JP4958143B2 - Composition for forming transparent conductive film, transparent conductive film and display - Google Patents
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本発明は透明導電膜形成用組成物、透明導電膜及び表示面に透明導電膜を有するディスプレイに関し、より詳しくは、多様な透明基材の表面、特にＬＣＤやプラズマディスプレイ等の表示面に塗布又は印刷し、乾燥させることにより、優れた帯電防止効果を有し、色相吸収が無いので膜の可視光透過率が非常に高く且つ透過画像の色相が自然である透明導電膜を形成し得る組成物、そのような透明導電膜並びにそのような透明導電膜を表示面に有するディスプレイに関する。 The present invention relates to a composition for forming a transparent conductive film, a transparent conductive film, and a display having a transparent conductive film on a display surface. More specifically, the present invention is applied to the surface of various transparent substrates, particularly display surfaces such as LCDs and plasma displays. A composition capable of forming a transparent conductive film having excellent antistatic effect, no hue absorption, and a very high visible light transmittance of the film and a natural color of the transmitted image by printing and drying. The present invention also relates to such a transparent conductive film and a display having such a transparent conductive film on a display surface.
ＴＶブラウン管やコンピュータのディスプレイ等として用いられている陰極線管は、赤色、緑色、青色に発光する蛍光面に電子ビームを衝突させることによって文字や画像を表示面に映し出すものであるから、この表示面に発生する静電気により埃が付着して視認性が低下する。また最近、壁掛けテレビ等としての応用が進められているプラズマディスプレイにおいても、静電気の発生が指摘されている。 A cathode ray tube used as a TV cathode ray tube or a computer display projects characters and images on a display screen by colliding an electron beam against a fluorescent screen emitting red, green, and blue light. Visibility is reduced due to dust adhering to static electricity. Recently, the generation of static electricity has been pointed out in plasma displays that are being applied as wall-mounted televisions.
これらの問題を解決するために、従来は、銀、金等の微粒子を液中に均一に分散させた塗布液を表示装置の表示面上に塗布し乾燥させるか、又はスパッタ法や蒸着法によって導電性の透明金属薄膜を形成し、この透明金属薄膜の上層及び／又は下層に、これとは屈折率が異なる透明層を積層して帯電防止並びに反射防止を図っている。例えば、電磁波遮蔽効果及び反射防止効果に優れた透明導電膜として、平均粒径２ｎｍ〜２００ｎｍの金属微粒子からなる透明導電性微粒子層と、これとは屈折率が異なる透明被膜とからなるものが提案されている（例えば、特許文献１参照）。 In order to solve these problems, conventionally, a coating liquid in which fine particles such as silver and gold are uniformly dispersed in the liquid is applied on the display surface of the display device and dried, or by sputtering or vapor deposition. A conductive transparent metal thin film is formed, and a transparent layer having a different refractive index is laminated on the upper layer and / or the lower layer of the transparent metal thin film in order to prevent charging and reflection. For example, as a transparent conductive film excellent in electromagnetic wave shielding effect and antireflection effect, a transparent conductive fine particle layer composed of metal fine particles having an average particle diameter of 2 nm to 200 nm and a transparent film having a refractive index different from this are proposed. (For example, refer to Patent Document 1).
また、酸化物半導体透明膜は、一般に可視光に対して高い光透過率を示し、低抵抗でかつ膜強度が強いために、液晶ディスプレイなどの透明電極や太陽電池の窓材料、熱線反射膜、帯電防止膜など多方面に利用されている。このような酸化物半導体として、酸化錫、アンチモンを含有する酸化錫（以下、ＡＴＯ）、錫を含有する酸化インジウム（以下、ＩＴＯ）等が知られている（例えば、特許文献２〜７参照）。 In addition, an oxide semiconductor transparent film generally exhibits high light transmittance with respect to visible light, and has low resistance and strong film strength. Therefore, a transparent electrode such as a liquid crystal display, a window material for a solar cell, a heat ray reflective film, It is used in various fields such as antistatic film. As such an oxide semiconductor, tin oxide, tin oxide containing antimony (hereinafter referred to as ATO), indium oxide containing tin (hereinafter referred to as ITO), and the like are known (for example, see Patent Documents 2 to 7). .
従来は、絶縁体上に金属又は半導体性金属酸化物を真空蒸着、スパッタリング、イオンプレーティングなどの気相法により堆積させる方法、バインダー成分（結合剤）である樹脂溶液中に分散させた分散液を塗料又はインクとして塗布又は印刷する塗工法等が知られている。
しかし、金属微粒子として銀を用いた場合に得られる導電膜では、銀の光透過スペクトルに依存して４００ｎｍ〜５００ｎｍの透過光に吸収が生じ、導電膜が黄色に着色し、透過画像の色相が不自然に変化するという問題や、膜の可視光平均透過率が低いために膜厚分布に起因した透過色のムラが目立ち易く、その防止のために生産性が悪化するという問題があった。 However, in the conductive film obtained when silver is used as the metal fine particles, absorption occurs in transmitted light of 400 nm to 500 nm depending on the light transmission spectrum of silver, the conductive film is colored yellow, and the hue of the transmission image is There was a problem that it changed unnaturally, and since the average visible light transmittance of the film was low, unevenness in the transmitted color due to the film thickness distribution was easily noticeable, and there was a problem that productivity deteriorated to prevent it.
