JP2875486B2 - Tantalum oxide sol and method for producing the same - Google Patents
Tantalum oxide sol and method for producing the sameInfo
- Publication number
- JP2875486B2 JP2875486B2 JP6309581A JP30958194A JP2875486B2 JP 2875486 B2 JP2875486 B2 JP 2875486B2 JP 6309581 A JP6309581 A JP 6309581A JP 30958194 A JP30958194 A JP 30958194A JP 2875486 B2 JP2875486 B2 JP 2875486B2
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- JP
- Japan
- Prior art keywords
- sol
- tantalum
- tantalum oxide
- present
- oxalic acid
- Prior art date
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- Inorganic Compounds Of Heavy Metals (AREA)
- Colloid Chemistry (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は酸化タンタルゾル及びそ
の製造方法に関し、更に詳しくは酸化タンタルゾル粒子
がしゅう酸によって強固に結合することにより安定化さ
れた、新規な酸化タンタルゾルによって、例えば触媒、
オプトエレクトロニクス材料、半導体材料等へのタンタ
ル原料の提供に好適な酸化タンタルゾルを提供するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tantalum oxide sol and a method for producing the same. More specifically, the present invention relates to a novel tantalum oxide sol, which is stabilized by oxalic acid firmly binding tantalum oxide sol particles, such as a catalyst,
An object of the present invention is to provide a tantalum oxide sol suitable for providing a tantalum raw material to an optoelectronic material, a semiconductor material, and the like.
【０００２】[0002]
【従来の技術】近年、セラミックス原料、電子材料等に
酸化タンタルを使用する需要が高く、殊にオプトエレク
トロニクス、触媒等の材料としては粒子径が小さく、均
一な粒度分布を有する酸化タンタル原料が要求されてい
る。しかしながら、酸化タンタル原料は一般に水酸化タ
ンタル、酸化タンタル等の原料粉末を焼成し、これを粉
砕して使用されるため、その粒子は不均一であるだけで
なく、比較的粒子径の大きなタンタル原料が使用されて
いるのが現状である。従って、前述のような均一、微細
粒子径の酸化タンタル原料の要求が高くなっているのが
現状である。2. Description of the Related Art In recent years, there has been a high demand for the use of tantalum oxide for ceramic raw materials, electronic materials, and the like. Have been. However, the tantalum oxide raw material is generally used by baking raw material powder such as tantalum hydroxide and tantalum oxide and pulverizing the raw material, so that the particles are not only non-uniform, but also have a relatively large particle diameter. Is currently used. Therefore, at present, there is an increasing demand for a tantalum oxide raw material having a uniform and fine particle diameter as described above.
【０００３】このような現状に於いて、上述の要求に応
じるべく近年各種の元素を微細粒子で得る技術が開発さ
れている。例えば、特開昭62-96319号公報では、タンタ
ルアルコキシドを原料として使用し、これを加水分解す
る方法によって酸化タンタルの水和物粒子を得る技術が
開示されている。しかし、このような酸化タンタル粒子
の粒子径は、最も低いものでも500オンク゛ストローム程度であ
り、必ずしも均一微細なタンタル原料として好適なもの
ではない。従って、酸化タンタル原料として均一微細な
酸化タンタル原料の出現が要望されているのが現状であ
る。Under such circumstances, techniques for obtaining various elements in the form of fine particles have recently been developed to meet the above requirements. For example, Japanese Patent Application Laid-Open No. Sho 62-96319 discloses a technique of using tantalum alkoxide as a raw material and obtaining hydrate particles of tantalum oxide by a method of hydrolyzing tantalum alkoxide. However, the particle diameter of such tantalum oxide particles is about 500 angstroms at the lowest, and is not necessarily suitable as a uniform fine tantalum raw material. Therefore, at present, there is a demand for the appearance of uniformly fine tantalum oxide raw materials as tantalum oxide raw materials.
【０００４】[0004]
【発明が解決しようとする課題】本発明者らは、上述の
ような現状に於いて、均一微細な酸化タンタル原料を得
るべく、このような酸化タンタル原料を均一微細なゾル
状態で得る方法について鋭意検討を重ねた。その結果、
酸化タンタルのゾルを得る手段として、その原料に活性
な水酸化タンタル化合物を使用し、このタンタル化合物
としゅう酸とを特定の割合で反応させることによって得
られるゾルが均一微細な粒子であって、しかも安定なゾ
ルとして得られ前述の課題を解決する新規なゾルである
ことを見い出し、係る知見に基づき本発明を完成させる
に至ったものである。Under the circumstances described above, the present inventors have proposed a method of obtaining such a tantalum oxide raw material in a uniformly fine sol state in order to obtain a uniformly fine tantalum oxide raw material. We studied diligently. as a result,
As a means of obtaining a sol of tantalum oxide, using an active tantalum hydroxide compound as a raw material, the sol obtained by reacting this tantalum compound and oxalic acid at a specific ratio is uniform fine particles, In addition, the inventors have found that the sol is a novel sol that is obtained as a stable sol and solves the above-mentioned problems, and has completed the present invention based on such findings.
