JP2018131346A - Niobic acid powder - Google Patents
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- JP2018131346A JP2018131346A JP2017024298A JP2017024298A JP2018131346A JP 2018131346 A JP2018131346 A JP 2018131346A JP 2017024298 A JP2017024298 A JP 2017024298A JP 2017024298 A JP2017024298 A JP 2017024298A JP 2018131346 A JP2018131346 A JP 2018131346A
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- 239000002253 acid Substances 0.000 title claims abstract description 57
- 239000000843 powder Substances 0.000 title claims abstract description 46
- 239000006185 dispersion Substances 0.000 claims abstract description 48
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 25
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 24
- 230000014759 maintenance of location Effects 0.000 claims abstract description 23
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012153 distilled water Substances 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 23
- 239000010419 fine particle Substances 0.000 claims description 19
- 238000012360 testing method Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 10
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 7
- 229960001231 choline Drugs 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 abstract 4
- 239000000203 mixture Substances 0.000 abstract 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 229910000484 niobium oxide Inorganic materials 0.000 description 5
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical compound [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- KVFVBPYVNUCWJX-UHFFFAOYSA-M ethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)C KVFVBPYVNUCWJX-UHFFFAOYSA-M 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002822 niobium compounds Chemical class 0.000 description 1
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 1
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- OLNCQUXQEJCISO-UHFFFAOYSA-M trimethyl(propyl)azanium;hydroxide Chemical compound [OH-].CCC[N+](C)(C)C OLNCQUXQEJCISO-UHFFFAOYSA-M 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
本発明は、ニオブ酸粉体に関する。 The present invention relates to niobic acid powder.
粉体の形態のニオブ化合物として、例えば、光学、電子、電池、触媒材料などの原料や添加剤として用いられるニオブ酸（酸化ニオブ、水酸化ニオブ、ニオブのポリ酸）が知られている。また、その他に水溶性粉体として、合成触媒の原料として用いられるシュウ酸ニオブ、シュウ酸ニオブアンモニウム等が知られている。 As niobium compounds in the form of powder, for example, niobic acid (niobium oxide, niobium hydroxide, polyacid of niobium) used as a raw material or additive for optical, electronic, battery, and catalyst materials is known. Other known water-soluble powders include niobium oxalate and ammonium niobium oxalate used as raw materials for synthetic catalysts.
また、特許文献１には、酸化ニオブの微粒子粉に関する技術が開示されており、当該微粒子粉はスラリーとして用いることができる旨が記載されている。 Patent Document 1 discloses a technique related to fine particle powder of niobium oxide, and describes that the fine particle powder can be used as a slurry.
本発明は、水に分散させたときに、分散継続性の高いニオブ酸粉体の提供を課題とする。 An object of the present invention is to provide a niobic acid powder having high dispersion continuity when dispersed in water.
ところで、特許文献１に記載の酸化ニオブの微粒子粉は、粒径が小さい故に水への分散が可能であるが、分散継続性を一定期間保持させるための工夫がなされていないため、改善の余地があった。 By the way, the fine particle powder of niobium oxide described in Patent Document 1 can be dispersed in water because of its small particle size, but there is no room for improvement because no measures have been taken to maintain the dispersion continuity for a certain period of time. was there.
本発明者らは上記課題について鋭意検討した結果、水酸化第四級アンモニウムを巧みに用いることによって上記課題が解決されることを見出し、かかる知見に基づき本発明を完成させた。 As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by skillfully using quaternary ammonium hydroxide, and have completed the present invention based on such knowledge.
