JPS59182229A - Production of tin oxide fine powder - Google Patents

Abstract

PURPOSE:To obtain the titled fine powder useful as a catalyst, gas sensor, electrically conductive powder, etc., by adding a tin chloride solution to a strongly alkaline solution at or above a specific temperature to obtain an acidic solution finally, and calcining the resultant product. CONSTITUTION:A solution of the chloride (e.g. a solution obtained by dissolving SnCl4 in water, aqueous solution of hydrochloric acid, etc.) is added to an alkaline aqueous solution having a pH of >=10 (e.g. aqueous solution of NaOH, Na2CO3, etc.) while keeping the temperature at >=65 deg.C, and the mixture is made finally to <=5pH. Precipitation of Sn(OH)4 takes place vigorously at <=10pH, and the dispersibility of the precipitate is improved by keeping the pH at <=5. Fine SnO2 powder can be prepared by calcining the obtained Sn(OH)4 powder at 350-700 deg.C.

Description

【発明の詳細な説明】 本発明は酸化スズ微粉末の製法に関する。[Detailed description of the invention] The present invention relates to a method for producing fine tin oxide powder.

酸化スズ粉末は触媒、ガスセンサー、導電性粉体として
用いられている。触媒としては、オレフィンのアリル型
酸化用触媒、たとえばプロはンから７クロレイン、ｎ−
ブテンからブタジェン、イソペンテンからイソプレン合
成の触媒として用いられている。Tin oxide powder is used as a catalyst, gas sensor, and conductive powder. Catalysts include catalysts for allylic oxidation of olefins, such as propane to 7chlorein, n-
It is used as a catalyst for the synthesis of butadiene from butene and isoprene from isopentene.

ガスセンサーとしては、可燃性ガス、たとえば都市ガス
、プロパンガス、水素ガス等を吸着した時、電気抵抗が
変化することが利用されている。Gas sensors utilize the fact that electrical resistance changes when a flammable gas such as city gas, propane gas, hydrogen gas, etc. is adsorbed.

導電性粉体としては、　ｓｂをドープした５ｎ０２が低
抵抗となることが知られているが、Ｓｂの毒性の問題が
あＩＳｂを含まないものが望まれている。この場合抵抗
は高くなるが、帯電防止としては使用でき１色も白色に
近いものとなるので１紙、樹脂。As a conductive powder, it is known that sb-doped 5n02 has a low resistance, but due to the toxicity of Sb, a powder that does not contain ISb is desired. In this case, the resistance will be high, but it can be used as an antistatic agent and the color will be close to white, so one paper and one resin.

繊維の帯電防止として使用出来る。また可視光の波長（
０，４〜０．８μｍ）以下の粒子にすることによシ透明
性が出てくるため、塗料中に混入し、帯電防止塗料とす
ることもできる。この塗料を塗布した塗膜は透明帯電防
止フィルムになるばかシでなく、帯電圧を制御するだめ
の感光様用塗膜ともなる。いずれの場合も、粉末が微細
であることが望ましい。すなわち、触媒、ならびにセン
サーにおいても粉末の表面を利用することから、微細な
種活性が高く、また、粉末が微細になる程透明性も向上
する。更に粉末の分散性も高いことが望まれている。It can be used to prevent static electricity on textiles. Also, the wavelength of visible light (
Since particles with a particle size of 0.4 to 0.8 μm or less provide transparency, they can be mixed into paints to form antistatic paints. A coating film coated with this paint not only becomes a transparent antistatic film, but also a photosensitive coating film for controlling charging voltage. In either case, it is desirable that the powder be fine. That is, since the surface of the powder is used in catalysts and sensors, the activity of fine seeds is high, and the finer the powder, the better the transparency. Furthermore, it is desired that the powder has high dispersibility.

酸化スズ粉末の製造法としては以下の方法が知られてい
る。The following methods are known as methods for producing tin oxide powder.

（１）金籾スズを空気中で高温加熱酸化する。(1) Oxidize gold rice tin by heating at high temperature in air.

（２）スズを濃硝酸で処理して得た白色沈澱を高温で焼
成する。(2) The white precipitate obtained by treating tin with concentrated nitric acid is calcined at a high temperature.