【０００５】[0005]
【課題を解決するための手段】即ち、本発明はしゅう酸
とタンタル酸化物が(HCOO)2/Ta2O5モル比0.5〜5の範囲
で構成される粒子径500オンク゛ストローム以下の酸化タンタルゾ
ルに関する。更に、本発明は活性な水酸化タンタル化合
物に、(HCOO)2/Ta2O5モル比5.0〜30の範囲となるように
しゅう酸を加え、温度90℃以上で2時間以上の加熱反応
を行うことを特徴とするしゅう酸とタンタル酸化物が(H
COO) 2 /Ta 2 O 5 モル比0.5〜5の範囲で構成される粒子径500
オンク゛ストローム 以下の酸化タンタルゾルの製造方法に関す
る。[SUMMARY OF Namely, the present invention relates to tantalum oxide and oxalic acid (HCOO) 2 / Ta 2 O 5 particle size 500 comprised in the range of molar ratio 0.5 to 5 angstroms following oxidation Tantaruzoru . Further, the present invention adds an oxalic acid to the active tantalum hydroxide compound so that the molar ratio of (HCOO) 2 / Ta 2 O 5 is in the range of 5.0 to 30, and performs a heating reaction at a temperature of 90 ° C. or more for 2 hours or more. Oxalic acid and tantalum oxide are characterized in that (H
(COO) 2 / Ta 2 O 5 Particle ratio 500 composed of a molar ratio in the range of 0.5 to 5
The present invention relates to a method for producing a tantalum oxide sol having a thickness of less than angstroms .
【０００６】[0006]
【作用】先ず、本発明のしゅう酸とタンタル酸化物が(H
COO)2／Ta2O5モル比0.5〜5の範囲で構成される粒子径50
0オンク゛ストローム以下の酸化タンタルゾルについて詳記する。
本発明の酸化タンタルゾルは、酸化タンタルの粒子がし
ゅう酸によって強固に結合することにより安定化された
新規なゾルである。本発明のゾルを更に詳述するに当た
り、以下具体例を用いて説明を行う。First, the oxalic acid and tantalum oxide of the present invention are (H
(COO) 2 / Ta 2 O 5 Particle ratio 50 consisting of a molar ratio of 0.5 to 5 50
The tantalum oxide sol of 0 Å or less will be described in detail.
The tantalum oxide sol of the present invention is a novel sol stabilized by the particles of tantalum oxide being firmly bound by oxalic acid. In further detailing the sol of the present invention, a description will be given below using specific examples.
【０００７】（具体例１）酸化タンタル(スタルク社製)
400gを、フッ化水素酸(HF10％)4.2Lに溶解した。この溶
液をアンモニア水(NH315％)2.8Lに60分間で添加した
後、フィルタープレスでろ過、洗浄し水酸化タンタルを
得た。この活性な水酸化タンタルの組成分析を行った結
果、Ta2O5は23％であった。この水酸化タンタル174g
に、(HCOO)2／Ta2O5モル比20となるようにしゅう酸二水
和物(関東化学製試薬)230gを添加し、次いで水を添加し
て全量0.8kgとした。この溶液を攪拌しながら還流条件
下100℃で3時間の反応を行った。反応の進行に伴い、液
は次第に青色を帯び均一なゾル状態を呈した。(Specific example 1) Tantalum oxide (manufactured by Starck)
400 g was dissolved in 4.2 L of hydrofluoric acid (HF 10%). This solution was added to 2.8 L of aqueous ammonia (NH 3 15%) over 60 minutes, and then filtered and washed with a filter press to obtain tantalum hydroxide. As a result of composition analysis of this active tantalum hydroxide, Ta 2 O 5 was 23%. 174g of this tantalum hydroxide
To this was added 230 g of oxalic acid dihydrate (Kanto Chemical Reagent) so that the molar ratio of (HCOO) 2 / Ta 2 O was 5 to 20, and then water was added to bring the total amount to 0.8 kg. The solution was reacted at 100 ° C. for 3 hours under reflux with stirring. As the reaction progressed, the liquid gradually became blue and exhibited a uniform sol state.
