JPH06298532A - Production of antibacterial titania and antibacterial titania produced by the process - Google Patents
Production of antibacterial titania and antibacterial titania produced by the processInfo
- Publication number
- JPH06298532A JPH06298532A JP10723793A JP10723793A JPH06298532A JP H06298532 A JPH06298532 A JP H06298532A JP 10723793 A JP10723793 A JP 10723793A JP 10723793 A JP10723793 A JP 10723793A JP H06298532 A JPH06298532 A JP H06298532A
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- titania
- metatitanic acid
- acid slurry
- silver
- 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.)
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- Inorganic Compounds Of Heavy Metals (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は優れた抗菌性を有する抗
菌性チタニアの製造方法及び該製造方法により得られる
抗菌性チタニアに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing antibacterial titania having excellent antibacterial properties and an antibacterial titania obtained by the method.
【０００２】[0002]
【従来の技術】抗菌性物質の多くは有機系抗菌剤による
ものであり、有機銅化合物、有機錫化合物、有機砒素化
合物、有機塩素化合物などが広く用いられてきた。しか
し、一般にこれらの化合物が有効であればあるほど有毒
性が強まることが最大の問題であった。一方、抗菌性金
属イオンを微量溶出させる方法も検討されている。この
例としては、銀、銅、亜鉛およびそれらの酸化物などの
抗菌剤を、抗菌性を賦与するべき器具や成型物などの表
面に固定したり、これら金属抗菌剤を塗料中に仕込んで
構造物に塗装したり、成型用樹脂中に練り込んでそれら
樹脂を成型したり、さらに繊維表面に固定、あるいは繊
維中に練り込みその繊維を織布に織込んだりすることが
行われている。2. Description of the Related Art Most of antibacterial substances are based on organic antibacterial agents, and organic copper compounds, organic tin compounds, organic arsenic compounds, organic chlorine compounds and the like have been widely used. However, generally, the more effective these compounds were, the more serious the toxicity was. On the other hand, a method of eluting a trace amount of antibacterial metal ions has also been studied. Examples of this include fixing antibacterial agents such as silver, copper, zinc and their oxides to the surface of equipment or molded articles to which antibacterial properties are to be imparted, or charging these metallic antibacterial agents into paint. BACKGROUND ART It has been practiced to coat an object, knead it into a molding resin to mold the resin, fix it on the fiber surface, or knead it into the fiber and woven the fiber into a woven cloth.
【０００３】金属抗菌剤を使用した代表的例を医療分野
より選んで例示すると、例えばカテーテル表面に銀粒子
を固定する（米国特許第４，０５４，１３９号明細
書）、医用高分子材料への銀、亜鉛、セリウムなどの金
属塩をコーティングする方法（米国特許第４，６１２，
３３７号明細書、特開昭６２−１１４５７号公報）など
を挙げることができる。しかし、いずれも、使用する金
属粉末などの粒状が十分細かくない、あるいは分散性が
不充分などの欠陥があるためか、現状では殆ど実用化に
至っていない。A typical example of using a metal antibacterial agent is selected from the medical field and exemplified. For example, silver particles are fixed on the surface of a catheter (US Pat. No. 4,054,139), which is used as a medical polymer material. A method of coating a metal salt such as silver, zinc or cerium (US Pat. No. 4,612,
No. 337, JP-A No. 62-11457) and the like. However, all of them have not been put into practical use at present, probably because the particles of the metal powder to be used are not sufficiently fine or there is a defect such as insufficient dispersibility.
