃｒ2 Ｏ3 ，ＣｕＯ−
Ｆｅ 3 Ｏ4 −Ｍｎ2 Ｏ3 ，ＣｏＯ−Ｆｅ2 Ｏ3 −Ｃｒ2
Ｏ3 などが使用可能である。このうち、特に、カーボン
ブラックが好ましい。[Black pigment] contains an electroless plating catalyst
The paste is on the back of the transparent substrate due to the metallic luster of the plating film
Black face to prevent reflection of color and to suppress color unevenness and metallic color
It is desirable to include a filler. In this case, the black pigment
Therefore, the particle size of 0.1μm or less that can be easily dispersed in the paste
A black pigment having a large coloring power is preferred. For example, carbon
Black, FeThreeOFour, CuO-CrTwoOThree, CuO-
Fe ThreeOFour-MnTwoOThree, CoO-FeTwoOThree−CrTwo
OThreeEtc. can be used. Of these, especially carbon
Black is preferred.
【００３４】〔パターン印刷〕印刷法としては、特に制
限しないが、スクリーン印刷法が好適である。スクリー
ンマスクとしては、成膜後得られる透明導電膜の透明性
を維持するため、格子状構造または網目構造を有した開
口率 60 ％以上、平均開口径が７ｍｍ以下、平均開口径
／平均線幅≧７としたものを用いることが好ましい。ス
キージ走査速度、角度、印圧、スクリーンマスクの乳剤
の厚さ、紗の太さ、オープニング等は適宜選択可能であ
る。[Pattern Printing] The printing method is not particularly limited, but a screen printing method is preferred. As a screen mask, in order to maintain the transparency of the transparent conductive film obtained after the film formation, an aperture ratio of 60% or more, an average aperture diameter of 7 mm or less, and an average aperture diameter / average line width having a lattice structure or a mesh structure is used. It is preferable to use those having ≧ 7. The squeegee scanning speed, angle, printing pressure, thickness of the emulsion of the screen mask, thickness of the gauze, opening and the like can be appropriately selected.
【００３５】〔無電解メッキ処理〕通常の無電解メッキ
浴が使用可能である。使用できる金属としてはＡｕ，Ａ
ｇ，Ｃｕ，Ｃｒ，Ｎｉ，Ｓｕ，Ｚｎ，Ｃｏの一種以上を
含有する金属である。これらの金属の導電性の点から
は、Ａｇ，Ｃｕ，Ａｕ，Ｎｉ等が好ましい。例えば、無
電解Ｃｕメッキ浴、無電解Ｎｉ−Ｐメッキ浴、無電解Ｎ
ｉ−Ｂメッキ浴、無電解Ａｕメッキ浴等が使用可能であ
る。[Electroless Plating Treatment] An ordinary electroless plating bath can be used. Au, A as usable metals
g, a metal containing at least one of Cu, Cr, Ni, Su, Zn, and Co. From the viewpoint of the conductivity of these metals, Ag, Cu, Au, Ni and the like are preferable. For example, electroless Cu plating bath, electroless Ni-P plating bath, electroless N
An i-B plating bath, an electroless Au plating bath, or the like can be used.
【００３６】無電解メッキ処理においては、先の工程で
無電解メッキ触媒を含有するペーストをパターン印刷し
ているので、無電解メッキ時にはパターン印刷した部分
のみに金属の析出が起こり、高開口率の、即ち高い光透
過性を有した高導電性の皮膜を得ることができる。In the electroless plating treatment, since the paste containing the electroless plating catalyst is pattern-printed in the previous step, during electroless plating, metal deposition occurs only in the pattern-printed portion, and a high aperture ratio is obtained. That is, a highly conductive film having high light transmittance can be obtained.
