JP2994020B2 - Method for producing conductive titanium dioxide powder - Google Patents
Method for producing conductive titanium dioxide powderInfo
- Publication number
- JP2994020B2 JP2994020B2 JP2278059A JP27805990A JP2994020B2 JP 2994020 B2 JP2994020 B2 JP 2994020B2 JP 2278059 A JP2278059 A JP 2278059A JP 27805990 A JP27805990 A JP 27805990A JP 2994020 B2 JP2994020 B2 JP 2994020B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium dioxide
- dioxide powder
- titanium
- conductive
- heat treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、導電性二酸化チタン粉末の製造方法に関す
る。Description: TECHNICAL FIELD The present invention relates to a method for producing conductive titanium dioxide powder.
科学技術の発達とニーズの多様化にともない、高性
能、多機能素材の開発が活発におこなわれつつあり、そ
の一つとして高隠蔽力の白色顔料としてよく知られてい
る二酸化チタンに、導電性を付与して種々の用途への適
用をはかり得る高付加価値化が注目され、とりわけ二酸
化チタン粒子表面に酸化スズと酸化アンチモンとからな
る被覆層を形成し、これを加熱処理して４価のスズの格
子に５価のアンチモンをドープしてキャリアー濃度を増
大せしめた導電性被膜を有する二酸化チタン粉末がよく
知られている。しかして、該導電性二酸化チタン粉末
は、アンチモン成分を必須とするものであるが、このも
のによる毒性上の問題やアンチモンドープにより白色度
の低下がさけられなかったりする。このため前記問題点
の解決が強く希求されている。With the development of science and technology and diversification of needs, the development of high-performance, multifunctional materials is being actively conducted.One of them is titanium dioxide, which is well known as a white pigment with high hiding power, Of high value-added which can be applied to various uses by imparting a coating layer is particularly noticed. In particular, a coating layer composed of tin oxide and antimony oxide is formed on the surface of titanium dioxide particles, and this is heat-treated to obtain a tetravalent tetravalent oxide. Titanium dioxide powder having a conductive coating in which a tin lattice is doped with pentavalent antimony to increase the carrier concentration is well known. The conductive titanium dioxide powder contains an antimony component as an essential component. However, there is a problem in toxicity due to the antimony component and a decrease in whiteness due to antimony doping. Therefore, there is a strong demand for a solution to the above problems.
本発明は、アンチモン成分を使用することなく、優れ
た導電性を有する高白色度の導電性二酸化チタン粉末の
製造方法を提供することを目的とするものである。An object of the present invention is to provide a method for producing a highly white conductive titanium dioxide powder having excellent conductivity without using an antimony component.
本発明者等は、かねてより前記の問題点を解決すべ
く、アンチモン成分を使用しないで優れた導電性能と白
色度とを有する導電性二酸化チタン粉末を製造する方法
について種々検討を進めてきた結果、粒子表面上に酸化
スズの水和物を被覆処理した二酸化チタン粒子粉末を、
特定条件下で加熱処理することにより、二酸化チタンの
優れた白色度を損なうことなく、粒子表面上に酸化スズ
からなる緻密な導電性被膜を形成して優れた導電性を有
する二酸化チタン粉末を製造し得ることの知見を得、本
発明を完成したものである。すなわち、本発明は、 １）．二酸化チタンまたは含水二酸化チタンの粒子表面
に、酸化スズの水和物からなる被覆層を形成させ、しか
る後得られた被覆処理物を非酸化性雰囲気中で250〜600
℃で加熱処理することを特徴とする導電性二酸化チタン
粉末の製造方法および、 ２）．非酸化性雰囲気が、不活性雰囲気であることを特
徴とする請求項１項記載の製造方法である。The present inventors have been conducting various studies on a method for producing a conductive titanium dioxide powder having excellent conductive performance and whiteness without using an antimony component in order to solve the above-described problems. , A titanium dioxide particle powder coated with tin oxide hydrate on the particle surface,
Producing titanium oxide powder with excellent conductivity by forming a dense conductive coating made of tin oxide on the particle surface without impairing the excellent whiteness of titanium dioxide by heat treatment under specific conditions The present invention has been completed, and the present invention has been completed. That is, the present invention provides: 1). A coating layer composed of a hydrate of tin oxide is formed on the surface of titanium dioxide or hydrated titanium dioxide particles, and then the obtained coating is 250-600 in a non-oxidizing atmosphere.
