JP2002293544A - Tungsten oxide fine particle and method for producing the same - Google Patents
Tungsten oxide fine particle and method for producing the sameInfo
- Publication number
- JP2002293544A JP2002293544A JP2001100078A JP2001100078A JP2002293544A JP 2002293544 A JP2002293544 A JP 2002293544A JP 2001100078 A JP2001100078 A JP 2001100078A JP 2001100078 A JP2001100078 A JP 2001100078A JP 2002293544 A JP2002293544 A JP 2002293544A
- Authority
- JP
- Japan
- Prior art keywords
- tungsten oxide
- fine
- crystal
- paste
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000010419 fine particle Substances 0.000 title abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000011362 coarse particle Substances 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 238000002441 X-ray diffraction Methods 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 239000003985 ceramic capacitor Substances 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 239000011882 ultra-fine particle Substances 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- 238000004898 kneading Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000010304 firing Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000010943 off-gassing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 229910004829 CaWO4 Inorganic materials 0.000 description 1
- 102100032566 Carbonic anhydrase-related protein 10 Human genes 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- 101000867836 Homo sapiens Carbonic anhydrase-related protein 10 Proteins 0.000 description 1
- XLYOFNOQVPJJNP-PWCQTSIFSA-N Tritiated water Chemical compound [3H]O[3H] XLYOFNOQVPJJNP-PWCQTSIFSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、微粒タングステン
酸化物及びその製造方法に関し、詳しくは，セラミック
コンデンサー構成材料用、エレクトロクロミック素子
用，及びはＴｉＯ２等との共存下での光触媒機能発現用
等に用いられる微粒タングステン酸化物及びその製造方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fine tungsten oxide and a method for producing the same, and more particularly, to a material for forming a ceramic capacitor, for an electrochromic device, and for expressing a photocatalytic function in the presence of TiO 2 or the like. The present invention relates to a fine-grained tungsten oxide used for, for example, and a method for producing the same.
【０００２】[0002]
【従来の技術】タングステン酸化物は、高い誘電率や最
外核原子の離脱に要するネルギーが小さくしかもその必
要エネルギーが少なくて済む事などから、セラミックコ
ンデンサー構成材料用、エレクトロクロミック素子用又
はＴｉＯ２等との共存下での光触媒機能発現用などに多
くの研究が進められている。2. Description of the Related Art Tungsten oxide has a high dielectric constant, a small energy required for detachment of an outermost nuclear atom, and requires only a small amount of energy. Therefore, tungsten oxide is used for a material for forming a ceramic capacitor, an electrochromic element, or TiO 2. Many studies have been conducted for the expression of a photocatalytic function in the coexistence with the like.
【０００３】このような目的の機能発現や工程途中で液
状形態にしてその取り扱いを容易にすることもある。ま
た、超微粒状態での機能性材料との混合・練り込み・分
散など、場合によっては反応させる事も多くある為、タ
ングステン酸化物が水と反応して酸性を示すなどの性質
のあることは良く知られており、強い酸性或いは塩基性
ではない状態での超微粒状態のペーストが望まれてい
る。[0003] In some cases, such a desired function is exhibited or a liquid state is formed during the process to facilitate the handling. In addition, since there are many cases of reaction such as mixing, kneading, and dispersion with a functional material in an ultra-fine particle state, tungsten oxide may have properties such as reacting with water to show acidity. It is well known that ultra-fine pastes in a non-acidic or non-basic state are desired.
【０００４】一方、タングステン酸化物が水と反応して
酸性を示すなどの性質のあることは良く知られており、
いろいろな工程操作に対応可能な、高い固形分濃度のペ
ースト状酸化物或いは弱酸の必要性が求められている。[0004] On the other hand, it is well known that tungsten oxide has properties such as being acidic when reacted with water.
There is a need for a paste-like oxide or a weak acid having a high solid content that can cope with various process operations.
【０００５】[0005]
【発明が解決しようとする課題】従来のタングステン化
合物は、その原料精製工程の途中にあるタングステン酸
化物或いはタングステン酸からのものを利用している。The conventional tungsten compound utilizes a tungsten oxide or a tungstic acid in the course of a raw material refining process.
