JP2002069335A - Coating liquid for forming transparent electroconductive layer - Google Patents

Coating liquid for forming transparent electroconductive layer

Info

Publication number
JP2002069335A
JP2002069335A JP2000256504A JP2000256504A JP2002069335A JP 2002069335 A JP2002069335 A JP 2002069335A JP 2000256504 A JP2000256504 A JP 2000256504A JP 2000256504 A JP2000256504 A JP 2000256504A JP 2002069335 A JP2002069335 A JP 2002069335A
Authority
JP
Japan
Prior art keywords
fine particles
gold
transparent conductive
transparent
noble metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2000256504A
Other languages
Japanese (ja)
Inventor
Kenichi Fujita
賢一 藤田
Junji Tofuku
淳司 東福
Masaya Yukinobu
雅也 行延
Kenji Kato
賢二 加藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Metal Mining Co Ltd
Original Assignee
Sumitomo Metal Mining Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Metal Mining Co Ltd filed Critical Sumitomo Metal Mining Co Ltd
Priority to JP2000256504A priority Critical patent/JP2002069335A/en
Publication of JP2002069335A publication Critical patent/JP2002069335A/en
Pending legal-status Critical Current

Links

Abstract

PROBLEM TO BE SOLVED: To provide a coating liquid for forming transparent electroconductive layer, containing noble metal-coated silver microparticles, prevented from microparticle flocculation as a cause of film defects even if preserved for a long period, and capable of producing transparent electroconductive bases having various characteristics including good electroconductivity, low reflectance and weatherability and chemical resistance. SOLUTION: This coating liquid for forming transparent electroconductive layer is characterized by consisting mainly of a polymeric resin, a solvent and noble metal-coated silver microparticles 1-100 nm in average size coated with gold or platinum simple substance or gold-platinum composite and containing 5-95 wt.% of gold and/or platinum; wherein the polymeric resin is e.g. polyvinyl alcohol, polyvinyl butyral, and the weight ratio of the noble metal-coated silver microparticles to the polymeric resin is 5-500.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、透明基板とこの上
に順次形成された透明導電層と透明コート層とで構成さ
れる透明２層膜を備え、例えば、ブラウン管（ＣＲＴ）
等表示装置の前面板等に利用される透明導電性基材の透
明導電層形成用塗液に係り、特に、良好な導電性、低反
射率並びに耐候性、耐薬品性等の諸特性を有する透明導
電性基材の製造を可能とし、かつ、保存安定性にも優れ
た透明導電層形成用塗液の改良に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention includes a transparent two-layer film composed of a transparent substrate, a transparent conductive layer and a transparent coat layer sequentially formed thereon, and includes, for example, a cathode ray tube (CRT).
The present invention relates to a coating liquid for forming a transparent conductive layer of a transparent conductive substrate used for a front plate of a display device, etc., and particularly has various properties such as good conductivity, low reflectance, weather resistance, and chemical resistance. The present invention relates to an improvement in a coating liquid for forming a transparent conductive layer, which enables production of a transparent conductive substrate and has excellent storage stability.

【０００２】[0002]

【従来の技術】近年のオフィスオートメーション（Ｏ
Ａ）化によりオフィスに多くのＯＡ機器が導入され、Ｏ
Ａ機器のディスプレイと向き合って終日作業を行わねば
ならないという環境が最近珍しくない。2. Description of the Related Art Recent office automation (O)
A) With the introduction of many OA equipment in the office,
In recent years, it is not unusual for an environment in which the user has to work all day facing the display of the device A.

【０００３】ところで、ＯＡ機器の一例としてコンピュ
ータの陰極線管（上記ブラウン管とも称する：ＣＲＴ）
等に接して仕事を行う場合、表示画面が見やすく、視覚
疲労を感じさせないことの外に、ＣＲＴ表面の帯電によ
るほこりの付着や電撃ショックがないこと等が要求され
ている。更に、これ等に加えて最近ではＣＲＴから発生
する低周波電磁波の人体に対する悪影響が懸念され、こ
のような電磁波が外部に漏洩しないことがＣＲＴに対し
て望まれている。As an example of an OA device, a cathode ray tube (CRT) of a computer is used as a computer.
When performing work in contact with, for example, it is required that the display screen is easy to see and does not cause visual fatigue, and that there is no adhesion of dust or electric shock due to electrification of the CRT surface. Further, in addition to these, recently, there is a concern that a low-frequency electromagnetic wave generated from the CRT may adversely affect the human body, and it is desired for the CRT not to leak such an electromagnetic wave to the outside.

【０００４】そして、上記電磁波は偏向コイルやフライ
バックトランスから発生し、テレビジョンの大型化に伴
って益々大量の電磁波が周囲に漏洩する傾向にある。[0004] The electromagnetic waves are generated from deflection coils and flyback transformers, and a larger amount of electromagnetic waves tends to leak to the surroundings as the television becomes larger.

【０００５】ところで、磁界の漏洩は偏向コイルの形状
を変える等の工夫で大部分を防止することができる。一
方、電界の漏洩もＣＲＴの前面ガラス表面に透明導電層
を形成することにより防止することが可能である。The leakage of the magnetic field can be largely prevented by changing the shape of the deflection coil. On the other hand, electric field leakage can be prevented by forming a transparent conductive layer on the front glass surface of the CRT.

【０００６】このような電界の漏洩に対する防止方法
は、近年、帯電防止のために採られてきた対策と原理的
には同一である。しかし、上記透明導電層は、帯電防止
用に形成されていた導電層よりもはるかに高い導電性が
求められている。すなわち、帯電防止用には表面抵抗で
１０8Ω／□程度で十分とされているが、漏洩電界を防
ぐ（電界シールド）ためには、少なくとも１０6Ω／□
以下、好ましくは５×１０3Ω／□以下、さらに好まし
くは１０3Ω／□以下である低抵抗の透明導電層を形成
する必要がある。The method for preventing such leakage of the electric field is in principle the same as the countermeasure that has been taken recently for preventing static charge. However, the transparent conductive layer is required to have much higher conductivity than the conductive layer formed for antistatic. That is, a surface resistance of about 10 8 Ω / □ is sufficient for antistatic, but at least 10 6 Ω / □ for preventing a leakage electric field (electric field shield).
It is necessary to form a low-resistance transparent conductive layer having a resistivity of preferably 5 × 10 3 Ω / □ or less, more preferably 10 3 Ω / □ or less.

【０００７】そこで、上記要求に対処するため、従来よ
りいくつかの提案がなされているが、その中でも低コス
トでかつ低い表面抵抗を実現できる方法として、導電性
微粒子をアルキルシリケート等の無機バインダーと共に
溶媒中に分散した透明導電層形成用塗液をＣＲＴの前面
ガラスに塗布・乾燥後、２００℃程度の温度で焼成する
方法が知られている。Therefore, several proposals have been made in the past to address the above-mentioned demands. Among them, as a method of realizing low cost and low surface resistance, conductive fine particles are combined with an inorganic binder such as alkyl silicate. A method is known in which a coating liquid for forming a transparent conductive layer dispersed in a solvent is applied to the front glass of a CRT, dried, and then fired at a temperature of about 200 ° C.

【０００８】そして、この透明導電層形成用塗液を用い
た方法は、真空蒸着やスパッタ法等他の透明導電層の形
成方法に比べてはるかに簡便であり、製造コストも低
く、ＣＲＴに処理可能な電界シールドとして極めて有利
な方法である。The method using the coating liquid for forming a transparent conductive layer is much simpler than other methods for forming a transparent conductive layer such as vacuum vapor deposition and sputtering, the production cost is low, and the process on a CRT is performed. This is a very advantageous method as a possible electric field shield.

【０００９】この方法に用いられる上記透明導電層形成
用塗液として、導電性微粒子にインジウム錫酸化物（Ｉ
ＴＯ）を適用したものが知られている。しかし、得られ
る膜の表面抵抗が１０4〜１０6Ω／□と高いため、漏洩
電界を十分に遮蔽するには電界キャンセル用の補正回路
が必要となることから、その分、製造コストが割高とな
る問題があった。一方、上記導電性微粒子に金属粉を用
いた透明導電層形成用塗液では、ＩＴＯを用いた塗液に
比べ、若干、膜の透過率が低くなるものの、１０2〜１
０3Ω／□という低抵抗膜が得られる。従って、上述し
た補正回路が必要なくなるためコスト的に有利となり、
今後主流になると思われる。As the coating liquid for forming a transparent conductive layer used in this method, indium tin oxide (I
One to which TO) is applied is known. However, since the surface resistance of the obtained film is as high as 10 4 to 10 6 Ω / □, a correction circuit for canceling the electric field is required to sufficiently shield the leakage electric field, so that the manufacturing cost is correspondingly high. There was a problem. On the other hand, in the transparent conductive layer forming coating liquid using a metal powder to the conductive fine particles, compared to a coating liquid using ITO, somewhat, although the transmittance of the film is low, 10 2-1
A low resistance film of 0 3 Ω / □ is obtained. Therefore, the above-described correction circuit becomes unnecessary, which is advantageous in terms of cost,
It is expected to become mainstream in the future.

【００１０】そして、上記透明導電層形成用塗液に適用
される金属微粒子としては、特開平８−７７８３２号公
報や特開平９−５５１７５号公報等に示されるように空
気中で酸化され難い、銀、金、白金、ロジウム、パラジ
ウム等の貴金属に限られている。これは、貴金属以外の
金属微粒子、例えば、鉄、ニッケル、コバルト等が適用
された場合、大気雰囲気下でこれ等金属微粒子の表面に
酸化物皮膜が必ず形成されてしまい透明導電層として良
好な導電性が得られなくなるからである。[0010] The metal fine particles applied to the transparent conductive layer forming coating liquid are hardly oxidized in the air as disclosed in JP-A-8-77832 and JP-A-9-55175. It is limited to noble metals such as silver, gold, platinum, rhodium and palladium. This is because when a metal fine particle other than a noble metal, for example, iron, nickel, cobalt or the like is applied, an oxide film is necessarily formed on the surface of the metal fine particle under an air atmosphere, and a good conductive property as a transparent conductive layer is obtained. This is because the property cannot be obtained.

【００１１】また、一方では表示画面を見易くするため
に、フェイスパネル表面に防眩処理を施して画面の反射
を抑えることも行われている。この防眩処理は、微細な
凹凸を設けて表面の拡散反射を増加させる方法によって
もなされるが、この方法を用いた場合、解像度が低下し
て画質が落ちるためあまり好ましい方法とはいえない。
従って、むしろ反射光が入射光に対して破壊的干渉を生
ずるように、透明皮膜の屈折率と膜厚とを制御する干渉
法によって防眩処理を行うことが好ましい。このような
干渉法により低反射効果を得るため、一般的には高屈折
率膜と低屈折率膜の光学的膜厚をそれぞれ１／４λと１
／４λ、あるいは１／２λと１／４λに設定した二層構
造膜が採用されており、前述のインジウム錫酸化物（Ｉ
ＴＯ）微粒子からなる膜もこの種の高屈折率膜として用
いられている。On the other hand, in order to make the display screen easier to see, a reflection of the screen is suppressed by performing an anti-glare treatment on the face panel surface. This antiglare treatment is also performed by a method of increasing the diffuse reflection of the surface by providing fine irregularities, but this method is not a very preferable method because the resolution is reduced and the image quality is reduced.
Therefore, it is preferable to perform the anti-glare treatment by an interference method that controls the refractive index and the film thickness of the transparent film so that the reflected light causes destructive interference with the incident light. In order to obtain a low reflection effect by such an interference method, generally, the optical thicknesses of the high refractive index film and the low refractive index film are set to 1 / 4λ and 1 respectively.
/ 4λ, or a two-layer structure film set to λλ and １ ／ λ is adopted, and the indium tin oxide (I
A film made of (TO) fine particles is also used as this kind of high refractive index film.

【００１２】尚、金属においては、光学定数（ｎ−ｉ
ｋ，ｎ：屈折率，ｉ2＝−１，ｋ：消衰係数）のうち、
ｎの値は小さいがｋの値がＩＴＯ等と比べ極端に大きい
ため、金属微粒子からなる透明導電層を用いた場合で
も、ＩＴＯ（高屈折率膜）と同様に、二層構造膜で光の
干渉による反射防止効果が得られる。In the case of metal, the optical constant (ni)
k, n: refractive index, i 2 = -1, k: extinction coefficient)
Although the value of n is small, but the value of k is extremely large as compared with ITO or the like, even when a transparent conductive layer made of metal fine particles is used, like a ITO (high-refractive-index film), light of a two-layer structure film is used. An anti-reflection effect due to interference is obtained.

【００１３】ところで、従来の透明導電層形成用塗液に
適用される金属微粒子としては、上述したように銀、
金、白金、ロジウム、パラジウム等の貴金属に限定され
ているが、これ等の比抵抗を比較した場合、白金、ロジ
ウム、パラジウムの比抵抗は、それぞれ１０．６、５．
１、１０．８μΩ・ｃｍで、銀、金の１．６２、２．２
μΩ・ｃｍに比べて高いため、表面抵抗の低い透明導電
層を形成するには銀微粒子や金微粒子を適用した方が有
利であった。As the metal fine particles applied to the conventional coating liquid for forming a transparent conductive layer, as described above, silver,
It is limited to noble metals such as gold, platinum, rhodium and palladium, but when these specific resistances are compared, the specific resistances of platinum, rhodium and palladium are 10.6 and 5.
1, 10.8 μΩcm, 1.62 of silver and gold, 2.2
Since it is higher than μΩ · cm, it is more advantageous to use silver fine particles or gold fine particles to form a transparent conductive layer having a low surface resistance.

【００１４】しかし、銀微粒子を適用した場合、硫化、
酸化や食塩水、紫外線等による劣化が激しく耐候性に問
題があり、他方、金微粒子を適用した場合、上記耐候性
の問題はなくなるが白金微粒子、ロジウム微粒子、パラ
ジウム微粒子等が適用された場合と同様にコスト上の問
題を有していた。However, when silver fine particles are applied, sulfuration,
Oxidation and salt solution, there is a problem in weather resistance is severely deteriorated by ultraviolet light, etc.On the other hand, when gold fine particles are applied, the above weather resistance problem is eliminated, but platinum fine particles, rhodium fine particles, palladium fine particles etc. are applied It also had cost problems.