A method for producing a conductive titanium dioxide powder, which is subjected to a heat treatment at 2 ° C., and 2). 2. The method according to claim 1, wherein the non-oxidizing atmosphere is an inert atmosphere.
本発明において、酸化スズ被覆層を形成する基体粒子
の二酸化チタンまたは含水二酸化チタンとしては、平均
粒子が通常0.1〜0.5μｍの顔料級二酸化チタン、平均粒
径が通常0.01〜0.1μｍの透明性二酸化チタン、平均長
軸径が0.1〜20μｍ、平均短軸径が0.02〜0.1μｍの針状
二酸化チタン、板状比（最長粒子径／最短粒子径）が３
以上、好ましくは10以上の板状二酸化チタンやこれらの
含水二酸化チタンを使用することができる。顔料級二酸
化チタンとしては、たとえば硫酸チタン溶液、四塩化チ
タン溶液あるいは有機チタン化合物溶液を、必要に応じ
核粒子の存在下に加水分解して含水二酸化チタンの沈澱
を生成させ、このものを焼成したり、あるいは四塩化チ
タンやアンモニウムチタニウムサルフェートを熱酸素分
解したりして得られる。なおこのようにして得られる基
体粒子の結晶が生成または成長する過程において、種々
の金属成分の調節剤を添加することができる。また必要
に応じ葡萄房またはそれらを不規則にいくつかに分割し
たような形状を有する吸油量が比較的大きいものを使用
する場合は、好ましい結果をもたらす場合がある。透明
性二酸化チタンまたは含水二酸化チタンとしては、たと
えばオキシ硫酸チタンなどのチタン硫酸塩類の酸性溶液
または四塩化チタンなどのチタン塩化物の酸性溶液を中
和して析出させたコロイド状チタン化合物を適当に熟成
し、そのままあるいは低温、たとえば400〜650℃で焼成
して得られる。針状二酸化チタンとしては、たとえば特
公昭47−44974号に記載されているように、ルチルTiO2
と塩化ナトリウムのようなアルカリ金属塩およびオキシ
リン化合物とを混合し、次に725〜1000℃で焼成して得
られたり、また特公昭45−18370号に記載されているよ
うにTiO2源、亜鉛化合物、アルカリ金属化合物およびリ
ン酸化合物を混合して焼成して得られたり、さらには繊
維状のチタン酸アルカリを水または酸で処理し、アルカ
リを除去して得られる。なお、前記特公昭45−18370号
で得られる針状二酸化チタンは普通、焼成後、水で侵出
することによってアルカリ金属、リン化合物などの不純
物を除去するが、酸、アルカリなどで抽出、除去して使
用することもできる。板状二酸化チタンとしては、たと
えば特公昭45−6424号に記載されているように、四塩化
チタンなどのチタン化合物を有機溶媒に溶解した後、高
温の加熱基板に塗布して得られる。また、酸化スズの水
和物の被覆層を形成させる前に予め分級処理を施し、所
望の長さの針状あるいは板状二酸化チタンを選別して用
いることもできる。In the present invention, as the titanium dioxide or hydrous titanium dioxide of the base particles forming the tin oxide coating layer, pigment-grade titanium dioxide having an average particle size of usually 0.1 to 0.5 μm, and transparent dioxide having an average particle size of usually 0.01 to 0.1 μm. Titanium, needle-like titanium dioxide having an average major axis diameter of 0.1 to 20 μm and an average minor axis diameter of 0.02 to 0.1 μm, and a plate ratio (longest particle diameter / shortest particle diameter) of 3
As described above, preferably, ten or more plate-like titanium dioxides or hydrated titanium dioxides thereof can be used. As the pigment-grade titanium dioxide, for example, a titanium sulfate solution, a titanium tetrachloride solution, or an organic titanium compound solution is hydrolyzed in the presence of core particles, if necessary, to form a precipitate of hydrous titanium dioxide, which is then calcined. Or by thermal oxygen decomposition of titanium tetrachloride or ammonium titanium sulfate. In the process of forming or growing the crystals of the base particles thus obtained, various metal component modifiers can be added. Use of grapes or a relatively large amount of oil having a shape such that they are divided into several portions as necessary may provide favorable results. As the transparent titanium dioxide or the hydrated titanium dioxide, for example, a colloidal titanium compound precipitated by neutralizing an acidic solution of a titanium sulfate such as titanium oxysulfate or an acidic solution of a titanium chloride such as titanium tetrachloride is appropriately used. It is obtained by aging and calcining as it is or at a low temperature, for example, at 400 to 650 ° C. As the acicular titanium dioxide, for example, as described in JP-B-47-44974, rutile TiO 2