本発明は以下のとおりである。
［１］水酸化第四級アンモニウムを含有し、以下の分散試験によって求められた分散保持率が50%以上であるニオブ酸粉体。
分散試験：Nb2O5として25質量%となるようにニオブ酸粉体と蒸留水とを混合して調製した混合液を50mLのスクリュー管瓶2本に50gずつ分取し、両瓶を超音波分散処理する。一方の瓶は上記超音波分散処理直後に上部10mLを採取（試料A）し、他方の瓶は上記超音波分散処理終了後静置し24時間後に上部10mLを採取（試料B）し、試料Aと試料B中のNb2O5濃度を測定する。分散保持率を、分散保持率(%)=(試料B中のNb2O5濃度)/(試料A中のNb2O5濃度)×100の式から求める。
ここで、超音波分散処理の条件は、発振周波数：23kHz、出力：240W、処理時間：10分間である。
［２］水酸化第四級アンモニウムが、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム又はコリンである上記［１］記載のニオブ酸粉体。
［３］水酸化第四級アンモニウムの含有割合が、Nb2O5に対するモル比で0.3〜1の範囲である上記［１］又は［２］記載のニオブ酸粉体。
［４］以下の工程を含む上記［１］〜［３］のいずれか１項記載のニオブ酸粉体の製造方法。
水酸化第四級アンモニウムの存在下で、平均分散粒子径が0.01〜10μmであるニオブ酸微粒子含有水溶液を50〜200℃で加熱した後、乾燥する工程。
The present invention is as follows.
[1] A niobic acid powder containing quaternary ammonium hydroxide and having a dispersion retention of 50% or more determined by the following dispersion test.
Dispersion test: Nb 2 O 5 was mixed with niobic acid powder and distilled water so that the concentration was 25% by mass, and 50 g each was dispensed into two 50 mL screw tube bottles. Sonic dispersion treatment. One bottle is taken immediately after the ultrasonic dispersion treatment (sample A), and the other bottle is left after the ultrasonic dispersion treatment is finished, and the upper 10 ml is collected 24 hours later (sample B). And Nb 2 O 5 concentration in sample B is measured. The dispersion retention, dispersion retention (%) = (Nb 2 O 5 concentration in the sample B) / determined from the equation × 100 (Nb 2 O 5 concentration in the sample A).
Here, the conditions of the ultrasonic dispersion treatment are an oscillation frequency: 23 kHz, an output: 240 W, and a processing time: 10 minutes.
[2] The niobic acid powder according to [1], wherein the quaternary ammonium hydroxide is tetramethylammonium hydroxide, tetraethylammonium hydroxide, or choline.
[3] The niobic acid powder according to the above [1] or [2], wherein the content ratio of quaternary ammonium hydroxide is in the range of 0.3 to 1 in terms of molar ratio to Nb 2 O 5 .
[4] The method for producing a niobic acid powder according to any one of [1] to [3], including the following steps.
A step of heating a niobic acid fine particle-containing aqueous solution having an average dispersed particle size of 0.01 to 10 μm in the presence of quaternary ammonium hydroxide at 50 to 200 ° C. and then drying.
本発明のニオブ酸粉体は、水に対して良好な分散継続性を有しているため、各種用途の添加剤や原料としての使用に好適であり、また、本発明のニオブ酸粉体を水に分散させたものにバインダーなどを含有させることで、機能膜の形成材料としても使用できる利点を有する。 Since the niobic acid powder of the present invention has good dispersion continuity with respect to water, it is suitable for use as an additive or raw material for various applications. By including a binder or the like in a material dispersed in water, there is an advantage that it can be used as a material for forming a functional film.
以下、好ましい実施形態に基づいて本発明を詳細に説明するが、本発明は以下の実施形態に限定されるものではなく、請求項に示した範囲で種々の変更が可能である。 Hereinafter, the present invention will be described in detail based on preferred embodiments. However, the present invention is not limited to the following embodiments, and various modifications can be made within the scope shown in the claims.
