JP2008166177A - Transparent conductive powder - Google Patents
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Abstract
Description
本発明は、アンチモン等の有害成分を含有せずに優れた導電性を有する透明粉末に関する。より詳しくは、本発明は、雲母を基材とし、アンチモン等の有害成分を含有せずに優れた導電性を有し、環境汚染等を生じる虞のない透明導電粉末に関する。 The present invention relates to a transparent powder having excellent conductivity without containing harmful components such as antimony. More specifically, the present invention relates to a transparent conductive powder which uses mica as a base material, has excellent conductivity without containing harmful components such as antimony, and does not cause environmental pollution.
導電粉末は帯電防止・帯電制御・静電防止・防塵等の用途に現在広く用いられている。従来、導電性を高めるために、アンチモン等をドープした導電粉末が使用されているが、アンチモンは有毒物質であり、近時、環境汚染防止等の観点から、アンチモンフリーの導電材料が求められている。さらに、従来の導電粉末は水に分散し難く、有機溶剤に分散させて使用しているが、環境への負荷を低減するため、水に分散可能であってプラスチックとの密着性も良い導電粉末が求められている。 Conductive powders are currently widely used in applications such as antistatic, charge control, antistatic, and dustproof. Conventionally, conductive powder doped with antimony or the like has been used in order to increase conductivity, but antimony is a toxic substance, and antimony-free conductive materials have recently been demanded from the viewpoint of preventing environmental pollution. Yes. Furthermore, conventional conductive powders are difficult to disperse in water and are used dispersed in organic solvents. However, in order to reduce environmental impact, conductive powders that can be dispersed in water and have good adhesion to plastics. Is required.
具体的には、従来、白色導電粉末として、例えば、酸化アルミニウムをドープした酸化亜鉛、二酸化チタン粉末等の表面に酸化アンチモンをドープした酸化錫膜を形成した白色導電粉末が知られている（特許文献１、特許文献２、特許文献３）。また、アンチモン成分を含有する酸化錫からなる導電被膜をチタン酸カリウム繊維に形成した白色導電繊維が知られている（特許文献４、特許文献５）。さらに、二酸化チタン粒子表面に酸化スズおよびリンを含む導電層を形成した白色導電性二酸化チタン粉末が知られている（特許文献６）。これらは、透明性を有しない。透明導電粉としては、アンチモンドープ酸化スズが知られている（特許文献７）。また、これらのドープ成分を含有しない表面改質した透明導電性酸化スズ粉末が知られている（特許文献８）。 Specifically, conventionally, as a white conductive powder, for example, a white conductive powder in which a tin oxide film doped with antimony oxide is formed on the surface of zinc oxide doped with aluminum oxide, titanium dioxide powder or the like (patent) Literature 1, Patent Literature 2, Patent Literature 3). Moreover, the white conductive fiber which formed the conductive film which consists of tin oxide containing an antimony component in the potassium titanate fiber is known (patent documents 4 and patent documents 5). Furthermore, white conductive titanium dioxide powder in which a conductive layer containing tin oxide and phosphorus is formed on the surface of titanium dioxide particles is known (Patent Document 6). These do not have transparency. As the transparent conductive powder, antimony-doped tin oxide is known (Patent Document 7). Further, a surface-modified transparent conductive tin oxide powder that does not contain these dope components is known (Patent Document 8).
しかし、酸化アンチモンをドープした酸化錫膜を有する白色導電粉末は、導電性が安定しているものの、アンチモンは有毒成分であるので、アンチモンフリーの導電粉末が求められている。一方、リンをドープした酸化錫は、導電性が不安定であり、またリンの偏在性の問題があった。さらに、表面改質されたノンドープ酸化錫からなる透明導電性酸化スズ粉末はカーボン残存等の問題がある。 However, although the white conductive powder having a tin oxide film doped with antimony oxide is stable in conductivity, antimony-free conductive powder is required because antimony is a toxic component. On the other hand, tin-doped tin oxide has unstable conductivity and has a problem of uneven distribution of phosphorus. Furthermore, the transparent conductive tin oxide powder made of surface-modified non-doped tin oxide has problems such as carbon remaining.
この他に、基板表面に気相反応によってフッ素含有酸化スズ膜を形成し、これを酸素導入下の不活性ガス下で熱処理することによって低抵抗にしたフッ素含有酸化スズ膜を形成する方法が知られているが（特許文献９）、粉体原料を気相処理したものは粉体表面に被膜が十分に形成されないので、粉体原料の処理方法として適さない。
本発明は、従来の透明導電粉末における上記問題を解決したものであり、雲母を基材とし、アンチモン等の有害成分を含有せずに優れた導電性を有し、環境汚染等を生じる虞れがなく、かつ水に分散可能で環境への負担が少ない透明導電粉末を提供するものである。 The present invention solves the above-mentioned problems in conventional transparent conductive powders, has mica as a base material, has excellent conductivity without containing harmful components such as antimony, and may cause environmental pollution and the like. In addition, the present invention provides a transparent conductive powder that can be dispersed in water and has a low environmental burden.