【００３７】〔パターン状透明導電膜の形成〕無電解メ
ッキ触媒を担持させた担持体を用いて透明導電膜を形成
させる場合について概略例示すると、図１（イ）〜
（ホ）に示すように、無電解メッキ触媒１を担持体２に
担持させてバインダー３とともに溶剤４に混合して分散
させたペースト５を調製し（イ）、スクリーン印刷によ
ってペースト５を基板６の表面上にパターン印刷し
（ロ）、印刷後に乾燥させて溶媒を揮散させ（ハ）、基
板６の表面にバインダー３により担持体２を結合した所
定形状のパターンを形成させるとともに、無電解メッキ
触媒１を担持体２の表面に露出させる（ニ）、さらに、
無電解メッキ処理を行って無電解メッキ触媒１を起点と
して金属を析出させ、基板６の表面に格子状または網目
状のパターンを有する金属層７を形成させる。[Formation of Patterned Transparent Conductive Film] A case where a transparent conductive film is formed by using a carrier carrying an electroless plating catalyst is schematically illustrated in FIGS.
As shown in (e), a paste 5 is prepared in which the electroless plating catalyst 1 is carried on a carrier 2 and mixed with a binder 4 in a solvent 4 to be dispersed (a). Is printed on the surface of the substrate 6 (b), dried after printing to evaporate the solvent (c), a pattern of a predetermined shape in which the carrier 2 is bonded to the surface of the substrate 6 with the binder 3 is formed, and electroless plating is performed. The catalyst 1 is exposed on the surface of the support 2 (d).
An electroless plating process is performed to deposit a metal starting from the electroless plating catalyst 1, and a metal layer 7 having a lattice or mesh pattern is formed on the surface of the substrate 6.
【００３８】また、この工程中でペースト５に無電解メ
ッキ触媒を直接に混入させても良い。その場合には、バ
インダーによって図中の担持体の代わりに触媒が基板６
に直接結合されていることになる。In this step, an electroless plating catalyst may be directly mixed into the paste 5. In that case, the catalyst is replaced by the binder instead of the carrier shown in FIG.
Will be directly linked to
【００３９】〔成膜後の透明導電膜〕このようにして、
無電解メッキ触媒含有印刷ペーストをパターン印刷する
と、印刷部のみ選択的に無電解メッキがなされるので、
得られる透明導電膜の特性はパターン印刷に大きく影響
される。メッキ皮膜（金属皮膜）部分は殆ど光透過性が
期待できないので開口部を設けて、透明性を確保する。
したがって、開口率は透明性に大きく影響する。このた
め、開口率を 60 ％以上とすることで必要な透明性を確
保する。[Transparent conductive film after film formation]
When pattern printing of electroless plating catalyst-containing printing paste, electroless plating is performed selectively only in the printed part,
The characteristics of the obtained transparent conductive film are greatly affected by pattern printing. Since almost no light transmittance can be expected in the plating film (metal film) portion, an opening is provided to ensure transparency.
Therefore, the aperture ratio greatly affects the transparency. Therefore, the necessary transparency is secured by setting the aperture ratio to 60% or more.
【００４０】開口パターンは、例えば格子状（網目状）
の構造が挙げられ、平均開口径／平均線幅≧７とするこ
とで、開口率（光透過率）60％以上を確保できる。開口
ピッチは大きいと格子状（網目状）構造が目立ち、視認
性が悪化するから、開口ピッチは細かい程好ましく、１
ｍｍ以下が好ましい。The opening pattern is, for example, a lattice shape (a mesh shape).
The average aperture diameter / average line width ≧ 7 can secure an aperture ratio (light transmittance) of 60% or more. If the opening pitch is large, a lattice-like (mesh-like) structure is conspicuous and visibility deteriorates.
mm or less is preferable.
