JPH1017406A - Antibacterial agent - Google Patents
Antibacterial agentInfo
- Publication number
- JPH1017406A JPH1017406A JP8195363A JP19536396A JPH1017406A JP H1017406 A JPH1017406 A JP H1017406A JP 8195363 A JP8195363 A JP 8195363A JP 19536396 A JP19536396 A JP 19536396A JP H1017406 A JPH1017406 A JP H1017406A
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- solution
- weight
- fine particles
- antibacterial agent
- 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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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は抗菌剤に関し、特
に、樹脂、塗料、繊維、紙、不織布、皮革、化粧品など
に添加または塗布して抗菌性、防黴性、消臭性などの効
果を発揮する抗菌剤に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial agent, and more particularly to an antibacterial, antifungal, deodorant, etc. effect when added or applied to resins, paints, fibers, papers, nonwoven fabrics, leather, cosmetics and the like. It is related to an antibacterial agent to be exerted.
【０００２】[0002]
【従来技術】抗菌剤としては、従来、ゼオライトなどの
粉末に抗菌性金属成分を担持したものが知られていた
が、これらの抗菌剤は、粒子径の大きい粉末状であるた
め、樹脂、塗料、繊維、紙、不織布、皮革、化粧品な
どに添加したときの分散性が悪い、抗菌性が効果的に
発現しにくく、所望の抗菌活性を得るためには多量の抗
菌剤を添加する必要がある、などの問題点があった。ま
た、このような抗菌剤を繊維などに付着させるために
は、粒子径が大きいため、付着力が弱くバインダーを使
用する必要があり、そのため繊維などの基材の風合いが
低下するという問題点があった。2. Description of the Related Art As antibacterial agents, those in which an antibacterial metal component is supported on a powder such as zeolite have been known. However, since these antibacterial agents are in the form of a powder having a large particle diameter, resins, paints, etc. Poor dispersibility when added to fibers, paper, non-woven fabric, leather, cosmetics, etc., it is difficult to effectively exhibit antibacterial properties, and it is necessary to add a large amount of antibacterial agent to obtain desired antibacterial activity , And so on. In addition, in order to attach such an antibacterial agent to fibers and the like, it is necessary to use a binder having a low particle adhesion because of a large particle diameter, and thus the texture of a substrate such as fibers is reduced. there were.
【０００３】そこで、本願の発明者等は特願平５−１９
８８９４号（特開平７−３３６１６号公報）により、抗
菌性金属成分と該抗菌性金属成分以外の無機酸化物とか
ら構成される微粒子が分散してなる抗菌性無機酸化物コ
ロイド溶液であって、当該コロイド溶液中の抗菌性金属
成分の重量をＡ、該コロイド溶液を超遠心分離処理して
遊離した抗菌性金属成分の重量をＢとしたとき、Ｂ／Ａ
で表される抗菌性金属成分の結合力指数Ｉの値が１．０
×１０-3以下であることを特徴とする抗菌剤を提案し
た。この抗菌剤は、分散性、抗菌活性、耐変色性、透明
性などの点で優れた効果を示すが、当該コロイド溶液の
微粒子は繊維の種類によってはバインダーを用いないと
付着力が弱く、耐洗濯性などの耐久性が劣る場合があっ
た。[0003] The inventors of the present application have disclosed in Japanese Patent Application No. Hei.
No. 8894 (Japanese Unexamined Patent Publication No. 7-33616) discloses an antibacterial inorganic oxide colloid solution in which fine particles composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component are dispersed, When the weight of the antimicrobial metal component in the colloid solution is A and the weight of the antimicrobial metal component released by ultracentrifugation of the colloid solution is B, B / A
The binding strength index I of the antibacterial metal component represented by
An antibacterial agent characterized by being at most 10-3 was proposed. This antibacterial agent exhibits excellent effects in terms of dispersibility, antibacterial activity, discoloration resistance, transparency, and the like. In some cases, durability such as washability was poor.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、分散性、抗
菌活性、耐変色性、透明性などに優れた抗菌性無機酸化
物コロイド溶液であって、コロイド溶液の微粒子（コロ
イド粒子）が繊維の種類に関係なく、バインダーを用い
なくても強い付着力を有し、耐洗濯性などの耐久性に優
れた抗菌剤を提供することを目的とするものである。DISCLOSURE OF THE INVENTION The present invention relates to an antibacterial inorganic oxide colloid solution having excellent dispersibility, antibacterial activity, discoloration resistance and transparency, wherein the fine particles (colloid particles) of the colloid solution are fibers. Regardless of the type, an object of the present invention is to provide an antibacterial agent having a strong adhesive force without using a binder and having excellent durability such as washing resistance.
【０００５】[0005]
【課題を解決するための手段】本発明の抗菌剤は、抗菌
性金属成分と該抗菌性金属成分以外の無機酸化物とから
構成される微粒子が分散してなる抗菌性無機酸化物コロ
イド溶液であって、該微粒子の形状が繊維状であること
を特徴とするものである。The antimicrobial agent of the present invention is an antimicrobial inorganic oxide colloid solution in which fine particles comprising an antimicrobial metal component and an inorganic oxide other than the antimicrobial metal component are dispersed. The fine particles are fibrous in shape.
【０００６】前記繊維状粒子のアスペクト比は３．０以
上であることが好ましい。また、前記抗菌性金属成分以
外の無機酸化物は酸化チタンを含有することが好まし
い。[0006] The fibrous particles preferably have an aspect ratio of 3.0 or more. The inorganic oxide other than the antibacterial metal component preferably contains titanium oxide.
【０００７】[0007]
【発明の実施の形態】本発明の抗菌剤は、抗菌性無機酸
化物コロイド溶液からなり、該コロイド溶液中に分散す
る無機酸化物微粒子の形状は繊維状である。該繊維状微
粒子は、短径が０．２〜１０ｎｍ、好ましくは０．３〜
５ｎｍの範囲にあり、長径が０．６〜１０００ｎｍ、好
ましくは１０〜５００ｎｍの範囲にあることが望まし
い。このような微粒子のアスペクト比は３．０以上、好
ましくは５以上、さらに好ましくは１０〜１００の範囲
であることが望ましい。アスペクト比が３．０未満の場
合には、該微粒子の繊維や皮革などの基材への付着力が
弱く、耐洗濯性、耐久性などに関し所望の効果が得られ
にくい。なお、本発明において、アスペクト比はコロイ
ド溶液中に分散しているコロイド粒子を透過型電子顕微
鏡写真で撮影し、該微粒子の短径と長径を少なくとも１
００個測定して求めた値である。BEST MODE FOR CARRYING OUT THE INVENTION The antibacterial agent of the present invention comprises an antibacterial inorganic oxide colloid solution, and the inorganic oxide fine particles dispersed in the colloid solution have a fibrous shape. The fibrous fine particles have a minor axis of 0.2 to 10 nm, preferably 0.3 to 10 nm.
