JP2010182648A - Transparent conductive substrate, transparent conductive substrate for dye-sensitized solar cell, and manufacturing method for transparent conductive substrate - Google Patents

Transparent conductive substrate, transparent conductive substrate for dye-sensitized solar cell, and manufacturing method for transparent conductive substrate Download PDF

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JP2010182648A
JP2010182648A JP2009027817A JP2009027817A JP2010182648A JP 2010182648 A JP2010182648 A JP 2010182648A JP 2009027817 A JP2009027817 A JP 2009027817A JP 2009027817 A JP2009027817 A JP 2009027817A JP 2010182648 A JP2010182648 A JP 2010182648A
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substrate
conductive layer
transparent conductive
layer
conductive
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JP5341544B2 (en
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Yasuo Kakihara
康男 柿原
Kyoichi Suzuki
教一 鈴木
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Fujicopian Co Ltd
Toda Kogyo Corp
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Fuji Kagakushi Kogyo Co Ltd
Fujicopian Co Ltd
Toda Kogyo Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent conductive substrate which is excellent on transparency at low resistance and flatness, and a manufacturing method capable of inexpensively manufacturing the transparent conductive substrate. <P>SOLUTION: In the transparent conductive substrate, a metal minute particle dispersed solution is applied to a substrate 2 and is dried up, a first conductive layer 3 is completely covered by a highly transparent adhesive layer 7 after forming a mesh-shaped first conductive layer 3 on the substrate 2, and the substrate 2 is exfoliated after pasting the substrate 2 and a transferred substrate 8 together. Thus, the first conductive layer 3 and the adhesive layer 7 are thermally transferred integrally to the transferred substrate 8. Then, the surface 15 of the thermally-transferred first conductive layer 3 is etched, etched holes 21 are plated. Consequently, the transparent conductive substrate 1 which is excellent in transparency at low resistance can be attained. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、低抵抗で透明性に優れる透明導電性基板及びその製造方法に関し、特に耐溶剤性、電解質溶液に対する耐食性に優れる色素増感型太陽電池用透明導電性基板として好適に使用可能な透明導電性基板及びその製造方法に関する。   The present invention relates to a transparent conductive substrate having low resistance and excellent transparency and a method for producing the same, and in particular, a transparent conductive substrate suitable for a dye-sensitized solar cell having excellent solvent resistance and corrosion resistance to an electrolyte solution. The present invention relates to a conductive substrate and a manufacturing method thereof.

近年、太陽光を用いたエネルギー創出法である太陽電池においては、化石燃料の高騰や枯渇、アジア諸国の経済成長に伴う消費電力の増加、化石燃料による炭酸ガス増加などの環境問題などを背景に注目され、研究開発が活発になされている。   In recent years, solar cells, an energy creation method using sunlight, have been against the backdrop of environmental problems such as soaring and depleting fossil fuels, increasing power consumption accompanying economic growth in Asian countries, and increasing carbon dioxide from fossil fuels. It is attracting attention and active research and development.

中でも結晶性シリコン又はアモルファスシリコンを用いた太陽電池が主流である。しかしながら結晶性シリコンなどを製造するためには多大なエネルギーが必要であり、省エネルギーを目指すに当たり、シリコンを利用することは太陽電池の本来の意図とは相反するものとなってしまう。また、シリコンは集積回路の基本となる材料でもあるため、シリコン需要の増加によるシリコンの不足及びシリコンの高価格化が生じている。   Among them, solar cells using crystalline silicon or amorphous silicon are the mainstream. However, a large amount of energy is required to produce crystalline silicon and the like, and the use of silicon is contrary to the original intention of the solar cell in order to save energy. In addition, since silicon is also a basic material for integrated circuits, there is a shortage of silicon due to an increase in silicon demand and an increase in the price of silicon.

このような理由から、シリコン太陽電池に比べて低エネルギーで作製でき、低コスト化が可能である色素増感型太陽電池が注目されている。   For these reasons, attention has been given to dye-sensitized solar cells that can be manufactured with lower energy and can be manufactured at lower costs than silicon solar cells.

代表的な色素増感型太陽電池は、ガラス基板上の片面に透明酸化物の電極（ＩＴＯ：酸化錫と酸化インジウムの複合酸化物）が製膜され、その上に色素を含有した多孔質酸化チタンが形成され、電解質としてヨウ素及びヨウ素化合物を含んだ電解質溶液が用いられ、その上に対電極（白金電極又は白金−炭素電極）が配置された構造を有している。   A typical dye-sensitized solar cell has a transparent oxide electrode (ITO: composite oxide of tin oxide and indium oxide) formed on one side of a glass substrate, and a porous oxide containing the dye on it. Titanium is formed, an electrolyte solution containing iodine and an iodine compound is used as an electrolyte, and a counter electrode (platinum electrode or platinum-carbon electrode) is disposed thereon.

一般的に基板にはガラス基板が用いられているが、透明樹脂基板を用いることで、軽量でかつ柔軟性に富んだ色素増感型太陽電池を作製することができ、太陽電池の設置場所を拡大させることが可能となる。   In general, a glass substrate is used as the substrate, but by using a transparent resin substrate, a light-weight and flexible dye-sensitized solar cell can be produced. It can be enlarged.

電解質にヨウ素及びヨウ素化合物を用いるのは、発電時のレドックス反応の担い手として、Ｉ−／Ｉ３ −が利用されるためである。前記ヨウ素系は電解質として効率がよいため一般的に良く用いられるが、電極に透明酸化物の代わりに、より低抵抗な金属材料を用いると金属電極が腐食してしまうという問題がある。そのため、腐食してしまう金属材料を保護するために、耐食性のある金属でめっきする方法や導電性樹脂などで保護する方法が検討されている（例えば特許文献１参照）。この他、色素増感型太陽電池用導電性基板に限定されるものではないが、網目状の導電性部上にめっきを施し透明導電性基板を製造する方法が提案されている（例えば特許文献２参照）。 The reason why iodine and an iodine compound are used for the electrolyte is that I − / I 3 − is used as a bearer of the redox reaction during power generation. The iodine system is generally used because it is efficient as an electrolyte, but there is a problem that the metal electrode is corroded when a metal material having a lower resistance is used instead of the transparent oxide. Therefore, in order to protect the corroded metal material, a method of plating with a corrosion-resistant metal or a method of protecting with a conductive resin has been studied (for example, see Patent Document 1). In addition, although not limited to a conductive substrate for a dye-sensitized solar cell, a method for producing a transparent conductive substrate by plating on a mesh-shaped conductive portion has been proposed (for example, Patent Documents). 2).

特開２００８−６６２１２号公報JP 2008-66212 A 特開２００７−２２７９０６号公報JP 2007-227906 A

特許文献１に記載の技術は、網目状の第一導電性部を覆うように導電性樹脂が形成された構成であり、該構成では過剰な導電性樹脂により全光線透過率が低下してしまうとともに、導電性にほとんど寄与しない導電性樹脂が必要になるため低コストな基板を得る手法とは言い難い。   The technique described in Patent Document 1 is a configuration in which a conductive resin is formed so as to cover the network-like first conductive portion, and in this configuration, the total light transmittance is reduced due to an excessive conductive resin. At the same time, since a conductive resin that hardly contributes to conductivity is required, it is difficult to say a technique for obtaining a low-cost substrate.

特許文献２では、金属微粒子で構成される網目状の導電性部上にめっきを施す方法が開示されている。前記特許文献２では特に色素増感型太陽電池用導電性基板については言及されていないけれども、電解質に対して耐食性のあるめっき処理を行うことも可能である。図２は、前記特許文献２に記載の方法により得られる透明導電性基板を模式的に示す図である。前記特許文献２に記載されている好ましい網目状の導電性部２６の形成方法では、図２（ａ）に示すように導電性部２６は基板２５に対して凸状に形成されているため、色素増感型太陽電池の発電層に相当する酸化チタンなどの半導体層を積層する際に平坦性の点で問題が残る。さらに導電性部２６にめっき２７処理を施すことで（図２（ｂ））、平坦性の悪化とともに、めっき処理により導電性部２６の幅が広がり、透過率の低下が懸念される。   Patent Document 2 discloses a method of performing plating on a mesh-like conductive portion made of metal fine particles. Although the patent document 2 does not particularly mention a conductive substrate for a dye-sensitized solar cell, it is possible to perform a plating process having corrosion resistance on the electrolyte. FIG. 2 is a diagram schematically showing a transparent conductive substrate obtained by the method described in Patent Document 2. As shown in FIG. In the preferable method for forming the mesh-like conductive portion 26 described in Patent Document 2, the conductive portion 26 is formed in a convex shape with respect to the substrate 25 as shown in FIG. When laminating a semiconductor layer such as titanium oxide corresponding to the power generation layer of the dye-sensitized solar cell, a problem remains in terms of flatness. Furthermore, when the conductive portion 26 is subjected to the plating 27 treatment (FIG. 2B), the width of the conductive portion 26 is widened by the plating treatment as the flatness is deteriorated, and there is a concern that the transmittance is lowered.

また、前記特許文献２において、その他の網目状の導電性部形成方法として記載されている手法である基板に網目状の溝を掘り、そこに金属微粒子を埋め込む手法では、フォトリソグラフィー法やレーザーエッチング法などを用いる必要があり、低コストで大面積の色素増感型太陽電池用導電性基板を得る手法としては課題が残る。   Further, in the above-mentioned Patent Document 2, a method of digging a mesh-like groove in a substrate, which is a method described as another method for forming a mesh-like conductive portion, and embedding metal fine particles therein, is a photolithography method or laser etching. For example, a method for obtaining a conductive substrate for a dye-sensitized solar cell having a large area at low cost remains.

さらに前記特許文献１又は特許文献２に記載の技術を用いて、高い導電性を得るためには金属微粒子分散溶液にせよ導電性ペーストにせよ、塗布又は印刷後に十分な加熱処理や化学処理が必要である。そのため耐熱性や耐薬品性に優れた基板しか用いることができないと言う問題が残っている。   Furthermore, in order to obtain high conductivity using the technique described in Patent Document 1 or Patent Document 2, sufficient heat treatment or chemical treatment is required after coating or printing, whether it is a metal fine particle dispersion solution or a conductive paste. It is. Therefore, there remains a problem that only a substrate excellent in heat resistance and chemical resistance can be used.

本発明の目的は、低抵抗で透明性に優れる共に平坦性に優れる透明導電性基板及び該透明導電性基板を安価に製造可能な製造方法を提供することである。   An object of the present invention is to provide a transparent conductive substrate having low resistance, excellent transparency and excellent flatness, and a production method capable of manufacturing the transparent conductive substrate at low cost.