【００４１】透明導電膜の厚みは、特に限定されない
が、厚くなると視認性が悪くなり、即ち、視野角が狭く
なる。無電解メッキで得られる金属膜の比抵抗は一般に
10 -6〜 10 -5Ω・ｃｍであり、開口率 60 ％の場合、
透明導電膜の面抵抗は厚さ１μｍで１Ω／□以下の低抵
抗のものが得られる。したがって、無電解メッキによっ
て得られる金属膜の厚みは、数μｍ以下で充分であり、
従来品と比較して薄膜化が可能となり、視野角の広角
化、視認性の向上が達成できる。The thickness of the transparent conductive film is not particularly limited. However, as the thickness increases, the visibility deteriorates, that is, the viewing angle decreases. The specific resistance of the metal film obtained by electroless plating is generally
When the aperture ratio is 10 -6 to 10 -5 Ωcm and the aperture ratio is 60%,
The transparent conductive film has a sheet resistance of 1 μm and a low resistance of 1Ω / □ or less. Therefore, the thickness of the metal film obtained by electroless plating is not more than several μm,
Compared to the conventional product, it can be made thinner, and a wider viewing angle and improved visibility can be achieved.
【００４２】成膜後の透明導電膜に含有させた黒色顔料
の効果は、メッキ皮膜の金属光沢による透明基板裏面
（透明基体側から透視した場合の面）の反射を防止する
ことができ、メッキによる析出金属皮膜の透明基板裏
面の色ムラ抑制および金属色呈示抑制ができる。The effect of the black pigment contained in the transparent conductive film after film formation can prevent reflection of the rear surface of the transparent substrate (the surface when viewed from the transparent substrate side) due to the metallic luster of the plating film. Can suppress color unevenness of the deposited metal film on the back surface of the transparent substrate and metal color presentation.
【００４３】その他、パターン形成金属層と組み合わせ
て使用することのできる皮膜には、 パターン状金属層上へのＡＧ（防眩）膜、パターン
状金属上あるいは裏面へのＮＩＲ（近赤外線）遮蔽膜、
裏面へのＡＲ（反射防止）膜等がある。Other films that can be used in combination with the pattern forming metal layer include an AG (anti-glare) film on the pattern metal layer and an NIR (near infrared) shielding film on the pattern metal or on the back surface. ,
There is an AR (anti-reflection) film or the like on the back surface.
【００４４】[0044]
【実施例】〔第１実施例〕 （パラジウムコロイドの作製）精製水 89 重量部に塩化
パラジウム 1重量部を溶解し、さらにクエン酸三ナトリ
ウム 10 重量部を溶解して均一に攪拌した後、水素化ホ
ウ素ナトリウム 0.01重量部を添加して塩化パラジウム
を還元させ、クエン酸で安定、保護コロイド化されたパ
ラジウムコロイドを得た。その後、限外濾過により濃縮
脱塩を行い、パラジウム 0.5重量部を含有するパラジウ
ムコロイドを得た。EXAMPLES [First Example] (Preparation of palladium colloid) 1 part by weight of palladium chloride was dissolved in 89 parts by weight of purified water, and 10 parts by weight of trisodium citrate was further dissolved and stirred uniformly. The palladium chloride was reduced by adding 0.01 parts by weight of sodium borohydride to obtain a palladium colloid which was stabilized with citric acid and made into a protective colloid. Thereafter, the mixture was concentrated and desalted by ultrafiltration to obtain a palladium colloid containing 0.5 parts by weight of palladium.
【００４５】（印刷用ペーストの作製）上記パラジウム
コロイド 10 重量部に適量の精製水を加え、この希薄パ
ラジウムコロイド溶液に日本アエロゾル製アルミナエア
ロゾルＡｌ2 Ｏ3 −Ｃ、 10 重量部を添加懸濁させる。
パラジウムコロイドはクエン酸で安定化されている為、
表面負荷電のコロイドであり、またアルミナゾルは逆に
表面正荷電を示す為、懸濁液中で静電的に吸着、ヘテロ
凝集を起こす。これを濾過により分離し、乾燥、解砕す
ることにより、パラジウムコロイドを担持したアルミナ
ゲルを得る。このパラジウムコロイド担持アルミナゲル
7重量部と 10 ％エチルセルローステルピネオール溶液
30 重量部を３本ロールミルを用いて均一に混練し、分
散させることにより印刷ペーストを作製した。得られた
ペーストの粘度は 80000ｃＰであった。(Preparation of Printing Paste) An appropriate amount of purified water is added to 10 parts by weight of the above-mentioned palladium colloid, and 10 parts by weight of alumina aerosol Al 2 O 3 -C manufactured by Nippon Aerosol are added and suspended in the diluted palladium colloid solution. .