It is in the range of 5 nm, and the major axis is desirably in the range of 0.6 to 1000 nm, preferably in the range of 10 to 500 nm. It is desirable that the aspect ratio of such fine particles is 3.0 or more, preferably 5 or more, and more preferably 10 to 100. When the aspect ratio is less than 3.0, the adhesion of the fine particles to a base material such as fiber or leather is weak, and it is difficult to obtain desired effects with respect to washing resistance and durability. In the present invention, the aspect ratio is such that the colloid particles dispersed in the colloid solution are photographed with a transmission electron micrograph, and the minor axis and the major axis of the fine particles are at least one.
This is a value obtained by measuring 00 pieces.
【０００８】前述の微粒子を構成する抗菌性金属成分と
しては、通常知られている抗菌性金属成分を用いること
ができ、例えば、銀、銅、亜鉛、錫、鉛、ビスマス、カ
ドミウム、クロム、水銀などが例示される。特に、銀、
銅、亜鉛から選択される１種以上の抗菌性金属成分は、
抗菌作用、変色及び人体に対する安全性などの観点から
好ましい。As the antibacterial metal component constituting the above-mentioned fine particles, a generally known antibacterial metal component can be used. For example, silver, copper, zinc, tin, lead, bismuth, cadmium, chromium, mercury And the like. In particular, silver,
One or more antibacterial metal components selected from copper and zinc are:
It is preferable from the viewpoints of antibacterial action, discoloration and safety to human body.
【０００９】抗菌性成分としての銅イオンは青色を呈す
るが、銀イオンはそもそも無色である。しかし、銀イオ
ンは光化学反応や酸化作用により金属銀の凝集体あるい
は酸化物となり、褐色または黒色に変色する。特に紫外
線の光化学反応による銀成分の変色を防止するために
は、チタン、ジルコニウム、セリウム、亜鉛などを銀成
分と組合わせて使用することが望ましい。これは、チタ
ン、ジルコニウム、セリウムおよび亜鉛成分が紫外線吸
収剤として作用して、銀成分の変色を防止する効果を有
しているからである。Copper ions as antibacterial components exhibit a blue color, whereas silver ions are colorless in the first place. However, silver ions become aggregates or oxides of metallic silver by a photochemical reaction or an oxidizing action, and change to brown or black. In particular, in order to prevent discoloration of the silver component due to the photochemical reaction of ultraviolet rays, it is desirable to use titanium, zirconium, cerium, zinc, or the like in combination with the silver component. This is because the titanium, zirconium, cerium and zinc components act as ultraviolet absorbers and have the effect of preventing discoloration of the silver component.
【００１０】本発明に係る抗菌剤中の抗菌性金属成分の
量は、固形分を基準として酸化物換算で０．１〜２５重
量％の範囲内であることが望ましい。抗菌性金属成分が
０．１重量％よりも少ない場合は、抗菌作用が十分に発
現しない。また、抗菌性金属成分を２５重量％よりも多
くしても、２５重量％の場合と比較して抗菌性作用に大
差がなく、また、銀成分などでは、結合量が多くなると
変色しやすい。好ましい抗菌性金属成分の量は、酸化物
換算で０．１〜１５重量％の範囲である。The amount of the antibacterial metal component in the antibacterial agent according to the present invention is desirably in the range of 0.1 to 25% by weight in terms of oxide based on the solid content. When the amount of the antibacterial metal component is less than 0.1% by weight, the antibacterial effect is not sufficiently exhibited. Further, even if the antibacterial metal component is more than 25% by weight, there is not much difference in the antibacterial action as compared with the case of 25% by weight, and in the case of a silver component or the like, discoloration is apt to occur when the binding amount is large. The preferred amount of the antibacterial metal component is in the range of 0.1 to 15% by weight in terms of oxide.
【００１１】一方、本発明の抗菌性金属成分以外の無機
酸化物としては、一般に知られているコロイド溶液を構
成する無機酸化物を挙げることができ、無機酸化物コロ
イド粒子としては、単一または複合酸化物コロイド粒
子、あるいはこれらの混合物を用いることが可能であ
る。On the other hand, examples of the inorganic oxide other than the antibacterial metal component of the present invention include generally known inorganic oxides constituting a colloid solution. It is possible to use composite oxide colloid particles or a mixture thereof.
【００１２】単一の酸化物コロイド粒子としては、Ｓｉ
Ｏ2 、ＴｉＯ2 、ＺｒＯ2 、Ｆｅ2Ｏ3 、Ｓｂ2 Ｏ5 、
ＷＯ3 、などが例示され、複合酸化物コロイド粒子とし
ては、前記各酸化物と他の無機酸化物の複合酸化物コロ
イド粒子、例えば、ＳｉＯ2・Ａｌ2 Ｏ3 、ＳｉＯ2 ・
Ｂ2 Ｏ3 、ＳｉＯ2 ・Ｐ2 Ｏ5 、ＴｉＯ2 ・ＣｅＯ2、
ＴｉＯ2 ・ＺｒＯ2 、ＳｉＯ2 ・ＺｒＯ2 、ＳｉＯ2 ・
ＴｉＯ2 、ＳｎＯ2 ・Ｓｂ2 Ｏ5 、ＳｉＯ2 ・Ａｌ2 Ｏ
3 ・ＴｉＯ2 、ＳｉＯ2 ・ＴｉＯ2 ・ＣｅＯ2、ＴｉＯ
2 ・ＳｉＯ2 ・ＺｒＯ2 、ＳｉＯ2 ・Ａｌ2 Ｏ3 ・Ｍｇ
Ｏ、ＳｉＯ2 ・Ａｌ2 Ｏ3 ・ＣａＯ、ＳｉＯ2 ・ＴｉＯ
2 ・Ｆｅ2 Ｏ3 などを挙げることができる。The single oxide colloidal particles include Si
O 2 , TiO 2 , ZrO 2 , Fe 2 O 3 , Sb 2 O 5 ,
WO 3 , and the like. Examples of the composite oxide colloid particles include composite oxide colloid particles of each of the above oxides and other inorganic oxides, for example, SiO 2 .Al 2 O 3 , SiO 2.