【００１５】このような技術的背景の下、本発明者等
は、上記銀若しくは金微粒子に代えて、銀微粒子表面に
金若しくは白金単体または金と白金の複合体をコーティ
ングした平均粒径１〜１００ｎｍの貴金属コート銀微粒
子が分散された透明導電層形成用塗液並びにこの塗液を
用いて製造した透明導電性基材やこの基材が適用された
表示装置等を既に提案している（特開平１１−２２８８
７２号公報、特開平１１−２０３９４３号公報および特
願平１１−３６６３４３号明細書等参照）。Under such a technical background, the present inventors have proposed that instead of the silver or gold fine particles described above, the average particle size of silver or fine particles coated with gold or platinum alone or a composite of gold and platinum is used. We have already proposed a coating liquid for forming a transparent conductive layer in which 100-nm noble metal-coated silver fine particles are dispersed, a transparent conductive substrate manufactured using this coating liquid, a display device to which this substrate is applied, and the like. Kaihei 11-2288
72, JP-A-11-203943 and Japanese Patent Application No. 11-366343).

【００１６】そして、銀微粒子の表面に金若しくは白金
単体または金と白金の複合体をコーティングすると、貴
金属コート銀微粒子内部の銀が金若しくは白金単体また
は金と白金の複合体により保護されるため、耐候性、耐
薬品性等の改善が図れる。When the surface of the silver fine particles is coated with gold or platinum alone or a composite of gold and platinum, the silver inside the noble metal-coated silver fine particles is protected by the gold or platinum alone or the composite of gold and platinum. Improvement of weather resistance, chemical resistance, etc. can be achieved.

【００１７】ここで、透明導電性基材の製造過程におい
て、銀微粒子表面に金若しくは白金単体または金と白金
の複合体がコーティングされた平均粒径１〜１００ｎｍ
の上記貴金属コート銀微粒子に対する製造時における加
熱処理条件如何(すなわち、貴金属コート銀微粒子が含
まれる透明導電層形成用塗液を透明基板上に塗布した後
の加熱処理条件如何)によっては、貴金属コート銀微粒
子内において金、白金、銀等の熱拡散による合金化層形
成の可能性があり、かつ、これを原因とする耐候性、耐
薬品性等が若干低下する現象も確認されている。Here, in the process of manufacturing the transparent conductive substrate, the average particle diameter of silver or platinum alone or a composite of gold and platinum coated on the surface of silver fine particles is 1 to 100 nm.
Depending on the heat treatment conditions during the production of the noble metal-coated silver fine particles (i.e., the heat treatment conditions after applying a transparent conductive layer forming coating solution containing the noble metal-coated silver fine particles on a transparent substrate), the noble metal coating It has been confirmed that there is a possibility that an alloyed layer may be formed by thermal diffusion of gold, platinum, silver or the like in the silver fine particles, and a phenomenon that the weather resistance, chemical resistance and the like due to this may be slightly reduced.

【００１８】この場合、上記貴金属コート銀微粒子内に
おける金および／または白金の含有割合を５０〜９５重
量％に設定すれば回避できることも確認されている。In this case, it has been confirmed that the problem can be avoided by setting the content ratio of gold and / or platinum in the noble metal-coated silver fine particles to 50 to 95% by weight.

【００１９】尚、銀と金等で構成される透明導電層内の
導電性微粒子については、上記加熱処理に起因した合金
化層形成の可能性があり、この合金化層の形成により銀
微粒子表面をコーティングする貴金属コート層が金およ
び／または白金のみによって構成されているとは限らな
い場合が存在するため、本明細書においては、透明導電
層内における銀と金等で構成される上記微粒子につい
て、以下、貴金属コート銀微粒子と表現せずに貴金属微
粒子と表現する。The conductive fine particles in the transparent conductive layer composed of silver and gold may form an alloyed layer due to the above-mentioned heat treatment. There is a case where the noble metal coat layer for coating is not always composed only of gold and / or platinum. In this specification, the fine particles composed of silver and gold in the transparent conductive layer are referred to. Hereinafter, it is expressed as noble metal fine particles without being expressed as noble metal coated silver fine particles.

【００２０】[0020]

【発明が解決しようとする課題】ところで、ＣＲＴ等の
量産工場において、上記貴金属コート銀微粒子が含まれ
る透明導電層形成用塗液を用い、スピンコート法等でＣ
ＲＴ表示装置等の前面板に透明導電層を形成する場合、
製品の歩留まりを向上させることが重要であり、そのた
め、貴金属コート銀微粒子が含まれる透明導電層形成用
塗液の保存安定性が良好であることが望まれる。In a mass-production factory such as a CRT, a coating liquid for forming a transparent conductive layer containing the above-mentioned noble metal-coated silver fine particles is used and spin-coating or the like is used.
When a transparent conductive layer is formed on a front plate of an RT display device or the like,
It is important to improve the product yield, and therefore, it is desired that the coating liquid for forming a transparent conductive layer containing noble metal-coated silver fine particles has good storage stability.

【００２１】しかし、上記貴金属コート銀微粒子は一次
粒子径が小さく、活性が非常に高いため凝集傾向が非常
に強く、貴金属コート銀微粒子が含まれる透明導電層形
成用塗液を長期間保存した場合、一次粒子同士がより大
きな二次粒子を形成してしまい、最終的には凝集物が沈
降し易かった。However, the noble metal-coated silver fine particles have a small primary particle diameter and a very high activity, so that they tend to agglomerate very strongly. When the transparent conductive layer forming coating liquid containing the noble metal-coated silver fine particles is stored for a long period of time, However, the primary particles formed larger secondary particles, and eventually aggregates were likely to settle.

【００２２】そして、このような貴金属コート銀微粒子
の凝集が生じた透明導電層形成用塗液を適用した場合、
塗布成膜時に膜欠陥を引き起こし易いため、ＣＲＴ等製
造ラインの歩留まりを著しく悪化させる問題があった。When a coating liquid for forming a transparent conductive layer in which such noble metal-coated silver fine particles are aggregated is applied,
Since a film defect is easily caused at the time of coating and film formation, there is a problem that the yield of a production line such as a CRT is remarkably deteriorated.

【００２３】尚、貴金属コート銀微粒子の凝集を防ぎ、
分散安定性を保つ方法としては、例えば界面活性剤の添
加が有効である（特開平１１−８０６１９号公報参
照）。It is to be noted that noble metal-coated silver fine particles are prevented from aggregating,
As a method for maintaining the dispersion stability, for example, the addition of a surfactant is effective (see JP-A-11-80619).

【００２４】しかし、十分な分散安定性を保つためには
多量の界面活性剤の添加が必要となり、成膜後も界面活
性剤が膜中に残るため、膜の抵抗値が上昇して十分な電
界シールド効果が得られない問題を有する。However, in order to maintain sufficient dispersion stability, it is necessary to add a large amount of a surfactant, and the surfactant remains in the film even after the film is formed. There is a problem that an electric field shielding effect cannot be obtained.

【００２５】本発明はこのような問題点に着目してなさ
れたもので、その課題とするところは、貴金属コート銀
微粒子が含まれる透明導電層形成用塗液を１０日以上保
存しても膜欠陥等の原因となる貴金属コート銀微粒子の
凝集を防止でき、しかも良好な導電性、低反射率並びに
耐候性、耐薬品性等の諸特性を有する透明導電性基材の
製造を可能とする透明導電層形成用塗液を提供すること
にある。The present invention has been made in view of such problems, and an object of the present invention is to provide a transparent conductive layer-forming coating solution containing noble metal-coated silver fine particles for 10 days or more. Prevents aggregation of noble metal-coated silver fine particles that cause defects, etc., and enables the production of a transparent conductive substrate that has good conductivity, low reflectance, and various properties such as weather resistance and chemical resistance. An object of the present invention is to provide a coating liquid for forming a conductive layer.

【００２６】[0026]

【課題を解決するための手段】すなわち、請求項１に係
る発明は、透明基板およびこの透明基板上に順次形成さ
れた透明導電層と透明コート層とで構成された透明２層
膜を備え、この透明２層膜の表面抵抗が１０〜５０００
Ω/□、可視光線領域の反射プロファイルにおいて極小
となる上記透明２層膜の反射率が０〜２．５％である透
明導電性基材の透明導電層形成用塗液を前提とし、銀微
粒子表面に金若しくは白金単体または金と白金の複合体
がコーティングされかつ金および／または白金を５〜９
５重量％含有する平均粒径１〜１００ｎｍの貴金属コー
ト銀微粒子、高分子樹脂および溶媒を主成分とし、か
つ、上記高分子樹脂が下記化学式（１）〜（３）で示さ
れる繰り返し単位成分の内少なくとも１種類以上を分子
内に有する重合体で構成されると共に、高分子樹脂１重
量部に対し上記貴金属コート銀微粒子が５重量部〜５０
０重量部の割合で配合されていることを特徴とし、That is, the invention according to claim 1 comprises a transparent substrate and a transparent two-layer film composed of a transparent conductive layer and a transparent coat layer sequentially formed on the transparent substrate, The surface resistance of this transparent two-layer film is 10 to 5000
Ω / □, a coating liquid for forming a transparent conductive layer of a transparent conductive substrate in which the reflectance of the transparent two-layer film is minimized in the reflection profile in the visible light region is 0 to 2.5%, and silver fine particles are used. The surface is coated with gold or platinum alone or a composite of gold and platinum, and the gold and / or platinum is
Noble metal-coated silver fine particles having an average particle diameter of 1 to 100 nm containing 5% by weight, a polymer resin and a solvent as main components, and the polymer resin is a repeating unit component represented by the following chemical formulas (1) to (3). Of the noble metal-coated silver fine particles in an amount of 5 to 50 parts by weight per 1 part by weight of the polymer resin.
It is characterized by being blended at a ratio of 0 parts by weight,

【００２７】[0027]

【化４】 Embedded image

【００２８】[0028]

【化５】 Embedded image

【００２９】[0029]

【化６】 Embedded image

【００３０】また、請求項２に係る発明は、請求項１記
載の発明に係る透明導電層形成用塗布液を前提とし、上
記貴金属コート銀微粒子が、金および／または白金を５
０〜９５重量％含有することを特徴とするものである。Further, the invention according to claim 2 is based on the premise that the coating liquid for forming a transparent conductive layer according to the invention according to claim 1 is used, wherein the noble metal-coated silver fine particles contain 5 and / or gold and / or platinum.
It is characterized by containing 0 to 95% by weight.

【００３１】[0031]

【発明の実施の形態】以下、本発明の実施の形態につい
て詳細に説明する。Embodiments of the present invention will be described below in detail.

【００３２】本発明は、透明導電層形成用塗布液におい
て上記化学式（１）〜（３）で示される繰り返し単位成
分の内少なくとも１種類以上を分子内に有する高分子樹
脂を添加することにより貴金属コート銀微粒子の分散安
定性が向上するという考え方に基づいている。これは、
上記化学式（１）〜（３）で示される繰り返し単位成分
が貴金属コート銀微粒子と相互作用し、上記繰り返し単
位成分の作用により高分子樹脂が貴金属コート銀微粒子
に吸着されることにより上記貴金属コート銀微粒子の分
散安定性が向上するものと考えられる。According to the present invention, a noble metal can be prepared by adding a polymer resin having at least one kind of the repeating unit components represented by the chemical formulas (1) to (3) in a molecule to a coating solution for forming a transparent conductive layer. It is based on the idea that the dispersion stability of coated silver fine particles is improved. this is,
The repeating unit components represented by the chemical formulas (1) to (3) interact with the noble metal-coated silver fine particles, and the polymer resin is adsorbed on the noble metal-coated silver fine particles by the action of the repeating unit component, whereby the noble metal-coated silver It is considered that the dispersion stability of the fine particles is improved.

【００３３】但し、上記貴金属コート銀微粒子が含まれ
る透明導電層形成用塗液をスピンコーター等でブラウン
管（ＣＲＴ）等表示装置の前面板等に塗布して透明導電
層を形成する過程において、良好な導電性を得るために
は、溶剤の乾燥過程で均一に分散している貴金属コート
銀微粒子が網目状に凝集して導電パスが形成されること
も必要である。However, in the process of forming a transparent conductive layer by applying the coating liquid for forming a transparent conductive layer containing the noble metal-coated silver fine particles to a front plate of a display device such as a cathode ray tube (CRT) by a spin coater or the like, In order to obtain good conductivity, it is necessary that the noble metal-coated silver fine particles uniformly dispersed in the drying process of the solvent are aggregated in a network to form a conductive path.

【００３４】そして、貴金属コート銀微粒子への上記高
分子樹脂の吸着が強過ぎると、貴金属コート銀微粒子の
分散安定性は向上するが、上記導電パスの形成が不十分
となり、形成される透明導電層の導電性が著しく悪化す
る場合がある。例えば、下記化学式（４）で示される繰
り返し単位成分を有するポリビニルピロリドン（ＰＶ
Ｐ）を用いた場合、貴金属コート銀微粒子へのＰＶＰの
吸着が強過ぎるため貴金属コート銀微粒子の分散安定性
は向上するものの、上記網目状の導電パスが十分に形成
されないため、透明導電層の導電性が低下して十分な電
界シールド効果を得られないことが確認されている。When the adsorption of the polymer resin to the noble metal-coated silver fine particles is too strong, the dispersion stability of the noble metal-coated silver fine particles is improved, but the formation of the conductive paths becomes insufficient, and the formed transparent conductive material becomes invisible. The conductivity of the layer may be significantly reduced. For example, polyvinylpyrrolidone (PV) having a repeating unit component represented by the following chemical formula (4)
When P) is used, the dispersion stability of the noble metal-coated silver fine particles is improved due to too strong adsorption of PVP to the noble metal-coated silver fine particles, but the above-mentioned mesh-shaped conductive path is not sufficiently formed. It has been confirmed that the conductivity is lowered and a sufficient electric field shielding effect cannot be obtained.

【００３５】[0035]

【化７】 Embedded image

【００３６】従って、本発明に使用される高分子樹脂と
しては、貴金属コート銀微粒子と適度な相互作用を有す
ると共に、塗布時における導電パスの形成を阻害しない
上記化学式（１）〜（３）で示される繰り返し単位成分
の内少なくとも１種類以上を分子内に有する高分子樹脂
であることを要する。Therefore, the polymer resin used in the present invention has the above-mentioned chemical formulas (1) to (3) which have an appropriate interaction with the noble metal-coated silver fine particles and which does not inhibit the formation of the conductive path at the time of coating. It must be a polymer resin having at least one or more of the repeating unit components shown in the molecule.

