JP3197126B2 - Antibacterial fiber - Google Patents
Antibacterial fiberInfo
- Publication number
- JP3197126B2 JP3197126B2 JP27776993A JP27776993A JP3197126B2 JP 3197126 B2 JP3197126 B2 JP 3197126B2 JP 27776993 A JP27776993 A JP 27776993A JP 27776993 A JP27776993 A JP 27776993A JP 3197126 B2 JP3197126 B2 JP 3197126B2
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- fiber
- metal component
- weight
- solution
- 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 - Lifetime
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Description
【０００１】[0001]
【産業上の利用分野】本発明は抗菌性、防カビ性、消臭
効果等に優れた繊維に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber excellent in antibacterial property, antifungal property, deodorizing effect and the like.
【０００２】[0002]
【従来技術およびその問題点】例えば、特開平３−２０
５４３６号公報等には、ゼオライトやシリカゲル、酸化
チタン等の粉末に抗菌性を有する金属成分をイオン交換
や含浸などにより担持した抗菌剤を樹脂に練り込み、そ
れを紡糸して、あるいは、この抗菌剤をバインダーを用
いて繊維に付着して抗菌性繊維を製造する方法が開示さ
れている。2. Description of the Related Art For example, Japanese Patent Laid-Open No. 3-20 / 1990
No. 5436 and the like disclose an antibacterial agent in which a metal component having an antibacterial property is carried by powder such as zeolite, silica gel, and titanium oxide by ion exchange or impregnation into a resin, and spinning it, or A method for producing an antibacterial fiber by attaching an agent to a fiber using a binder is disclosed.
【０００３】しかし、上記従来の抗菌剤は粉末状でその
粒子径が大きいため、添加したときの分散性が悪く、不
透明であり、更に、紡糸する場合には、糸切れを引き起
こす原因となるなどの問題があった。また、抗菌性金属
成分を粉末に担持しているため利用効率が悪くて、抗菌
効果が発現しにくく、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り、金属成分の含有量
も多くなるので、銀などの抗菌性金属成分を用いた抗菌
剤を使用した繊維では変色が起こるといった問題点があ
った。However, since the conventional antibacterial agent is powdery and has a large particle size, it has poor dispersibility when added and is opaque. In addition, it causes thread breakage when spinning. There was a problem. In addition, since the antibacterial metal component is supported on the powder, the utilization efficiency is poor, the antibacterial effect is hardly exhibited, and in order to obtain a desired antibacterial activity,
It is necessary to add a large amount of an antibacterial agent, and the content of a metal component also increases. Therefore, there has been a problem that discoloration occurs in a fiber using an antibacterial agent using an antibacterial metal component such as silver.
【０００４】特開昭５９−３０９６３号公報には、平均
粒径２μｍ以下、より好ましくは０．５μｍ以下の金属
銅、金属銀及びこれらの酸化物から選ばれた少なくとも
１種の金属化合物粉末の水性分散液と繊維とを接触加熱
して該繊維に上記金属化合物粉末を付着させてなる殺菌
性繊維が提案されている。しかし、該粉末の水性分散液
は、銀成分や銅成分そのものが微粒子であるため、凝集
し易く安定性に欠け、取扱いが困難であり、また、該分
散液は青や灰褐色に着色しているため、繊維を変色する
という問題点を有している。Japanese Patent Application Laid-Open No. 59-30963 discloses a powder of at least one metal compound selected from metallic copper, metallic silver and their oxides having an average particle size of 2 μm or less, more preferably 0.5 μm or less. A germicidal fiber has been proposed in which an aqueous dispersion and a fiber are contact-heated to adhere the metal compound powder to the fiber. However, the aqueous dispersion of the powder, because the silver component and the copper component itself are fine particles, easily agglomerates and lacks stability and is difficult to handle, and the dispersion is colored blue or gray-brown. Therefore, there is a problem that the fiber is discolored.