B 2 O 3 , SiO 2 .P 2 O 5 , TiO 2 .CeO 2 ,
TiO 2 .ZrO 2 , SiO 2 .ZrO 2 , SiO 2.
TiO 2 , SnO 2 · Sb 2 O 5 , SiO 2 · Al 2 O
3. TiO 2 , SiO 2 TiO 2 CeO 2 , TiO
2 · SiO 2 · ZrO 2 , SiO 2 · Al 2 O 3 · Mg
O, SiO 2 · Al 2 O 3 · CaO, SiO 2 · TiO
Such as 2 · Fe 2 O 3 can be mentioned.
【００１３】特に、酸化チタンを含有する無機酸化物
は、抗菌性金属成分である銀成分の変色を防止する効果
を有するとともに、安定性に優れた繊維状の微粒子が分
散したコロイド溶液（ゾル）が得られるので好適であ
る。In particular, an inorganic oxide containing titanium oxide has an effect of preventing discoloration of a silver component, which is an antibacterial metal component, and a colloid solution (sol) in which fibrous fine particles having excellent stability are dispersed. Is preferably obtained.
【００１４】本発明の繊維状微粒子が分散してなる抗菌
性無機酸化物コロイド溶液は、例えば次のようにして製
造することができるが、本発明はこの製造法に限定され
るものではない。The antibacterial inorganic oxide colloid solution in which the fibrous fine particles of the present invention are dispersed can be produced, for example, as follows, but the present invention is not limited to this production method.
【００１５】硫酸チタン水溶液にアンモニアを添加し中
和して得られる含水チタン酸のゲルまたはゾルに過酸化
水素を加えてチタン酸水溶液を調製する。このチタン酸
水溶液に抗菌性金属成分のアンモニア性水溶液とシリカ
ゾルとを混合し加熱処理して繊維状微粒子が分散してな
る抗菌性無機酸化物コロイド溶液が得られる。ただし、
該微粒子の形状は加熱処理の条件によって変わるので注
意を要する。微粒子の形状を繊維状にするためには、加
熱処理の温度を１００℃以下、好ましくは６０〜９５℃
の範囲でゾル状になるまで、約０．５〜２０時間撹拌処
理することが必要である。Hydrogen peroxide is added to a hydrous titanic acid gel or sol obtained by adding and neutralizing ammonia to an aqueous solution of titanium sulfate to prepare an aqueous solution of titanic acid. An aqueous antibacterial metal oxide component and a silica sol are mixed with this aqueous solution of titanic acid and heated to obtain an antibacterial inorganic oxide colloid solution in which fibrous fine particles are dispersed. However,
Note that the shape of the fine particles varies depending on the conditions of the heat treatment. In order to make the shape of the fine particles fibrous, the temperature of the heat treatment is 100 ° C. or less, preferably 60 to 95 ° C.
It is necessary to carry out a stirring treatment for about 0.5 to 20 hours until it becomes a sol in the range described above.
【００１６】なお、上記製造方法において、シリカゾル
を混合しないで加熱処理を行うと、沈殿が生成してゾル
状物と沈殿物が共存した形になる。このシリカゾルの作
用については必ずしも明らかではないが、チタン酸が重
合する際の種子となるか、または安定化剤として作用す
るものと推定される。In the above-mentioned production method, when the heat treatment is performed without mixing the silica sol, a precipitate is formed, and the sol and the precipitate coexist. Although the action of this silica sol is not necessarily clear, it is presumed that the silica sol acts as a seed when polymerizing or acts as a stabilizer.
【００１７】このようにして得られた抗菌性無機酸化物
コロイド溶液は、限外濾過膜などを用いる公知の方法に
より所望の濃度に調整される。また、公知の方法により
分散媒を有機溶媒とすることも可能である。The antibacterial inorganic oxide colloid solution thus obtained is adjusted to a desired concentration by a known method using an ultrafiltration membrane or the like. It is also possible to use a dispersion medium as an organic solvent by a known method.
【００１８】本発明の抗菌剤は、従来の抗菌剤の用途に
使用可能であるが、特に、繊維に抗菌性を付与するのに
好適である。即ち、繊維状の微粒子が分散したコロイド
溶液であるために繊維に使用した場合、該微粒子は強固
に繊維に付着して長期にわたり抗菌効果や防カビ、防臭
効果を持続することができる。更に、繊維自体の物性、
風合いなどは全く損なわれないので、各種の繊維に対し
て抗菌性を付与することができる。The antibacterial agent of the present invention can be used for conventional antibacterial agents, but is particularly suitable for imparting antibacterial properties to fibers. That is, when used in a fiber because it is a colloidal solution in which fibrous fine particles are dispersed, the fine particles are firmly attached to the fibers and can maintain the antibacterial effect, the fungicide prevention, and the deodorization effect for a long time. Furthermore, the physical properties of the fiber itself,
Since the texture is not impaired at all, antibacterial properties can be imparted to various fibers.
【００１９】繊維としては、天然繊維（綿、羊毛、絹、
麻、パルプなど）、半合成繊維（レーヨン、キュプラ、
アセテートなど）、合成繊維（ポリエステル、ポリウレ
タン、ポリビニルアセタール、ポリアミド、ポリオレフ
ィン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリアク
リルニトリル、ポリフッ素など）、または、無機繊維
（ガラス、セラミックスなど）を挙げることができる。
これらの繊維に抗菌性を付与するには、繊維と本発明の
抗菌剤を接触させた後、水洗、乾燥する方法、あるい
は、繊維に本発明の抗菌剤をスプレーする方法など、公
知の方法を採用する。As the fibers, natural fibers (cotton, wool, silk,
Hemp, pulp, etc.), semi-synthetic fibers (rayon, cupra,
Acetate, etc.), synthetic fibers (polyester, polyurethane, polyvinyl acetal, polyamide, polyolefin, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyfluorine, etc.) or inorganic fibers (glass, ceramics, etc.). .