【０００８】次いで、反応後に得られたゾルを限外ろ過
モジュール(旭化成工業製SLP-1053型)を使用し、不純物
の除去を行い、本発明のゾルを得た。得られたゾルの組
成分析を行い、その結果を表１に示した。Next, the sol obtained after the reaction was subjected to removal of impurities using an ultrafiltration module (SLP-1053 manufactured by Asahi Kasei Kogyo) to obtain a sol of the present invention. The composition of the obtained sol was analyzed, and the results are shown in Table 1.
【０００９】（比較例１）具体例１で使用した活性な水
酸化タンタルを130℃で乾燥し、水酸化タンタルの乾燥
物(Ta2O587％)を得た。この水酸化タンタル46gを水524g
に分散し、これに(HCOO)2／Ta2O5モル比20となるように
しゅう酸二水和物230gを加えた。次いで、この液を攪拌
を行いながら還流条件下100℃で8時間保持した。この液
は8時間後に於いてもスラリー状であった。このスラリ
ー液を限外ろ過モジュールを使用し不純物の除去を行っ
た後、スラリー液の組成分析を行い、結果を表１に示し
た。Comparative Example 1 The active tantalum hydroxide used in Example 1 was dried at 130 ° C. to obtain a dried product of tantalum hydroxide (Ta 2 O 5 87%). 46 g of this tantalum hydroxide is 524 g of water
And 230 g of oxalic acid dihydrate was added thereto so that the molar ratio of (HCOO) 2 / Ta 2 O was 5 to 20. Next, this liquid was kept at 100 ° C. for 8 hours under reflux while stirring. This liquid was still in a slurry state even after 8 hours. After the impurities were removed from the slurry using an ultrafiltration module, the composition of the slurry was analyzed. The results are shown in Table 1.
【００１０】尚、表１に示した組成分析に於いて、粒子
径の測定は動的散乱光による粒度分布測定装置(PACIFIC
SCIENTIFIC社製NICOMP Model-370型)及び遠心沈降式粒
度分布測定装置(島津製作所製SA-CP2型)により行った。
更に、具体例１で得たゾルを温度30℃で30日間静置した
後、ゾルの状態を観察した結果、この本発明のゾルは30
日後に於いても沈殿を生成せず安定な溶液状を呈してい
た。[0010] In the composition analysis shown in Table 1, the particle size was measured using a particle size distribution analyzer (PACIFIC
The measurement was performed using a NICOMP Model-370 (manufactured by SCIENTIFIC) and a centrifugal sedimentation type particle size distribution analyzer (SA-CP2 manufactured by Shimadzu Corporation).
Furthermore, after the sol obtained in Example 1 was allowed to stand at a temperature of 30 ° C. for 30 days, the state of the sol was observed.
Even after a day, the solution was stable without forming a precipitate.
【００１１】[0011]
【表１】 [Table 1]
【００１２】本発明の酸化タンタルゾルの特徴を新ため
て列挙すれば次の通りである。第一に、本発明のゾルは
均一安定な酸化タンタルの粒子で構成されているため、
長期間の保存が可能であり、しかもこれを各種の材料表
面に塗布、乾燥を行うことにより、均一組成の酸化物膜
を形成することができる。これは、従来の酸化タンタル
等の原料粉末の焼成、粉砕によって得られるタンタル原
料とは格段にその性質等を異にし、酸化タンタルの原料
としてその用途は広範なものとなる。The characteristics of the tantalum oxide sol of the present invention are newly listed as follows. First, since the sol of the present invention is composed of uniformly stable particles of tantalum oxide,
It can be stored for a long period of time, and can be applied to the surface of various materials and dried to form an oxide film having a uniform composition. This is significantly different from the conventional tantalum raw material obtained by baking and pulverizing a raw material powder such as tantalum oxide, and its use as a tantalum oxide raw material is widespread.
