JP4747286B2 - Fine tin oxide powder and its production method and use - Google Patents
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- 239000000843 powder Substances 0.000 title claims description 72
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims description 68
- 229910001887 tin oxide Inorganic materials 0.000 title claims description 68
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 239000002245 particle Substances 0.000 claims description 63
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 60
- 239000002244 precipitate Substances 0.000 claims description 45
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 claims description 28
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 27
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 24
- 235000006408 oxalic acid Nutrition 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 11
- 238000010304 firing Methods 0.000 claims description 11
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 9
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 9
- 230000001186 cumulative effect Effects 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000001119 stannous chloride Substances 0.000 claims description 9
- 235000011150 stannous chloride Nutrition 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 38
- AUYOHNUMSAGWQZ-UHFFFAOYSA-L dihydroxy(oxo)tin Chemical compound O[Sn](O)=O AUYOHNUMSAGWQZ-UHFFFAOYSA-L 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229910001432 tin ion Inorganic materials 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 235000017168 chlorine Nutrition 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005477 sputtering target Methods 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
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Description
本発明は、高密度なＩＴＯ焼結体の原料として好適な微細な酸化スズ粉末とその製造方法およびそのＩＴＯ焼結体に関する。 The present invention relates to a fine tin oxide powder suitable as a raw material for a high-density ITO sintered body, a method for producing the same, and the ITO sintered body.
スパッタリングによって良質なＩＴＯ膜を形成するために、スパッタリングターゲット用として高密度なＩＴＯ焼結体が要求されている。この高度ＩＴＯ焼結体の原料として、従来のものよりも微細でかつ均一な粒径の酸化スズ粉末が必要とされている。 In order to form a high-quality ITO film by sputtering, a high-density ITO sintered body is required for a sputtering target. As a raw material for this advanced ITO sintered body, a tin oxide powder having a finer and more uniform particle diameter than the conventional one is required.
高密度ＩＴＯターゲット用原料として用いられる微細な酸化スズ粉末の製造方法として、従来は次のような方法が知られている。
（イ）金属スズを硝酸に反応させて水酸化スズを沈澱させ、この沈澱を濾別回収して乾燥した後に焼成して酸化スズ粉末を得る方法。
（ロ）加熱した硝酸アンモニウム溶液に金属スズを加え、さらに硝酸を添加してメタスズを沈澱させ、これを濾別回収し焼成して酸化スズ粉末を得る方法（特許文献１：特開平１１−１３０４３２号）。
（ハ）塩酸と硝酸の混酸に金属スズを溶解して４価のスズイオンを主体とするスズ塩水溶液とし、これにアルカリ溶液を反応させてｐＨ５以上に中和してスズ化合物を沈殿させ、この沈澱を固液分離して乾操し、焼成して酸化スズ粉末を得る方法（特許文献２：特開２００２−２９７４４）。
Conventionally, the following method is known as a method for producing fine tin oxide powder used as a raw material for a high-density ITO target.
(A) A method in which tin metal is precipitated by reacting tin metal with nitric acid, and the precipitate is collected by filtration, dried and then fired to obtain tin oxide powder.
(B) A method in which tin metal is added to a heated ammonium nitrate solution and nitric acid is further added to precipitate metatin, which is collected by filtration and calcined to obtain a tin oxide powder (Patent Document 1: JP-A-11-130432). ).
(C) Metal tin is dissolved in a mixed acid of hydrochloric acid and nitric acid to form a tin salt aqueous solution mainly composed of tetravalent tin ions, and this is reacted with an alkaline solution to neutralize to pH 5 or more to precipitate a tin compound. A method in which a precipitate is solid-liquid separated, dried, and calcined to obtain a tin oxide powder (Patent Document 2: JP-A-2002-29744).
上記(イ)の方法は、金属スズを硝酸に反応させる際に反応速度を調整することができないので、生成した水酸化スズ沈澱を焼成して得た酸化スズ粉末は粒度が不揃いである。また、上記(ロ)の方法はこれを改善したものであり、硝酸アンモニウム溶液を用いてメタスズ酸を沈澱させ、これを焼成して比較的粒度の均一な酸化スズ粉末を得ている。しかし、この方法によって得られる酸化スズ粉末は主に二次粒子のピーク粒径が５〜８μｍ程度の粉末であり、１μｍ以下の微細な酸化スズ粉末の割合は少ないので高密度ＩＴＯターゲット用原料として適さない。上記(ハ)の方法ではメタスズ酸の沈澱を生成させる際に、粒子がコロイド状になるので沈澱の濾過性が非常に悪く、また残留塩素が多いと云う問題がある。 In the method (a), since the reaction rate cannot be adjusted when reacting metal tin with nitric acid, the tin oxide powder obtained by firing the produced tin hydroxide precipitate has irregular particle sizes. Further, the method (b) is an improvement of this method, in which metastannic acid is precipitated using an ammonium nitrate solution, and this is baked to obtain a tin oxide powder having a relatively uniform particle size. However, the tin oxide powder obtained by this method is mainly a powder having a secondary particle peak particle size of about 5 to 8 μm, and since the proportion of fine tin oxide powder of 1 μm or less is small, it is used as a raw material for high-density ITO targets. Not suitable. In the method (c), when the precipitation of metastannic acid is generated, the particles become colloidal, so that the filterability of the precipitate is very poor and there are many residual chlorines.