本発明のニオブ酸粉体は、水酸化第四級アンモニウムを含有するものであり、以下の分散試験によって求められた分散保持率が50%以上であるという特性を有する。
分散試験：Nb2O5として25質量%となるようにニオブ酸粉体と蒸留水とを混合して調製した混合液を50mLのスクリュー管瓶2本に50gずつ分取し、両瓶を超音波分散処理する。一方の瓶は上記超音波分散処理直後に上部10mLを採取（試料A）し、他方の瓶は上記超音波分散処理終了後静置し24時間後に上部10mLを採取（試料B）し、試料Aと試料B中のNb2O5濃度を測定する。分散保持率を、分散保持率(%)=(試料B中のNb2O5濃度)/(試料A中のNb2O5濃度)×100の式から求める。
ここで、超音波分散処理の条件は、発振周波数：23kHz、出力：240W、処理時間：10分間である。また、50mLのスクリュー管瓶は、実験用に市販されているものであればよく、好例はアズワン株式会社の「ラボランスクリュー管瓶No.7 50mL」である。
The niobic acid powder of the present invention contains quaternary ammonium hydroxide, and has a characteristic that the dispersion retention obtained by the following dispersion test is 50% or more.
Dispersion test: Nb 2 O 5 was mixed with niobic acid powder and distilled water so that the concentration was 25% by mass, and 50 g each was dispensed into two 50 mL screw tube bottles. Sonic dispersion treatment. One bottle is taken immediately after the ultrasonic dispersion treatment (sample A), and the other bottle is left after the ultrasonic dispersion treatment is finished, and the upper 10 ml is collected 24 hours later (sample B). And Nb 2 O 5 concentration in sample B is measured. The dispersion retention, dispersion retention (%) = (Nb 2 O 5 concentration in the sample B) / determined from the equation × 100 (Nb 2 O 5 concentration in the sample A).
Here, the conditions of the ultrasonic dispersion treatment are an oscillation frequency: 23 kHz, an output: 240 W, and a processing time: 10 minutes. Further, the 50 mL screw tube bottle may be any one commercially available for experimentation, and a good example is “Laboran screw tube No. 7 50 mL” manufactured by ASONE CORPORATION.
分散試験は、ニオブ酸粉体の水に対する分散継続性を評価するものであり、分散継続性が高いほどユーザーにおける利便性が向上する。上記分散保持率が50%以上であれば、濃度勾配や沈殿物発生を生じにくいことから、良好な分散継続性を有すると評価できる。上記分散保持率は、60%以上であることが好ましく、より好ましくは70%以上であり、さらに好ましくは80%以上であり、さらにより好ましくは90%以上である。 The dispersion test evaluates the dispersion continuity of niobic acid powder in water, and the higher the dispersion continuity, the more convenient the user is. If the dispersion retention rate is 50% or more, it is difficult to generate a concentration gradient and precipitates, so it can be evaluated that the dispersion has good continuity. The dispersion retention is preferably 60% or more, more preferably 70% or more, still more preferably 80% or more, and even more preferably 90% or more.
水酸化第四級アンモニウムとしては、例えば、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラプロピルアンモニウム、水酸化テトラブチルアンモニウム、水酸化トリメチルエチルアンモニウム、水酸化トリメチルプロピルアンモニウム、水酸化ジメチルジエチルアンモニウム、コリン等が挙げられる。本発明のニオブ酸粉体には、水酸化第四級アンモニウムとして、1種類の化合物だけ含有してもよいし、2種類以上の化合物を含有してもよい。上記列挙した化合物のうち、特に好ましいものは、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、コリンである。 Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, dimethyldiethyl hydroxide. Examples include ammonium and choline. The niobic acid powder of the present invention may contain only one kind of compound as quaternary ammonium hydroxide, or may contain two or more kinds of compounds. Of the compounds listed above, particularly preferred are tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline.
水酸化第四級アンモニウムの含有割合は、Nb2O5に対するモル比、即ち、水酸化第四級アンモニウム／Nb2O5（モル比）で、0.3〜1の範囲であることが好ましい。当該範囲内であれば、良好な分散継続性を得ることができる。上記モル比は、より好ましくは0.4〜1の範囲であり、さらに好ましくは0.5〜1の範囲である。 Content of quaternary ammonium hydroxide, the molar ratio Nb 2 O 5, i.e., quaternary ammonium / Nb 2 O 5 hydroxide (molar ratio) is preferably in the range of 0.3-1. Within this range, good dispersion continuity can be obtained. The molar ratio is more preferably in the range of 0.4 to 1, and still more preferably in the range of 0.5 to 1.