【０００６】このタングステン酸化物は、ＣａＷＯ４→
Ｈ２ＷＯ４（第１工程）及びこれをアンモニアに溶解後
更に酸分解して、Ｈ２ＷＯ４→（ＮＨ４）２ＷＯ４、次
いで酸分解して（ＮＨ４）２ＷＯ４→Ｈ２ＷＯ４（第２
工程）とすることで製造されている。[0006] This tungsten oxide is obtained by CaWO 4 →
H 2 WO 4 (first step) and after dissolving it in ammonia, further acid-decompose, H 2 WO 4 → (NH 4 ) 2 WO 4 , and then acid-decompose (NH 4 ) 2 WO 4 → H 2 WO 4 (2nd
Process).
【０００７】この場合、上記第１工程では分解不完全な
ＣａＷＯ４の残存により、極めて堅い粒子が残るためこ
のまま焼成しても、また上記第２工程では前記工程の順
にタングステンの精製が行われるのが通常な為、この第
２の工程では同様にＣａＷＯ ４の残存粒子が有り、更に
反応が完全で無い場合も多くこれら工程精製物の利用で
は困難である。In this case, in the first step, the decomposition is incomplete.
CaWO4This leaves extremely hard particles
Even if it is fired as it is, in the above-mentioned second step,
Since tungsten is usually purified in
In step 2, CaWO is also used. 4There are residual particles of
In many cases, the reaction is not complete.
It is difficult.
【０００８】加えて、Ｈ２ＷＯ４はその後の乾燥・焼
成、即ち、高温での分解含む完全なＷＯ３結晶にする工
程において、除去すべきガスの逃げ道が出来難く、微粒
子に成り難い欠点を有している。この点（ＮＨ４）２Ｗ
Ｏ４を煮詰めてパラタングステン酸アンモニウム（以
下、ＡＰＴと呼ぶ）結晶にし、それを空気中で熱分解し
て、ＷＯ３（第４工程）を得る方法は、ＡＰＴ結晶がＦ
ｓｓｓ法（空気透過法粉末粒度測定器：ブレーン測定
器）による粒度表示で４０〜５０μｍか、７０〜８０μ
ｍが通常であり製造上安定に作製可能である。In addition, H 2 WO 4 has a drawback that in the subsequent drying and firing, that is, in the step of forming complete WO 3 crystals including decomposition at a high temperature, it is difficult to form an escape route for gas to be removed, and it is difficult to form fine particles. Have. This point (NH 4 ) 2 W
A method of obtaining WO 3 (fourth step) by boiling O 4 into ammonium paratungstate (hereinafter referred to as APT) crystals and thermally decomposing the same in air is as follows.
40 to 50 μm or 70 to 80 μm in particle size display by the sss method (powder particle size measuring device by air permeation method: Blaine measuring device)
m is normal and can be manufactured stably in production.
【０００９】但し、後者は小さい粒子が多く熱分解した
後ガス抜け性が前記結晶より劣っている為、好ましくな
い。[0009] However, the latter is not preferable because the outgassing property after pyrolysis of many small particles is inferior to that of the crystal.
【００１０】従って４０−５０μｍの結晶（ＡＰＴはア
ンモニア、水分を含むためＢＥＴ測定は不能である）
を、７００〜７５０℃程度、３０分間で焼成するのに、
ボート状に結晶を盛り付けるのが通常で、この場合被表
面積測定による粒度測定値は概ねＢＥＴ（実際には装置
名称ＭＯＮＯＳＯＲＢ、１〜３ｇ程度３００℃で３０分
熱処理後測定）値で３〜５ｍ２／ｇであり、タングステ
ン酸化物の比重を７．３とすれば、粒径０．２〜０．３
μｍの粒子が得られる。Therefore, a crystal of 40 to 50 μm (BET measurement is impossible because APT contains ammonia and water)
Is fired at about 700 to 750 ° C. for 30 minutes,
Usually, crystals are arranged in a boat shape. In this case, the measured particle size by surface area measurement is approximately 3 to 5 m 2 as BET (actually, MONOSORB, 1 to 3 g measured after heat treatment at 300 ° C. for 30 minutes). / G, and if the specific gravity of the tungsten oxide is 7.3, the particle size is 0.2 to 0.3.
μm particles are obtained.