請求項１に記載の本発明は、透明導電性基板の製造方法において、下記の１から５の製造工程にて製造することを特徴とする透明導電性基板の製造方法である。
１、金属微粒子分散溶液を基材上に塗布し乾燥させ、網目状の第一導電性層を基材上に形成させる第一導電性層形成工程
２、前記第一導電性層を完全に覆う透明性の接着層を積層する接着層積層工程
３、前記接着層面と被転写基板とを貼り合せ、加熱加圧した後、基材を剥離し、第一導電性層と接着層が一体となった転写層を被転写基板に熱転写させる熱転写工程
４、熱転写された第一導電性層の表面をエッチングするエッチング工程
５、エッチングで形成された孔部にめっきを施し第二導電性層を積層する第二導電性層形成工程 The present invention according to claim 1 is a method for manufacturing a transparent conductive substrate, wherein the transparent conductive substrate is manufactured by the following manufacturing steps 1 to 5.
1. A metal fine particle dispersion solution is applied on a substrate and dried, and a first conductive layer forming step 2 for forming a network-like first conductive layer on the substrate. The first conductive layer is completely covered. Adhesive layer laminating step 3 for laminating a transparent adhesive layer, the adhesive layer surface and the substrate to be transferred are bonded together, heated and pressed, then the substrate is peeled off, and the first conductive layer and the adhesive layer are integrated. A thermal transfer process 4 for thermally transferring the transferred layer to the substrate to be transferred, an etching process 5 for etching the surface of the thermally transferred first conductive layer, and plating the holes formed by etching to laminate a second conductive layer. Second conductive layer formation process

請求項２に記載の本発明は、透明導電性基板の製造方法において、下記の１から５の製造工程にて製造することを特徴とする透明導電性基板の製造方法である。
１、金属微粒子分散溶液を基材上に塗布し乾燥させ、網目状の第一導電性層を基材上に形成させる第一導電性層形成工程
２、被転写基板に透明性の接着層を積層する接着層積層工程
３、前記第一導電性層面と被転写基板とを貼り合せ、加熱加圧した後、基材を剥離し、第一導電性層と接着層が一体となった転写層を被転写基板に熱転写させる熱転写工程
４、熱転写された第一導電性層の表面をエッチングするエッチング工程
５、エッチングで形成された孔部にめっきを施し第二導電性層を積層する第二導電性層形成工程 According to a second aspect of the present invention, in the method for manufacturing a transparent conductive substrate, the transparent conductive substrate is manufactured by the following manufacturing steps 1 to 5.
1. A metal fine particle dispersion solution is applied on a substrate and dried to form a first conductive layer having a mesh shape on the substrate. 2. A transparent adhesive layer is formed on the substrate to be transferred. Laminating adhesive layer laminating step 3, the first conductive layer surface and the substrate to be transferred are bonded, heated and pressed, then the substrate is peeled off, and the transfer layer in which the first conductive layer and the adhesive layer are integrated Is transferred to the substrate to be transferred, thermal transfer step 4 for etching, etching step 5 for etching the surface of the thermally transferred first conductive layer, and second conductive layer for plating the hole formed by etching and laminating the second conductive layer. Layer formation process

請求項３に記載の本発明は、前記第一導電性層形成工程が、金属微粒子ペーストを基材上に印刷し乾燥させ、網目状の第一導電性層を基材上に形成させる第一導電性層形成工程であることを特徴とする請求項１又２に記載の透明導電性基板の製造方法である。   According to a third aspect of the present invention, in the first conductive layer forming step, the metal fine particle paste is printed on the substrate and dried to form a network-like first conductive layer on the substrate. 3. The method for producing a transparent conductive substrate according to claim 1, wherein the transparent conductive substrate is a conductive layer forming step.

請求項４に記載の本発明は、前記第一導電性層形成工程が、金属微粒子の前駆体である金属塩の溶液を、基材に塗布し乾燥させた後、金属微粒子の前駆体を加熱又は紫外線照射又は還元性ガスにより還元析出させ、網目状の第一導電性層を基材上に形成させる第一導電性層形成工程であることを特徴とする請求項１又２に記載の透明導電性基板の製造方法である。   According to a fourth aspect of the present invention, in the first conductive layer forming step, after a metal salt solution, which is a precursor of metal fine particles, is applied to a substrate and dried, the precursor of the metal fine particles is heated. Alternatively, the transparent conductive layer according to claim 1 or 2, wherein the transparent conductive layer is a first conductive layer forming step in which a net-like first conductive layer is formed on a substrate by reduction deposition with ultraviolet irradiation or a reducing gas. It is a manufacturing method of a conductive substrate.

請求項５に記載の本発明は、前記第一導電性層形成工程と、前記接着層積層工程との間に、前記第一導電性層に加熱処理及び／又は化学処理を行う工程を備えることを特徴とする請求項１から４のいずれか１項に記載の透明導電性基板の製造方法である。   The present invention according to claim 5 includes a step of performing heat treatment and / or chemical treatment on the first conductive layer between the first conductive layer forming step and the adhesive layer laminating step. The method for producing a transparent conductive substrate according to any one of claims 1 to 4, wherein:

請求項６に記載の本発明は、前記基材に前記金属微粒子分散溶液、前記金属微粒子ペースト又は前記金属塩の溶液を塗布するに先立ち、前記基材に表面処理を施すことを特徴とする請求項１から５のいずれか１項に記載の透明導電性基板の製造方法である。   The present invention described in claim 6 is characterized in that the substrate is subjected to a surface treatment before the metal fine particle dispersion solution, the metal fine particle paste or the metal salt solution is applied to the substrate. Item 6. The method for producing a transparent conductive substrate according to any one of Items 1 to 5.

請求項７に記載の本発明は、前記接着層の厚みは、前記第一導電性層の高さよりも高く、前記被転写基板に前記第一導電性層は接触しないことを特徴とする請求項１から６のいずれか１項に記載の透明導電性基板の製造方法である。   The present invention according to claim 7 is characterized in that the thickness of the adhesive layer is higher than the height of the first conductive layer, and the first conductive layer does not contact the transfer substrate. It is a manufacturing method of the transparent conductive substrate of any one of 1-6.

請求項８に記載の本発明は、請求項１から７のいずれか１項に記載の透明導電性基板の製造方法により得られる透明導電性基板の表面に、さらに第三導電性層を積層する第三導電性層形成工程を備えることを特徴とする請求項１から７のいずれか１項に記載の透明導電性基板の製造方法である。   In the present invention described in claim 8, a third conductive layer is further laminated on the surface of the transparent conductive substrate obtained by the method for manufacturing a transparent conductive substrate according to any one of claims 1 to 7. It is a manufacturing method of the transparent conductive substrate of any one of Claim 1 to 7 provided with a 3rd conductive layer formation process.

請求項９に記載の本発明は、請求項１から８のいずれか１項に記載の透明導電性基板の製造方法により得られる透明導電性基板である。   The present invention according to claim 9 is a transparent conductive substrate obtained by the method for producing a transparent conductive substrate according to any one of claims 1 to 8.

請求項１０に記載の本発明は、前記第一導電性層と前記接着層の最大段差が３００ｎｍ以下であり、表面の表面抵抗値が５Ω／□以下であることを特徴とする請求項９に記載の透明導電性基板である。   The present invention according to claim 10 is characterized in that the maximum step between the first conductive layer and the adhesive layer is 300 nm or less, and the surface resistance value of the surface is 5 Ω / □ or less. It is a transparent conductive substrate of description.

請求項１１に記載の本発明は、前記接着層がアクリル系接着剤、ポリエステル系接着剤からなる群より選ばれる少なくとも１種の接着剤を含有することを特徴とする請求項９又は１０に記載の透明導電性基板である。   The present invention described in claim 11 is characterized in that the adhesive layer contains at least one adhesive selected from the group consisting of an acrylic adhesive and a polyester adhesive. This is a transparent conductive substrate.

請求項１２に記載の本発明は、請求項９から１１のいずれか１項に記載の透明導電性基板であって、前記第二導電性層及び前記第三導電性層が電解質溶液に対して耐性を有することを特徴とする色素増感型太陽電池用透明導電性基板である。   The present invention described in claim 12 is the transparent conductive substrate according to any one of claims 9 to 11, wherein the second conductive layer and the third conductive layer are in contact with an electrolyte solution. It is a transparent conductive substrate for dye-sensitized solar cells, characterized by having resistance.

本発明に係る透明導電性基板の製造方法によれば、金属微粒子分散溶液、金属微粒子ペースト又は金属微粒子の前駆体である金属塩の溶液を塗布又は印刷することにより第一導電性層を形成するので低コストで、大面積な網目状の第一導電性層を形成することが出来る。さらに、耐熱性のある基材を用いることで金属微粒子の焼結に十分な加熱処理が行え、低抵抗な第一導電性層が得られる。続いて、高透明性の接着層を介在させ、第一導電性層を所望の被転写基板上に熱転写することにより、第一導電性層と接着層が一体となった転写層の表面が平坦となる。さらに、転写層の表面を酸又はアルカリなどの化学処理によりエッチングし、導電性部上のみに孔を形成し、続いて金属又は金属合金のめっきを平坦性に注意しながら孔部に施すことで、平坦性に優れ、さらにはめっきによる導電性部幅の拡大を防ぐことが出来るので、低抵抗で透明性に優れる透明導電性基板を得ることができる。   According to the method for producing a transparent conductive substrate according to the present invention, the first conductive layer is formed by applying or printing a metal fine particle dispersion solution, a metal fine particle paste, or a metal salt solution that is a precursor of metal fine particles. Therefore, a large-area network-like first conductive layer can be formed at low cost. Furthermore, by using a heat-resistant base material, heat treatment sufficient for sintering the metal fine particles can be performed, and a low-resistance first conductive layer can be obtained. Subsequently, the surface of the transfer layer in which the first conductive layer and the adhesive layer are integrated is flattened by interposing a highly transparent adhesive layer and thermally transferring the first conductive layer onto a desired transfer target substrate. It becomes. Furthermore, the surface of the transfer layer is etched by a chemical treatment such as acid or alkali to form a hole only on the conductive part, and then metal or metal alloy plating is applied to the hole while paying attention to flatness. Moreover, since it is excellent in flatness, and further, it is possible to prevent the conductive part width from being expanded by plating, a transparent conductive substrate having low resistance and excellent transparency can be obtained.

また前記接着層の厚みを前記第一導電性層の高さよりも高くすることで、基板全面に接着層を接触させることができ接着力が向上する。   Further, by making the thickness of the adhesive layer higher than the height of the first conductive layer, the adhesive layer can be brought into contact with the entire surface of the substrate, and the adhesive force is improved.

また本発明に係る透明導電性基板の製造方法によれば、高透過率と低抵抗を同時に満足させると共に、透明導電性基板の表面の平坦性も高いので、電解質に対して耐食性のある金属又は金属合金をめっき材料とすれば色素増感型太陽電池用透明導電性基板として好適に使用することができる。   Further, according to the method for producing a transparent conductive substrate according to the present invention, a high transmittance and a low resistance are satisfied at the same time, and the flatness of the surface of the transparent conductive substrate is high. If a metal alloy is used as a plating material, it can be suitably used as a transparent conductive substrate for a dye-sensitized solar cell.

本発明の実施の一形態としての透明導電性基板１の製造方法を模式的に示す図である。It is a figure which shows typically the manufacturing method of the transparent conductive substrate 1 as one Embodiment of this invention. 従来の透明導電性基板の製造方法を模式的に示す図である。It is a figure which shows typically the manufacturing method of the conventional transparent conductive substrate.

本発明に係る透明導電性基板の製造方法は、大略的には、金属微粒子分散溶液又は金属微粒子ペーストを基材上に塗布又は印刷、乾燥させ網目状の第一導電性層を形成し、その後、必要に応じて熱処理及び／又は化学処理を施した後、該網目状の第一導電性層を別の基板（被転写基板）上に、高透明性の接着層を介して熱転写し、熱転写後の第一導電性層の表面を酸処理などの化学処理によりエッチングし、次にめっき処理によりエッチングにより形成された孔部の第一導電性層上に第二導電性層を形成させ、透明導電性基板を製造する方法である。さらに、必要に応じて表面を導電性樹脂で被覆する。   The method for producing a transparent conductive substrate according to the present invention generally comprises applying a metal fine particle dispersion solution or metal fine particle paste on a substrate, printing, and drying to form a network-like first conductive layer, and then After performing heat treatment and / or chemical treatment as necessary, the network-like first conductive layer is thermally transferred onto another substrate (transfer target substrate) through a highly transparent adhesive layer, and thermal transfer is performed. The surface of the subsequent first conductive layer is etched by chemical treatment such as acid treatment, and then the second conductive layer is formed on the first conductive layer in the hole formed by etching by plating treatment. This is a method for manufacturing a conductive substrate. Further, the surface is coated with a conductive resin as necessary.

図１は、本発明の実施の一形態としての透明導電性基板１の製造方法を模式的に示す図である。以下、色素増感型太陽電池用の透明導電性基板１を例として製造方法を説明する。   FIG. 1 is a diagram schematically showing a method for manufacturing a transparent conductive substrate 1 as one embodiment of the present invention. Hereinafter, the manufacturing method will be described using the transparent conductive substrate 1 for a dye-sensitized solar cell as an example.