（３）４価のスズ塩の水溶液をアルカリで中和して白色
沈澱を得、これを高温で焼成する。(3) An aqueous solution of a tetravalent tin salt is neutralized with an alkali to obtain a white precipitate, which is then calcined at a high temperature.

（１）、、（２）の方法ではせいぜい比表面積が１０ｍ
／ｒ以下の粉末しか得られず、（３）の方法でも焼成時
に焼結が起シ易く、比表面積としては５０ｉ／Ｐまで可
能であるが９分散性が悪く透明性を出す目的には望まし
くない。In methods (1) and (2), the specific surface area is at most 10 m
Even with method (3), sintering is likely to occur during firing, and the specific surface area can be up to 50i/P, but 9 has poor dispersibility and is not desirable for the purpose of transparency. do not have.

本発明者等は（３）の方法を特定の条件で実施するとき
極めて微細な酸化スズ粉末が得られることを見出した。The present inventors have discovered that extremely fine tin oxide powder can be obtained when method (3) is carried out under specific conditions.

本発明方法では、６５℃以上に保ったアルカリ水浴液中
に、塩化スズ（１ｖ）水溶液を加え、最終的にｐＨを５
以下にする。アルカリ水中に塩化スズを加えていった場
合、初期の声は当然１４に近く。In the method of the present invention, a tin chloride (1v) aqueous solution is added to an alkaline water bath kept at 65°C or higher, and the pH is finally adjusted to 5.
Do the following. If tin chloride is added to alkaline water, the initial voice will naturally be close to 14.

−１が１０になるまで塩化スズ水溶液を加えてぃっても
沈澱が析出しない。声が１０以下で急激に沈澱が析出す
る。すなわち虜が１０以上で溶解していた塩化スズがｐ
ｌ（が下がることにょ夛、−気に水酸化スズとして析出
し、微細な生成物となる。さらに塩化スズを加えて最終
的に−を５以下に保つことによシ分散性が高まることが
わかった。すな・わち、その後の粉末の焼成処理におい
て、焼結することか少なくなり、粉末の粒子を細かいま
ま保っておくことができる。この範囲外で反応を終了さ
せると焼成時に粉末が焼結しゃすくなる。以上のことに
よジ、粉禾の粒子は５０ｍ“７２以上の微細なものでし
かも分散性の良いものが得られることを見い出した。こ
れに対し、塩化スズ水溶液をアルカリで中和していく方
法であると、アルカリを添加した時点から沈澱が生成し
始め２反応が進むにしたがい粒子が成長を起し、微細な
粉末が得られない。Even if an aqueous tin chloride solution is added until -1 becomes 10, no precipitate is formed. When the voice is below 10, a precipitate is rapidly deposited. In other words, the tin chloride that was dissolved when the concentration was 10 or more was
As l() decreases, it precipitates as tin hydroxide and becomes a fine product.Furthermore, by adding tin chloride and finally keeping - below 5, the dispersibility can be increased. Understood.In other words, in the subsequent firing process of the powder, there will be less sintering and the powder particles can be kept fine.If the reaction is terminated outside this range, the powder will not be sintered during the firing process. As a result of the above, it was found that fine particles of 50 m"72 or more and with good dispersibility could be obtained.On the other hand, when a tin chloride aqueous solution was used, If the method involves neutralizing with an alkali, a precipitate will begin to form from the time the alkali is added, and as the two reactions proceed, particles will grow, making it impossible to obtain a fine powder.

アルカリ水酊液としては、水酸化ナトリウム。Sodium hydroxide is used as an alkaline liquid.

アンモニア、水酸化カリウム、炭酸ナトリウムを　　　
　□水に溶解した溶液を使用できる。塩化スズ溶液は４
価の塩化スズを水に溶かしたもの、または塩酸水溶液に
浴かしたもの、またはアルコールに溶かした溶液を用い
ることができる。ammonia, potassium hydroxide, sodium carbonate
□A solution dissolved in water can be used. Tin chloride solution is 4
A solution prepared by dissolving tin chloride in water, bathing it in an aqueous solution of hydrochloric acid, or dissolving it in alcohol can be used.

