JP2006338899A - Conductive fine powder having high dispersibility and its application - Google Patents
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本発明は、酸性域からアルカリ域の幅広いｐＨ域で高い分散性と優れた導電性を有する導電性微粉末とその分散液およびこの導電性微粉末を含有する塗料組成物、この塗料組成物によって形成された透明導電膜などに関する。本発明の導電性微粉末は幅広いｐＨ域で高い分散性を有し、導電性および透明性に優れた導電膜を形成することができ、帯電防止・帯電制御・静電防止・防塵等の各種材料として利用することができる。 The present invention relates to a conductive fine powder having high dispersibility and excellent conductivity in a wide pH range from an acidic range to an alkaline range, a dispersion thereof, a coating composition containing the conductive fine powder, and a coating composition containing the conductive fine powder. The present invention relates to the formed transparent conductive film. The conductive fine powder of the present invention has high dispersibility in a wide pH range, can form a conductive film excellent in conductivity and transparency, and various types such as antistatic, charge control, antistatic, and dustproof. It can be used as a material.
導電性粉末として酸化スズ粉末、アンチモンをドープした酸化スズ粉末（ＡＴＯ粉末）などが従来から知られており、これらを塗料成分等に分散させた分散組成物によって導電膜が形成されている。しかし、ＡＴＯ粉末はアンチモンの毒性が問題であるため、アンチモンに代えてゲルマニウム、リン、リチウム、亜鉛などを所定量ドープすることによって低抵抗で無害な白色導電性粉末が知られている（特許文献１）。 Conventionally known are tin oxide powder, antimony-doped tin oxide powder (ATO powder), and the like as conductive powder, and a conductive film is formed by a dispersion composition in which these are dispersed in a paint component or the like. However, since ATO powder has a problem of toxicity of antimony, a low-resistance and harmless white conductive powder is known by doping a predetermined amount of germanium, phosphorus, lithium, zinc or the like instead of antimony (patent document) 1).
一方、酸化スズはｐＨ３〜６付近に等電点があり、ＡＴＯはｐＨ２.５〜５付近に等電点をもつので、これらの酸化スズ系粉末はｐＨが中性域付近の溶媒中では粉末どうしの表面電荷による反発が小さくなるので粉末の分散性が悪く、凝集しやすいために均一な導電性を有する導電膜を形成するのが難しく、また膜に曇りを生じ、透明性が低下すると云う問題がある。 On the other hand, tin oxide has an isoelectric point around pH 3-6, and ATO has an isoelectric point around pH 2.5-5. Therefore, these tin oxide powders are powders in a solvent near neutral pH. Since the repulsion due to the surface charge is small, the dispersibility of the powder is poor and it is easy to agglomerate, so it is difficult to form a conductive film having uniform conductivity, and the film is clouded and the transparency is lowered. There's a problem.
そこで、これら酸化スズ系粉末の分散性を改善する手段が検討されてきた。例えば、これらの酸化スズ系粉末をシリカによって表面処理することが知られている。シリカの等電点はｐＨ２〜３付近であり、酸化スズ系粉末をシリカで表面処理することによって、ｐＨが中性付近域での分散性を高めることができる。ただし、この方法ではｐＨ４以下の低ｐＨ領域では分散性が低下すると云う問題がある。 Therefore, means for improving the dispersibility of these tin oxide powders have been studied. For example, it is known that these tin oxide-based powders are surface-treated with silica. The isoelectric point of silica is around pH 2 to 3, and the dispersibility in the vicinity of neutral pH can be enhanced by surface-treating the tin oxide powder with silica. However, this method has a problem that the dispersibility is lowered in a low pH range of pH 4 or lower.
一方、酸化スズやＡＴＯにリンをドープさせることによって分散性を高めることも知られている。例えば、特許第２８１８０５８号公報（特許文献２）には、酸化スズを導電性フィラーとして分散させた帯電防止膜を設けた光ディスクにおいて、リンを３〜７wt％ドープした酸化スズ粉末を用いることが記載されている。また、特許第３３６５８２１号公報（特許文献３）には、酸化スズを主成分とし、リンをＰ/Ｓｎ原子比で２.７×１０-2〜１.４×１０-1の割合で含有させた導電性微粉末が記載されている。 On the other hand, it is also known to increase dispersibility by doping tin oxide or ATO with phosphorus. For example, Japanese Patent No. 2818058 (Patent Document 2) describes using tin oxide powder doped with 3 to 7 wt% phosphorus in an optical disk provided with an antistatic film in which tin oxide is dispersed as a conductive filler. Has been. Japanese Patent No. 3365821 (Patent Document 3) contains tin oxide as a main component and phosphorus in a P / Sn atomic ratio of 2.7 × 10 −2 to 1.4 × 10 −1. Conductive fine powders are described.