【００１１】しかし、ボート方式によるとガス抜けの均
一性は充分とは言えず、この値はＢＥＴで２〜１０程度
のバラツキがあるのが通常である。However, according to the boat method, the uniformity of outgassing cannot be said to be sufficient, and this value usually varies from about 2 to about 10 in BET.
【００１２】現行技術の延長では、所望の微粒酸化物は
得られ難く、実用上有効な解決が求められている。With the extension of the current technology, it is difficult to obtain a desired fine oxide, and a practically effective solution is required.
【００１３】更に、一方、混合等の工程において、タン
グステン成分が母材より大幅に少量でかつ均一に分散で
きているには、粘性を有しているペースト状の性状が好
ましい。つまり、固形分濃度より高いものなら、どんな
組成にも対応可能で有利である。[0013] On the other hand, in the mixing step or the like, a viscous paste-like property is preferable so that the tungsten component can be dispersed in a much smaller amount and uniformly than the base material. In other words, if the concentration is higher than the solid content, it can be applied to any composition and is advantageous.
【００１４】そこで、本発明の目的は、上記用途などに
実質的に供し得る、微粒タングステン酸化物及びその製
造方法を提供することにある。It is an object of the present invention to provide a fine tungsten oxide and a method for producing the same, which can be substantially used for the above-mentioned applications.
【００１５】[0015]
【課題を解決するための手段】本発明によれば、水分を
含むペースト状のタングステン酸化物であって、強い酸
性下或いは塩基性下に無い状態において、超微粒で、粗
大粒子の見られず、且つ高い粘性を有し、固形分含有量
が３３ｃｃ／ｌ００ｇより高いペースト状である事を特
徴とする微粒タングステン酸化物が得られる。According to the present invention, according to the present invention, a tungsten oxide in the form of a paste containing water, which is ultrafine and does not show coarse particles in a state without strong acidity or basicity. A fine-grained tungsten oxide having a high viscosity and being a paste having a solid content higher than 33 cc / 100 g is obtained.
【００１６】また、本発明によれば、前記微粒タングス
テン酸化物において、前記タングステン酸化物はパラタ
ングステン酸アンモニウム（以下、ＡＰＴと呼ぶ）結晶
を緩やかにアンモニア、水分を除去してＸ線回折による
トリクリニック構造の確認出来る結晶からなることを特
徴とする微粒タングステン酸化物が得られる。Further, according to the present invention, in the fine tungsten oxide, the tungsten oxide slowly removes ammonium and water from an ammonium paratungstate (hereinafter referred to as APT) crystal to form a tritium oxide by X-ray diffraction. A fine-grained tungsten oxide characterized by being composed of a crystal whose clinic structure can be confirmed is obtained.
【００１７】また、本発明によれば、アルミナ製乳鉢に
タングステン酸化物を入れ、水を乳棒が過負荷によって
作動しなくならない程度に順次霧状に僅かのみ噴霧させ
ながら、粉砕・練り込みだけを、当該タングステン酸化
物が乳棒を被処理物から剥がした際、糸状の粘着性を描
くように１０時間以上行い、固形分濃度が３３ｃｃ／ｌ
００ｇより高い微粒タングステン酸化物のペース卜を得
ることを特徴とする微粒タングステン酸化物の製造方法
が得られる。Further, according to the present invention, tungsten oxide is put into an alumina mortar, and water is sprayed only slightly in order to prevent the pestle from operating due to overload. When the tungsten oxide peels off the pestle from the object to be processed, it is carried out for 10 hours or more so as to draw a thread-like adhesive, and the solid content concentration is 33 cc / l.
A method for producing a fine tungsten oxide, characterized by obtaining a paste of fine tungsten oxide of higher than 00 g, is obtained.
【００１８】ここで、本発明において、粉砕及び練り込
みは、２０時間以上が望ましい。Here, in the present invention, the pulverization and kneading are preferably performed for 20 hours or more.
【００１９】また、本発明によれば、前記微粒タングス
テン酸化物の製造方法において、前記タングステン酸化
物は、ＡＰＴ結晶を緩やかにアンモニア、水分を除去し
てＸ線回折によるトリクリニック構造の確認出来る結晶
から作製されている事を特徴とする微粒タングステン酸
化物の製造方法が得られる。Further, according to the present invention, in the method for producing a fine tungsten oxide, the tungsten oxide is a crystal whose triclinic structure can be confirmed by X-ray diffraction by slowly removing ammonia and water from the APT crystal. The method for producing fine tungsten oxide is characterized in that the method is manufactured from.