【００３７】そして、上記化学式（１）〜（３）で示さ
れる繰り返し単位成分の内少なくとも１種類以上を分子
内に有する高分子樹脂としては、例えば、ポリビニルア
ルコール、ポリビニルアセタール（ポリビニルブチラー
ル、ポリビニルフォルマール等）、ポリビニルエステル
（ポリ酢酸ビニル、ポリプロピオン酸ビニル等）等が挙
げられる。尚、上記化学式（１）〜（３）で示される繰
り返し単位成分の内少なくとも１種類以上を分子内に有
する重合体であれよく、例示した上記材料に限定される
ものではない。また、上記高分子樹脂の２種類以上を混
合して使用することも可能である。Examples of the polymer resin having at least one or more of the repeating unit components represented by the chemical formulas (1) to (3) in the molecule include, for example, polyvinyl alcohol, polyvinyl acetal (polyvinyl butyral, polyvinyl phthalate). Marl, etc.) and polyvinyl esters (polyvinyl acetate, polyvinyl propionate, etc.). In addition, a polymer having at least one or more of the repeating unit components represented by the chemical formulas (1) to (3) in the molecule may be used, and is not limited to the above-described materials. It is also possible to use a mixture of two or more of the above polymer resins.

【００３８】また、酢酸ビニルとエチレン、プロピレ
ン、α−オクテン、α−オタデセン等のオレフィン等と
の共重合体、あるいは、上記酢酸ビニルとアクリル酸、
メタクリル酸、クロトン酸、マレイン酸、フマール酸、
イタコン酸等の不飽和カルボン酸およびその部分または
完全エステルとの共重合体、若しくは、酢酸ビニルと上
記不飽和カルボン酸の無水物、不飽和カルボン酸のニト
リル、不飽和カルボン酸のアミド等との共重合体、ある
いは上記酢酸ビニルと塩化ビニル、ビニルエーテル等と
の共重合体も本発明に係る高分子樹脂として使用でき
る。また、酢酸ビニルと上記化合物との共重合体を既知
の方法でケン化し得られる重合体、およびケン化により
得られた重合体を更にアセタール化した重合体も適用す
ることができる。Further, a copolymer of vinyl acetate and an olefin such as ethylene, propylene, α-octene, α-otadecene or the like, or the above-mentioned vinyl acetate and acrylic acid,
Methacrylic acid, crotonic acid, maleic acid, fumaric acid,
Copolymer of unsaturated carboxylic acid such as itaconic acid and its partial or complete ester, or of vinyl acetate and anhydride of unsaturated carboxylic acid, nitrile of unsaturated carboxylic acid, amide of unsaturated carboxylic acid and the like Copolymers or copolymers of the above-mentioned vinyl acetate with vinyl chloride, vinyl ether and the like can also be used as the polymer resin according to the present invention. Further, a polymer obtained by saponifying a copolymer of vinyl acetate and the above compound by a known method, and a polymer obtained by further acetalizing a polymer obtained by saponification can also be applied.

【００３９】また、上記化学式(１)〜(３)で示された繰
り返し単位成分の内少なくとも１種類以上を有する高分
子樹脂を既知の合成方法で他の樹脂に共重合させたブロ
ック共重合体、グラフト共重合体も適用することができ
る。A block copolymer obtained by copolymerizing a polymer resin having at least one of the repeating unit components represented by the chemical formulas (1) to (3) with another resin by a known synthesis method. And a graft copolymer can also be applied.

【００４０】尚、高分子樹脂の分子量については特に制
限はないが、塗液の分散安定性への寄与、溶媒への溶解
性等を考慮すると、重合度１００〜５０００が好まし
い。The molecular weight of the polymer resin is not particularly limited. However, in consideration of the contribution to the dispersion stability of the coating solution, the solubility in a solvent, and the like, the polymerization degree is preferably 100 to 5000.

【００４１】次に、上記高分子樹脂と貴金属コート銀微
粒子については、高分子樹脂１重量部に対し貴金属コー
ト銀微粒子が５重量部〜５００重量部の割合で配合され
ることを要する。高分子樹脂１重量部に対し貴金属コー
ト銀微粒子が５００重量部を超えた場合、貴金属コート
銀微粒子を分散安定化させる効果が少なく、また、高分
子樹脂１重量部に対し貴金属コート銀微粒子が５重量部
未満である場合、形成された透明導電層の導電性が低下
し、十分な電界シールド効果が得られないからである。Next, with respect to the polymer resin and the noble metal-coated silver fine particles, it is necessary that the noble metal-coated silver fine particles are blended in a ratio of 5 parts by weight to 500 parts by weight with respect to 1 part by weight of the high molecular resin. When the amount of the noble metal-coated silver fine particles exceeds 500 parts by weight with respect to 1 part by weight of the polymer resin, the effect of stabilizing the dispersion of the noble metal-coated silver fine particles is small. If the amount is less than part by weight, the conductivity of the formed transparent conductive layer is reduced, and a sufficient electric field shielding effect cannot be obtained.

【００４２】また、本発明においては、銀微粒子表面に
金若しくは白金単体または金と白金の複合体がコーティ
ングされた貴金属コート銀微粒子が適用されている。こ
れは、金若しくは白金が化学的に安定で、耐候性、耐薬
品性、耐酸化性等に優れているため、銀微粒子の表面に
金若しくは白金単体または金と白金の複合体をコーティ
ングすればその化学的安定性を高めることができるから
である。また、白金の比抵抗は、上述したように銀、金
に較べて若干高いため、透明導電膜の表面抵抗として
は、Ａｇ−Ｐｔ系、Ａｇ−Ａｕ−Ｐｔ系に比べＡｇ−Ａ
ｕ系が好ましいが、金若しくは白金単体または金と白金
の複合体材料は上記銀微粒子表面のコーティング層とし
て適用されていることから、銀の良好な導電性を実用レ
ベル以下となる程に著しく損なうこともない。In the present invention, noble metal-coated silver fine particles in which silver or platinum alone or a composite of gold and platinum is coated on the surface of silver fine particles are applied. This is because gold or platinum is chemically stable and has excellent weather resistance, chemical resistance, oxidation resistance, etc., so if the surface of silver fine particles is coated with gold or platinum alone or a composite of gold and platinum This is because its chemical stability can be improved. Further, since the specific resistance of platinum is slightly higher than that of silver or gold as described above, the surface resistance of the transparent conductive film is higher than that of Ag-Pt or Ag-Au-Pt.
Although a u-based material is preferable, since gold or platinum alone or a composite material of gold and platinum is applied as a coating layer on the surface of the silver fine particles, the good conductivity of silver is significantly impaired to a practical level or less. Not even.

【００４３】尚、金若しくは白金単体または金と白金の
複合体を銀微粒子にコーティングする代わりに、銀を金
若しくは白金または金並びに白金と合金化させて合金微
粒子とし、上述した耐候性等の特性を改善させる方法も
考えられる。しかし、一般的に微粒子調製に採用されて
いる湿式法においては、上記合金微粒子を作製するため
の原料溶液として塩化金酸塩あるいは塩化白金酸塩と銀
塩の水溶液を用いた場合、それらの混合時に難溶性の塩
化銀を生じる問題がある。また、金塩、白金塩、銀塩と
してシアン錯塩を用いた場合に上記問題は生じないが、
有毒なシアン化合物の取扱が必要になるという点で問題
があり、金あるいは白金と銀の合金微粒子の合成は容易
でない。そこで、本発明においては、透明導電層形成用
塗液における金属微粒子として、銀微粒子の表面に金若
しくは白金単体または金と白金の複合体がコーティング
された貴金属コート銀微粒子を適用することで、この透
明導電層形成用塗液を用いて形成される透明導電層にお
ける耐候性、耐薬品性等の特性改善を図っている。Instead of coating gold or platinum alone or a composite of gold and platinum on silver fine particles, silver is alloyed with gold, platinum or gold or platinum to form alloy fine particles, and the above-mentioned properties such as weather resistance are obtained. There is also a method of improving the above. However, in the wet method generally used for the preparation of fine particles, when an aqueous solution of chloroaurate or chloroplatinate and silver salt is used as a raw material solution for producing the above alloy fine particles, a mixture thereof is used. There is a problem that sometimes hardly soluble silver chloride is produced. The above problem does not occur when a cyanide complex is used as a gold salt, a platinum salt, or a silver salt,
There is a problem in that toxic cyanide must be handled, and it is not easy to synthesize fine particles of gold or alloys of platinum and silver. Therefore, in the present invention, as the fine metal particles in the coating liquid for forming a transparent conductive layer, noble metal-coated silver fine particles in which the surface of silver fine particles is coated with gold or platinum alone or a composite of gold and platinum is applied. The transparent conductive layer formed using the coating liquid for forming a transparent conductive layer is improved in properties such as weather resistance and chemical resistance.

【００４４】ここで、本発明における貴金属コート銀微
粒子は、その平均粒径が１〜１００ｎｍであることを要
する。上記貴金属コート銀微粒子において、１ｎｍ未満
の場合、この微粒子の製造が困難であると同時に、塗料
化において分散も容易でなく実用的でない。また、１０
０ｎｍを超えると、形成された透明２層膜の可視光線の
散乱が大きくなり（つまり膜のヘーズ値が高くなり）、
実用的ではないからである。尚、ここで言う平均粒径と
は、透過電子顕微鏡（ＴＥＭ）で観察される微粒子の平
均粒径を示している。The noble metal-coated silver fine particles in the present invention need to have an average particle diameter of 1 to 100 nm. When the noble metal-coated silver fine particles have a particle size of less than 1 nm, production of the fine particles is difficult, and at the same time, dispersion in coating is not easy and not practical. Also, 10
If it exceeds 0 nm, the scattering of visible light of the formed transparent two-layer film increases (that is, the haze value of the film increases),
It is not practical. Here, the average particle size indicates the average particle size of the fine particles observed by a transmission electron microscope (TEM).

【００４５】次に、上記貴金属微粒子が含まれる透明導
電層は、透明基板上に塗布された本発明に係る透明導電
層形成用塗液を加熱処理して形成されるが、この加熱処
理により透明導電層形成用塗液の構成成分である貴金属
コート銀微粒子は上述したように合金化されあるいは銀
微粒子表面に金若しくは白金単体または金と白金の複合
体がコーティングされたまま上記貴金属微粒子を構成す
る。そして、この貴金属微粒子は電界シールド用として
適用され、最終的に１０〜５０００Ω/□の表面抵抗の
透明２層膜が得られる。Next, the transparent conductive layer containing the noble metal fine particles is formed by heat-treating the coating liquid for forming a transparent conductive layer according to the present invention applied on a transparent substrate. The noble metal-coated silver fine particles, which are constituents of the coating liquid for forming a conductive layer, are alloyed as described above or constitute the noble metal fine particles while the surface of the silver fine particles is coated with gold or platinum alone or a composite of gold and platinum. . The noble metal fine particles are applied for electric field shielding, and finally a transparent two-layer film having a surface resistance of 10 to 5000 Ω / □ is obtained.

【００４６】上記貴金属コート銀微粒子（貴金属微粒
子）内の金および／または白金の含有量は５〜９５重量
％の範囲に設定される。金および／または白金の含有量
が５重量％未満だと、形成される上記貴金属微粒子の耐
候性が悪くなる場合があり、逆に、９５重量％を超える
と金微粒子に代えて貴金属コート銀微粒子（貴金属微粒
子）を適用する経済的メリットが少ないからである。The content of gold and / or platinum in the noble metal-coated silver fine particles (noble metal fine particles) is set in the range of 5 to 95% by weight. When the content of gold and / or platinum is less than 5% by weight, the weather resistance of the noble metal fine particles to be formed may be deteriorated. Conversely, when the content exceeds 95% by weight, noble metal-coated silver fine particles are used instead of gold fine particles. This is because there is little economic merit of applying (noble metal fine particles).

【００４７】尚、透明導電性基材の製造段階における貴
金属コート銀微粒子に対する加熱処理条件によって、
金、白金、銀等が合金化し耐候性、耐薬品性が若干低下
する現象を回避するため、好ましくは、貴金属コート銀
微粒子内の金および／または白金の含有量を５０〜９５
重量％の範囲に設定するとよい（請求項２）。ここで、
透明導電層形成用塗液内の貴金属コート銀微粒子におけ
る金および／または白金の含有量が５０重量％を超えた
場合、この透明導電層形成用塗液を用いて形成された貴
金属微粒子内における銀の重量割合は形式的に低下する
が、金、白金に較べて銀の原子量は半分程度でモル％で
比較した場合の割合低下はそれ程でもないため、貴金属
微粒子の特性における銀の寄与は依然として維持され
る。The heat treatment conditions for the noble metal-coated silver fine particles in the production stage of the transparent conductive substrate are as follows:
In order to avoid the phenomenon that gold, platinum, silver and the like are alloyed and the weather resistance and the chemical resistance are slightly reduced, the content of gold and / or platinum in the noble metal-coated silver fine particles is preferably 50 to 95.
It may be set in the range of weight% (claim 2). here,
When the content of gold and / or platinum in the noble metal-coated silver fine particles in the transparent conductive layer forming coating liquid exceeds 50% by weight, silver in the noble metal fine particles formed using this transparent conductive layer forming coating liquid is used. Although the weight ratio of silver is formally reduced, the atomic weight of silver is about half that of gold and platinum, and the reduction in the molar ratio is not so large, so that the silver contribution to the properties of the noble metal fine particles is still maintained. Is done.

【００４８】次に、貴金属コート銀微粒子を適用する本
発明に係る透明導電層形成用塗液は、以下のような方法
で製造することができる。まず、既知の方法［例えば、
Carey−Lea法、Am.J.Sci.、37、47（1889）、Am.J.Sc
i.、38（1889）］により銀微粒子のコロイド分散液を調
製する。すなわち、硝酸銀水溶液に、硫酸鉄（II）水溶
液とクエン酸ナトリウム水溶液の混合液を加えて反応さ
せ、沈降物を濾過・洗浄した後、純水を加えることによ
り簡単に銀微粒子のコロイド分散液（Ａｇ：０．１〜１
０重量％）が調製される。この銀微粒子のコロイド分散
液の調製方法は平均粒径１〜１００ｎｍの銀微粒子が分
散されたものであれば任意でありかつこれに限定される
ものではない。Next, the coating liquid for forming a transparent conductive layer according to the present invention using the noble metal-coated silver fine particles can be produced by the following method. First, a known method [for example,
Carey-Lea method, Am. J. Sci., 37, 47 (1889), Am. J. Sc
i., 38 (1889)] to prepare a colloidal dispersion of fine silver particles. That is, a mixed solution of an aqueous solution of iron (II) sulfate and an aqueous solution of sodium citrate is added to an aqueous solution of silver nitrate to cause a reaction, and the precipitate is filtered and washed, and then pure water is added to easily produce a colloidal dispersion of fine silver particles ( Ag: 0.1-1
0% by weight) is prepared. The method for preparing the colloidal dispersion liquid of silver fine particles is arbitrary and is not limited to this as long as silver fine particles having an average particle diameter of 1 to 100 nm are dispersed.

