JP2008150258A - Precursor particle for tin dioxide, method for producing the same, and method for producing tin dioxide using the precursor particle - Google Patents

Precursor particle for tin dioxide, method for producing the same, and method for producing tin dioxide using the precursor particle Download PDF

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JP2008150258A
JP2008150258A JP2006341670A JP2006341670A JP2008150258A JP 2008150258 A JP2008150258 A JP 2008150258A JP 2006341670 A JP2006341670 A JP 2006341670A JP 2006341670 A JP2006341670 A JP 2006341670A JP 2008150258 A JP2008150258 A JP 2008150258A
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tin dioxide
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JP5058580B2 (en
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Norihiko Saneto
憲彦 實藤
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Ishihara Sangyo Kaisha Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide precursor particles for tin dioxide, which are suitable for obtaining tin dioxide not requiring pulverization after firing in a method for producing tin dioxide by firing a precursor for tin dioxide. <P>SOLUTION: The precursor particles for tin dioxide have a flaky shape, and contain 60-88 wt.% Sn and 1-15 wt.%, based on C, of an organic substance. In a method for producing the precursor particles for tin dioxide, a tin(II) salt is neutralized in an aqueous medium to obtain a hydrolysate, which is subjected to washing and solid-liquid separation, and at least one kind of organic substance selected from citric acid, lactic acid, and amino acids is added into the aqueous medium during neutralization and/or after neutralization. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、二酸化スズ前駆体粒子及びその製造方法並びにそれを用いてなる二酸化スズの製造方法に関する。   The present invention relates to a tin dioxide precursor particle, a method for producing the same, and a method for producing tin dioxide using the same.

二酸化スズは、優れた耐熱性、耐酸化性、耐還元性、耐食性、電気化学特性などを有し、従来から顔料、ガスセンサー、陶磁器、触媒等の多方面の分野において使用されている。これらの機能やその性能は、例えばガスセンサー特性に見られるように、母体の組成や一次粒子径、二次粒子径といった構造に敏感に依存することが知られている。これらの用途に用いられる酸化スズ粉末は、通常、金属スズを強熱酸化させる方法、水溶性スズ化合物を酸性あるいは塩基性溶液で処理して加水分解によって得られるスズ酸を熱分解する方法、有機金属塩を直接加熱処理する方法、または、スズアルコキシドの加水分解で得られる前駆体を加熱分解する方法等により生産されている（非特許文献１及び２）。   Tin dioxide has excellent heat resistance, oxidation resistance, reduction resistance, corrosion resistance, electrochemical characteristics, and the like, and has been conventionally used in various fields such as pigments, gas sensors, ceramics, and catalysts. It is known that these functions and their performance depend sensitively on structures such as the matrix composition, primary particle diameter, and secondary particle diameter, as seen in the gas sensor characteristics, for example. The tin oxide powder used in these applications is usually a method in which metallic tin is ignited by ignition, a method in which a water-soluble tin compound is treated with an acidic or basic solution, and stannic acid obtained by hydrolysis is thermally decomposed, organic It is produced by a method of directly heat-treating a metal salt or a method of thermally decomposing a precursor obtained by hydrolysis of tin alkoxide (Non-patent Documents 1 and 2).

ファインセラミックス辞典編集委員会編「ファインセラミックス事典、第１版、技報堂出版株式会社、１９８７年４月発行、ｐ２６４Edited by the Fine Ceramics Dictionary Editorial Committee, “Fine Ceramics Encyclopedia, 1st edition, published by Gihodo Publishing Co., Ltd., April 1987, p264 田部浩三、清山哲郎、苗木和雄著、「金属酸化物と複合酸化物」、第６版、講談社、１９９１年８月発行、ｐ１２６Kozo Tabe, Tetsuro Kiyoyama, Kazuo Naegi, “Metal oxide and composite oxide”, 6th edition, Kodansha, August 1991, p126