In order to impart antibacterial properties to these fibers, a known method such as a method of contacting the fibers with the antibacterial agent of the present invention, washing with water and drying, or a method of spraying the fibers with the antibacterial agent of the present invention is used. adopt.
【００２０】抗菌性付与の対象となる繊維としては、原
料繊維、中間繊維製品、および最終繊維製品のいずれも
が対象となる。最終繊維製品としては、例えば、一般衣
料品（ブラウス、スカート、ワイシャツ、ズボン、ドレ
ス、セーター、カーディガン、エプロン、ユニホーム、
パンツ、ストッキング、ソックス、パンティストッキン
グ、ブラジャー、ガードル、和装品、足袋、芯地、帯芯
地など）、身回品（ハンカチ、スカーフ、帽子、手袋、
時計バンド、カバン、手提げ袋、靴、履物、靴敷物な
ど）、インテリア用品（カーテン、ブラインド、カーペ
ット、マット、テーブルクロス、トイレタリー用品、カ
ーシートカバーなど）、日用雑貨品（タオル、ふきん、
モップ類、テント、寝袋、ぬいぐるみ、フィルター、ブ
ラシなど）、寝具類（毛布、敷布、タオルケット、寝装
カバー、布団側地、中綿など）、病院内で使用される製
品（看護婦などが着用する白衣、手術用着衣、マスク、
オムツ、オムツカバーなど）などが挙げられる。The fibers to be imparted with antibacterial properties include any of raw fibers, intermediate fiber products, and final fiber products. Examples of final textile products include general clothing (blouses, skirts, shirts, pants, dresses, sweaters, cardigans, aprons, uniforms,
Pants, stockings, socks, pantyhose, brassiere, girdle, kimono, tabi, interlining, obi interlining, etc., personal items (handkerchief, scarf, hat, gloves,
Watch bands, bags, handbags, shoes, footwear, shoe rugs, etc., interior goods (curtains, blinds, carpets, mats, tablecloths, toiletries, car seat covers, etc.), daily miscellaneous goods (towels, cloths,
Mops, tents, sleeping bags, stuffed animals, filters, brushes, etc., beddings (blankets, mattresses, towels, bedding covers, quilts, batting, etc.), products used in hospitals (nurses, etc.) White coat, surgical clothes, mask,
Diapers, diaper covers, etc.).
【００２１】また、本発明の抗菌剤に界面活性剤を含有
させれば、繊維とのなじみ性に優れるから、上記最終繊
維製品を洗濯した後、すすぎ洗時に該抗菌剤を添加して
抗菌性を手軽に付与することができる。本発明の抗菌剤
は、樹脂、ゴム、塗料などにも好適に使用される。Further, if a surfactant is contained in the antibacterial agent of the present invention, it is excellent in compatibility with fibers. Can be easily provided. The antibacterial agent of the present invention is suitably used for resins, rubbers, paints and the like.
【００２２】[0022]
【実施例】以下に実施例を示し、本発明を更に具体的に
説明する。The present invention will be described more specifically with reference to the following examples.
【００２３】〔抗菌性無機酸化物コロイド溶液の調製〕実施例１ 硫酸チタンを純水に溶解し、ＴｉＯ2 として１．０重量
％を含む水溶液を得た。この水溶液を撹拌しながら、１
５重量％アンモニア水を徐々に添加し、白色スラリー液
を得、このスラリー液を濾過、洗浄し、含水チタン酸の
ケーキを得た。このケーキ３３．０ｇに、純水と３３重
量％過酸化水素水２３０．８ｇを加えた後、８０℃で１
４時間加熱し、過酸化水素を加熱分解させ、ＴｉＯ2 と
して１．０重量％の溶液３２９３ｇを得た。このチタン
酸溶液は、黄褐色透明でｐＨは８．２であった。[0023] The [antimicrobial preparation of inorganic oxide colloidal solution] Example 1 titanium sulfate was dissolved in pure water to obtain an aqueous solution containing 1.0 wt% as TiO 2. While stirring this aqueous solution, 1
A 5% by weight aqueous ammonia was gradually added to obtain a white slurry, which was filtered and washed to obtain a wet titanic acid cake. After adding pure water and 230.8 g of 33% by weight hydrogen peroxide solution to 33.0 g of this cake,
The mixture was heated for 4 hours to thermally decompose hydrogen peroxide to obtain 3293 g of a 1.0% by weight solution as TiO 2 . This titanic acid solution was yellow-brown and transparent and had a pH of 8.2.
【００２４】次いで、１５重量％アンモニア水２１．３
ｇを純水６１８．１ｇで希釈したアンモニア水中で酸化
銀０．６８ｇを溶解して、銀のアンミン錯塩水溶液と
し、この水溶液を前記チタン酸溶液に加え、次に、２０
重量％シリカゾル３８．７ｇを加えた後、９５℃で６時
間加熱してコロイド溶液（Ａ）を得た。Next, 21.3% by weight of 15% aqueous ammonia was added.
g was dissolved in aqueous ammonia diluted with 618.1 g of pure water to dissolve 0.68 g of silver oxide to obtain an aqueous solution of an ammine complex salt of silver. This aqueous solution was added to the titanic acid solution.
After adding 38.7 g of a silica sol by weight, the mixture was heated at 95 ° C. for 6 hours to obtain a colloid solution (A).
【００２５】コロイド溶液（Ａ）は、酸化物換算で１．
５重量％の銀成分を含み、ｐＨは８．０で、固形分濃度
は１．０重量％であった。コロイド溶液（Ａ）の分散質
である微粒子の電子顕微鏡写真を図１に示す。該微粒子
の形状は繊維状であり、平均短径が２．２ｎｍ、平均長
径が２５ｎｍであり、平均アスペクト比は１１．４であ
った。The colloid solution (A) contains 1.1 in terms of oxide.
It contained 5% by weight of a silver component, had a pH of 8.0 and a solid content of 1.0% by weight. FIG. 1 shows an electron micrograph of fine particles which are dispersoids of the colloid solution (A). The shape of the fine particles was fibrous, the average minor axis was 2.2 nm, the average major axis was 25 nm, and the average aspect ratio was 11.4.