【００４９】得られた銀微粒子のコロイド分散液に還元
剤を加え、更にそこにアルカリ金属の金酸塩溶液若しく
は白金酸塩溶液を加えるか、アルカリ金属の白金酸塩溶
液並びに金酸塩溶液、またはアルカリ金属の白金酸塩並
びに金酸塩の混合溶液を加えることで上記銀微粒子の表
面に金若しくは白金単体または金と白金の複合体をコー
ティングし、貴金属コート銀微粒子のコロイド状分散液
を得ることができる。尚、この貴金属コート銀微粒子調
製工程で、必要により、銀微粒子のコロイド分散液、ア
ルカリ金属の金酸塩溶液、アルカリ金属の白金酸塩溶
液、アルカリ金属の金酸塩並びに白金酸塩の混合溶液の
少なくともいずれか一つ、または、それぞれに少量の分
散剤を加えてもよい。A reducing agent is added to the obtained colloidal dispersion of fine silver particles, and then an alkali metal goldate solution or a platinum salt solution is added thereto, or an alkali metal platinumate solution and a goldate solution are added. Alternatively, the surface of the silver fine particles is coated with gold or platinum alone or a composite of gold and platinum by adding a mixed solution of an alkali metal platinate and a gold salt to obtain a colloidal dispersion of noble metal-coated silver fine particles. be able to. In this noble metal-coated silver fine particle preparation step, if necessary, a colloidal dispersion of silver fine particles, an alkali metal aurate solution, an alkali metal platinate solution, an alkali metal aurate and a mixed solution of platinate And a small amount of a dispersant may be added to at least one of them or each of them.

【００５０】また、上記貴金属コート銀微粒子調製工程
において銀微粒子表面への金若しくは白金単体または
金、白金複合体のコーティング反応が起こるのは、金酸
塩、白金酸塩の還元により金、白金が生じる際に、既に
液中に微細な銀微粒子が多量に存在するためで、金、白
金が単独で核発生（均一核発生）するよりも、銀微粒子
を核としてその表面に成長する方がエネルギー的に有利
な条件で進行するからである。In the above-mentioned noble metal-coated silver fine particle preparation step, a coating reaction of silver or platinum alone or a gold / platinum composite on the surface of silver fine particles occurs because gold and platinum are reduced by reduction of aurate and platinate. When this occurs, a large amount of fine silver particles are already present in the liquid, and it is more energy to grow on the surface of silver particles as nuclei than to generate nuclei (uniform nucleation) of gold and platinum alone. This is because it proceeds under economically advantageous conditions.

【００５１】従って、金酸塩、白金酸塩の還元により
金、白金が生じる際、液中に微細な銀微粒子が多量に存
在することを前提としているため、貴金属コート銀微粒
子調製工程における金酸塩溶液若しくは白金酸塩溶液、
または、白金酸塩溶液並びに金酸塩溶液あるいはこれ等
混合溶液と上記還元剤との添加タイミングについては、
少なくとも金酸塩溶液若しくは白金酸塩溶液、または、
金酸塩溶液並びに白金酸塩溶液あるいはこれ等混合溶液
より先に上記還元剤が添加されるよう調整することが好
ましい。すなわち、還元剤と金酸塩溶液若しくは白金酸
塩溶液、還元剤と金酸塩溶液並びに白金酸塩溶液、還元
剤と金酸塩並びに白金酸塩の混合溶液を混ぜた状態で銀
微粒子のコロイド分散液に添加した場合には、金酸塩溶
液若しくは白金酸塩溶液、金酸塩溶液並びに白金酸塩溶
液、金酸塩並びに白金酸塩の混合溶液を上記還元剤に混
ぜた段階で金酸塩、白金酸塩の還元により金、白金が生
じてしまい、かつ、金、白金が単独で核発生（均一核発
生）してしまうため、金酸塩溶液、白金酸塩溶液等と還
元剤とを混ぜた後に銀微粒子のコロイド分散液に添加し
ても銀微粒子表面への金若しくは白金単体または金、白
金複合体のコーティング反応が起こらなくなることがあ
るからである。Therefore, when gold and platinum are generated by the reduction of aurate and platinate, it is assumed that a large amount of fine silver fine particles are present in the solution. Salt solution or platinate solution,
Or, about the addition timing of the reducing agent with a platinum salt solution and a gold salt solution or a mixed solution thereof,
At least a gold salt solution or a platinum salt solution, or
It is preferable to adjust so that the above-mentioned reducing agent is added earlier than the aurate solution and the platinate solution or a mixed solution thereof. That is, the colloid of silver fine particles in a state where a reducing agent and a gold salt solution or a platinum salt solution, a reducing agent and a gold salt solution and a platinum salt solution, and a mixed solution of a reducing agent and a gold salt and a platinum salt are mixed. When added to the dispersion, a gold salt solution or a platinum salt solution, a gold salt solution and a mixed solution of a platinum salt solution, a gold salt and a platinum salt are mixed with the above reducing agent at the stage where gold acid is added. Since gold and platinum are generated by the reduction of salt and platinate, and nucleation of gold and platinum alone (homogeneous nucleation), a reducing agent is used with a gold salt solution, a platinate solution and the like. This is because, even if the mixture is mixed and added to a colloidal dispersion of silver fine particles, the surface of the silver fine particles may not be coated with gold or platinum alone or with a gold-platinum composite.

【００５２】尚、上記還元剤には、ヒドラジン（Ｎ
2Ｈ4）、水素化ホウ素ナトリウム（ＮａＢＨ4）等の水
素化ホウ素化合物、ホルムアルデヒド等を用いることが
できるが、銀微粒子のコロイド分散液に加えられたとき
に銀超微粒子の凝集を起こさず、金酸塩、白金酸塩を
金、白金に還元できれば任意でありこれらに限定される
ものではない。The reducing agent may be hydrazine (N
2 H 4), boron hydride compounds such as hydrogen sodium borohydride (NaBH 4), can be used such as formaldehyde, without causing agglomeration of the ultra-fine silver particles when added to the colloidal dispersion of silver microparticles, Any method can be used as long as it can reduce a gold salt or a platinum salt to gold or platinum, and the present invention is not limited thereto.

【００５３】例えば、金酸カリウム［ＫＡｕ（Ｏ
Ｈ）4］、および白金酸カリウム［Ｋ2Ｐｔ（ＯＨ）6］
をヒドラジンあるいは水素化ホウ素ナトリウムで還元す
る場合の還元反応は、それぞれ以下の様に示される。For example, potassium aurate [KAu (O
H) 4 ], and potassium platinate [K 2 Pt (OH) 6 ]
In the case where is reduced with hydrazine or sodium borohydride, the reduction reaction is shown as follows, respectively.

【００５４】ＫＡｕ（ＯＨ）4＋３／４Ｎ2Ｈ4→Ａｕ＋
ＫＯＨ＋３Ｈ2Ｏ＋３／４Ｎ2↑ Ｋ2Ｐｔ（ＯＨ）6＋Ｎ2Ｈ4→Ｐｔ＋２ＫＯＨ＋４Ｈ2Ｏ
＋Ｎ2↑ ＫＡｕ（ＯＨ）4＋３／４ＮａＢＨ4→Ａｕ＋ＫＯＨ＋３
／４ＮａＯＨ＋３／４Ｈ3ＢＯ3＋３／２Ｈ2↑ Ｋ2Ｐｔ（ＯＨ）6＋ＮａＢＨ4→Ｐｔ＋２ＫＯＨ＋Ｎａ
ＯＨ＋Ｈ3ＢＯ3＋２Ｈ2↑ ここで、還元剤として上記水素化ホウ素ナトリウムを用
いた場合、上記反応式から確認できるように還元反応に
より生じる電解質の濃度が高くなるため、後述するよう
に微粒子が凝集し易く、還元剤としての添加量が限ら
れ、用いる銀微粒子のコロイド分散液における銀濃度を
高くできない不便さがある。KAu (OH) 4 + 3 / 4N 2 H 4 → Au +
KOH + 3H 2 O + 3 / 4N 2 ↑ K 2 Pt (OH) 6 + N 2 H 4 → Pt + 2KOH + 4H 2 O
+ N 2 ↑ KAu (OH) 4 + 3 / 4NaBH 4 → Au + KOH + 3
/ 4NaOH + 3 / 4H 3 BO 3 + 3 / 2H 2 ↑ K 2 Pt (OH) 6 + NaBH 4 → Pt + 2KOH + Na
OH + H 3 BO 3 + 2H 2 ↑ Here, when the above-mentioned sodium borohydride is used as the reducing agent, the concentration of the electrolyte generated by the reduction reaction increases as can be confirmed from the above reaction formula, so that the fine particles aggregate as described later. This is inconvenient in that the amount of silver added as a reducing agent is limited, and the silver concentration in the colloidal dispersion of the used silver fine particles cannot be increased.

【００５５】一方、還元剤として上記ヒドラジンを用い
た場合、上記反応式から確認できるように還元反応によ
り生じる電解質が少なく、還元剤としてより適してい
る。On the other hand, when the above-mentioned hydrazine is used as the reducing agent, as can be confirmed from the above reaction formula, the amount of the electrolyte generated by the reduction reaction is small, and it is more suitable as the reducing agent.

【００５６】尚、金、白金のコーティング原料として、
アルカリ金属の金酸塩、アルカリ金属の白金酸塩以外の
塩、例えば塩化金酸（ＨＡｕＣｌ4）、塩化白金酸（Ｈ2
ＰｔＣｌ6）、または、塩化金酸塩（ＮａＡｕＣｌ4、Ｋ
ＡｕＣｌ4等）、塩化白金酸塩（Ｎａ2ＰｔＣｌ6、Ｋ2Ｐ
ｔＣｌ6等）を用いると、ヒドラジンによる還元反応は
以下のように示される。As a coating material for gold and platinum,
Alkali metal aurate, salts other than alkali metal platinates, for example, chloroauric acid (HAuCl 4 ), chloroplatinic acid (H 2
PtCl 6 ) or chloroaurate (NaAuCl 4 , K
AuCl 4 ), chloroplatinate (Na 2 PtCl 6 , K 2 P
When tCl 6 or the like is used, the reduction reaction with hydrazine is shown as follows.

【００５７】ＸＡｕＣｌ4＋３／４Ｎ2Ｈ4→Ａｕ＋ＸＣ
ｌ＋３ＨＣｌ＋３／４Ｎ2↑ Ｘ2ＰｔＣｌ6＋Ｎ2Ｈ4→Ｐｔ＋２ＸＣｌ＋４ＨＣｌ＋Ｎ
2↑ （Ｘ＝Ｈ，Ｎａ，Ｋ等） この様に塩化金酸等を適用した場合、上記金酸塩、白金
酸塩を用いた場合と比較して、還元反応による電解質濃
度が高くなるだけでなく塩素イオンを生じるため、これ
が銀微粒子と反応し、難溶性の塩化銀を生成してしまう
ことから、本発明に係る透明導電層形成用塗液の原料に
用いることは困難である。XAuCl 4 + 3 / 4N 2 H 4 → Au + XC
1 + 3HCl + 3 / 4N 2 ↑ X 2 PtCl 6 + N 2 H 4 → Pt + 2XCl + 4HCl + N
2 ↑ (X = H, Na, K, etc.) When chloroauric acid or the like is applied in this way, the concentration of the electrolyte due to the reduction reaction becomes higher as compared with the case of using the above aurate or platinate. However, since chlorine ions are generated instead of these, they react with silver fine particles to generate hardly soluble silver chloride, so that it is difficult to use them as a raw material for the coating liquid for forming a transparent conductive layer according to the present invention.

【００５８】以上のようにして得られた貴金属コート銀
微粒子のコロイド状分散液は、この後、透析、電気透
析、イオン交換、限外濾過等の脱塩処理方法により分散
液内の電解質濃度を下げることが好ましい。これは、電
解質濃度を下げないとコロイドは電解質で一般に凝集し
てしまうからであり、この現象は、Schulze−Hardy則と
しても知られている。The colloidal dispersion of the noble metal-coated silver fine particles obtained as described above is then subjected to a desalting treatment such as dialysis, electrodialysis, ion exchange, or ultrafiltration to reduce the electrolyte concentration in the dispersion. It is preferable to lower it. This is because the colloid generally aggregates in the electrolyte unless the electrolyte concentration is reduced, and this phenomenon is also known as the Schulze-Hardy rule.

【００５９】次に、脱塩処理された貴金属コート銀微粒
子のコロイド状分散液を濃縮処理して貴金属コート銀微
粒子の分散濃縮液を得、この貴金属コート銀微粒子の分
散濃縮液と溶媒、および前記高分子樹脂を混合すると、
本発明に係る透明導電層形成用塗液が得られる。尚、脱
塩処理方式として限外濾過が適用された場合、この限外
濾過は以下に述べるように濃縮処理としても作用するこ
とから、脱塩処理と濃縮処理を同時進行で行うことも可
能である。従って、貴金属コート銀微粒子が分散された
コロイド状分散液の脱塩処理と濃縮処理については、適
用する処理方式によりその順序は任意に設定され、限外
濾過等が適用された場合には同時処理も可能である。Next, the desalted colloidal dispersion of the noble metal-coated silver fine particles is concentrated to obtain a dispersion concentrate of the noble metal-coated silver fine particles. When polymer resin is mixed,
The coating liquid for forming a transparent conductive layer according to the present invention is obtained. When ultrafiltration is applied as a desalination treatment method, since the ultrafiltration also acts as a concentration treatment as described below, it is possible to perform desalination treatment and concentration treatment simultaneously. is there. Therefore, regarding the desalting treatment and the concentration treatment of the colloidal dispersion liquid in which the noble metal-coated silver fine particles are dispersed, the order is arbitrarily set depending on the treatment method to be applied, and when ultrafiltration or the like is applied, simultaneous treatment is performed. Is also possible.

【００６０】尚、上記高分子樹脂の添加タイミングは、
例えば、貴金属コート銀微粒子の分散濃縮液と溶媒を混
合した後添加する方法、貴金属コート銀微粒子の分散濃
縮液と前記高分子樹脂を溶解した溶液を混合する方法等
が考えられるが、これらに限定されるものではない。The timing of adding the polymer resin is as follows.
For example, a method of mixing and adding a dispersion and a solvent of noble metal-coated silver fine particles and a solvent, a method of mixing a dispersion and a solution of the noble metal-coated silver fine particles and a solution of the polymer resin, and the like are conceivable, but are not limited thereto. It is not something to be done.

