JP2649435B2 - Production method of metal colloid - Google Patents
Production method of metal colloidInfo
- Publication number
- JP2649435B2 JP2649435B2 JP2240568A JP24056890A JP2649435B2 JP 2649435 B2 JP2649435 B2 JP 2649435B2 JP 2240568 A JP2240568 A JP 2240568A JP 24056890 A JP24056890 A JP 24056890A JP 2649435 B2 JP2649435 B2 JP 2649435B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- colloid
- ascorbic acid
- phosphate
- salt
- 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.)
- Expired - Fee Related
Links
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、金属コロイドの製造法に関し、更に詳細に
は、広いpH範囲で凝集を生じず長期間安定であり、飲料
等の食品、栄養薬、輪液等の医薬品、化粧料などの分野
で有用な金属コロイドの製造法に関する。Description: FIELD OF THE INVENTION The present invention relates to a method for producing a metal colloid, and more specifically, to a method for producing food, nutrition such as beverages, which is stable for a long period of time without causing aggregation in a wide pH range. The present invention relates to a method for producing a metal colloid useful in the fields of drugs, ring fluids and other pharmaceuticals, cosmetics, and the like.
［従来の技術］ 近年、金属又は金属塩の微粒子を含有するコロイド、
無機粉末への関心が高まっている。例えば、金属又は金
属塩の粒子径が小さくなると、比表面積や粒子全体に対
する表面の原子又は分子の割合が増加するため、触媒活
性が大幅に増加し、また、光の散乱が小さくなるため、
樹脂中に分散させると光の透過量が増した透明なフィル
ムやシートを得ることができる。さらに、磁気特性が大
きく変化するなど、新しい機能が現れることも知られて
いる。[Related Art] In recent years, colloids containing fine particles of metal or metal salt,
Interest in inorganic powders is growing. For example, when the particle size of the metal or metal salt is reduced, the specific surface area or the ratio of surface atoms or molecules to the entire particle is increased, so that the catalytic activity is significantly increased, and light scattering is reduced.
When dispersed in a resin, a transparent film or sheet having an increased light transmission amount can be obtained. It is also known that new functions appear, such as a large change in magnetic characteristics.
従来、これらの金属塩、金属水酸化物又は金属酸化物
の微粒子を含有するコロイドは、例えば粉砕法、ガス中
蒸発法、活性水素−溶融金属反応法、スパッタリング
法、流動油面上真空蒸着法、通電加熱蒸発法、ハイブリ
ッド・プラズマ法等のビルドアップ法などの物理的方
法、あるいは沈澱法、加水分解法、噴霧法、酸化還元
法、凍結乾燥法、レーザー合成法、火花放電法などの化
学的方法により製造されていた。Conventionally, these metal salts, metal hydroxides or colloids containing fine particles of metal oxides are, for example, pulverization method, gas evaporation method, active hydrogen-molten metal reaction method, sputtering method, and vacuum evaporation method on fluid oil surface. , Physical methods such as build-up method such as electric heating evaporation method and hybrid plasma method, or chemical methods such as precipitation method, hydrolysis method, spray method, redox method, freeze drying method, laser synthesis method, spark discharge method, etc. Was manufactured by a standard method.
［発明が解決しようとする課題］ しかしながら、これらの製造法は複雑な装置や操作が
必要であったり、金属塩、金属水酸化物又は金属酸化物
の粒子径が十分小さいものが得られない、あるいはこれ
らの微粒子を分散させたコロイド溶液の安定性が悪いな
どの問題があった。[Problems to be Solved by the Invention] However, these production methods require complicated devices and operations, or do not provide metal salts, metal hydroxides or metal oxides having sufficiently small particle diameters. Alternatively, there has been a problem that the stability of the colloidal solution in which these fine particles are dispersed is poor.