一方、金属スズを溶解した液のｐＨを調整して沈澱を生成させる従来の上記各方法に代えて、(ニ)金属スズを陽極とし、硝酸アンモニウム水溶液を電解液として、スズの電解を行なうことによってメタスズ酸を沈澱させ、これを回収し焼成して酸化スズ粉末を得る方法（特許文献３：特開平６−１９９５２３号〔特許第２８２９５５７号〕）が知られている。しかし、この方法によって得られる酸化スズ粉末も上記従来法と同様に粒径が不揃いであり、これを原料とした焼結体の密度を高めるのが難しい。
本発明は、従来の製造方法における上記問題を解決したものであり、従来のものよりも微細でかつ均一な粒径の酸化スズ粉末を提供するものであり、また、生成した沈澱の濾過性が良く、上記酸化スズ粉末を容易に製造することができる方法を提供する。 The present invention solves the above-mentioned problems in the conventional production method, provides a tin oxide powder having a finer and more uniform particle size than the conventional one, and the filterability of the generated precipitate is A method is provided that can easily produce the tin oxide powder.
本発明によれば、以下の構成からなる酸化スズ粉末の製造方法が提供される。
〔１〕塩化スズ溶液を酸化した後に、アルカリを加えてｐＨを１〜２に調整し、ｐＨ調整した塩化スズ溶液にシュウ酸を加えてシュウ酸スズを主体とする沈澱を生成させ、該沈澱を固液分離して回収し、乾燥した後に、２５０〜３５０℃で予備焼成した後に、５５０〜８５０℃で本焼成して酸化スズ粉末を製造することを特徴とする方法。
〔２〕塩化スズ溶液を銀−塩化銀電極基準で−２００〜＋２００mVに酸化した後に、アルカリを加えてｐＨ１〜２に調整する上記[１]に記載する酸化スズ粉末の製造方法。
〔３〕シュウ酸と共にシュウ酸アンモニウムを加えてシュウ酸スズを主体とする沈澱を生成させる上記[１]または上記[２]に記載する酸化スズ粉末の製造方法。
〔４〕金属スズを塩酸に溶解して塩化第一スズ溶液を調製する工程、この塩化第一スズ溶液を銀−塩化銀電極基準で−２００〜＋２００mVに酸化する工程、酸化した塩化第一スズ溶液にアンモニアを添加してｐＨを１〜２に調整する工程、ｐＨ調整した塩化第一スズ溶液にシュウ酸を加えてシュウ酸スズ沈澱を生成させる工程、この沈澱を固液分離して乾燥する工程、乾燥した沈澱を２５０〜３５０℃で予備焼成した後に５５０〜８５０℃で本焼成する工程を含む上記[１]〜上記[３]の何れかに記載する酸化スズ粉末の製造方法。
〔５〕平均粒径０.４μm〜２μm、ＢＥＴ比表面積５ｍ 2 /ｇ以上、粒径２μm以下の累積重量６０％以上、および粒径５μm以下の累積重量９０％以上であって、粒径０.２μm以下および粒径５μm以上の頻度が何れも５％以下の粒度分布を有する酸化スズ粉末を製造する上記[１]〜上記[４]の何れかに記載する酸化スズ粉末の製造方法。
According to this invention, the manufacturing method of the tin oxide powder which consists of the following structures is provided.
[1] After oxidizing the tin chloride solution, pH was adjusted to 1-2 by addition of alkali, to produce a precipitate mainly composed of tin oxalate by adding oxalic acid to the pH-adjusted tin chloride solution, the precipitate The solid oxide is recovered by solid-liquid separation, dried, pre-baked at 250 to 350 ° C., and then main-fired at 550 to 850 ° C. to produce tin oxide powder.