まず、基材２上に金属微粒子の分散溶液を塗布、乾燥し、網目状構造物からなる第一導電性層３を基材２上に形成させる。さらに必要に応じて第一導電性層３に対して加熱処理及び／又は化学的処理を施す。これにより網目状構造物からなる第一導電性層３が積層された基材２を得ることができる。図１（ａ）は、第一導電性層３が積層された基材２を示す。   First, a dispersion solution of metal fine particles is applied on the substrate 2 and dried to form the first conductive layer 3 made of a network structure on the substrate 2. Further, heat treatment and / or chemical treatment is performed on the first conductive layer 3 as necessary. Thereby, the base material 2 on which the first conductive layer 3 made of a network structure is laminated can be obtained. FIG. 1A shows a base material 2 on which a first conductive layer 3 is laminated.

ここで使用可能な金属微粒子分散溶液は、基材２上へ塗布、乾燥後に、金属微粒子が自己組織化現象により網目状構造物を形成し、必要に応じて該積層基材を加熱処理及び化学処理又はいずれかの処理を行うことで網目状構造物が低抵抗、高透過率を示すものであればいずれの金属微粒子分散溶液を用いても良い。また金属微粒子分散溶液に代え、金属微粒子ペーストを用いて基材上２に印刷し、網目状構造物を形成させても良い。さらに金属微粒子分散溶液に代え、網目状構造物を形成可能な金属微粒子の前駆体である金属塩の溶液（以下、金属微粒子前駆体溶液と記す場合もある）を使用することもできる。金属微粒子前駆体溶液の場合、耐熱性及び／又は耐薬品性を有する基材２に塗布し乾燥させた後、金属微粒子の前駆体を加熱又は紫外線照射又は還元性ガスにより還元析出させることで網目状構造物を得ることができる。   The metal fine particle dispersion solution that can be used here forms a network structure by self-organization after coating and drying on the base material 2, and heat treatment and chemical treatment of the laminated base material as necessary. Any metal fine particle dispersion solution may be used as long as the network structure exhibits low resistance and high transmittance by performing the treatment or any treatment. Further, instead of the metal fine particle dispersion solution, a fine metal paste may be used to print on the substrate 2 to form a network structure. Furthermore, instead of the metal fine particle dispersion solution, a solution of a metal salt which is a precursor of metal fine particles capable of forming a network structure (hereinafter, may be referred to as a metal fine particle precursor solution) may be used. In the case of a metal fine particle precursor solution, after applying to the substrate 2 having heat resistance and / or chemical resistance and drying, the metal fine particle precursor is reduced or precipitated by heating, ultraviolet irradiation or a reducing gas. A shaped structure can be obtained.

金属微粒子分散容液、金属微粒子ペースト又は金属微粒子前駆体溶液に含まれる金属微粒子は、Ａｕ、Ａｇ、Ｃｕ、Ｎｉ、Ｃｏ、Ｆｅ、Ｃｒ、Ｚｎ、Ａｌ、Ｓｎ、Ｐｄ、Ｔｉ、Ｔａ、Ｗ、Ｍｏ、Ｉｎ、Ｐｔ、Ｒｕなどの金属微粒子又は金属合金微粒子又は金属酸化物微粒子又は金属硫化物微粒子、又は炭素を含む炭素微粒子又はカーボンナノチューブやフラーレン、カーボンナノホーンなどの所謂ナノカーボン材料、又は珪素を含む珪素微粒子又は珪素と他金属との珪素合金微粒子、珪素酸化物微粒子又は珪素炭化物微粒子、珪素窒化物微粒子を用いることができる。耐酸化性と低コストの導電性基板を得ることを考慮するとＡｕ、Ａｇの金属微粒子分散液、金属微粒子ペースト又は金属微粒子前駆体溶液が好ましい。   The metal fine particles contained in the metal fine particle dispersion solution, the metal fine particle paste or the metal fine particle precursor solution are Au, Ag, Cu, Ni, Co, Fe, Cr, Zn, Al, Sn, Pd, Ti, Ta, W, Metal fine particles such as Mo, In, Pt, Ru, metal alloy fine particles, metal oxide fine particles, metal sulfide fine particles, carbon fine particles containing carbon, so-called nanocarbon materials such as carbon nanotubes, fullerenes, carbon nanohorns, or silicon. Silicon fine particles or silicon alloy fine particles of silicon and other metals, silicon oxide fine particles, silicon carbide fine particles, or silicon nitride fine particles can be used. In consideration of obtaining an oxidation resistance and a low-cost conductive substrate, a metal fine particle dispersion of Au, Ag, a metal fine particle paste or a metal fine particle precursor solution is preferable.

金属微粒子の調製法としては、従来から用いられている気相法（ガス中蒸発法など）、液相法（金属塩と還元剤による液相還元法）、熱分解法（金属錯体の熱分解法など）などの手法を用いることが出来る。   Methods for preparing fine metal particles include conventional gas phase methods (evaporation in gas, etc.), liquid phase methods (liquid phase reduction methods using metal salts and reducing agents), and thermal decomposition methods (thermal decomposition of metal complexes). Or the like) can be used.

金属微粒子の平均粒子径は１０ｎｍ以上１μｍ以下が好ましく、より好ましくは１０ｎｍ〜５００ｎｍ、さらに好ましくは５０ｎｍ〜２００ｎｍである。平均粒子径が１μｍを超える場合、又は１０ｎｍ未満の場合には、良く発達した網目状構造が得にくくなり、結果、低抵抗と高透過率が得にくい。   The average particle size of the metal fine particles is preferably 10 nm or more and 1 μm or less, more preferably 10 nm to 500 nm, still more preferably 50 nm to 200 nm. When the average particle diameter exceeds 1 μm or less than 10 nm, a well-developed network structure is difficult to obtain, and as a result, low resistance and high transmittance are difficult to obtain.

上記のような金属微粒子分散溶液、金属微粒子ペースト又は金属微粒子前駆体溶液は、例えば、特許文献３〜５を参考に調製した金属微粒子分散溶液、金属微粒子ペースト又は金属微粒子前駆体溶液を用いることが出来る。
特開２００７−２３４２９９号公報 特表２００５−５３０００５号公報 特開平１０−３１２７１５号公報 As the metal fine particle dispersion solution, the metal fine particle paste or the metal fine particle precursor solution as described above, for example, a metal fine particle dispersion solution, a metal fine particle paste or a metal fine particle precursor solution prepared with reference to Patent Documents 3 to 5 may be used. I can do it.
JP 2007-234299 A JP 2005-530005 Gazette Japanese Patent Laid-Open No. 10-312715

基材２は、金属微粒子分散溶液、金属微粒子ペースト又は金属微粒子前駆体溶液を塗布又は印刷し、網目状構造物を安定に形成させるものであり、金属微粒子分散溶液、金属微粒子ペースト又は金属微粒子前駆体溶液に含まれる有機溶剤に対して腐食又は溶解せず、続く加熱処理又は化学処理により網目状構造物の電気的特性（抵抗値）や光学的特性（透過率）が劣化しないものであれば特に限定されない。なお、基材２上に金属微粒子前駆体溶液を塗布し乾燥させた後、金属微粒子の前駆体を加熱又は紫外線照射又は還元性ガスにより還元析出させる場合には、これら操作に耐性を有するものである必要があることは言うまでもない。   The base material 2 is one in which a metal fine particle dispersion solution, a metal fine particle paste, or a metal fine particle precursor solution is applied or printed to stably form a network structure, and the metal fine particle dispersion solution, the metal fine particle paste, or the metal fine particle precursor is formed. If it does not corrode or dissolve in the organic solvent contained in the body solution, and the electrical properties (resistance value) and optical properties (transmittance) of the network structure are not deteriorated by subsequent heat treatment or chemical treatment There is no particular limitation. In addition, after apply | coating and drying a metal fine particle precursor solution on the base material 2, when carrying out reduction | restoration precipitation of the metal fine particle precursor with heating, ultraviolet irradiation, or a reducing gas, it has resistance to these operation. It goes without saying that there must be.

また基材２は、表面６の平滑度が重要である。基材２上に形成された網目状構造物からなる第一導電性層３は、接着層７を介して被転写基板８上に熱転写されるため、基材２上の第一導電性層の底面９は、被転写基板８上では表面１５となる。このため基材の表面６の平滑度が低いと、最終的に得られる透明導電性基板１の表面１１の平滑度が低くなる。   Further, the smoothness of the surface 6 is important for the substrate 2. Since the first conductive layer 3 made of a network structure formed on the base material 2 is thermally transferred onto the transfer substrate 8 via the adhesive layer 7, the first conductive layer on the base material 2 The bottom surface 9 becomes the surface 15 on the transfer substrate 8. For this reason, if the smoothness of the surface 6 of a base material is low, the smoothness of the surface 11 of the transparent conductive substrate 1 finally obtained will become low.

また、金属微粒子分散溶液、金属微粒子ペースト又は金属微粒子前駆体溶液を塗布又は印刷する基材２の表面は、予め金属微粒子、金属微粒子ペースト又は金属微粒子前駆体が網目状構造を再現性良く形成するため、プライマー処理又はコロナ処理、酸・アルカリ処理による洗浄などを行う方が好ましい。上記手法は特に限定されないが、各金属微粒子分散溶液、金属微粒子ペースト又は金属微粒子前駆体溶液に適した処理を行うことが好ましい。   Further, on the surface of the substrate 2 on which the metal fine particle dispersion solution, the metal fine particle paste or the metal fine particle precursor solution is applied or printed, the metal fine particles, the metal fine particle paste or the metal fine particle precursor form a network structure with good reproducibility in advance. Therefore, it is preferable to perform a primer treatment, a corona treatment, an acid / alkali treatment or the like. Although the said method is not specifically limited, It is preferable to perform the process suitable for each metal microparticle dispersion solution, metal microparticle paste, or metal microparticle precursor solution.

また基材２上の第一導電性層３を被転写基板８に破壊されずスムーズに転写されるように、基材２上に予め弱い離型層（図示省略）を設けることが好ましい。離型層はシリコーン系高分子やフッ素系高分子など塗工液として、乾燥厚みが０．０１〜１．０μｍで塗布することで形成する。上記離型層は金属微粒子、金属微粒子ペースト又は金属微粒子前駆体の網目状構造を再現性良く形成させる程度に処理する。   In addition, it is preferable to provide a weak release layer (not shown) in advance on the base material 2 so that the first conductive layer 3 on the base material 2 is smoothly transferred to the transfer substrate 8 without being broken. The release layer is formed by coating with a dry thickness of 0.01 to 1.0 μm as a coating liquid such as a silicone polymer or a fluorine polymer. The release layer is treated to such an extent that a network structure of metal fine particles, metal fine particle paste or metal fine particle precursor is formed with good reproducibility.

基材２は、工業的にはより安価な樹脂フィルムを用いることが好ましい。具体的にはポリエチレンテレフタレート、ポリエチレンナフタレート、ポリアミド、ポリイミド、ポリフェニレンサルファイド等の樹脂フィルムを用いることが出来る。また熱転写時の操作性等を考慮すれば基材２は、柔軟性を有することが好ましい。基材２は繰り返し使用することもできる。基材２の厚みは、６〜２００μｍが好ましい。さらに、好ましくは、１２〜１５０μｍの厚みのものを使用する。特に好ましくは、２５〜１２５μｍの厚みのものを使用する。   As the base material 2, it is preferable to use a less expensive resin film industrially. Specifically, a resin film of polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polyphenylene sulfide, or the like can be used. In consideration of operability during thermal transfer, the substrate 2 preferably has flexibility. The substrate 2 can be used repeatedly. As for the thickness of the base material 2, 6-200 micrometers is preferable. Further, preferably, a thickness of 12 to 150 μm is used. Particularly preferably, one having a thickness of 25 to 125 μm is used.

金属微粒子分散溶液又は金属微粒子前駆体溶液の基材２上への塗布方法は、例えばバーコーター、ディップコーター、スプレーコーター、ダイコーター、スピンコーターなど公知のコーティング方法を用いることが出来る。   As a method for applying the metal fine particle dispersion solution or the metal fine particle precursor solution onto the base material 2, a known coating method such as a bar coater, a dip coater, a spray coater, a die coater, or a spin coater can be used.

金属微粒子ペーストの基材２上への印刷方法は、公知のスクリーン印刷法を用いることができる。   A known screen printing method can be used as a method for printing the metal fine particle paste on the substrate 2.