And an alkali metal salt such as sodium chloride and an oxyphosphorus compound, and then calcined at 725 to 1000 ° C., or as described in JP-B-45-18370, a TiO 2 source, zinc, It can be obtained by mixing and firing a compound, an alkali metal compound and a phosphoric acid compound, or by treating a fibrous alkali titanate with water or an acid to remove the alkali. The acicular titanium dioxide obtained in JP-B No. 45-18370 usually removes impurities such as alkali metals and phosphorus compounds by leaching with water after baking, but extracting and removing with acids, alkalis, and the like. It can also be used. As described in JP-B-45-6424, for example, plate-like titanium dioxide is obtained by dissolving a titanium compound such as titanium tetrachloride in an organic solvent, and then coating it on a high-temperature heated substrate. In addition, before forming a coating layer of a hydrate of tin oxide, a classification treatment is performed in advance, and needle-like or plate-like titanium dioxide having a desired length can be selected and used.
本発明において、基体粒子に酸化スズの導電性被覆層
を形成させるには、種々の方法によっておこなうことが
できる。まず、基体粒子上に酸化スズの水和物の被覆層
を形成させるには、たとえば基体粒子の水性懸濁液を調
製し、前記水性懸濁液にスズの金属塩溶液と、アルカリ
または酸とを添加し基体粒子上に酸化スズの水和物の沈
澱を析出せしめて被覆層を形成させる。前記の被覆処理
は、スズの金属塩溶液と、アルカリまたは酸とを別個に
添加して処理し、沈澱を析出させても、あるいは並行的
に添加処理して沈澱を析出させてもよい。また前記懸濁
液をたとえば40〜90℃の加温下でおこなったり、さらに
は前記添加処理速度を制御しながら沈澱を徐々に析出さ
せる場合には、緻密な被覆層が形成され易く、一層好ま
しい結果をもたらし得る。前記のスズの金属塩溶液とし
ては、たとえば通常スズの塩化物、硫酸塩、硝酸塩など
またスズ酸ナトリウムやスズ酸カリウム等のスズ酸塩な
どの水溶液を挙げることができ、またアルカリ成分とし
ては、たとえば通常水酸化ナトリウム、水酸化カリウ
ム、炭酸ナトリウム、炭酸カリウム、アンモニアなどの
水溶液、アンモニアガスなど、また酸として塩酸、硫
酸、硝酸などを使用することができる。In the present invention, various methods can be used to form the conductive coating layer of tin oxide on the base particles. First, in order to form a coating layer of hydrated tin oxide on the base particles, for example, an aqueous suspension of the base particles is prepared, and a tin metal salt solution, an alkali or an acid are added to the aqueous suspension. To precipitate a hydrate of tin oxide on the base particles to form a coating layer. The coating treatment may be performed by separately adding a metal salt solution of tin and an alkali or an acid to precipitate the precipitate, or may be added in parallel to precipitate the precipitate. Further, when the suspension is heated at a temperature of, for example, 40 to 90 ° C., or when the precipitate is gradually deposited while controlling the addition rate, a dense coating layer is easily formed, which is more preferable. Can have consequences. Examples of the tin metal salt solution include, for example, aqueous solutions of tin chlorides, sulfates, nitrates, and the like, and stannates such as sodium stannate and potassium stannate. For example, aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and the like, ammonia gas and the like, and acids such as hydrochloric acid, sulfuric acid and nitric acid can be used.