本発明は、以下の構成によって上記課題を解決した透明導電粉末を提供する。
（１）雲母を基材とし、アンチモン、リン、およびインジウムを含まない酸化スズ層を該基材表面に有することを特徴とする透明導電粉末。
（２）酸化スズ層の含有量が２０〜６０％であり、粉末体積抵抗が１０5Ω・cm以下である上記(１)に記載する透明導電粉末。
（３）雲母を基材とし、アンチモン、リン、およびインジウムを含まず、０.１〜５.０％のフッ素を含有する酸化スズ層を該基材表面に有することを特徴とする透明導電粉末。
（４）フッ素含有酸化スズ層の含有量が２０〜６０％であり、粉末体積抵抗が１００００Ω・cm以下である上記(３)に記載する透明導電粉末。
（５）酸化スズ層が、雲母表面に湿式処理によってスズ化合物を形成し、これを雰囲気調整した不活性ガス雰囲気下で熱処理したものである上記(１)または上記(２)に記載する透明導電粉末。
（６）フッ素含有酸化スズ層が、雲母表面に湿式処理によってスズ化合物を形成し、これにフッ素を導入し、雰囲気調整した不活性ガス雰囲気下で熱処理したものである上記(３)または上記(４)に記載する透明導電粉末。
This invention provides the transparent conductive powder which solved the said subject with the following structures.
(1) A transparent conductive powder comprising a mica as a base material and a tin oxide layer containing no antimony, phosphorus and indium on the surface of the base material.
(2) The transparent conductive powder according to the above (1), wherein the content of the tin oxide layer is 20 to 60% and the powder volume resistance is 10 5 Ω · cm or less.
(3) A transparent conductive powder characterized by having a tin oxide layer containing mica as a base material, containing no antimony, phosphorus and indium and containing 0.1 to 5.0% fluorine on the surface of the base material. .
(4) The transparent conductive powder according to (3), wherein the content of the fluorine-containing tin oxide layer is 20 to 60% and the powder volume resistance is 10,000 Ω · cm or less.
(5) The transparent conductive material according to (1) or (2) above, wherein the tin oxide layer is formed by forming a tin compound on the mica surface by wet treatment and heat-treating the tin compound in an inert gas atmosphere in which the atmosphere is adjusted. Powder.
(6) The above-described (3) or (), wherein the fluorine-containing tin oxide layer is formed by forming a tin compound on the mica surface by wet treatment, introducing fluorine into the mica surface, and heat-treating the atmosphere under an inert gas atmosphere. The transparent conductive powder described in 4).
本発明はさらに以下の製造方法および用途を提供する。
（７）基材の雲母を水に分散し、これにスズ源を加え、低ｐＨ下で加水分解して該雲母表面にスズ化合物を析出させ、乾燥後、不活性ガス雰囲気および水蒸気の存在下、酸素を排除し、熱処理して、雲母表面に導電性酸化スズ層を形成することを特徴とする透明導電粉末の製造方法。
（８）基材の雲母を水に分散し、これにスズ源を加え、低ｐＨ下で加水分解して該雲母表面にスズ化合物を析出させ、この析出時またはその後にフッ素を導入して該雲母表面にフッ素含有スズ化合物を形成し、乾燥後、不活性ガス雰囲気および水蒸気の存在下、酸素を排除し、熱処理して、雲母表面に導電性フッ素含有酸化スズ層を形成する透明導電粉末の製造方法。
（９）上記(１)〜上記(６)の何れかに記載する透明導電粉末を水に分散してなる分散液。
（１０）上記(１)〜上記(６)の何れかに記載する透明導電粉末を含有する膜組成物。
The present invention further provides the following production methods and uses.
(7) Disperse the mica of the base material in water, add a tin source thereto, hydrolyze under low pH to precipitate a tin compound on the surface of the mica, and after drying, in the presence of an inert gas atmosphere and water vapor A method for producing a transparent conductive powder, characterized by excluding oxygen and heat-treating to form a conductive tin oxide layer on the surface of mica.
(8) Disperse the mica of the base material in water, add a tin source thereto, hydrolyze under low pH to precipitate a tin compound on the surface of the mica, and introduce fluorine at or after the precipitation to introduce the tin compound. A transparent conductive powder that forms a fluorine-containing tin compound on the surface of mica and forms a conductive fluorine-containing tin oxide layer on the surface of mica by drying, excluding oxygen in the presence of an inert gas atmosphere and water vapor, and heat treatment. Production method.
(9) A dispersion obtained by dispersing the transparent conductive powder described in any one of (1) to (6) in water.
(10) A film composition containing the transparent conductive powder according to any one of (1) to (6) above.
本発明の導電粉末は、雲母を基材とした高い導電性を有する透明導電粉末である。雲母を基材とするので透明性を有し、従って、透明性が要求される用途、例えば、自動車ガラスや、帯電防止プレート、帯電防止シート、静電プライマーなどにおける導電材料として好適である。 The conductive powder of the present invention is a transparent conductive powder having high conductivity based on mica. Since mica is used as a base material, it has transparency and is therefore suitable as a conductive material in applications requiring transparency, such as automobile glass, antistatic plates, antistatic sheets, electrostatic primers, and the like.
また、本発明の透明導電粉末は、酸スズ層にアンチモン、リン、インジウムを何れも含まないので環境汚染等を生じる懸念がない。また、アンチモン、リン、インジウムを含まないので低コストである。なお、本発明において、アンチモン、リン、およびインジウムを含まないとは、原料および工程中でアンチモン、リン、およびインジウム源を使用せず、従って検出限界５００ppmの標準的な測定装置によってこれらの元素が検出されないことを云う。 Moreover, since the transparent conductive powder of the present invention does not contain any of antimony, phosphorus, and indium in the tin oxide layer, there is no concern of causing environmental pollution. Further, since it does not contain antimony, phosphorus, and indium, it is low cost. In the present invention, “antimony, phosphorus, and indium are not included” means that no source of antimony, phosphorus, and indium is used in the raw materials and processes, and therefore these elements are detected by a standard measuring device having a detection limit of 500 ppm. It is said that it is not detected.