[2] The method for producing a tin oxide powder according to the above [1], wherein the tin chloride solution is oxidized to -200 to +200 mV based on a silver-silver chloride electrode, and then adjusted to pH 1-2 by adding an alkali.
[3] The method for producing a tin oxide powder according to the above [1] or [2], wherein ammonium oxalate is added together with oxalic acid to produce a precipitate mainly composed of tin oxalate.
[4] A step of preparing a stannous chloride solution by dissolving metal tin in hydrochloric acid, a step of oxidizing this stannous chloride solution to -200 to +200 mV on a silver-silver chloride electrode basis, oxidized stannous chloride A step of adding ammonia to the solution to adjust the pH to 1 to 2, a step of adding oxalic acid to the pH-adjusted stannous chloride solution to form a tin oxalate precipitate, and separating the precipitate into solid and liquid and drying The method for producing a tin oxide powder according to any one of the above [1] to [3], comprising a step of pre-calcining the dried precipitate at 250 to 350 ° C. followed by a main firing at 550 to 850 ° C.
[5] Average particle size of 0.4 μm to 2 μm , BET specific surface area of 5 m 2 / g or more, cumulative weight of particle size of 2 μm or less, 60% or more of cumulative weight, and cumulative weight of particle size of 5 μm or less of 90% or more. The method for producing a tin oxide powder according to any one of [1] to [4] above, wherein a tin oxide powder having a particle size distribution in which a frequency of 2 μm or less and a particle size of 5 μm or more is 5% or less is used.
〔具体的な説明〕
以下、本発明を具体的に説明する。
本発明の製造方法は、塩化スズ溶液を酸化した後に、アルカリを加えてｐＨを１〜２に調整し、ｐＨ調整した塩化スズ溶液にシュウ酸を加えてシュウ酸スズを主体とする沈澱を生成させ、該沈澱を固液分離して回収し、乾燥した後に、２５０〜３５０℃で予備焼成した後に、５５０〜８５０℃で本焼成して酸化スズ粉末を製造することを特徴とする方法である。本発明の製造方法の基本的な工程を図１および図２に示した。
[Specific description]
Hereinafter, the present invention will be specifically described.
In the production method of the present invention, after oxidizing a tin chloride solution, the pH is adjusted to 1 to 2 by adding an alkali, and oxalic acid is added to the pH-adjusted tin chloride solution to form a precipitate mainly composed of tin oxalate. The precipitate is recovered by solid-liquid separation, dried, pre-baked at 250 to 350 ° C., and then main-fired at 550 to 850 ° C. to produce tin oxide powder. . The basic steps of the production method of the present invention are shown in FIGS.
上記塩化スズ溶液は、金属スズを塩酸に溶解した液であり、塩化第一スズを主体とする溶液が好ましい。適量の沈澱を生成させるため、塩化スズの濃度は１００g/l〜５００g/lが適当である。金属スズを硝酸に溶解させるとメタスズ酸（水酸化スズ）がそのまま生成して沈澱するので、目的の粒径を有する酸化スズ粉末を得るのが難しい。一方、金属スズは硫酸には殆ど溶解しない。また、塩酸と硝酸の混酸も好ましくない。先に述べたように、金属スズを塩酸と硝酸の混酸に溶解させるとコロイド状のメタスズ酸の沈澱が生成し、濾過性が著しく低下する。 The tin chloride solution is a solution in which metallic tin is dissolved in hydrochloric acid, and a solution mainly composed of stannous chloride is preferable. In order to produce an appropriate amount of precipitate, the concentration of tin chloride is suitably 100 g / l to 500 g / l. When metallic tin is dissolved in nitric acid, metastannic acid (tin hydroxide) is generated and precipitated as it is, and it is difficult to obtain a tin oxide powder having a target particle size. On the other hand, metallic tin hardly dissolves in sulfuric acid. Also, a mixed acid of hydrochloric acid and nitric acid is not preferable. As described above, when metallic tin is dissolved in a mixed acid of hydrochloric acid and nitric acid, colloidal metastannic acid precipitates are formed, and the filterability is remarkably lowered.