前記被覆量は、基体粒子の重量基準に対してSnO2とし
て１〜30％、望ましくは５〜20％である。被覆量が前記
範囲より少なきに過ぎると所望の導電性能が得られず、
また多きに過ぎると白色度の低下をきたすなど好ましく
ない。The coating amount is 1% to 30% as SnO 2 with respect to weight of substrate particles, preferably 5 to 20%. If the coating amount is less than the above range, the desired conductive performance is not obtained,
On the other hand, if the amount is too large, the whiteness is undesirably reduced.
本発明において、前記の基体粒子表面に酸化スズの水
和物を被覆処理して得られた懸濁液は、濾過、さらには
洗浄をおこなったりして処理ケーキを分別回収し、必要
に応じ乾燥し、粉砕した後、非酸化性雰囲気中で加熱処
理して所望の導電性を有する二酸化チタン粉末とする。
前記非酸化性雰囲気を維持する上で、使用するガスとし
ては、不活性ガス、還元性ガスなどがあるが、不活性ガ
スとしては、たとえば窒素、アルゴンなどを、また還元
性ガスとしては、たとえば水素、アンモニアガス、一酸
化炭素などを使用することができるが、不活性ガス雰囲
気中で加熱処理をおこなう場合は、処理操作上や経済性
面で一層望ましい。前記の加熱処理は、250〜600℃、望
ましくは300〜450℃でおこなう。加熱処理温度が前記範
囲より低きに過ぎると所望の導電性能が得られず、また
高きに過ぎると粒子成長や焼結が起こり易く、隠蔽力や
白色度が損なわれたりする。なお加熱処理時間は、被覆
層の厚さや、加熱処理装置の形式などにより異なり一概
にいえないが、通常30分〜５時間、望ましくは１〜２時
間程度である。In the present invention, the suspension obtained by coating the surface of the base particles with tin oxide hydrate is subjected to filtration and further washing to separate and collect the treated cake, followed by drying if necessary. Then, after pulverization, heat treatment is performed in a non-oxidizing atmosphere to obtain titanium dioxide powder having desired conductivity.
In maintaining the non-oxidizing atmosphere, examples of a gas used include an inert gas and a reducing gas. Examples of the inert gas include nitrogen and argon. Although hydrogen, ammonia gas, carbon monoxide and the like can be used, when heat treatment is performed in an inert gas atmosphere, it is more desirable in terms of treatment operation and economical efficiency. The heat treatment is performed at 250 to 600 ° C, preferably 300 to 450 ° C. If the heat treatment temperature is lower than the above range, desired conductive properties cannot be obtained. If the heat treatment temperature is too high, particle growth and sintering are likely to occur, and the hiding power and whiteness are impaired. The heat treatment time varies depending on the thickness of the coating layer, the type of the heat treatment device, and the like, and cannot be determined unconditionally.
本発明の方法によって得られる導電性二酸化チタン粉
末は、種々の分野の導電性付与材としてきわめて有用な
ものであり、たとえば電子写真感光材料、静電記録材料
などの記録材料の支持体の表面または中間層などの導電
性付与材、高分子フィルムやプラスチックス成形物の帯
電防止剤、電子機器等の種々の導電性塗料など種々の分
野で適用し得る。The conductive titanium dioxide powder obtained by the method of the present invention is extremely useful as a conductivity imparting material in various fields, for example, an electrophotographic photosensitive material, a surface of a support of a recording material such as an electrostatic recording material or the like. It can be applied in various fields such as a conductivity-imparting material such as an intermediate layer, an antistatic agent for polymer films and plastics molded articles, and various conductive paints such as electronic devices.