【０００４】上記従来の抗菌剤の欠点を改良する試みと
して、銀などの金属イオンを交換した天然および合成ゼ
オライトを抗菌剤とし、工業用品、日用品あるいは医療
用品に適用することが試みられている（特公昭６３−５
４０１３号公報など）。また、三塩化チタン水溶液にア
ンモニア水を加えてチタニアの多孔性白色ゲルを合成
し、このゲルに銀イオン、銅イオン、あるいは／及び亜
鉛イオンなどの抗菌性金属イオンを吸着させて抗菌性チ
タニアを合成した例が開示されている（特開平５−４８
１６号公報）。この抗菌性金属イオンを吸着させた抗菌
性チタニアは、抗菌性チタニア自身がコロイド状に分散
できるので、抗菌性組成物に加工した時均一に分散し安
定である。この抗菌性組成物を溶融樹脂に分散して抗菌
性を有する樹脂成型品に成型する例、安定に抗菌剤を分
散した塗料を得て構造物に塗装し構造物を抗菌性にする
例、抗菌性チタニアを繊維に固定し壁紙など建材に適用
する例や樹脂に仕込んでその樹脂から抗菌性の食品包装
材料を製造した例などが開示されている（特開平４−２
３１０６３号公報）。As an attempt to improve the drawbacks of the above-mentioned conventional antibacterial agents, it has been attempted to use natural and synthetic zeolites having metal ions such as silver exchanged as antibacterial agents and applied to industrial articles, daily necessities or medical articles ( Japanese Patent Publication Sho 63-5
No. 4013). Ammonia water is added to an aqueous solution of titanium trichloride to synthesize a porous white gel of titania, and the gel is adsorbed with antibacterial metal ions such as silver ions, copper ions, and / or zinc ions to produce antibacterial titania. A synthesized example is disclosed (JP-A-5-48).
16 publication). The antibacterial titania to which the antibacterial metal ions are adsorbed can disperse the antibacterial titania itself in a colloidal form, and thus is uniformly dispersed and stable when processed into an antibacterial composition. An example in which this antibacterial composition is dispersed in a molten resin to form a resin molded article having antibacterial properties, an example in which a paint in which an antibacterial agent is stably dispersed is obtained and applied to a structure to make the structure antibacterial, antibacterial There are disclosed examples in which the active titania is fixed to fibers and applied to a building material such as wallpaper, and an example in which an antibacterial food packaging material is produced from the resin by charging the resin (JP-A-4-2).
31063).
【０００５】[0005]
【発明が解決しようとする課題】上記特公昭６３−５４
０１３号公報などに開示された、天然および合成ゼオラ
イト中に銀などの抗菌性金属イオンをイオン交換によっ
て固定化した抗菌剤は、ゼオライト自体の粒状性が十分
に微細でなく、従って安定性のより塗料あるいは噴霧用
液となし得ず、また価格が高くなるなど、まだ実用化に
は問題点を残している。また、上記特開平５−４８１６
号公報に開示されている抗菌性チタニアは、担体である
チタニアの製造法が、三塩化チタン水溶液にアンモニア
水を加えて、多孔性白色ゲルとしてチタニアを得る方法
であるので、製造条件によってチタニアの品質が変化し
易く、従って後に示す如く抗菌性状が安定していない。
本発明の目的は、従来の抗菌剤の有する分散性、安定性
などの品質上の欠点や高価につくなどの経済上の問題を
解決し、抗菌性金属の分散性が良好で、抗菌剤自身の粒
状性が十分微細にでき、しかも低コストに生産し得る新
規な抗菌剤とその製造方法を確立することにある。[Problems to be Solved by the Invention] Japanese Patent Publication No. 63-54
The antibacterial agent disclosed in Japanese Patent Publication No. 013, etc. in which antibacterial metal ions such as silver are immobilized by ion exchange in natural and synthetic zeolites does not have sufficiently fine granularity of the zeolite itself, and therefore has a higher stability. It cannot be used as a paint or a spray liquid, and the price becomes high. In addition, the above-mentioned JP-A-5-4816
The antibacterial titania disclosed in the publication is a method for producing titania which is a carrier, because it is a method in which aqueous ammonia is added to an aqueous solution of titanium trichloride to obtain titania as a porous white gel. The quality is liable to change, and therefore the antibacterial properties are not stable, as will be shown later.
The object of the present invention is to solve the problems of quality such as dispersibility and stability of conventional antibacterial agents and economic problems such as being expensive, and the dispersibility of antibacterial metal is good, and the antibacterial agent itself. The present invention aims to establish a novel antibacterial agent that can be produced at a low cost and has a sufficiently fine granularity, and a method for producing the same.