また、錫を含有する酸化インジウムを用いた導電膜形成用組成物で得られる透明導電膜でも、同様に黄色や青色に着色し、透過画像の色相が不自然に変化するという問題があった。ＡＴＯやＩＴＯの酸化物半導体透明膜は、赤外線領域、特に近赤外線領域に急峻な吸収があるために青味を帯びている。また、酸化錫などの赤外線領域に吸収の無い酸化物半導体透明膜においても４００ｎｍ付近の光透過率が低く、黄味を帯びている。そのため従来の酸化物半導体透明膜においては可視光領域の分光曲線がフラットにならず、透過光の色相が不自然に変化するという問題があった（図１のＩＴＯの場合の波長と光透過率との相関関係及びＳｎＯ2の場合の波長と光透過率との相関関係を示すグラフを参照のこと）。そのため透明基板を用いても、透明性が高く、導電性などの膜特性が実用目的に必要な水準に達している透明導電膜を得ることが困難であった。 Further, the transparent conductive film obtained from the conductive film-forming composition using indium oxide containing tin also has the problem that the color of the transmitted image changes unnaturally in the same manner as yellow or blue. An oxide semiconductor transparent film of ATO or ITO is bluish due to steep absorption in the infrared region, particularly the near infrared region. Further, even in an oxide semiconductor transparent film that does not absorb in the infrared region such as tin oxide, the light transmittance near 400 nm is low and yellowish. Therefore, the conventional oxide semiconductor transparent film has a problem that the spectral curve in the visible light region is not flat, and the hue of transmitted light changes unnaturally (wavelength and light transmittance in the case of ITO in FIG. 1). And the graph showing the correlation between the wavelength and the light transmittance in the case of SnO 2 ). Therefore, even when a transparent substrate is used, it has been difficult to obtain a transparent conductive film having high transparency and having film properties such as conductivity reaching a level necessary for practical purposes.
本発明は、上記の諸問題を解決するためになされたものであり、優れた帯電防止効果を有し、色相吸収が無いので膜の可視光透過率が非常に高く且つ透過画像の色相が自然である透明導電膜を形成し得る組成物、そのような透明導電膜並びにそのような透明導電膜を表示面に有するディスプレイを提供することを目的としている。 The present invention has been made to solve the above-described problems, and has an excellent antistatic effect and no hue absorption, so that the visible light transmittance of the film is very high and the hue of the transmitted image is natural. It is an object to provide a composition capable of forming a transparent conductive film, a transparent conductive film, and a display having such a transparent conductive film on a display surface.
本発明者らは、上記の目的を達成するためにバインダー成分中に分散させる導電性粉体について鋭意検討した結果、導電性粉体として水酸化錫〔Ｓｎ(ＯＨ) ４ 〕（以下、水酸化錫と記載する）粉体、又はドーパントとしてＰ、Ａｌ、Ｉｎ、Ｚｎ及びＳｂの少なくとも一種を含む水酸化錫粉体を用いることにより望ましい結果が得られることを見出し、本発明に到達した。 As a result of intensive studies on the conductive powder dispersed in the binder component in order to achieve the above object, the present inventors have found that the conductive powder is tin hydroxide [Sn (OH) 4 ] (hereinafter referred to as hydroxide). The present inventors have found that desirable results can be obtained by using a powder ( described as tin) or a tin hydroxide powder containing at least one of P, Al, In, Zn and Sb as a dopant.
即ち、本発明の透明導電膜形成用組成物は、バインダー成分及び該バインダー成分中に分散した導電性粉体からなり、該導電性粉体は水酸化錫粉体であることを特徴とする。 That is, the composition for forming a transparent conductive film of the present invention comprises a binder component and conductive powder dispersed in the binder component, and the conductive powder is tin hydroxide powder.
また、本発明の透明導電膜形成用組成物は、バインダー成分及び該バインダー成分中に分散した導電性粉体からなり、該導電性粉体はドーパントとしてＰ、Ａｌ、Ｉｎ、Ｚｎ及びＳｂの少なくとも一種を含む水酸化錫粉体であることを特徴とする。 The composition for forming a transparent conductive film of the present invention comprises a binder component and a conductive powder dispersed in the binder component, and the conductive powder contains at least P, Al, In, Zn and Sb as dopants. It is a tin hydroxide powder containing one kind.