【００２０】[0020]
【発明の実施の形態】以下、本発明の実施の形態につい
て説明する。Embodiments of the present invention will be described below.
【００２１】まず、本発明の実施の形態による微粒タン
グステン酸化物の製造方法について説明する。First, a method for producing fine tungsten oxide according to the embodiment of the present invention will be described.
【００２２】ＡＰＴ結晶は多くの水分とアンモニウム分
を含んでいるため、回転式焼成炉によればガス抜けは極
めてスムーズで均一に成し得ると仮定し、実際に先述に
対し、示した条件で焼成した処、ＢＥＴはほぼ３〜５ｍ
２／ｇで安定していた。（微細な酸化物を得るのが眼目
であり、寧ろ粗い粒子と言える）。Since the APT crystal contains a large amount of water and ammonium, it is assumed that outgassing can be performed extremely smoothly and uniformly by the rotary firing furnace. After firing, BET is almost 3-5m
It was stable at 2 / g. (It is an eye to obtain a fine oxide, and it can be said that it is rather a coarse particle).
【００２３】また、ＸＲＤ検証によれば、トリクリニッ
クの結晶性を有していた。次いでこの結晶を乳鉢で粉砕
・練りこみをする際、加える水分は過剰にならぬように
噴霧状にして、乳棒の動作負荷が過度にならないように
し、更に結晶の焼成により得られるタングステン酸化物
の粒度が安定したものが良い事が判明した。According to XRD verification, the crystal had triclinic crystallinity. Then, when this crystal is crushed and kneaded in a mortar, the water to be added is sprayed so as not to be excessive, so that the operation load of the pestle is not excessive, and the tungsten oxide obtained by firing the crystal is further It turned out that the one with stable particle size was good.
【００２４】ここで、ＢＥＴが３ｍ２／ｇ品を試料Ａ，
５ｍ２／ｇ品を試料Ｂ、１０ｍ２／ｇ品を試料Ｃとす
る。Here, a sample having a BET of 3 m 2 / g was sample A,
The sample of 5 m 2 / g is designated as sample B and the sample of 10 m 2 / g is designated as sample C.
【００２５】噴霧状に水分補給しつつ、乳鉢で粉砕・練
りこみを２０時間行った場合と、４０時間行った場合に
ついて比較する。出来たペーストは１２５℃で２４時間
徐々に真空乾燥した後、ＢＥＴ測定をした。A comparison is made between the case where crushing and kneading are performed in a mortar for 20 hours and the case where crushing and kneading are performed for 40 hours while supplying water in a spray form. The resulting paste was gradually dried under vacuum at 125 ° C. for 24 hours and then subjected to BET measurement.
【００２６】試料Ａは７６ｍ２／ｇ、試料Ｂは８２ｍ２
／ｇであり、試料Ｃは２２ｍ２／ｇの結果となった。[0026] Sample A 76m 2 / g, sample B is 82m 2
/ G, and the result of Sample C was 22 m 2 / g.
【００２７】それぞれを粒度に換算すると、０．０１１
μｍ、０．０１０μｍ、０．０３８μｍであった。試料
Ｃには顕微鏡観察によれば、粗大粒子が時々見出せた。
ここで、試料Ｃがより微細にならないのは、焼成時不安
定な状態で得られたタングステン酸化物であるとガス抜
け不均一や急な部分焼成による粉砕し難い微粒酸化物が
多く存在している為であると考えられる。事実、再現実
験によっても、概ね同じような結果が得られた。When each of them is converted to particle size, 0.011
μm, 0.010 μm, and 0.038 μm. Microscopic observation sometimes revealed coarse particles in Sample C.
Here, the reason why the sample C does not become finer is that if the tungsten oxide is obtained in an unstable state at the time of firing, there are a lot of fine oxides which are difficult to pulverize due to uneven gas release or rapid partial firing. It is considered that there is. In fact, reproducible experiments yielded generally similar results.
【００２８】一方、５〜７時間の処理では、ＢＥＴが安
定せず、酸化物の粒子が均一に処理されてない事と一致
すると考えられる。そして、１０時間以上粉砕・練り込
み概ねＢＥＴが安定した。On the other hand, the treatment for 5 to 7 hours is considered to be consistent with the fact that the BET is not stable and the oxide particles are not uniformly treated. Then, the BET was crushed and kneaded for 10 hours or more, and the BET was generally stable.