【０００６】[0006]
【課題を解決するための手段】本発明の上記目的は、下
記の本発明の抗菌性チタニアおよびその製造方法によっ
て達成される。すなわち、 （１）メタチタン酸スラリー中に抗菌性金属塩水溶液を
投入し、該メタチタン酸スラリー中のアナターゼ型チタ
ニアに該抗菌性金属イオンを担持せしめることを特徴と
する抗菌性チタニアの製造方法。 （２）メタチタン酸スラリー中のアナターゼ型チタニア
に担持せしめる抗菌性金属イオンが銀イオンであること
を特徴とする上記（１）記載の抗菌性チタニアの製造方
法。 （３）メタチタン酸スラリー中に抗菌性金属塩水溶液を
投入し、該メタチタン酸スラリー中のアナターゼ型チタ
ニアに該抗菌性金属イオンを担持せしめて得られる抗菌
性チタニア。 （４）メタチタン酸スラリー中のアナターゼ型チタニア
に担持せしめる抗菌性金属イオンが銀イオンである上記
（３）記載の抗菌性チタニア。である。The above objects of the present invention are achieved by the following antibacterial titania of the present invention and a method for producing the same. That is, (1) A method for producing antibacterial titania, which comprises introducing an antibacterial metal salt aqueous solution into a metatitanic acid slurry and allowing the anatase type titania in the metatitanic acid slurry to carry the antibacterial metal ion. (2) The method for producing antibacterial titania according to the above (1), wherein the antibacterial metal ion supported on the anatase type titania in the metatitanic acid slurry is silver ion. (3) An antibacterial titania obtained by introducing an antibacterial metal salt aqueous solution into a metatitanic acid slurry, and supporting the antibacterial metal ion on anatase-type titania in the metatitanic acid slurry. (4) The antibacterial titania according to the above (3), wherein the antibacterial metal ion supported on the anatase type titania in the metatitanic acid slurry is silver ion. Is.
【０００７】本発明のメタチタン酸スラリーは、ＴｉＣ
ｌ4 ，Ｔｉ（ＮＯ3 ）4 ，Ｔｉ（ＳＯ4 ）2 などの水溶
性チタン塩の水溶液に、水酸化アルカリまたはアンモニ
アを加えて得られる白色のゲル状物で、スラリー中のチ
タニアは酸および濃アルカリの両方に溶解するアナター
ゼ型の含水二酸化チタン（ＴｉＯ2 ・ｘＨ2 Ｏ）微粒子
であり、上記特開平５−４８１６号公報に開示されてい
るチタニアに比し製造再現性が優れているという特徴を
有する。本発明の抗菌性チタニアの製造方法の１例を図
１により説明する。ただし、本発明の抗菌性チタニアの
製造方法は以下の説明の方法に限られることはない。図
１において、槽１に上記アナターゼ型チタニアを含むメ
タチタン酸スラリーを、槽２には０．１０ｍｏｌ／リッ
トル以下の濃度の硝酸銀水溶液を用意し、槽３に両者を
注入して３時間攪拌混合し、攪拌を中止した後さらに１
時間静置し、内容物を吸引濾過して白色固形物を濾別
し、白色固形物を水洗し、乾燥して抗菌性チタニアを得
る。The metatitanic acid slurry of the present invention comprises TiC
It is a white gel-like substance obtained by adding alkali hydroxide or ammonia to an aqueous solution of a water-soluble titanium salt such as l 4 , Ti (NO 3 ) 4 or Ti (SO 4 ) 2 and the titania in the slurry is acid or acid. It is anatase type hydrous titanium dioxide (TiO 2 · xH 2 O) fine particles which are soluble in both concentrated alkalis, and is said to be excellent in manufacturing reproducibility as compared with the titania disclosed in JP-A-5-4816. It has characteristics. One example of the method for producing antibacterial titania of the present invention will be described with reference to FIG. However, the method for producing the antibacterial titania of the present invention is not limited to the method described below. In FIG. 1, a metatitanic acid slurry containing the above anatase-type titania is prepared in a tank 1, an aqueous solution of silver nitrate having a concentration of 0.10 mol / liter or less is prepared in a tank 2, and both are poured into a tank 3 and stirred and mixed for 3 hours. , 1 more after stopping stirring
The mixture is allowed to stand for a while, the content is suction filtered to separate a white solid matter by filtration, the white solid matter is washed with water and dried to obtain antibacterial titania.