更に、本発明の透明導電膜は、上記の透明導電膜形成用組成物を塗布又は印刷し、乾燥させて得られるものであることを特徴とする。また、本発明のディスプレイは、表示面に上記の透明導電膜を有することを特徴とする。 Furthermore, the transparent conductive film of the present invention is obtained by applying or printing the above composition for forming a transparent conductive film and drying it. The display of the present invention is characterized by having the transparent conductive film on the display surface.
本発明の透明導電膜形成用組成物は、塗料又はインクとして基板に塗布又は印刷し、乾燥させることによって基板上に透明導電膜を形成することができる。従って、比較的耐熱性の低い樹脂基板や多様な形状の基板にも適用でき、透明導電膜を連続的に大量生産でき、また大面積化も容易である。得られる透明導電膜については、成膜条件を調整することにより、例えば、表面抵抗値が好ましくは１０7〜１０12Ω／□、より好ましくは１０7〜１０11Ω／□、光透過率が好ましくは８５％以上、ヘイズが好ましくは２．５％以下という、透明性、導電性のいずれにも優れた透明導電膜となる。従って、本発明の透明導電膜形成用組成物は、液晶などの透明電極や、太陽電池の窓材料、赤外線反射膜、帯電防止膜、タッチパネル、面発熱体、電子写真記録など広範囲な分野に利用可能であり、各分野において優れた性能を示すことができる。 The composition for forming a transparent conductive film of the present invention can be applied or printed on a substrate as a paint or ink, and dried to form a transparent conductive film on the substrate. Therefore, it can be applied to resin substrates having relatively low heat resistance and substrates having various shapes, and the transparent conductive film can be continuously mass-produced and the area can be easily increased. About the transparent conductive film obtained, by adjusting the film forming conditions, for example, the surface resistance is preferably 10 7 to 10 12 Ω / □, more preferably 10 7 to 10 11 Ω / □, and the light transmittance is A transparent conductive film excellent in both transparency and conductivity, preferably 85% or more and haze preferably 2.5% or less. Therefore, the composition for forming a transparent conductive film of the present invention is used in a wide range of fields such as transparent electrodes such as liquid crystals, solar cell window materials, infrared reflective films, antistatic films, touch panels, surface heating elements, and electrophotographic recording. It is possible to show excellent performance in each field.
本発明で用いる水酸化錫粉体は図１に示すように、広範囲の波長に渡って光透過率の優れたものであり、このような水酸化錫粉体は市販品を利用してもよく、或いは公知の方法（例えば、錫の塩化物が溶解した酸性溶液をアルカリで中和して水酸化物を共沈させ、この共沈物を乾燥させる）で製造することもできる。この水酸化錫粉体は平均一次粒子径が０．２μｍ以下の超微粒子であることが好ましい。粒子径が０．２μｍ以下では透明膜が得られるが、０．２μｍを超えると透明性が低下するからである。しかし、透明性が重要でない用途に対しては、０．２μｍより大粒径の水酸化錫粉体も使用できる。なお、使用した水酸化錫の結晶性はＸ線回折分析よりアモルファス状態であった。また水酸化錫の圧粉体抵抗は１×１０9Ω・ｃｍ以下であることが好ましい。 As shown in FIG. 1, the tin hydroxide powder used in the present invention has excellent light transmittance over a wide range of wavelengths, and such a tin hydroxide powder may be a commercially available product. Alternatively, it can also be produced by a known method (for example, an acidic solution in which tin chloride is dissolved is neutralized with alkali to coprecipitate a hydroxide, and the coprecipitate is dried). The tin hydroxide powder is preferably ultrafine particles having an average primary particle size of 0.2 μm or less. If the particle diameter is 0.2 μm or less, a transparent film is obtained, but if it exceeds 0.2 μm, the transparency is lowered. However, for applications where transparency is not important, tin hydroxide powder having a particle size larger than 0.2 μm can also be used. In addition, the crystallinity of the used tin hydroxide was amorphous by X-ray diffraction analysis. The green compact resistance of tin hydroxide is preferably 1 × 10 9 Ω · cm or less.