Since the palladium colloid is stabilized with citric acid,
Since it is a surface-charged colloid and alumina sol exhibits a surface positive charge, it is electrostatically adsorbed and hetero-aggregated in suspension. This is separated by filtration, dried and crushed to obtain an alumina gel supporting a palladium colloid. This palladium colloid-supported alumina gel
7 parts by weight and 10% ethyl cellulose terpineol solution
A 30 parts by weight was uniformly kneaded using a three-roll mill and dispersed to prepare a printing paste. The viscosity of the obtained paste was 80,000 cP.
【００４６】（スクリーン印刷）上記により得られたペ
ーストを次に示すスクリーンマスクに載せ、マイクロテ
ック社製スクリーン印刷機ＭＴ−７５０型を用い、３ｍ
ｍ厚（ 320×320 （ｍｍ））の正方形アクリル板上に印
刷を行った。スクリーンマスクは、枠サイズ 750×750
（ｍｍ）、パターンサイズ 300×300 （ｍｍ）、Ｌ／Ｓ
＝50／450 （μｍ）の格子状（メッシュ状）のパターン
を有し、乳剤の厚み： 10 μｍ、メッシュ開き（ステン
レス鋼）：325 メッシュ、線径： 16 μｍ、オープニン
グ： 62 ％である。また、スクリーン印刷条件は、印
圧：1.6 Ｋｇ／ｃｍ2 、スキージ速度：250ｍｍ／ｓｅ
ｃ、クリアランス：3.0 ｍｍである。印刷後、室温で 1
5 分静置後、 60 ℃の乾燥器にて 2時間乾燥を行った。
得られた印刷パターンは約Ｌ／Ｓ＝60／440 の格子状の
もので、ラインの切れ、印刷ムラ等は特に認められなか
った。(Screen printing) The paste obtained above was placed on a screen mask shown below, and a screen printing machine MT-750 manufactured by Microtech Co., Ltd. was used.
Printing was performed on a square acrylic plate having an m thickness (320 × 320 (mm)). Screen mask, frame size 750 × 750
(Mm), pattern size 300 × 300 (mm), L / S
= 50/450 (μm) lattice pattern (mesh shape), emulsion thickness: 10 μm, mesh opening (stainless steel): 325 mesh, wire diameter: 16 μm, opening: 62%. The screen printing conditions were as follows: printing pressure: 1.6 kg / cm 2 , squeegee speed: 250 mm / sec.
c, clearance: 3.0 mm. After printing, at room temperature 1
After standing for 5 minutes, drying was performed for 2 hours in a dryer at 60 ° C.
The obtained print pattern was a lattice-like pattern of about L / S = 60/440, and no breaks in the line, no print unevenness, etc. were particularly observed.
【００４７】（無電解Ｃｕメッキ）上記得られたパラジ
ウムコロイド含有ペースト印刷基板を奥野製薬（株）製
無電解銅メッキ液（ＯＰＣ−７５０シリーズ）中に浸漬
させ、20分間、20℃で無電解銅メッキを行った。攪拌は
エアー攪拌で行った。メッキ処理後に水洗い、乾燥を行
った。(Electroless Cu Plating) The palladium colloid-containing paste printed substrate obtained above was immersed in an electroless copper plating solution (OPC-750 series) manufactured by Okuno Pharmaceutical Co., Ltd., and electroless at 20 ° C. for 20 minutes. Copper plating was performed. Stirring was performed by air stirring. After the plating treatment, it was washed with water and dried.