このことは、食品、香化粧品、医薬品等に応用される
金属塩、金属水酸化物又は金属酸化物のコロイドについ
ては特に重要な問題であった。すなわち、食品、香化粧
品、医薬品等のように金属塩等を経口などにより生体内
に吸収させたり、皮膚や毛髪などに付着させたりする製
品においては、金属塩等をコロイド化することにより人
体への吸収能を高めたり、皮膚や毛髪への付着性を高め
ている。しかしながら、従来の金属コロイドの製造法は
上記のような問題点を有しているため、かかる分野への
適用において充分満足し得る方法ではなかった。This was a particularly important problem for metal salts, metal hydroxides or metal oxide colloids applied to foods, fragrance cosmetics, pharmaceuticals, and the like. That is, in products such as foods, fragrance cosmetics, and pharmaceuticals that absorb metal salts or the like into the body orally or adhere to the skin or hair, etc., the metal salts are colloidally converted into the human body. It enhances the absorption capacity of the skin and the adhesion to the skin and hair. However, since the conventional method for producing a metal colloid has the above-described problems, it has not been a method that is sufficiently satisfactory for application to such fields.
このため、安定なコロイド溶液が得られ、しかも複雑
な装置や操作を必要としない金属コロイドの製造法の開
発が望まれていた。Therefore, it has been desired to develop a method for producing a metal colloid that can obtain a stable colloid solution and does not require complicated equipment or operation.
［課題を解決するための手段］ かかる実情において、本発明者らは鋭意研究を行なっ
た結果、特定の金属塩等とアスコルビン酸リン酸エステ
ルとを水性媒体中で混合することにより、金属コロイド
を簡易に製造することができ、しかも得られた金属コロ
イドは長期間安定であることを見出し、本発明を完成し
た。[Means for Solving the Problems] Under such circumstances, the present inventors have conducted intensive studies, and as a result, by mixing a specific metal salt or the like with an ascorbic acid phosphate in an aqueous medium, the metal colloid was formed. It has been found that the metal colloid can be easily produced, and that the obtained metal colloid is stable for a long period of time.
すなわち、本発明は、金属塩、金属水酸化物及び金属
酸化物から選ばれる少なくとも一種と、アスコルビン酸
リン酸エステル又はその塩から選ばれる少なくとも一種
とを水性媒体中で混合することを特徴とする金属コロイ
ドの製造法を提供するものである。That is, the present invention is characterized in that at least one selected from metal salts, metal hydroxides and metal oxides, and at least one selected from ascorbic acid phosphate or a salt thereof are mixed in an aqueous medium. A method for producing a metal colloid is provided.
本発明で用いられる金属塩、金属水酸化物及び金属酸
化物（以下、「金属塩等」という）としては、例えばM
g、Sr等のアルカリ土類金属、Ag、Au、Fe、Zn、Ti、C
r、Mn、Cu、Ni、Co、Bi等の遷移金属などの金属の塩化
物、硫酸化物、硝酸化物等の塩、水酸化物及び酸化物が
挙げられる。これらのうち、特にFe、Zn、Ti、Al、Sn、
Cu、Ni、Si、Mg、Ba、Sr、Ｖ、Mn、Mo、Ag、Nb、Zr、S
b、In又はランタノイドの塩、水酸化物又は酸化物が好
ましい。これらの金属塩等は、単独で、又は二種以上を
組合わせて用いることができる。Examples of the metal salt, metal hydroxide and metal oxide (hereinafter, referred to as “metal salt or the like”) used in the present invention include M
g, alkaline earth metals such as Sr, Ag, Au, Fe, Zn, Ti, C
Examples include salts, hydroxides and oxides of metals such as transition metals such as r, Mn, Cu, Ni, Co, and Bi, such as chlorides, sulfates, and nitrates. Among these, in particular, Fe, Zn, Ti, Al, Sn,
Cu, Ni, Si, Mg, Ba, Sr, V, Mn, Mo, Ag, Nb, Zr, S
b, In or lanthanoid salts, hydroxides or oxides are preferred. These metal salts and the like can be used alone or in combination of two or more.
また、本発明で用いられるアスコルビン酸リン酸エス
テル又はその塩としては、アスコルビン酸−２−リン
酸、アスコルビン酸−３−リン酸、アスコルビン酸−５
−リン酸、アスコルビン酸−６−リン酸、アスコルビン
酸−２−ピロリン酸、アスコルビン酸−３−ピロリン
酸、ビス（アスコルビン酸−2,2′）リン酸、ビス（ア
スコルビン酸−3,3′）リン酸等及びこれらのアルカリ
金属、アルカリ土類金属、アミン等の塩が挙げられる。
これらのうち、アスコルビン酸−２−リン酸又はアスコ
ルビン酸−３−リン酸が特に好ましい。これらは単独
で、又は二種以上を組合わせて用いることができる。The ascorbic acid phosphate or a salt thereof used in the present invention includes ascorbic acid-2-phosphate, ascorbic acid-3-phosphate, and ascorbic acid-5.