【００６１】ここで、本発明に係る透明導電層形成用塗
液において、銀微粒子表面に白金単体若しくは金と白金
の複合体がコーティングされていることの根拠は、透過
電子顕微鏡（ＴＥＭ）による粒子観察と成分分析（ＥＤ
Ｘ：エネルギー分散型Ｘ線解析装置）にて、金若しくは
白金単体または金、白金複合体のコーティング前後で粒
子径がほとんど変化してないこと、および、金若しくは
白金単体または金、白金複合体の分布が各粒子に対して
一様であること、更にはＥＸＡＦＳ（ExtendedX-ray Ab
sorption Fine Structure：広域Ｘ線吸収微細構造）解
析による金若しくは白金単体または金、白金複合体の配
位数から技術的に確認されている。Here, in the coating liquid for forming a transparent conductive layer according to the present invention, the reason that the surface of the silver fine particles is coated with a simple substance of platinum or a composite of gold and platinum is based on a particle obtained by a transmission electron microscope (TEM). Observation and component analysis (ED
X: energy dispersive X-ray analyzer) that the particle diameter is hardly changed before and after coating of gold or platinum alone or gold / platinum composite, and that of gold or platinum alone or gold / platinum composite. The distribution is uniform for each particle, and EXAFS (Extended X-ray Ab
It has been technically confirmed from the coordination number of gold or platinum alone or a gold-platinum composite by sorption fine structure (wide-range X-ray absorption fine structure) analysis.

【００６２】尚、銀微粒子に対する金、白金複合体の被
覆形態については、金、白金複合体のコーティング工程
（すなわち貴金属コート銀微粒子調製工程）で金酸塩の
溶液と白金酸塩の溶液を適用するか、金酸塩と白金酸塩
の混合溶液を適用するかの違いにより、また、これ等溶
液の配合タイミングや適用する金酸塩と白金酸塩の濃度
の違い等により各種の形態が考えられる。すなわち、こ
れ等条件の違いにより銀微粒子の全表面若しくは一部を
金が被覆しかつその全体を白金が被覆していたり、この
逆で銀微粒子の全表面若しくは一部を白金が被覆しかつ
その全体を金が被覆していたり、あるいは銀微粒子の全
表面を互いに重なることなく白金と金がそれぞれ単体で
または合金化された状態で被覆している形態等が考えら
れる。As for the coating form of the gold / platinum composite on the silver fine particles, a gold salt solution and a platinum salt solution are applied in the coating step of the gold / platinum composite (ie, the noble metal-coated silver fine particle preparation step). Or the application of a mixed solution of aurate and platinate, and various forms are considered depending on the mixing timing of these solutions and the difference in the concentration of aurate and platinate to be applied. Can be That is, due to the difference in these conditions, the whole surface or a part of the silver fine particles is covered with gold and the whole is covered with platinum, or conversely, the whole surface or part of the silver fine particles is covered with platinum and the whole is covered with platinum. It is possible to consider a form in which the whole is covered with gold, or a form in which platinum and gold are covered individually or in an alloyed state without overlapping the entire surfaces of the silver fine particles.

【００６３】ところで、本発明に係る透明導電層形成用
塗液を用いて形成される透明導電層内の導電性微粒子
は、透明導電層の形成過程において、例えば２００℃程
度の加熱処理条件にて焼成が行われた場合、上述したよ
うに金、白金、銀等の熱拡散による合金化層形成の可能
性があるが、その詳細は明らかではない。By the way, the conductive fine particles in the transparent conductive layer formed using the coating liquid for forming a transparent conductive layer according to the present invention are subjected to, for example, heat treatment at about 200 ° C. in the process of forming the transparent conductive layer. When firing is performed, as described above, there is a possibility that an alloyed layer is formed by thermal diffusion of gold, platinum, silver, or the like, but details thereof are not clear.

【００６４】従って、本明細書においては、透明導電層
内における銀と金等で構成される上記導電性微粒子につ
いて、上述したように貴金属コート銀微粒子と表現せず
に貴金属微粒子と表現している。Accordingly, in the present specification, the conductive fine particles composed of silver, gold, and the like in the transparent conductive layer are expressed as noble metal fine particles, not as noble metal coated silver fine particles as described above. .

【００６５】また、上記貴金属コート銀微粒子のコロイ
ド状分散液の濃縮処理は、減圧エバポレーター、限外濾
過等の常用の方法で行うことができる。また、透明導電
層形成用塗液中の水分濃度は、１〜５０重量％が好まし
い。５０重量％を超えると、透明基板上にこの透明導電
層形成用塗液を塗布した後、乾燥中に、水の高い表面張
力によりはじきを生じ易くなる場合があるからである。The concentration treatment of the colloidal dispersion of the noble metal-coated silver fine particles can be performed by a conventional method such as a reduced-pressure evaporator or ultrafiltration. The water concentration in the coating liquid for forming a transparent conductive layer is preferably 1 to 50% by weight. If the content is more than 50% by weight, repelling may easily occur due to high surface tension of water during drying after applying the coating liquid for forming a transparent conductive layer on a transparent substrate.

【００６６】尚、透明導電層形成用塗液中に界面活性剤
を加えれば上記はじきの問題は解決可能である。しか
し、界面活性剤の配合による塗布欠陥が生じ易くなる別
の問題を生ずることがある。従って、透明導電層形成用
塗液中の水分濃度は１〜５０重量％が好ましい。The repelling problem can be solved by adding a surfactant to the coating liquid for forming the transparent conductive layer. However, there may be another problem that coating defects are likely to occur due to the blending of the surfactant. Therefore, the water concentration in the coating liquid for forming a transparent conductive layer is preferably 1 to 50% by weight.

【００６７】また、上記溶媒としては特に制限はなく、
塗布方法や製膜条件により、適宜に選定される。例え
ば、メタノール、エタノール、イソプロパノール、ブタ
ノール、ベンジルアルコール、ジアセトンアルコール等
のアルコール系溶媒、アセトン、メチルエチルケトン
（ＭＥＫ）、メチルイソブチルケトン（ＭＩＢＫ）、シ
クロヘキサノン、イソホロン等のケトン系溶媒、プロピ
レングリコールメチルエーテル、プロピレングリコール
エチルエーテル等のグリコール誘導体、フォルムアミ
ド、Ｎ−メチルフォルムアミド、ジメチルホルムアミド
（ＤＭＦ）、ジメチルアセトアミド、ジメチルスルフォ
キシド(ＤＭＳＯ)、Ｎ−メチル−２−ピロリドン（ＮＭ
Ｐ）等が挙げられるが、これらに限定されるものではな
い。The solvent is not particularly limited.
It is appropriately selected depending on the coating method and film forming conditions. For example, alcohol solvents such as methanol, ethanol, isopropanol, butanol, benzyl alcohol, and diacetone alcohol; ketone solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, and isophorone; propylene glycol methyl ether; Glycol derivatives such as propylene glycol ethyl ether, formamide, N-methylformamide, dimethylformamide (DMF), dimethylacetamide, dimethylsulfoxide (DMSO), N-methyl-2-pyrrolidone (NM
P) and the like, but are not limited thereto.

【００６８】次に、この様にして得られた本発明に係る
透明導電層形成用塗液を用いて、透明基板、および、こ
の透明基板上に形成され平均粒径１〜１００ｎｍの貴金
属コート銀微粒子と高分子樹脂およびバインダーマトリ
ックスを主成分とする透明導電層とこの上に形成された
透明コート層から成る透明２層膜とでその主要部が構成
される透明導電性基材を得ることができる。Next, using the thus obtained coating liquid for forming a transparent conductive layer according to the present invention, a transparent substrate and a noble metal-coated silver having an average particle size of 1 to 100 nm formed on the transparent substrate. It is possible to obtain a transparent conductive base material whose main part is composed of a transparent conductive layer mainly composed of fine particles, a polymer resin and a binder matrix, and a transparent two-layer film formed on the transparent conductive layer. it can.

【００６９】そして、透明基板上に上記透明２層膜を形
成するには以下の方法でこれを行うことができる。すな
わち、平均粒径１〜１００ｎｍの貴金属コート銀微粒
子、高分子樹脂および溶媒を主成分とする本発明に係る
透明導電層形成用塗液を、ガラス基板、プラスチック基
板等の透明基板上にスプレーコート、スピンコート、ワ
イヤーバーコート、ドクターブレードコート等の手法に
て塗布し、必要に応じて乾燥した後、例えばシリカゾル
等を主成分とする透明コート層形成用塗布液を上述した
手法によりオーバーコートする。The above-mentioned transparent two-layer film can be formed on a transparent substrate by the following method. That is, the coating liquid for forming a transparent conductive layer according to the present invention, which contains a noble metal-coated silver fine particle having an average particle diameter of 1 to 100 nm, a polymer resin and a solvent as main components, is spray-coated on a transparent substrate such as a glass substrate or a plastic substrate. After applying by a method such as spin coating, wire bar coating, doctor blade coating, and drying if necessary, for example, a coating liquid for forming a transparent coat layer containing silica sol or the like as a main component is overcoated by the method described above. .

【００７０】次に、オーバーコートした後、例えば５０
〜３００℃程度の温度で加熱処理を施しオーバーコート
した透明コート層形成用塗布液の硬化を行って上記透明
２層膜を形成する。尚、５０〜３００℃程度の加熱処理
では、貴金属コート銀微粒子は金若しくは白金単体また
は金と白金の複合体で保護されているため問題を生じな
いが、銀微粒子であると２００℃を超えた場合に酸化拡
散により表面抵抗値が上昇し膜の劣化が生じる。Next, after overcoating, for example, 50
The transparent two-layer film is formed by curing the overcoated transparent coating layer-forming coating liquid by performing a heat treatment at a temperature of about 300 ° C. In the heat treatment at about 50 to 300 ° C., no problem occurs because the noble metal-coated silver fine particles are protected by gold or platinum alone or a composite of gold and platinum, but the silver fine particles exceeded 200 ° C. In this case, the surface resistance increases due to oxidation diffusion, and the film is deteriorated.

【００７１】ここで、例えばシリカゾル等を主成分とす
る透明コート層形成用塗布液を上述した手法によりオー
バーコートした際、予め塗布された貴金属コート銀微粒
子、高分子樹脂および溶媒を主成分とする透明導電層形
成用塗液により形成された貴金属コート銀微粒子層と高
分子樹脂の間隙に、オーバーコートしたシリカゾル液
（このシリカゾル液は上記加熱処理により酸化ケイ素を
主成分とするバインダーマトリックスとなる）がしみ込
むことで、導電性の向上、強度の向上、耐候性の一層の
向上が同時に達成される。更に、貴金属微粒子と高分子
樹脂が酸化ケイ素を主成分とする上記バインダーマトリ
ックス中に分散された透明導電層の光学定数（ｎ−ｉ
ｋ）において、屈折率ｎはさほど大きくないが消衰係数
ｋが大きいため、上記透明導電層と透明コート層の透明
２層膜構造により、透明２層膜の反射率を大幅に低下で
きる。Here, for example, when a coating solution for forming a transparent coat layer mainly composed of silica sol or the like is overcoated by the above-mentioned method, it is mainly composed of pre-coated noble metal-coated silver fine particles, a polymer resin and a solvent. A silica sol solution overcoated in the gap between the noble metal-coated silver fine particle layer formed by the coating liquid for forming a transparent conductive layer and the polymer resin (this silica sol solution becomes a binder matrix containing silicon oxide as a main component by the above heat treatment). By soaking, improvement of conductivity, improvement of strength, and further improvement of weather resistance are simultaneously achieved. Further, the optical constant (ni) of the transparent conductive layer in which the noble metal fine particles and the polymer resin are dispersed in the binder matrix containing silicon oxide as a main component.
In k), since the refractive index n is not so large but the extinction coefficient k is large, the reflectance of the transparent two-layer film can be significantly reduced by the transparent two-layer film structure of the transparent conductive layer and the transparent coat layer.

【００７２】上記シリカゾルとしては、オルトアルキル
シリケートに水や酸触媒を加えて加水分解し、脱水縮重
合を進ませた重合物、あるいは既に４〜５量体まで加水
分解縮重合を進ませた市販のアルキルシリケート溶液
を、さらに加水分解と脱水縮重合を進行させた重合物等
を利用することができる。尚、脱水縮重合が進行する
と、溶液粘度が上昇して最終的には固化してしまうの
で、脱水縮重合の度合いについては、ガラス基板やプラ
スチック基板等の透明基板上に塗布可能な上限粘度以下
のところに調整する。但し、脱水縮重合の度合いは上記
上限粘度以下のレベルであれば特に指定されないが、膜
強度、耐候性等を考慮すると重量平均分子量で５００か
ら３０００程度が好ましい。そして、アルキルシリケー
ト部分加水分解重合物は、透明２層膜の加熱焼成時に脱
水縮重合反応がほぼ完結して、硬いシリケート膜（酸化
ケイ素を主成分とする膜）になる。As the silica sol, a polymer obtained by hydrolyzing ortho-alkyl silicate with water or an acid catalyst to promote dehydration-condensation polymerization, or a commercially available polymer having already undergone hydrolysis-condensation polymerization to tetramer to pentamer The alkyl silicate solution of the above can be used as a polymer obtained by further promoting hydrolysis and dehydration-condensation polymerization. As the dehydration-condensation polymerization proceeds, the solution viscosity increases and eventually solidifies, so the degree of dehydration-condensation polymerization is not more than the upper limit viscosity that can be applied on a transparent substrate such as a glass substrate or a plastic substrate. Adjust to. However, the degree of dehydration polycondensation is not particularly limited as long as the level is not more than the above upper limit viscosity, but is preferably about 500 to 3000 in terms of weight average molecular weight in consideration of film strength, weather resistance and the like. The alkyl silicate partially hydrolyzed polymer almost completes the dehydration-condensation polymerization reaction when the transparent two-layer film is heated and baked, and becomes a hard silicate film (a film mainly composed of silicon oxide).