【００４８】得られた膜はラインの平均線幅が約 62 μ
ｍ、平均開口径が 438μｍの格子状パターンでメッキ施
工表面は黄金色の銅金属光沢、裏面は若干銅金属光沢を
示すがほぼ黒色の色調を呈していた。膜の平均厚みは 8
μｍである。The obtained film had an average line width of about 62 μm.
m, a grid-like pattern with an average opening diameter of 438 μm, the plating surface showed a golden copper metallic luster, and the back surface showed a little copper metallic luster, but almost black color tone. Average film thickness is 8
μm.
【００４９】また、この膜の表面抵抗値を三菱化学
（株）製ロレスタＡＰ（４端針法）を用いて測定した結
果、0.8 Ω／□であった。なお、平均線幅は、光学顕微
鏡を用い、膜の平面方向の形状を観察し、写真撮影して
50 カ所の線幅を測定し、平均化して求めた。Further, the surface resistance of this film was measured by using Loresta AP (four-needle method) manufactured by Mitsubishi Chemical Corporation, and was found to be 0.8 Ω / □. The average line width was obtained by observing the shape of the film in the plane direction using an optical microscope and taking a photograph.
The line widths at 50 locations were measured and averaged.
【００５０】膜厚は膜の一部を切り出し、熱硬化型の埋
め込み樹脂中に封入し、ミクロトームで断面方向に薄片
を切り出し、透過型電子顕微鏡で観察、線部の最高部の
厚みを 10 カ所測定し、平均化して求めた。A part of the film was cut out, sealed in a thermosetting resin, cut out in a cross section with a microtome, and observed with a transmission electron microscope. It was measured and averaged.
【００５１】膜の全光線透過率は、膜の一部を切り出
し、自動ヘーズメータ（東京電色（株）製）を用いて裏
面より測定した結果、72.7％であった。また、印刷面の
裏面の反射率は 4.1％であった。The total light transmittance of the film was 72.7% as a result of cutting a part of the film and measuring from the back surface using an automatic haze meter (manufactured by Tokyo Denshoku Co., Ltd.). The reflectance on the back side of the printing surface was 4.1%.
【００５２】〔第２実施例〕実施例１のペースト作製条
件が下記に変更になる以外は同じ。 パラジウムコロイド担持アルミナゲル 6.5 重量部 カーボンブラック（三菱化学製 ＃990 ） 0.5 重量部 10％エチルセルロースのテルピネオール溶液 30 重量部 ペースト粘度 72000 ｃＰ[Second Embodiment] The same as in the first embodiment except that the paste preparation conditions are changed as follows. Palladium colloid-supported alumina gel 6.5 parts by weight Carbon black (Mitsubishi Chemical # 990) 0.5 parts by weight Terpineol solution of 10% ethyl cellulose 30 parts by weight Paste viscosity 72000 cP
【００５３】スクリーン印刷条件、使用マスク … 実
施例１と同じ 無電解Ｃｕメッキも同様 平均ライン線幅 60 μｍ 開口径 440 μｍ 膜厚 7 μｍScreen printing conditions, mask used: Same as in Example 1 Same for electroless Cu plating Average line width 60 μm Opening diameter 440 μm Film thickness 7 μm
【００５４】表面抵抗 0.9 Ω／□ 全光線透過率 75.3 ％ メッキ施工表面は黄金色の銅金属光沢 メッキ施工裏面は金属光沢が全く見られない黒色を呈し
ていた。裏面の反射率は 2.9％Surface resistance 0.9 Ω / □ Total light transmittance 75.3% The plating surface had a golden copper metallic luster. The plating reverse surface had a black color with no metallic luster. 2.9% backside reflectance
【００５５】 [0055]
【００５６】[0056]
【発明の効果】以上のように本発明では、請求項１に係
る透明導電膜では、透明基体表面に所定のパターンに形
成された金属超微粒子触媒層と、この金属超微粒子触媒
層上に形成された金属層とからなるから、最適な透明性
と導電性とに調整することができ、高い透明性と導電性
とを兼ね備えることができるとともに、金属層による反
射や金属光沢の程度を少なくすることができる。As described above, according to the present invention, in the transparent conductive film according to the first aspect, the metal ultrafine particle catalyst layer formed in a predetermined pattern on the surface of the transparent substrate and the metal ultrafine particle catalyst layer formed on the metal ultrafine particle catalyst layer are formed. Since it is made of a metal layer, it can be adjusted to optimal transparency and conductivity, and can have both high transparency and conductivity, and reduce the degree of reflection and metal luster by the metal layer. be able to.