塗布した後は、静置乾燥又は一定流量で空気などのガスを通風しながら乾燥させる方法、さらに加熱を組み合わせる方法などを用いることができる。   After the application, it is possible to use a stationary drying method, a method of drying while passing a gas such as air at a constant flow rate, or a method of combining heating.

金属微粒子分散溶液を塗布、乾燥させた後、又は金属微粒子ペーストを印刷、乾燥させた後、又は金属微粒子前駆体溶液の場合、金属微粒子の前駆体を加熱又は紫外線照射又は還元性ガスにより還元析出させた網目状構造物を加熱処理及び／又は化学的処理することが好ましい。化学的処理は、金属微粒子中に含まれる分散剤や樹脂などを取り除き、網目状構造物の抵抗値をより低くすることを主目的とするものであり、有機溶剤及び無機酸又は有機酸に浸漬することが好ましい。有機溶剤してはアセトン、メチルエチルケトンなどのケトン類、メタノール、エタノール、イソプロパノールなどのアルコール類が例示される。好ましくはアセトンなどのケトン類である。無機酸又は有機酸としては塩酸、硝酸、蟻酸、酢酸が例示され、好ましくは塩酸又は蟻酸である。浸漬後は純水又はエタノールなどでリンスした後、静置乾燥又は加熱乾燥などにより乾燥させることが好ましい。   After applying and drying the metal fine particle dispersion solution, or after printing and drying the metal fine particle paste, or in the case of a metal fine particle precursor solution, the metal fine particle precursor is reduced or precipitated by heating, ultraviolet irradiation or a reducing gas. It is preferable to heat-process and / or chemically-process the made network structure. The main purpose of chemical treatment is to remove the dispersant, resin, etc. contained in the metal fine particles, and to lower the resistance value of the network structure, and it is immersed in an organic solvent and an inorganic or organic acid. It is preferable to do. Examples of the organic solvent include ketones such as acetone and methyl ethyl ketone, and alcohols such as methanol, ethanol and isopropanol. Ketones such as acetone are preferred. Examples of the inorganic acid or organic acid include hydrochloric acid, nitric acid, formic acid, and acetic acid, and hydrochloric acid or formic acid is preferable. After the immersion, it is preferable to rinse with pure water or ethanol and then dry by standing drying or heat drying.

さらに、金属微粒子同士の焼結を促進し、抵抗値をより低くすることを目的に加熱処理を施すことがより好ましい。加熱処理温度は用いる基材２によって異なるが、十分な導電性を得るためには１００〜３００℃の範囲が好ましい。より好ましくは１００〜２００℃である。   Furthermore, it is more preferable to perform heat treatment for the purpose of promoting the sintering of the metal fine particles and lowering the resistance value. Although heat processing temperature changes with the base materials 2 to be used, in order to obtain sufficient electroconductivity, the range of 100-300 degreeC is preferable. More preferably, it is 100-200 degreeC.

金属微粒子前駆体を還元する場合には、加熱又は紫外線や放射線などの光照射又は還元性ガスの手法を組み合わせて行うことも出来る。   In the case of reducing the metal fine particle precursor, heating, light irradiation such as ultraviolet rays or radiation, or a reducing gas method can be combined.

上記網目状構造物からなる第一導電性層３の全光線透過率は７０％以上であり、より好ましくは８０％以上である。   The total light transmittance of the first conductive layer 3 made of the network structure is 70% or more, more preferably 80% or more.

次に、基材２上に形成した網目状構造物からなる第一導電性層３を所望の被転写基板８に熱転写させるため、図１（ｂ）に示すように第一導電性層３が積層された基材２の一面全体を透明性の高い接着剤で覆い接着層７を形成する。このとき第一導電性層３の全ての開口部１２に接着剤を充填し、開口部１２を接着剤で埋設することが重要である。第一導電性層３は、次の工程で、接着層７と一体的に熱転写されるため基材２上で底面９となっている第一導電性層の面が、熱転写後は表面となる（図１（ｃ）、（ｄ））。このため第一導電性層３の開口部１２が接着剤で完全に埋設されていないと、熱転写後の転写層１０（第一導電性層と接着層）の表面１４は、局所的に穴の開いた状態となる。次工程以降において、熱転写後の第一導電性層３の表面１５はエッチングされ、エッチング箇所にめっき処理が施され第二導電性層５が形成されるけれども、穴あき部はめっきが施されずそのまま状態で残るため、最終的に透明導電性基板１の表面１１は、平坦とならず好ましくない。さらに第二導電性層５の表面１７を覆うように導電性樹脂を含む樹脂を塗布し、第二導電性層５と接続する第三導電性層１８を形成する場合にあっても、転写層１０の上面１４に局所的に穴が開いていると、第三導電性層１８の表面１９は平坦とならず、さらには第三導電性層１８を形成する樹脂が穴に入り込み、透過率を低下させるので好ましくない。   Next, in order to thermally transfer the first conductive layer 3 made of a network structure formed on the base material 2 to a desired transfer target substrate 8, as shown in FIG. The entire surface of the laminated base material 2 is covered with a highly transparent adhesive to form the adhesive layer 7. At this time, it is important to fill all the openings 12 of the first conductive layer 3 with an adhesive and bury the openings 12 with the adhesive. Since the first conductive layer 3 is thermally transferred integrally with the adhesive layer 7 in the next step, the surface of the first conductive layer which is the bottom surface 9 on the substrate 2 becomes the surface after the thermal transfer. (FIGS. 1C and 1D). For this reason, if the opening 12 of the first conductive layer 3 is not completely embedded with an adhesive, the surface 14 of the transfer layer 10 (the first conductive layer and the adhesive layer) after the thermal transfer is locally perforated. Opened. In the subsequent steps, the surface 15 of the first conductive layer 3 after the thermal transfer is etched, and the etching portion is plated to form the second conductive layer 5, but the perforated portion is not plated. Since it remains as it is, the surface 11 of the transparent conductive substrate 1 is not preferable because it does not become flat. Further, even when a resin containing a conductive resin is applied so as to cover the surface 17 of the second conductive layer 5 and the third conductive layer 18 connected to the second conductive layer 5 is formed, the transfer layer 10 has a hole locally, the surface 19 of the third conductive layer 18 does not become flat, and the resin forming the third conductive layer 18 enters the hole, and the transmittance is increased. Since it lowers, it is not preferable.

また接着層７の厚みは、第一導電性層３の高さを僅かに超える高さとする。本発明では、第一導電性層３の高さとは、第一導電性層３の中の最大高さを指すものである。接着層７は、次工程で被転写基板８に第一導電性層３と一体的に熱転写される。このため、基材２上で表面となっている接着層７の表面１３は、熱転写後は、被転写基板８と接触する面となる。このため基材２上の第一導電性層３が接着層７に完全に覆われていなければ、熱転写後、十分な接着強度を得ることができない。接着層７の高さを第一導電性層３の高さと同一とすると、熱転写後、被転写基板８との接着面に局所的に接着剤が存在しない部分が生じるので好ましくない。一方、接着層７の厚さを必要以上に高くすると、透過率が低下するため好ましくない。   Further, the thickness of the adhesive layer 7 is set to a height slightly exceeding the height of the first conductive layer 3. In the present invention, the height of the first conductive layer 3 refers to the maximum height in the first conductive layer 3. The adhesive layer 7 is thermally transferred integrally with the first conductive layer 3 to the transfer substrate 8 in the next step. For this reason, the surface 13 of the adhesive layer 7 which is the surface on the base material 2 becomes a surface in contact with the substrate to be transferred 8 after thermal transfer. Therefore, if the first conductive layer 3 on the substrate 2 is not completely covered with the adhesive layer 7, sufficient adhesive strength cannot be obtained after thermal transfer. If the height of the adhesive layer 7 is the same as the height of the first conductive layer 3, a portion where no adhesive is locally present on the adhesive surface with the transfer substrate 8 occurs after thermal transfer. On the other hand, if the thickness of the adhesive layer 7 is increased more than necessary, the transmittance decreases, which is not preferable.

接着層７は、基材２側に設ける代わりに被転写基板８の一面に設けておいてもよい。   The adhesive layer 7 may be provided on one surface of the transfer substrate 8 instead of being provided on the substrate 2 side.

接着層７を形成する接着剤は、高透明性である他、次の点を注意して選定する必要がある。第一導電性層３が被転写基板８に熱転写された後、第一導電性層３の表面１５は、次工程で酸液などを用いたエッチングが行われる。さらにエッチング工程の後には、エッチングで形成された孔部２１をめっき被膜で塞ぐめっき操作が行われる。これら操作で接着層７は薬剤に接触し、エッチング操作及びめっき操作の環境下に置かれるため、エッチング工程及びめっき工程で使用される薬剤、環境に耐性を有する材料を選定する必要がある。   In addition to being highly transparent, the adhesive forming the adhesive layer 7 must be selected with the following points in mind. After the first conductive layer 3 is thermally transferred to the transfer substrate 8, the surface 15 of the first conductive layer 3 is etched using an acid solution or the like in the next step. Further, after the etching step, a plating operation for closing the hole 21 formed by etching with a plating film is performed. By these operations, the adhesive layer 7 comes into contact with the chemical and is placed in the environment of the etching operation and the plating operation. Therefore, it is necessary to select a chemical used in the etching process and the plating process and a material resistant to the environment.

接着層７に使用される接着剤としては各種接着剤が使用可能である。接着剤材料としては、ポリ塩化ビニル、ポリカーボネート、ポリスチレン、ポリメチルメタクリレート、ポリブチルメタクリレート、ポリエステル、ポリスルホン、ポリビニルブチラール、ポリビニルアセタール、ポリフェニレンオキシド、ポリブタジエン、ポリ（Ｎ−ビニルカルバゾール）、ポリビニルピロリドン、炭化水素樹脂、ケトン樹脂、フェノキシ樹脂、ポリアミド、塩素化ポリプロピレン、ポリイミド、ウレア、セルロース、酢酸ビニル、ＡＢＳ樹脂、ポリウレタン、フェノール樹脂、メラミン樹脂、不飽和ポリエステル樹脂、アルキド樹脂、エポキシ樹脂、シリコーン樹脂及びこれらの共重合体からなる群の少なくとも１つ、及び又はこれらいずれか混合物などが例示される。また、最終的に得られる透明導電性基板の電解質溶液に対する高い耐性を得ることを目的としてイソシアネート系、メラミン系、エポキシ系等従来公知の硬化剤を添加することも可能である。   Various adhesives can be used as the adhesive used for the adhesive layer 7. Adhesive materials include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyvinyl butyral, polyvinyl acetal, polyphenylene oxide, polybutadiene, poly (N-vinylcarbazole), polyvinyl pyrrolidone, hydrocarbon Resin, ketone resin, phenoxy resin, polyamide, chlorinated polypropylene, polyimide, urea, cellulose, vinyl acetate, ABS resin, polyurethane, phenol resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin and these Examples include at least one of the group consisting of copolymers, and / or any mixture thereof. Moreover, it is also possible to add conventionally well-known hardening | curing agents, such as an isocyanate type, a melamine type, and an epoxy type, in order to acquire the high tolerance with respect to the electrolyte solution of the transparent conductive substrate finally obtained.

また、接着層７には添加剤として紫外線吸収剤、着色顔料、帯電防止剤、酸化防止剤、シランカップリング剤等も適宜、必要に応じて使用することができる。   Moreover, an ultraviolet absorber, a color pigment, an antistatic agent, an antioxidant, a silane coupling agent, and the like can be appropriately used as necessary for the adhesive layer 7 as additives.