二酸化スズを合成する処方において、加水分解によって得られるスズ酸を強熱して二酸化スズを得る場合、通常の一価のスズを含有する沈殿物を強熱すると、途中、一酸化スズの生成が見られ、一酸化スズの形状が維持された二酸化スズが得られる。この材料は一酸化スズの異方形状（薄片状粒子が凝集して粒子を形成しているような形態）を維持した形態をとり、新たに粉砕等の方法が必要になる。   When tin dioxide is obtained by igniting stannic acid obtained by hydrolysis in a formulation for synthesizing tin dioxide, if a precipitate containing normal monovalent tin is ignited, formation of tin monoxide is observed during the process. And tin dioxide in which the shape of tin monoxide is maintained is obtained. This material takes a form in which the anisotropic shape of tin monoxide (a form in which flaky particles are aggregated to form particles) is maintained, and a new method such as pulverization is required.

本発明者らは鋭意研究を重ねた結果、特定の製造方法により得られる二酸化スズ前駆体は、このものを焼成して二酸化スズとしても粉砕の必要のない粒子が直ちに得られることを見出し、本発明を完成させた。   As a result of intensive research, the present inventors have found that a tin dioxide precursor obtained by a specific production method can be immediately calcined to obtain particles that do not need to be pulverized as tin dioxide. Completed the invention.

即ち、本発明は、薄片状の粒子形状を有し、Ｓｎを６０〜８８重量％、有機物をＣ基準で１〜１５重量％含有することを特徴とする二酸化スズ前駆体粒子である。また、本発明は前記二酸化スズ前駆体粒子を製造する方法であって、スズ（ＩＩ）塩を水系媒液中で中和し加水分解物を得、洗浄、固液分離する二酸化スズ前駆体粒子の製造方法において、中和時及び／又は中和後に水系媒液中にクエン酸、乳酸、アミノ酸から選ばれる少なくとも一種の有機物を添加することを特徴とする二酸化スズ前駆体粒子の製造方法である。さらに本発明は前記二酸化スズ前駆体粒子を焼成することからなる二酸化スズの製造方法である。また、本発明は上記二酸化スズ前駆体粒子を有機溶媒に分散してなる分散体である。   That is, the present invention is a tin dioxide precursor particle having a flake-like particle shape, containing 60 to 88% by weight of Sn and 1 to 15% by weight of an organic substance based on C. The present invention is also a method for producing the tin dioxide precursor particles, wherein the tin (II) salt is neutralized in an aqueous medium to obtain a hydrolyzate, which is washed and solid-liquid separated. In the production method of the present invention, at least one organic substance selected from citric acid, lactic acid, and amino acid is added to the aqueous medium during and / or after neutralization. . Furthermore, the present invention is a method for producing tin dioxide comprising firing the tin dioxide precursor particles. Moreover, this invention is a dispersion formed by dispersing the tin dioxide precursor particles in an organic solvent.

本発明の二酸化スズ前駆体粒子は有機物を適度に含んでいるため、このものを焼成して二酸化スズとする際に、有機物が分解し、二酸化スズとなった時点では前記前駆体の粒子形状をとどめることなく、しかも粉砕の必要のない粒子が得られるという効果を奏するものである   Since the tin dioxide precursor particles of the present invention contain moderately organic substances, when this is baked into tin dioxide, the organic substances decompose and become tin dioxide. There is an effect that particles that do not need to be crushed and that do not need to be crushed can be obtained.

本発明は二酸化スズ前駆体粒子であって、薄片状の粒子形状を有し、Ｓｎを６０〜８８重量％、有機物をＣ基準で１〜１５重量％含有することを特徴とする。なお、本発明において二酸化スズ前駆体とは、このものを焼成することで二酸化スズが生成するもののことをいい、一酸化スズと有機物との単なる混合物とは異なり、一酸化スズ骨格中に有機物が取り込まれた複雑な構造を有しているものである。本発明の二酸化スズ前駆体粒子の形状は薄片状であって、その平均粒子厚みが０．００１〜２μｍであることが好ましい。   This invention is tin dioxide precursor particle | grains, Comprising: It has the shape of a flaky particle | grain, It is characterized by containing 60 to 88 weight% of Sn, and 1 to 15 weight% of organic substances on the C basis. In the present invention, the tin dioxide precursor means that tin dioxide is produced by firing this, and unlike a simple mixture of tin monoxide and organic matter, the organic matter is present in the tin monoxide skeleton. It has a complicated structure taken in. The shape of the tin dioxide precursor particles of the present invention is flaky, and the average particle thickness is preferably 0.001 to 2 μm.