しかし、これらの酸化スズ粉末の分散性は従来のものよりは改善されるものの、幅広いｐＨ域で高い分散性を有するものではなく、分散性に限界がある。また、後者の酸化スズ粉末は８００℃以上の高温で焼成することによって粉体抵抗を下げているが、一方で粉体の焼結が進行するために粗粒子化して比表面積が小さくなり、一次粒子にまで分散できないために分散液中で沈降し、透明性が大きく低下すると云う問題がある。 However, although the dispersibility of these tin oxide powders is improved as compared with the conventional one, it does not have a high dispersibility in a wide pH range, and the dispersibility is limited. In addition, the latter tin oxide powder lowers the powder resistance by firing at a high temperature of 800 ° C. or higher, but on the other hand, since the sintering of the powder progresses, it becomes coarser and the specific surface area becomes smaller. There is a problem that since it cannot be dispersed into particles, it settles in the dispersion and the transparency is greatly reduced.
さらに、透明導電膜については、膜の導電性および透明性と共に色味が問題になる場合がある。例えば、ＡＴＯ粉末は青味が帯びているので、ＡＴＯ粉末を用いた透明導電膜は光学フィルターなどには適さない。
本発明は、従来の酸化スズ系粉末を用いた透明導電膜における上記問題を解決したものであり、分散性が良く、かつ導電性および透明性に優れた導電性微粉末とその分散液等を提供する。 The present invention solves the above-mentioned problems in a transparent conductive film using a conventional tin oxide-based powder, and provides a conductive fine powder having good dispersibility and excellent conductivity and transparency, a dispersion thereof, and the like. provide.
本発明によれば以下の高分散性導電性微粉末、およびその分散液等に関する。
（１） ｐＨ２〜１２の範囲で等電点を持たないことを特徴とする高分散性の導電性微粉末。
（２）リンを０.１〜５wt％および窒素を１０ppm〜５０００ppm含有した酸化スズ微粉末からなり、ｐＨ２〜１２の範囲で等電点を持たない高分散性の導電性微粉末。
（３）リンを０.１〜５wt％および窒素を１０ppm〜５０００ppm含有した酸化スズ微粉末からなり、ｐＨ２〜１２の範囲で等電点を持たず、粉体体積抵抗率が７００〜３×１０6Ω・ｃｍであって、ＢＥＴ比表面積が１００ｍ2／ｇ以上、粉末の色味のＬ値が６０以上、ａ値が−３〜＋３、ｂ値が２〜８である高分散性の透明導電性微粉末。
（４）上記(1)〜(3)の何れかに記載する導電性微粉末が媒体に分散した分散液であって、分散液中の導電性粉末の累積重量９５％粒子径〔Ｄ95〕が２５０nm以下であり、該分散液の色味がＬ値３０〜５５、ａ値−２〜＋２、ｂ値−４〜＋４である導電性微粉末分散液。
（５）上記(1)〜(3)の何れかに記載する導電性微粉末を塗料成分に配合してなる塗料組成物。
（６）上記(5)の塗料組成物によって形成された、表面抵抗値が１０12Ω/□以下、膜厚５μmの光透過率が８５％以上およびヘーズ値が３％以下の透明導電膜。
（７）リン酸存在下で水酸化スズを沈澱させ、該沈澱を乾燥後、窒素雰囲気下において４００〜７５０℃で焼成し、リンを０.１〜５wt％および窒素を１０ppm〜５０００ppm含有した酸化スズ微粉末からなる導電性微粉末を製造する方法。
The present invention relates to the following highly dispersible conductive fine powder, a dispersion thereof, and the like.
(1) A highly dispersible conductive fine powder characterized by having no isoelectric point in a pH range of 2 to 12.
(2) A highly dispersible conductive fine powder comprising tin oxide fine powder containing 0.1 to 5 wt% phosphorus and 10 ppm to 5000 ppm nitrogen and having no isoelectric point in the pH range of 2-12.
(3) It consists of tin oxide fine powder containing 0.1 to 5 wt% of phosphorus and 10 ppm to 5000 ppm of nitrogen, has no isoelectric point in the range of pH 2 to 12, and has a powder volume resistivity of 700 to 3 x 10 Highly dispersible transparent with 6 Ω · cm, BET specific surface area of 100 m 2 / g or more, powder color L value of 60 or more, a value of −3 to +3, b value of 2 to 8 Conductive fine powder.