本発明で用いる、ドーパントとしてＰ、Ａｌ、Ｉｎ、Ｚｎ及びＳｂの少なくとも一種を含む水酸化錫粉体は市販品を利用してもよく、或いは公知の方法（例えば、リンと錫の各塩化物が溶解した酸性溶液をアルカリで中和してリン／錫の水酸化物を共沈させ、この共沈物を乾燥させる）で製造することもできる。ドーパントとしてＰ、Ａｌ、Ｉｎ、Ｚｎ及びＳｂの少なくとも一種を含む水酸化錫粉体においては、（ドーパント＋Ｓｎ）に対するドーパントの量が好ましくは０．１〜２０ａｔ％の範囲内、より好ましくは１〜１５ａｔ％の範囲内のものが導電性が高いことから好ましい。ドーパント含有量がこの範囲を外れると、ドープした水酸化錫粒子自体の抵抗が高くなるため、形成された膜の導電性が低下する傾向がある。このドーパントとしてＰ、Ａｌ、Ｉｎ、Ｚｎ及びＳｂの少なくとも一種を含む水酸化錫粉体は上記と同様に平均一次粒子径が０．２μｍ以下の超微粒子であることが好ましい。 As the tin hydroxide powder containing at least one of P, Al, In, Zn, and Sb as a dopant used in the present invention, a commercially available product may be used, or a known method (for example, phosphorus and tin chlorides). An acidic solution in which is dissolved is neutralized with an alkali to coprecipitate phosphorus / tin hydroxide, and the coprecipitate is dried. In a tin hydroxide powder containing at least one of P, Al, In, Zn and Sb as a dopant, the amount of dopant relative to (dopant + Sn) is preferably within a range of 0.1 to 20 at%, more preferably 1 to 1. A material in the range of 15 at% is preferable because of its high conductivity. If the dopant content is out of this range, the resistance of the doped tin hydroxide particles themselves increases, and the conductivity of the formed film tends to decrease. The tin hydroxide powder containing at least one of P, Al, In, Zn, and Sb as the dopant is preferably ultrafine particles having an average primary particle diameter of 0.2 μm or less as described above.
本発明の透明導電膜形成用組成物においては、水酸化錫粉体又はドーパントとしてＰ、Ａｌ、Ｉｎ、Ｚｎ及びＳｂの少なくとも一種を含む水酸化錫粉体からなる導電性粉体とバインダー成分との質量比（導電性粉体／バインダー成分）は、好ましくは５／９５〜９５／５の範囲内、より好ましくは２０／８０〜９０／１０の範囲内、最も好ましくは３０／７０〜８５／１５の範囲内である。導電性粉体の量が上記質量比で５／９５より少ないと、得られる膜の透明性は十分であっても、導電性が悪くなる傾向がある。逆に、導電性粉体が上記質量比で９５／５より多いと、粉体の分散性が悪くなり、得られた導電膜の透明性、基板への密着性が低くなり、膜性能が低下する傾向がある。 In the composition for forming a transparent conductive film of the present invention, a conductive powder comprising a tin hydroxide powder or a tin hydroxide powder containing at least one of P, Al, In, Zn and Sb as a dopant, and a binder component The mass ratio (conductive powder / binder component) is preferably in the range of 5/95 to 95/5, more preferably in the range of 20/80 to 90/10, and most preferably 30/70 to 85 /. It is within the range of 15. When the amount of the conductive powder is less than 5/95 in the above mass ratio, the conductivity tends to deteriorate even if the resulting film has sufficient transparency. On the contrary, when the conductive powder is more than 95/5 in the above mass ratio, the dispersibility of the powder is deteriorated, the transparency of the obtained conductive film and the adhesion to the substrate are lowered, and the film performance is lowered. Tend to.
本発明の透明導電膜形成用組成物においては、使用する溶媒に溶解でき、導電性微粒子を分散させることができ、成膜できるバインダー成分であれば、一般的に塗料で用いられている任意のバインダー成分を特に制限なく用いることができ、例えば、アルキド樹脂、ポリエステル樹脂、不飽和ポリエステル樹脂、ポリウレタン樹脂、アクリル樹脂、エポキシ樹脂、フェノール樹脂、ビニル樹脂、シリコーン樹脂、フッ素樹脂、フタル酸樹脂、アミノ樹脂、ポリアミド樹脂、ポリアクリルシリコーン樹脂、メラミン樹脂、尿素樹脂、もしくはこれらを変性したバインダー樹脂等を１種単独でもしくは２種類以上併用することができる。 In the composition for forming a transparent conductive film of the present invention, any binder component that can be dissolved in a solvent to be used, can disperse conductive fine particles, and can be formed into a film can be used. The binder component can be used without any particular limitation. For example, alkyd resin, polyester resin, unsaturated polyester resin, polyurethane resin, acrylic resin, epoxy resin, phenol resin, vinyl resin, silicone resin, fluorine resin, phthalic acid resin, amino acid A resin, a polyamide resin, a polyacryl silicone resin, a melamine resin, a urea resin, or a binder resin obtained by modifying these resins can be used alone or in combination of two or more.
さらに上記バインダー成分中には必要に応じて架橋剤を含有させても良く、例えば、アミノ基等の塩基性官能基、ＯＨ基等の中性官能基、カルボキシル基等の酸性官能基、イソシアネート基等の反応性官能基を１分子中に２つ以上有する任意の架橋剤を用いることができる。 Further, the binder component may contain a cross-linking agent as necessary. For example, basic functional groups such as amino groups, neutral functional groups such as OH groups, acidic functional groups such as carboxyl groups, isocyanate groups Any cross-linking agent having two or more reactive functional groups in one molecule can be used.