Ｓｎの含有量は、６０〜８８重量％、好ましくは６５〜７５重量％である。また、有機物の含有量はＣ基準で１〜１５重量％、好ましくは５〜１０重量％である。Ｓｎ、Ｃ以外の残部はＨ、Ｏが主な元素である。Ｓｎの含有量が上記範囲より多いと、それだけ有機物の含有量が少なくなり、二酸化スズ前駆体粒子を焼成して二酸化スズとする際に薄片状の前駆体粒子がその形状を保ったまま二酸化スズになりやすく、焼成後に粉砕する必要が生じやすくなる。また、Ｓｎの含有量が上記範囲より少ないと、生産性が低下することになる。   The content of Sn is 60 to 88% by weight, preferably 65 to 75% by weight. Moreover, content of organic substance is 1-15 weight% on the C basis, Preferably it is 5-10 weight%. The balance other than Sn and C is mainly composed of H and O. When the Sn content is larger than the above range, the organic content is decreased accordingly, and when the tin dioxide precursor particles are baked to form tin dioxide, the flaky precursor particles maintain their shape while maintaining the shape. And it becomes necessary to pulverize after firing. Further, when the Sn content is less than the above range, the productivity is lowered.

二酸化スズ前駆体粒子に含まれるＳｎは、その価数が２価のＳｎ（Ｓｎ２＋）が主であるが、一部４価のＳｎ（Ｓｎ４＋）を含んでいてもよい。また、導電性を付与する目的で、Ｓｎの一部をＳｂ、Ｐ、Ｎｂ、Ｗ等の元素で置換してもよい。Ｓｎの一部を上記元素で置換した二酸化スズ前駆体粒子は、このものを焼成すると、導電性を有する二酸化スズ粒子が得られる。また、本発明の二酸化スズ前駆体粒子はＳｎとしてＳｎ（Ｓｎ２＋）を主に含んでいるため還元能を有する。この還元能を活用できる分野として廃棄物処理分野が考えられる。有害金属イオンを含有する廃水にリン酸塩粉末及び酸化マグネシウム粉末を添加し、化学結合リン酸塩セラミックス（Ｃｈｅｍｉｃａｌｌｙ ｂｏｎｄｅｄ Ｐｈｏｓｐｈａｔｅ ｃｅｒａｍｉｃｓ）として有害金属を固定化する方法が知られている。例えば、廃水中のクロム酸イオン（Ｃｒ２Ｏ７ ２−）を固定化させる場合、廃水にリン酸塩粉末及び酸化マグネシウム粉末を添加する際に、還元剤として塩化スズ（ＩＩ）を一緒に添加しておくことで、廃水中のクロムイオンは還元されて安定性が高まり、化学結合リン酸塩セラミックス中に固定化され、環境中への溶出低減が可能である（例えば、ＵＳＰ６１３３４９８参照）。還元剤として塩化スズ（ＩＩ）を用いる場合はそれ自体に潮解性があることから、取り扱いが面倒である。一方本発明の二酸化スズ前駆体は取り扱いが容易であることから、前記塩化スズ（ＩＩ）に代えて用いることができる。 Sn contained in the tin dioxide precursor particles is mainly divalent Sn (Sn 2+ ), but may partially contain tetravalent Sn (Sn 4+ ). For the purpose of imparting conductivity, a part of Sn may be substituted with an element such as Sb, P, Nb, W or the like. When tin dioxide precursor particles in which a part of Sn is substituted with the above elements are fired, tin dioxide particles having conductivity are obtained. Moreover, since the tin dioxide precursor particles of the present invention mainly contain Sn (Sn2 +) as Sn, they have reducing ability. The field of waste treatment can be considered as a field where this reducing ability can be utilized. A method is known in which phosphate powder and magnesium oxide powder are added to wastewater containing harmful metal ions, and the harmful metal is immobilized as chemically bonded phosphate ceramics. For example, when chromate ions (Cr 2 O 7 2− ) in wastewater are immobilized, tin (II) chloride is added together as a reducing agent when adding phosphate powder and magnesium oxide powder to wastewater. As a result, the chromium ions in the wastewater are reduced to increase the stability, and are immobilized in the chemically bonded phosphate ceramics, so that elution into the environment can be reduced (see, for example, USP 6133498). When tin (II) chloride is used as the reducing agent, it is deliquescent in itself, which is troublesome to handle. On the other hand, since the tin dioxide precursor of the present invention is easy to handle, it can be used in place of the tin (II) chloride.