本発明のニオブ酸粉体において、良好な分散継続性が得られるメカニズムについては定かではないが、表面電荷が負であるニオブ酸微粒子が水酸化第四級アンモニウムによって修飾されていることによって、水に対して優れた分散性を発揮するものと推測される。 In the niobic acid powder of the present invention, the mechanism for obtaining good dispersion continuity is not clear. However, the niobic acid fine particles having a negative surface charge are modified with quaternary ammonium hydroxide, so that It is speculated that it exhibits excellent dispersibility.
本発明のニオブ酸粉体には、前記分散保持率が損なわれない範囲であれば、その他化合物を含有しても構わない。例えば、酸化チタン、酸化タンタル、酸化ケイ素、酸化アルミニウム等の無機成分、樹脂、界面活性剤、多糖類等の有機成分が挙げられる。 The niobic acid powder of the present invention may contain other compounds as long as the dispersion retention is not impaired. Examples thereof include inorganic components such as titanium oxide, tantalum oxide, silicon oxide, and aluminum oxide, and organic components such as resins, surfactants, and polysaccharides.
本発明のニオブ酸粉体の好適な一製造方法は、水酸化第四級アンモニウムの存在下で、平均分散粒子径が0.01〜10μmであるニオブ酸微粒子含有水溶液を50〜200℃で加熱した後、乾燥する工程を含むものである。 One preferred method for producing the niobic acid powder of the present invention is to heat a niobic acid fine particle-containing aqueous solution having an average dispersed particle diameter of 0.01 to 10 μm at 50 to 200 ° C. in the presence of quaternary ammonium hydroxide. And a step of drying.
上記ニオブ酸微粒子含有水溶液は、公知の方法によって製造されることができ、その製造方法は特に限定されない。一例は、ニオブ酸の粉体を水に分散させることによって製造するものである。なお、当該粉体としては、ニオブ酸微粒子含有水溶液としたときに、平均分散粒子径が上記範囲内となるものを用いる。平均分散粒子径が10μmよりも大きい場合は、所定の粒子径になるまでビーズミルなどで粉砕してもよい。また、別の一例は、フッ酸又はフッ酸と硫酸との混酸にニオブ酸を溶解させた水溶液とアンモニア水溶液とをpHを8以上に維持しつつ混合、反応させることによって製造するものである。平均分散粒子径の範囲については、0.01μm未満の場合は、ニオブ酸微粒子の水酸化第四級アンモニウムに対する溶解反応の進行により、微粒子としての形態維持が困難となる。一方、10μm超の場合は、本発明のニオブ酸粉体としたときに水に対する分散性が著しく低下するため好ましくない。なお、平均分散粒子径の上限については、5μmであることが好ましく、より好ましくは3μmである。 The niobic acid fine particle-containing aqueous solution can be produced by a known method, and the production method is not particularly limited. One example is to manufacture by dispersing niobic acid powder in water. As the powder, those having an average dispersed particle diameter within the above range when an aqueous solution containing niobic acid fine particles is used are used. When the average dispersed particle size is larger than 10 μm, the particles may be pulverized with a bead mill or the like until a predetermined particle size is obtained. Another example is to manufacture by mixing and reacting an aqueous solution obtained by dissolving niobic acid in hydrofluoric acid or a mixed acid of hydrofluoric acid and sulfuric acid and an aqueous ammonia solution while maintaining the pH at 8 or more. With respect to the range of the average dispersed particle size, when it is less than 0.01 μm, it is difficult to maintain the shape as fine particles due to the progress of dissolution reaction of niobic acid fine particles with respect to quaternary ammonium hydroxide. On the other hand, when the particle size exceeds 10 μm, the dispersibility in water is remarkably lowered when the niobic acid powder of the present invention is used. The upper limit of the average dispersed particle size is preferably 5 μm, more preferably 3 μm.