【００２９】従って、良い微粒酸化物を得る条件として
は、練りこみは１０時間以上、望ましくは２０時間以上
が良いことが得られた。Therefore, as a condition for obtaining good fine-grained oxides, it was found that kneading was good for 10 hours or more, preferably 20 hours or more.
【００３０】乳棒に付着した酸化物は当然粗いが硬質ゴ
ム等を乳棒に接して回転毎に掻き落とせばほぼ粗大粒は
見出せず、数ｋｇ程度の処理（薄膜で用いるのが通常
で、数ｋｇは工業的材料の量として充分な場合が多いと
言える）には寧ろ最適で、実用上有効である。またこの
時、水分は乳棒の駆動に対し過負荷にならない程度に噴
霧状に添加するのが良く、初めから設定量の水を添加し
ても酸化物が均一に分散、粉砕されない為たちまちモー
タ過負荷スイッチが作動し運転停止するか、乳鉢に乳棒
が強く押し付けられるだけで（こうすると乳鉢からのＡ
ｌ２Ｏ３汚染考えられる）意味が無い。繰り返しの実験
により、凡そ３３〜５０ｃｃ／１００ｇは可能である事
が得られた。The oxides adhering to the pestle are coarse, but if hard rubber or the like is brought into contact with the pestle and scraped off at every rotation, almost no coarse particles can be found, and a treatment of about several kg (usually used as a thin film, several kg Is often sufficient as the amount of industrial materials), but rather is optimal and practically effective. Also, at this time, the water is preferably added in a spray form so as not to overload the driving of the pestle, and even if a predetermined amount of water is added from the beginning, the oxides are not uniformly dispersed and pulverized, so that the motor is immediately overloaded. The load switch is activated and shuts down, or the pestle is simply pressed against the mortar (this causes the A
l 2 O 3 contamination possible) Not meaningful. Repeated experiments have shown that approximately 33-50 cc / 100 g is possible.
【００３１】先述の粒度のＡＰＴからの酸化物だけの嵩
は凡そ３０〜４０ｃｃ／１００ｇであった。The bulk of the oxide alone from APT having the above-mentioned particle size was about 30 to 40 cc / 100 g.
【００３２】得られた微粒酸化物ペーストにおける固形
分は、１０時間品が３３ｃｃ／１００ｇで、２０時間品
が４１ｃｃ／１００ｇであった。The solid content of the obtained fine oxide paste was 33 cc / 100 g for a 10-hour product and 41 cc / 100 g for a 20-hour product.
【００３３】更なる微細な酸化物を得るには、先述に示
した通りパラタングステンン酸アンモニウム結晶の工程
を経ていることは同様であるが、この後更に弱酸（１〜
２ＮのＨＣ１）のより先の結晶を乳化し、そのスラリー
を酸分解し焼成すると得られたタングステン酸化物は、
粒径を制御したパラタングステン酸アンモニウムから直
接タングステン酸化物にするよりも遥かに微細な酸化物
となる。実際に前記同様の検査によれば、ＢＥＴ８７ｍ
２／ｇであった。In order to obtain a finer oxide, it is the same as that through the step of crystallizing ammonium paratungstate as described above.
Tungsten oxide obtained by emulsifying the earlier crystal of 2N HC1), acid-decomposing the slurry and calcining,
It is a much finer oxide than directly converting ammonium paratungstate with a controlled particle size to tungsten oxide. According to the same inspection as above, BET 87m
2 / g.
【００３４】しかし、この工程は工程が増えるとともに
大量のアンモニウムとＨＣｌが直接反応し固体ＮＨ４Ｃ
ｌが発生しその処理も考慮しなければならず、実用上高
価な上回収率の低下もあり有効な方法とは言えない。However, in this step, as the number of steps increases, a large amount of ammonium and HCl react directly to form solid NH 4 C.
1 is generated and its treatment must be taken into consideration, which is not practically expensive due to the practically expensive and reduced recovery rate.