本発明の透明導電粉末は、上記アンチモン等のドープ成分を含まずに高い導電性を有しており、とくに酸化スズ層にフッ素が含有されているものは安定した高い導電性を有するので、安全な導電材料として各種の機器に広く用いることができる。具体的には、例えば、静電塗装プライマー、帯電防止効果を有する樹脂やタイル、導電性塗料、静電記録材料、複写機関連の帯電ローラー、感光ドラム、トナー、静電ブラシなどにおける導電材料として好適である。 The transparent conductive powder of the present invention has high conductivity without containing the above-mentioned antimony and other doped components, and particularly those containing fluorine in the tin oxide layer have stable high conductivity. As a conductive material, it can be widely used in various devices. Specifically, for example, as conductive materials in electrostatic coating primers, resins and tiles having antistatic effects, conductive paints, electrostatic recording materials, copier-related charging rollers, photosensitive drums, toners, electrostatic brushes, etc. Is preferred.
本発明の透明導電粉末は水に分散可能であるので、水性塗料等の導電材料として用いることができる。さらに本発明の透明導電粉末は平板状を有する雲母を基材としているので樹脂成分や塗料成分に分散させて用いるときに、使用量が従来の導電粉末より少量で足り、コスト低下に有利であると共に樹脂等の性質を損なう懸念が少ない。 Since the transparent conductive powder of the present invention can be dispersed in water, it can be used as a conductive material such as an aqueous paint. Further, since the transparent conductive powder of the present invention is based on a mica having a flat plate shape, when used in a resin component or paint component, the amount used is less than that of a conventional conductive powder, which is advantageous for cost reduction. At the same time, there are few concerns that damage the properties of the resin and the like.
以下、本発明を実施形態に基づいて具体的に説明する。なお、％は特に示さない限り、また数値固有の場合を除いて質量％である。
〔透明導電粉末〕
本発明に係る第一態様の導電粉末は、雲母を基材とし、アンチモン、リン、およびインジウムを含まない酸化スズ層を該基材表面に有することを特徴とする透明導電粉末である。
また、本発明に係る第二態様の導電粉末は、雲母を基材とし、アンチモン、リン、およびインジウムを含まず、０.１〜５.０％のフッ素を含有する酸化スズ層を該基材表面に有することを特徴とする透明導電粉末である。
Hereinafter, the present invention will be specifically described based on embodiments. Unless otherwise indicated, “%” means “% by mass” unless otherwise specified.
[Transparent conductive powder]
The conductive powder according to the first aspect of the present invention is a transparent conductive powder characterized by having a mica as a base material and a tin oxide layer containing no antimony, phosphorus and indium on the surface of the base material.
The conductive powder according to the second aspect of the present invention comprises a tin oxide layer containing mica as a base material, containing no antimony, phosphorus and indium and containing 0.1 to 5.0% fluorine. It is a transparent conductive powder characterized by having on the surface.
本発明の透明導電粉末は、その基材として雲母を用いる。一般に雲母は薄片状をなし、薄いものは光を透過する透明材料であるので、雲母を基材として透明導電粉末を得ることができる。雲母の大きさは１〜３０μmのものが好ましい。 The transparent conductive powder of the present invention uses mica as its base material. In general, mica has a flake shape, and a thin material is a transparent material that transmits light. Therefore, a transparent conductive powder can be obtained using mica as a base material. The size of mica is preferably 1 to 30 μm.
上記雲母表面に形成された酸化スズ層はアンチモン、リン、およびインジウムを含まない。従来の導電粉末は上記アンチモンやリン等をドープすることによって導電性を高めているが、本発明の透明導電粉末は、雲母表面に湿式処理によってスズ化合物を形成し、これを雰囲気調整した不活性ガス雰囲気下で熱処理することによって、高い導電性を達成しているので、上記各元素を含有する必要がない。 The tin oxide layer formed on the mica surface does not contain antimony, phosphorus, and indium. The conventional conductive powder has improved conductivity by doping with antimony, phosphorus or the like, but the transparent conductive powder of the present invention forms a tin compound by wet treatment on the mica surface, and the inertness is adjusted by adjusting the atmosphere. Since high conductivity is achieved by heat treatment in a gas atmosphere, it is not necessary to contain each of the above elements.
また、本発明のフッ素含有酸化スズ層を有する透明導電粉末は、雲母表面に湿式処理によってスズ化合物を形成し、これにフッ素を導入し、雰囲気調整した不活性ガス雰囲気下で熱処理することによって、高い導電性を達成しているので、上記各元素を含有する必要がない。さらに上記フッ素を含有した酸化スズ層は導電性が高く、かつ安定である。 In addition, the transparent conductive powder having a fluorine-containing tin oxide layer of the present invention is formed by forming a tin compound by wet treatment on the mica surface, introducing fluorine into the mica surface, and heat-treating under an inert gas atmosphere whose atmosphere is adjusted, Since high conductivity is achieved, it is not necessary to contain the above elements. Further, the above tin oxide layer containing fluorine has high conductivity and is stable.