また、上記バインダー成分はラジカル重合性モノマーであってもよく、ラジカル重合性
の不飽和基（α，β−エチレン性不飽和基）を有しているモノマーであれば、アミノ基等の塩基性官能基を有するもの、ＯＨ基等の中性官能基を有するもの、カルボキシル基等の酸性官能基を有するもの、或いはこのような官能基を有していないもの、のいずれでもよい。
The binder component may be a radical polymerizable monomer, and may be a basic group such as an amino group as long as it is a monomer having a radical polymerizable unsaturated group (α, β-ethylenically unsaturated group). Any of those having a functional group, those having a neutral functional group such as an OH group, those having an acidic functional group such as a carboxyl group, or those not having such a functional group may be used.
さらに、本発明の透明導電膜形成用組成物には、その目的を損なわない範囲内で、慣用の各種添加剤を配合してもよい。このような添加剤の例として、分散剤、分散助剤、重合禁止剤、硬化触媒、酸化防止剤、レベリング剤等を挙げることができる。 Furthermore, you may mix | blend various conventional additives in the composition for transparent conductive film formation of this invention in the range which does not impair the objective. Examples of such additives include a dispersant, a dispersion aid, a polymerization inhibitor, a curing catalyst, an antioxidant, and a leveling agent.
本発明の透明導電膜形成用組成物においては、上記バインダー成分を溶解または分散させるとともに、導電性微粒子を分散させることができるが基材を侵さない溶剤であれば、一般的に塗料で用いられている任意の溶剤を特に制限なく用いることができ、例えば、ヘキサン、ヘプタン、シクロヘキサン、トルエン、ｍ−キシレン等の炭化水素、テトラクロロメタン、トリクロロエチレン等のハロゲン化炭化水素、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン、イソホロン、シクロヘキサン等のケトン、ジエチルエーテル、ジオキサン、テトラヒドロフラン等のエーテル、酢酸エチル、酢酸ブチル、酢酸イソアミル等のエステル、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、ｎ−ペンタノール、２−エチルヘキサノール、シクロヘキサノール、ジアセトンアルコール、エチレングリコール、プロピレングリコール、ジエチレングリコール、グリセリン等のアルコール、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテルアセテート等のエーテル／アルコールやエーテル／エステル、およびこれらの混合系である。そのような溶剤の使用量については、水酸化錫粉体又はドーパントとしてＰ、Ａｌ、Ｉｎ、Ｚｎ及びＳｂの少なくとも一種を含む水酸化錫粉体を分散させて最終的に得られる組成物の粘性が塗布又は印刷に適したものとなるように調整する。本発明の透明導電膜形成用組成物においては粘度が２〜１００００ｃｐｓ（Ｅ型粘度計：２０℃）の範囲内にあることが好ましい。 In the composition for forming a transparent conductive film of the present invention, any solvent that can dissolve or disperse the binder component and disperse the conductive fine particles but does not attack the substrate is generally used in paints. Any solvent can be used without particular limitation, for example, hydrocarbons such as hexane, heptane, cyclohexane, toluene, m-xylene, halogenated hydrocarbons such as tetrachloromethane, trichloroethylene, acetone, methyl ethyl ketone, methyl isobutyl. Ketones, ketones such as diisobutyl ketone, isophorone and cyclohexane, ethers such as diethyl ether, dioxane and tetrahydrofuran, esters such as ethyl acetate, butyl acetate and isoamyl acetate, methanol, ethanol, n-propanol, isopropanol and n-butano , N-pentanol, 2-ethylhexanol, cyclohexanol, diacetone alcohol, ethylene glycol, propylene glycol, diethylene glycol, glycerin and other alcohols, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, These are ethers / alcohols such as propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, ether / esters, and mixtures thereof. Regarding the amount of such a solvent used, the viscosity of the composition finally obtained by dispersing tin hydroxide powder or tin hydroxide powder containing at least one of P, Al, In, Zn and Sb as a dopant is dispersed. Is adjusted to be suitable for coating or printing. In the composition for forming a transparent conductive film of the present invention, the viscosity is preferably in the range of 2 to 10000 cps (E-type viscometer: 20 ° C.).