接着層７の形成方法としては、上記の接着剤材料を有機溶剤又は水に溶解あるいは水に分散し粘度を調整したコーティング剤を作製し、グラビヤコーティング、スピンコーティングなど従来公知のコーティング法により塗布乾燥する方法を用いることができる。接着層７の厚みは好ましくは０．５〜５０μｍ、さらに好ましくは１〜３０μｍである。接着層７の厚みが０．５μｍ未満では第一導電性層３の開口部１２が接着剤で完全に埋設されず、熱転写後の転写層１０の表面１４は、局所的に穴の開いた状態となる。次工程以降において、熱転写後の第一導電性層３の表面１５はエッチングされ、エッチング箇所にめっき処理が施され第二導電性層５が形成されるけれども、穴あき部はめっきが施されずそのまま状態で残るため、最終的に透明導電性基板１の表面１１は、平坦とならず好ましくない。さらに第二導電性層５の表面１７を覆うように導電性樹脂を含む樹脂を塗布し、第二導電性層５と接続する第三導電性層１８を形成する場合にあっても、転写層１０の上面１４に局所的に穴が開いていると、第三導電性層１８の表面１９は平坦とならず、さらには第三導電性層１８を形成する樹脂が穴に入り込み、透過率を低下させるので好ましくない。また、接着層７の厚みが５０μｍよりも厚いと透明導電性基板２０の透過率が低下するため好ましくない。   As a method of forming the adhesive layer 7, a coating agent in which the above-mentioned adhesive material is dissolved in an organic solvent or water or dispersed in water to adjust the viscosity is prepared, and applied and dried by a conventionally known coating method such as gravure coating or spin coating. Can be used. The thickness of the adhesive layer 7 is preferably 0.5 to 50 μm, more preferably 1 to 30 μm. When the thickness of the adhesive layer 7 is less than 0.5 μm, the opening 12 of the first conductive layer 3 is not completely embedded with the adhesive, and the surface 14 of the transfer layer 10 after the thermal transfer is locally perforated. It becomes. In the subsequent steps, the surface 15 of the first conductive layer 3 after the thermal transfer is etched, and the etching portion is plated to form the second conductive layer 5, but the perforated portion is not plated. Since it remains as it is, the surface 11 of the transparent conductive substrate 1 is not preferable because it does not become flat. Further, even when a resin containing a conductive resin is applied so as to cover the surface 17 of the second conductive layer 5 and the third conductive layer 18 connected to the second conductive layer 5 is formed, the transfer layer 10 has a hole locally, the surface 19 of the third conductive layer 18 does not become flat, and the resin forming the third conductive layer 18 enters the hole, and the transmittance is increased. Since it lowers, it is not preferable. Moreover, since the transmittance | permeability of the transparent conductive substrate 20 will fall when the thickness of the contact bonding layer 7 is thicker than 50 micrometers, it is unpreferable.

次に図１（ｃ）に示すように、基材２と被転写基板８とを貼り合せた後、加熱処理、加圧処理などを行い、基材２を剥離し、第一導電性層３を接着層７を介して被転写基板８に熱転写させる。熱転写方法は、公知の熱転写方法が使用可能であり、使用する基材２と被転写基板８の材質、接着層に応じて、適宜選択すればよい。例えば、ホットラミネーターで熱転写する方法、ホットプレス機で熱転写する方法、サーマルヘッドで熱転写する方法などを用いることができる。   Next, as shown in FIG. 1C, after the base material 2 and the transfer substrate 8 are bonded together, heat treatment, pressure treatment, and the like are performed, the base material 2 is peeled off, and the first conductive layer 3 is removed. Is transferred to the transfer substrate 8 through the adhesive layer 7. As the thermal transfer method, a known thermal transfer method can be used, and it may be appropriately selected according to the material of the base material 2 and the substrate to be transferred 8 and the adhesive layer. For example, a thermal transfer method using a hot laminator, a thermal transfer method using a hot press machine, a thermal transfer method using a thermal head, or the like can be used.

上記のようにして得られた被転写基板８上の転写層１０の表面は、基材２と被転写基板８とを貼り合せた後、基材２が剥離されるので、非常に平坦であり（図１（ｄ））、熱転写後の第一導電性層３と接着層７の段差は３００ｎｍ以下とすることで、転写層１０の表面の表面抵抗値が５Ω／□以下となるようにする。上述の製造方法により調製した第一導電性層３の表面抵抗値に対して、熱転写後の表面抵抗値の上昇率が１０％以下になるように熱転写を行うことが好ましい。熱転写後の表面抵抗値の上昇率が１０％以上になる場合は、接着層７が第一導電性層３と第二導電性層５との間に挿入され、第二導電性層５を含めた透明導電性基板１の表面抵抗値を上昇させてしまうため好ましくない。   The surface of the transfer layer 10 on the transfer substrate 8 obtained as described above is very flat because the substrate 2 is peeled after the substrate 2 and the transfer substrate 8 are bonded together. (FIG. 1 (d)), the step difference between the first conductive layer 3 and the adhesive layer 7 after thermal transfer is 300 nm or less so that the surface resistance value of the surface of the transfer layer 10 is 5 Ω / □ or less. . It is preferable to perform thermal transfer so that the increase rate of the surface resistance value after thermal transfer is 10% or less with respect to the surface resistance value of the first conductive layer 3 prepared by the above-described manufacturing method. When the rate of increase in the surface resistance value after thermal transfer is 10% or more, the adhesive layer 7 is inserted between the first conductive layer 3 and the second conductive layer 5 and includes the second conductive layer 5. Further, the surface resistance value of the transparent conductive substrate 1 is increased, which is not preferable.

基材２の代わりに被転写基板８上に接着層７を設け、第一導電性層３を被転写基板８に熱転写させる場合も、基材２の第一導電性層面と被転写基板８とを貼り合せ、第一導電性層３の底面９を残した状態で第一導電性層３を接着層７に埋没させ、熱転写後、基材２を剥離することで、基材２に接着層７を設けた場合と同一の状態を得ることができる。   Even when the adhesive layer 7 is provided on the transferred substrate 8 instead of the base material 2 and the first conductive layer 3 is thermally transferred to the transferred substrate 8, the first conductive layer surface of the base material 2 and the transferred substrate 8 The first conductive layer 3 is embedded in the adhesive layer 7 with the bottom surface 9 of the first conductive layer 3 left, and after the thermal transfer, the base material 2 is peeled off, whereby the adhesive layer is adhered to the base material 2. The same state as when 7 is provided can be obtained.

被転写基板８は、各用途によって広範に選択することが出来る。但し、次の点を注意して選定する必要がある。熱転写後の第一導電性層３の表面１５は、次工程で酸液を用いたエッチングが行われる。さらにエッチング工程の後には、エッチングで形成された孔部２１をめっき被膜で塞ぐめっき操作が行われる。これら操作で被転写基板８は薬剤に接触し、エッチング操作及びめっき操作の環境下に置かれるため、エッチング工程及びめっき工程で使用される薬剤、環境に耐性を有する材料を選定する必要がある。被転写基板８としては、例えば、ガラス、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリアミド、ポリイミド、ポリフェニレンサルファイドの他、ポリエチレン、ポリスチレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリカーボネート、アクリル樹脂、Ｓｉ基材、多孔質セラミックスなどが例示される。これらの中でも、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリアミド、ポリイミド、ポリフェニレンサルファイド等の樹脂フィルムを用いることが、ロールツーロールで安価に製造ができることから好ましい。   The substrate 8 to be transferred can be selected widely depending on each application. However, the following points need to be selected carefully. The surface 15 of the first conductive layer 3 after the thermal transfer is etched using an acid solution in the next step. Further, after the etching step, a plating operation for closing the hole 21 formed by etching with a plating film is performed. By these operations, the substrate 8 to be transferred comes into contact with the chemical and is placed in the environment of the etching operation and the plating operation. Therefore, it is necessary to select the chemical used in the etching process and the plating process and a material having resistance to the environment. As the transfer substrate 8, for example, glass, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polyphenylene sulfide, polyethylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, acrylic resin, Si base material, porous material Examples thereof include ceramics. Among these, it is preferable to use a resin film such as polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polyphenylene sulfide and the like because it can be produced at low cost by roll-to-roll.

次に図１（ｅ）に示すように、熱転写後の第一導電性層３の表面１５をエッチングする。エッチング方法は、薬液を使用するウエットエッチングで行うことができる。   Next, as shown in FIG. 1E, the surface 15 of the first conductive layer 3 after the thermal transfer is etched. The etching method can be performed by wet etching using a chemical solution.

エッチングに用いるエッチング溶液は、第一導電性層３を形成している金属微粒子の種類により、種類及び濃度を適宜選択すればよい。Ａｇの場合であれば、硝酸、リン酸と硝酸の混合用液、硝酸第二鉄、硝酸第二鉄と亜塩素酸ナトリウム混合溶液、硫酸と硫酸第二鉄の混合溶液、硫酸第二鉄などがあげられる。その他の金属では、ＣｕやＮｉであれば塩化第二鉄を主成分とするエッチング溶液を用いるのが好ましい。また、各種界面活性剤などを含んだエッチング溶液であっても良い。あるいは市販されているものを用いても良い。エッチングのし易さ及びコストを考慮すると、Ａｇと硝酸第二鉄−硝酸混合用液又はＣｕと塩酸又は塩酸−塩化第二鉄混合用液の組み合わせが好ましい。金属微粒子がＡｌあるいはＳｎなどの両性元素の場合には、アルカリ液として水酸化ナトリウム水溶液あるいは水酸化カリウム水溶液などを用いることが出来る。酸あるいはアルカリ液を用いてエッチングする場合には、接着層７が変性・変形しない条件で行なうことが好ましい。   The type and concentration of the etching solution used for the etching may be appropriately selected depending on the type of metal fine particles forming the first conductive layer 3. In the case of Ag, nitric acid, liquid for mixing phosphoric acid and nitric acid, ferric nitrate, mixed solution of ferric nitrate and sodium chlorite, mixed solution of sulfuric acid and ferric sulfate, ferric sulfate, etc. Can be given. For other metals, it is preferable to use an etching solution mainly composed of ferric chloride in the case of Cu or Ni. Moreover, the etching solution containing various surfactant etc. may be sufficient. Or what is marketed may be used. In consideration of the ease of etching and cost, a combination of Ag and a solution for mixing ferric nitrate-nitric acid or Cu and a solution for mixing hydrochloric acid or hydrochloric acid-ferric chloride is preferable. When the metal fine particles are amphoteric elements such as Al or Sn, an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution can be used as the alkaline solution. In the case of etching using an acid or alkali solution, it is preferable to carry out the etching under the condition that the adhesive layer 7 is not modified or deformed.

エッチングは、上記網目状の第一導電性層３が積層された被転写基板８を前記エッチング溶液中に浸漬するか、又は前記エッチング溶液を転写層１０の表面１４に吹き付けた後、所定の時間静置、続いて純水などで洗浄を行う。エッチングの程度（深さ）は、色素増感型太陽電池導電性基板の電解質に対する耐性、導電性を考慮して適宜最適化することが出来る。   The etching is performed by immersing the transfer substrate 8 on which the mesh-like first conductive layer 3 is laminated in the etching solution or spraying the etching solution on the surface 14 of the transfer layer 10 and then for a predetermined time. Let stand, and then wash with pure water. The degree of etching (depth) can be appropriately optimized in consideration of the resistance and conductivity of the dye-sensitized solar cell conductive substrate to the electrolyte.

次に図１（ｆ）に示すように、先のエッチング工程でエッチングされて形成された第一導電性層３の孔部２１を塞ぐようにめっきを施す。このめっき操作により第一導電性層３と電気的に接続する第二導電性層５を形成する。めっき処理の金属としては、電解質に対して耐食性のある金属を用い、Ｎｉ、Ｚｎ、Ａｕ、Ｐｔ、Ｃｒ、Ａｌ、Ｃｄ、Ｗ、Ｓｎ、Ｃｏ、Ｆｅなどの金属および前記金属を１種類以上含む合金が好ましい。   Next, as shown in FIG. 1F, plating is performed so as to close the hole 21 of the first conductive layer 3 formed by etching in the previous etching step. By this plating operation, the second conductive layer 5 that is electrically connected to the first conductive layer 3 is formed. As the metal for the plating treatment, a metal having corrosion resistance to the electrolyte is used, and includes one or more kinds of metals such as Ni, Zn, Au, Pt, Cr, Al, Cd, W, Sn, Co, and Fe, and the above metals. Alloys are preferred.