【００１３】第二に、本発明のゾルは500オンク゛ストローム以下
の酸化タンタル粒子で構成されるため、各種材料への微
量添加、均一混合性等に優れる。これは湿度センサー素
子や耐酸被覆膜等の用途に適し、性能の優れたものとな
る。また、本発明のゾルはこのような特徴によって、セ
ラミックスのミクロ構造の制御が容易であり、誘電体用
原料等の用途に適するものである。更に、本発明のゾル
は固体酸性の酸性質の制御や耐熱性の向上に優れ触媒等
への利用に優れる。以上のような優れた特徴を有する本
発明のゾルは、上述したような用途だけでなく、例えば
圧電体、半導体、各種オプトエレクトロニクス材料、超
伝導体等を製造するためのタンタル原料として好適であ
る。Secondly, since the sol of the present invention is composed of tantalum oxide particles of 500 Å or less, it is excellent in the addition of a small amount to various materials and uniform mixing. This is suitable for applications such as a humidity sensor element and an acid-resistant coating film, and has excellent performance. Further, the sol of the present invention can easily control the microstructure of ceramics due to such characteristics, and is suitable for use as a raw material for a dielectric. Further, the sol of the present invention is excellent in control of solid acidic acidity and improvement in heat resistance, and is excellent in use as a catalyst and the like. The sol of the present invention having the above-mentioned excellent characteristics is suitable not only for the applications described above but also as a tantalum raw material for producing, for example, piezoelectrics, semiconductors, various optoelectronic materials, superconductors, and the like. .
【００１４】次に、本発明の酸化タンタルゾルの製造方
法について詳記する。本発明のゾルの製造方法は、活性
な水酸化タンタル化合物に、(HCOO)2／Ta2O5モル比5.0
〜30の範囲となるようにしゅう酸を加え、温度90℃以上
で2時間以上の加熱反応を行うことを特徴とするもので
ある。本発明で使用する活性な水酸化タンタル化合物
は、本願出願人が先に出願した公知の方法(特公平4-576
16号、特公平5-2614号)によって得ることができる。即
ち、タンタルまたはタンタルを含有する鉱石あるいは他
のタンタル原料を使用し、これをフッ酸によって溶解し
た後、溶媒抽出によってタンタルを分離し、更にタンタ
ルを水相に剥離した溶液をアンモニア水と反応させて水
酸化物として沈澱させることにより得ることができる。Next, the method for producing the tantalum oxide sol of the present invention will be described in detail. The method for producing a sol according to the present invention comprises adding an active tantalum hydroxide compound to a (HCOO) 2 / Ta 2 O 5 molar ratio of 5.0.
Oxalic acid is added so as to be within the range of 30 to 30, and a heating reaction is carried out at a temperature of 90 ° C. or more for 2 hours or more. The active tantalum hydroxide compound used in the present invention can be produced by a known method previously filed by the present applicant (Japanese Patent Publication No. 4-576).
No. 16, No. 5-2614). That is, using tantalum or ore containing tantalum or other tantalum raw materials, dissolving them with hydrofluoric acid, separating tantalum by solvent extraction, and further reacting the solution obtained by stripping tantalum into an aqueous phase with aqueous ammonia. To precipitate as hydroxide.
【００１５】また別に、このような活性な水酸化タンタ
ル化合物は、別段上述の方法に限ることなく、例えば水
酸化タンタル、酸化タンタル、塩化タンタル等の原料を
使用し、これを鉱酸及び／又はフッ酸で分解溶解した溶
液を、アンモニア水等のアルカリで中和し、生成した水
酸化タンタルを水等で洗浄し不純物を除去して得たもの
を使用してもよい。また、本発明に於いて殊に重要なこ
とは、このようにして得られる活性なタンタルの水酸化
物は、これを乾燥等の手段で水分を除去することなく使
用することにあり、この活性なタンタルの水酸化物を乾
燥し、水分を除去したものを使用すると、後述の本発明
のゾルを得る手段に供してもその収率は低くなり本発明
のゾルは殆ど得られないものとなる。Alternatively, such an active tantalum hydroxide compound is not limited to the above-mentioned method. For example, a raw material such as tantalum hydroxide, tantalum oxide, or tantalum chloride may be used, and this may be used as a mineral acid and / or a mineral acid. A solution obtained by neutralizing a solution decomposed and dissolved with hydrofluoric acid with an alkali such as ammonia water and washing the generated tantalum hydroxide with water or the like to remove impurities may be used. It is particularly important in the present invention that the active tantalum hydroxide thus obtained is used without removing water by means such as drying. When using a tantalum hydroxide that has been dried to remove water, the yield of the sol of the present invention will be low even if it is subjected to means for obtaining the sol of the present invention described later, and the sol of the present invention will hardly be obtained. .