アルカリ水浴液中に注入する塩化スズ両液はその一度に
特に限定はないが、好ましい濃度１．０〜６０チである
。注入速度にも特に限定はない。沈澱析出温度は約６５
℃が臨界値であることが分かった。これより低いと焼成
時に粒子が焼結を起しやすい。生成した沈澱を洗浄後乾
燥を行ないさらにｌ！Ａ成をすることにより、二酸化ス
ズ粉末とす・ることかできるが、焼成温度が３５０℃以
下でＨ結晶の発達が悪く非晶質であ、９，７００℃以上
にすると焼結が起る。このため焼成温度を６５０℃〜７
００℃としたが、粉末の抵抗と粒度との関連上。There are no particular limitations on the tin chloride solution injected into the alkaline water bath at one time, but the preferred concentration is 1.0-60%. There is also no particular limitation on the injection rate. The precipitation temperature is approximately 65
It was found that ℃ is the critical value. If it is lower than this, particles tend to sinter during firing. The generated precipitate is washed and dried, and then the precipitate is washed and dried. By performing A formation, it can be made into tin dioxide powder, but if the firing temperature is below 350°C, the H crystals will not develop well and it will be amorphous, and if the temperature is above 9,700°C, sintering will occur. . For this reason, the firing temperature should be set at 650℃~7.
The temperature was set at 00°C due to the relationship between powder resistance and particle size.

望ましくは４００℃〜６００℃である。粉末の微細性１
分散性の目安としては、比表面積または粉末をｐｔｌ＝
１０の水浴液中で分散後、０．３μｍ以下の粒子が何％
あるかで示した。The temperature is preferably 400°C to 600°C. Fineness of powder 1
As a guideline for dispersibility, the specific surface area or powder is expressed as ptl=
After dispersing in the water bath solution of 10, what percentage of particles are 0.3 μm or less?
It was shown that there is.

実施例１ 水１０１に水酸化ナトリウム３６５ｔを加え７０℃に加
熱した。これに、塩化第二スズの６０チ水溶液５００ｔ
に塩酸と水の１＝１の混合溶液を６１０ｄ加えたものを
定量ポンプで滴下させ反応を行ない最終β量を２とした
。出来た沈澱を捕集し水で洗浄後乾燥し、５００℃で焼
成した。得られた粉末をアトマイザ−で粉砕後柴田化学
器機工業＠）の８Ａ−１０００型表面積計で比表面積を
測定したところ７５．９　ｖｒｌ／　ｔであった。また
この粉末５ｆに水酸化ナトリウムの７２／を溶液４〇−
加え−＝１０とし、直径１０順のアルミナボール５０箇
を入れた１００ｄのボールミルで分散処理した後、遠心
沈降法で０．６μｍ以上の粒子を沈澱分離し０．６μｍ
以下の粒子量を測定した。その結果０．３μｍ以下の粒
子の割合は６１．５％であった。粉末を１−ｏ　ｏ　ｋ
ｇ／ｃＩＩｉ加圧して比抵抗を測定した結果５ｘｉｏ’
Ω・ａであった。Example 1 365 t of sodium hydroxide was added to 10 liters of water and heated to 70°C. To this, 500 tons of a 60-t aqueous solution of stannic chloride
610 d of a 1=1 mixed solution of hydrochloric acid and water was added to the solution, which was added dropwise using a metering pump to carry out the reaction, and the final amount of β was set at 2. The resulting precipitate was collected, washed with water, dried, and calcined at 500°C. After the obtained powder was pulverized with an atomizer, the specific surface area was measured using an 8A-1000 surface area meter manufactured by Shibata Kagaku Kiki Kogyo @) and found to be 75.9 vrl/t. Also, add 72% of sodium hydroxide to 5f of this powder in a solution of 40%.
Add - = 10, and after dispersion treatment in a 100 d ball mill containing 50 alumina balls with diameters in order of 10, particles of 0.6 μm or more were precipitated and separated using a centrifugal sedimentation method.
The following particle amounts were measured. As a result, the proportion of particles of 0.3 μm or less was 61.5%. 1-o ok powder
The result of measuring the specific resistance by pressurizing g/cIIi is 5xio'
It was Ω・a.