【００２６】実施例２ 硫酸チタンを純水に溶解し、ＴｉＯ2 として１．０重量
％を含む水溶液を得た。この水溶液を撹拌しながら、１
５重量％アンモニア水を徐々に添加し、白色スラリー液
を得、このスラリー液を濾過、洗浄し、含水チタン酸の
ケーキを得た。このケーキ３３．０ｇに、純水と３３重
量％過酸化水素水２３０．８ｇを加えた後、８０℃で１
４時間加熱し、過酸化水素を加熱分解させ、ＴｉＯ2 と
して１．０重量％の溶液３２９３ｇを得た。このチタン
酸溶液は、黄褐色透明でｐＨは８．２であった。このチ
タン酸溶液に２０重量％シリカゾル３８．７ｇを加えた
後、９５℃で２０時間加熱して、チタニア・シリカ複合
酸化物のコロイド溶液を得た。 Example 2 Titanium sulfate was dissolved in pure water to obtain an aqueous solution containing 1.0% by weight as TiO 2 . While stirring this aqueous solution, 1
A 5% by weight aqueous ammonia was gradually added to obtain a white slurry, which was filtered and washed to obtain a wet titanic acid cake. After adding pure water and 230.8 g of 33% by weight hydrogen peroxide solution to 33.0 g of this cake,
The mixture was heated for 4 hours to thermally decompose hydrogen peroxide to obtain 3293 g of a 1.0% by weight solution as TiO 2 . This titanic acid solution was yellow-brown and transparent and had a pH of 8.2. After adding 38.7 g of a 20% by weight silica sol to the titanic acid solution, the mixture was heated at 95 ° C. for 20 hours to obtain a colloid solution of a titania / silica composite oxide.
【００２７】次いで、１５重量％アンモニア水２１．３
ｇを純水６１８．１ｇで希釈したアンモニア水中で酸化
銀０．６８ｇを溶解して、銀のアンミン錯塩水溶液と
し、この水溶液を前記複合酸化物のコロイド溶液に加
え、９５℃で６時間加熱した。このコロイド溶液（Ｂ）
は、酸化物換算で１．５重量％の銀成分を含み、ｐＨは
８．１で、固形分濃度は１．０重量％であった。コロイ
ド溶液（Ｂ）の分散質である微粒子の形状は繊維状であ
り、平均短径が３．５ｎｍ、平均長径が１９．２ｎｍで
あり、平均アスペクト比は５．５であった。Then, 21.3% by weight of 15% aqueous ammonia was added.
g of silver oxide was dissolved in aqueous ammonia diluted with 618.1 g of pure water to obtain 0.68 g of silver oxide to obtain an aqueous solution of an ammine complex salt of silver. This aqueous solution was added to the colloid solution of the composite oxide, and heated at 95 ° C. for 6 hours. . This colloid solution (B)
Contained 1.5% by weight of a silver component in terms of oxide, had a pH of 8.1 and a solid content of 1.0% by weight. The fine particles as the dispersoid of the colloid solution (B) were fibrous, having an average minor axis of 3.5 nm, an average major axis of 19.2 nm, and an average aspect ratio of 5.5.
【００２８】比較例１ 硫酸チタンを純水に溶解し、ＴｉＯ2 として１．０重量
％を含む水溶液を得た。この水溶液を撹拌しながら、１
５重量％アンモニア水を徐々に添加し、白色スラリー液
を得、このスラリー液を濾過、洗浄し、含水チタン酸の
ケーキを得た。このケーキ３１．４ｇに、純水と３３重
量％過酸化水素水２１９．８ｇを加えた後、８０℃で１
４時間加熱し、過酸化水素を加熱分解させ、ＴｉＯ2 と
して１．０重量％の溶液３１３６ｇを得た。このチタン
酸溶液は、黄褐色透明でｐＨは８．２であった。 Comparative Example 1 Titanium sulfate was dissolved in pure water to obtain an aqueous solution containing 1.0% by weight as TiO 2 . While stirring this aqueous solution, 1
A 5% by weight aqueous ammonia was gradually added to obtain a white slurry, which was filtered and washed to obtain a wet titanic acid cake. To 31.4 g of this cake, 219.8 g of pure water and 33% by weight of hydrogen peroxide were added,
The mixture was heated for 4 hours to thermally decompose the hydrogen peroxide to obtain 3136 g of a 1.0% by weight solution as TiO 2 . This titanic acid solution was yellow-brown and transparent and had a pH of 8.2.
【００２９】次いで、１５重量％アンモニア水２１．３
ｇを純水６１８．１ｇで希釈したアンモニア水中で酸化
銀０．６８ｇを溶解して、銀のアンミン錯塩水溶液と
し、この水溶液に炭酸ジルコニウムアンモニウム１５．
４ｇを純水１６９．９ｇに溶解したものを添加した。こ
の混合水溶液を前記チタン酸溶液に加え、次に、２０重
量％シリカゾル３８．７ｇを加えた後、１５０℃で３６
時間加熱した。この溶液は、初期黄褐色液であったが、
３６時間後に淡乳白色透明なコロイド溶液（Ｃ）となっ
た。Then, 21.3% by weight of 15% aqueous ammonia was added.
0.68 g of silver oxide was dissolved in aqueous ammonia diluted with 618.1 g of pure water to obtain an aqueous solution of silver ammine complex salt.
A solution obtained by dissolving 4 g in 169.9 g of pure water was added. This mixed aqueous solution was added to the titanic acid solution, and then 38.7 g of a 20% by weight silica sol was added.
Heated for hours. This solution was initially a tan liquid,
After 36 hours, a pale milky white transparent colloid solution (C) was obtained.
【００３０】コロイド溶液（Ｃ）は、酸化物換算で１．
５重量％の銀成分を含み、ｐＨは７．５で、固形分濃度
は１．０重量％であった。コロイド溶液（Ｃ）の分散質
である微粒子の電子顕微鏡写真を図２に示す。該微粒子
の形状は棒状であり、平均短径が７．６ｎｍ、平均長径
が１８．１ｎｍであり、平均アスペクト比は２．４であ
った。The colloidal solution (C) has an oxide equivalent of 1.