水酸化第四級アンモニウムの存在下とは、平均分散粒子径が0.01〜10μmであるニオブ酸微粒子含有水溶液中に水酸化第四級アンモニウムが含有されていればよく、好適には上記ニオブ酸微粒子含有水溶液と水酸化第四級アンモニウムとを混合することによって得ることができる。 In the presence of quaternary ammonium hydroxide, it is sufficient that quaternary ammonium hydroxide is contained in an aqueous solution containing niobic acid fine particles having an average dispersed particle diameter of 0.01 to 10 μm. It can be obtained by mixing the aqueous solution containing and quaternary ammonium hydroxide.
水酸化第四級アンモニウムの存在下で上記ニオブ酸微粒子含有水溶液を50〜200℃で加熱することによって、水に対して良好な分散継続性を示すニオブ酸粉体を得ることができる。前記メカニズムにおける水酸化第四級アンモニウムによるニオブ酸微粒子の修飾は加熱によって促進されるものと推測されるため、前記分散保持率が得られるように加熱温度を適宜設定することが好ましい。例えば、加熱温度が低過ぎる場合は、水酸化第四級アンモニウムの修飾反応が十分に進行しないためと推測されるが、乾燥性が大きく低下する傾向にある。また、加熱温度が高過ぎる場合は、水酸化第四級アンモニウムの分解反応等が危惧されるため好ましくない。加熱温度の範囲については、70〜180℃が好ましく、より好ましくは90〜150℃である。なお、加熱温度が低めであったとしても加熱時間を長くすることで対応することが可能であるが、工業的製造を考えると例えば1〜24時間の加熱時間で対応できる加熱温度に設定することが好ましい。 By heating the niobic acid fine particle-containing aqueous solution at 50 to 200 ° C. in the presence of quaternary ammonium hydroxide, a niobic acid powder exhibiting good dispersion continuity with respect to water can be obtained. Since the modification of niobic acid fine particles with quaternary ammonium hydroxide in the mechanism is presumed to be promoted by heating, it is preferable to appropriately set the heating temperature so as to obtain the dispersion retention rate. For example, when the heating temperature is too low, it is presumed that the modification reaction of quaternary ammonium hydroxide does not proceed sufficiently, but the drying property tends to be greatly reduced. On the other hand, when the heating temperature is too high, the decomposition reaction of quaternary ammonium hydroxide is concerned, which is not preferable. About the range of heating temperature, 70-180 degreeC is preferable, More preferably, it is 90-150 degreeC. In addition, even if the heating temperature is low, it is possible to cope with it by lengthening the heating time, but considering industrial production, for example, it should be set to a heating temperature that can be handled with a heating time of 1 to 24 hours Is preferred.
乾燥は、本発明のニオブ酸粉体が得られるのであれば、その方法や得られる粉体の粒子径については特に制限されることはない。乾燥方法は、好適には常法によって行えばよく、例えば、噴霧乾燥、静置乾燥、凍結乾燥等を挙げることができる。また、乾燥条件（温度、時間）は、適宜設定することが好ましい。なお、乾燥を行うまでに、任意の処理として、余分な成分を可能な限り除去するために洗浄処理を行ってもよい。洗浄は、限外洗浄、ろ過洗浄等の常法により実施すればよい。 As long as the niobic acid powder of the present invention can be obtained, the drying is not particularly limited with respect to the method and the particle diameter of the obtained powder. The drying method is preferably carried out by a conventional method, and examples thereof include spray drying, stationary drying, freeze drying and the like. Moreover, it is preferable to set drying conditions (temperature, time) suitably. In addition, you may perform a washing | cleaning process in order to remove an extra component as much as possible as an arbitrary process before drying. Washing may be carried out by conventional methods such as ultra-cleaning, filtration and washing.
以下に、本発明を実施例によりさらに詳細に説明するが、本発明はこれらに制限されるものではない。なお、実施例において%は、分散保持率を除いて、特に断らない限り全て質量%を示す。 EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In Examples, “%” means “% by mass” unless otherwise specified, except for the dispersion retention rate.