次の本発明は、上記二酸化スズ前駆体粒子の製造方法であって、スズ（ＩＩ）塩を水系媒液中で中和し加水分解物を得、洗浄、固液分離する二酸化スズ前駆体粒子の製造方法において、中和時及び／又は中和後に水系媒液中にクエン酸、乳酸、アミノ酸から選ばれる少なくとも一種の有機物を添加することを特徴とする。   The following present invention is a method for producing the above tin dioxide precursor particles, wherein a tin (II) salt is neutralized in an aqueous medium to obtain a hydrolyzate, which is washed and solid-liquid separated. In the production method, at least one organic substance selected from citric acid, lactic acid and amino acid is added to the aqueous medium during and / or after neutralization.

スズ（ＩＩ）塩としては、塩化スズ（ＩＩ）、硫酸スズ（ＩＩ）、硝酸スズ（ＩＩ）等の水溶性のものであれば用いることができるが、塩化スズ（ＩＩ）が好ましい。このものを水系媒液に溶解した水溶液を中和し、加水分解物を水系媒液中に析出させる。中和には、水酸化ナトリウム水溶液、水酸化リチウム水溶液等の中和剤（アルカリ）を用いることができるが、水酸化ナトリウム水溶液が好ましい。スズ（ＩＩ）塩水溶液の濃度は、１０〜５０ｗｔ％が好ましく、より好ましくは１５〜３５ｗｔ％である。また、中和時の温度は２５〜１００℃の範囲が好ましく、より好ましくは７０〜９５℃である。さらに、中和剤の添加量は、水溶液中のＳｎ２＋を全量中和するに必要な量の１〜５倍が好ましく、より好ましくは２〜４倍の量である。 As the tin (II) salt, any water-soluble one such as tin (II) chloride, tin (II) sulfate, tin (II) nitrate can be used, but tin (II) chloride is preferred. An aqueous solution obtained by dissolving this in an aqueous medium is neutralized to precipitate a hydrolyzate in the aqueous medium. For neutralization, a neutralizing agent (alkali) such as an aqueous sodium hydroxide solution or an aqueous lithium hydroxide solution can be used, but an aqueous sodium hydroxide solution is preferred. The concentration of the tin (II) salt aqueous solution is preferably 10 to 50 wt%, more preferably 15 to 35 wt%. Moreover, the temperature at the time of neutralization has the preferable range of 25-100 degreeC, More preferably, it is 70-95 degreeC. Furthermore, the addition amount of the neutralizing agent is preferably 1 to 5 times, more preferably 2 to 4 times the amount necessary to neutralize the total amount of Sn 2+ in the aqueous solution.