以下実施例を挙げて本発明をさらに説明する。 Hereinafter, the present invention will be further described with reference to examples.
実施例１ 平均粒径0.25μｍのルチル型二酸化チタン粉末30g
を、水300mlに分散させて懸濁液とした。前記懸濁液を
撹拌しながら75℃に加熱した。このものに四塩化スズ水
和物（SnCl4を75重量％含有）100gを3N塩酸1200mlに溶
かした溶液（以下Ａ液という）の83mlと、2.5Nの水酸化
ナトリウム水溶液とをpH2〜３に保ちながら約30分間か
けて同時滴下した。さらに20分間撹拌して二酸化チタン
粒子上に水和酸化スズを被覆処理した。次いで処理懸濁
液を濾過、洗浄し、得られた濾別ケーキを110℃で乾燥
した。しかる後、得られた前記乾燥状粉末を電気炉にて
窒素ガス気流中（２／分）350℃で２時間加熱処理し
て、目的とする導電性二酸化チタン粉末を得た（試料
Ａ）。Example 1 30 g of rutile-type titanium dioxide powder having an average particle size of 0.25 μm
Was dispersed in 300 ml of water to form a suspension. The suspension was heated to 75 ° C. with stirring. 83 ml of a solution of 100 g of tin tetrachloride hydrate (containing 75% by weight of SnCl 4 ) in 1200 ml of 3N hydrochloric acid (hereinafter referred to as solution A) and a 2.5N aqueous sodium hydroxide solution were adjusted to pH 2-3. The solution was dropped simultaneously over about 30 minutes while maintaining. The mixture was further stirred for 20 minutes to coat the hydrated tin oxide on the titanium dioxide particles. Next, the treated suspension was filtered and washed, and the obtained filtered cake was dried at 110 ° C. Thereafter, the obtained dried powder was heat-treated in an electric furnace at 350 ° C. for 2 hours in a stream of nitrogen gas (2 / min) to obtain a desired conductive titanium dioxide powder (sample A).
実施例２ 実施例１において、Ａ液83mlの代わりに166mlを用い
たことのほかは、同例の場合と同様に処理して、目的と
する導電性二酸化チタン粉末を得た（試料Ｂ）。Example 2 The same procedure as in Example 1 was repeated, except that 166 ml was used instead of 83 ml of solution A, to obtain a desired conductive titanium dioxide powder (sample B).
実施例３ 実施例２において、加熱処理を350℃で２時間に代え
て600℃で１時間にしたことのほかは、同例の場合と同
様に処理して、目的とする導電性二酸化チタン粉末を得
た（試料Ｃ）。Example 3 The same procedure as in Example 2 was repeated, except that the heat treatment was performed at 600 ° C. for 1 hour instead of 350 ° C. for 2 hours. Was obtained (Sample C).
比較例１ 実施例１において、窒素ガス雰囲気下の加熱処理に代
えて、空気中600℃で１時間加熱処理することのほか
は、同例の場合と同様に処理した（試料Ｄ）。Comparative Example 1 The procedure of Example 1 was repeated, except that the heat treatment was performed in air at 600 ° C. for 1 hour in place of the heat treatment in the nitrogen gas atmosphere (sample D).
比較例２ 実施例２において、窒素ガス雰囲気下の加熱処理に代
えて、空気中600℃で１時間加熱処理することのほか
は、同例の場合と同様に処理した（試料Ｅ）。Comparative Example 2 The procedure of Example 2 was repeated, except that the heat treatment was performed in air at 600 ° C. for 1 hour in place of the heat treatment in the nitrogen gas atmosphere (sample E).