【０００８】さらに以下にのべる通り、本発明において
メタチタン酸スラリーに硝酸銀を添加してアナターゼ型
チタニア中に銀イオンを固定した場合、アナターゼ型チ
タニア（担体）中に固定される銀イオン濃度の再現性
は、特開平５−４８１６号公報に開示されているチタニ
アに銀イオンを固定する場合の再現性に比し、非常に良
い。本発明のアナターゼ型チタニアには、銀イオン以外
の抗菌性金属イオン、例えばＣｕイオン、Ｚｎイオン、
Ｓｎイオンなどはいずれも固定可能である。また、本発
明の抗菌性チタニアは乾燥し、粉砕して、上記特開平５
−４８１６号公報に開示されているチタニアの場合と同
様その平均粒径は平均５０μｍ、好ましくは１０μｍ以
下、より好ましくは５μｍ以下に調製することができ
る。これら抗菌性チタニアの粒状性はＢＥＴ法により窒
素ガスの吸着挙動から測定された。Further, as described below, in the present invention, when silver nitrate is added to the metatitanic acid slurry to fix silver ions in the anatase type titania, the reproducibility of the silver ion concentration fixed in the anatase type titania (carrier). Is very good in comparison with the reproducibility when fixing silver ions to titania disclosed in JP-A-5-4816. The anatase-type titania of the present invention includes antibacterial metal ions other than silver ions, for example, Cu ions, Zn ions,
Any Sn ion or the like can be fixed. Further, the antibacterial titania of the present invention is dried and pulverized to obtain the above-mentioned JP-A-5-58
As in the case of titania disclosed in Japanese Patent Publication No. 4816, the average particle size can be adjusted to 50 μm on average, preferably 10 μm or less, more preferably 5 μm or less. The granularity of these antibacterial titanias was measured by the BET method from the adsorption behavior of nitrogen gas.
【０００９】本発明の抗菌性チタニアの抗菌力は「最小
発育阻止濃度（ＭＩＣ）」の測定によった。すなわち、
三角フラスコに検体（各種抗菌性チタニア）を投入す
る。それらを高圧蒸気滅菌した後、フラスコにＭＨ培地
を加え攪拌し、１０6 ／ｍｌに調製した接種菌液を注入
する。フラスコを３７℃恒温振蕩機で２０時間振蕩後の
菌液について、顕微鏡下で菌増加の有無を判定する。菌
の増加が無い場合が陰性であり、陰性となる最小検体濃
度を最小発育阻止濃度（ＭＩＣ値）とする。The antibacterial activity of the antibacterial titania of the present invention was determined by measuring the "minimum inhibitory concentration (MIC)". That is,
Put the specimen (various antibacterial titania) into the Erlenmeyer flask. After sterilizing them by high-pressure steam, MH medium is added to the flask and stirred, and the inoculum solution prepared to 10 6 / ml is injected. The presence or absence of increase in bacteria is determined under a microscope for the bacterial solution after shaking the flask for 20 hours with a constant temperature shaker at 37 ° C. The case where there is no increase in the bacteria is negative, and the minimum sample concentration that gives a negative result is the minimum inhibitory concentration (MIC value).
【００１０】[0010]
【実施例】本発明の抗菌性チタニアを製造する例を以下
に実施例を示して説明する。しかし本発明は以下の実施
例によって制限されるものではない。EXAMPLES An example of producing the antibacterial titania of the present invention will be described below with reference to examples. However, the present invention is not limited to the examples below.
【００１１】実施例１ ３０重量％メタチタン酸スラリーを表１に示した濃度の
硝酸銀水溶液中に投入し、アンモニア水で弱アルカリ性
（ｐＨ＝８．００）に調整後、３時間攪拌混合し、攪拌
を中止した後さらに１時間放置した後、内容物を吸引濾
過して残渣を水洗、１１０℃で２４時間乾燥することに
より表１に示した各種銀成分量（分析値）を吸着した抗
菌性チタニアを得た。この試料の大腸菌に対する最小発
育阻止濃度（ＭＩＣ値）を上記各種銀成分濃度と対比し
て表１に掲載した。Example 1 A 30 wt% metatitanic acid slurry was put into an aqueous silver nitrate solution having the concentration shown in Table 1, adjusted to be weakly alkaline (pH = 8.00) with aqueous ammonia, and stirred and mixed for 3 hours, followed by stirring. After quitting, the contents were left to stand for another 1 hour, the contents were suction filtered, the residue was washed with water, and dried at 110 ° C. for 24 hours to adsorb various silver component amounts (analytical values) shown in Table 1 to the antibacterial titania. Got The minimum inhibitory concentration (MIC value) of this sample against Escherichia coli is shown in Table 1 in comparison with the above various silver component concentrations.