本発明の透明導電粉末において、粉末中の酸化スズ層ないしフッ素含有酸化スズ層の割合は２０〜６０％が適当であり、３０〜５０％が好ましい。この量が２０％未満では所望の導電性が得るのが難しい。また、この量が６０％より多いと低抵抗にはなるものの、凝集の問題が生じるので好ましくない。 In the transparent conductive powder of the present invention, the proportion of the tin oxide layer or the fluorine-containing tin oxide layer in the powder is suitably 20 to 60%, preferably 30 to 50%. If this amount is less than 20%, it is difficult to obtain desired conductivity. On the other hand, if the amount is more than 60%, the resistance becomes low, but the problem of aggregation occurs, which is not preferable.
フッ素を含有する酸化スズ層において、酸化スズ層中のフッ素量は０.１〜５.０％である。フッ素量が０.１％未満では粉末体積抵抗が低下しない。またフッ素量が５.０％より多くても粉末体積抵抗は５.０％の場合と大差なく、抵抗値の低下の割合は小さい。 In the tin oxide layer containing fluorine, the amount of fluorine in the tin oxide layer is 0.1 to 5.0%. When the fluorine content is less than 0.1%, the powder volume resistance does not decrease. Further, even if the fluorine content is more than 5.0%, the powder volume resistance is not much different from the case of 5.0%, and the rate of decrease in the resistance value is small.
本発明の透明導電粉末の導電性は、粉末中の酸化スズ層の量が２０〜６０％において、例えば、酸化スズ層がフッ素を含有しないものは粉末体積抵抗が１０5Ω・cm以下の導電性を有することができる。また、酸化スズ層がフッ素を含有するものは粉末体積抵抗が１００００Ω・cm以下、好ましくは５０００Ω・cm以下の導電性を有することができる。
なお、粉末体積抵抗が１０5Ω・cmより大きいと、この粉末を樹脂に混入したときの表面抵抗が概ね１０10Ω／□以上になるので帯電防止効果が不十分になる。本発明の透明導電粉末の導電性は粉末体積抵抗が小さいのでこのような問題がない。
The conductivity of the transparent conductive powder of the present invention is such that when the amount of the tin oxide layer in the powder is 20 to 60%, for example, the tin oxide layer containing no fluorine has a powder volume resistance of 10 5 Ω · cm or less. Can have sex. In addition, the tin oxide layer containing fluorine can have a conductivity with a powder volume resistance of 10,000 Ω · cm or less, preferably 5000 Ω · cm or less.
If the powder volume resistance is greater than 10 5 Ω · cm, the surface resistance when this powder is mixed into the resin is approximately 10 10 Ω / □ or more, and the antistatic effect is insufficient. The conductivity of the transparent conductive powder of the present invention does not have such a problem because the powder volume resistance is small.
〔製造方法〕
本発明の透明導電粉末について、フッ素を含有しない酸化スズ層を有するものは、雲母の表面に湿式処理によってスズ化合物を形成し、これを雰囲気調整した不活性ガス雰囲気下で熱処理して酸化スズ層を形成することによって製造することができる。
〔Production method〕
The transparent conductive powder of the present invention having a tin oxide layer not containing fluorine is formed by forming a tin compound on the surface of mica by wet treatment and heat-treating it in an inert gas atmosphere in which the atmosphere is adjusted. Can be manufactured.
好ましくは、基材の雲母を水に分散させ、これにスズ源を加え、低ｐＨ下、例えばｐＨ４以下で加水分解して雲母表面にスズ化合物を析出させ、乾燥後、不活性ガス雰囲気および水蒸気の存在下、酸素を排除し、熱処理して雲母表面に導電性酸化スズ層を形成する。 Preferably, the mica of the base material is dispersed in water, a tin source is added thereto, and the tin compound is precipitated on the surface of the mica by hydrolysis at a low pH, for example, pH 4 or less, and after drying, an inert gas atmosphere and water vapor In the presence of oxygen, oxygen is excluded and heat treatment is performed to form a conductive tin oxide layer on the mica surface.
また、フッ素含有酸化スズ層を有するものは、雲母の表面に湿式処理によってスズ化合物を析出させ、これにフッ素を導入し、雰囲気調整した不活性ガス雰囲気下で熱処理してフッ素含有酸化スズ層を形成することによって製造することができる。 In addition, for those having a fluorine-containing tin oxide layer, a tin compound is deposited on the surface of mica by wet treatment, fluorine is introduced into this, and heat treatment is performed in an inert gas atmosphere with an atmosphere adjusted to form the fluorine-containing tin oxide layer. It can be manufactured by forming.
好ましくは、基材の雲母を水に分散し、これにスズ源を加え、低ｐＨ下、例えばｐＨ４以下で加水分解して雲母表面にスズ化合物を析出させ、この析出時またはその後にフッ素を導入して該粉末表面にフッ素含有スズ化合物を形成し、乾燥後、不活性ガス雰囲気および水蒸気の存在下、酸素を排除し、熱処理して基材表面にフッ素含有酸化スズ層を形成する。 Preferably, mica of the base material is dispersed in water, a tin source is added thereto, and the tin compound is precipitated on the surface of mica by hydrolysis at a low pH, for example, pH 4 or less, and fluorine is introduced at or after the precipitation. Then, a fluorine-containing tin compound is formed on the powder surface, and after drying, oxygen is excluded in the presence of an inert gas atmosphere and water vapor, and heat treatment is performed to form a fluorine-containing tin oxide layer on the substrate surface.
具体的には、基材の雲母を水に分散させて４０〜１００℃に加温し、スズ源を加え、これを加水分解して雲母表面にスズ化合物を析出させる。スズ源としては塩化スズ、硝酸スズ、酢酸スズ、その他の可溶性スズ塩を用いることができる。 Specifically, mica as a base material is dispersed in water and heated to 40 to 100 ° C., a tin source is added, and this is hydrolyzed to deposit a tin compound on the surface of mica. As the tin source, tin chloride, tin nitrate, tin acetate, and other soluble tin salts can be used.