【０００５】また、特開平４−２５５７６７号公報に
は、（ａ）合成樹脂エマルジョン、（ｂ）コロイド状も
しくは微粒子状の金属酸化物、シリカゲルおよび／また
はゼオライト、（ｃ）抗菌性金属の錯イオン、および
（ｄ）水、を主成分とするコーティング用組成物と、こ
の組成物を用いた繊維材料が開示されている。しかしな
がら、合成樹脂の使用によって繊維の風合いを損ね易く
なったり、また、合成樹脂中に抗菌性成分が埋没して、
抗菌活性を発現しにくく、更に、抗菌効果の持続性の点
において改良の余地が残されている。JP-A-4-255767 discloses (a) a synthetic resin emulsion, (b) a colloidal or particulate metal oxide, silica gel and / or zeolite, and (c) a complex ion of an antibacterial metal. , And (d) water, and a fiber material using the composition. However, the use of synthetic resin makes it easier to impair the texture of the fiber, and the antibacterial component is buried in the synthetic resin,
It is difficult to exhibit antibacterial activity, and there is still room for improvement in the sustainability of the antibacterial effect.
【０００６】[0006]
【発明の目的】本発明は、前述したような問題点を解決
して、優れた抗菌効果を長時間にわたり安定して維持す
ることができ、しかも、繊維製品の風合いを損なわず加
工が容易で、変色することがない抗菌性繊維を提供する
ことを目的とするものである。An object of the present invention is to solve the above-mentioned problems, to maintain an excellent antibacterial effect stably for a long time, and to facilitate processing without impairing the texture of textile products. It is an object of the present invention to provide an antibacterial fiber which does not discolor.
【０００７】[0007]
【発明の概要】本発明に係る抗菌性繊維は、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、平均粒子径が５００ｎｍ以下の微粒子が分散してな
る抗菌性無機酸化物コロイド溶液と、繊維を接触させて
得られる抗菌性繊維であって、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もので
ある。前記微粒子は無機複合酸化物であることが好まし
い。SUMMARY OF THE INVENTION The antimicrobial fiber according to the present invention comprises an antimicrobial metal component and an inorganic oxide other than the antimicrobial metal component, and is composed of fine particles having an average particle diameter of 500 nm or less dispersed therein. An antimicrobial fiber obtained by contacting an oxide colloid solution with a fiber, wherein the weight of the antimicrobial metal component in the colloid solution is A, and the antimicrobial metal component released by ultracentrifuging the colloid solution Let B be the weight of
The antibacterial metal component represented by B / A has a bonding strength index (I) of 1.0 × 10 −3 or less. The fine particles are preferably an inorganic composite oxide.
【０００８】[0008]
【０００９】[0009]
【発明の具体的な説明】本発明において、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
る微粒子は、抗菌性金属成分が無機酸化物と混合物また
は化合物の形で微粒子を形成するか、あるいは、該抗菌
性金属成分が無機酸化物微粒子の表面に結合している。
特に、該微粒子が抗菌性金属成分と無機酸化物との混合
物または化合物の形、即ち、複合酸化物を形成している
ことが、長時間にわたり抗菌効果を持続して有する上で
好ましい。DETAILED DESCRIPTION OF THE INVENTION In the present invention, fine particles comprising an antibacterial metal component and an inorganic oxide other than the antibacterial metal component are prepared by mixing the antibacterial metal component with the inorganic oxide in the form of a mixture or a compound. Fine particles are formed, or the antibacterial metal component is bonded to the surface of the inorganic oxide fine particles.
In particular, it is preferable that the fine particles form a mixture or compound of an antibacterial metal component and an inorganic oxide, that is, a composite oxide, in order to maintain the antibacterial effect for a long time.
【００１０】抗菌性金属成分としては、通常知られてい
るもの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, generally known ones can be used. For example, silver, copper, zinc,
Examples include tin, lead, bismuth, cadmium, chromium, and mercury. In particular, one or more antibacterial metal components selected from silver, copper, and zinc are preferable from the viewpoints of antibacterial action, discoloration, and safety to the human body.
【００１１】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。[0011] Copper ions as antibacterial components exhibit a blue color, whereas silver ions are originally colorless. 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.
【００１２】一方、本発明において、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, in the present invention, examples of the inorganic oxide other than the antibacterial metal component include a commonly known inorganic oxide constituting a colloid solution. Alternatively, it is possible to use composite oxide colloid particles or a mixture thereof.