(4) A dispersion in which the conductive fine powder described in any one of (1) to (3) is dispersed in a medium, and the cumulative weight 95% particle diameter [D95] of the conductive powder in the dispersion is A conductive fine powder dispersion having a color value of 250 nm or less and having a color value of 30 to 55, an a value of −2 to +2, and a b value of −4 to +4.
(5) A coating composition comprising the conductive fine powder described in any one of (1) to (3) above in a coating component.
(6) A transparent conductive film having a surface resistance value of 10 12 Ω / □ or less, a light transmittance of 85% or more and a haze value of 3% or less, formed from the coating composition of (5).
(7) Tin hydroxide is precipitated in the presence of phosphoric acid, and the precipitate is dried and then calcined at 400 to 750 ° C. in a nitrogen atmosphere. The oxidation contains 0.1 to 5 wt% phosphorus and 10 to 5000 ppm nitrogen. A method for producing a conductive fine powder comprising tin fine powder.
本発明の導電性微粉末はｐＨ２〜１２の範囲で等電点を持たないので、これらのｐＨ域を有する分散媒中でも凝集し難く、分散性のよい分散体を得ることができる。従って、本発明の導電性微粉末分散体によれば、優れた帯電防止効果を有し、また透明性が高く、低ヘーズであり、可視光透過率が非常に高く、透過画像の色相が自然であり、平滑性、耐擦性にも優れた透明導電膜を形成することができる。また、本本発明はそのような透明導電膜を提供することができる。さらに、本発明の導電性微粉末はアンチモンを含有する必要がないので、アンチモンの毒性の問題が無く、安全性が高い。 Since the conductive fine powder of the present invention does not have an isoelectric point in the pH range of 2 to 12, it is difficult to aggregate even in a dispersion medium having these pH ranges, and a dispersion with good dispersibility can be obtained. Therefore, according to the conductive fine powder dispersion of the present invention, it has excellent antistatic effect, high transparency, low haze, very high visible light transmittance, and natural color of transmitted images. In addition, a transparent conductive film excellent in smoothness and abrasion resistance can be formed. Moreover, this invention can provide such a transparent conductive film. Furthermore, since the conductive fine powder of the present invention does not need to contain antimony, there is no problem of antimony toxicity and high safety.
本発明の導電性微粉末は、ｐＨ２〜１２の範囲で等電点を持たないことを特徴とする高分散性の導電性微粉末であり、好ましくは、リンを０.１〜５wt％および窒素を１０ppm〜５０００ppm含有した酸化スズ微粉末からなり、ｐＨ２〜１２の範囲で等電点を持たない高分散性の導電性微粉末である。 The conductive fine powder of the present invention is a highly dispersible conductive fine powder characterized by having no isoelectric point in the pH range of 2 to 12, preferably 0.1 to 5 wt% of phosphorus and nitrogen Is a highly dispersible conductive fine powder having an isoelectric point in a pH range of 2 to 12.
酸化スズにリンおよび窒素を上記所定量含有させることによって、ｐＨ２〜１２の範囲で等電点を持たない、分散性に優れた導電性微粉末を得ることができる。なお、酸化スズにリンをドープすることによって、酸化スズ微粉末の中性域での分散性を高めたものが従来知られているが、先に述べたように、これらの酸化スズ粉末の分散性は従来の酸化スズよりは改善されるものの、幅広いｐＨ域で高い分散性を有するものではなく、分散性に限界がある。本発明の導電性微粉末は、酸化スズにリンと共に窒素を所定量含有させることによって、幅広いｐＨ域で高い分散性を有することができるようにした。 By containing the predetermined amounts of phosphorus and nitrogen in tin oxide, it is possible to obtain a conductive fine powder excellent in dispersibility and having no isoelectric point in the pH range of 2-12. In addition, what has been conventionally known that tin oxide is doped with phosphorus to increase the dispersibility in the neutral region of tin oxide fine powder. As described above, the dispersion of these tin oxide powders is known. Although the property is improved as compared with conventional tin oxide, it does not have a high dispersibility in a wide pH range, and the dispersibility is limited. The conductive fine powder of the present invention can have high dispersibility in a wide pH range by containing a predetermined amount of nitrogen together with phosphorus in tin oxide.