It contained 5% by weight of a silver component, had a pH of 7.5 and a solid content of 1.0% by weight. FIG. 2 shows an electron micrograph of fine particles which are dispersoids of the colloid solution (C). The fine particles had a rod shape, an average minor axis of 7.6 nm, an average major axis of 18.1 nm, and an average aspect ratio of 2.4.
【００３１】比較例２ ＳｉＯ2 濃度２０重量％のコロイド溶液２０ｇと純水３
８０ｇの混合物を８０℃に加温した。この反応母液のｐ
Ｈは１０．７であり、同母液にＳｉＯ2 として１．５重
量％の珪酸ソーダ水溶液１５００ｇとＡｌ2 Ｏ3 として
０．５重量％のアルミン酸ソーダ水溶液１５００ｇとを
同時に添加して、ｐＨ１２．３のシリカ・アルミナ複合
酸化物コロイド溶液とした後、限外濾過膜で濃縮して固
形分濃度２２．２重量％のコロイド溶液を調製した。 Comparative Example 2 20 g of a colloid solution having a SiO 2 concentration of 20% by weight and pure water 3
80 g of the mixture was warmed to 80 ° C. P of this reaction mother liquor
H is 10.7, and 1500 g of a 1.5 wt% aqueous sodium silicate solution as SiO 2 and 1500 g of a 0.5 wt% aqueous sodium aluminate solution as Al 2 O 3 are simultaneously added to the mother liquor to obtain a pH of 12.2. The silica / alumina composite oxide colloid solution of No. 3 was then concentrated by an ultrafiltration membrane to prepare a colloid solution having a solid content of 22.2% by weight.
【００３２】一方、酸化銀０．５２ｇを約８０ｇの水に
懸濁し、次いで１５重量％のアンモニア水を酸化銀が溶
解するまで加え、銀の酸化物としての濃度が０．５重量
％となる様に水を加えて調整した。この銀アンミン錯塩
水溶液を前記コロイド溶液に添加して十分に撹拌し、銀
成分とシリカ・アルミナ複合酸化物コロイド粒子とから
なるコロイド溶液を調製した。このコロイド溶液を限外
濾過膜で濃縮して、固形分濃度１．０重量％のシリカ・
アルミナコロイド溶液（Ｄ）を得た。コロイド溶液
（Ｄ）は、酸化物換算で１．５重量％の銀成分を含み、
コロイド微粒子の平均粒径は１０．７ｎｍであり、ほぼ
球状であった。微粒子の電子顕微鏡写真を図３に示す。On the other hand, 0.52 g of silver oxide is suspended in about 80 g of water, and then 15% by weight of aqueous ammonia is added until the silver oxide is dissolved, so that the concentration of silver as an oxide becomes 0.5% by weight. Water was added in the same manner as above. This aqueous solution of silver ammine complex was added to the above colloid solution and stirred sufficiently to prepare a colloid solution comprising a silver component and silica / alumina composite oxide colloid particles. The colloid solution is concentrated by an ultrafiltration membrane to obtain a silica / silica having a solid content of 1.0% by weight.
An alumina colloid solution (D) was obtained. The colloid solution (D) contains 1.5% by weight of a silver component in terms of oxide,
The average particle size of the colloidal fine particles was 10.7 nm, and was almost spherical. An electron micrograph of the fine particles is shown in FIG.
【００３３】比較例３ 〔ゼオライト系抗菌剤の調製〕Ｎａ−Ｙ型ゼオライトを
水に懸濁して、濃度５重量％の懸濁スラリー４００ｇを
調製した。ついで、この懸濁スラリーを７０℃に加温
し、濃度５重量％のＡｇＮ０3 水溶液９．２ｇを添加
し、９０℃に加温して１時間放置することにより銀のイ
オン交換を行った。このスラリーを濾過し、６０℃の温
水で十分に洗浄後、１２０℃で乾燥し、更に５５０℃で
１時間焼成して粉末状の抗菌剤を調製した。この抗菌剤
は、酸化物換算で１．５重量％の銀成分を含み、平均粒
子径は、１．０μｍであり、四角形状を有し、平均アス
ペクト比は１．０であった。この抗菌剤を水に懸濁して
固形分濃度１．０重量％の懸濁液（Ｅ）を得た。 Comparative Example 3 [Preparation of Zeolite Antibacterial Agent] Na-Y type zeolite was suspended in water to prepare 400 g of a suspension slurry having a concentration of 5% by weight. Then warmed the suspension slurry 70 ° C., was added AgNO 3 aqueous solution 9.2g of 5 wt%, the ion exchange of silver was carried out by leaving warmed for 1 hour to 90 ° C.. The slurry was filtered, sufficiently washed with warm water at 60 ° C., dried at 120 ° C., and calcined at 550 ° C. for 1 hour to prepare a powdery antibacterial agent. This antibacterial agent contained 1.5% by weight of a silver component in terms of oxide, had an average particle size of 1.0 μm, had a square shape, and had an average aspect ratio of 1.0. This antibacterial agent was suspended in water to obtain a suspension (E) having a solid content of 1.0% by weight.
【００３４】〔抗菌剤の評価〕実施例３ （１）試料調製 実施例１、２で得た抗菌性無機酸化物コロイド溶液
（Ａ）、（Ｂ）、比較例１、２で得た抗菌性無機酸化物
コロイド溶液（Ｃ）、（Ｄ）、および、比較例３で得た
ゼオライト系抗菌剤懸濁液（Ｅ）の各２００ｇを、水１
９．８ｋｇに添加して、それぞれ、固形分濃度０．０１
重量％のコロイド溶液および懸濁液を調製した。[Evaluation of Antibacterial Agents] Example 3 (1) Sample Preparation The antibacterial inorganic oxide colloid solutions (A) and (B) obtained in Examples 1 and 2 and the antibacterial properties obtained in Comparative Examples 1 and 2 200 g of each of the inorganic oxide colloid solutions (C) and (D) and the zeolite-based antibacterial agent suspension (E) obtained in Comparative Example 3 were added to water 1
9.8 kg, and the solid content concentration was 0.01
Weight percent colloidal solutions and suspensions were prepared.