【００１３】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 、ＳｎＯ2 ・
Ｓｂ2 Ｏ5 、ＳｉＯ2・Ａｌ2 Ｏ3 ・ＴｉＯ2 、ＳｉＯ
2 ・ＴｉＯ2 ・ＣｅＯ2 、ＴｉＯ2 ・ＳｉＯ2・ＺｒＯ
2 、ＳｉＯ2 ・Ａｌ2 Ｏ3 ・ＭｇＯ、ＳｉＯ2 ・Ａｌ2
Ｏ3 ・ＣａＯ、ＳｉＯ2 ・ＴｉＯ2 ・Ｆｅ2 Ｏ3 などを
挙げることができる。The single oxide colloid 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 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 , 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 · MgO, SiO 2 · Al 2
O 3 .CaO, SiO 2 .TiO 2 .Fe 2 O 3 and the like can be mentioned.
【００１４】本発明において抗菌性金属成分の量は、微
粒子中に酸化物換算で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、多量の微粒子を用いないと抗菌作用が
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。In the present invention, the amount of the antibacterial metal component is preferably in the range of 0.1 to 25% by weight in terms of oxide in the fine particles. When the amount of the antibacterial metal component is less than 0.1% by weight, the antibacterial effect is not sufficiently exhibited unless a large amount of fine particles are used. 25% by weight of antibacterial metal component
Even if the amount is larger, there is no great 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 increased. The preferred amount of the antibacterial metal component is
It is in the range of 0.1 to 15% by weight in terms of oxide.
【００１５】本発明において、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
は、コロイド粒子の次元の大きさのもので、その平均粒
子径は５００ｎｍ以下である。平均粒子径が５００ｎｍ
よりも大きくなると、該微粒子の透明性が悪くなり、繊
維製品の加工において変色が生じたり、また、該微粒子
と繊維との結合力が弱くなり、洗濯等の際に脱落し易
く、優れた抗菌効果を長時間にわたり安定して維持する
ことができない。該微粒子の平均粒子径は、好ましく
は、３００ｎｍ以下、更に好ましくは、３〜２５０ｎｍ
の範囲であることが望ましい。In the present invention, the fine particles composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component have a dimension of colloidal particles, and have an average particle diameter of 500 nm or less. . Average particle size is 500nm
If it is larger than this, the transparency of the fine particles deteriorates, discoloration occurs in the processing of fiber products, and the bonding force between the fine particles and the fibers is weakened, the particles easily fall off during washing, etc., and excellent antibacterial properties The effect cannot be stably maintained for a long time. The average particle diameter of the fine particles is preferably 300 nm or less, more preferably 3 to 250 nm.
Is desirably within the range.
【００１６】本発明が適用される繊維には、格別の制限
はなく、天然または合成の有機繊維、無機繊維を挙げる
ことができる。有機繊維としては、綿、亜麻、パルプな
どの植物繊維、羊毛、絹などの動物繊維、ナイロン、ビ
ニロン、ビニリデン、ポリエステル、アクリル、ポリウ
レタン、アセテートなどの合成繊維、また、無機繊維と
しては、アルミナ、アルミナ・シリカ、ジルコニア、ア
スベストなどの繊維が例示される。また、繊維の形態に
も特に制限はなく、例えば撚糸による繊維状、紡糸され
た糸状や長繊維、短繊維およびモノフイラメントなどが
例示され、それらの加工製品として織布、不織布が例示
される。The fibers to which the present invention is applied are not particularly limited, and include natural or synthetic organic fibers and inorganic fibers. As organic fibers, vegetable fibers such as cotton, flax, and pulp; animal fibers such as wool and silk; synthetic fibers such as nylon, vinylon, vinylidene, polyester, acrylic, polyurethane, and acetate; and inorganic fibers such as alumina, Fibers such as alumina / silica, zirconia, and asbestos are exemplified. The form of the fiber is also not particularly limited, and examples thereof include a fibrous form of twisted yarn, a spun yarn form, a long fiber, a short fiber, and a monofilament, and examples of the processed products thereof include a woven fabric and a nonwoven fabric.