【００７３】尚、上記シリカゾルに、弗化マグネシウム
微粒子、アルミナゾル、チタニアゾル、ジルコニアゾル
等を加え、透明コート層の屈折率を調節して透明２層膜
の反射率を変えることも可能である。更に、シリカゾル
にγ−メルカプトプロピルトリメトキシシラン等のメル
カプト基含有化合物を加えてもよい。メルカプト基(Ｓ
Ｈ基)は金と比較的強固な結合を形成するため、金を含
有する貴金属微粒子に対し適用した場合、貴金属微粒子
とバインダーマトリックスとの界面強度が向上し、膜強
度、耐候性が向上する。It is also possible to change the reflectance of the transparent two-layer film by adjusting the refractive index of the transparent coat layer by adding magnesium fluoride fine particles, alumina sol, titania sol, zirconia sol, or the like to the silica sol. Further, a compound containing a mercapto group such as γ-mercaptopropyltrimethoxysilane may be added to the silica sol. Mercapto group (S
Since the (H group) forms a relatively strong bond with gold, when applied to noble metal fine particles containing gold, the interface strength between the noble metal fine particles and the binder matrix is improved, and the film strength and weather resistance are improved.

【００７４】以上説明したように、本発明に係る透明導
電層形成用塗液を適用して形成された透明導電層を具備
する透明導電性基材は、良好な導電性、低反射率を有
し、かつ、耐候性、耐薬品性等の諸特性を有するため、
例えば、上述したブラウン管（ＣＲＴ）、プラズマディ
スプレイパネル（ＰＤＰ）、蛍光表示管（ＶＦＤ）、フ
ィールドエミッションディスプレイ（ＦＥＤ）、エレク
トロルミネッセンスディスプレイ（ＥＬＤ）、液晶ディ
スプレイ（ＬＣＤ）等表示装置における前面板等に用い
ることができる。As described above, a transparent conductive substrate having a transparent conductive layer formed by applying the coating liquid for forming a transparent conductive layer according to the present invention has good conductivity and low reflectance. And, because it has various properties such as weather resistance and chemical resistance,
For example, a front panel of a display device such as a cathode ray tube (CRT), a plasma display panel (PDP), a fluorescent display tube (VFD), a field emission display (FED), an electroluminescence display (ELD), and a liquid crystal display (LCD). Can be used.

【００７５】[0075]

【実施例】以下、本発明の実施例を具体的に説明する
が、本発明はこれら実施例に限定されるものではない。
また、本文中の「％」は、透過率、反射率、ヘーズ値の
（％）を除いて「重量％」を示し、また「部」は「重量
部」を示している。EXAMPLES Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.
Further, “%” in the text indicates “% by weight” excluding (%) of transmittance, reflectance, and haze value, and “part” indicates “part by weight”.

【００７６】［実施例１］前述のＣａｒｅｙ−Ｌｅａ法
により銀微粒子のコロイド分散液を調製した。Example 1 A colloidal dispersion of fine silver particles was prepared by the Carey-Lea method described above.

【００７７】具体的には、９％硝酸銀水溶液３３ｇに、
２３％硫酸鉄（II）水溶液３９ｇと３７．５％クエン酸
ナトリウム水溶液４８ｇの混合液を加えた後、沈降物を
ろ過・洗浄した後、純水を加えて、銀微粒子のコロイド
分散液（Ａｇ：０．１５％）を調製した。Specifically, 33 g of a 9% aqueous silver nitrate solution was added to
After adding a mixed solution of 39 g of a 23% aqueous solution of iron (II) sulfate and 48 g of a 37.5% aqueous solution of sodium citrate, the precipitate was filtered and washed, and pure water was added thereto to obtain a colloidal dispersion of silver fine particles (Ag : 0.15%).

【００７８】この銀微粒子のコロイド分散液６０ｇにヒ
ドラジン１水和物（Ｎ2Ｈ4・Ｈ2Ｏ）の１％水溶液８．
０ｇ、金酸カリウム［ＫＡｕ（ＯＨ）4］水溶液（Ａ
ｕ：０．０７５％）４８０ｇと１％分散剤水溶液０．２
ｇの混合液を攪拌しながら加え、金単体がコーティング
された金コート銀微粒子のコロイド分散液を得た。7. A 1% aqueous solution of hydrazine monohydrate (N 2 H 4 .H 2 O) was added to 60 g of the colloidal dispersion of silver fine particles.
0 g, potassium aurate [KAu (OH) 4 ] aqueous solution (A
u: 0.075%) 480 g and 1% aqueous dispersant solution 0.2
g of the mixed solution was added with stirring to obtain a colloidal dispersion of gold-coated silver fine particles coated with simple gold.

【００７９】この金コート銀微粒子のコロイド分散液を
イオン交換樹脂（三菱化学社製商品名ダイヤイオンＳＫ
１Ｂ，ＳＡ２０ＡＰ）で脱塩した後、限外ろ過により濃
縮し金コート銀微粒子の濃縮液（Ａ液）を得た。This colloidal dispersion of gold-coated silver fine particles was converted to an ion-exchange resin (Diaion SK manufactured by Mitsubishi Chemical Corporation).
1B, SA20AP) and concentrated by ultrafiltration to obtain a concentrated solution (solution A) of gold-coated silver fine particles.

【００８０】次に、上記Ａ液に、化学式（５）で示され
るポリビニルアルコール、および、エタノール（Ｅ
Ａ）、ジアセトンアルコール（ＤＡＡ）を加えて実施例
１に係る透明導電層形成用塗液（Ａｇ：０．０８％、Ａ
ｕ：０．３２％、ポリビニルアルコール：０.００４
％、水：１１．２％、ＥＡ：７３．３％、ＤＡＡ：１
５．０％）を得た。Next, the above solution A was added to the polyvinyl alcohol represented by the chemical formula (5) and ethanol (E
A), diacetone alcohol (DAA) was added, and the coating liquid for forming a transparent conductive layer according to Example 1 (Ag: 0.08%, A
u: 0.32%, polyvinyl alcohol: 0.004
%, Water: 11.2%, EA: 73.3%, DAA: 1
5.0%).

【００８１】[0081]

【化８】 Embedded image

【００８２】得られた実施例１に係る透明導電層形成用
塗液を透過電子顕微鏡で観察した結果、金コート銀微粒
子の平均粒径は、８.７ｎｍであった。As a result of observing the obtained coating liquid for forming a transparent conductive layer according to Example 1 with a transmission electron microscope, the average particle diameter of the gold-coated silver fine particles was 8.7 nm.

【００８３】次に、この実施例１に係る透明導電層形成
用塗液を、１μｍのメンブレンフィルターでろ過した
後、底部丸型形状の１５ｍｍ径ガラス製試験管に２ｇ分
取し、２５℃に設定した恒温槽に１０日間静置した。Next, the coating liquid for forming a transparent conductive layer according to Example 1 was filtered through a 1 μm membrane filter, and 2 g of the coating liquid was placed in a 15 mm-diameter glass test tube having a round bottom shape. It was left still for 10 days in the set thermostat.

【００８４】そして、１０日間静した試験管をゆっくり
ひっくり返し、試験管底部に付着した金コート銀微粒子
の沈殿を黙視で評価した。沈殿の評価基準を以下に示
す。Then, the test tube, which had been still for 10 days, was slowly turned upside down, and the precipitation of the gold-coated silver fine particles adhering to the bottom of the test tube was evaluated by visual observation. The evaluation criteria for precipitation are shown below.

【００８５】目視で沈殿が確認できない：○ 目視で沈殿が確認でき、その大きさが１mm以下である：
△ 目視で沈殿が確認でき、その大きさが１mm以上である：
× 次に、この実施例１に係る透明導電層形成用塗液を、３
５℃に加熱されたガラス基板（厚さ３ｍｍのソーダライ
ムガラス）上に、スピンコート（１５０ｒｐｍ，１２０
秒間）した後、続けて、シリカゾル液から成る透明コー
ト層形成用塗布液をスピンコート（１５０ｒｐｍ，６０
秒間）し、更に、１８０℃、２０分間硬化させて、金と
銀の貴金属微粒子を含有する透明導電層と、酸化ケイ素
を主成分とするシリケート膜から成る透明コート層とで
構成された透明２層膜付きのガラス基板、すなわち、実
施例１に係る透明導電性基材を得た。No sediment can be visually confirmed: ○ Precipitate can be visually confirmed, and the size is 1 mm or less:
△ Precipitation can be visually confirmed and the size is 1 mm or more:
× Next, the coating liquid for forming a transparent conductive layer according to Example 1 was applied to 3
Spin coating (150 rpm, 120 rpm) on a glass substrate (3 mm thick soda lime glass) heated to 5 ° C.
After that, a coating liquid for forming a transparent coat layer composed of a silica sol liquid is continuously spin-coated (150 rpm, 60 rpm).
For 2 seconds) and further cured at 180 ° C. for 20 minutes to form a transparent layer 2 comprising a transparent conductive layer containing noble metal fine particles of gold and silver and a transparent coat layer composed of a silicate film containing silicon oxide as a main component. A glass substrate with a layer film, that is, a transparent conductive substrate according to Example 1 was obtained.

【００８６】ここで、上記シリカゾル液は、メチルシリ
ケート５１（コルコート社製商品名）を１９．６部、エ
タノール５７．８部、１％硝酸水溶液７．９部、純水１
４．７部を用いて、ＳｉＯ2（酸化ケイ素）固形分濃度
が１０％で、重量平均分子量が１７３０のものを調製
し、最終的に、ＳｉＯ2固形分濃度が０．８％となるよ
うにイソプロピルアルコール（ＩＰＡ）とｎ−ブタノー
ル（ＮＢＡ）の混合物（ＩＰＡ／ＮＢＡ＝３／１）によ
り希釈した液（Ｃ液）１００ｇに、γ−メルカプトプロ
ピルトリメトキシシラン０．０２ｇを加えて得た。Here, the above silica sol solution was composed of 19.6 parts of methyl silicate 51 (trade name, manufactured by Colcoat), 57.8 parts of ethanol, 7.9 parts of 1% nitric acid aqueous solution, and 1 part of pure water.
Using 4.7 parts, a product having a SiO 2 (silicon oxide) solid content concentration of 10% and a weight average molecular weight of 1,730 was prepared, and finally, a SiO 2 solid content concentration of 0.8% was obtained. To 100 g of a liquid (solution C) diluted with a mixture of isopropyl alcohol (IPA) and n-butanol (NBA) (IPA / NBA = 3/1), and 0.02 g of γ-mercaptopropyltrimethoxysilane was added. .

【００８７】そして、透明導電層形成用塗液の沈殿評価
とガラス基板上に形成された透明２層膜の膜特性（可視
光線透過率、ヘーズ値、ボトム反射率／ボトム波長、表
面抵抗）を以下の表１に示す。Then, the precipitation evaluation of the coating liquid for forming the transparent conductive layer and the film properties (visible light transmittance, haze value, bottom reflectance / bottom wavelength, surface resistance) of the transparent two-layer film formed on the glass substrate were evaluated. It is shown in Table 1 below.

【００８８】尚、上記ボトム反射率とは透明導電性基材
の反射プロファイルにおいて極小の反射率をいい、ボト
ム波長とは反射率が極小における波長を意味している。The bottom reflectance refers to a minimum reflectance in the reflection profile of the transparent conductive substrate, and the bottom wavelength refers to a wavelength at which the reflectance is minimum.

【００８９】また、表１において可視光線波長域（３８
０〜７８０ｎｍ）の５ｎｍおきの各波長における透明基
板（ガラス基板）を含まない透明２層膜だけの透過率
は、以下の様にして求められている。In Table 1, the visible light wavelength range (38
The transmittance of only the transparent two-layer film not including the transparent substrate (glass substrate) at each wavelength of 5 nm (0 to 780 nm) is determined as follows.

【００９０】すなわち、 透明基板を含まない透明２層膜だけの透過率（％）＝
［（透明基板ごと測定した透過率）／（透明基板の透過
率）］×１００ ここで、本明細書においては、特に言及しない限り、透
過率および透過率プロファイルとしては、透明基板を含
まない透明２層膜だけの透過率および透過率プロファイ
ルを用いている。That is, the transmittance (%) of only the transparent two-layer film not including the transparent substrate =
[(Transmittance measured for each transparent substrate) / (Transmittance of transparent substrate)] × 100 In this specification, unless otherwise specified, the transmittance and the transmittance profile are defined as transparent without the transparent substrate. The transmittance and transmittance profile of only the two-layer film are used.

【００９１】尚、各実施例と比較例において透明基板
（ガラス基板）上に形成された透明２層膜の膜厚につい
ては、上述のＴＥＭによる膜断面観察により計測してお
り、透明導電層については２５〜３５ｎｍ、透明コート
層については６０〜８０ｎｍの範囲であった。In each of the examples and comparative examples, the thickness of the transparent two-layer film formed on the transparent substrate (glass substrate) was measured by the above-described TEM observation of the film cross section. Was in the range of 25 to 35 nm, and the transparent coat layer was in the range of 60 to 80 nm.

【００９２】また、透明２層膜の表面抵抗は、三菱化学
(株)製の表面抵抗計ロレスタＡＰ（ＭＣＰ−Ｔ４００）
を用い測定した。ヘイズ値と可視光線透過率は、村上色
彩技術研究所製ヘイズメーター（ＨＲ−２００）を用い
て測定した。反射率、および反射・透過プロファイル
は、日立製作所(株)製分光光度計（Ｕ−４０００）を用
いて測定した。また、金コート銀微粒子の粒径は日本電
子製の透過電子顕微鏡で評価している。The surface resistance of the transparent two-layer film was determined by Mitsubishi Chemical.
Surface resistance meter Loresta AP (MCP-T400) manufactured by Co., Ltd.
It measured using. The haze value and the visible light transmittance were measured using a haze meter (HR-200) manufactured by Murakami Color Research Laboratory. The reflectance and the reflection / transmission profile were measured using a spectrophotometer (U-4000) manufactured by Hitachi, Ltd. The particle size of the gold-coated silver fine particles was evaluated by a transmission electron microscope manufactured by JEOL.

【００９３】［実施例２］実施例１で、ポリビニルアル
コールの配合量を変えて、実施例２に係る透明導電層形
成用塗液（Ａｇ：０．０８％、Ａｕ：０．３２％、ポリ
ビニルアルコール：０.００８％、水：１０．７％、Ｅ
Ａ：７３．７％、ＤＡＡ：１５．０％）を得た以外は、
実施例１と同様にを行い、金と銀の貴金属微粒子を含有
する透明導電層と、酸化ケイ素を主成分とするシリケー
ト膜から成る透明コート層とで構成された透明２層膜付
きのガラス基板、すなわち、実施例２に係る透明導電性
基材を得た。Example 2 The coating liquid for forming a transparent conductive layer according to Example 2 (Ag: 0.08%, Au: 0.32%, polyvinyl Alcohol: 0.008%, water: 10.7%, E
A: 73.7%, DAA: 15.0%).
A glass substrate with a transparent two-layer film composed of a transparent conductive layer containing noble metal fine particles of gold and silver and a transparent coat layer composed of a silicate film containing silicon oxide as a main component was prepared in the same manner as in Example 1. That is, a transparent conductive substrate according to Example 2 was obtained.