好ましくは、調製した上記塩化スズ溶液を酸化した後にアルカリを添加してｐＨを調整する。塩化スズ溶液を酸化せずにシュウ酸スズ主体の沈澱を生成させると、所望の微細な酸化スズ粉末を得るのが難しい。酸化の程度は、銀−塩化銀電極基準で、−２００〜＋２００mVの範囲が好ましい。この酸化還元電位が−２００mVよりも低いとＢＥＴ比表面積が５ｍ2/ｇ以上の酸化スズ粉末を得るのが難しく、一方、＋２００mVより高いと４価のスズイオンが増すため、次工程でこの塩化スズ溶液にシュウ酸を添加しても、シュウ酸と反応しないスズが増加し、シュウ酸スズの回収率が低下する。 Preferably, the prepared tin chloride solution is oxidized and then alkali is added to adjust the pH. If a tin oxalate-based precipitate is formed without oxidizing the tin chloride solution, it is difficult to obtain a desired fine tin oxide powder. The degree of oxidation is preferably in the range of -200 to +200 mV based on the silver-silver chloride electrode. If this redox potential is lower than -200 mV, it is difficult to obtain a tin oxide powder having a BET specific surface area of 5 m 2 / g or more. On the other hand, if it is higher than +200 mV, tetravalent tin ions increase. Even if oxalic acid is added to the solution, tin that does not react with oxalic acid increases, and the recovery rate of tin oxalate decreases.
この塩化スズ溶液にアルカリを添加して溶液のｐＨを１〜２に調整する。アルカリとしては不純物金属が混入しないようにアンモニアが好ましい。ｐＨが１未満では残留している遊離の酸が多いため、次工程でシュウ酸を添加したときに、シュウ酸スズ沈澱が十分に生成しない。一方、ｐＨが２より高いと加水分解反応が起こり、濾過性が極めて悪いメタスズ酸の沈澱が生成するので好ましくない。本発明の製造方法は塩化スズ溶液のｐＨを１〜２に調整することによって、メタスズ酸の沈澱を生成させずに次工程でシュウ酸スズ沈澱を生成させる環境を整える。 An alkali is added to the tin chloride solution to adjust the pH of the solution to 1-2. As the alkali, ammonia is preferable so that an impurity metal is not mixed. When the pH is less than 1, a large amount of free acid remains. Therefore, when oxalic acid is added in the next step, the tin oxalate precipitate is not sufficiently formed. On the other hand, when the pH is higher than 2, hydrolysis reaction occurs, and precipitation of metastannic acid with extremely poor filterability is generated, which is not preferable. The production method of the present invention adjusts the pH of the tin chloride solution to 1 to 2 to prepare an environment for producing a tin oxalate precipitate in the next step without producing a metastannic acid precipitate.
ｐＨを１〜２に調整した塩化スズ溶液にシュウ酸を加えてシュウ酸スズを主体とする沈澱を生成させる。スズが液中に残留しないように、シュウ酸の添加量は塩化スズに対して反応等量より僅かに多い程度が好ましい。シュウ酸の量が多過ぎると未反応のシュウ酸が多くなるので好ましくない。 Oxalic acid is added to a tin chloride solution whose pH is adjusted to 1 to 2 to produce a precipitate mainly composed of tin oxalate. The amount of oxalic acid added is preferably slightly greater than the reaction equivalent with respect to tin chloride so that tin does not remain in the solution. An excessive amount of oxalic acid is not preferable because unreacted oxalic acid increases.
好ましくは、シュウ酸と共にシュウ酸アンモニウムを添加する。シュウ酸アンモニウムを併用することによって、調整したｐＨ範囲の変動を抑制することができる。シュウ酸アンモニウムを併用せずにシュウ酸を単独で用いると、調整したｐＨが低下してシュウ酸スズの回収率が低下し、また最終的に得られる酸化スズ粉末のＢＥＴ比表面積が小さく、従って所望の微細な粉末が少なくなる傾向がある。 Preferably, ammonium oxalate is added together with oxalic acid. By using ammonium oxalate in combination, fluctuations in the adjusted pH range can be suppressed. When oxalic acid is used alone without using ammonium oxalate alone, the adjusted pH is lowered and the recovery rate of tin oxalate is lowered, and the finally obtained tin oxide powder has a small BET specific surface area. There is a tendency to reduce the desired fine powder.
なお、シュウ酸アンモニウムの添加量が過剰で塩化スズ溶液のｐＨが２を超えると、先に述べたように加水分解によって濾過性が極めて悪いメタスズ酸の沈澱が生成し、また最終的に得られる酸化スズ粉末の平均粒径が大きくなるので好ましくない。塩化スズ溶液のｐＨを１〜２に維持してシュウ酸スズ主体の沈澱を生成させる。この沈澱は濾過性が良いので短時間で固液分離することができる。 When the amount of ammonium oxalate added is excessive and the pH of the tin chloride solution exceeds 2, precipitation of metastannic acid with extremely poor filterability is generated by hydrolysis as described above, and finally obtained. Since the average particle diameter of a tin oxide powder becomes large, it is not preferable. The pH of the tin chloride solution is maintained at 1-2 to produce a tin oxalate-based precipitate. Since this precipitate has good filterability, it can be solid-liquid separated in a short time.