-Phosphoric acid, ascorbic acid-6-phosphate, ascorbic acid-2-pyrophosphate, ascorbic acid-3-pyrophosphate, bis (ascorbic acid-2,2 ') phosphoric acid, bis (ascorbic acid-3,3') ) Phosphoric acid and the like and salts thereof such as alkali metals, alkaline earth metals and amines.
Of these, ascorbic acid-2-phosphate or ascorbic acid-3-phosphate is particularly preferred. These can be used alone or in combination of two or more.
かかるアスコルビン酸リン酸エステル又はその塩は、
公知の方法、例えばChem.Pharm.Bull.,17,381−393（19
69）、特開昭52−136160号公報、日本農芸化学会昭和62
年度大会講演要旨集4L−１第696頁、特開昭63−214190
号公報、特開平２−42996号公報等に記載されている方
法により、容易に製造することができる。Such ascorbic acid phosphate or a salt thereof,
Known methods, for example, Chem. Pharm. Bull., 17 , 381-393 (19
69), JP-A-52-136160, Japanese Society of Agricultural Chemistry Showa 62
Annual Meeting Abstracts 4L-1 696, JP-A-63-214190
And JP-A-2-42996 can be easily manufactured.
本発明において用いられる水性媒体としては、水が特
に好ましく、反応を妨害しない範囲でアルコール等の有
機溶媒を混合して用いることもできる。As the aqueous medium used in the present invention, water is particularly preferred, and an organic solvent such as an alcohol can be mixed and used as long as the reaction is not hindered.
金属塩等とアスコルビン酸リン酸エステル又はその塩
との混合方法は特に制限されず、例えばアスコルビン酸
リン酸エステル又はその塩の水溶液に金属塩等を混合し
てもよいし、金属塩等の水溶液にアスコルビン酸リン酸
エステル又はその塩を混合してもよい。また、金属塩等
の水溶液とアスコルビン酸リン酸エステル又はその塩の
水溶液を混合してもよく、更に、これらを固定のまま混
合した後に水を加えて溶解させてもよい。The method of mixing the metal salt or the like with the ascorbic acid phosphate or a salt thereof is not particularly limited. For example, a metal salt or the like may be mixed with an aqueous solution of the ascorbic acid phosphate or a salt thereof, or the aqueous solution of the metal salt or the like may be mixed. May be mixed with ascorbic acid phosphate or a salt thereof. Also, an aqueous solution of a metal salt or the like and an aqueous solution of ascorbic acid phosphate or a salt thereof may be mixed, and further, these may be mixed and fixed, and then dissolved by adding water.
金属塩等とアスコルビン酸リン酸エステル又はその塩
との混合量は特に制限されないが、金属塩等に対してア
スコルビン酸リン酸エステル又はその塩が0.5倍モル以
上、特に等モル以上とするのが好ましい。また、金属塩
等とアスコルビン酸リン酸エステル又はその塩を混合し
た溶液のpHは、１〜10、特に４〜10、更に６〜８に調整
するのが好ましい。pHが１未満では、目的とする金属コ
ロイドが得られず、また、10を超えると金属コロイド粒
子の凝集が生じやすく、安定な金属コロイド溶液を得る
ことは困難である。混合溶液のpHは、適当な酸又は塩基
を用いて調整することができる。なお、温度等その他の
条件についても特に制限されず、適宜設定して行なうこ
とができる。The mixing amount of the metal salt or the like and the ascorbic acid phosphate or a salt thereof is not particularly limited. preferable. Further, the pH of a solution in which a metal salt or the like and ascorbic acid phosphate or a salt thereof are mixed is preferably adjusted to 1 to 10, particularly 4 to 10, and more preferably 6 to 8. If the pH is less than 1, the desired metal colloid cannot be obtained, and if it exceeds 10, aggregation of the metal colloid particles tends to occur, and it is difficult to obtain a stable metal colloid solution. The pH of the mixed solution can be adjusted using an appropriate acid or base. The temperature and other conditions are not particularly limited, and can be set as appropriate.