【００５７】請求項２に係る透明導電膜では、前記所定
のパターンを格子状あるいは網目状としたことにより、
最適な透明性と導電性とを容易に調整する事ができる。In the transparent conductive film according to the second aspect, the predetermined pattern is formed in a lattice shape or a mesh shape.
Optimal transparency and conductivity can be easily adjusted.
【００５８】請求項３に係る透明導電膜では、所定のパ
ターンの開口率を 60 ％以上としたことによって、導電
性を有しながら高い透明性を確保することができる。In the transparent conductive film according to the third aspect, by setting the aperture ratio of the predetermined pattern to 60% or more, high transparency can be ensured while having conductivity.
【００５９】請求項４に係る透明導電膜では、金属超微
粒子触媒層が貴金属超微粒子からなるから、無電解メッ
キにより金属超微粒子触媒層上に金属層を析出させるこ
とができ、効果的に金属超微粒子触媒層に金属層を形成
させることができる。In the transparent conductive film according to the fourth aspect, since the metal ultrafine particle catalyst layer is made of precious metal ultrafine particles, the metal layer can be deposited on the metal ultrafine particle catalyst layer by electroless plating, and the metal can be effectively formed. A metal layer can be formed on the ultrafine particle catalyst layer.
【００６０】請求項５に係る透明導電膜では、金属超微
粒子触媒層が貴金属超微粒子と反対の表面電荷をもった
粒子に前記貴金属超微粒子を担持させて作製した担持体
からなることによって、印刷用ペーストにチキソトロピ
ー性を与え、微細な格子状あるいは網目状等のパターン
を形成させることができる。In the transparent conductive film according to the fifth aspect, the metal ultrafine particle catalyst layer is formed of a carrier prepared by supporting the noble metal ultrafine particles on particles having a surface charge opposite to that of the noble metal ultrafine particles. Thixotropy can be imparted to the paste for use to form a fine lattice-like or mesh-like pattern.
【００６１】請求項６に係る透明導電膜では、金属層が
Ａｕ，Ａｇ，Ｃｕ，Ｃｒ，Ｎｉ，Ｓｎ，Ｚｎ，Ｃｏの１
種以上を含有することによって、良好な導電性を付与す
ることができる。In the transparent conductive film according to claim 6, the metal layer is made of one of Au, Ag, Cu, Cr, Ni, Sn, Zn, and Co.
By containing more than one species, good conductivity can be imparted.
【００６２】また、請求項７に係る透明導電膜の製造方
法では、透明基体表面上に無電解メッキ触媒を含有する
ペーストでパターン印刷を行い、このパターン印刷され
た無電解メッキ触媒層上に無電解メッキ処理を施して、
パターン印刷部のみに透明導電性の金属層を形成させた
ことによって、形成されたパターン状に導電性金属層を
形成できて、所定の透明性および導電性を有する透明導
電膜を低コストで効果的に形成させることができる。In the method for producing a transparent conductive film according to the present invention, a pattern is printed on the surface of the transparent substrate using a paste containing an electroless plating catalyst, and a pattern is printed on the electroless plating catalyst layer on which the pattern is printed. Subject to electrolytic plating,
By forming a transparent conductive metal layer only on the pattern printing portion, a conductive metal layer can be formed in the formed pattern, and a transparent conductive film having a predetermined transparency and conductivity can be produced at a low cost. Can be formed.