＜処理・分析＞
(1)平均分散粒子径の測定
・1μm未満の平均分散粒子径は、動的光散乱式粒径分布測定装置LB-500（堀場製作所(株)製）を用いて測定した。
・1μm以上の平均分散粒子径は、レーザー回折・散乱式 粒子径分布測定装置MT-3000II（マイクロ・ベル(株)製）を用いて測定した。
なお、上記いずれの測定においても供試液は希釈や濃縮を行わずに、そのまま供試した。
(2)分散試験
以下の各実施例と比較例で得られたニオブ酸粉体と蒸留水とをNb2O5として25%となるように混合して混合液を調製した。この混合液を50mLのスクリュー管瓶（アズワン(株)「ラボランスクリュー管瓶No.7 50mL」）2本に50gずつ分取し、両瓶を超音波分散処理に供した。超音波分散処理の条件は、超音波分散処理装置として超音波洗浄機ASU-10D（アズワン(株)製）を用い、発振周波数：23kHz、出力：240W、処理時間：10分間である。
一方の瓶は、上記超音波分散処理直後に上部10mLを採取（試料A）した。
他方の瓶は、上記超音波分散処理終了後24時間室温で静置してから上部10mLを採取（試料B）した。
次に、試料Aと試料B中のNb2O5濃度を測定した。
分散保持率を以下の式から求めた。
分散保持率(%)=(試料B中のNb2O5濃度)/(試料A中のNb2O5濃度)×100
<Processing and analysis>
(1) Measurement of average dispersed particle diameter • The average dispersed particle diameter of less than 1 μm was measured using a dynamic light scattering particle size distribution analyzer LB-500 (manufactured by Horiba, Ltd.).
The average dispersed particle size of 1 μm or more was measured using a laser diffraction / scattering particle size distribution measuring device MT-3000II (manufactured by Micro Bell Co., Ltd.).
In any of the above measurements, the test solution was used as it was without dilution or concentration.
(2) Dispersion test Niobic acid powders obtained in each of the following Examples and Comparative Examples and distilled water were mixed at 25% as Nb 2 O 5 to prepare a mixed solution. 50 g of this mixed solution was dispensed into two 50 mL screw tube bottles (Aswan Co., Ltd. “Laboran screw tube No. 7 50 mL”), and both bottles were subjected to ultrasonic dispersion treatment. The conditions of the ultrasonic dispersion treatment are as follows: an ultrasonic cleaning machine ASU-10D (manufactured by ASONE Co., Ltd.) is used as the ultrasonic dispersion treatment apparatus, the oscillation frequency is 23 kHz, the output is 240 W, and the treatment time is 10 minutes.
In one bottle, immediately after the ultrasonic dispersion treatment, the upper 10 mL was collected (sample A).
The other bottle was allowed to stand at room temperature for 24 hours after the completion of the ultrasonic dispersion treatment, and 10 mL of the upper part was collected (sample B).
Next, the Nb 2 O 5 concentration in Sample A and Sample B was measured.
The dispersion retention was determined from the following formula.
Distributed retention (%) = (Nb 2 O 5 concentration in the sample B) / (Nb 2 O 5 concentration in the sample A) × 100
〔実施例１〕
フッ酸に酸化ニオブを溶解させた水溶液とアンモニア水溶液とをpHを8以上に維持しつつ混合し反応させることによって得られた平均粒子径が1.2μmのニオブ酸微粒子含有水溶液（Nb2O5=28.1%、NH3=3.3%、pH10.7）355.9gに、35%水酸化テトラエチルアンモニウム水溶液47.5gを添加し、140℃/3hで加熱した。得られた水溶液を100℃/12hの条件で通風乾燥機にて乾燥し、ニオブ酸粉体（水酸化テトラエチルアンモニウム/Nb2O5(モル比)=0.3）を得た。
このニオブ酸粉体を用いて分散試験を行ったところ、分散保持率は59.5%であった。
[Example 1]
An aqueous solution containing niobic acid fine particles with an average particle size of 1.2 μm (Nb 2 O 5 =) obtained by mixing and reacting an aqueous solution of niobium oxide dissolved in hydrofluoric acid and an aqueous ammonia solution while maintaining the pH at 8 or higher. 28.1%, NH 3 = 3.3%, pH 10.7) To 355.9 g, 47.5 g of 35% tetraethylammonium hydroxide aqueous solution was added and heated at 140 ° C./3 h. The obtained aqueous solution was dried with a ventilator at 100 ° C./12 h to obtain niobic acid powder (tetraethylammonium hydroxide / Nb 2 O 5 (molar ratio) = 0.3).