【００１６】本発明は次いで、このようにして得た活性
な水酸化タンタル化合物に、(HCOO)2／Ta2O5モル比5.0
〜30の範囲となるようにしゅう酸を加え、適度な攪拌を
行いながらこれを温度90℃以上で2時間以上の加熱反応
に供する。この場合に、本発明に於いてしゅう酸を使用
することは殊に重要であり、しゅう酸以外の他の有機酸
として、例えば酢酸、マレイン酸、マロン酸等を使用し
ても本発明のゾルを得ることができない。The present invention then provides the active tantalum hydroxide compound thus obtained with a (HCOO) 2 / Ta 2 O 5 molar ratio of 5.0
Oxalic acid is added so as to be in the range of ~ 30, and subjected to a heating reaction at a temperature of 90 ° C or more for 2 hours or more with appropriate stirring. In this case, the use of oxalic acid in the present invention is particularly important, and the sol of the present invention can be used even if acetic acid, maleic acid, malonic acid, or the like is used as an organic acid other than oxalic acid. Can not get.
【００１７】本発明の酸化タンタルは、500オンク゛ストローム以
下の粒子径のゾルとして得られるものであるが、このよ
うな粒子径の調整は、上述の活性な水酸化タンタルの製
造時のタンタル原料を鉱酸、フッ酸で分解した溶液のタ
ンタル濃度の調整、あるいは中和時のアルカリ剤の濃
度、添加速度の調整によって行うことができる。例え
ば、この場合に於けるタンタル濃度、アルカリ剤の濃度
を高くする程、あるいはアルカリ剤の添加速度を高くす
る程、後述の本発明の処理によって得られる酸化タンタ
ルゾルの粒子径は小さいものとなる。また、粒子径の調
整方法は、本発明のゾル製造過程に於いて、反応時の温
度、時間、タンタル濃度及びしゅう酸使用量を調整する
ことによっても行うことができる。The tantalum oxide of the present invention is obtained as a sol having a particle diameter of 500 angstroms or less, and such adjustment of the particle diameter is achieved by converting the tantalum raw material at the time of producing the above-mentioned active tantalum hydroxide into a mineral. The concentration can be adjusted by adjusting the tantalum concentration of the solution decomposed with acid or hydrofluoric acid, or by adjusting the concentration of alkaline agent and the rate of addition during neutralization. For example, in this case, as the concentration of the tantalum and the concentration of the alkali agent are increased, or as the addition speed of the alkali agent is increased, the particle size of the tantalum oxide sol obtained by the treatment of the present invention described later becomes smaller. The particle size can be adjusted by adjusting the temperature, time, tantalum concentration, and oxalic acid usage during the reaction in the sol production process of the present invention.
【００１８】しゅう酸の使用量に関しては、活性な水酸
化タンタル化合物に対して(HCOO)2/Ta2O5モル比5.0〜30
の範囲となるように添加することが重要である。即ち、
しゅう酸の添加量がこの範囲を逸脱し、(HCOO)2/Ta2O5
モル比が5.0を下廻ると、後段の反応を長時間行っても
ゾルが得られず、また反対に(HCOO)2/Ta2O5モル比が30
を上廻ると、反応後に得られるゾルの収率が極めて低下
し工業的でない。尚、このようなモル比の範囲で反応を
行うことにより、本発明のしゅう酸とタンタル酸化物が
(HCOO) 2 /Ta 2 O 5 モル比0.5〜5の範囲で構成される粒子径5
00 オンク゛ストローム 以下の酸化タンタルゾルを得ることができ
る。 With respect to the amount of oxalic acid used, the molar ratio of (HCOO) 2 / Ta 2 O 5 to the active tantalum hydroxide compound is 5.0 to 30.
Is important. That is,
The amount of oxalic acid deviates from this range, and (HCOO) 2 / Ta 2 O 5
If the molar ratio is less than 5.0, no sol can be obtained even if the subsequent reaction is carried out for a long time, and conversely, the (HCOO) 2 / Ta 2 O 5 molar ratio becomes 30.
If it exceeds, the yield of the sol obtained after the reaction is extremely reduced, which is not industrial. It should be noted that the reaction was carried out in such a molar ratio range.
By performing, oxalic acid and tantalum oxide of the present invention
(HCOO) 2 / Ta 2 O 5 Particle ratio 5 composed of molar ratio 0.5 to 5
It is possible to obtain tantalum oxide sol of less than 00 angstroms
You.