【００９４】そして、透明導電層形成用塗液の沈殿評価
とガラス基板上に形成された透明２層膜の膜特性を以下
の表１に示す。Table 1 below shows the evaluation of the precipitation of the coating liquid for forming the transparent conductive layer and the film properties of the transparent two-layer film formed on the glass substrate.

【００９５】［実施例３］実施例１において、上記化学
式（５）で示されるポリビニルアルコールに代えて下記
化学式（６）で示されるポリビニルブチラールを用い、
実施例３に係る透明導電層形成用塗液（Ａｇ：０．０８
％、Ａｕ：０．３２％、ポリビニルブチラール：０.０
０８％、水：１０．７％、ＥＡ：７３．８％、ＤＡＡ：
１５．０％）を得た以外は、実施例１と同様に行い、金
と銀の貴金属微粒子を含有する透明導電層と、酸化ケイ
素を主成分とするシリケート膜から成る透明コート層と
で構成された透明２層膜付きのガラス基板、すなわち、
実施例３に係る透明導電性基材を得た。Example 3 In Example 1, a polyvinyl butyral represented by the following chemical formula (6) was used instead of the polyvinyl alcohol represented by the above chemical formula (5).
The coating liquid for forming a transparent conductive layer according to Example 3 (Ag: 0.08)
%, Au: 0.32%, polyvinyl butyral: 0.0
08%, water: 10.7%, EA: 73.8%, DAA:
(15.0%) was obtained in the same manner as in Example 1, and was composed of a transparent conductive layer containing fine gold and silver fine particles and a transparent coat layer composed of a silicate film containing silicon oxide as a main component. Glass substrate with a transparent two-layer film, ie,
A transparent conductive substrate according to Example 3 was obtained.

【００９６】[0096]

【化９】 Embedded image

【００９７】そして、透明導電層形成用塗液の沈殿評価
とガラス基板上に形成された透明２層膜の膜特性を以下
の表１に示す。Table 1 below shows the evaluation of the precipitation of the coating liquid for forming a transparent conductive layer and the film properties of the transparent two-layer film formed on the glass substrate.

【００９８】［実施例４］実施例１において、上記ポリ
ビニルアルコールに代えて上記化学式（６）で示される
ポリビニルブチラールを用い、実施例４に係る透明導電
層形成用塗液（Ａｇ：０．０８％、Ａｕ：０．３２％、
ポリビニルブチラール：０.０２％、水：１０．７％、
ＥＡ：７３．８％、ＤＡＡ：１５．０％）を得た以外
は、実施例１と同様行い、金と銀の貴金属微粒子を含有
する透明導電層と、酸化ケイ素を主成分とするシリケー
ト膜から成る透明コート層とで構成された透明２層膜付
きのガラス基板、すなわち、実施例４に係る透明導電性
基材を得た。Example 4 A transparent conductive layer forming coating solution (Ag: 0.08) according to Example 4 was obtained by using the polyvinyl butyral represented by the chemical formula (6) in place of the polyvinyl alcohol in Example 1. %, Au: 0.32%,
Polyvinyl butyral: 0.02%, water: 10.7%,
EA: 73.8%, DAA: 15.0%), except that a transparent conductive layer containing fine gold and silver fine particles and a silicate film mainly containing silicon oxide were obtained. , A glass substrate with a transparent two-layer film composed of a transparent conductive layer according to Example 4.

【００９９】そして、透明導電層形成用塗液の沈殿評価
とガラス基板上に形成された透明２層膜の膜特性を以下
の表１に示す。Table 1 below shows the evaluation of the precipitation of the coating liquid for forming a transparent conductive layer and the film characteristics of the transparent two-layer film formed on the glass substrate.

【０１００】［実施例５］実施例１において、上記ポリ
ビニルアルコールに代えて下記化学式（７）で示される
ポリ酢酸ビニルを用い、実施例５に係る透明導電層形成
用塗液（Ａｇ：０．０８％、Ａｕ：０．３２％、ポリ酢
酸ビニル：０.００８％、水：１０．７％、ＥＡ：７
３．８％、ＤＡＡ：１５．０％）を得た以外は、実施例
１と同様に行い、金と銀の貴金属微粒子を含有する透明
導電層と、酸化ケイ素を主成分とするシリケート膜から
成る透明コート層とで構成された透明２層膜付きのガラ
ス基板、すなわち、実施例５に係る透明導電性基材を得
た。[Example 5] In Example 1, the polyvinyl alcohol represented by the following chemical formula (7) was used in place of the polyvinyl alcohol, and the coating liquid for forming a transparent conductive layer (Ag: 0. 08%, Au: 0.32%, polyvinyl acetate: 0.008%, water: 10.7%, EA: 7
(3.8%, DAA: 15.0%) was obtained in the same manner as in Example 1, except that a transparent conductive layer containing fine gold and silver fine particles and a silicate film containing silicon oxide as a main component were used. Thus, a glass substrate with a transparent two-layer film composed of a transparent coat layer and a transparent conductive substrate according to Example 5 was obtained.

【０１０１】[0101]

【化１０】 Embedded image

【０１０２】そして、透明導電層形成用塗液の沈殿評価
とガラス基板上に形成された透明２層膜の膜特性を以下
の表１に示す。Table 1 below shows the evaluation of the precipitation of the coating liquid for forming a transparent conductive layer and the film characteristics of the transparent two-layer film formed on the glass substrate.

【０１０３】［実施例６］実施例１において、上記ポリ
ビニルアルコールに代えて上記化学式（７）で示される
ポリ酢酸ビニルを用い、実施例６に係る透明導電層形成
用塗液（Ａｇ：０．０８％、Ａｕ：０．３２％、ポリ酢
酸ビニル：０.０２％、水：１０．７％、ＥＡ：７３．
８％、ＤＡＡ：１５．０％）を得た以外は、実施例１と
同様に行い、金と銀の貴金属微粒子を含有する透明導電
層と、酸化ケイ素を主成分とするシリケート膜から成る
透明コート層とで構成された透明２層膜付きのガラス基
板、すなわち、実施例６に係る透明導電性基材を得た。Example 6 The same procedure as in Example 1 was repeated except that the polyvinyl alcohol represented by the chemical formula (7) was used in place of the polyvinyl alcohol, and the coating liquid for forming a transparent conductive layer (Ag: 0. 08%, Au: 0.32%, polyvinyl acetate: 0.02%, water: 10.7%, EA: 73.
8%, DAA: 15.0%), except that a transparent conductive layer containing fine gold and silver fine particles and a silicate film containing silicon oxide as a main component were obtained. A glass substrate with a transparent two-layer film composed of a coat layer and a transparent conductive substrate according to Example 6 was obtained.

【０１０４】そして、透明導電層形成用塗液の沈殿評価
とガラス基板上に形成された透明２層膜の膜特性を以下
の表１に示す。The following Table 1 shows the evaluation of the precipitation of the coating liquid for forming a transparent conductive layer and the film properties of the transparent two-layer film formed on the glass substrate.

【０１０５】［実施例７］実施例１において、上記ポリ
ビニルアルコールに代えて下記化学式（８）で示される
アクリル−酢酸ビニル共重合体を用い、実施例７に係る
透明導電層形成用塗液（Ａｇ：０．０８％、Ａｕ：０．
３２％、アクリル−酢酸ビニル共重合体：０.００４
％、水：１０．７％、ＥＡ：７３．８％、ＤＡＡ：１
５．０％）を得た以外は、実施例１と同様に行い、金と
銀の貴金属微粒子を含有する透明導電層と、酸化ケイ素
を主成分とするシリケート膜から成る透明コート層とで
構成された透明２層膜付きのガラス基板、すなわち、実
施例７に係る透明導電性基材を得た。[Example 7] In Example 1, an acrylic-vinyl acetate copolymer represented by the following chemical formula (8) was used in place of the polyvinyl alcohol, and the coating liquid for forming a transparent conductive layer according to Example 7 ( Ag: 0.08%, Au: 0.
32%, acryl-vinyl acetate copolymer: 0.004
%, Water: 10.7%, EA: 73.8%, DAA: 1
5.0%), a transparent conductive layer containing noble metal fine particles of gold and silver, and a transparent coat layer composed of a silicate film containing silicon oxide as a main component. The obtained glass substrate with a transparent two-layer film, that is, the transparent conductive substrate according to Example 7 was obtained.

【０１０６】[0106]

【化１１】 Embedded image

【０１０７】そして、透明導電層形成用塗液の沈殿評価
とガラス基板上に形成された透明２層膜の膜特性を以下
の表１に示す。The following Table 1 shows the evaluation of the precipitation of the coating liquid for forming a transparent conductive layer and the film properties of the transparent two-layer film formed on the glass substrate.

【０１０８】［実施例８］実施例１において、上記ポリ
ビニルアルコールに代えて上記化学式（８）で示される
アクリル−酢酸ビニル共重合体を用い、実施例８に係る
透明導電層形成用塗液（Ａｇ：０．０８％、Ａｕ：０．
３２％、アクリル−酢酸ビニル樹脂共重合体：０.００
８％、水：１０．７％、ＥＡ：７３．８％、ＤＡＡ：１
５．０％）を得た以外は、実施例１と同様に行い、金と
銀の貴金属微粒子を含有する透明導電層と、酸化ケイ素
を主成分とするシリケート膜から成る透明コート層とで
構成された透明２層膜付きのガラス基板、すなわち、実
施例８に係る透明導電性基材を得た。Example 8 In Example 1, the acryl-vinyl acetate copolymer represented by the chemical formula (8) was used in place of the polyvinyl alcohol, and the coating liquid for forming a transparent conductive layer according to Example 8 ( Ag: 0.08%, Au: 0.
32%, acrylic-vinyl acetate resin copolymer: 0.00
8%, water: 10.7%, EA: 73.8%, DAA: 1
5.0%), a transparent conductive layer containing noble metal fine particles of gold and silver, and a transparent coat layer composed of a silicate film containing silicon oxide as a main component. The obtained glass substrate with a transparent two-layer film, that is, the transparent conductive substrate according to Example 8 was obtained.

【０１０９】そして、透明導電層形成用塗液の沈殿評価
とガラス基板上に形成された透明２層膜の膜特性を以下
の表１に示す。Table 1 below shows the evaluation of the precipitation of the coating liquid for forming a transparent conductive layer and the film characteristics of the transparent two-layer film formed on the glass substrate.

【０１１０】［比較例１］実施例１において、Ａ液に、
エタノール（ＥＡ）、ジアセトンアルコール（ＤＡＡ）
を加え高分子樹脂を含有しない比較例１に係る透明導電
層形成用塗液（Ａｇ：０．０８％、Ａｕ：０．３２％、
水：１０．７％、ＥＡ：７３．９％、ＤＡＡ：１５．０
％）を得た以外は、実施例１と同様に行い、金と銀の貴
金属微粒子を含有する透明導電層と、酸化ケイ素を主成
分とするシリケート膜から成る透明コート層とで構成さ
れた透明２層膜付きのガラス基板、すなわち、比較例１
に係る透明導電性基材を得た。[Comparative Example 1] In Example 1, solution A was added to
Ethanol (EA), diacetone alcohol (DAA)
And a coating liquid for forming a transparent conductive layer according to Comparative Example 1 containing no polymer resin (Ag: 0.08%, Au: 0.32%,
Water: 10.7%, EA: 73.9%, DAA: 15.0
%) Except that a transparent conductive layer containing gold and silver noble metal fine particles and a transparent coat layer composed of a silicate film containing silicon oxide as a main component were obtained. Glass substrate with two-layer film, ie, Comparative Example 1
Was obtained.

【０１１１】そして、透明導電層形成用塗液の沈殿評価
とガラス基板上に形成された透明２層膜の膜特性を以下
の表１に示す。Table 1 below shows the evaluation of the precipitation of the coating liquid for forming a transparent conductive layer and the film characteristics of the transparent two-layer film formed on the glass substrate.

【０１１２】［比較例２］実施例１において、上記ポリ
ビニルアルコールに代えて下記化学式（９）で示される
ポリビニルピロリドンを用い、比較例２に係る透明導電
層形成用塗液（Ａｇ：０．０８％、Ａｕ：０．３２％、
ポリビニルピロリドン：０.００８％、水：１０．７
％、ＥＡ：７３．７％、ＤＡＡ：１５．０％）を得た以
外は、実施例１と同様に行い、金と銀の貴金属微粒子を
含有する透明導電層と、酸化ケイ素を主成分とするシリ
ケート膜から成る透明コート層とで構成された透明２層
膜付きのガラス基板、すなわち、比較例２に係る透明導
電性基材を得た。Comparative Example 2 The coating liquid for forming a transparent conductive layer according to Comparative Example 2 (Ag: 0.08) was prepared by using polyvinyl pyrrolidone represented by the following chemical formula (9) in place of the polyvinyl alcohol in Example 1. %, Au: 0.32%,
Polyvinyl pyrrolidone: 0.008%, water: 10.7
%, EA: 73.7%, DAA: 15.0%) in the same manner as in Example 1, except that a transparent conductive layer containing gold and silver noble metal fine particles and silicon oxide as main components were used. A glass substrate with a transparent two-layer film composed of a transparent coat layer made of a silicate film, that is, a transparent conductive substrate according to Comparative Example 2 was obtained.

【０１１３】[0113]

【化１２】 Embedded image

【０１１４】そして、透明導電層形成用塗液の沈殿評価
とガラス基板上に形成された透明２層膜の膜特性を以下
の表１に示す。 ［比較例３］実施例１において、上記ポリビニルアルコ
ールに代えて上記化学式（７）で示されるポリ酢酸ビニ
ルを用い、比較例３に係る透明導電層形成用塗液（Ａ
ｇ：０．０８％、Ａｕ：０．３２％、ポリ酢酸ビニル：
０.０００６７％、水：１０．７％、ＥＡ：７３．７
％、ＤＡＡ：１５．０％）を得た以外は、実施例１と同
様に行い、金と銀の貴金属微粒子を含有する透明導電層
と、酸化ケイ素を主成分とするシリケート膜から成る透
明コート層とで構成された透明２層膜付きのガラス基
板、すなわち、比較例３に係る透明導電性基材を得た。Table 1 below shows the evaluation of the precipitation of the coating liquid for forming a transparent conductive layer and the film characteristics of the transparent two-layer film formed on the glass substrate. Comparative Example 3 In Example 1, the polyvinyl alcohol represented by the chemical formula (7) was used in place of the polyvinyl alcohol, and the transparent conductive layer forming coating liquid (A
g: 0.08%, Au: 0.32%, polyvinyl acetate:
0.000067%, water: 10.7%, EA: 73.7
%, DAA: 15.0%) in the same manner as in Example 1, except that a transparent conductive layer containing fine gold and silver fine particles and a silicate film containing silicon oxide as a main component were used. Thus, a glass substrate with a transparent two-layer film composed of layers, that is, a transparent conductive substrate according to Comparative Example 3 was obtained.