本発明の透明導電膜形成用組成物は、例えば、上記バインダー成分に必要に応じて有機溶媒を加えて希釈したバインダー成分溶液中に水酸化錫粉体又はドーパントとしてＰ、Ａｌ、Ｉｎ、Ｚｎ及びＳｂの少なくとも一種を含む水酸化錫粉体を分散させることにより製造することができる。また、水酸化錫粉体又はドーパントとしてＰ、Ａｌ、Ｉｎ、Ｚｎ及びＳｂの少なくとも一種を含む水酸化錫粉体を有機溶媒に分散させ、その後、上記バインダー成分を加えて分散させることによっても製造することができる。無論、バインダー成分、水酸化錫粉体又はドーパントとしてＰ、Ａｌ、Ｉｎ、Ｚｎ及びＳｂの少なくとも一種を含む水酸化錫粉体、及び有機溶媒の３成分を同時に混合し、分散させることによっても製造することができる。このような分散操作は、常法により、ペイントシェーカー、ボールミル、サンドミル、セントリミル、三本ロール等によって行うことができる。無論、通常の攪拌操作によって分散させることもできる。 The composition for forming a transparent conductive film of the present invention includes, for example, P, Al, In, Zn as a tin hydroxide powder or a dopant in a binder component solution diluted by adding an organic solvent to the binder component as necessary. It can be produced by dispersing tin hydroxide powder containing at least one kind of Sb. Also produced by dispersing tin hydroxide powder or tin hydroxide powder containing at least one of P, Al, In, Zn and Sb as a dopant in an organic solvent, and then adding and dispersing the binder component. can do. Of course, the binder component, tin hydroxide powder or tin hydroxide powder containing at least one of P, Al, In, Zn and Sb as a dopant, and the organic solvent three components are also mixed and dispersed at the same time. can do. Such a dispersion operation can be performed by a conventional method using a paint shaker, a ball mill, a sand mill, a sentry mill, a triple roll or the like. Of course, it can also be dispersed by a normal stirring operation.
本発明の透明導電膜形成用組成物を塗布して本発明の透明導電膜を形成する基板としては、電気・電子機器をはじめとして様々な分野において広く用いられている各種の合成樹脂、ガラス、セラミックス等を挙げることができ、これらはシート状、フィルム状、板状等の任意の形状であり得る。合成樹脂の具体例としては、ポリエチレン、ポリプロピレン、ポリカーボネート、アクリル樹脂、メタクリル樹脂、ポリ塩化ビニル、ポリエステル樹脂、ポリアミド樹脂及びフェノール樹脂等を挙げることができるが、これらに制限されるものではない。 As a substrate on which the transparent conductive film-forming composition of the present invention is applied to form the transparent conductive film of the present invention, various synthetic resins, glass, widely used in various fields including electrical and electronic equipment, Ceramics etc. can be mentioned, These can be arbitrary shapes, such as sheet form, film form, and plate shape. Specific examples of the synthetic resin include, but are not limited to, polyethylene, polypropylene, polycarbonate, acrylic resin, methacrylic resin, polyvinyl chloride, polyester resin, polyamide resin, and phenol resin.
本発明の透明導電膜形成用組成物の基板への塗布又は印刷は常法により、例えば、ロールコート、スピンコート、スクリーン印刷などの手法で行うことができる。その後、塗膜を硬化させる。上記バインダー成分が重合し、水酸化錫粉体又はドーパントとしてＰ、Ａｌ、Ｉｎ、Ｚｎ及びＳｂの少なくとも一種を含む水酸化錫粉体が樹脂で結合された透明導電膜が形成される。この透明導電膜の膜厚は一般的に０．１〜１０．０μｍの範囲内であることが好ましい。 Application or printing of the composition for forming a transparent conductive film of the present invention on a substrate can be performed by a conventional method, for example, by a method such as roll coating, spin coating, or screen printing. Thereafter, the coating film is cured. The binder component is polymerized to form a transparent conductive film in which tin hydroxide powder or tin hydroxide powder containing at least one of P, Al, In, Zn and Sb as a dopant is bonded with a resin. In general, the thickness of the transparent conductive film is preferably in the range of 0.1 to 10.0 μm.
基板上に本発明の透明導電膜形成用組成物から形成された本発明の透明導電膜は、例えば、表面抵抗値が好ましくは１０7〜１０12Ω／□、より好ましくは１０7〜１０11Ω／□、光透過率が好ましくは８５％以上、ヘイズが好ましくは２．５％以下という、透明性、導電性のいずれにも優れた透明導電膜となる。このような透明導電膜は電子写真記録の埃防止膜として、或いは帯電防止膜等として利用可能であり、例えば、ディスプレイの表示面に用いることができる。 The transparent conductive film of the present invention formed on the substrate from the composition for forming a transparent conductive film of the present invention has, for example, a surface resistance value of preferably 10 7 to 10 12 Ω / □, more preferably 10 7 to 10 11. A transparent conductive film excellent in both transparency and conductivity, with Ω / □ and a light transmittance of preferably 85% or more and a haze of preferably 2.5% or less. Such a transparent conductive film can be used as a dust prevention film or an antistatic film for electrophotographic recording, and can be used, for example, on a display surface of a display.