生成したシュウ酸スズ主体の沈澱を固液分離して回収し、乾燥後、焼成して酸化スズ粉末にする。焼成は大気下、５５０℃〜１０００℃で行えばよく、焼成時間はシュウ酸スズの焼成量に応じて定めれば良い。 The produced tin oxalate-based precipitate is recovered by solid-liquid separation, dried and fired to obtain tin oxide powder. The firing may be performed at 550 ° C. to 1000 ° C. in the atmosphere, and the firing time may be determined according to the firing amount of tin oxalate.
この焼成工程は、乾燥した沈澱を２５０〜３５０℃で予備焼成した後に、５５０〜８５０℃で本焼成すると良い。高温での急激な焼成を行うと、シュウ酸スズが酸化スズに変化する際に、粉体集合体の内部と表面との間に生じる温度差のために焼成が不均一になり、粒径が不揃いになる傾向があるが、最初に予備焼成を行うことによってこのような傾向を防止し、均一な粒径の微細な酸化スズ粉末を得ることができる。 In this baking step, the dried precipitate is pre-baked at 250 to 350 ° C., and then main baking is performed at 550 to 850 ° C. When rapid firing is performed at a high temperature, when tin oxalate changes to tin oxide, the firing becomes uneven due to the temperature difference between the inside and the surface of the powder aggregate, and the particle size is reduced. Although it tends to be irregular, such a tendency can be prevented by performing preliminary firing first, and fine tin oxide powder having a uniform particle size can be obtained.
本発明の上記製造方法によれば、平均粒径０.４μm〜２μmであって、好ましくはＢＥＴ比表面積が５ｍ2/ｇ以上の微細な酸化スズ粉末を得ることができる。具体的には、例えば、粒径２μm以下の累積重量が６０％以上であって粒径５μm以下の累積重量が９０％以上であり、さらに粒径０.２μm以下および粒径５μm以上の頻度が何れも５％以下の粒度分布を有する酸化スズ粉末を得ることができる。 According to the production method of the present invention, fine tin oxide powder having an average particle diameter of 0.4 μm to 2 μm and preferably having a BET specific surface area of 5 m 2 / g or more can be obtained. Specifically, for example, the cumulative weight of the particle size of 2 μm or less is 60% or more, the cumulative weight of the particle size of 5 μm or less is 90% or more, and the frequency of the particle size of 0.2 μm or less and the particle size of 5 μm or more In any case, a tin oxide powder having a particle size distribution of 5% or less can be obtained.
本発明の製造方法によって得た酸化スズ粉末を図２〜図５に示す。図示するように、本発明の酸化スズ粉末は、何れも０.４μm〜２μmの間に単一の分布ピークが存在する粒度分布を有しており、図６〜図８に示す従来の酸化スズ粉末よりも微細であり、かつ均一な粒径を有している。 The tin oxide powder obtained by the production method of the present invention is shown in FIGS. As shown in the figure, each of the tin oxide powders of the present invention has a particle size distribution in which a single distribution peak exists between 0.4 μm and 2 μm, and the conventional tin oxide shown in FIGS. It is finer than powder and has a uniform particle size.
本発明の酸化スズ粉末は従来のものよりも微細で均一な粒径を有しており、不純物も少ないので、高密度ＩＴＯ焼結体の原料粉として最適である。酸化インジウム粉末と本発明の酸化スズ粉末とを目的の量比に混合し、焼成することによって、スパッタリングターゲット用として好適な高密度ＩＴＯ焼結体を得ることができる。 The tin oxide powder of the present invention has a finer and more uniform particle size than conventional ones and has few impurities, and is therefore optimal as a raw material powder for a high-density ITO sintered body. A high-density ITO sintered body suitable for a sputtering target can be obtained by mixing indium oxide powder and the tin oxide powder of the present invention in a target quantitative ratio and firing.
以下、本発明を実施例および比較例によって具体的に示す。また、各例の製造条件および結果を表１にまとめて示した。 Hereinafter, the present invention will be specifically described by Examples and Comparative Examples. The production conditions and results for each example are summarized in Table 1.