【０１１５】そして、透明導電層形成用塗液の沈殿評価
とガラス基板上に形成された透明２層膜の膜特性を以下
の表１に示す。Table 1 below shows the evaluation of the precipitation of the coating liquid for forming a transparent conductive layer and the film characteristics of the transparent two-layer film formed on the glass substrate.

【０１１６】［比較例４］実施例１において、上記ポリ
ビニルアルコールに代えて上記化学式（７）で示される
ポリ酢酸ビニルを用い、比較例３に係る透明導電層形成
用塗液（Ａｇ：０．０８％、Ａｕ：０．３２％、ポリ酢
酸ビニル：０.１％、水：１０．７％、ＥＡ：７３．７
％、ＤＡＡ：１５．０％）を得た以外は、実施例１と同
様に行い、金と銀の貴金属微粒子を含有する透明導電層
と、酸化ケイ素を主成分とするシリケート膜から成る透
明コート層とで構成された透明２層膜付きのガラス基
板、すなわち、比較例4に係る透明導電性基材を得た。[Comparative Example 4] In Example 1, the polyvinyl alcohol represented by the chemical formula (7) was used in place of the polyvinyl alcohol, and the coating liquid for forming a transparent conductive layer (Ag: 0. 08%, Au: 0.32%, polyvinyl acetate: 0.1%, water: 10.7%, EA: 73.7
%, DAA: 15.0%) in the same manner as in Example 1, except that a transparent conductive layer containing fine gold and silver fine particles and a silicate film containing silicon oxide as a main component were used. A glass substrate with a transparent two-layer film composed of the above-mentioned layers, that is, a transparent conductive substrate according to Comparative Example 4 was obtained.

【０１１７】そして、透明導電層形成用塗液の沈殿評価
とガラス基板上に形成された透明２層膜の膜特性を以下
の表１に示す。The following Table 1 shows the evaluation of the precipitation of the coating liquid for forming a transparent conductive layer and the film properties of the transparent two-layer film formed on the glass substrate.

【０１１８】[0118]

【表１】 [Table 1]

【０１１９】［評 価］ １．表１に示された「沈澱評価」の結果から明らかなよ
うに、各実施例に係る透明導電層形成用塗液においては
貴金属コート銀微粒子（金コート銀微粒子）の良好な分
散安定性が得られ、１０日以上保存しても貴金属コート
銀微粒子（金コート銀微粒子）の凝集が生じないことが
確認される。[Evaluation] As is clear from the results of the “precipitation evaluation” shown in Table 1, the dispersion liquid of the noble metal-coated silver fine particles (gold-coated silver fine particles) was obtained in the coating liquid for forming the transparent conductive layer according to each example. It was confirmed that no noble metal-coated silver fine particles (gold-coated silver fine particles) were aggregated even after storage for 10 days or more.

【０１２０】他方、高分子樹脂が添加されていない比較
例１においては上記「沈澱評価」が×（沈澱物の大きさ
が１ｍｍ以上）となっており、貴金属コート銀微粒子
（金コート銀微粒子）の分散安定性が不良であることが
確認される。On the other hand, in Comparative Example 1 in which the polymer resin was not added, the above “precipitation evaluation” was x (the size of the precipitate was 1 mm or more), and noble metal-coated silver fine particles (gold-coated silver fine particles). Is confirmed to have poor dispersion stability.

【０１２１】また、各実施例に係る透明導電層において
は貴金属微粒子の網目状の導電パスが形成されているこ
とがＴＥＭ観察により確認されたが、高分子樹脂として
ポリビニルピロリドンが添加された比較例２においては
上記「沈澱評価」が○であるが、上記網目状の導電パス
の形成がされず「表面抵抗」が１０5Ω／□以上となり
良好な導電性を有する透明導電層が形成できないことが
確認される。Further, it was confirmed by TEM observation that a network-shaped conductive path of noble metal fine particles was formed in the transparent conductive layer according to each example. However, the comparative example in which polyvinylpyrrolidone was added as a polymer resin was used. In No. 2, the above “precipitation evaluation” is ○, but the network-like conductive path was not formed and the “surface resistance” was 10 5 Ω / □ or more and a transparent conductive layer having good conductivity could not be formed. Is confirmed.

【０１２２】また、高分子樹脂としてポリ酢酸ビニルが
添加された比較例３においては、ポリ酢酸ビニルの貴金
属コート銀微粒子（金コート銀微粒子）に対する配合割
合の条件が満たされていないため（高分子樹脂１重量部
に対し貴金属コート銀微粒子６００重量部となってい
る）、上記「沈澱評価」が△（沈澱物の大きさが１ｍｍ
以下）となっている。但し、「表面抵抗」は３２０Ω／
□であり良好な導電性を有する透明導電層の形成は可能
であることが確認される。In Comparative Example 3 in which polyvinyl acetate was added as a polymer resin, the condition of the mixing ratio of polyvinyl acetate to noble metal-coated silver fine particles (gold-coated silver fine particles) was not satisfied (polymer The noble metal-coated silver fine particles were 600 parts by weight with respect to 1 part by weight of the resin), and the above “precipitation evaluation” was Δ (the size of the precipitate was 1 mm
Below). However, the “surface resistance” is 320Ω /
It is confirmed that it is possible to form a transparent conductive layer having □ and good conductivity.

【０１２３】また、高分子樹脂としてポリ酢酸ビニルが
添加された比較例４においても、ポリ酢酸ビニルの貴金
属コート銀微粒子（金コート銀微粒子）に対する配合割
合の条件が満たされていないため（高分子樹脂１重量部
に対し貴金属コート銀微粒子４重量部となっている）、
「表面抵抗」が１０5Ω／□以上となり良好な導電性を
有する透明導電層が形成できないことが確認される。但
し、上記「沈澱評価」は○であり、貴金属コート銀微粒
子（金コート銀微粒子）の良好な分散安定性が得られる
ことも確認される。 ２．次に、表１に示された「表面抵抗」の結果から明ら
かなように、各実施例においては透明導電層内に高分子
樹脂が残留しているにも拘わらずその透明２層膜の表面
抵抗は許容範囲（１０〜５０００Ω／□）内にあり、実
用上問題無いことが確認される。 ３．また、表１に示された「ボトム反射率／ボトム波
長」の結果から明らかなように、各実施例に係る透明導
電性基材においては比較的良好な低反射率が得られてい
ることも確認される。 ４．尚、各実施例に係る透明導電性基材に対しては以下
に述べるような「耐候性試験」も合わせて行なってい
る。すなわち、各実施例に係る透明導電性基材を１０％
食塩水溶液に２４時間浸漬し、透明基板（ガラス基板）
上に設けた透明２層膜の透過率および外観を調べたが変
化は観察されなかった。Also, in Comparative Example 4 in which polyvinyl acetate was added as a polymer resin, the condition of the mixing ratio of polyvinyl acetate to the noble metal-coated silver fine particles (gold-coated silver fine particles) was not satisfied (polymer 4 parts by weight of noble metal-coated silver fine particles per 1 part by weight of resin),
The "surface resistance" is 10 5 Ω / □ or more, and it is confirmed that a transparent conductive layer having good conductivity cannot be formed. However, the above “precipitation evaluation” is ○, which confirms that good dispersion stability of the noble metal-coated silver fine particles (gold-coated silver fine particles) can be obtained. 2. Next, as is apparent from the results of “surface resistance” shown in Table 1, in each of the examples, although the polymer resin remained in the transparent conductive layer, the surface of the transparent two-layer film was not changed. The resistance is within the allowable range (10 to 5000 Ω / □), and it is confirmed that there is no practical problem. 3. Further, as is clear from the result of “bottom reflectance / bottom wavelength” shown in Table 1, the transparent conductive base material according to each example may have a relatively good low reflectance. It is confirmed. 4. In addition, the "weather resistance test" described below is also performed on the transparent conductive substrate according to each example. That is, 10% of the transparent conductive base material according to each example was used.
Transparent substrate (glass substrate) immersed in saline solution for 24 hours
The transmittance and appearance of the transparent two-layer film provided above were examined, but no change was observed.

【０１２４】従って、各実施例に係る透明導電性基材
は、従来と同様に、耐候性、耐薬品性の特性も具備して
いることが確認される。Accordingly, it is confirmed that the transparent conductive base material according to each of the examples also has weather resistance and chemical resistance characteristics as in the prior art.

【０１２５】[0125]

【発明の効果】請求項１〜２記載の発明に係る透明導電
層形成用塗液によれば、貴金属コート銀微粒子が含まれ
る透明導電層形成用塗液を１０日以上保存しても、塗布
欠陥等の原因となる貴金属コート銀微粒子の凝集を防ぐ
ことができ、しかも良好な導電性、低反射率並びに耐候
性、耐薬品性等の諸特性を有する透明導電性基材を製造
できる効果を有する。According to the coating liquid for forming a transparent conductive layer according to the first and second aspects of the present invention, even if the coating liquid for forming a transparent conductive layer containing noble metal-coated silver fine particles is stored for 10 days or more, the coating liquid can be applied. Prevents aggregation of noble metal-coated silver fine particles that cause defects, etc., and has the effect of producing a transparent conductive substrate having good conductivity, low reflectance, and various properties such as weather resistance and chemical resistance. Have.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｄ 131/04 Ｃ０９Ｄ 131/04 Ｈ０１Ｂ 1/22 Ｈ０１Ｂ 1/22 Ａ 5/00 5/00 Ｃ // Ｈ０１Ｂ 5/14 5/14 Ａ (72)発明者 行延 雅也 千葉県市川市中国分３丁目18番５号 住友 金属鉱山株式会社中央研究所内 (72)発明者 加藤 賢二 千葉県市川市中国分３丁目18番５号 住友 金属鉱山株式会社中央研究所内 Ｆターム(参考） 4J038 CE021 CE051 CE061 CE071 CF011 CF021 HA066 KA06 KA12 KA20 NA01 NA03 NA04 NA19 NA20 NA26 5G301 DA03 DA05 DA12 DA42 DD02 5G307 AA02 FA01 FB02 FC04 FC08 FC10 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C09D 131/04 C09D 131/04 H01B 1/22 H01B 1/22 A 5/00 5/00 C // H01B 5/14 5/14 A (72) Inventor Masaya Yukinobu 3-18-5, Chugoku-ku, Ichikawa-shi, Chiba Prefecture Sumitomo Metal Mining Co., Ltd. Central Research Laboratory (72) Inventor Kenji Kato 3-chome, Chugoku-ku, Ichikawa-shi, Chiba No. 18-5 Sumitomo Metal Mining Co., Ltd. Central Research Laboratory F term (reference) 4J038 CE021 CE051 CE061 CE071 CF011 CF021 HA066 KA06 KA12 KA20 NA01 NA03 NA04 NA19 NA20 NA26 5G301 DA03 DA05 DA12 DA42 DD02 5G307 AA02 FA01 FB02 FC04 FC08 FC10

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】透明基板およびこの透明基板上に順次形成
された透明導電層と透明コート層とで構成された透明２
層膜を備え、この透明２層膜の表面抵抗が１０〜５００
０Ω/□、可視光線領域の反射プロファイルにおいて極
小となる上記透明２層膜の反射率が０〜２．５％である
透明導電性基材の透明導電層形成用塗液において、 銀微粒子表面に金若しくは白金単体または金と白金の複
合体がコーティングされかつ金および／または白金を５
〜９５重量％含有する平均粒径１〜１００ｎｍの貴金属
コート銀微粒子、高分子樹脂および溶媒を主成分とし、
かつ、上記高分子樹脂が下記化学式（１）〜（３）で示
される繰り返し単位成分の内少なくとも１種類以上を分
子内に有する重合体で構成されると共に、高分子樹脂１
重量部に対し上記貴金属コート銀微粒子が５重量部〜５
００重量部の割合で配合されていることを特徴とする透
明導電層形成用塗液。 【化１】 【化２】 【化３】 1. A transparent substrate comprising a transparent substrate and a transparent conductive layer and a transparent coat layer sequentially formed on the transparent substrate.
The transparent two-layer film has a surface resistance of 10 to 500.
In a coating liquid for forming a transparent conductive layer of a transparent conductive substrate, wherein the reflectance of the transparent two-layer film is 0 Ω / □, the reflectance of the transparent two-layer film being the minimum in the reflection profile in the visible light region is 0 to 2.5%, Gold or platinum alone or a composite of gold and platinum is coated and gold and / or platinum
Noble metal-coated silver fine particles having an average particle size of 1 to 100 nm, containing a polymer resin and a solvent as main components;
Further, the polymer resin is composed of a polymer having at least one or more of the repeating unit components represented by the following chemical formulas (1) to (3) in the molecule, and the polymer resin 1
5 parts by weight of the noble metal-coated silver fine particles to 5 parts by weight
A coating liquid for forming a transparent conductive layer, which is blended at a ratio of 00 parts by weight. Embedded image Embedded image Embedded image 【請求項２】上記貴金属コート銀微粒子が、金および／
または白金を５０〜９５重量％含有することを特徴とす
る請求項１記載の透明導電層形成用塗液。2. The method of claim 1, wherein the noble metal-coated silver fine particles are gold and / or gold.
The coating liquid for forming a transparent conductive layer according to claim 1, wherein the coating liquid contains 50 to 95% by weight of platinum.
JP2000256504A 2000-08-25 2000-08-25 Coating liquid for forming transparent electroconductive layer Pending JP2002069335A (en)

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Country Link
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190123139A (en) * 2018-04-23 2019-10-31 삼성에스디아이 주식회사 Composition for forming electrode, electrode manufactured using the same and solar cell

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190123139A (en) * 2018-04-23 2019-10-31 삼성에스디아이 주식회사 Composition for forming electrode, electrode manufactured using the same and solar cell
KR102238769B1 (en) * 2018-04-23 2021-04-09 삼성에스디아이 주식회사 Composition for forming electrode, electrode manufactured using the same and solar cell

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