酸化スズ中のリン含有量は０.１〜５wt％が好ましい。酸化スズ中の窒素含有量は１０ppm〜５０００ppmが好ましい。リンの含有量が０.１wt％よりも少なく、また窒素含有量が１０ppmより少ないと、等電点を上記ｐＨ域から外す効果が不十分であり、凝集し易くなるので導電性が低下し、また導電性の経時的な安定性も低下する傾向がある。一方、リン含有量が５wt％より多いと、粉末のＬ値が低くなり、透明性が低下する傾向がある。また、窒素含有量が５０００ppmより多いと、透明性が低下し、好ましい色調の範囲から外れるようになる。 The phosphorus content in tin oxide is preferably 0.1 to 5 wt%. The nitrogen content in the tin oxide is preferably 10 ppm to 5000 ppm. If the phosphorus content is less than 0.1 wt% and the nitrogen content is less than 10 ppm, the effect of removing the isoelectric point from the above pH range is insufficient, and the electroconductivity is lowered because it tends to aggregate. Also, the stability of the conductivity over time tends to decrease. On the other hand, if the phosphorus content is more than 5 wt%, the L value of the powder tends to be low, and the transparency tends to decrease. On the other hand, when the nitrogen content is more than 5000 ppm, the transparency is lowered and the color tone is not within the preferable range.
本発明のリン窒素含有酸化スズからなる導電性微粉末は、Ｌ値が６０以上、ａ値が−３〜＋３、ｂ値が２〜８の色調を有することができる。Ｌ値が６０より小さいと透明性が低くなり、ａ値が上記範囲を外れると緑色や赤味が濃くなり、またｂ値が８より高いと茶色が入り、また２より小さいと青色が入るようになるので好ましくない。 The conductive fine powder comprising the phosphorous nitrogen-containing tin oxide of the present invention can have a color tone having an L value of 60 or more, an a value of −3 to +3, and a b value of 2 to 8. If the L value is less than 60, the transparency will be low. If the a value is outside the above range, green and reddish will become dark. If the b value is higher than 8, brown will appear. If it is less than 2, blue will appear. This is not preferable.
本発明のリン窒素含有酸化スズからなる導電性微粉末は、粉体体積抵抗率７００〜９×１０6Ω・ｃｍの導電性を有することができる。湿式法によって酸化スズ微粉末を製造する際に、焼成温度を上げると一般に酸化スズ粉末の粉体体積抵抗率は低下するが、７００Ω・ｃｍより低くなるまで焼成温度を高くすると、粉末の焼結が進行するため粉末の分散性が低下し、透明性が低下する。一方、粉体体積抵抗率が９×１０6Ω・ｃｍよりも高いと導電性が低過ぎるので好ましくない。本発明のリン窒素含有酸化スズ微粉末は高い透明性と共に優れた導電性を有することができる。 The conductive fine powder comprising the phosphorus nitrogen-containing tin oxide of the present invention can have a powder volume resistivity of 700 to 9 × 10 6 Ω · cm. When producing tin oxide fine powder by a wet method, increasing the firing temperature generally reduces the powder volume resistivity of the tin oxide powder, but increasing the firing temperature to lower than 700 Ω · cm will result in powder sintering. Progresses, the dispersibility of the powder decreases and the transparency decreases. On the other hand, if the powder volume resistivity is higher than 9 × 10 6 Ω · cm, the conductivity is too low, which is not preferable. The phosphorus nitrogen-containing tin oxide fine powder of the present invention can have excellent conductivity as well as high transparency.
本発明のリン窒素含有酸化スズからなる導電性微粉末は、１００ｍ2／ｇ以上のＢＥＴ比表面積を有することができる。本発明の酸化スズ微粉末は、湿式法による酸化スズの製造方法において、酸化スズにリンと窒素をドーピングすることによって、酸化スズ粉末を焼成する際に焼成温度を下げることができ、焼結によって粉末が粗粒子化するのを避けることができるので、ＢＥＴ比表面積１００ｍ2／ｇ以上の微粉末を得ることができる。本発明のリン窒素含有酸化スズからなる導電性微粉末はＢＥＴ比表面積が大きく、微細であるので、透明性と導電性に優れた透明導電膜を形成することができる。 The conductive fine powder comprising the phosphorous nitrogen-containing tin oxide of the present invention can have a BET specific surface area of 100 m 2 / g or more. The tin oxide fine powder of the present invention is a method for producing tin oxide by a wet method. By doping phosphorus oxide with phosphorus and nitrogen, the firing temperature can be lowered when firing the tin oxide powder. Since the powder can be prevented from becoming coarse particles, a fine powder having a BET specific surface area of 100 m 2 / g or more can be obtained. Since the conductive fine powder comprising the phosphorus nitrogen-containing tin oxide of the present invention has a large BET specific surface area and is fine, a transparent conductive film excellent in transparency and conductivity can be formed.