得られた金属コロイドは、例えば超遠心分離、凍結乾
燥などの方法を用いて溶媒を除去することにより、単離
することができる。なお、本発明により製造された金属
コロイドの粒子径は、通常１〜100nmである。The obtained metal colloid can be isolated by removing the solvent using a method such as ultracentrifugation or freeze-drying. The particle diameter of the metal colloid produced according to the present invention is usually 1 to 100 nm.
［発明の効果］ 本発明によれば、金属塩等とアスコルビン酸リン酸エ
ステル又はその塩とを水性媒体中で混合するという簡便
な方法により、金属コロイドを製造することができる。
また、得られた金属コロイドは、広いpH範囲で長期間安
定であり、しかも生体に対する安全性が高いため、飲料
等の食品、栄養薬、輪液等の医薬品、化粧料などの分野
で広く利用することができる。[Effects of the Invention] According to the present invention, a metal colloid can be produced by a simple method of mixing a metal salt or the like and an ascorbic acid phosphate or a salt thereof in an aqueous medium.
In addition, the obtained metal colloid is stable for a long period of time in a wide pH range and has high safety for living organisms, so it is widely used in the fields of foods such as beverages, nutrients, pharmaceuticals such as wheel fluids, and cosmetics. can do.
［実施例］ 次に、実施例及び比較例を挙げ、本発明をさらに説明
するが、本発明はこれら実施例に限定されるものではな
い。[Examples] Next, the present invention will be further described with reference to examples and comparative examples, but the present invention is not limited to these examples.
実施例１ アスコルビン酸−２−リン酸２ナトリウム４水和物5.
6g（0.015mol）をイオン交換水に溶解し、150mMのアス
コルビン酸−２−リン酸ナトリウム水溶液100mlを調製
する。これに塩化アルミニウム６水和物1.2g（0.005mo
l）を加え溶解し、1N NaOHでpH7.0に調整してコロイド
溶液を調製した。得られたコロイド溶液は無色の透明溶
液であり、レーザー（He−Neレーザー）を照射した結
果、チンダル現象を観察できコロイドの存在を確認し
た。また、コロイドの平均粒子径は透過型電子顕微鏡
（TEM）で測定した結果、約34nmであった。Example 1 Disodium ascorbic acid-2-phosphate tetrahydrate 5.
6 g (0.015 mol) is dissolved in ion-exchanged water to prepare 100 ml of a 150 mM sodium ascorbic acid-2-phosphate aqueous solution. 1.2 g of aluminum chloride hexahydrate (0.005mo
l) was added and dissolved, and adjusted to pH 7.0 with 1N NaOH to prepare a colloid solution. The obtained colloid solution was a colorless transparent solution, and as a result of irradiation with a laser (He-Ne laser), a Tyndall phenomenon was observed and the presence of the colloid was confirmed. The average particle diameter of the colloid was about 34 nm as measured by a transmission electron microscope (TEM).
比較例１ 塩化アルミニウム６水和物1.2g（0.005mol）をイオン
交換水100mlに加え溶解し、1N NaOHでpH7.0に調整し
た。その結果、沈澱が生成し、その粒子径は3000nm以上
であった。Comparative Example 1 1.2 g (0.005 mol) of aluminum chloride hexahydrate was added to and dissolved in 100 ml of ion-exchanged water, and adjusted to pH 7.0 with 1N NaOH. As a result, a precipitate was formed, and the particle size was 3000 nm or more.
実施例２ アスコルビン酸−３−リン酸２ナトリウム４水和物5.
6g（0.015mol）をイオン交換水に溶解し、150mMのアス
コルビン酸−３−リン酸ナトリウム水溶液100mlを調製
する。これに塩化アルミニウム６水和物1.2g（0.005mo
l）を加え溶解し、1N NaOHでpH7.0に調整してコロイド
溶液を調製した。得られたコロイド溶液は無色の透明溶
液であり、レーザー（He−Neレーザー）を照射した結
果、チンダル現象を観察できコロイドの存在を確認し
た。コロイドの平均粒子径はTEM測定の結果、約29nmで
あった。Example 2 Disodium ascorbic acid-3-phosphate tetrahydrate 5.