本発明においては、上記の中和時及び／又は中和後にクエン酸、乳酸、アミノ酸から選ばれる少なくとも一種の有機物を添加することを特徴とする。なお、アミノ酸としてはグルタミン酸、アスパラギン酸、リジン、アルギニン、グリシン等を例示することができる。上記有機物を添加することで、加水分解物との間で反応が進み、本発明の二酸化スズ前駆体粒子が生成する。用いる有機物としてはクエン酸が好ましい。前記有機物の添加量は有機物に含まれるＣとスズ（ＩＩ）塩に含まれるＳｎの重量比（Ｃ／Ｓｎ）で表わして、０．００５〜０．４の範囲が好ましく、より好ましくは０．０１〜０．２５である。また、スズ（ＩＩ）塩の一部をＳｂ、Ｐ、Ｎｂ、Ｗ等の元素の水溶性塩で置換することにより、Ｓｎの一部を上記元素で置換した二酸化スズ前駆体粒子が得られる。   In the present invention, at least one organic substance selected from citric acid, lactic acid, and amino acid is added during and / or after the neutralization. Examples of amino acids include glutamic acid, aspartic acid, lysine, arginine, glycine and the like. By adding the organic substance, the reaction proceeds with the hydrolyzate, and the tin dioxide precursor particles of the present invention are generated. As the organic substance to be used, citric acid is preferable. The amount of the organic substance added is expressed by the weight ratio (C / Sn) of C contained in the organic substance and Sn contained in the tin (II) salt, and is preferably in the range of 0.005 to 0.4, more preferably 0.8. 01 to 0.25. Further, by replacing a part of the tin (II) salt with a water-soluble salt of an element such as Sb, P, Nb, or W, tin dioxide precursor particles in which a part of Sn is replaced with the above element can be obtained.

次いで、水溶液中に存在する不要な電解質を除去するため、洗浄する。洗浄に際しては生成した前駆体粒子を凝集させるためにｐＨ調整剤を添加する。用いるｐＨ調整剤としては、塩酸、硫酸等の無機酸が挙げられる。また、ｐＨ調整剤として前記の有機物を用いることもできる。洗浄後、固液分離して、本発明の二酸化スズ前駆体粒子を得る。   Next, washing is performed to remove unnecessary electrolyte present in the aqueous solution. In washing, a pH adjuster is added to agglomerate the produced precursor particles. Examples of the pH adjuster to be used include inorganic acids such as hydrochloric acid and sulfuric acid. Moreover, the said organic substance can also be used as a pH adjuster. After washing, solid-liquid separation is performed to obtain the tin dioxide precursor particles of the present invention.

次の本発明は二酸化スズ粒子の製造方法であって、前記二酸化スズ前駆体粒子を焼成することからなる。   The following present invention is a method for producing tin dioxide particles, comprising firing the tin dioxide precursor particles.

焼成の温度は、二酸化スズ前駆体粒子に含まれる有機物が分解する温度より高い温度であればよく、５００℃〜１１００℃の範囲の温度が好ましい。より好ましくは６００〜９００℃の範囲である。焼成温度が前記範囲より高いと、生成する二酸化スズ粒子間の焼結が進むため好ましくない。また、焼成の雰囲気は特に制限がないが、空気（大気）雰囲気が好ましい。   The temperature of baking should just be a temperature higher than the temperature which the organic substance contained in a tin dioxide precursor particle decomposes | disassembles, and the temperature of the range of 500 to 1100 degreeC is preferable. More preferably, it is the range of 600-900 degreeC. When the firing temperature is higher than the above range, sintering between the generated tin dioxide particles proceeds, which is not preferable. The firing atmosphere is not particularly limited, but an air (air) atmosphere is preferable.

さらに本発明は、前記二酸化スズ前駆体粒子を有機溶媒に分散させてなる分散体である。本発明の分散体は、例えば、前記の二酸化スズ前駆体粒子の製造方法において、水溶液中に存在する不要な電解質を除去するため、洗浄した後、濾過して得られる湿ケーキを有機溶媒に分散させることで得ることができる。用いる有機溶媒としては、ジメチルホルムアミド（ＤＭＦ）、ケトンが挙げられる。なお、ケトンとしてはアセトン、２−ブタノン、メチルエチルケトン等を例示することができる。得られる分散体の濃度は０．１〜１０ｇ／リットルである。   Furthermore, the present invention is a dispersion obtained by dispersing the tin dioxide precursor particles in an organic solvent. The dispersion of the present invention is, for example, dispersed in an organic solvent by washing and then filtering the wet cake in order to remove unnecessary electrolytes present in the aqueous solution in the method for producing tin dioxide precursor particles. Can be obtained. Examples of the organic solvent to be used include dimethylformamide (DMF) and ketone. Examples of ketones include acetone, 2-butanone, methyl ethyl ketone, and the like. The concentration of the resulting dispersion is 0.1-10 g / liter.