本発明のリン窒素含有酸化スズからなる導電性微粉末は水、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、アセトン、シクロヘキサン、トルエン、キシレン、テトラクロロメタン、トリクロロエチレン、シクロヘキサノン、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、ジエチルエーテル、ジオキサン、テトラヒドロフラン、酢酸エチル、酢酸ブチル、酢酸イソアミルやエーテル／アルコール、エーテル／エステル等およびこれら混合系である媒体に分散させたときに、導電性微粉末の分散性に優れた分散液を得ることができる。また、必要に応じて珪酸ソーダ等を用いることもできる。 The conductive fine powder comprising the phosphorus nitrogen-containing tin oxide of the present invention is water, methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, 2-ethylhexanol, cyclohexanol, diacetone alcohol, ethylene glycol. , Propylene glycol, diethylene glycol, acetone, cyclohexane, toluene, xylene, tetrachloromethane, trichloroethylene, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexane, diethyl ether, dioxane, tetrahydrofuran, ethyl acetate, butyl acetate, isoamyl acetate Fine powders when dispersed in a medium such as benzene, ether / alcohol, ether / ester, etc. It is possible to obtain an excellent dispersion in a dispersion property. Moreover, sodium silicate etc. can also be used as needed.
具体的には、本発明の分散液は、分散液中の導電性粉末の累積重量９５％粒子径〔Ｄ95〕が２５０nm以下であり、該分散液の色味がＬ値３０〜５５、ａ値−２〜＋２、ｂ値−４〜＋４である導電性微粉末分散液を得ることができる。この分散液を用いたコーティング組成物によれば透明性が高く、かつ青色等の色味のない導電膜を形成することができる。なお、分散液中の導電性粉末（酸化スズ微粉末）の累積重量９５％粒子径〔Ｄ95〕は、動的光散乱方式粒度分布計やレーザー回折粒度分布計等を用いて測定する事ができ、２５０nmよりも大きいと粉末が沈降し、透明性が低下する傾向がある。また、必要に応じて分散剤を添加することができる。 Specifically, in the dispersion of the present invention, the cumulative weight 95% particle diameter [D95] of the conductive powder in the dispersion is 250 nm or less, and the color of the dispersion has an L value of 30 to 55 and an a value. A conductive fine powder dispersion having −2 to +2 and a b value of −4 to +4 can be obtained. According to the coating composition using this dispersion, it is possible to form a conductive film having high transparency and having no color such as blue. The cumulative weight 95% particle size [D95] of the conductive powder (tin oxide fine powder) in the dispersion can be measured using a dynamic light scattering particle size distribution meter, a laser diffraction particle size distribution meter, or the like. If larger than 250 nm, the powder tends to settle and the transparency tends to decrease. Moreover, a dispersing agent can be added as needed.
本発明のリン窒素含有酸化スズからなる導電性微粉末の分散液を塗料成分と混合することによって透明導電膜を形成するコーティング組成物（塗料組成物）を得ることができる。この塗料組成物によって、表面抵抗値が１０12Ω/□以下、膜厚５μmの光透過率が８５％以上およびヘーズ値が３％以下の透明導電膜を形成することができる。
また、本発明の透明導電膜は膜硬度が高く、硬度Ｈ以上の透明導電膜を形成することができる。
The coating composition (coating composition) which forms a transparent conductive film can be obtained by mixing the dispersion liquid of the electroconductive fine powder which consists of phosphorus nitrogen containing tin oxide of this invention with a coating component. With this coating composition, it is possible to form a transparent conductive film having a surface resistance value of 10 12 Ω / □ or less, a light transmittance of 5 μm film thickness of 85% or more, and a haze value of 3% or less.
Further, the transparent conductive film of the present invention has a high film hardness, and can form a transparent conductive film having a hardness of H or higher.
本発明のリン窒素含有酸化スズは、リン酸存在下で水酸化スズを沈澱させ、該沈澱を乾燥後、窒素雰囲気下において、リンを０.１〜５wt％および窒素を１０ppm〜５０００ppm含有するように、４００〜７５０℃で焼成することによって製造することができる。焼成温度が４００℃よりも低いと窒素を上記含有量ドープさせることが難しい。また、焼成温度が７５０℃より高いと粒子の焼結が進行して粗粒子化する傾向があるので好ましくない。 The phosphorus nitrogen-containing tin oxide of the present invention precipitates tin hydroxide in the presence of phosphoric acid, and after drying the precipitate, contains 0.1 to 5 wt% phosphorus and 10 ppm to 5000 ppm nitrogen in a nitrogen atmosphere. Furthermore, it can manufacture by baking at 400-750 degreeC. If the firing temperature is lower than 400 ° C., it is difficult to dope the nitrogen content. Further, if the firing temperature is higher than 750 ° C., the sintering of the particles tends to progress and coarse particles are not preferable.