以下に、実施例及び比較例により本発明を具体的に説明する。実施例で使用した水酸化錫粉体は平均一次粒子径が０．０５μｍの粒子であり、粉体抵抗が１×１０7Ω・ｃｍで あり、またドーパントとしてリンを含む水酸化錫粉体はＳｎ＋Ｐに対するＰの量が５．０ａｔ％であり、平均一次粒子径が０．０５μｍの粒子であった。また、実施例及び比較例において「部」は全て「質量部」である。 The present invention will be specifically described below with reference to examples and comparative examples. The tin hydroxide powder used in the examples is particles having an average primary particle diameter of 0.05 μm, the powder resistance is 1 × 10 7 Ω · cm, and the tin hydroxide powder containing phosphorus as a dopant is The amount of P with respect to Sn + P was 5.0 at%, and the average primary particle size was 0.05 μm. In Examples and Comparative Examples, “parts” are all “parts by mass”.
実施例１
バインダー成分としてのアクリルレジン溶液（ダイヤナールＬＲ−９０、固形分３０％、三菱レイヨン株式会社製商品名）１００部を、水酸化錫粉体７０部、溶剤としてのイソプロピルアルコール１５０部及びガラスビーズ２５０部とともに容器に入れ、ペイントシェカーで、粒ゲージにより分散状態を確認しながら、５時間練合した。練合後、ガラスビーズを取り除き、粘稠な液状物を得た。その後、ロールコーターを用いてその粘稠な液状物を膜厚７５μｍのＰＥＴフィルム（東洋紡Ａ４３００、光透過率９１％、ヘイズ０．７％）上に塗布し、有機溶媒を蒸発させた後、６０℃で１０分間乾燥させて厚み５μｍの透明硬化被膜を作製した。
Example 1
100 parts of an acrylic resin solution (Dianar LR-90, solid content 30%, trade name, manufactured by Mitsubishi Rayon Co., Ltd.) as a binder component, 70 parts of tin hydroxide powder, 150 parts of isopropyl alcohol as a solvent, and
実施例２
バインダー成分としてのエポキシ樹脂（エピコート１００４、ジャパンエポキシレジン株式会社製商品名）１５部を、ドーパントとしてリンを含む水酸化錫粉体８５部、溶剤としてのシクロヘキサノン／キシレンの重量比４／６からなる混合溶媒２５０部及びガラスビーズ２５０部とともに容器に入れ、ペイントシェカーで、粒ゲージにより分散状態を確認しながら、５時間練合した。練合後、ガラスビーズを取り除き、粘稠な液状物を得た。その後、ロールコーターを用いてその粘稠な液状物を膜厚７５μｍのＰＥＴフィルム（東洋紡Ａ４３００、光透過率９１％、ヘイズ０．７％）上に塗布し、有機溶媒を蒸発させた後、８０℃で１０分間乾燥させて厚み５μｍの透明硬化被膜を作製した。
Example 2
15 parts of epoxy resin (Epicoat 1004, product name manufactured by Japan Epoxy Resin Co., Ltd.) as a binder component, 85 parts of tin hydroxide powder containing phosphorus as a dopant, and a weight ratio of 4/6 of cyclohexanone / xylene as a solvent The mixture was placed in a container together with 250 parts of the mixed solvent and 250 parts of glass beads, and kneaded for 5 hours with a paint shaker while confirming the dispersion state with a particle gauge. After kneading, the glass beads were removed to obtain a viscous liquid. Thereafter, the viscous liquid material was applied onto a 75 μm-thick PET film (Toyobo A4300, light transmittance 91%, haze 0.7%) using a roll coater, and the organic solvent was evaporated. A transparent cured film having a thickness of 5 μm was produced by drying at 10 ° C. for 10 minutes.
実施例３
水酸化錫粉体７０部、溶剤としての酢酸ブチル２００部及びガラスビーズ２５０部を容器に入れ、ペイントシェカーで、粒ゲージにより分散状態を確認しながら、５時間練合した。練合後、ガラスビーズを取り除き、その分散液をバインダー成分としてのアクリル樹脂（ダイヤナールＨＲ−６３３、固形分５０％、三菱レイヨン株式会社製商品名）４２部及びメラミン樹脂（ユーバン２２５、固形分６０％、三井化学株式会社製商品名）１５部とともに、ディスパーにより十分に撹拌しながら混合し、粘稠な液状物を得た。その後、ロールコーターを用いてその粘稠な液状物を膜厚７５μｍのＰＥＴフィルム（東洋紡Ａ４３００、光透過率９１％、ヘイズ０．７％）上に塗布し、有機溶媒を蒸発させた後、１２０℃で１５分間乾燥させて厚み５μｍの透明硬化被膜を作製した。
Example 3
70 parts of tin hydroxide powder, 200 parts of butyl acetate as a solvent and 250 parts of glass beads were placed in a container and kneaded for 5 hours with a paint shaker while confirming the dispersion state with a particle gauge. After kneading, the glass beads are removed, and the dispersion is 42 parts acrylic resin (Dianar HR-633, solid content 50%, trade name, manufactured by Mitsubishi Rayon Co., Ltd.) as a binder component and melamine resin (Uban 225, solid content). 60%, Mitsui Chemicals Co., Ltd. trade name) and 15 parts were mixed while being sufficiently stirred with a disper to obtain a viscous liquid. Thereafter, the viscous liquid material was applied onto a 75 μm-thick PET film (Toyobo A4300, light transmittance 91%, haze 0.7%) using a roll coater, and the organic solvent was evaporated. A transparent cured film having a thickness of 5 μm was produced by drying at 15 ° C. for 15 minutes.