本発明の分散体は、長期保存安定性に優れており、この分散体を基材にコートし、焼成することで、二酸化スズ膜を得ることができる。   The dispersion of the present invention is excellent in long-term storage stability, and a tin dioxide film can be obtained by coating the dispersion on a base material and baking it.

以下、本発明を実施例により説明するが、本発明はそれら実施例に限定されるものではない。   EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

実施例１
ＳｎＣｌ２・２Ｈ２Ｏ試薬８．６３ｇを３５％塩酸水溶液１５．６ｇ中に溶解した。この溶解液の中に純水を１４．８ｇ添加して濃度調整を行った。９０℃の純水０．５リットル中に上記の塩酸水溶液と５規定の水酸化ナトリウム水溶液をｐＨ５になるように３０分かけて同時添加を行った。添加後、１０分間熟成し、その後、５０％クエン酸水溶液４．６９ｇを添加して、ｐＨ３．０とした。その後５分間攪拌放置して洗浄を開始した。濾液比抵抗値が１０万Ωｃｍとなった時点で洗浄を中止し、そのケーキを１０５℃で一晩放置して、乾燥した。乾燥物をメノウ乳鉢で手粉砕を行い、本発明の二酸化スズ前駆体粉末（試料Ａ）を得た。 Example 1
8.63 g of SnCl 2 .2H 2 O reagent was dissolved in 15.6 g of 35% aqueous hydrochloric acid. The concentration was adjusted by adding 14.8 g of pure water to the solution. The above hydrochloric acid aqueous solution and 5 N aqueous sodium hydroxide solution were simultaneously added to 0.5 liter of pure water at 90 ° C. over 30 minutes so that the pH was 5. After the addition, the mixture was aged for 10 minutes, and then 4.69 g of 50% aqueous citric acid solution was added to adjust the pH to 3.0. Thereafter, the mixture was left stirring for 5 minutes to start washing. When the filtrate specific resistance value reached 100,000 Ωcm, washing was stopped, and the cake was left at 105 ° C. overnight and dried. The dried product was manually pulverized in an agate mortar to obtain a tin dioxide precursor powder (sample A) of the present invention.

実施例２
実施例１で得られた試料Ａを、大気中７００℃の温度で３０分間焼成して、本発明の二酸化スズ粉末（試料Ｂ）を得た。 Example 2
Sample A obtained in Example 1 was baked for 30 minutes at a temperature of 700 ° C. in the atmosphere to obtain a tin dioxide powder (Sample B) of the present invention.

実施例３
実施例１において洗浄後のケーキの一部を採取して固形分濃度を測定したところ固形分濃度は３５重量％であった。このケーキサンプル０．１１５ｇを試薬瓶の中に入れ、更にＤＭＦを４０．０ｇ加えた。試薬瓶を超音波洗浄機の中にいれ、６０分間の超音波照射を行い、本発明の分散体を得た。得られた分散体を１週間放置したが、沈降が見られず、分散したままであった。 Example 3
In Example 1, a portion of the cake after washing was sampled and the solid content concentration was measured. The solid content concentration was 35% by weight. 0.115 g of this cake sample was put in a reagent bottle, and 40.0 g of DMF was further added. The reagent bottle was placed in an ultrasonic cleaner and subjected to ultrasonic irradiation for 60 minutes to obtain a dispersion of the present invention. The obtained dispersion was allowed to stand for 1 week, but no settling was observed, and it remained dispersed.

実施例４
実施例３においてＤＭＦに代えてアセトン４０．０ｇを用いたほかは、実施例３と同様にして本発明の分散体を得た。得られた分散体を２日間放置したが、沈降が見られず、分散したままであった。 Example 4
A dispersion of the present invention was obtained in the same manner as in Example 3, except that 40.0 g of acetone was used instead of DMF in Example 3. The obtained dispersion was allowed to stand for 2 days, but no sedimentation was observed and it remained dispersed.