本発明のリン窒素含有酸化スズからなる導電性微粉末は、アンチモンを含有する必要がないので、アンチモンの毒性が問題視される分野、例えば食品包装材や梱包材の材料として好適である。また、本発明の酸化スズ微粉末は導電性に優れるので、静電記録材料として荷電制御が要求されるプリンタ、複写機関連の帯電ローラー、感光ドラム、トナー、静電ブラシ等の分野、ガスセンサー用焼結体原料粉末、光ディスク、ＦＤ、テープ等の磁気記録媒体などの各分野に広く用いることができる。 Since the conductive fine powder comprising the phosphorus nitrogen-containing tin oxide of the present invention does not need to contain antimony, it is suitable as a material for fields in which the toxicity of antimony is regarded as a problem, such as food packaging materials and packaging materials. In addition, since the tin oxide fine powder of the present invention is excellent in electrical conductivity, it is required to be charged as an electrostatic recording material, such as printers, copier-related charging rollers, photosensitive drums, toners, electrostatic brushes, etc., gas sensors Can be widely used in various fields such as sintered raw material powders, magnetic recording media such as optical disks, FDs, and tapes.
さらに、本発明の酸化スズ微粉末は導電性と共に高い透明性を有するので、埃付着防止が要求されるプラズマディスプレイ、液晶ディスプレイ、ＣＲＴ、ブラウン管等の分野の材料として好適である。また、薄膜塗料分野、太陽電池、液晶ディスプレイ等の内部電極、更には電極改質剤として電池等の分野における材料として好適である。また、各分野における利用の際に、塗料、インク、エマルジョン、繊維その他のポリマー中に容易に分散混練でき、また塗料成分に混合して塗料組成物を得ることができ、これによって高透明性および導電性に優れた薄膜を形成することができる。また、本発明の酸化スズ微粉末は熱線遮蔽材料、蓄熱材料として利用することができる。 Furthermore, since the tin oxide fine powder of the present invention has high transparency as well as conductivity, it is suitable as a material in the fields of plasma display, liquid crystal display, CRT, cathode ray tube and the like that are required to prevent dust adhesion. Moreover, it is suitable as a material in the field of thin film paints, internal electrodes for solar cells, liquid crystal displays and the like, and further as an electrode modifier in the field of batteries and the like. In addition, when used in various fields, it can be easily dispersed and kneaded in paints, inks, emulsions, fibers and other polymers, and can be mixed with paint components to obtain a paint composition. A thin film having excellent conductivity can be formed. Moreover, the tin oxide fine powder of this invention can be utilized as a heat ray shielding material and a heat storage material.
以下、本発明の実施例を比較例と共に示す。なお、等電点は水酸化ナトリウムおよび硝酸を用いてｐＨを調整した水に粉末を分散させてゼータ電位測定方法によって測定した。粉末の粉体体積抵抗率は、横河電機製測定装置(DM-7561)を用い、試料５ｇで１００ｋｇ/ｃｍ2加圧にて測定した。粉末のＢＥＴ比表面積は柴田化学社製の迅速表面積測定装置(SA-1100型)を用いた。粒子径は堀場製作所社製品(LB550)を用いて体積粒子径基準にて測定した。塗膜の表面抵抗は三菱油化社製装置（ハイレスタ表面高抵抗計HT-210）、ヘーズ、光透過率はスガ試験機社製装置（ＳＭカラーコンピューターSM-7-IS-2B）、膜強度は鉛筆硬度試験機をそれぞれ用いて測定した。 Examples of the present invention are shown below together with comparative examples. The isoelectric point was measured by a zeta potential measurement method by dispersing the powder in water adjusted in pH using sodium hydroxide and nitric acid. The powder volume resistivity of the powder was measured using a measuring device (DM-7561) manufactured by Yokogawa Electric Corporation at a pressure of 100 kg / cm 2 with a sample of 5 g. For the BET specific surface area of the powder, a rapid surface area measuring device (SA-1100 type) manufactured by Shibata Chemical Co., Ltd. was used. The particle size was measured on a volume particle size basis using a product of Horiba Ltd. (LB550). The surface resistance of the coating is a device manufactured by Mitsubishi Oil Chemical Co., Ltd. (Hiresta Surface High Resistance Meter HT-210), haze, and the light transmittance is a device manufactured by Suga Test Instruments Co., Ltd. (SM color computer SM-7-IS-2B). Was measured using a pencil hardness tester.