雲母表面にスズ化合物を析出させた後、デカンテーションにより残留塩分を除去して乾燥する。なお、スズ源として塩化スズを用いる場合には、塩酸水溶液を加え、ｐＨ４以下でスズ化合物を析出させ、その後の洗浄は塩酸が僅かに残留する程度に止めるのが良い。 After depositing a tin compound on the mica surface, the residual salt is removed by decantation and dried. When tin chloride is used as the tin source, an aqueous hydrochloric acid solution is added to precipitate a tin compound at a pH of 4 or lower, and the subsequent washing should be stopped to the extent that hydrochloric acid remains slightly.
フッ素を導入するには、デカンテーションの後に、フッ素源、例えば、フッ化第一スズを加える。このとき、水酸基とフッ素が置換してフッ素が取り込まれる。フッ素を含むことによって紛体はやや黄色味を帯びる。このフッ素はほとんど全てがスズ化合物に取り込まれるので遊離のフッ素が無く、熱処理において炉を傷めることが少ない。
なお、スズ源の塩化スズと共にフッ素源のフッ化第一スズを加え、フッ素を含むスズ化合物を析出させても良い。
To introduce fluorine, a fluorine source, for example stannous fluoride, is added after decantation. At this time, the hydroxyl group and fluorine are substituted and fluorine is taken in. By containing fluorine, the powder is slightly yellowish. Almost all of this fluorine is taken into the tin compound, so there is no free fluorine and the furnace is less likely to be damaged during heat treatment.
A tin compound containing fluorine may be deposited by adding stannous fluoride as a fluorine source together with tin chloride as a tin source.
なお、従来、ＣＶＤ法などの気相反応によってシリカ基板表面にフッ素ドープ酸化スズ膜を形成することが知られているが（特許文献９）、粉末原料を用いる場合には気相処理では粉末全体に十分な酸化スズ層を形成することができない。 Conventionally, it is known that a fluorine-doped tin oxide film is formed on the surface of a silica substrate by a gas phase reaction such as a CVD method (Patent Document 9). Insufficient tin oxide layer can be formed.
本発明の透明導電粉末は、上記湿式処理の後に乾燥し、熱処理を行って酸化スズ層ないしフッ素含有酸化スズ層を形成する。熱処理温度は４００℃以上〜８００℃以下が好ましい。熱処理温度が４００℃より低いと十分な導電性が得られず、また８００℃より高いと粉末の焼結が始まるので好ましくない。 The transparent conductive powder of the present invention is dried after the above wet treatment and subjected to heat treatment to form a tin oxide layer or a fluorine-containing tin oxide layer. The heat treatment temperature is preferably 400 ° C. or higher and 800 ° C. or lower. If the heat treatment temperature is lower than 400 ° C., sufficient conductivity cannot be obtained, and if it is higher than 800 ° C., powder sintering starts, which is not preferable.
この熱処理は、雰囲気調整した不活性ガス雰囲気下で行うのが良く、具体的には、窒素ガスやアルゴンガスなどの不活性ガス雰囲気および水蒸気の存在下、酸素を排除して行うのが好ましい。水蒸気はアルコール蒸気でも良い。水蒸気またはアルコール蒸気を導入する方法は限定されない。熱処理炉の不活性ガス雰囲気中に水蒸気またはアルコール蒸気を導入してもよく、湿式処理後の原料粉末の乾燥を適度にして湿った状態にし、または原料粉末に水をまたはアルコールを噴霧しても良い。あるいは不活性ガスを水やアルコールに通じてバブリングさせて熱処理炉に導入しても良い。 This heat treatment is preferably performed in an inert gas atmosphere whose atmosphere is adjusted. Specifically, it is preferably performed in the presence of an inert gas atmosphere such as nitrogen gas or argon gas and water vapor, excluding oxygen. The water vapor may be alcohol vapor. The method for introducing water vapor or alcohol vapor is not limited. Water vapor or alcohol vapor may be introduced into the inert gas atmosphere of the heat treatment furnace, the raw material powder after the wet treatment may be appropriately dried to be moistened, or the raw material powder may be sprayed with water or alcohol. good. Alternatively, an inert gas may be bubbled through water or alcohol and introduced into the heat treatment furnace.
水またはアルコールの蒸気圧は飽和蒸気圧３０％以上が好ましい。この蒸気圧を保って熱処理するには密閉型の熱処理炉を用いるのが好ましい。なお、スズ化合物の加熱時には水分が抜けるので、この水分を利用して同様の効果を得るようにしても良い。 The vapor pressure of water or alcohol is preferably 30% or higher. In order to perform the heat treatment while maintaining the vapor pressure, it is preferable to use a closed heat treatment furnace. In addition, since a water | moisture content lose | disappears at the time of the heating of a tin compound, you may make it acquire the same effect using this water | moisture content.
また、雰囲気から酸素を排除して加熱する。従来、酸素を含む不活性ガス下で熱処理する方法が知られているが（特許文献９）、酸素が含まれていると、安定して低抵抗粉末が得られず、また不均一である。 Also, heating is performed by removing oxygen from the atmosphere. Conventionally, a method of performing a heat treatment under an inert gas containing oxygen is known (Patent Document 9). However, if oxygen is contained, a low-resistance powder cannot be obtained stably and is not uniform.