【００１７】本発明の抗菌性繊維は、前記した微粒子を
０．０５〜５重量％の範囲で含有することが望ましい。
該微粒子は粒径が小さく、比表面積が大きいため、この
範囲内において繊維との密着性が高く、当該繊維と強く
付着する。一方、抗菌性繊維中における微粒子の含有量
が０．０５重量％より少ない場合には、所望の抗菌効果
が得られない。また、５重量％よりも多い場合には、微
粒子の凝集が多くなり、繊維にコーティングされた状態
となって、繊維との剥離が起こりやすく、また、繊維の
風合いを損なうようになる。The antimicrobial fiber of the present invention desirably contains the fine particles in a range of 0.05 to 5% by weight.
Since the fine particles have a small particle size and a large specific surface area, the fine particles have high adhesiveness to the fibers and strongly adhere to the fibers within this range. On the other hand, if the content of the fine particles in the antibacterial fiber is less than 0.05% by weight, the desired antibacterial effect cannot be obtained. On the other hand, if the content is more than 5% by weight, the aggregation of the fine particles increases, and the fiber is coated, so that the fiber easily peels off and the texture of the fiber is impaired.
【００１８】次に、本発明に係る抗菌性繊維の製造方法
について説明する。本発明方法で使用する抗菌性無機酸
化物コロイド溶液としては、本出願人が先に提案した特
願平５−１９８８９４号に記載の抗菌剤が好適である。Next, a method for producing the antibacterial fiber according to the present invention will be described. As the antibacterial inorganic oxide colloid solution used in the method of the present invention, the antibacterial agent described in Japanese Patent Application No. 5-198894 previously proposed by the present applicant is suitable.
【００１９】すなわち、該抗菌剤は、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、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ものである。That is, the antibacterial agent is 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 sample is A and the weight of the antimicrobial metal component released by ultracentrifugation of the colloid solution is B, the binding force index of the antimicrobial metal component represented by B / A The value of (I) is 1.0 × 10 −3
It is characterized by the following.
【００２０】前記結合力指数（Ｉ）は、次の方法により
求める。すなわち、抗菌性無機酸化物コロイド溶液中の
抗菌性金属成分の重量をプラズマ発光分光分析装置によ
り、金属原子を定量して求め、次いで、所定量の該抗菌
性無機酸化物コロイド溶液を回転数４５，０００ｒｐｍ
の超遠心分離機にて１時間処理して固形分と溶液に分離
し、この分離された溶液中に含まれる抗菌性金属成分の
金属原子をプラズマ発光分析装置で定量して、遊離した
抗菌性金属成分の重量とする。The bonding strength index (I) is obtained by the following method. That is, the weight of the antibacterial metal component in the antibacterial inorganic oxide colloid solution was determined by quantifying the metal atoms by a plasma emission spectrometer, and then a predetermined amount of the antibacterial inorganic oxide colloid solution was rotated at 45 rpm. 2,000rpm
1 hour by ultracentrifuge to separate the solid content and the solution, the metal atom of the antibacterial metal component contained in the separated solution is quantified by plasma emission analyzer, and the released antibacterial property It is the weight of the metal component.
【００２１】結合力指数（Ｉ）が１．０×１０-3より大
きい場合には、抗菌性金属成分の無機酸化物コロイド粒
子への結合力が弱いため、抗菌性無機酸化物コロイド溶
液の溶媒中に抗菌性金属成分が溶出しやすく、該微粒子
を繊維に含有せしめた際に抗菌効果の持続性に劣り、ま
た、抗菌性金属成分として銀を用いた場合には変色の原
因ともなるので好ましくない。抗菌性金属成分の結合力
指数（Ｉ）は、好ましくは５．０×１０-4以下、特に、
１．０×１０-4以下であることが望ましい。抗菌性金属
成分が２種以上の場合には、それぞれの抗菌性金属成分
の結合力指数が１．０×１０-3以下であることを要す
る。When the binding strength index (I) is larger than 1.0 × 10 -3 , the binding strength of the antibacterial metal component to the inorganic oxide colloid particles is weak, so that the solvent of the antibacterial inorganic oxide colloid solution is The antimicrobial metal component is easily eluted in the fiber, and the durability of the antimicrobial effect is inferior when the fine particles are contained in the fiber. In addition, when silver is used as the antimicrobial metal component, it is preferable because it causes discoloration. Absent. The bonding strength index (I) of the antibacterial metal component is preferably 5.0 × 10 −4 or less, particularly,
Desirably, it is 1.0 × 10 −4 or less. When there are two or more antibacterial metal components, the binding strength index of each antibacterial metal component needs to be 1.0 × 10 −3 or less.