【００１２】[0012]
【表１】 [Table 1]
【００１３】また、図２は本発明の抗菌性チタニアに吸
着した銀イオン量とＭＩＣ値との関係を示したグラフで
ある。ここで、横軸の銀イオン量は本発明の抗菌性チタ
ニアに吸着した銀イオン量（Ａｇ）を重量％で表した値
である。FIG. 2 is a graph showing the relationship between the amount of silver ions adsorbed on the antibacterial titania of the present invention and the MIC value. Here, the amount of silver ions on the abscissa is a value in which the amount of silver ions (Ag) adsorbed on the antibacterial titania of the present invention is expressed in% by weight.
【００１４】図２には比較のため特開平５−４８１６号
公報に開示されているチタニアに吸着した銀イオン量と
ＭＩＣ値との関係（以下比較例という）を併せてプロッ
トした。この図から比較例の場合は吸着銀イオン量とＭ
ＩＣ値との関係が円滑な関数関係で表せず、変動幅が大
きいことが判る。これは多分比較例では担体である抗菌
性チタニアの品質の再現性にバラツキがあることによる
と思われる。これに対し本発明の抗菌性チタニアでは吸
着銀イオン量とＭＩＣ値との関係は広い範囲にわたり円
滑な関数関係にある。しかも比較例で使用される抗菌性
チタニアに吸着される吸着銀イオン量は本発明の抗菌性
チタニアにも容易に吸着可能であることが判る。For comparison, FIG. 2 also plots the relationship between the amount of silver ions adsorbed on titania and the MIC value (hereinafter referred to as a comparative example) disclosed in JP-A-5-4816. From this figure, in the case of the comparative example, the amount of adsorbed silver ions and M
It can be seen that the relationship with the IC value cannot be expressed as a smooth functional relationship, and the fluctuation range is large. This is probably because the reproducibility of the quality of the antibacterial titania, which is a carrier in the comparative example, varies. On the other hand, in the antibacterial titania of the present invention, the relationship between the amount of adsorbed silver ions and the MIC value has a smooth functional relationship over a wide range. Moreover, it can be seen that the amount of adsorbed silver ions adsorbed on the antibacterial titania used in the comparative example can be easily adsorbed on the antibacterial titania of the present invention.
【００１５】[0015]
【発明の効果】本発明の抗菌性チタニアの製造方法によ
り、 （１）天然および合成ゼオライトを担体とする金属イオ
ン抗菌剤より微粒子の抗菌剤が得られる。 （２）三塩化チタンを原料とする抗菌性チタニアより、
抗菌性金属イオンの担体への固定化の再現性が優れてい
る。 （３）本発明の抗菌性チタニアは製造し易い。 （４）銀イオン量とＭＩＣ値との関係で表した抗菌性チ
タニアの品質は三塩化チタンを原料とする抗菌性チタニ
アに比し、同等あるいはそれ以上の品質である。According to the method for producing antibacterial titania of the present invention, (1) a fine particle antibacterial agent can be obtained from a metal ion antibacterial agent using natural or synthetic zeolite as a carrier. (2) From antibacterial titania made from titanium trichloride as a raw material,
Excellent reproducibility of immobilization of antibacterial metal ions on the carrier. (3) The antibacterial titania of the present invention is easy to manufacture. (4) The quality of the antibacterial titania expressed by the relationship between the amount of silver ions and the MIC value is equal to or higher than that of the antibacterial titania made from titanium trichloride.