【００１９】更に、反応温度と時間に関しては、反応温
度が高くあるいは時間が長い程、得られる酸化タンタル
ゾルの粒子径は小さいものとなるが、本発明に於いては
反応は温度90℃以上で2時間以上の加熱反応を行うこと
が必要である。また、温度が100℃を越える場合には、
反応はオートクレーブ等を使用した水熱処理によって行
えばよい。また、加熱反応後に得られるゾルは、限外ろ
過等の手段により過剰のしゅう酸、あるいはその製造時
に使用した原料の種類によっては、塩素イオン、フッ素
イオン等の不純物を除去する。このような反応を行うこ
とにより、所望する粒子径のしかも安定で均一分散した
微細な本発明の酸化タンタルゾルを得ることができる。Further, with respect to the reaction temperature and time, the higher the reaction temperature or the longer the time, the smaller the particle size of the obtained tantalum oxide sol. However, in the present invention, the reaction is carried out at a temperature of 90 ° C. or more and 2 ° C. It is necessary to carry out the heating reaction for more than an hour. If the temperature exceeds 100 ° C,
The reaction may be performed by hydrothermal treatment using an autoclave or the like. The sol obtained after the heating reaction removes excess oxalic acid by means such as ultrafiltration or impurities such as chlorine ions and fluorine ions depending on the type of raw materials used in the production. By carrying out such a reaction, a fine, tantalum oxide sol of the present invention having a desired particle size and stable and uniformly dispersed can be obtained.
【００２０】[0020]
【実施例】以下に本発明の実施例を掲げ更に説明を行う
が、本発明はこれらに限定されるものではない。また、
％は特に断らない限り全て重量％を示す。The present invention will be further described below with reference to examples of the present invention, but the present invention is not limited to these examples. Also,
All percentages are by weight unless otherwise specified.
【００２１】（実施例１）本願出願人が先に出願した発
明である特公平4-57616号の実施例１に基づき活性な水
酸化タンタル3kgを得た。この水酸化タンタルの組成分
析の結果、Ta2O5は25％であった。この水酸化タンタル1
60gに、(HCOO)2／Ta2O5モル比20となるようにしゅう酸
二水和物(関東化学製試薬)230gを添加し、次いで水を添
加して全量0.8kgとした。この溶液を攪拌しながら還流
条件下100℃で3時間の反応を行った。反応の進行に伴
い、液は次第に青色を帯び、均一なゾル状態を呈してい
た。次いで、反応後に得られたゾルを限外ろ過モジュー
ル(旭化成工業製SLP-1053型)を使用し、不純物の除去を
行い本発明のゾルを得た。得られたゾルの組成分析の結
果、Ta2O510％でpHは1.2であった。また粒子径の測定と
ゾルの状態観察を行い、その結果を表２に示した。Example 1 3 kg of active tantalum hydroxide was obtained based on Example 1 of Japanese Patent Publication No. 4-57616, which was an invention previously filed by the present applicant. As a result of a composition analysis of this tantalum hydroxide, Ta 2 O 5 was 25%. This tantalum hydroxide 1
230 g of oxalic acid dihydrate (Kanto Chemical Reagent) was added to 60 g to give a (HCOO) 2 / Ta 2 O 5 molar ratio of 20, and then water was added to bring the total amount to 0.8 kg. The solution was reacted at 100 ° C. for 3 hours under reflux with stirring. With the progress of the reaction, the liquid gradually turned blue and exhibited a uniform sol state. Next, the sol obtained after the reaction was subjected to removal of impurities using an ultrafiltration module (SLP-1053, manufactured by Asahi Kasei Kogyo Co., Ltd.) to obtain a sol of the present invention. As a result of a composition analysis of the obtained sol, the pH was 1.2 at Ta 2 O 5 10%. The particle size was measured and the state of the sol was observed. The results are shown in Table 2.
【００２２】（比較例２〜４）実施例１で使用した活性
な水酸化タンタルを使用し、実施例１のしゅう酸に代え
て同モル比となるように酢酸(比較例２)、マレイン酸
(比較例３)及びマロン酸(比較例４)を使用し同様に試験
を行った。尚、水酸化タンタルにこれらの酸を添加後、
攪拌を行いながら還流条件下100℃で8時間保持したが、
これらの液は8時間後も殆どスラリー状を呈していた。
また、これらスラリーの粒子径の測定と液の状態観察を
行い、その結果を表２に示した。Comparative Examples 2 to 4 Using the active tantalum hydroxide used in Example 1, acetic acid (Comparative Example 2) and maleic acid were used instead of the oxalic acid of Example 1 so as to have the same molar ratio.
The same test was performed using (Comparative Example 3) and malonic acid (Comparative Example 4). After adding these acids to tantalum hydroxide,
While stirring, it was kept at 100 ° C for 8 hours under reflux conditions,
These liquids were almost in a slurry state even after 8 hours.
Further, the particle diameter of these slurries was measured and the state of the liquid was observed, and the results are shown in Table 2.