6 g (0.015 mol) is dissolved in ion-exchanged water to prepare 100 ml of a 150 mM sodium ascorbic acid-3-phosphate aqueous solution. 1.2 g of aluminum chloride hexahydrate (0.005mo
l) was added and dissolved, and adjusted to pH 7.0 with 1N NaOH to prepare a colloid solution. The obtained colloid solution was a colorless transparent solution, and as a result of irradiation with a laser (He-Ne laser), a Tyndall phenomenon was observed and the presence of the colloid was confirmed. The average particle diameter of the colloid was about 29 nm as a result of TEM measurement.
実施例３ アスコルビン酸−３−リン酸２ナトリウム４水和物5.
6g（0.015mol）をイオン交換水に溶解し、150mMのアス
コルビン酸−３−リン酸ナトリウム水溶液100mlを調整
する。これに硫酸アルミニウム18水和物1.7g（0.0025mo
l）を加え溶解し、1N NaOHでpH8.0に調整してコロイド
溶液を調製した。得られたコロイド溶液は無色の透明溶
液であり、レーザー（He−Neレーザー）を照射した結
果、チンダル現象を観察できコロイドの存在を確認し
た。コロイドの平均粒子径はTEM測定の結果、約38nmで
あった。Example 3 Disodium ascorbic acid-3-phosphate tetrahydrate 5.
6 g (0.015 mol) is dissolved in ion-exchanged water, and 100 ml of a 150 mM sodium ascorbic acid-3-phosphate aqueous solution is prepared. 1.7 g of aluminum sulfate 18 hydrate (0.0025mo
l) was added and dissolved, and adjusted to pH 8.0 with 1N NaOH to prepare a colloid solution. The obtained colloid solution was a colorless transparent solution, and as a result of irradiation with a laser (He-Ne laser), a Tyndall phenomenon was observed and the presence of the colloid was confirmed. The average particle size of the colloid was about 38 nm as a result of TEM measurement.
実施例４ アスコルビン酸−３−リン酸２ナトリウム４水和物0.
74g（0.002mol）をイオン交換水に溶解し、10mMのアス
コルビン酸−３−リン酸ナトリウム水溶液200mlを調製
する。これに塩化亜鉛0.27g（0.002mol）を加え溶解
し、1N NaOHでpH7.0に調整してコロイド溶液を調製し
た。得られたコロイド溶液は無色の透明溶液であり、レ
ーザー（He−Neレーザー）を照射した結果、チンダル現
象を観察できコロイドの存在を確認した。コロイドの平
均粒子径はTEM測定の結果、約18nmであった。Example 4 Ascorbic acid-3-phosphate disodium tetrahydrate
74 g (0.002 mol) is dissolved in ion-exchanged water to prepare 200 ml of a 10 mM sodium ascorbic acid-3-phosphate aqueous solution. To this, 0.27 g (0.002 mol) of zinc chloride was added and dissolved, and adjusted to pH 7.0 with 1N NaOH to prepare a colloid solution. The obtained colloid solution was a colorless transparent solution, and as a result of irradiation with a laser (He-Ne laser), a Tyndall phenomenon was observed and the presence of the colloid was confirmed. The average particle diameter of the colloid was about 18 nm as a result of TEM measurement.
実施例５ アスコルビン酸−２−リン酸２ナトリウム４水和物5.
1g（0.014mol）をイオン交換水に溶解し、70mMのアスコ
ルビン酸−２−リン酸ナトリウム水溶液100mlを調製し
た。これに四塩化チタン0.19ml（0.0017mol）を撹拌し
ながら加えて溶解し、1N NaOHでpH7.5に調整し、コロイ
ド溶液を調製した。得られたコロイド溶液は薄い黄色の
透明溶液であり、レーザー（He−Neレーザー）を照射し
た結果、チンダル現象を観察できコロイドの存在を確認
した。コロイドの平均粒子径は光散乱法測定の結果、約
8nmであった。Example 5 Disodium ascorbic acid-2-phosphate tetrahydrate 5.