比較例１ 水１０ｔに水酸化ナトリウム３３５ｆを加え８０℃に加
熱した。これに塩化第二スズの６０％水浴液５００ｔに
塩酸と水の１；１の混合溶液を６００ｄ加えたものを前
記水酸化ナトリウム液に加えて反応を行ない、最終−を
６とした。沈澱を捕集し洗浄後乾燥し、５００℃で焼成
し、実施例１と同様の測定をした。その結果比表面積は
４４　ｍ”　／　ＳＦであシ０．６μ以下の粒子の含有
率は６ｏチであった。Comparative Example 1 335 f of sodium hydroxide was added to 10 t of water and heated to 80°C. To this, 600 d of a 1:1 mixed solution of hydrochloric acid and water was added to 500 t of a 60% water bath solution of stannic chloride, and the mixture was added to the sodium hydroxide solution to carry out a reaction, and the final value was 6. The precipitate was collected, washed, dried, and calcined at 500°C, and the same measurements as in Example 1 were carried out. As a result, the specific surface area was 44 m''/SF, and the content of particles of 0.6 μm or less was 6°.

実施例２ 実施例１で反応によって得られた沈澱乾燥物を３５０℃
で焼成した。焼成粉末の比表面積１ｄ７８１１１　／　
ｔ　、　０．３μｍ以下は６２チ、比抵抗は１０”Ω・
鑞以上であった。Example 2 The dried precipitate obtained by the reaction in Example 1 was heated at 350°C.
It was fired in Specific surface area of fired powder 1d78111 /
t, 0.3μm or less is 62cm, specific resistance is 10''Ω・
It was better than a charm.

実施例６ 実施例１で反応によって得られた沈澱乾燥物を７００℃
で焼成した。比表面積は５２　ｙｙｉ”　／　ｔ　、０
．３μｍ以下の粒子の含有率は４１チ、比抵抗は６Ｘ１
０’Ω・αであった。Example 6 The dried precipitate obtained by the reaction in Example 1 was heated to 700°C.
It was fired in The specific surface area is 52 yyi”/t, 0
．． The content of particles of 3μm or less is 41cm, and the specific resistance is 6X1.
It was 0'Ω・α.

実施例４ 実施例１で得た焼成粉末１７りを、トルエン：メチルエ
テルケトンの４：１混合物７５１にポリエステル樹脂８
ｔを溶解したフェノに加え、直径１０ｍのアルミナボー
ル１２５箇を入れた２５０ｄのボールミルで１７時間分
散させ帯電防止塗料を製造した。これをポリエステルフ
ィルム上に１μｍの厚さ、にワイヤーパーで塗布した。Example 4 17% of the calcined powder obtained in Example 1 was added to 751% of a 4:1 mixture of toluene: methyl ether ketone and 8% of the polyester resin.
In addition to the dissolved phenol, the mixture was dispersed for 17 hours in a 250D ball mill containing 125 alumina balls with a diameter of 10m to produce an antistatic paint. This was applied onto a polyester film to a thickness of 1 μm using a wire spar.

この塗膜のヘーズ値（曇価）は１７％で表面抵抗はｉ、
５ＸｉＯ’Ωであった。The haze value of this coating film is 17%, and the surface resistance is i.
5XiO'Ω.

実施例５ 実施例４と同様の手法で実施例６で製造した粉末を塗料
化した。これをポリエステルフィルムにワイヤーバーで
塗布した。厚みは１．１μｍあった。Example 5 The powder produced in Example 6 was made into a paint using the same method as in Example 4. This was applied to a polyester film using a wire bar. The thickness was 1.1 μm.

ヘーズ値は６５％で表面抵抗は７．２Ｘ１０’Ωであっ
た。The haze value was 65% and the surface resistance was 7.2×10'Ω.

比較例２ アルカリ水溶液の加熱温度を６０℃にする他は。Comparative example 2 Except that the heating temperature of the alkaline aqueous solution was 60°C.

実施例１と同じ条件で粉末を製造した。得られた粉末の
比表面積は７７ｙｌ／ｆであったが、０．３μ以下の粒
子の含有量は４０チであった。A powder was produced under the same conditions as in Example 1. The specific surface area of the obtained powder was 77yl/f, and the content of particles of 0.3μ or less was 40yl/f.