めっきの手法は無電解めっき又は電解めっきを用いることが出来る。無電解めっきを行う場合には触媒としてＰｄ又はＰｄ−Ｓｎなどの触媒を用いることが出来る。めっき処理条件は、前記の第一導電性層３の孔部２１のみが埋まるように最適化した条件で行うのが好ましく、第二導電性層の表面１７と接着層の表面１６に段差が生じないようにすることが好ましい。第二導電性層５の厚さは０．１〜１０μｍ、好ましくは０．１〜５μｍである。第二導電性層５の厚さが、０．１μｍ未満であると、十分な耐食性を得ることが出来ない。１０μｍを超えると平坦性が悪化する。   As the plating method, electroless plating or electrolytic plating can be used. When electroless plating is performed, a catalyst such as Pd or Pd—Sn can be used as the catalyst. The plating conditions are preferably optimized so that only the holes 21 of the first conductive layer 3 are filled, and a step is generated between the surface 17 of the second conductive layer and the surface 16 of the adhesive layer. It is preferable not to do so. The thickness of the second conductive layer 5 is 0.1 to 10 μm, preferably 0.1 to 5 μm. If the thickness of the second conductive layer 5 is less than 0.1 μm, sufficient corrosion resistance cannot be obtained. If it exceeds 10 μm, the flatness deteriorates.

以上の製造方法で得られる色素増感型太陽電池用の透明導電性基板１は、第二導電性層５が電解質溶液に対して耐性を有し、低抵抗で透明性に優れるので色素増感型太陽電池用の透明導電性基板として好適に使用することができる。さらに透明導電性基板１の表面１１の平坦性にも優れるのでこの点も色素増感型太陽電池用の透明導電性基板として好都合である。   The transparent conductive substrate 1 for a dye-sensitized solar cell obtained by the above production method is dye-sensitized because the second conductive layer 5 is resistant to an electrolyte solution, and has low resistance and excellent transparency. It can be suitably used as a transparent conductive substrate for a solar cell. Further, since the flatness of the surface 11 of the transparent conductive substrate 1 is excellent, this point is also advantageous as a transparent conductive substrate for a dye-sensitized solar cell.

さらに図１（ｇ）に示すように、前記透明導電性基板上１にさらなる耐食性と電極の局在化防止のために、透明導電性基板上１の表面１１に導電性樹脂を含む樹脂を塗布し第三導電性層１８を形成させてもよい（図１（ｇ））。   Further, as shown in FIG. 1 (g), a resin containing a conductive resin is applied to the surface 11 of the transparent conductive substrate 1 for further corrosion resistance and prevention of electrode localization on the transparent conductive substrate 1. Then, the third conductive layer 18 may be formed (FIG. 1 (g)).

第三導電性層１８としては従来公知の導電性ポリマーを主成分とする塗液を塗布乾燥して形成することが望ましい。導電性ポリマーの種類に特に制限はないが、好ましい導電性ポリマーとしてポリチオフェン、ポリアニリン、ポリピロールおよびその誘導体、並びにそれらの混合物を挙げることが出来る。中でもポリ（３，４−ジアルコキシチオフェン）とポリ陰イオンとの複合体が透明導電性に優れており特に好ましい。導電性ポリマーの塗液に含有される溶媒又は分散媒は導電性ポリマーを溶解または分散できるものであれば特に制限はなく、水、水系溶剤、有機溶剤のいずれもが使用可能である。   The third conductive layer 18 is preferably formed by applying and drying a coating liquid containing a conventionally known conductive polymer as a main component. Although there is no restriction | limiting in particular in the kind of electrically conductive polymer, Polythiophene, polyaniline, polypyrrole, its derivative (s), and mixtures thereof can be mentioned as a preferable electrically conductive polymer. Among them, a complex of poly (3,4-dialkoxythiophene) and polyanion is particularly preferable because of its excellent transparent conductivity. The solvent or dispersion medium contained in the conductive polymer coating solution is not particularly limited as long as it can dissolve or disperse the conductive polymer, and any of water, aqueous solvents, and organic solvents can be used.

導電性ポリマーの塗布乾燥方法としては、上記の接着剤材料を有機溶剤又は水に溶解あるいは水に分散し粘度を調整したコーティング剤を作製し、グラビヤコーティング、スピンコーティングなど従来公知のコーティング法により塗布乾燥する方法を用いることができる。   As a method for applying and drying the conductive polymer, a coating agent in which the above adhesive material is dissolved in an organic solvent or water or dispersed in water to prepare a viscosity is prepared and applied by a conventionally known coating method such as gravure coating or spin coating. A drying method can be used.

水系溶剤の場合は、水と、水に混和可能な有機溶剤との混合溶剤が使用可能である。水に混和可能な有機溶剤は特に制限はないが、例えば、次の溶剤が挙げられる：メタノール、エタノール、２−プロパノール、１−プロパノール、ｎ−ブタノールなどのアルコール類；エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコールなどのエチレングリコール類；エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテルなどのグリコールエーテル類；エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテートなどのグリコールエーテルアセテート類；プロピレングリコール、ジプロピレングリコール、トリプロピレングリコールなどのプロピレングリコール類；プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、プロピレングリコールジメチルエーテル、ジプロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、ジプロピレングリコールジエチルエーテルなどのプロピレングリコールエーテル類；プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノエチルエーテルアセテートなどのプロピレングリコールエーテルアセテート類；Ｎ−メチルホルムアミド、Ｎ，Ｎ-ジメチルホルムアミド、Ｎ−メチルピロリドン、ジメチルアセトアミド、ジメチルスルホキシド、アセトン、アセトニトリルおよびそれらの混和物。   In the case of an aqueous solvent, a mixed solvent of water and an organic solvent miscible with water can be used. The organic solvent miscible with water is not particularly limited, and examples thereof include the following solvents: alcohols such as methanol, ethanol, 2-propanol, 1-propanol, n-butanol; ethylene glycol, diethylene glycol, triethylene Ethylene glycols such as glycol and tetraethylene glycol; glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and diethylene glycol dimethyl ether; ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, Glycol ethers such as diethylene glycol monobutyl ether acetate Acetates; propylene glycols such as propylene glycol, dipropylene glycol, tripropylene glycol; propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol Propylene glycol ethers such as dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether Propylene glycol ether acetates such as Tate; N- methylformamide, N, N- dimethylformamide, N- methylpyrrolidone, dimethylacetamide, dimethyl sulfoxide, acetone, acetonitrile and their blends.

溶媒又は分散媒が有機溶剤系の場合は、上記水と混和する溶剤として挙げた溶剤及び水と混和しない溶剤が挙げられ、後者としては、トルエン、キシレン（ｏ-、ｍ-、あるいはｐ-キシレン）、ベンゼン、酢酸エチル、酢酸ブチル、メチルエチルケトン、メチルイソブチルケトン、ジエチルエーテル、ジイソプロピルエーテル、メチル-t-ブチルエーテル、ヘキサン、ヘプタンなどが使用できる。なお、通常、導電性ポリマーや必要に応じて含有される添加剤が上記溶剤に完全に溶解している場合は、該溶剤は「溶媒」、何れかの成分が溶解せずに分散している場合は「分散媒」と記載される。   When the solvent or dispersion medium is an organic solvent system, the above-mentioned solvents that are miscible with water and the solvents that are immiscible with water may be mentioned. The latter includes toluene, xylene (o-, m-, or p-xylene). ), Benzene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, diethyl ether, diisopropyl ether, methyl-t-butyl ether, hexane, heptane, and the like. Normally, when the conductive polymer and the additive contained as necessary are completely dissolved in the solvent, the solvent is a “solvent” and any component is not dissolved but is dispersed. The case is described as “dispersion medium”.

本発明の第三導電性層１８が導電性ポリマーの場合、導電性を向上させる目的で導電性向上剤を含有させることができる。このような導電性向上剤としては、水に混和する有機溶剤が利用される。それには、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、トリメチレングリコール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコール、カテコール、シクロヘキサンジオール、ジエチレングリコールモノエチルエーテル、シクロヘキサンジメタノール、グリセリン、ジメチルスルホキシド、Ｎ−メチルピロリドン、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、γ−ブチロラクトン、イソホロン、プロピレンカーボネート、シクロヘキサノンなどがある。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。これらの有機溶剤は、溶媒又は分散媒を兼ねて用いられてもよい。導電性向上剤が含有される場合には、その量は特に限定されないが、通常、組成物中に９５質量％以下の割合で含有される。   When the third conductive layer 18 of the present invention is a conductive polymer, a conductivity improver can be contained for the purpose of improving the conductivity. As such a conductivity improver, an organic solvent miscible with water is used. For example, ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, catechol, cyclohexanediol, diethylene glycol monoethyl Examples include ether, cyclohexanedimethanol, glycerin, dimethyl sulfoxide, N-methylpyrrolidone, N-methylformamide, N, N-dimethylformamide, γ-butyrolactone, isophorone, propylene carbonate, and cyclohexanone. These may be used individually by 1 type and may use 2 or more types together. These organic solvents may be used also as a solvent or a dispersion medium. When the conductivity improver is contained, the amount is not particularly limited, but it is usually contained in the composition at a ratio of 95% by mass or less.

導電性ポリマー塗液は、塗膜の耐傷性や表面硬度が高くなり、電解質溶液に対する耐性が向上することから、バインダーを含むことが好ましい。
バインダーとしては、熱硬化性樹脂であってもよいし、熱可塑性樹脂であってもよい。例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステル；ポリイミド；ポリアミドイミド；ポリアミド６、ポリアミド６，６、ポリアミド１２、ポリアミド１１等のポリアミド；ポリフッ化ビニリデン、ポリフッ化ビニル、ポリテトラフルオロエチレン、エチレンテトラフルオロエチレンコポリマー、ポリクロロトリフルオロエチレン等のフッ素樹脂；ポリビニルアルコール、ポリビニルエーテル、ポリビニルブチラール、ポリ酢酸ビニル、ポリ塩化ビニル等のビニル樹脂；エポキシ樹脂；キシレン樹脂；アラミド樹脂；ポリイミドシリコーン；ポリウレタン；ポリウレア；メラミン樹脂；フェノール樹脂；ポリエーテル；アクリル樹脂及びこれらの共重合体等が挙げられる。これらバインダーは、有機溶剤に溶解されていてもよいし、スルホン酸基やカルボン酸基などの官能基が付与されて水溶液化されていてもよいし、乳化など水に分散されていてもよい。 The conductive polymer coating liquid preferably contains a binder because scratch resistance and surface hardness of the coating film are increased, and resistance to the electrolyte solution is improved.
The binder may be a thermosetting resin or a thermoplastic resin. For example, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyimides; polyamideimides; polyamides such as polyamide 6, polyamide 6,6, polyamide 12, and polyamide 11; polyvinylidene fluoride, polyvinyl fluoride, polytetrafluoroethylene Fluoropolymers such as ethylene tetrafluoroethylene copolymer and polychlorotrifluoroethylene; vinyl resins such as polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl acetate, and polyvinyl chloride; epoxy resins; xylene resins; aramid resins; Polyurea; polyurea; melamine resin; phenol resin; polyether; acrylic resin and copolymers thereof. These binders may be dissolved in an organic solvent, may be provided with a functional group such as a sulfonic acid group or a carboxylic acid group, may be formed into an aqueous solution, or may be dispersed in water such as emulsification.

バインダーの含有量は、導電性ポリマーに対して０．１〜１０００倍量であることが好ましく、１〜１００倍量であることがより好ましい。バインダーの含有量が前記下限値未満であると、得られる導電性塗膜の膜強度が低くなる傾向にあり、前記上限値を超えると、導電性ポリマー濃度の低下に起因する導電性の低下が起こることがある。   The content of the binder is preferably 0.1 to 1000 times, more preferably 1 to 100 times the amount of the conductive polymer. When the content of the binder is less than the lower limit, the film strength of the resulting conductive coating film tends to be low. When the content exceeds the upper limit, there is a decrease in conductivity due to a decrease in the conductive polymer concentration. May happen.