〔実施例〕
塩化スズ溶液にリン酸、珪酸ソーダを加え、苛性ソーダ溶液を添加して沈殿物を生成させた。その後、この沈殿物を窒素雰囲気下で十分乾燥した後、窒素雰囲気下、表１に示す温度で焼成してリンおよび窒素含有酸化スズを得た。この酸化スズを粉砕し、表１に示す酸化スズ微粉末を得た。この酸化スズ微粉末のリン含有量、窒素含有量、ＢＥＴ比表面積、等電点、Ｌ、ａ、ｂの各値、粉体体積抵抗率を表１に示した。
この酸化スズ微粉末３００ｇを、トルエン５１６ｇ、キシレン５１６ｇに分散した分散液を得、さらに市販のアクリル樹脂（商品名：アクリディックA-168、樹脂分50wt％）２５８ｇと混合し、ダイノーミルでビーズ分散して塗料組成物を得た。この分散液および塗料組成物の性状を表２に示した。また、この塗料組成物をＰＥＴフィルム（厚み100mm、ヘーズ1.8％、光透過率90％）の表面に市販の自動アプリケータ（RODNo.3）を用いて塗布し、膜厚５μmの薄膜を形成した。この薄膜にＵＶ照射した後、表面抵抗、光透過率、ヘーズを測定した。この結果を表２に示した。
〔Example〕
Phosphoric acid and sodium silicate were added to the tin chloride solution, and a caustic soda solution was added to form a precipitate. Thereafter, the precipitate was sufficiently dried in a nitrogen atmosphere and then fired at a temperature shown in Table 1 in a nitrogen atmosphere to obtain phosphorus and nitrogen-containing tin oxide. This tin oxide was pulverized to obtain tin oxide fine powder shown in Table 1. Table 1 shows the phosphorus content, nitrogen content, BET specific surface area, isoelectric point, L, a, and b values and powder volume resistivity of the tin oxide fine powder.
A dispersion in which 300 g of this tin oxide fine powder is dispersed in 516 g of toluene and 516 g of xylene is obtained, and further mixed with 258 g of a commercially available acrylic resin (trade name: Acrydic A-168, resin content 50 wt%), and the beads are dispersed with a dyno mill. Thus, a coating composition was obtained. The properties of this dispersion and coating composition are shown in Table 2. This coating composition was applied to the surface of a PET film (thickness 100 mm, haze 1.8%, light transmittance 90%) using a commercially available automatic applicator (ROD No. 3) to form a thin film having a thickness of 5 μm. . After the thin film was irradiated with UV, surface resistance, light transmittance, and haze were measured. The results are shown in Table 2.
〔比較例〕
窒素を含有せず、かつリンの含有量を表１に示すように調整した以外は実施例と同様にして酸化スズ微粉末を得た。この酸化スズ微粉末の性状を表１に示し、酸化スズ微粉末を含有する薄膜の性状を表２に示した。
[Comparative Example]
A tin oxide fine powder was obtained in the same manner as in the example except that nitrogen was not contained and the phosphorus content was adjusted as shown in Table 1. The properties of the tin oxide fine powder are shown in Table 1, and the properties of the thin film containing the tin oxide fine powder are shown in Table 2.
本発明の酸化スズ微粉末（試料No.A-1〜No.A-6）は何れもリンと共に窒素を所定量含有するので、等電点が測定されず、従って、溶媒中での分散性が良いので表面抵抗が比較試料（No.B-1〜No.B-3）よりも大幅に低い導電膜を形成することができる。また、この酸化スズ微粉末はＬ値が６０以上であって明るく、ａ値およびｂ値も目的の範囲内であって、白色度が良好であり、この酸化スズ微粉末を含む導電膜の光透過率は８５％以上であり、ヘーズも３.０以下であって透明度が高い。 Since the tin oxide fine powders of the present invention (samples No. A-1 to No. A-6) all contain a predetermined amount of nitrogen together with phosphorus, the isoelectric point is not measured, and therefore the dispersibility in a solvent. Therefore, it is possible to form a conductive film whose surface resistance is significantly lower than that of the comparative samples (No. B-1 to No. B-3). Further, the tin oxide fine powder has a bright L value of 60 or more, the a value and the b value are also within the target range, and the whiteness is good. The light of the conductive film containing the tin oxide fine powder The transmittance is 85% or more, the haze is 3.0 or less, and the transparency is high.