1 g (0.014 mol) was dissolved in ion-exchanged water to prepare 100 ml of a 70 mM sodium ascorbic acid-2-phosphate aqueous solution. To this, 0.19 ml (0.0017 mol) of titanium tetrachloride was added with stirring to dissolve, and the mixture was adjusted to pH 7.5 with 1N NaOH to prepare a colloid solution. The obtained colloid solution was a light yellow transparent solution, and as a result of irradiation with a laser (He-Ne laser), a Tyndall phenomenon was observed and the presence of the colloid was confirmed. The average particle size of the colloid was about
It was 8 nm.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ａ６１Ｋ 33/06 Ａ６１Ｋ 33/06 33/24 33/24 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code Agency reference number FI Technical display location A61K 33/06 A61K 33/06 33/24 33/24
Claims (4)
選ばれる少なくとも一種と、アスコルビン酸リン酸エス
テル又はその塩から選ばれる少なくとも一種とを水性媒
体中で混合することを特徴とする金属コロイドの製造
法。1. A metal comprising mixing at least one selected from a metal salt, a metal hydroxide and a metal oxide with at least one selected from ascorbic acid phosphate or a salt thereof in an aqueous medium. Manufacturing method of colloid.
の金属コロイドの製造法。2. The method for producing a metal colloid according to claim 1, wherein the pH of the mixed solution is 4 to 10.
Fe、Zn、Ti、Al、Sn、Cu、Ni、Si、Mg、Ba、Sr、Ｖ、M
n、Mo、Ag、Nb、Zr、Sb、In又はランタノイドの塩、水
酸化物又は酸化物である請求項１又は２記載の金属コロ
イドの製造法。3. The method according to claim 1, wherein the metal salt, the metal hydroxide and the metal oxide are
Fe, Zn, Ti, Al, Sn, Cu, Ni, Si, Mg, Ba, Sr, V, M
The method for producing a metal colloid according to claim 1 or 2, which is a salt, hydroxide or oxide of n, Mo, Ag, Nb, Zr, Sb, In or a lanthanoid.
が、アスコルビン酸−２−リン酸及びアスコルビン酸−
３−リン酸並びにこれらの塩から選ばれる少なくとも１
種であることを特徴とする請求項１又は２記載の金属コ
ロイドの製造法。4. The method of claim 1, wherein the ascorbic acid phosphate or a salt thereof is ascorbic acid-2-phosphate or ascorbic acid-phosphate.
At least one selected from 3-phosphoric acid and salts thereof
3. The method for producing a metal colloid according to claim 1, wherein the metal colloid is a seed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2240568A JP2649435B2 (en) | 1990-09-11 | 1990-09-11 | Production method of metal colloid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2240568A JP2649435B2 (en) | 1990-09-11 | 1990-09-11 | Production method of metal colloid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04122433A JPH04122433A (en) | 1992-04-22 |
| JP2649435B2 true JP2649435B2 (en) | 1997-09-03 |
Family
ID=17061459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2240568A Expired - Fee Related JP2649435B2 (en) | 1990-09-11 | 1990-09-11 | Production method of metal colloid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2649435B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6299912B1 (en) * | 1999-04-23 | 2001-10-09 | Showa Denko Kabushiki Kaisha | Preparation for administration to animals and feeding method thereof |
| KR100899349B1 (en) * | 2001-10-12 | 2009-05-26 | 파일드 가부시키가이샤 | Producing Method and Apparatus for Titanium-Group Metal powder Containing Water |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3686819B2 (en) * | 2000-05-10 | 2005-08-24 | ファイルド株式会社 | Titanium-containing high-performance water and production method and apparatus |
| TWI255695B (en) | 2001-10-12 | 2006-06-01 | Phild Co Ltd | Method and device for producing ultrafine dispersion of noble metal |
-
1990
- 1990-09-11 JP JP2240568A patent/JP2649435B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6299912B1 (en) * | 1999-04-23 | 2001-10-09 | Showa Denko Kabushiki Kaisha | Preparation for administration to animals and feeding method thereof |
| KR100899349B1 (en) * | 2001-10-12 | 2009-05-26 | 파일드 가부시키가이샤 | Producing Method and Apparatus for Titanium-Group Metal powder Containing Water |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04122433A (en) | 1992-04-22 |
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