第三導電性層１８の厚みは好ましくは、０．１〜１０μｍ、さらに好ましくは０．２〜３．５μｍである。０．１μｍ未満であると、耐ヨウ素性が低下する。１０μｍを超えると透明性が劣化する。   The thickness of the third conductive layer 18 is preferably 0.1 to 10 μm, more preferably 0.2 to 3.5 μm. When it is less than 0.1 μm, iodine resistance is lowered. If it exceeds 10 μm, the transparency deteriorates.

以上の製造方法で得られる透明導電性基板２２は、第三導電性層１８が電解質溶液に対して耐性を有し、低抵抗で透明性に優れるので色素増感型太陽電池用の透明導電性基板として好適に使用することができる。   The transparent conductive substrate 22 obtained by the above manufacturing method is transparent for a dye-sensitized solar cell because the third conductive layer 18 is resistant to an electrolyte solution, and has low resistance and excellent transparency. It can be suitably used as a substrate.

作成した透明導電性基板の電気抵抗の測定は、ＪＩＳ−Ｋ−７１９４に準拠した形で、ロレスタ−ＧＰ（株式会社ダイアインスツルメンツ製、型番：ＭＣＰ−Ｔ６１０）において直列４探針プローブ（ＡＳＰ）を用いて４端子４探針法で実施した。   The measurement of the electrical resistance of the transparent conductive substrate was measured in accordance with JIS-K-7194 using a series 4-probe probe (ASP) in Loresta-GP (manufactured by Dia Instruments, model number: MCP-T610). The four-terminal four-probe method was used.

光学的透過率は全光線透過率として評価した。前記透明導電性基板をヘイズメーター（型番：ＮＤＨ−２０００、日本電飾工業株式会社製）を用いてＪＩＳ Ｋ−７１０５に準拠して測定した。   The optical transmittance was evaluated as the total light transmittance. The transparent conductive substrate was measured according to JIS K-7105 using a haze meter (model number: NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.).

評価に利用したヨウ素電解質溶液は市販されている色素増感型太陽電池製作キットの内容物を用いた（西野田電工株式会社製）。作製した透明導電性基板の上に前記ヨウ素電解質溶液を塗布し、そのまま、室温下２４時間暗所で静置した。前記ヨウ素電解質溶液を純水及びエタノールで洗浄した後、乾燥し、表面抵抗値を透明導電性基板作製後と耐ヨウ素性試験後で比較した。   The iodine electrolyte solution used for evaluation was the content of a commercially available dye-sensitized solar cell production kit (manufactured by Nishinoda Electric Co., Ltd.). The iodine electrolyte solution was applied onto the produced transparent conductive substrate, and allowed to stand in the dark at room temperature for 24 hours. The iodine electrolyte solution was washed with pure water and ethanol and then dried, and the surface resistance value was compared after the transparent conductive substrate was produced and after the iodine resistance test.

実施例１
＜銀微粒子１の調製法＞
金属微粒子の例として銀微粒子の液相還元調製法を説明するが、金属微粒子の種類や製造法を限定するものではない。
硝酸銀４０ｇ、ブチルアミン３７．９ｇ、メタノール２００ｍＬを加え、１時間攪拌しＡ液を調製した。別にイソアスコルビン酸６２．２ｇを取り、水４００ｍＬを加え攪拌して溶解し、続いてメタノール２００ｍＬを加えＢ液を調製した。Ｂ液をよく攪拌しＡ液をＢ液に１時間２０分かけて滴下した。滴下終了後、３時間３０分攪拌を継続した。
攪拌終了後、３０分間静置し固形物を沈降させた。上澄みをデカンテーションにより取り除いた後、新たに水５００ｍＬを加え、攪拌、静置、デカンテーションにより上澄み液を取り除いた。この精製操作を３回繰り返した。沈降した固形物を４０℃の乾燥機中で乾燥し、水分を除去した。さらに、得られた銀微粒子２０ｇとＤＩＳＰＥＲＢＹＫ−１０６（ビックケミージャパン社製）０．２ｇをメタノール１００ｍＬと純水５ｍＬとの混合溶液中に混合し、１時間混合した後に、純水１００ｍＬを加えて、スラリーをろ過した後、４０℃の乾燥機中で乾燥させて、銀微粒子１を得た。銀微粒子は電子顕微鏡による観察から一次粒子の平均粒子径が６０ｎｍであった。 Example 1
<Preparation method of silver fine particles 1>
The liquid phase reduction preparation method for silver fine particles will be described as an example of the metal fine particles, but the kind of metal fine particles and the production method are not limited.
40 g of silver nitrate, 37.9 g of butylamine, and 200 mL of methanol were added and stirred for 1 hour to prepare solution A. Separately, 62.2 g of isoascorbic acid was taken, 400 mL of water was added and dissolved by stirring, and then 200 mL of methanol was added to prepare solution B. B liquid was stirred well and A liquid was dripped at B liquid over 1 hour and 20 minutes. After completion of the dropwise addition, stirring was continued for 3 hours and 30 minutes.
After completion of stirring, the mixture was allowed to stand for 30 minutes to precipitate the solid. After removing the supernatant by decantation, 500 mL of water was newly added, and the supernatant was removed by stirring, standing, and decantation. This purification operation was repeated three times. The settled solid was dried in a dryer at 40 ° C. to remove moisture. Furthermore, 20 g of the obtained silver fine particles and 0.2 g of DISPERBYK-106 (manufactured by Big Chemie Japan) were mixed in a mixed solution of 100 mL of methanol and 5 mL of pure water, mixed for 1 hour, and then 100 mL of pure water was added. After filtering the slurry, the slurry was dried in a dryer at 40 ° C. to obtain silver fine particles 1. Silver fine particles had an average primary particle diameter of 60 nm as observed with an electron microscope.

＜銀微粒子分散溶液２の調製＞
銀微粒子の分散溶液の調製は、特許文献４を参考に行った（特表２００５−５３０００５号公報を参考に調製）。
すなわち、前記銀微粒子１を４ｇ、トルエン３０ｇ、ＢＹＫ−４１０（ビックケミージャパン社製）０．２ｇを混合し、出力１８０Ｗの超音波分散機で１．５分間分散化処理を行い、純水１５ｇを添加し、得られた乳濁液を出力１８０Ｗの超音波分散機で３０秒間分散処理を行い、銀微粒子分散溶液２を調製した。 <Preparation of silver fine particle dispersion 2>
The dispersion of silver fine particles was prepared with reference to Patent Document 4 (prepared with reference to JP 2005-530005 A).
That is, 4 g of the silver fine particles 1, 30 g of toluene, and 0.2 g of BYK-410 (manufactured by Big Chemie Japan) were mixed, and subjected to a dispersion treatment for 1.5 minutes with an ultrasonic disperser with an output of 180 W to obtain 15 g of pure water. Was added, and the obtained emulsion was subjected to a dispersion treatment for 30 seconds with an ultrasonic disperser with an output of 180 W to prepare a silver fine particle dispersion solution 2.

＜第一導電性層の形成法＞
厚み１００μｍのポリエチレンテレフタレート基材上に前記銀微粒子分散溶液２を、バーコーターを用いてコーティングした。続いて、大気中で自然乾燥させることで、銀微粒子が自己組織化現象により網目状構造を形成した。次に、１５０℃で２分間加熱した後、アセトン及び１Ｎ塩酸にそれぞれ浸漬した後、１５０℃で５分間加熱乾燥させ、第一導電性層を形成した。第一導電性層を基材上に形成した後の全光線透過率は８５％、表面抵抗値は４．５Ω／□であった。 <Method for forming first conductive layer>
The silver fine particle dispersion 2 was coated on a polyethylene terephthalate substrate having a thickness of 100 μm using a bar coater. Subsequently, by spontaneous drying in the air, the silver fine particles formed a network structure by the self-organization phenomenon. Next, after heating at 150 ° C. for 2 minutes, each was immersed in acetone and 1N hydrochloric acid, and then heated and dried at 150 ° C. for 5 minutes to form a first conductive layer. After the first conductive layer was formed on the substrate, the total light transmittance was 85%, and the surface resistance value was 4.5Ω / □.

＜接着層の形成＞
第一導電性層が形成された基材の第一導電性層表面側に下記の接着層コーティング液１を乾燥後の厚みが５.１μｍ（実施例１）、６．０μｍ（実施例２）、６．５μｍ（実施例３）となるよう塗布し、１００℃の温度で５分乾燥させて接着層を形成した。 <Formation of adhesive layer>
The thickness after drying the following adhesive layer coating solution 1 on the first conductive layer surface side of the substrate on which the first conductive layer is formed is 5.1 μm (Example 1), 6.0 μm (Example 2). , 6.5 μm (Example 3), and dried at a temperature of 100 ° C. for 5 minutes to form an adhesive layer.

＜接着層コーティング液１＞
アクリル樹脂(三菱レイヨン製、ダイヤナールＢＲ８３)８．５ｇ＋ポリエステル樹脂(東洋紡製、バイロン２００）１．５ｇ＋トルエン７５ｇ＋メチルエチルケトン１５ｇを加えて攪拌し、接着層コーティング液１を作製した。 <Adhesive layer coating solution 1>
An adhesive resin coating solution 1 was prepared by adding 8.5 g of an acrylic resin (manufactured by Mitsubishi Rayon, Dianar BR83) +1.5 g of a polyester resin (byron 200, Byron 200) +75 g of toluene + 15 g of methyl ethyl ketone and stirring.

＜熱転写＞
厚み１２５μｍのポリエチレンテレフタレート基板表面に、第一導電性層と接着層が形成された厚み１００μｍのポリエチレンテレフタレート基材の接着層が形成された表面を対向させ、ホットラミネーター（大成ラミネーター製、大成ファーストラミネーターＶＡＩＩ−７００）を用いて１８０℃で熱圧接し、室温に下がるまで放置した後、ポリエチレンテレフタレート基材を剥離して第一導電性層及び接着層をポリエチレンテレフタレート基板上に熱転写した。 <Thermal transfer>
A hot laminator (manufactured by Taisei Laminator, Taisei First Laminator) is made to face the surface of the polyethylene terephthalate substrate having a thickness of 100 μm on which the surface of the 125 μm thick polyethylene terephthalate substrate is formed and the first conductive layer and the adhesive layer are formed. VAII-700) was used for heat pressure welding at 180 ° C. and left to cool to room temperature, and then the polyethylene terephthalate substrate was peeled off, and the first conductive layer and the adhesive layer were thermally transferred onto the polyethylene terephthalate substrate.

＜第二導電層の形成＞
エッチング溶液として硝酸第二鉄１０ｗｔ％−硝酸１４ｗｔ％の混合水溶液を調製した。前記転写操作により作製した透明導電性基板を、該エッチング溶液中に浸漬させて、基板表面から０．８μｍ（実施例１）、１．０μｍ（実施例２）、１．５μｍ（実施例３）の深さでエッチングできる条件下、エッチング処理を行なった。
続いてＮｉ−Ｚｎ無電解めっき溶液を調製し、０．８μｍ（実施例１）、１．０μｍ（実施例２）、１．５μｍ（実施例３）の膜厚になる条件下でめっき処理を行ない、エッチング孔にＮｉ−Ｚｎの第二導電性層を形成させた。
作製した透明導電性基板の表面抵抗値は０．０８Ω／□（実施例１）、０．０８Ω／□（実施例２）、０．０５Ω／□（実施例３）、全光線透過率は８５％（実施例１〜３）であった。 <Formation of second conductive layer>
A mixed aqueous solution of 10 wt% ferric nitrate-14 wt% nitric acid was prepared as an etching solution. The transparent conductive substrate produced by the transfer operation is immersed in the etching solution, and 0.8 μm (Example 1), 1.0 μm (Example 2), and 1.5 μm (Example 3) from the substrate surface. The etching process was performed under the condition that etching can be performed at a depth of 5 mm.
Subsequently, a Ni—Zn electroless plating solution was prepared, and the plating treatment was performed under conditions of film thicknesses of 0.8 μm (Example 1), 1.0 μm (Example 2), and 1.5 μm (Example 3). Then, a second conductive layer of Ni—Zn was formed in the etching hole.
The produced transparent conductive substrate has a surface resistance of 0.08Ω / □ (Example 1), 0.08Ω / □ (Example 2), 0.05Ω / □ (Example 3), and a total light transmittance of 85. % (Examples 1 to 3).