湿式処理した原料粉末を、水蒸気またはアルコール蒸気を含む不活性ガス雰囲気下で酸化を排除して熱処理することによって、低抵抗の透明導電粉末が得られる。なお、フッ素含有酸化スズ層を有するものは、不活性ガスが水蒸気やアルコール蒸気を含まない場合でも抵抗が比較的低い粉末が得られる。また、フッ素含有酸化スズ層を有する場合、水蒸気またはアルコール蒸気の存在下で熱処理することによって粉末の抵抗をさらに低下させることができる。本発明の製造方法は、フッ素含有酸化スズ層を有する透明導電粉末について、不活性ガスが水蒸気やアルコール蒸気を含まない熱処理、および不活性ガスが水蒸気やアルコール蒸気を含む熱処理の何れも含む。 A low-resistance transparent conductive powder is obtained by heat-treating the wet-treated raw material powder in an inert gas atmosphere containing water vapor or alcohol vapor while eliminating oxidation. In addition, what has a fluorine-containing tin oxide layer can obtain a powder with relatively low resistance even when the inert gas does not contain water vapor or alcohol vapor. Moreover, when it has a fluorine-containing tin oxide layer, the resistance of the powder can be further reduced by heat treatment in the presence of water vapor or alcohol vapor. The production method of the present invention includes both heat treatment in which the inert gas does not contain water vapor or alcohol vapor, and heat treatment in which the inert gas contains water vapor or alcohol vapor, with respect to the transparent conductive powder having a fluorine-containing tin oxide layer.
以下に本発明の実施例を比較例と共に示す。実施例および比較例において、粉末体積抵抗は試料粉末を圧力容器に入れて１００kgf/cm2で圧縮し、この圧粉をデジタルマルチメーター（横河電機製品：型式7561-02）によって測定した。塗布膜の表面抵抗は透明導電粉末を含む膜厚約１００μmの薄膜について表面抵抗計（ハイレスタ：三菱油化製品：型式HT-210、供給電圧１００Ｖ）を用いて測定した。全光線透過率は透明導電粉末を含む膜厚約１００μmの薄膜についてスガ試験機社製装置（SM-7-IS-2B）を用いて測定した。 Examples of the present invention are shown below together with comparative examples. In Examples and Comparative Examples, the powder volume resistance was measured with a digital multimeter (Yokogawa Electric product: Model 7561-02) after putting the sample powder into a pressure vessel and compressing the powder at 100 kgf / cm 2 . The surface resistance of the coating film was measured using a surface resistance meter (Hiresta: Mitsubishi Yuka product: model HT-210, supply voltage 100 V) for a thin film having a film thickness of about 100 μm containing transparent conductive powder. The total light transmittance was measured using a device (SM-7-IS-2B) manufactured by Suga Test Instruments Co., Ltd. for a thin film having a film thickness of about 100 μm containing transparent conductive powder.
〔実施例１〕
雲母粉末（キララ社製品）５０ｇを水３００ccに分散させて、９０℃に加温した。この分散液に、粉体中の酸化スズ含有量が表１の値になるように所定量の塩化スズを加え、塩酸水溶液を２０分〜３０分かけて添加してｐＨ３〜４に調整した。この湿式処理した雲母を取り出して洗浄し乾燥した。上記湿式処理で加えた塩化スズは実質的に全量が加水分解され、雲母表面にスズ化合物（Ｘ線回折ではＳｎＯ2パターンを示す水酸化スズ）が析出していた。この乾燥雲母粉末２０ｇを石英管状炉に入れ、水を通して水蒸気を飽和させた窒素ガスを０.３Ｌ/分の割合で３０分間炉内に流し、酸素を排除して、表１に示す温度で熱処理した。処理した雲母粉末を取り出し、１００kgf/cm2で圧粉し、粉末体積抵抗を測定した。また上記粉末のＬａｂ表色系の値を測定した。この結果を表１に示した。
[Example 1]
50 g of mica powder (Kirara product) was dispersed in 300 cc of water and heated to 90 ° C. A predetermined amount of tin chloride was added to this dispersion so that the tin oxide content in the powder would be the value shown in Table 1, and an aqueous hydrochloric acid solution was added over 20 to 30 minutes to adjust the pH to 3 to 4. The wet-treated mica was taken out, washed and dried. The entire amount of tin chloride added by the wet treatment was hydrolyzed, and a tin compound (tin hydroxide showing SnO 2 pattern in X-ray diffraction) was precipitated on the surface of mica. 20 g of this dry mica powder was put into a quartz tube furnace, and nitrogen gas saturated with water vapor through water was passed through the furnace at a rate of 0.3 L / min for 30 minutes to exclude oxygen, and heat treatment was carried out at the temperatures shown in Table 1. did. The treated mica powder was taken out and compacted at 100 kgf / cm 2 to measure the powder volume resistance. Moreover, the value of the Lab color system of the powder was measured. The results are shown in Table 1.
〔比較例１〕
酸化スズ含有量、熱処理温度、および加熱雰囲気を表２に示す条件にした以外は実施例１と同様にして透明導電粉末を製造した。この透明導電粉末について粉末体積抵抗を測定した。この結果を表１に示した。
[Comparative Example 1]
A transparent conductive powder was produced in the same manner as in Example 1 except that the tin oxide content, the heat treatment temperature, and the heating atmosphere were changed to the conditions shown in Table 2. The powder volume resistance of this transparent conductive powder was measured. The results are shown in Table 1.