When a dispersion test was performed using this niobic acid powder, the dispersion retention was 59.5%.
〔実施例２〕
フッ酸に酸化ニオブを溶解させた水溶液とアンモニア水溶液とをpHを8以上に維持しつつ混合し反応させることによって得られた平均粒子径が0.02μmのニオブ酸微粒子含有水溶液（Nb2O5=6.2%、NH3=0.5%、pH8.7）1612.9gに、35%水酸化テトラエチルアンモニウム水溶液63.3gを添加し、70℃/10hで加熱した。得られた水溶液を100℃/12hの条件で通風乾燥機にて乾燥し、ニオブ酸粉体（水酸化テトラエチルアンモニウム/Nb2O5(モル比)=0.5）を得た。
このニオブ酸粉体を用いて分散試験を行ったところ、分散保持率は99.1%であった。
[Example 2]
An aqueous solution containing niobic acid fine particles with an average particle size of 0.02 μm obtained by mixing and reacting an aqueous solution of niobium oxide dissolved in hydrofluoric acid and an aqueous ammonia solution while maintaining the pH at 8 or higher (Nb 2 O 5 = (6.2%, NH 3 = 0.5%, pH 8.7) To 1612.9 g, 63.3 g of 35% tetraethylammonium hydroxide aqueous solution was added and heated at 70 ° C./10 h. The obtained aqueous solution was dried with a ventilator at 100 ° C./12 h to obtain niobic acid powder (tetraethylammonium hydroxide / Nb 2 O 5 (molar ratio) = 0.5).
When a dispersion test was performed using this niobic acid powder, the dispersion retention was 99.1%.
〔実施例３〕
実施例１の平均粒子径が1.2μmのニオブ酸微粒子含有水溶液（Nb2O5=28.1%、NH3=3.3%、pH10.7）355.9gに、48%コリン水溶液95.0gを添加し、90℃/6hで加熱した。得られた水溶液をヤマト科学(株)製スプレードライヤADL310（入口温度：200℃、出口温度：100℃）にて乾燥し、ニオブ酸粉体（コリン/Nb2O5(モル比)=1.0）を得た。
このニオブ酸粉体を用いて分散試験を行ったところ、分散保持率は98.4%であった。
Example 3
95.0 g of 48% choline aqueous solution was added to 355.9 g of the niobic acid fine particle-containing aqueous solution (Nb 2 O 5 = 28.1%, NH 3 = 3.3%, pH 10.7) having an average particle size of 1.2 μm in Example 1, Heated at ℃ / 6h. The obtained aqueous solution was dried with a spray dryer ADL310 (inlet temperature: 200 ° C., outlet temperature: 100 ° C.) manufactured by Yamato Scientific Co., Ltd., and niobic acid powder (choline / Nb 2 O 5 (molar ratio) = 1.0) Got.
When a dispersion test was performed using this niobic acid powder, the dispersion retention was 98.4%.