【００３５】これらの液をそれぞれ８０℃に加温し、１
ｋｇの綿タオルを入れ、３０分間浸漬した。その後、そ
れぞれ、ｐｉｃｋ−ｕｐ１００％になるようにしぼり、
１００℃で乾燥して、試料タオル（Ａ１）、（Ｂ１）、
（Ｃ１）、（Ｄ１）、（Ｅ１）を得た。Each of these solutions was heated to 80 ° C.
kg of cotton towel was placed and soaked for 30 minutes. Then, squeeze each to pick-up 100%,
After drying at 100 ° C., sample towels (A1), (B1),
(C1), (D1) and (E1) were obtained.
【００３６】さらに、上記試料タオルの一部を洗剤（花
王石鹸（株）製、ハイトップ）を使用して１０分間洗濯
した後、１リットルの水道水により５分間水洗する操作
を５０回繰り返し、最後に１００℃で乾燥して、試料タ
オル（Ａ２）、（Ｂ２）、（Ｃ２）、（Ｄ２）、（Ｅ
２）を得た。Further, the operation of washing a part of the sample towel for 10 minutes using a detergent (manufactured by Kao Soap Co., Ltd., High Top) and then washing with 1 liter of tap water for 5 minutes was repeated 50 times. Finally, the sample was dried at 100 ° C., and the sample towels (A2), (B2), (C2), (D2), (E
2) was obtained.
【００３７】前記１ｋｇの綿タオルの代わりに、１ｋｇ
のポリエステル繊維布を使用した以外は、全く同様にし
て、試料ポリエステル繊維布（ａ１）、（ｂ１）、（ｃ
１）、（ｄ１）、（ｅ１）を得た。さらに、上記試料タ
オルの場合と同様に洗濯、水洗操作を５０回繰り返し、
最後に１００℃で乾燥して、試料ポリエステル繊維布
（ａ２）、（ｂ２）、（ｃ２）、（ｄ２）、（ｅ２）を
得た。Instead of the 1 kg cotton towel, 1 kg
Sample polyester fiber cloths (a1), (b1), (c)
1), (d1) and (e1) were obtained. Further, the washing and washing operations are repeated 50 times as in the case of the sample towel,
Finally, it was dried at 100 ° C. to obtain sample polyester fiber cloths (a2), (b2), (c2), (d2), and (e2).
【００３８】（２）抗菌試験 大腸菌と黄色葡萄状球菌をリン酸バッファーに懸濁さ
せ、２００ｍｌの三角フラスコにこの溶液７５ｍｌと上
記各試料０．７５ｇを入れ、２５℃±５℃に保持して、
回転数３３０ｒｐｍで１時間振とう処理した。この処理
液の生菌数を測定して、下記の数１により減菌率を求め
た。結果を表１と表２に示す。(2) Antibacterial test Escherichia coli and Staphylococcus aureus were suspended in a phosphate buffer, and 75 ml of this solution and 0.75 g of each of the above samples were placed in a 200 ml Erlenmeyer flask and kept at 25 ° C. ± 5 ° C. ,
The shaking process was performed at 330 rpm for 1 hour. The number of viable bacteria in this treatment liquid was measured, and the sterilization rate was determined by the following equation (1). The results are shown in Tables 1 and 2.
【００３９】[0039]
【数１】減菌率（％）＝１００×（初期生菌数−１時間
後の生菌数）／初期生菌数[Equation 1] Sterility rate (%) = 100 × (initial viable cell count-1 viable cell count after 1 hour) / initial viable cell count
【００４０】[0040]
【表１】 綿タオルの減菌率（％） 洗濯０回の試料 洗濯50回の試料 試料No . 大腸菌 葡萄状球菌 試料No. 大腸菌 葡萄状球菌 Ａ１ 100 100 Ａ２ 99.2 99.8 Ｂ１ 100 100 Ｂ２ 95.0 92.6 Ｃ１ 100 99.9 Ｃ２ 80.3 76.0 Ｄ１ 100 98.1 Ｄ２ 50.3 49.0 Ｅ１ 0.0 0.0 Ｅ２ 0.0 0.0[Table 1]Cotton towel sterilization rate (%)Sample with no washing 50 samples of washing Sample No .E. coli Staphylococci Sample No.E. coli Staphylococci A1 100 100 A2 99.2 99.8 B1 100 100 B2 95.0 92.6 C1 100 99.9 C2 80.3 76.0 D1 100 98.1 D2 50.3 49.0 E1 0.0 0.0 E2 0.0 0.0
【００４１】[0041]
【表２】 ポリエステル繊維布の減菌率（％） 洗濯０回の試料 洗濯50回の試料 試料No . 大腸菌 葡萄状球菌 試料No. 大腸菌 葡萄状球菌 ａ１ 100 100 ａ２ 98.0 98.7 ｂ１ 100 100 ｂ２ 91.8 93.0 ｃ１ 98.1 92.0 ｃ２ 23.1 25.0 ｄ１ 79.2 71.0 ｄ２ 2.0 10.0 ｅ１ 5.2 0.0 ｅ２ 1.2 5.1[Table 2]Sterilization rate of polyester fiber cloth (%)Sample with no washing 50 samples of washing Sample No .E. coli Staphylococci Sample No.E. coli Staphylococci a1 100 100 a2 98.0 98.7 b1 100 100 b2 91.8 93.0 c1 98.1 92.0 c2 23.1 25.0 d1 79.2 71.0 d2 2.0 10.0 e1 5.2 0.0 e2 1.2 5.1
【００４２】表１と表２の結果から、本発明の抗菌剤
は、綿布は勿論のこと、ポリエステル繊維に対しても優
れた抗菌性を示し、また洗濯してもその抗菌性は殆ど低
下しないことが分かる。これは、本発明の抗菌剤の微粒
子が繊維に対する付着力が強いことを示している。From the results shown in Tables 1 and 2, the antibacterial agent of the present invention exhibits excellent antibacterial properties not only on cotton fabrics but also on polyester fibers, and its antibacterial properties hardly decrease even when washed. You can see that. This indicates that the fine particles of the antibacterial agent of the present invention have a strong adhesive force to fibers.