〔実施例２・比較例２〕
実施例１および比較例１において製造した透明導電微粉末４.３ｇ（３０％）、または２.５ｇ（２０％）をおのおの市販のアクリル塗料（樹脂含有量10％）１００ｇに加え、ビーズを入れたペイントシェーカーで３０分攪拌した。この塗料をワーヤーバー（No.8）でＰＥＴフィルムに塗布し、乾燥後の表面抵抗を表面抵抗計にて測定した。また、塗膜の性状（凝集体によるブツの有無）を目視にて確認した。この結果を表１に示した。
[Example 2 and Comparative Example 2]
Add 4.3 g (30%) or 2.5 g (20%) of transparent conductive fine powder produced in Example 1 and Comparative Example 1 to 100 g of each commercially available acrylic paint (resin content 10%), and put beads. The mixture was stirred for 30 minutes with a paint shaker. This paint was applied to a PET film with a wire bar (No. 8), and the surface resistance after drying was measured with a surface resistance meter. In addition, the properties of the coating film (the presence or absence of irregularities due to aggregates) were visually confirmed. The results are shown in Table 1.
表１に示すように、本発明に係るＡ１〜Ａ５は何れも粉末体積抵抗が１０5Ω・cm以下であり、酸化スズ量が２０％以上であって、熱処理温度が５００℃のＡ２〜Ａ３は粉末体積抵抗が５０００Ω・cmであり、導電性が高い。また、全光線透過率も８０％以上の良好な透明性を有している。一方、比較試料Ｂ１、Ｂ２，Ｂ４、Ｂ５は何れも粉末体積抵抗が各段に高く、導電性が低い。 As shown in Table 1, all of A1 to A5 according to the present invention have a powder volume resistance of 10 5 Ω · cm or less, a tin oxide amount of 20% or more, and a heat treatment temperature of 500 ° C. A2 to A3. Has a powder volume resistance of 5000 Ω · cm and high conductivity. Further, the total light transmittance is excellent transparency of 80% or more. On the other hand, all of the comparative samples B1, B2, B4, and B5 have high powder volume resistance at each stage and low conductivity.
〔実施例３〕
雲母粉末（キララ社製品）５０ｇを水３００ccに分散させて、９０℃に加温した。この分散液に、粉体中の酸化スズ含有量が表２の値になるように所定量の塩化スズを加え、塩酸水溶液を２０分〜３０分かけて添加してｐＨ３〜４に調整した。この湿式処理した粉末を取り出して洗浄した。上記湿式処理で加えた塩化スズは実質的に全量が加水分解され、粉末表面にスズ化合物（Ｘ線回折ではＳｎＯ2パターンを示す水酸化スズ）が析出していた。これにフッ化第一スズを表２に示すフッ素含有量になるように所定量を加え、攪拌し乾燥した。この乾燥雲母粉末２０ｇを石英管状炉に入れ、水を通して水蒸気を飽和させた窒素ガスを０.３Ｌ/分の割合で３０分間炉内に流し、酸素を排除して、表２に示す温度で熱処理した。処理した雲母粉末を取り出し、１００kgf/cm2で圧粉し、粉末体積抵抗を測定した。
Example 3
50 g of mica powder (Kirara product) was dispersed in 300 cc of water and heated to 90 ° C. A predetermined amount of tin chloride was added to this dispersion so that the tin oxide content in the powder would be the value shown in Table 2, and an aqueous hydrochloric acid solution was added over 20 to 30 minutes to adjust to pH 3 to 4. The wet-processed powder was taken out and washed. The entire amount of tin chloride added by the wet treatment was hydrolyzed, and a tin compound (tin hydroxide showing SnO 2 pattern in X-ray diffraction) was precipitated on the powder surface. A predetermined amount of stannous fluoride was added to the fluorine content shown in Table 2, and the mixture was stirred and dried. 20 g of this dry mica powder was put in a quartz tube furnace, and nitrogen gas saturated with water vapor was passed through the furnace at a rate of 0.3 L / min for 30 minutes to exclude oxygen, and heat treatment was performed at the temperatures shown in Table 2. did. The treated mica powder was taken out and compacted at 100 kgf / cm 2 to measure the powder volume resistance.
〔比較例３〕
酸化スズ含有量、酸化スズ中のフッ素量、熱処理温度、および加熱雰囲気を表２に示す条件にした以外は実施例３と同様にして透明導電粉末を製造した。この粉末について粉末体積抵抗の値を測定した。この結果を表２に示した。
[Comparative Example 3]
A transparent conductive powder was produced in the same manner as in Example 3 except that the tin oxide content, the fluorine content in the tin oxide, the heat treatment temperature, and the heating atmosphere were changed to the conditions shown in Table 2. The powder volume resistance was measured for this powder. The results are shown in Table 2.
〔実施例４・比較例４〕
実施例３および比較例３において製造した透明導電微粉末４.３ｇ（３０％）、または２.５ｇ（２０％）をおのおの市販のアクリル塗料（樹脂含有量10％）１００ｇに加え、ビーズを入れたペイントシェーカーで３０分攪拌した。この塗料をワイヤーバー（No.8）でＰＥＴフィルムに塗布し、乾燥後の表面抵抗を表面抵抗計にて測定した。また、塗膜の性状（凝集体によるブツの有無）を目視にて確認した。この結果を表２に示した。
Example 4 and Comparative Example 4
4.3 g (30%) or 2.5 g (20%) of transparent conductive fine powder produced in Example 3 and Comparative Example 3 was added to 100 g of each commercially available acrylic paint (resin content 10%), and beads were added. The mixture was stirred for 30 minutes with a paint shaker. This paint was applied to a PET film with a wire bar (No. 8), and the surface resistance after drying was measured with a surface resistance meter. In addition, the properties of the coating film (the presence or absence of irregularities due to aggregates) were visually confirmed. The results are shown in Table 2.