【００２２】上記抗菌性無機酸化物コロイド溶液の中で
も、特に、微粒子が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の複合酸化物から構成されるもの
は、上記結合力指数（Ｉ）の値が小さいので好適であ
る。該複合酸化物の微粒子が分散した抗菌性無機酸化物
コロイド溶液は、例えば、特開平５−１３２３０９号公
報に記載された複合酸化物コロイド溶液の製造方法に準
じて調製することができる。即ち、アルカリ金属、アン
モニウムまたは有機塩基の珪酸塩と、アルカリ可溶の無
機化合物と、抗菌性金属成分の水溶液とを、ｐＨ１０以
上のアルカリ水溶液中に同時に添加し、抗菌性金属成分
と複合酸化物を形成した無機酸化物コロイド粒子を生成
させる方法である。Among the above antibacterial inorganic oxide colloid solutions, those in which the fine particles are composed of a composite oxide of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component are particularly suitable for the above-mentioned binding strength index ( This is suitable because the value of I) is small. The antibacterial inorganic oxide colloid solution in which the fine particles of the composite oxide are dispersed can be prepared, for example, according to the method for producing a composite oxide colloid solution described in JP-A-5-132309. That is, an alkali metal, ammonium or organic base silicate, an alkali-soluble inorganic compound, and an aqueous solution of an antibacterial metal component are simultaneously added to an aqueous alkaline solution having a pH of 10 or more, and the antibacterial metal component and the composite oxide are added. This is a method for generating inorganic oxide colloid particles formed with.
【００２３】また、特開昭６３−２７０６２０号公報に
記載された製造方法に準じて調製することもできる。即
ち、含水チタン酸のゲルまたはゾルに過酸化水素を加え
て得られるチタン酸水溶液と抗菌性金属成分の水溶液と
を、必要に応じてケイ素化合物および／またはジルコニ
ウム化合物等の存在下で加熱処理して、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
複合無機酸化物微粒子が分散したコロイド溶液を調製す
る方法である。Also, it can be prepared according to the production method described in JP-A-63-270620. That is, an aqueous solution of a titanic acid obtained by adding hydrogen peroxide to a gel or sol of hydrous titanic acid and an aqueous solution of an antibacterial metal component are subjected to a heat treatment in the presence of a silicon compound and / or a zirconium compound, if necessary. And preparing a colloid solution in which composite inorganic oxide fine particles composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component are dispersed.
【００２４】上記方法で得られた抗菌性無機酸化物コロ
イド溶液の分散媒である水は公知の方法により有機溶媒
と置換して、有機溶媒を分散媒とする抗菌性無機酸化物
コロイド溶液とすることも可能である。また、本発明に
おいて抗菌性無機酸化物コロイド溶液の濃度は、通常使
用に適したコロイド溶液の濃度に調節可能であるが、コ
ロイド溶液の安定性から言えば、酸化物として１〜１０
重量％の範囲とすることが好ましい。該コロイド溶液
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。Water, which is a dispersion medium of the antibacterial inorganic oxide colloid solution obtained by the above method, is replaced with an organic solvent by a known method to obtain an antibacterial inorganic oxide colloid solution using an organic solvent as a dispersion medium. It is also possible. Further, in the present invention, the concentration of the antibacterial inorganic oxide colloid solution can be adjusted to a concentration of the colloid solution suitable for normal use.
It is preferably in the range of% by weight. The colloid solution is adjusted to a desired concentration by a known method using an ultrafiltration membrane or the like.
【００２５】抗菌性無機酸化物コロイド溶液と繊維を接
触させる方法としては、該繊維にコロイド溶液中のコロ
イド粒子が付着あるいは混入し得る方法であれば、どの
ような方法であってもよい。例えば、該コロイド溶液を
繊維原料の樹脂と混合した後に紡糸する方法、あるい
は、該コロイド溶液を塗料として繊維に塗布または噴霧
する方法などを挙げることができる。最も簡便で、コロ
イド溶液の使用量が少なく、効率よく抗菌効果を持続し
て発現させる方法として、コロイド溶液に繊維を浸漬加
熱する方法を推奨することができる。As a method for bringing the fibers into contact with the colloidal solution of the antibacterial inorganic oxide, any method may be used as long as the colloidal particles in the colloidal solution can adhere to or mix with the fibers. For example, a method of spinning after mixing the colloid solution with a resin of a fiber raw material, or a method of applying or spraying the colloid solution as a paint on the fiber can be used. As the simplest method, the use amount of the colloid solution is small, and the method of continuously exhibiting the antibacterial effect efficiently, a method of immersing and heating the fiber in the colloid solution can be recommended.