【００４３】[0043]
【発明の効果】本発明の抗菌剤は繊維状の微粒子が分散
したコロイド溶液であるから、特に、繊維に使用した場
合、該微粒子は強固に繊維に付着して長期にわたり抗菌
効果や防カビ、防臭効果を持続することができる。ま
た、繊維状のコロイド粒子はバインダーを用いなくても
強い付着力を有し、付着する繊維の種類に関係なく、耐
洗濯性などの耐久性に優れた抗菌性を発揮する。更に、
繊維自体の物性、風合いなどは全く損なわれない。Since the antibacterial agent of the present invention is a colloidal solution in which fibrous fine particles are dispersed, especially when used for fibers, the fine particles adhere firmly to the fibers and have a long-term antibacterial effect, antifungal property, The deodorant effect can be maintained. Further, the fibrous colloid particles have a strong adhesive force without using a binder, and exhibit excellent antibacterial properties such as washing resistance, etc., regardless of the type of fibers to be adhered. Furthermore,
The physical properties and texture of the fibers themselves are not impaired at all.
【図１】本発明の抗菌性無機酸化物微粒子の電子顕微鏡
写真（２５万倍）である。FIG. 1 is an electron micrograph (250,000 times) of the antibacterial inorganic oxide fine particles of the present invention.
【図２】比較例１における抗菌性無機酸化物微粒子の電
子顕微鏡写真（２５万倍）である。FIG. 2 is an electron micrograph (250,000 times) of antibacterial inorganic oxide fine particles in Comparative Example 1.
【図３】比較例２における抗菌性無機酸化物微粒子の電
子顕微鏡写真（２５万倍）である。FIG. 3 is an electron micrograph (250,000 times) of antibacterial inorganic oxide fine particles in Comparative Example 2.
───────────────────────────────────────────────────── 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 Ｃ１１Ｄ 3/48 Ｃ１１Ｄ 3/48 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code Agency reference number FI Technical display location C11D 3/48 C11D 3/48
Claims (3)
の無機酸化物とから構成される微粒子が分散してなる抗
菌性無機酸化物コロイド溶液であって、該微粒子の形状
が繊維状であることを特徴とする抗菌剤。An antibacterial inorganic oxide colloid solution comprising fine particles comprising an antibacterial metal component and an inorganic oxide other than the antibacterial metal component, wherein the fine particles have a fibrous shape. An antibacterial agent characterized by the following.
以上であることを特徴とする請求項１記載の抗菌剤。2. An aspect ratio of the fibrous particles is 3.0.
The antibacterial agent according to claim 1, which is the above.
酸化チタンを含有することを特徴とする請求項１または
請求項２記載の抗菌剤。3. The antibacterial agent according to claim 1, wherein the inorganic oxide other than the antibacterial metal component contains titanium oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19536396A JP3558460B2 (en) | 1996-07-05 | 1996-07-05 | Antibacterial agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19536396A JP3558460B2 (en) | 1996-07-05 | 1996-07-05 | Antibacterial agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1017406A true JPH1017406A (en) | 1998-01-20 |
| JP3558460B2 JP3558460B2 (en) | 2004-08-25 |
Family
ID=16339937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19536396A Expired - Lifetime JP3558460B2 (en) | 1996-07-05 | 1996-07-05 | Antibacterial agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3558460B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10237362A (en) * | 1997-02-26 | 1998-09-08 | Catalysts & Chem Ind Co Ltd | Electrodeposition coating material and electrodeposition coating |
| JPH11349423A (en) * | 1998-02-19 | 1999-12-21 | Daido Steel Co Ltd | Antibacterial and deodorant material and its production |
| JP2001271428A (en) * | 2000-03-24 | 2001-10-05 | Marukou Sangyo:Kk | Underfloor humidity control agent |
| US8486433B2 (en) | 2004-05-07 | 2013-07-16 | Jgc Catalysts And Chemicals Ltd. | Antibacterial deodorant |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01258792A (en) * | 1988-04-09 | 1989-10-16 | Kenji Ichikawa | Antibacterial agent, antibacterial base material and antibacterial water tank |
| JPH0680527A (en) * | 1992-08-31 | 1994-03-22 | Catalysts & Chem Ind Co Ltd | Antimicrobial agent |
| JPH0733616A (en) * | 1993-07-16 | 1995-02-03 | Catalysts & Chem Ind Co Ltd | Antimicrobial agent |
| JPH07118114A (en) * | 1993-10-22 | 1995-05-09 | Fukuda Metal Foil & Powder Co Ltd | Metallic powder for antimicrobial use and antimicrobial coating composition |
| JPH08104605A (en) * | 1994-10-05 | 1996-04-23 | Catalysts & Chem Ind Co Ltd | Antibacterial agent |
| JPH0913269A (en) * | 1995-06-28 | 1997-01-14 | Mitsubishi Rayon Co Ltd | Production of antimicrobial fiber |
-
1996
- 1996-07-05 JP JP19536396A patent/JP3558460B2/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01258792A (en) * | 1988-04-09 | 1989-10-16 | Kenji Ichikawa | Antibacterial agent, antibacterial base material and antibacterial water tank |
| JPH0680527A (en) * | 1992-08-31 | 1994-03-22 | Catalysts & Chem Ind Co Ltd | Antimicrobial agent |
| JPH0733616A (en) * | 1993-07-16 | 1995-02-03 | Catalysts & Chem Ind Co Ltd | Antimicrobial agent |
| JPH07118114A (en) * | 1993-10-22 | 1995-05-09 | Fukuda Metal Foil & Powder Co Ltd | Metallic powder for antimicrobial use and antimicrobial coating composition |
| JPH08104605A (en) * | 1994-10-05 | 1996-04-23 | Catalysts & Chem Ind Co Ltd | Antibacterial agent |
| JPH0913269A (en) * | 1995-06-28 | 1997-01-14 | Mitsubishi Rayon Co Ltd | Production of antimicrobial fiber |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10237362A (en) * | 1997-02-26 | 1998-09-08 | Catalysts & Chem Ind Co Ltd | Electrodeposition coating material and electrodeposition coating |
| JPH11349423A (en) * | 1998-02-19 | 1999-12-21 | Daido Steel Co Ltd | Antibacterial and deodorant material and its production |
| JP2001271428A (en) * | 2000-03-24 | 2001-10-05 | Marukou Sangyo:Kk | Underfloor humidity control agent |
| US8486433B2 (en) | 2004-05-07 | 2013-07-16 | Jgc Catalysts And Chemicals Ltd. | Antibacterial deodorant |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3558460B2 (en) | 2004-08-25 |
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