【００３５】因みに、粉砕前の結晶検証で、不明ピーク
の多いものや、別の酸化物結晶系の混ざった物は、出来
た微粒酸化物のＢＥＴは粗い結果であった。By the way, in the verification of the crystals before the pulverization, those having many unknown peaks and those mixed with another oxide crystal system were found to have a coarse BET of the resulting fine oxide.
【００３６】これは、部分的に硬く・粗い粒子や酸化物
性状が得られていない事が理由と思われる。This is presumably because partially hard and coarse particles or oxide properties were not obtained.
【００３７】本発明の実施の形態による微粒タングステ
ン酸化物の製造の具体例について説明する。A specific example of the production of the fine tungsten oxide according to the embodiment of the present invention will be described.
【００３８】（例）回転焼成炉の条件として、耐熱ステ
ンレス製チューブ（直径２５０ｍｍ×５．０００ｍｍ
Ｌ、内側に掻き揚げ用等のフイン、ビレット等敷設無
し）を大気中で３〜６回／分、チューブ角度４〜６度で
回転させ、ＡＰＴ結晶を６〜８ｋｇ／Ｈｒ．で処理し
た。(Example) As a condition of the rotary firing furnace, a heat-resistant stainless steel tube (diameter 250 mm × 5.000 mm) was used.
L, no fins, billets, etc. for scraping inside are laid in the atmosphere at 3 to 6 times / minute at a tube angle of 4 to 6 degrees, and the APT crystal is rotated at 6 to 8 kg / hr. Processed.
【００３９】得られたタングステン酸化物の結晶系につ
いて調べた。ＡＰＴを焼成して得られるタングステン酸
化物をＸＲＤ検査すると、ＪＣＰＤＳの２０−１３２
３、三斜晶系が得られた。焼成条件によっては、偽斜方
晶系に似てくる。The crystal system of the obtained tungsten oxide was examined. An XRD inspection of the tungsten oxide obtained by sintering the APT revealed that JCPDS 20-132
3, a triclinic system was obtained. Depending on the sintering conditions, it resembles a pseudo-orthorhombic system.
【００４０】このようにして得られた本発明の実施の形
態によるタングステン酸化物は、実際サブμｍ若しくは
サブμｍ以下であり、超微粒と言え、粗大粒子も見出せ
ない。酸化物表面が極めて僅かに水分と反応しペースト
自体は弱酸性を呈するがそれは小さくその後の処理及び
その内容を左右しない。The tungsten oxide according to the embodiment of the present invention thus obtained is actually sub-μm or sub-μm or less, and can be said to be ultrafine and no coarse particles can be found. The oxide surface reacts very slightly with moisture and the paste itself is slightly acidic, but it is small and does not affect the subsequent processing and its contents.
【００４１】加えて、他の物質との混合・分散・混練に
おいて水分が最小になっており且つ、粘性も有している
ことから粉末特有の飛散及びそれによる収支を危惧する
必要も無く都合が良い。従来のタングステン酸化物では
得られなかった程の微細な酸化物である上、そのペース
トも取り扱いが容易で、セラミックコンデンサー構成材
料用、エレクトロクロミック素子用，及びはＴｉＯ２等
との共存下での光触媒機能発現用に有効と言える。In addition, since the water content is minimized in mixing, dispersing, and kneading with other substances and the material has viscosity, there is no need to worry about scattering peculiar to powder and the resulting balance, which is convenient. good. It is a fine oxide that cannot be obtained with conventional tungsten oxide, and its paste is easy to handle. It is used for ceramic capacitor constituent materials, for electrochromic devices, and in the presence of TiO 2 and the like. It can be said to be effective for photocatalytic function expression.
【００４２】ところで、近年できたセラミックコンデン
サにＰｂ（Ｃｏ１／２Ｗ１／２）Ｏ ３なるペロブスカイ
ト系結晶の利用が進んでいる。これら複合材料の生成に
おいても、本発明による微粒酸化物は混合・混練性も良
く、強い酸性も塩基性も有しない事から、工業的利用に
対して実に都合が良い。この場合、練りこみ工程がある
為極めて有効と言える。By the way, ceramic condensate made recently
Pb (Co1/2W1/2) O 3Naru perovsk
The use of G-based crystals is increasing. For the production of these composite materials
However, the fine oxide according to the present invention has good mixing and kneading properties.
It has no strong acidity or basicity and is suitable for industrial use.