比較例１
実施例１において、５０％クエン酸水溶液の代わりに３規定の塩酸水溶液を用いてｐＨを３．０とした以外は実施例１と同様にして比較試料の二酸化スズ前駆体粉末（試料Ｃ）を得た。 Comparative Example 1
In Example 1, a tin dioxide precursor powder (sample C) as a comparative sample was prepared in the same manner as in Example 1 except that 3N hydrochloric acid aqueous solution was used instead of 50% citric acid aqueous solution and the pH was adjusted to 3.0. Obtained.

比較例２
比較例１で得られた試料Ｃを、大気中７００℃の温度で３０分間焼成して、比較試料の二酸化スズ粉末（試料Ｄ）を得た。 Comparative Example 2
Sample C obtained in Comparative Example 1 was baked for 30 minutes at a temperature of 700 ° C. in the atmosphere to obtain a tin dioxide powder (Sample D) as a comparative sample.

実施例１及び比較例１で得られた二酸化スズ前駆体粉末（試料Ａ及びＣ）の粉末Ｘ線回折分析を実施し、Ｘ線回折プロファイルを図１及び図２に示した。図１より、本発明の二酸化スズ前駆体粉末には、一酸化スズに特有の回折ピークは見られず、薄片状粒子形状に由来する低角側（面間隔で表現して０．７〜１．０ｎｍ）に鋭いピークを有していることがわかった。一方、比較試料の前駆体粉末（試料Ｃ）は、従来から知られている面間隔の狭い一酸化スズに特有のピークを有していることがわかった。   Powder X-ray diffraction analysis of the tin dioxide precursor powders (samples A and C) obtained in Example 1 and Comparative Example 1 was performed, and the X-ray diffraction profiles are shown in FIGS. From FIG. 1, the tin dioxide precursor powder of the present invention does not have a diffraction peak peculiar to tin monoxide, and is a low angle side derived from a flaky particle shape (expressed as a surface interval of 0.7 to 1). (0.0 nm) was found to have a sharp peak. On the other hand, it was found that the precursor powder (sample C) of the comparative sample had a peak specific to conventionally known tin monoxide having a narrow face spacing.

次に、実施例１及び比較例１で得られた二酸化スズ前駆体粉末（試料Ａ及びＣ）の走査型電子顕微鏡写真を図３及び図４にそれぞれ示した。試料Ａ、Ｃ共に、平均粒子厚みは０．１μｍの薄片状粒子であることがわかった。   Next, scanning electron micrographs of the tin dioxide precursor powders (samples A and C) obtained in Example 1 and Comparative Example 1 are shown in FIGS. 3 and 4, respectively. Both samples A and C were found to be flaky particles having an average particle thickness of 0.1 μm.

また、実施例１で得られた二酸化スズ前駆体粉末（試料Ａ）のＳｎ及びＣの含有量を測定したところ、Ｓｎを７２．９重量％、Ｃを５．４重量％それぞれ含有していた。   Moreover, when the content of Sn and C of the tin dioxide precursor powder (sample A) obtained in Example 1 was measured, it contained 72.9% by weight of Sn and 5.4% by weight of C, respectively. .

さらに、実施例２及び比較例２で得られた二酸化スズ粉末の走査型電子顕微鏡写真を図５及び図６にそれぞれ示した。図５より、本発明の二酸化スズ粉末は、焼成時に前駆体粉末の薄片状形状が消失し、粉砕の必要のない粒状の二酸化スズが得られたことがわかった。一方、比較試料の二酸化スズ粉末（試料Ｄ）は、薄片形状を焼成後も維持しており、しかも粒子間の凝集が強く、粉砕する必要があることがわかった。また、得られた二酸化スズ粉末（試料Ｂ及びＤ）の粉末Ｘ線回折分析を実施したところ、何れの試料も、二酸化スズに特有のＸ線回折プロファイルを有していた。   Further, scanning electron micrographs of the tin dioxide powder obtained in Example 2 and Comparative Example 2 are shown in FIGS. 5 and 6, respectively. From FIG. 5, it was found that the tin dioxide powder of the present invention lost the flaky shape of the precursor powder during firing, and obtained granular tin dioxide that did not require pulverization. On the other hand, it was found that the tin dioxide powder (sample D) as a comparative sample maintained the flake shape even after firing, and also had strong aggregation between particles and needed to be pulverized. Moreover, when the powder X-ray-diffraction analysis of the obtained tin dioxide powder (samples B and D) was implemented, all the samples had the X-ray-diffraction profile peculiar to tin dioxide.