【００２３】[0023]
【表２】 [Table 2]
【００２４】（実施例２〜４）酸化タンタル(スタルク社製)
400gをフッ化水素酸(HF10％)4.2Lに溶解した。この溶液
をアンモニア水(NH315％)2.8Lに60分で添加した後、フ
ィルタープレスでろ過、洗浄し、活性な水酸化タンタル
を得た。この水酸化タンタル(Ta2O523％)174gに、(HCO
O)2／Ta2O5モル比5.0(実施例２)となるようにしゅう酸5
8gを添加し、次いで水を添加して全量0.8kgとした。こ
の溶液を攪拌しながら還流条件下100℃で30時間の反応
を行った。また別に、上記モル比に代えて各々モル比が
10(実施例３)及び30(実施例４)について同様に試験を行
った。Examples 2 to 4 Tantalum oxide (manufactured by Starck)
400 g was dissolved in 4.2 L of hydrofluoric acid (HF 10%). This solution was added to 2.8 L of aqueous ammonia (NH 3 15%) over 60 minutes, followed by filtration and washing with a filter press to obtain active tantalum hydroxide. To 174 g of this tantalum hydroxide (Ta 2 O 5 23%), (HCO
O) 2 / Ta 2 O 5 Oxalic acid 5 in a molar ratio of 5.0 (Example 2)
8 g was added followed by water to a total volume of 0.8 kg. The solution was reacted at 100 ° C. for 30 hours under reflux with stirring. Separately, instead of the above molar ratio, each molar ratio is
The same test was performed for 10 (Example 3) and 30 (Example 4).
【００２５】このようにして得たゾルを限外ろ過装置を
使用し、不純物の除去を行い本発明のゾルを得た。得ら
れたゾルの組成分析を行い、併せてその分析結果からゾ
ルの収率を算出した。また別に、得られた本発明のゾル
をTa2O5として10％になるように調整し、これを30℃で3
0日間及び3ケ月間静置し、その状態を観察した。これら
の結果を表３に示した。The sol thus obtained was subjected to removal of impurities using an ultrafiltration apparatus to obtain a sol of the present invention. The composition of the obtained sol was analyzed, and the sol yield was calculated from the analysis result. Separately, the obtained sol of the present invention was adjusted to 10% as Ta 2 O 5 and this was adjusted at 30 ° C. to 3%.
After standing for 0 days and 3 months, the condition was observed. Table 3 shows the results.
【００２６】（比較例５〜６）上記実施例２に於いて、
水酸化タンタルに添加するしゅう酸のモル比が(HCOO)2
／Ta2O5モル比として各々2.5(比較例５)及び35(比較例
６)となるように使用し、同様に試験を行った。得られ
た生成物について同様に組成分析等を行い、その結果を
表３に示した。(Comparative Examples 5 to 6) In Example 2 described above,
The molar ratio of oxalic acid added to tantalum hydroxide is (HCOO) 2
The test was carried out in the same manner with the use of 2.5 (comparative example 5) and 35 (comparative example 6) in terms of / Ta 2 O 5 molar ratio, respectively. A composition analysis and the like were similarly performed on the obtained product, and the results are shown in Table 3.
【００２７】[0027]
【表３】 注) ◎:低粘性安定[Table 3] Note) ◎: Low viscosity stable
【００２８】（実施例５〜７）実施例１で使用した水酸
化タンタル(Ta2O525％)を使用し、この水酸化タンタル1
60gに、(HCOO)2／Ta2O5モル比20となるようにしゅう酸
二水和物230gを添加し、次いで水を添加して全量を0.8k
gとした。この溶液を攪拌しながら還流条件下90℃で5時
間の反応を行った。(実施例５) また別に、加熱反応条件のみを上記の条件と変え、100
℃で6時間(実施例６)及び100℃で8時間(実施例７)の条
件で反応を行った。このようにして得たゾル液を限外ろ
過装置を使用し、不純物の除去を行い本発明のゾルを得
た。得られたゾルをTa2O5として10％になるように調整
し、これを30℃で30日間及び3ケ月間静置した状態の観察
を行い、その結果を表４に示した。(Examples 5 to 7) The tantalum hydroxide (Ta 2 O 5 25%) used in Example 1 was used.
To 60 g, the total amount by adding (HCOO) 2 / Ta 2 O such that the 5 mole ratio of 20 was added oxalic acid dihydrate 230 g, then water 0.8k
g. The solution was reacted at 90 ° C. for 5 hours under reflux with stirring. (Example 5) Separately, only the heating reaction conditions were changed from the above conditions to 100
The reaction was carried out under the conditions of 6 ° C. for 6 hours (Example 6) and 100 ° C. for 8 hours (Example 7). The sol solution thus obtained was subjected to removal of impurities by using an ultrafiltration apparatus to obtain a sol of the present invention. The obtained sol was adjusted to 10% as Ta 2 O 5 , and the sol was allowed to stand at 30 ° C. for 30 days and for 3 months, and the results were shown in Table 4.