実施例４
バインダー成分としてのアクリルレジン溶液（ダイヤナールＬＲ−９０、固形分３０％、三菱レイヨン株式会社製商品名）２００部を、水酸化錫粉体４０部、溶剤としてのイソブチルアルコール１００部を用いた以外は実施例１と同様にして厚み５μｍの透明硬化被膜を作製した。
Example 4
Aside from using 200 parts of an acrylic resin solution (Dianar LR-90, solid content 30%, trade name, manufactured by Mitsubishi Rayon Co., Ltd.) as a binder component, 40 parts of tin hydroxide powder, and 100 parts of isobutyl alcohol as a solvent. Produced a transparent cured film having a thickness of 5 μm in the same manner as in Example 1.
実施例５
バインダー成分としてのアクリルレジン溶液（ダイヤナールＬＲ−９０、固形分３０％、三菱レイヨン株式会社製商品名）３００部を、水酸化錫粉体１０部、溶剤としてのジアセトンアルコール３０部を用いた以外は実施例１と同様にして厚み５μｍの透明硬化被膜を作製した。
Example 5
300 parts of an acrylic resin solution (Dianar LR-90, solid content 30%, trade name, manufactured by Mitsubishi Rayon Co., Ltd.) as a binder component, 10 parts of tin hydroxide powder, and 30 parts of diacetone alcohol as a solvent were used. A transparent cured film having a thickness of 5 μm was produced in the same manner as in Example 1 except for the above.
比較例１
水酸化錫粉体７０部の代わりにＩＴＯ粉体７０部を用いた以外は実施例１と同様にして厚み５μｍの透明硬化被膜を作製した。
Comparative Example 1
A transparent cured film having a thickness of 5 μm was prepared in the same manner as in Example 1 except that 70 parts of ITO powder was used instead of 70 parts of tin hydroxide powder.
比較例２
水酸化錫粉体７０部の代わりに酸化錫粉体７０部を用いた以外は実施例１と同様にして厚み５μｍの透明硬化被膜を作製した。
Comparative Example 2
A transparent cured film having a thickness of 5 μm was prepared in the same manner as in Example 1 except that 70 parts of tin oxide powder was used instead of 70 parts of tin hydroxide powder.
比較例３
水酸化錫粉体１０部の代わりに酸化錫粉体１０部を用いた以外は実施例５と同様にして厚み５μｍの透明硬化被膜を作製した。
Comparative Example 3
A transparent cured film having a thickness of 5 μm was prepared in the same manner as in Example 5 except that 10 parts of tin oxide powder was used instead of 10 parts of tin hydroxide powder.
実施例及び比較例で得た透明硬化被膜について、その全線光透過率及びヘイズを東京電色技術センター製ＴＣ−ＨＩＩＩ ＤＰＫで測定した。測定値は基材を含んだ値である。また、表面抵抗値を三菱化学株式会社製のハイレスタＩＰ ＭＣＰ−ＨＴ２６０表面抵抗器で測定した。それらの測定結果を第１表にまとめて示す。 About the transparent cured film obtained by the Example and the comparative example, the whole-line light transmittance and haze were measured by TC-HIII DPK by Tokyo Denshoku Technical Center. The measured value is a value including the base material. Further, the surface resistance value was measured with a Hiresta IP MCP-HT260 surface resistor manufactured by Mitsubishi Chemical Corporation. The measurement results are summarized in Table 1.
第１表に示すデータから明らかなように、水酸化錫粉体を含んでいる本発明の導電膜形成用組成物を塗布した場合（実施例１〜５）には、表面抵抗値が１０7〜１０11Ω／□、光透過率が８５％以上、ヘイズ２．５％以下という、透明性、導電性のいずれにも優れた透明導電膜が得られたが、ＩＴＯ粉体又は酸化錫粉体を含んでいる導電膜形成用組成物を塗布した場合（比較例１〜３）には、光透過率が８５％未満であった。 As apparent from the data shown in Table 1, when the composition for forming a conductive film of the present invention containing tin hydroxide powder was applied (Examples 1 to 5), the surface resistance value was 10 7. ~10 11 Ω / □, the light transmittance of 85% or more, that a haze of 2.5% or less, transparency, the transparent conductive film excellent in any of conductivity obtained, ITO powder or tin oxide powder When the composition for forming a conductive film containing a body was applied (Comparative Examples 1 to 3), the light transmittance was less than 85%.
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