【００６３】請求項８に係る透明導電膜の製造方法で
は、ペーストが無電解メッキ触媒として貴金属超微粒子
を含有するから、無電解メッキ触媒を無電解メッキによ
るメッキ金属を析出させる核として効果的に機能させる
ことができ、金属層を容易に形成させることができる。In the method for producing a transparent conductive film according to claim 8, since the paste contains ultra-fine particles of noble metal as an electroless plating catalyst, the electroless plating catalyst can be effectively used as a nucleus for depositing a plating metal by electroless plating. It can function and a metal layer can be easily formed.
【００６４】請求項９に係る透明導電膜の製造方法で
は、ペーストがチキソトロピー性を有するために、印刷
パターンを微細な形状に形成させることができる。In the method for producing a transparent conductive film according to the ninth aspect, since the paste has thixotropy, a printed pattern can be formed in a fine shape.
【００６５】請求項１０に係る透明導電膜の製造方法で
は、ペーストが前記無電解メッキ触媒と反対の表面電荷
をもった粒子に前記無電解メッキ触媒を担持させて作製
した担持体を含有することにより、ペーストにチキソト
ロピー性を付与することができ、微細な印刷パターンを
実現させることができる。According to a tenth aspect of the present invention, in the method for manufacturing a transparent conductive film, the paste contains a carrier prepared by supporting the electroless plating catalyst on particles having a surface charge opposite to that of the electroless plating catalyst. Accordingly, the paste can be given thixotropy, and a fine print pattern can be realized.
【００６６】請求項１１に係る透明導電膜の製造方法で
は、ペーストが黒色顔料を含むことにより、メッキによ
り形成した金属層の透明基板裏面側の反射を防止できる
とともに色ムラを抑制することができる。In the method for producing a transparent conductive film according to the eleventh aspect, since the paste contains the black pigment, it is possible to prevent reflection of the metal layer formed by plating on the rear surface side of the transparent substrate and to suppress color unevenness. .
【００６７】請求項１２に係る透明導電膜の製造方法で
は、パターン印刷がスクリーン印刷であることにより、
印刷工程を簡略化でき、作業性を向上させることができ
るとともに低コスト化させることができる。In the method for manufacturing a transparent conductive film according to the twelfth aspect, the pattern printing is screen printing.
The printing process can be simplified, the workability can be improved, and the cost can be reduced.
【図１】本発明によるパターン状透明導電膜の形成過程
を示す工程説明図であり、（イ）は調整されたペース
ト、（ロ）は基板上に印刷されたペースト、（ハ）は乾
燥中の印刷基板、（ニ）は基板上に形成された無電解メ
ッキ触媒を担持させた担持体のパターン、（ホ）は基板
上に形成された透明導電膜をそれぞれ示す側面拡大説明
図である。FIG. 1 is a process explanatory view showing a process of forming a patterned transparent conductive film according to the present invention. (A) is a prepared paste, (B) is a paste printed on a substrate, and (C) is during drying. (D) is an enlarged side view showing a pattern of a carrier carrying an electroless plating catalyst formed on the substrate, and (e) is an enlarged side view showing a transparent conductive film formed on the substrate.
１ 無電解メッキ触媒 ２ 担持体 ３ バインダー ４ 溶媒 ５ ペースト ６ 基板 ７ 金属層 DESCRIPTION OF SYMBOLS 1 Electroless plating catalyst 2 Carrier 3 Binder 4 Solvent 5 Paste 6 Substrate 7 Metal layer
Claims (12)
た金属超微粒子触媒層と、この金属超微粒子触媒層上に
形成された金属層とからなることを特徴とする透明導電
膜。1. A transparent conductive film comprising: a metal ultrafine particle catalyst layer formed in a predetermined pattern on a surface of a transparent substrate; and a metal layer formed on the metal ultrafine particle catalyst layer.