粉体抵抗の測定 前記の実施例および比較例で得られた各試料を、200k
g/cm2の圧力にて成形して圧粉体（直径17mm、厚1.5mm）
とし、その直流抵抗を測定した。これらの結果を表１に
示す。Measurement of powder resistance Each sample obtained in the above Examples and Comparative Examples, 200k
Compacted with a pressure of g / cm 2 (diameter 17mm, thickness 1.5mm)
And its DC resistance was measured. Table 1 shows the results.
〔発明の効果〕 本発明は、毒性の危惧がなく、優れた導電性能と白色
度とを有する種々の適用分野で有用な導電性二酸化チタ
ン粉末を、比較的簡潔な手段で製造し得るものであっ
て、甚だ工業的に有利な方法である。 [Effects of the Invention] The present invention is capable of producing conductive titanium dioxide powder useful in various application fields having excellent conductivity and whiteness without fear of toxicity by relatively simple means. This is a very industrially advantageous method.
フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C01G 23/00 H01B 1/08 Continuation of front page (58) Field surveyed (Int.Cl. 6 , DB name) C01G 23/00 H01B 1/08
Claims (2)
子表面に、酸化スズの水和物からなる被覆層を形成さ
せ、しかる後得られた被覆処理物を非酸化性雰囲気中で
250〜600℃で加熱処理することを特徴とする導電性二酸
化チタン粉末の製造方法。1. A coating layer comprising a hydrate of tin oxide is formed on the surface of titanium dioxide or hydrated titanium dioxide particles, and the resulting coating is treated in a non-oxidizing atmosphere.
A method for producing a conductive titanium dioxide powder, comprising heat-treating at 250 to 600 ° C.
とを特徴とする請求項１項記載の製造方法。2. The method according to claim 1, wherein the non-oxidizing atmosphere is an inert atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2278059A JP2994020B2 (en) | 1990-10-17 | 1990-10-17 | Method for producing conductive titanium dioxide powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2278059A JP2994020B2 (en) | 1990-10-17 | 1990-10-17 | Method for producing conductive titanium dioxide powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04154621A JPH04154621A (en) | 1992-05-27 |
| JP2994020B2 true JP2994020B2 (en) | 1999-12-27 |
Family
ID=17592084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2278059A Expired - Fee Related JP2994020B2 (en) | 1990-10-17 | 1990-10-17 | Method for producing conductive titanium dioxide powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2994020B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3195072B2 (en) * | 1992-09-29 | 2001-08-06 | 三井金属鉱業株式会社 | Fibrous conductive filler and method for producing the same |
| JP2959928B2 (en) * | 1993-06-23 | 1999-10-06 | チタン工業株式会社 | White conductive resin composition |
| ATE402985T1 (en) * | 2003-07-23 | 2008-08-15 | Kansai Paint Co Ltd | ELECTRICALLY CONDUCTIVE WHITE PRIMER AND METHOD FOR PRODUCING MULTI-LAYER PAINT COATS |
| EP1647997B1 (en) | 2003-07-23 | 2012-04-11 | Ishihara Sangyo Kaisha, Ltd. | Electroconductive powder and method for production thereof |
| JP4702950B2 (en) | 2005-03-28 | 2011-06-15 | キヤノン株式会社 | Electrophotographic photosensitive member, process cartridge and electrophotographic apparatus, and method for manufacturing electrophotographic photosensitive member |
| US7534537B2 (en) | 2005-04-12 | 2009-05-19 | Canon Kabushiki Kaisha | Electrophotographic photosensitive member, process cartridge and electrophotographic apparatus |
| CN102020311B (en) * | 2010-12-03 | 2012-05-02 | 上海大学 | Method for preparing nanometer TiO2 with hierarchical structure |
| JP5755162B2 (en) * | 2011-03-03 | 2015-07-29 | キヤノン株式会社 | Method for producing electrophotographic photosensitive member |
-
1990
- 1990-10-17 JP JP2278059A patent/JP2994020B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04154621A (en) | 1992-05-27 |
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