〔実施例１：参考例〕
３５％塩酸４８０mlに、金属スズショット（粒径２〜３mmφ）８０ｇを投入して６０℃で溶解し、スズ濃度１７０ｇ/lの塩化スズ溶液を得た。これに２８％濃度のアンモニア水１８０mlを添加してｐＨ１に調整した。このｐＨ調整後の塩化スズ溶液に１.５molシュウ酸溶液３００mlを添加してシュウ酸スズ沈澱を生成させた。これを濾過し、水濾過洗浄を３回（約８００mlづつ）行い、残渣（シュウ酸スズ沈澱）を回収した。これを１００℃で乾燥した後に軽く粉砕し、さらに、８５０℃で４時間焼成してＢＥＴ比表面積５.５ｍ2/ｇの酸化スズ粉末を得た。この酸化スズ粉末の粒度分布を図３に示した。
[Example 1: Reference Example ]
To 480 ml of 35% hydrochloric acid, 80 g of metal tin shot (particle diameter 2 to 3 mmφ) was added and dissolved at 60 ° C. to obtain a tin chloride solution having a tin concentration of 170 g / l. To this, 180 ml of 28% strength aqueous ammonia was added to adjust the pH to 1. To this tin chloride solution after pH adjustment, 300 ml of a 1.5 mol oxalic acid solution was added to form a tin oxalate precipitate. This was filtered, washed with water three times (about 800 ml each), and the residue (tin oxalate precipitate) was recovered. This was dried at 100 ° C. and then lightly pulverized, and further calcined at 850 ° C. for 4 hours to obtain a tin oxide powder having a BET specific surface area of 5.5 m 2 / g. The particle size distribution of this tin oxide powder is shown in FIG.
図３に示す酸化スズ粉末は、粒径２μm以下の累積重量が６０％以上および粒径５μm以下の累積重量が９０％以上であって、粒径０.２μm以下および粒径５μm以上の頻度が何れも５％以下であって、０.４μm〜２μmの間に単一の分布ピークが存在する粒度分布を有しており、粒径が微細であり、かつ均一である。 The tin oxide powder shown in FIG. 3 has a cumulative weight of 60% or more with a particle size of 2 μm or less, a cumulative weight of 90% or more with a particle size of 5 μm or less, and a frequency of 0.2 μm or less and a particle size of 5 μm or more. All are 5% or less, have a particle size distribution in which a single distribution peak exists between 0.4 μm and 2 μm, and the particle size is fine and uniform.
〔実施例２〕
３５％塩酸２００mlに、金属スズショット（粒径２〜３mmφ）６０ｇを投入して９０℃で溶解し、スズ濃度３００ｇ/lの塩化スズ溶液を得た。これを１日空気中に放置して自然酸化を行い、Ag-AgCl電極基準で０mVの状態に調整した。これに２８％濃度のアンモニア水６５mlを添加してｐＨ１に調整した。このｐＨ調整後の塩化スズ溶液に０.２４molシュウ酸溶液３００mlおよび０.８５molシュウ酸アンモニウム溶液７００mlを添加してシュウ酸スズ沈澱を生成させた。これを濾過し、水濾過洗浄を３回（約８００mlづつ）行い、残渣（シュウ酸スズ沈澱）を回収した。これを１００℃で乾燥した後に軽く粉砕し、さらに、３００℃で４時間予備焼成を行って軽く粉砕した後に、６５０℃で４時間本焼成を行い、ＢＥＴ比表面積１２.３ｍ3/ｇの酸化スズ粉末を得た。この酸化スズ粉末は、図４に示すように粒径０.１〜１０μmの範囲でシャープな粒度分布を有しており、粒径のバラツキが少なく、再現性に優れている。
[Example 2]
In 200 ml of 35% hydrochloric acid, 60 g of metal tin shot (particle diameter 2 to 3 mmφ) was added and dissolved at 90 ° C. to obtain a tin chloride solution having a tin concentration of 300 g / l. This was left in the air for one day for natural oxidation and adjusted to 0 mV based on the Ag-AgCl electrode standard. The pH was adjusted to 1 by adding 65 ml of 28% ammonia water. To this tin chloride solution after pH adjustment, 300 ml of 0.24 mol oxalic acid solution and 700 ml of 0.85 mol ammonium oxalate solution were added to form a tin oxalate precipitate. This was filtered, washed with water three times (about 800 ml each), and the residue (tin oxalate precipitate) was recovered. This was dried at 100 ° C. and then lightly pulverized. Further, pre-calcined at 300 ° C. for 4 hours and lightly pulverized, followed by main calcination at 650 ° C. for 4 hours, and oxidation with a BET specific surface area of 12.3 m 3 / g. Tin powder was obtained. As shown in FIG. 4, this tin oxide powder has a sharp particle size distribution in a particle size range of 0.1 to 10 μm, has little variation in particle size, and is excellent in reproducibility.