一方、リンおよび窒素を含まない比較試料No.B-1はｐＨ３.４に等電点を有し、従って、分散液中で凝集しやいので、薄膜の表面抵抗が本発明の酸化スズ微粉末よりも大きい。また、リンのみを１０wt％含有する比較試料No.B-2はリン含有量が過剰であるためにＬ値が低く、粉体体積抵抗率および薄膜の表面抵抗が何れも大幅に高い。さらに、リンを２wt％含有する比較試料No.B-3は焼成温度が高いので圧粉体での粉体体積抵抗率は低いが、窒素を含有しないので溶媒中での分散性が悪く、薄膜の表面抵抗が高い。また、粉体および分散液のＬ値が大幅に小さく、明度および透明度が低い。 On the other hand, Comparative Sample No. B-1, which does not contain phosphorus and nitrogen, has an isoelectric point at pH 3.4 and therefore easily aggregates in the dispersion. Larger than powder. Further, Comparative Sample No. B-2 containing only 10 wt% of phosphorus has a low L value due to the excessive phosphorus content, and both the powder volume resistivity and the surface resistance of the thin film are significantly high. Further, Comparative Sample No. B-3 containing 2 wt% phosphorus has a low powder volume resistivity in the green compact due to its high firing temperature, but does not contain nitrogen, so its dispersibility in the solvent is poor, and the thin film High surface resistance. Further, the L value of the powder and the dispersion is significantly small, and the brightness and transparency are low.
Claims (7)
A highly dispersible conductive fine powder characterized by having no isoelectric point in a pH range of 2 to 12.
A highly dispersible conductive fine powder comprising tin oxide fine powder containing 0.1 to 5 wt% phosphorus and 10 ppm to 5000 ppm nitrogen and having no isoelectric point in the pH range of 2-12.
It consists of tin oxide fine powder containing 0.1 to 5 wt% of phosphorus and 10 ppm to 5000 ppm of nitrogen, has no isoelectric point in the range of pH 2 to 12, and has a powder volume resistivity of 700 to 9 × 10 6 Ω · highly dispersible transparent conductive fine particles having a BET specific surface area of 100 m 2 / g or more, a powder color L value of 60 or more, an a value of −3 to +3, and a b value of 2 to 8. Powder.
A dispersion in which the conductive fine powder according to any one of claims 1 to 3 is dispersed in a medium, and the cumulative weight 95% particle diameter [D95] of the conductive powder in the dispersion is 250 nm or less, A conductive fine powder dispersion in which the color of the dispersion is L value 30 to 55, a value −2 to +2, and b value −4 to +4.
The coating composition formed by mix | blending the electroconductive fine powder in any one of Claims 1-3 with a coating-material component.
A transparent conductive film having a surface resistance value of 10 12 Ω / □ or less, a light transmittance of 85% or more and a haze value of 3% or less formed by the coating composition of claim 5.
Tin hydroxide is precipitated in the presence of phosphoric acid, dried, and calcined at 400 to 750 ° C. in a nitrogen atmosphere. Fine tin oxide powder containing 0.1 to 5 wt% of phosphorus and 10 to 5000 ppm of nitrogen A method for producing a conductive fine powder comprising:
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| JP2008184373A (en) * | 2007-01-31 | 2008-08-14 | Mitsubishi Materials Corp | Transparent tin oxide powder |
| JP2009018979A (en) * | 2007-07-13 | 2009-01-29 | Mitsubishi Materials Corp | Electroconductive tin oxide powder, and manufacturing method and use thereof |
| CN101661974B (en) * | 2009-09-03 | 2011-05-18 | 无锡尚品太阳能电力科技有限公司 | Woolen-making liquid in a solar battery and production method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS60260424A (en) * | 1984-06-05 | 1985-12-23 | Mitsubishi Metal Corp | Manufacture of fine tin oxide powder with low flectric resistance |
| JPH1053417A (en) * | 1996-08-02 | 1998-02-24 | Ishihara Sangyo Kaisha Ltd | Electroconductive tin oxide powder, its production and electroconductive suspended composition, electroconductive coating composition and antistatic material using the same |
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| JPS60260424A (en) * | 1984-06-05 | 1985-12-23 | Mitsubishi Metal Corp | Manufacture of fine tin oxide powder with low flectric resistance |
| JPH1053417A (en) * | 1996-08-02 | 1998-02-24 | Ishihara Sangyo Kaisha Ltd | Electroconductive tin oxide powder, its production and electroconductive suspended composition, electroconductive coating composition and antistatic material using the same |
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| JP2008184373A (en) * | 2007-01-31 | 2008-08-14 | Mitsubishi Materials Corp | Transparent tin oxide powder |
| JP2009018979A (en) * | 2007-07-13 | 2009-01-29 | Mitsubishi Materials Corp | Electroconductive tin oxide powder, and manufacturing method and use thereof |
| CN101661974B (en) * | 2009-09-03 | 2011-05-18 | 无锡尚品太阳能电力科技有限公司 | Woolen-making liquid in a solar battery and production method thereof |
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