【００２６】当該浸漬加熱は、通常の方法に従い、予め
調製されたコロイド溶液を所定温度、例えば５０〜１０
０℃までに昇温した後、１０〜６０分間、被処理繊維を
液中に浸漬し、次いで、乾熱法、蒸気法、電磁波法など
の一般的な方法により加熱するものである。The immersion heating is performed according to a usual method by heating the colloid solution prepared in advance at a predetermined temperature, for example, 50 to 10
After the temperature is raised to 0 ° C., the fiber to be treated is immersed in the liquid for 10 to 60 minutes, and then heated by a general method such as a dry heat method, a steam method, and an electromagnetic wave method.
【００２７】本発明のコロイド粒子は粒径が小さく、高
表面積を有しているため、繊維への付着力が強く、ま
た、コロイド粒子が有する電荷と繊維が有する電荷との
結合により繊維表面に定着する。なお、少量のカップリ
ング剤やアンカー剤等を併用して、該コロイド粒子の付
着、定着を促進してもよい。The colloidal particles of the present invention have a small particle size and a high surface area, so that they have a strong adhesive force to the fiber, and the charge of the colloidal particle and the charge of the fiber combine to form a particle on the fiber surface. Establish. Incidentally, a small amount of a coupling agent or an anchoring agent may be used in combination to promote the adhesion and fixation of the colloid particles.
【００２８】さらに、繊維に対しコロイド溶液を直接添
加して当該微粒子を繊維に付着させる方法も採用可能で
あり、繊維などを洗濯した後、すすぎ洗い時にコロイド
溶液を添加して抗菌性繊維を手軽に得ることができる。Further, a method of directly adding a colloid solution to the fibers to adhere the fine particles to the fibers can be adopted. After washing the fibers and the like, the colloid solution is added at the time of rinsing to easily remove the antibacterial fibers. Can be obtained.
【００２９】即ち、本発明の製造方法の一つの態様とし
ては、各家庭で行う通常の洗濯方法に従い、また、該抗
菌性無機酸化物コロイド溶液を洗剤の中に１成分として
加えたり、洗剤と同時に洗濯水の中に混入しても良い
が、すすぎ洗いの時に混入するのが好ましい。例えば、
５０Ｌの水に１０重量％の該抗菌性無機酸化物コロイド
溶液を１０〜１００ｍｌ、好ましくは３０〜６０ｍｌを
添加した後、衣類を投入し、所定時間すすぎ洗いをし
て、この衣類を干すという手順が取られる。That is, in one embodiment of the production method of the present invention, a normal washing method performed in each household is used, and the antibacterial inorganic oxide colloid solution is added as one component to the detergent, At the same time, it may be mixed in the washing water, but it is preferable to mix it during rinsing. For example,
A procedure of adding 10 to 100 ml, preferably 30 to 60 ml of the 10% by weight of the antibacterial inorganic oxide colloid solution to 50 L of water, putting in clothes, rinsing for a predetermined time, and drying the clothes. Is taken.
【００３０】[0030]
【実施例】以下に実施例を挙げ、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.
【００３１】製造例１ 〔抗菌性無機酸化物コロイド溶液の調製〕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、１５重量％アン
モニア水を徐々に添加し、白色のスラリー液を得、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に水溶液濃度が１．０重量％
になるように純水を加えて希釈し、更に３３重量％過酸
化水素２１９．８ｇを加えた後、８０℃で１４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。[0031] Production Example 1 [Preparation of antibacterial inorganic oxide colloidal solution] sulfuric acid titanium was dissolved in pure water to obtain an aqueous solution containing 1.0 wt% as TiO 2. While stirring this aqueous solution, 15% by weight aqueous ammonia was gradually added to obtain a white slurry, which was filtered and washed to obtain a wet titanic acid cake. An aqueous solution concentration of 1.0% by weight was added to 31.4 g of the cake.