〔実施例３〕
シュウ酸アンモニウムを併用せずに、０.８０molシュウ酸溶液６５０mlのみを添加してシュウ酸スズ沈澱を生成させ、このシュウ酸スズを回収して６５０℃で直接に本焼成を行った以外は実施例２と同様にして、ＢＥＴ比表面積８.７ｍ3/ｇの酸化スズ粉末を得た。この酸化スズ粉末は、図５に示すように粒径０.１〜１０μmの範囲でシャープな粒度分布を有しており、粒径のバラツキが少なく、再現性に優れている。
Example 3
This was carried out except that only 650 ml of a 0.80 mol oxalic acid solution was added without using ammonium oxalate to produce a tin oxalate precipitate, and this tin oxalate was recovered and directly calcined at 650 ° C. In the same manner as in Example 2, a tin oxide powder having a BET specific surface area of 8.7 m 3 / g was obtained. As shown in FIG. 5, this tin oxide powder has a sharp particle size distribution in the particle size range of 0.1 to 10 μm, has little variation in particle size, and is excellent in reproducibility.
〔実施例４〕
塩化スズ溶液を酸化せずに、Ag-AgCl電極基準で−３００mVの状態でｐＨ調整し、さらに、シュウ酸スズ沈澱を回収して６５０℃で直接に本焼成を行った以外は実施例２と同様にして、ＢＥＴ比表面積９.０ｍ3/ｇの酸化スズ粉末を得た。この酸化スズ粉末は、図６に示すように粒径０.１〜１０μmの範囲でシャープな粒度分布を有しており、粒径のバラツキが少なく、再現性に優れている。
Example 4
Example 2 except that the tin chloride solution was not oxidized and the pH was adjusted to -300 mV with respect to the Ag-AgCl electrode, and the tin oxalate precipitate was recovered and directly calcined at 650 ° C. Similarly, a tin oxide powder having a BET specific surface area of 9.0 m 3 / g was obtained. As shown in FIG. 6, this tin oxide powder has a sharp particle size distribution in a particle size range of 0.1 to 10 μm, has little variation in particle size, and is excellent in reproducibility.
〔実施例５〕
塩化スズ溶液を酸化せずに、Ag-AgCl電極基準で−３００mVの状態でｐＨ調整し、さらに、シュウ酸アンモニウムを併用せずにシュウ酸を添加してシュウ酸スズ沈澱を生成させ、これを回収して６５０℃で直接に本焼成を行った以外は実施例２と同様にして、ＢＥＴ比表面積１１.０ｍ3/ｇの酸化スズ粉末を得た。この酸化スズ粉末は、図７に示すように粒径０.１〜１０μmの範囲でシャープな粒度分布を有しており、粒径のバラツキが少なく、再現性に優れている。
Example 5
Without oxidizing the tin chloride solution, the pH was adjusted to -300 mV with respect to the Ag-AgCl electrode, and oxalic acid was added without using ammonium oxalate together to produce a tin oxalate precipitate. A tin oxide powder having a BET specific surface area of 11.0 m 3 / g was obtained in the same manner as in Example 2 except that it was recovered and directly fired at 650 ° C. As shown in FIG. 7, this tin oxide powder has a sharp particle size distribution in a particle size range of 0.1 to 10 μm, has little variation in particle size, and is excellent in reproducibility.
〔比較例１〕
６１％濃硝酸１２０mlを水３８０mlで希釈した硝酸溶液に金属スズショット（粒径２〜３mmφ）５０ｇを毎分５ｇづつ９分間かけて投入し、７０℃で２時間反応させて、メタスズ酸の沈澱を生成させた。これを濾過し、水濾過洗浄を３回（約８００mlづつ）行い、残渣（メタスズ酸沈澱）を回収した。これを１００℃で乾燥した後に軽く粉砕し、さらに、６５０℃で４時間焼成して酸化スズ粉末を得た。この酸化スズ粉末の粒度分布を図８に示した。
[Comparative Example 1]
Precipitation of metastannic acid by pouring 50 g of metal tin shot (particle size 2 to 3 mmφ) over 5 minutes per minute for 9 minutes in a nitric acid solution in which 120 ml of 61% concentrated nitric acid was diluted with 380 ml of water. Was generated. This was filtered, washed with water three times (about 800 ml each), and the residue (metastannic acid precipitate) was recovered. This was dried at 100 ° C. and then lightly pulverized, and further fired at 650 ° C. for 4 hours to obtain a tin oxide powder. The particle size distribution of this tin oxide powder is shown in FIG.