This is really convenient. In this case, there is a kneading step
This is extremely effective.
【００４３】一般にも、強い酸性或いは塩基性を有しな
いため、（元来タングステン等と特別な化学反応起こさ
ない物質を除けば）混合・分散・混練において相手とな
る物質との危惧される反応性（時として爆発など）や接
触する装置・容器との反応性も殆ど不安無く良い。In general, since it does not have strong acidity or basicity, except for a substance that does not cause a special chemical reaction with tungsten or the like, there is a fear of reactivity with a partner substance in mixing, dispersion, and kneading. (Sometimes explosion, etc.) and reactivity with contacting equipment / containers are good with almost no worries.
【００４４】[0044]
【発明の効果】以上説明したように、本発明によれば、
タングステン酸化物のペーストの酸化物表面が極めて僅
かに水分と反応しペースト自体は弱酸性を呈するがそれ
は小さくその後の処理及びその内容を左右せず、加え
て、他の物質との混合・分散・混錬において水分が最小
になっており且つ、粘性も有していることから粉末特有
の飛散及びそれによる収支を危惧する必要も無く、都合
が良い微粒タングステン酸化物とその製造方法が得られ
る。As described above, according to the present invention,
The oxide surface of the tungsten oxide paste reacts very slightly with moisture, and the paste itself exhibits a weak acidity, but it is small and does not affect the subsequent processing and its contents. In addition, mixing and dispersion with other substances Since the water content is minimized in the kneading and the viscosity is high, there is no need to worry about the scattering and the balance due to the powder, and a convenient fine tungsten oxide and a method for producing the same can be obtained.
【００４５】また、本発明によれば、微細な酸化物であ
る上、そのペーストも取り扱いが容易である微粒タング
ステン酸化物とその製造方法が得られる。Further, according to the present invention, a fine tungsten oxide which is a fine oxide and whose paste can be easily handled, and a method for producing the same can be obtained.
【００４６】さらに、本発明によれば、セラミックコン
デンサにＰｂ（Ｃｏ１／２Ｗ１／２）Ｏ３なるペロブス
カイト系結晶等の複合材料の生成においても、微粒酸化
物は混合・混練性も良く、強い酸性も塩基性も有しない
事から、工業的利用に対して実に都合が良く、また、こ
の複合材料の場合、練りこみ工程がある為極めて有効で
ある微粒タングステン酸化物とその製造方法とを提供す
ることができる。Further, according to the present invention, the fine oxides have good mixing and kneading properties even in the formation of a composite material such as a perovskite crystal of Pb (Co 1/2 W 1/2 ) O 3 in a ceramic capacitor. Since it has neither strong acidity nor basicity, it is very convenient for industrial use, and in the case of this composite material, there is a kneading step, which is very effective because of the fine tungsten oxide and its production method. Can be provided.
【００４７】さらに、本発明の微粒タングステン酸化物
は、強い酸性或いは塩基性を有しないため、混合・分散
・混練において、相手となる物質との危惧される反応性
や接触する装置・容器との反応性も殆ど不安無い微粒タ
ングステン酸化物とその製造方法とを提供することがで
きる。Further, since the fine tungsten oxide of the present invention does not have strong acidity or basicity, in mixing, dispersing and kneading, there is a possibility of reacting with a partner substance or reacting with a contacting device / container. It is possible to provide a fine-grained tungsten oxide which has almost no concern about its properties and a method for producing the same.
フロントページの続き Ｆターム(参考） 4G048 AA02 AB02 AC02 AC08 AD03 AD06 AE07 4G069 AA02 AA03 AA12 BA04B BA48A BA48C BC60A BC60B BC60C CA01 CA07 CA10 EA01X EA01Y EC22X EC22Y FB06 5E001 AE00 Continued on the front page F term (reference) 4G048 AA02 AB02 AC02 AC08 AD03 AD06 AE07 4G069 AA02 AA03 AA12 BA04B BA48A BA48C BC60A BC60B BC60C CA01 CA07 CA10 EA01X EA01Y EC22X EC22Y FB06 5E001 AE00
Claims (4)
化物であって、強い酸性下或いは塩基性下に無い状態に
おいて、超微粒で、粗大粒子の見られず、且つ高い粘性
を有し、固形分含有量が３３ｃｃ／ｌ００ｇより高いペ
ースト状である事を特徴とする微粒タングステン酸化
物。1. A paste-like tungsten oxide containing water, which is ultrafine, has no coarse particles, has high viscosity, and has a high solid content in a state without strong acidity or basicity. Fine-grained tungsten oxide having a paste content higher than 33 cc / 100 g.