比較例６ 実施例１と同じ条件で、塩化スズ溶液中にアルカリ水溶
液を加え、以下同様に操作して酸化スズ粉末を得た。得
られた粉末の比表面積は４　Ｇｒｒｊ／ｌであ、９，０
．３μ以下の粒子の含有率は６０チであった。Comparative Example 6 Under the same conditions as in Example 1, an alkaline aqueous solution was added to the tin chloride solution, and the same procedure was repeated to obtain tin oxide powder. The specific surface area of the obtained powder was 4 Grrj/l and 9.0
．． The content of particles of 3 μm or less was 60 μm.

特許出願人　三菱金属株式会社 代理人弁理士　松　井　政　広 手続補正書 昭和５８年８月２３日 特許庁長官　若杉和夫　殿 １、事件の表示 昭和５８年　特　許　願第０５２４３９号２、発明の名
称　酸化スズ微粉末の製法３、　補正をする者 事件との関係　特許出願人 住　所東京都千代田区大手町−丁目５番２号氏　名（名
称）（６２６）三菱金属株式会社４、代理人 ５、　補正命令の日付　自発 ６、　補正により増加する発明の数なし補正の内容 （１）特；／１：請求の範囲の記載を次のように訂正す
る。Patent Applicant: Mitsubishi Metals Co., Ltd. Representative Patent Attorney Masa Matsui Broad Procedural Amendment August 23, 1980 Commissioner of the Patent Office Kazuo Wakasugi 1. Indication of Case 1981 Patent Application No. 052439 2. Name of the Invention Manufacturing method for tin oxide fine powder 3, Relationship with the case of the person making the amendment Patent applicant address: 5-2 Otemachi-chome, Chiyoda-ku, Tokyo Name (626) Mitsubishi Metals Co., Ltd. 4, Agent 5 , Date of amendment order Voluntary 6, No number of inventions increased by amendment Contents of amendment (1) Particulars; /1: The statement of the scope of claims is corrected as follows.

１　ｔ　　ｐｕ　ｌｏ以上のアルカリ水溶液を６５℃以
上に保ちながら、この中に塩化スズ溶液を加え、最終的
にｐＨを５〜１にすることにより生成物を得。A tin chloride solution is added to an alkaline aqueous solution of 1 t pu lo or higher while maintaining the temperature at 65° C. or higher, and the pH is finally adjusted to 5 to 1 to obtain a product.

これを３５０℃〜７００℃で焼成することによる酸化ス
ズ微粉末の製法。A method for producing fine tin oxide powder by firing this at 350°C to 700°C.

２、特許ＲＩｓ求の範囲第１項に記載の酸化スズ微粉末
の製法でりって、塩化スズ溶液の敵度が１０〜６０チで
ある方法。」 、−プ剤を含まないものは」と訂正する。2. Scope of Patent RIs A method for producing fine tin oxide powder according to item 1, in which the degree of adhesion of a tin chloride solution is 10 to 60. ``For those that do not contain a detergent.''

２．４ペ一ジ５行目に１−５以下」とあるを観″５〜１
」と訂正する。2. Look at the 5th line of page 4 that says ``1-5 or less''.
” he corrected.

以上 ＝１６０＝that's all =160=

Claims (1)

【特許請求の範囲】 １、ｐＨ１０以上のアルカリ水溶液を６５℃以上に保ち
ながら、との中に塩化スズ溶液を加え、最終的に田を５
以下にすることによシ生成物を得、これを′５５０℃〜
７００℃で焼成することによる酸化スズ微粉末の製法。 ２、特許請求の範囲第１項に記載の酸化スズ微粉末の製
法であって、塩化スズ溶液の濃度が１０〜６０％である
方法。[Claims] 1. While keeping an alkaline aqueous solution with a pH of 10 or higher at 65°C or higher, a tin chloride solution is added to the solution, and finally the rice is
A product was obtained by doing the following, and it was heated from 550°C to
A method for producing fine tin oxide powder by firing at 700°C. 2. A method for producing fine tin oxide powder according to claim 1, wherein the concentration of the tin chloride solution is 10 to 60%.