【図１】本発明の抗菌性チタニア製造の工程説明図FIG. 1 is an explanatory view of a process of manufacturing an antibacterial titania of the present invention
【図２】抗菌性チタニアに吸着した銀イオン量とＭＩＣ
値との関係を示したグラフ[Fig. 2] MIC and silver ion amount adsorbed on antibacterial titania
Graph showing the relationship with values
１ メタチタン酸スラリー槽 ２ 硝酸銀溶解槽 ３ 反応槽 1 Metatitanic acid slurry tank 2 Silver nitrate dissolution tank 3 Reaction tank
───────────────────────────────────────────────────── フロントページの続き (72)発明者 野納 敏展 東京都千代田区丸の内２丁目３番２号 日 鉄鉱業株式会社内 (72)発明者 斯波 徹 神奈川県横浜市緑区佐江戸町182 クリエ ートメディック株式会社技術研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshinori Nono 2-3-2 Marunouchi, Chiyoda-ku, Tokyo Nittetsu Mining Co., Ltd. (72) Toru Saba 182 Saedo-cho, Midori-ku, Yokohama-shi, Kanagawa Create Medic Co., Ltd. Technical Research Center
Claims (4)
水溶液を投入し、該メタチタン酸スラリー中のアナター
ゼ型チタニアに該抗菌性金属イオンを担持せしめること
を特徴とする抗菌性チタニアの製造方法。1. A method for producing antibacterial titania, which comprises introducing an antibacterial metal salt aqueous solution into a metatitanic acid slurry and allowing the anatase type titania in the metatitanic acid slurry to carry the antibacterial metal ion.
チタニアに担持せしめる抗菌性金属イオンが銀イオンで
あることを特徴とする請求項１記載の抗菌性チタニアの
製造方法。2. The method for producing antibacterial titania according to claim 1, wherein the antibacterial metal ion supported on the anatase type titania in the metatitanic acid slurry is silver ion.
水溶液を投入し、該メタチタン酸スラリー中のアナター
ゼ型チタニアに該抗菌性金属イオンを担持せしめて得ら
れる抗菌性チタニア。3. An antibacterial titania obtained by introducing an antibacterial metal salt aqueous solution into a metatitanic acid slurry, and supporting the antibacterial metal ion on anatase type titania in the metatitanic acid slurry.
チタニアに担持せしめる抗菌性金属イオンが銀イオンで
ある請求項３記載の抗菌性チタニア。4. The antibacterial titania according to claim 3, wherein the antibacterial metal ion supported on the anatase type titania in the metatitanic acid slurry is silver ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10723793A JPH06298532A (en) | 1993-04-12 | 1993-04-12 | Production of antibacterial titania and antibacterial titania produced by the process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10723793A JPH06298532A (en) | 1993-04-12 | 1993-04-12 | Production of antibacterial titania and antibacterial titania produced by the process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06298532A true JPH06298532A (en) | 1994-10-25 |
Family
ID=14453965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10723793A Pending JPH06298532A (en) | 1993-04-12 | 1993-04-12 | Production of antibacterial titania and antibacterial titania produced by the process |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06298532A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0802162A3 (en) * | 1996-04-15 | 1998-05-27 | Nittetsu Mining Co., Ltd. | Antibacterial titania and process for producing the same |
| US5961843A (en) * | 1994-10-05 | 1999-10-05 | Toto Ltd. | Antimicrobial solid material, process for producing the same, and method of utilizing the same |
| WO2009044523A1 (en) | 2007-10-01 | 2009-04-09 | Yhs Ltd. | Antibiotic composition and process for production of the same |
-
1993
- 1993-04-12 JP JP10723793A patent/JPH06298532A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5961843A (en) * | 1994-10-05 | 1999-10-05 | Toto Ltd. | Antimicrobial solid material, process for producing the same, and method of utilizing the same |
| EP0802162A3 (en) * | 1996-04-15 | 1998-05-27 | Nittetsu Mining Co., Ltd. | Antibacterial titania and process for producing the same |
| US5935608A (en) * | 1996-04-15 | 1999-08-10 | Nittetsu Mining Co., Ltd. | Antibacterial titania and process for producing the same |
| WO2009044523A1 (en) | 2007-10-01 | 2009-04-09 | Yhs Ltd. | Antibiotic composition and process for production of the same |
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