において、前記タングステン酸化物はパラタングステン
酸アンモニウム結晶を緩やかにアンモニア、水分を除去
してＸ線回折によるトリクリニック構造の確認出来る結
晶からなることを特徴とする微粒タングステン酸化物。2. The fine-grained tungsten oxide according to claim 1, wherein said tungsten oxide is a crystal in which a triclinic structure can be confirmed by X-ray diffraction by slowly removing ammonia and water from an ammonium paratungstate crystal. A fine-grained tungsten oxide characterized by the following.
入れ、水を乳棒が過負荷によって作動しなくならない程
度に順次霧状に僅かのみ噴霧させながら、粉砕・練り込
みだけを、当該タングステン酸化物が乳棒を被処理物か
ら剥がした際、糸状の粘着性を描くように１０時間以上
行い、固形分濃度が３３ｃｃ／ｌ００ｇより高い微粒タ
ングステン酸化物のペース卜を得ることを特徴とする微
粒タングステン酸化物の製造方法。3. Tungsten oxide is put into an alumina mortar, and water is sprayed only slightly in order to prevent the pestle from operating due to overload. When the pestle is peeled off from the object to be treated, the paste is applied for at least 10 hours so as to draw a thread-like tackiness, and a paste of fine tungsten oxide having a solid content higher than 33 cc / 100 g is obtained. Manufacturing method.
の製造方法において、前記タングステン酸化物はパラタ
ングステン酸アンモニウム（以下ＡＰＴ）結晶を緩やか
にアンモニア、水分を除去してＸ線回折によるトリクリ
ニック構造の確認出来る結晶から作製されている事を特
徴とする微粒タングステン酸化物の製造方法。4. The method for producing fine tungsten oxide according to claim 3, wherein said tungsten oxide has a triclinic structure by X-ray diffraction by slowly removing ammonia and water from an ammonium paratungstate (APT) crystal. A method for producing fine-grained tungsten oxide, characterized by being made from a crystal that can be confirmed.
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| WO2009096177A1 (en) | 2008-01-28 | 2009-08-06 | Kabushiki Kaisha Toshiba | Visible light response-type photocatalyst powder, visible light response-type photocatalyst material using the visible light response-type photocatalyst powder, photocatalyst coating material, and photocatalyst product |
| US8173573B2 (en) | 2008-01-28 | 2012-05-08 | Kabushiki Kaisha Toshiba | Visible light response-type photocatalyst powder, visible light response-type photocatalyst material using the visible light response-type photocatalyst powder, photocatalyst coating material, and photocatalyst product |
| US8702858B2 (en) | 2008-03-04 | 2014-04-22 | Kabushiki Kaisha Toshiba | Aqueous dispersion liquid and coating material, film, and product using the same |
| US8273169B2 (en) | 2008-03-04 | 2012-09-25 | Kabushiki Kaisha Toshiba | Aqueous dispersion liquid and coating material, film, and product using the same |
| US9321034B2 (en) | 2008-03-04 | 2016-04-26 | Kabushiki Kaisha Toshiba | Aqueous dispersion liquid and coating material, film, and product using the same |
| US9457377B2 (en) | 2008-03-04 | 2016-10-04 | Kabushiki Kaisha Toshiba | Hydrophilic member and hydrophilic product using the same |
| JP2014098542A (en) * | 2008-09-16 | 2014-05-29 | Toshiba Corp | Refrigerator |
| WO2010032445A1 (en) | 2008-09-16 | 2010-03-25 | 株式会社 東芝 | Hydrophilic films and components and structures using same |
| JP6103414B1 (en) * | 2016-08-12 | 2017-03-29 | 株式会社アンディーン | Cockroach repellent paint |
| JP2018024623A (en) * | 2016-08-12 | 2018-02-15 | 株式会社アンディーン | Cockroach repellent coating material |
| WO2018029732A1 (en) * | 2016-08-12 | 2018-02-15 | 株式会社アンディーン | Cockroach-repellent coating material |
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