〔実施例４〕
実施例１の平均粒子径が1.2μmのニオブ酸微粒子含有水溶液（Nb2O5=28.1%、NH3=3.3%、pH10.7）355.9gに、35%水酸化テトラエチルアンモニウム水溶液79.1gを添加し、140℃/3hで加熱した。得られた水溶液をヤマト科学(株)製スプレードライヤADL310（入口温度：200℃、出口温度：100℃）にて乾燥し、ニオブ酸粉体（水酸化テトラエチルアンモニウム/Nb2O5(モル比)=0.5）を得た。
このニオブ酸粉体を用いて分散試験を行ったところ、分散保持率は90.1%であった。
Example 4
79.1 g of 35% tetraethylammonium hydroxide aqueous solution was added to 355.9 g of the niobic acid fine particle-containing aqueous solution (Nb 2 O 5 = 28.1%, NH 3 = 3.3%, pH 10.7) having an average particle diameter of 1.2 μm in Example 1. And heated at 140 ° C./3 h. The resulting aqueous solution was dried with a spray dryer ADL310 (inlet temperature: 200 ° C, outlet temperature: 100 ° C) manufactured by Yamato Scientific Co., Ltd., and niobic acid powder (tetraethylammonium hydroxide / Nb 2 O 5 (molar ratio)) = 0.5) was obtained.
When a dispersion test was performed using this niobic acid powder, the dispersion retention was 90.1%.
〔比較例１〕
実施例１の平均粒子径が1.2μmのニオブ酸微粒子含有水溶液（Nb2O5=28.1%、NH3=3.3%、pH10.7）355.9gを140℃/3hで加熱した。得られた水溶液をヤマト科学(株)製スプレードライヤADL310（入口温度：200℃、出口温度：100℃）にて乾燥し、ニオブ酸粉体を得た。
このニオブ酸粉体を用いて分散試験を行ったところ、分散保持率は10.6%であった。
[Comparative Example 1]
355.9 g of the niobic acid fine particle-containing aqueous solution (Nb 2 O 5 = 28.1%, NH 3 = 3.3%, pH 10.7) having an average particle diameter of 1.2 μm in Example 1 was heated at 140 ° C./3 h. The obtained aqueous solution was dried with a spray dryer ADL310 (inlet temperature: 200 ° C., outlet temperature: 100 ° C.) manufactured by Yamato Scientific Co., Ltd. to obtain niobic acid powder.
When a dispersion test was performed using this niobic acid powder, the dispersion retention was 10.6%.
Claims (4)
分散試験：Nb2O5として25質量%となるようにニオブ酸粉体と蒸留水とを混合して調製した混合液を50mLのスクリュー管瓶2本に50gずつ分取し、両瓶を超音波分散処理する。一方の瓶は上記超音波分散処理直後に上部10mLを採取（試料A）し、他方の瓶は上記超音波分散処理終了後静置し24時間後に上部10mLを採取（試料B）し、試料Aと試料B中のNb2O5濃度を測定する。分散保持率を、分散保持率(%)=(試料B中のNb2O5濃度)/(試料A中のNb2O5濃度)×100の式から求める。
ここで、超音波分散処理の条件は、発振周波数：23kHz、出力：240W、処理時間：10分間である。 A niobic acid powder containing quaternary ammonium hydroxide and having a dispersion retention of 50% or more determined by the following dispersion test.
Dispersion test: Nb 2 O 5 was mixed with niobic acid powder and distilled water so that the concentration was 25% by mass, and 50 g each was dispensed into two 50 mL screw tube bottles. Sonic dispersion treatment. One bottle is taken immediately after the ultrasonic dispersion treatment (sample A), and the other bottle is left after the ultrasonic dispersion treatment is finished, and the upper 10 ml is collected 24 hours later (sample B). And Nb 2 O 5 concentration in sample B is measured. The dispersion retention, dispersion retention (%) = (Nb 2 O 5 concentration in the sample B) / determined from the equation × 100 (Nb 2 O 5 concentration in the sample A).
Here, the conditions of the ultrasonic dispersion treatment are an oscillation frequency: 23 kHz, an output: 240 W, and a processing time: 10 minutes.
水酸化第四級アンモニウムの存在下で、平均分散粒子径が0.01〜10μmであるニオブ酸微粒子含有水溶液を50〜200℃で加熱した後、乾燥する工程。 The manufacturing method of the niobic acid powder of any one of Claims 1-3 including the following processes.
A step of heating a niobic acid fine particle-containing aqueous solution having an average dispersed particle size of 0.01 to 10 μm in the presence of quaternary ammonium hydroxide at 50 to 200 ° C. and then drying.
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