〔比較例２〕
濃度１６０g/lの硝酸アンモニウム３リットルを電解液とし、３０ｇの金属スズ板を陽極とし、ＳＵＳ板を陰極として、電流密度６００Ａ/m2で電解を行い、メタスズ酸の沈澱を得た。これを濾過し、水濾過洗浄を３回（約８００mlづつ）行い、残渣（メタスズ酸沈澱）を回収した。これを１００℃で乾燥した後に軽く粉砕し、さらに、６５０℃で４時間焼成して酸化スズ粉末を得た。この酸化スズ粉末の粒度分布を図９に示した。
[Comparative Example 2]
Electrolysis was performed at a current density of 600 A /
〔比較例３〕
濃硝酸２００mlと濃塩酸６００mlを混合した混酸に金属スズを溶解して、２価のスズイオン５７g/lと、４価のスズイオン１２g/lとを含むスズ塩水溶液を調製した。この水溶液８００mlに６０℃で、２５％濃度のアンモニア水を１０ml/分の割合で４０分間定量添加し（合計４００ml）、溶液のｐＨを２に調整して沈澱を生成させた。これを濾過し、水濾過洗浄を３回（約１０００mlづつ）行い、残渣（スズ含有沈澱）を回収した。これを１００℃で乾燥した後に軽く粉砕し、さらに、６５０℃で４時間焼成して酸化スズ粉末を得た。この酸化スズ粉末の粒度分布を図１０に示した。
[Comparative Example 3]
Metal tin was dissolved in a mixed acid obtained by mixing 200 ml of concentrated nitric acid and 600 ml of concentrated hydrochloric acid to prepare a tin salt aqueous solution containing 57 g / l of divalent tin ions and 12 g / l of tetravalent tin ions. Aqueous solution of 25% concentration was added to 800 ml of this aqueous solution at a rate of 10 ml / min for 40 minutes at 60 ° C. (total 400 ml), and the pH of the solution was adjusted to 2 to form a precipitate. This was filtered, washed with water three times (about 1000 ml each), and the residue (tin-containing precipitate) was recovered. This was dried at 100 ° C. and then lightly pulverized, and further fired at 650 ° C. for 4 hours to obtain a tin oxide powder. The particle size distribution of this tin oxide powder is shown in FIG.
〔比較試験〕
実施例１で得たシュウ酸スズ沈澱を含むスラリーと、比較例３で得たメタスズ酸（水酸化スズ）沈澱を含むスラリーについて濾過性を調べた。濾過条件は、スズ量換算で５０g/lのスズ化合物を含むスラリー１リットルを用い、濾過面積１７６.６cm2、５Ｃの定量濾紙を用い、減圧濾過を行った。さらに蒸留水による洗浄濾過を繰り返した。この水洗３回目に完全に固液分離できた時間と、残留塩素量を表２に示した。
[Comparative test]
The filterability of the slurry containing the tin oxalate precipitate obtained in Example 1 and the slurry containing the metastannic acid (tin hydroxide) precipitate obtained in Comparative Example 3 were examined. Filtration was performed under reduced pressure using 1 liter of slurry containing 50 g / l tin compound in terms of tin, using a quantitative filter paper with a filtration area of 176.6 cm 2 and 5C. Further, washing filtration with distilled water was repeated. Table 2 shows the time during which the solid-liquid separation can be completely performed in the third washing with water and the amount of residual chlorine.
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| JP5486049B2 (en) * | 2012-07-10 | 2014-05-07 | 石原産業株式会社 | Method for producing tin dioxide precursor particles, and method for producing tin dioxide particles |
| CN105948106B (en) * | 2016-06-29 | 2017-10-31 | 渤海大学 | A kind of preparation method of narrow band gap tin ash semiconductor nano material |
| CN112707434B (en) * | 2020-12-11 | 2022-09-20 | 广西晶联光电材料有限责任公司 | Preparation method of nano tin dioxide with large specific surface area |
| CN114315341A (en) * | 2021-12-28 | 2022-04-12 | 广州市石基耐火材料厂 | Manganese-containing high-purity tin ceramic, preparation method thereof, manganese-containing high-purity tin brick and application |
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| JP2687361B2 (en) * | 1987-07-22 | 1997-12-08 | 日産化学工業株式会社 | Method for producing tin oxide sol |
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| JPH05179439A (en) * | 1992-01-06 | 1993-07-20 | Mitsubishi Materials Corp | Target for sputtering made of indium oxide-tin oxide sintered compact |
| JP3173440B2 (en) * | 1997-10-24 | 2001-06-04 | 三菱マテリアル株式会社 | Method for producing tin oxide powder |
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