状であることを特徴とする請求項１記載の透明導電膜。2. The transparent conductive film according to claim 1, wherein said predetermined pattern has a lattice shape or a mesh shape.
であることを特徴とする請求項１記載の透明導電膜。3. The transparent conductive film according to claim 1, wherein said predetermined pattern has an aperture ratio of 60% or more.
からなることを特徴とする請求項１記載の透明導電膜。4. The transparent conductive film according to claim 1, wherein said metal ultrafine particle catalyst layer is made of noble metal ultrafine particles.
と反対の表面電荷をもった粒子に前記貴金属超微粒子を
担持させて作製した担持体からなることを特徴とする請
求項１記載の透明導電膜。5. The transparent metal ultrafine particle catalyst layer according to claim 1, wherein the catalyst layer is formed by carrying the noble metal ultrafine particles on particles having a surface charge opposite to that of the noble metal ultrafine particles. Conductive film.
ｉ，Ｓｎ，Ｚｎ，Ｃｏの１種以上を含有することを特徴
とする請求項１記載の透明導電膜。6. The metal layer is made of Au, Ag, Cu, Cr, N
2. The transparent conductive film according to claim 1, comprising at least one of i, Sn, Zn, and Co.
するペーストでパターン印刷を行い、このパターン印刷
された無電解メッキ触媒上に無電解メッキ処理を施し
て、パターン印刷部のみに透明導電性の金属層を形成さ
せることを特徴とする透明導電膜の製造方法。7. A pattern is printed on a surface of a transparent substrate with a paste containing an electroless plating catalyst, and the electroless plating catalyst on which the pattern is printed is subjected to an electroless plating treatment so that a transparent conductive material is applied only to the pattern printed portion. A method for producing a transparent conductive film, comprising forming a conductive metal layer.
て貴金属超微粒子を含有することを特徴とする請求項７
記載の透明導電膜の製造方法。8. The paste according to claim 7, wherein said paste contains noble metal ultrafine particles as said electroless plating catalyst.
The method for producing a transparent conductive film according to the above.
ことを特徴とする請求項７に記載の透明導電膜の製造方
法。9. The method according to claim 7, wherein the paste has thixotropic properties.
反対の表面電荷をもった粒子に前記無電解メッキ触媒を
担持させて作製した担持体を含有することを特徴とする
請求項７記載の透明導電膜の製造方法。10. The transparent material according to claim 7, wherein said paste contains a carrier prepared by carrying said electroless plating catalyst on particles having a surface charge opposite to that of said electroless plating catalyst. A method for manufacturing a conductive film.
ることを特徴とする請求項７記載の透明導電膜の製造方
法。11. The method according to claim 7, wherein the paste contains a black pigment.
ることを特徴とする請求項７記載の透明導電膜の製造方
法。12. The method according to claim 7, wherein said pattern printing is screen printing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34816197A JP3363083B2 (en) | 1997-12-17 | 1997-12-17 | Transparent substrate and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34816197A JP3363083B2 (en) | 1997-12-17 | 1997-12-17 | Transparent substrate and method for producing the same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002227332A Division JP3895229B2 (en) | 2002-08-05 | 2002-08-05 | Method for producing transparent conductive film and transparent conductive film produced by this method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11170420A true JPH11170420A (en) | 1999-06-29 |
| JP3363083B2 JP3363083B2 (en) | 2003-01-07 |
Family
ID=18395164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34816197A Expired - Fee Related JP3363083B2 (en) | 1997-12-17 | 1997-12-17 | Transparent substrate and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3363083B2 (en) |
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