表２に示すように、Ｃ１〜Ｃ５は何れも粉末体積抵抗が１００００Ω・cm以下であり、導電性が高い。また、全光線透過率も８０％以上で良好な透明性を有している。一方、比較試料Ｄ１、Ｄ２、Ｄ４、Ｄ５は何れも粉末体積抵抗が各段に高く、導電性が低い。 As shown in Table 2, all of C1 to C5 have a powder volume resistance of 10,000 Ω · cm or less, and have high conductivity. Further, the total light transmittance is 80% or more, and it has good transparency. On the other hand, the comparative samples D1, D2, D4, and D5 all have high powder volume resistance at each stage and low conductivity.
Claims (10)
A transparent conductive powder comprising a mica as a base material and a tin oxide layer containing no antimony, phosphorus and indium on the surface of the base material.
The transparent conductive powder according to claim 1, wherein the content of the tin oxide layer is 20 to 60%, and the powder volume resistance is 10 5 Ω · cm or less.
A transparent conductive powder comprising a tin oxide layer containing mica as a base material, containing no antimony, phosphorus and indium and containing 0.1 to 5.0% fluorine on the surface of the base material.
The transparent conductive powder according to claim 3, wherein the content of the fluorine-containing tin oxide layer is 20 to 60%, and the powder volume resistance is 10,000 Ω · cm or less.
The transparent conductive powder according to claim 1 or 2, wherein the tin oxide layer is obtained by heat-treating a tin compound on the surface of mica by wet treatment under an inert gas atmosphere in which the tin compound is adjusted.
The transparent conductive film according to claim 3 or 4, wherein the fluorine-containing tin oxide layer is formed by forming a tin compound on the mica surface by wet treatment, introducing fluorine into the mica surface, and heat-treating the atmosphere under an inert gas atmosphere. Powder.
Disperse the mica of the base material in water, add a tin source thereto, hydrolyze it at a low pH to precipitate a tin compound on the surface of the mica, and after drying, oxygen is added in the presence of an inert gas atmosphere and water vapor. A method for producing a transparent conductive powder, characterized in that a conductive tin oxide layer is formed on the surface of mica by eliminating and heat-treating.
Disperse the mica of the base material in water, add a tin source to this, hydrolyze it at a low pH to precipitate a tin compound on the surface of the mica, and introduce fluorine at or after this precipitation to introduce a tin compound onto the surface of the mica. A method for producing a transparent conductive powder in which a fluorine-containing tin compound is formed, dried, then subjected to heat treatment in the presence of an inert gas atmosphere and water vapor, and subjected to heat treatment to form a conductive fluorine-containing tin oxide layer on the mica surface.
The dispersion liquid which disperse | distributes the transparent conductive powder in any one of Claims 1-6 in water.
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| JP2016118739A (en) * | 2014-12-24 | 2016-06-30 | 株式会社リコー | Laminated inorganic mineral, toner, and image forming apparatus |
| CN114736405A (en) * | 2022-03-28 | 2022-07-12 | 金发科技股份有限公司 | Polyphenyl ether conductive master batch, low CLTE nylon alloy and application thereof |
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| JPH05229826A (en) * | 1992-02-18 | 1993-09-07 | Res Inst For Prod Dev | Electrically conductive substance and its production |
| JP2005108733A (en) * | 2003-09-30 | 2005-04-21 | Mitsui Mining & Smelting Co Ltd | Conductive powder and its producing method |
| JP2005108734A (en) * | 2003-09-30 | 2005-04-21 | Mitsui Mining & Smelting Co Ltd | Conductive powder and its producing method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05229826A (en) * | 1992-02-18 | 1993-09-07 | Res Inst For Prod Dev | Electrically conductive substance and its production |
| JP2005108733A (en) * | 2003-09-30 | 2005-04-21 | Mitsui Mining & Smelting Co Ltd | Conductive powder and its producing method |
| JP2005108734A (en) * | 2003-09-30 | 2005-04-21 | Mitsui Mining & Smelting Co Ltd | Conductive powder and its producing method |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011054508A (en) * | 2009-09-04 | 2011-03-17 | Mitsubishi Materials Corp | White conductive powder |
| JP2016118739A (en) * | 2014-12-24 | 2016-06-30 | 株式会社リコー | Laminated inorganic mineral, toner, and image forming apparatus |
| WO2016103582A1 (en) * | 2014-12-24 | 2016-06-30 | Ricoh Company, Ltd. | Layered inorganic mineral, toner, and image forming apparatus |
| EP3237327A4 (en) * | 2014-12-24 | 2017-11-29 | Ricoh Company, Ltd. | Layered inorganic mineral, toner, and image forming apparatus |
| US10088766B2 (en) | 2014-12-24 | 2018-10-02 | Ricoh Company, Ltd. | Layered inorganic mineral, toner, and image forming apparatus |
| CN114736405A (en) * | 2022-03-28 | 2022-07-12 | 金发科技股份有限公司 | Polyphenyl ether conductive master batch, low CLTE nylon alloy and application thereof |
| CN114736405B (en) * | 2022-03-28 | 2024-05-14 | 金发科技股份有限公司 | Polyphenyl ether conductive master batch, low-CLTE nylon alloy and application thereof |
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