本発明の二酸化スズ前駆体粉末は、焼成により粉砕の必要のない二酸化スズが得られるため、顔料、ガスセンサー、陶磁器、触媒等の二酸化スズが用いられている従来からの多方面の分野において有用なものである。   The tin dioxide precursor powder of the present invention is useful in various fields in which tin dioxide such as pigments, gas sensors, ceramics, and catalysts is used because tin dioxide that does not need to be pulverized can be obtained by firing. It is a thing.

試料ＡのＸ線回折プロファイルを示す図である。3 is a diagram showing an X-ray diffraction profile of sample A. FIG. 試料ＣのＸ線回折プロファイルを示す図である。3 is a diagram showing an X-ray diffraction profile of Sample C. FIG. 試料Ａの粒子形状を示す走査型電子顕微鏡写真である。2 is a scanning electron micrograph showing the particle shape of sample A. FIG. 試料Ｃの粒子形状を示す走査型電子顕微鏡写真である。3 is a scanning electron micrograph showing the particle shape of Sample C. FIG. 試料Ｂの粒子形状を示す走査型電子顕微鏡写真である。3 is a scanning electron micrograph showing the particle shape of Sample B. FIG. 試料Ｄの粒子形状を示す走査型電子顕微鏡写真である。3 is a scanning electron micrograph showing the particle shape of sample D. FIG.

Claims (8)

薄片状の粒子形状を有し、Ｓｎを６０〜８８重量％、有機物をＣ基準で１〜１５重量％含有することを特徴とする二酸化スズ前駆体粒子。 A tin dioxide precursor particle having a flaky particle shape, containing 60 to 88% by weight of Sn and 1 to 15% by weight of an organic substance on a C basis. 平均粒子厚みが０．００1〜２μｍであることを特徴とする請求項１記載の二酸化スズ前駆体粒子。 The tin dioxide precursor particles according to claim 1, wherein the average particle thickness is 0.001 to 2 μm. スズ（ＩＩ）塩を水系媒液中で中和し加水分解物を得、洗浄、固液分離する二酸化スズ前駆体粒子の製造方法において、中和時及び／又は中和後に水系媒液中にクエン酸、乳酸、アミノ酸から選ばれる少なくとも一種の有機物を添加することを特徴とする二酸化スズ前駆体粒子の製造方法。 In the method for producing tin dioxide precursor particles by neutralizing tin (II) salt in an aqueous medium to obtain a hydrolyzate, washing and solid-liquid separation, in the aqueous medium during and / or after neutralization A method for producing tin dioxide precursor particles, comprising adding at least one organic substance selected from citric acid, lactic acid, and amino acids. 有機物がクエン酸であることを特徴とする請求項４記載の二酸化スズ前駆体粒子の製造方法。 The method for producing tin dioxide precursor particles according to claim 4, wherein the organic substance is citric acid. 請求項１に記載の二酸化スズ前駆体粒子を焼成することからなる二酸化スズ粒子の製造方法。 A method for producing tin dioxide particles, comprising firing the tin dioxide precursor particles according to claim 1. 焼成の温度が５００〜１１００℃の範囲であることを特徴とする請求項５に記載の二酸化スズ粒子の製造方法。 The method for producing tin dioxide particles according to claim 5, wherein the firing temperature is in the range of 500 to 1100 ° C. 請求項１に記載の二酸化スズ前駆体粒子を有機溶媒に分散してなる分散体。 A dispersion formed by dispersing the tin dioxide precursor particles according to claim 1 in an organic solvent. 有機溶媒がジメチルホルムアミド（ＤＭＦ）及び／又はケトンであることを特徴とする請求項７に記載の分散体。 The dispersion according to claim 7, wherein the organic solvent is dimethylformamide (DMF) and / or a ketone.
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