【００２９】（比較例７〜８）上記実施例５の条件に於
いて、加熱反応条件のみを変え、80℃で5時間(比較例
７)及び100℃で1時間(比較例８)の条件で同様に反応を
行った。得られた生成物について同様の試験に行い、そ
の結果を表４に示した。(Comparative Examples 7 and 8) The same conditions as in Example 5 were used except that only the heating reaction conditions were changed, and the conditions were 80 ° C. for 5 hours (Comparative Example 7) and 100 ° C. for 1 hour (Comparative Example 8). In the same manner. The obtained product was subjected to a similar test, and the results are shown in Table 4.
【００３０】[0030]
【表４】 注) ◎:低粘性安定、○:高粘性安定[Table 4] Note) ◎: Low viscosity stable, ○: High viscosity stable
【００３１】[0031]
【発明の効果】本発明の酸化タンタルゾルは、均一な酸
化タンタルの粒子で構成され、またしゅう酸が酸化タン
タルに強固に結合することに起因すると推定される粒子
の安定形態をとるため、ゾル液が非常に安定であり、長
期間にわたり保存が可能である。また、本発明のゾルは
500オンク゛ストローム以下の酸化タンタル粒子で構成されるた
め、各種材料への微量添加、均一混合性等に優れる。従
って、本発明の酸化タンタルゾルは、触媒、オプトエレ
クトロニクス材、半導体、圧電体等を製造するためのタ
ンタル原料として好適であり、その用途は広範なもので
ある。The tantalum oxide sol of the present invention is composed of uniform tantalum oxide particles, and takes a stable form of particles presumed to be caused by oxalic acid being strongly bonded to tantalum oxide. Is very stable and can be stored for a long time. Also, the sol of the present invention
Since it is composed of tantalum oxide particles of 500 angstroms or less, it is excellent in small amount addition to various materials, uniform mixing property, and the like. Therefore, the tantalum oxide sol of the present invention is suitable as a tantalum raw material for producing a catalyst, an optoelectronic material, a semiconductor, a piezoelectric body, and the like, and its application is wide.
Claims (2)
2O5モル比0.5〜5の範囲で構成される粒子径500オンク゛ストロー
ム以下の酸化タンタルゾル。(1) Oxalic acid and tantalum oxide are (HCOO) 2 / Ta
A tantalum oxide sol having a particle diameter of 500 angstroms or less and a 2 O 5 molar ratio in the range of 0.5 to 5.
2/Ta2O5モル比5.0〜30の範囲となるようにしゅう酸を加
え、温度90℃以上で2時間以上の加熱反応を行うことを
特徴とするしゅう酸とタンタル酸化物が(HCOO) 2 /Ta 2 O 5
モル比0.5〜5の範囲で構成される粒子径500 オンク゛ストローム 以
下の酸化タンタルゾルの製造方法。2. An active tantalum hydroxide compound, comprising (HCOO)
Oxalic acid and tantalum oxide are characterized by adding oxalic acid so that the molar ratio of 2 / Ta 2 O 5 is in the range of 5.0 to 30 and performing a heating reaction at a temperature of 90 ° C. or more for 2 hours or more (HCOO) 2 / Ta 2 O 5
Particle size comprised within the range of molar ratio 0.5 to 5 500 angstroms or less
The method for producing the tantalum oxide sol below .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6309581A JP2875486B2 (en) | 1994-11-18 | 1994-11-18 | Tantalum oxide sol and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6309581A JP2875486B2 (en) | 1994-11-18 | 1994-11-18 | Tantalum oxide sol and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08143315A JPH08143315A (en) | 1996-06-04 |
| JP2875486B2 true JP2875486B2 (en) | 1999-03-31 |
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| WO2018092573A1 (en) * | 2016-11-16 | 2018-05-24 | 株式会社堀場製作所 | Particle diameter distribution measuring device, particle diameter distribution measuring method, and program for particle diameter distribution measuring device |
| EP3638627A4 (en) * | 2017-06-16 | 2021-01-20 | Essilor International | High refractive index nanoparticles |
| JP7166492B2 (en) | 2020-07-22 | 2022-11-07 | 三井金属鉱業株式会社 | Tantalic acid dispersion and tantalic acid compound |
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