＜耐ヨウ素性の評価結果＞
耐ヨウ素性の評価結果を表１に示す。実施例１〜３および比較例１〜２で作製した透明導電性基板は耐ヨウ素性を有していた。一方、比較例２の透明導電性基板はめっき膜が薄いため十分な耐ヨウ素性を有していなかった。 <Iodine resistance evaluation results>
The evaluation results of iodine resistance are shown in Table 1. The transparent conductive substrates prepared in Examples 1 to 3 and Comparative Examples 1 and 2 had iodine resistance. On the other hand, the transparent conductive substrate of Comparative Example 2 did not have sufficient iodine resistance because the plating film was thin.

Figure 2010182648
Figure 2010182648

比較例１
実施例１の方法でポリエチレンテレフタレート基板上に第一導電性層を形成させた。続いて、Ｎｉ−Ｚｎ無電解めっき溶液を調製し、１．５μｍの膜厚になる条件下でめっき処理を行ない、第二導電性層を形成させた。
作製した透明導電性基板の表面抵抗値は０．０５Ω／□、全光線透過率は６５％であり、めっき処理により表面抵抗値は下がったが、網目状構造における導電性部の幅が広がり、全光線透過率が低下してしまった。 Comparative Example 1
The first conductive layer was formed on the polyethylene terephthalate substrate by the method of Example 1. Subsequently, a Ni—Zn electroless plating solution was prepared, and a plating process was performed under the condition of a film thickness of 1.5 μm to form a second conductive layer.
The surface resistance value of the produced transparent conductive substrate was 0.05Ω / □, the total light transmittance was 65%, and the surface resistance value was lowered by the plating treatment, but the width of the conductive portion in the network structure was widened. The total light transmittance has decreased.

比較例２
実施例１の方法でポリエチレンテレフタレート基板上に第一導電性層を形成させた。続いて、Ｎｉ−Ｚｎ無電解めっき溶液を調製し、０．０５μｍの膜厚になる条件下でめっき処理を行ない、第二導電性層を形成させた。
作製した透明導電性基板の耐ヨウ素性試験を行ったところ、導電性部がヨウ素電解質溶液に溶解してしまい、表面抵抗値は測定できなくなった。 Comparative Example 2
The first conductive layer was formed on the polyethylene terephthalate substrate by the method of Example 1. Subsequently, a Ni—Zn electroless plating solution was prepared, and a plating process was performed under the condition of a film thickness of 0.05 μm to form a second conductive layer.
When the iodine resistance test of the produced transparent conductive substrate was performed, the conductive portion was dissolved in the iodine electrolyte solution, and the surface resistance value could not be measured.

本発明に係る透明導電性基板は、色素増感型太陽電池用電極基板に限らず、タッチパネル用導電性フィルム、電磁波シールドフィルムなどの耐食性、耐候性が要求される透明導電性基板にも応用することが出来る。また耐食性等が特に要求されない透明導電性基板であっても、本発明に係る透明導電性基板は、低抵抗でかつ高透過性を有しさらには基板上面の平坦性にも優れるので、透明導電性基板として好適に使用することができる。   The transparent conductive substrate according to the present invention is not limited to a dye-sensitized solar cell electrode substrate, but is also applied to a transparent conductive substrate requiring corrosion resistance and weather resistance, such as a conductive film for a touch panel and an electromagnetic shielding film. I can do it. Further, even if the transparent conductive substrate is not particularly required to have corrosion resistance or the like, the transparent conductive substrate according to the present invention has a low resistance and a high transmittance and also has an excellent flatness on the upper surface of the substrate. It can be suitably used as a conductive substrate.

１ 透明導電性基板
２ 基材
３ 第一導電性層
５ 第二導電性層
７ 接着層
８ 被転写基板
１０ 転写層
１１ 透明導電性基板の表面
１２ 開口部
１４ 転写層の表面
１５ 熱転写後の第一導電性層の表面
１６ 熱転写後の接着層の表面
１７ 第二導電性層の表面
１８ 第三導電性層
２１ 孔部 DESCRIPTION OF SYMBOLS 1 Transparent conductive substrate 2 Base material 3 1st conductive layer 5 2nd conductive layer 7 Adhesive layer 8 Transferred substrate 10 Transfer layer 11 Surface of transparent conductive substrate 12 Opening 14 Surface of transfer layer 15 1st after heat transfer Surface of one conductive layer 16 Surface of adhesive layer after thermal transfer 17 Surface of second conductive layer 18 Third conductive layer 21 Hole

Claims (12)

透明導電性基板の製造方法において、下記の１から５の製造工程にて製造することを特徴とする透明導電性基板の製造方法。
１、金属微粒子分散溶液を基材上に塗布し乾燥させ、網目状の第一導電性層を基材上に形成させる第一導電性層形成工程
２、前記第一導電性層を完全に覆う透明性の接着層を積層する接着層積層工程
３、前記接着層面と被転写基板とを貼り合せ、加熱加圧した後、基材を剥離し、第一導電性層と接着層が一体となった転写層を被転写基板に熱転写させる熱転写工程
４、熱転写された第一導電性層の表面をエッチングするエッチング工程
５、エッチングで形成された孔部にめっきを施し第二導電性層を積層する第二導電性層形成工程 In the manufacturing method of a transparent conductive substrate, it manufactures in the manufacturing process of the following 1 to 5, The manufacturing method of the transparent conductive substrate characterized by the above-mentioned.
1. A metal fine particle dispersion solution is applied on a substrate and dried, and a first conductive layer forming step 2 for forming a network-like first conductive layer on the substrate. The first conductive layer is completely covered. Adhesive layer laminating step 3 for laminating a transparent adhesive layer, the adhesive layer surface and the substrate to be transferred are bonded together, heated and pressed, then the substrate is peeled off, and the first conductive layer and the adhesive layer are integrated. A thermal transfer process 4 for thermally transferring the transferred layer to the substrate to be transferred, an etching process 5 for etching the surface of the thermally transferred first conductive layer, and plating the holes formed by etching to laminate a second conductive layer. Second conductive layer formation process 透明導電性基板の製造方法において、下記の１から５の製造工程にて製造することを特徴とする透明導電性基板の製造方法。
１、金属微粒子分散溶液を基材上に塗布し乾燥させ、網目状の第一導電性層を基材上に形成させる第一導電性層形成工程
２、被転写基板に透明性の接着層を積層する接着層積層工程
３、前記第一導電性層面と被転写基板とを貼り合せ、加熱加圧した後、基材を剥離し、第一導電性層と接着層が一体となった転写層を被転写基板に熱転写させる熱転写工程
４、熱転写された第一導電性層の表面をエッチングするエッチング工程
５、エッチングで形成された孔部にめっきを施し第二導電性層を積層する第二導電性層形成工程 In the manufacturing method of a transparent conductive substrate, it manufactures in the manufacturing process of the following 1 to 5, The manufacturing method of the transparent conductive substrate characterized by the above-mentioned.
1. A metal fine particle dispersion solution is applied on a substrate and dried to form a first conductive layer having a mesh shape on the substrate. 2. A transparent adhesive layer is formed on the substrate to be transferred. Laminating adhesive layer laminating step 3, the first conductive layer surface and the substrate to be transferred are bonded, heated and pressed, then the substrate is peeled off, and the transfer layer in which the first conductive layer and the adhesive layer are integrated Is transferred to the substrate to be transferred, thermal transfer step 4 for etching, etching step 5 for etching the surface of the thermally transferred first conductive layer, and second conductive layer for plating the hole formed by etching and laminating the second conductive layer. Layer formation process 前記第一導電性層形成工程が、金属微粒子ペーストを基材上に印刷し乾燥させ、網目状の第一導電性層を基材上に形成させる第一導電性層形成工程であることを特徴とする請求項１又２に記載の透明導電性基板の製造方法。   The first conductive layer forming step is a first conductive layer forming step in which a metal fine particle paste is printed on a substrate and dried to form a network-like first conductive layer on the substrate. A method for producing a transparent conductive substrate according to claim 1 or 2. 前記第一導電性層形成工程が、金属微粒子の前駆体である金属塩の溶液を、基材に塗布し乾燥させた後、金属微粒子の前駆体を加熱又は紫外線照射又は還元性ガスにより還元析出させ、網目状の第一導電性層を基材上に形成させる第一導電性層形成工程であることを特徴とする請求項１又２に記載の透明導電性基板の製造方法。   In the first conductive layer forming step, a solution of a metal salt, which is a precursor of metal fine particles, is applied to a substrate and dried, and then the metal fine particle precursor is reduced or precipitated by heating, ultraviolet irradiation or a reducing gas. 3. The method for producing a transparent conductive substrate according to claim 1, wherein the method is a first conductive layer forming step of forming a network-like first conductive layer on a base material. 前記第一導電性層形成工程と、前記接着層積層工程との間に、前記第一導電性層に加熱処理及び／又は化学処理を行う工程を備えることを特徴とする請求項１から４のいずれか１項に記載の透明導電性基板の製造方法。   5. The method according to claim 1, further comprising a step of performing heat treatment and / or chemical treatment on the first conductive layer between the first conductive layer forming step and the adhesive layer laminating step. The manufacturing method of the transparent conductive substrate of any one of Claims 1. 前記基材に前記金属微粒子分散溶液、前記金属微粒子ペースト又は前記金属塩の溶液を塗布するに先立ち、前記基材に表面処理を施すことを特徴とする請求項１から５のいずれか１項に記載の透明導電性基板の製造方法。   The surface treatment is applied to the base material before applying the metal fine particle dispersion solution, the metal fine particle paste, or the metal salt solution to the base material. The manufacturing method of the transparent conductive substrate of description. 前記接着層の厚みは、前記第一導電性層の高さよりも高く、前記被転写基板に前記第一導電性層は接触しないことを特徴とする請求項１から６のいずれか１項に記載の透明導電性基板の製造方法。   The thickness of the adhesive layer is higher than the height of the first conductive layer, and the first conductive layer is not in contact with the substrate to be transferred. Manufacturing method of transparent conductive substrate. 請求項１から７のいずれか１項に記載の透明導電性基板の製造方法により得られる透明導電性基板の表面に、さらに第三導電性層を積層する第三導電性層形成工程を備えることを特徴とする請求項１から７のいずれか１項に記載の透明導電性基板の製造方法。   A third conductive layer forming step of further laminating a third conductive layer on the surface of the transparent conductive substrate obtained by the method for producing a transparent conductive substrate according to claim 1. The manufacturing method of the transparent conductive substrate of any one of Claim 1 to 7 characterized by these. 請求項１から８のいずれか１項に記載の透明導電性基板の製造方法により得られる透明導電性基板。   The transparent conductive substrate obtained by the manufacturing method of the transparent conductive substrate of any one of Claim 1 to 8. 前記第一導電性層と前記接着層の最大段差が３００ｎｍ以下であり、表面の表面抵抗値が５Ω／□以下であることを特徴とする請求項９に記載の透明導電性基板。   The transparent conductive substrate according to claim 9, wherein a maximum step between the first conductive layer and the adhesive layer is 300 nm or less, and a surface resistance value of the surface is 5Ω / □ or less. 前記接着層がアクリル系接着剤、ポリエステル系接着剤からなる群より選ばれる少なくとも１種の接着剤を含有することを特徴とする請求項９又は１０に記載の透明導電性基板。   The transparent conductive substrate according to claim 9 or 10, wherein the adhesive layer contains at least one adhesive selected from the group consisting of an acrylic adhesive and a polyester adhesive. 請求項９から１１のいずれか１項に記載の透明導電性基板であって、前記第二導電性層及び前記第三導電性層が電解質溶液に対して耐性を有することを特徴とする色素増感型太陽電池用透明導電性基板。   The transparent conductive substrate according to any one of claims 9 to 11, wherein the second conductive layer and the third conductive layer are resistant to an electrolyte solution. Transparent conductive substrate for sensitive solar cells.
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