Pure water was added to dilute the mixture, and 219.8 g of 33% by weight of hydrogen peroxide was further added. The mixture was heated at 80 ° C. for 14 hours to thermally decompose the hydrogen peroxide to form TiO 2 of 1.0%.
3136 g of a% by weight solution were obtained. This titanic acid solution
It was tan transparent and had a PH of 8.2.
【００３２】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水溶液に加え、次に、２０
重量％シリカゾル３８．７ｇを加えた後、１５０℃で４
８時間加熱した。この溶液は、初期黄褐色液であった
が、４８時間後に淡乳白色透明なコロイド溶液となっ
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 is added to the titanic acid aqueous solution.
After adding 38.7 g of a silica sol by weight,
Heated for 8 hours. This solution was initially a yellow-brown liquid, but became a pale milky white transparent colloid solution after 48 hours.
【００３３】この複合酸化物コロイド溶液（Ａ）は、酸
化物換算で１．５重量％の銀成分を含み、ＰＨは７．５
で、固形分濃度は１．０重量％であり、コロイド粒子の
平均粒径は、５．０ｎｍであった。なお、このコロイド
溶液（Ａ）の抗菌性金属成分の結合力指数（Ｉ）の値
は、０．６×１０-4であった。This composite oxide colloid solution (A) contains 1.5% by weight of a silver component in terms of oxide, and has a pH of 7.5.
The solid content concentration was 1.0% by weight, and the average particle size of the colloid particles was 5.0 nm. The value of the binding force index (I) of the antibacterial metal component of the colloid solution (A) was 0.6 × 10 −4 .
【００３４】製造例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。 Production 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.
【００３５】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濃度
調整して、固形分濃度１．０重量％のシリカ・アルミナ
コロイド溶液を得た。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、コロイド粒子の
平均粒径は１０．７ｎｍでり、抗菌性金属成分の結合力
指数（Ｉ）の値は、４．８×１０-4であった。On the other hand, 0.52 g of silver oxide is suspended in about 80 g of water, and 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 concentration of this colloid solution was adjusted to obtain a silica-alumina colloid solution having a solid concentration of 1.0% by weight. This colloid solution (B) contains 1.5% by weight of a silver component in terms of oxide, the average particle size of the colloid particles is 10.7 nm, and the value of the binding force index (I) of the antibacterial metal component is 4.8 × 10 -4 .
【００３６】製造例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
（Ｃ）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であった。 Production 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 (C) contains 1.5% by weight of a silver component in terms of oxide,
The average particle size was 1.0 μm.
【００３７】実施例１ 製造例１で得たコロイド溶液（Ａ）の５００ｇに５００
ｍｌの純水を添加して、０．５重量％のコロイド溶液を
調製した。この溶液を６０℃に加温し、溶液中に５０ｃ
ｍ×５０ｃｍの綿ガーゼを入れ、３０分間浸漬した。そ
の後、ガーゼを純水にてすすぎ洗いし、６０℃で乾燥し
て抗菌性繊維を得た。 Example 1 500 g of the colloid solution (A) obtained in Production Example 1
A 0.5% by weight colloid solution was prepared by adding ml of pure water. This solution is heated to 60 ° C., and 50 c
A cotton gauze of mx 50 cm was put and immersed for 30 minutes. Thereafter, the gauze was rinsed with pure water and dried at 60 ° C. to obtain an antibacterial fiber.
【００３８】更に、このガーゼを洗剤（ハイトップ、花
王石鹸（株）製）を使用して１０分間洗濯し、その後、
１Ｌの水道水で５分間の水洗いを行った。これらの操作
を３０回繰り返した。Further, the gauze was washed for 10 minutes using a detergent (HITOP, manufactured by Kao Soap Co., Ltd.), and thereafter,
Washing was performed with 1 L of tap water for 5 minutes. These operations were repeated 30 times.
【００３９】実施例２ ポリエチレンモノフィラメントからなる絨毯５０ｃｍ×
５０ｃｍに対して、実施例１と同様の処理を行い、抗菌
性繊維を得た。また、実施例１と同様に、洗濯操作を３
０回繰り返した。 Example 2 A carpet made of polyethylene monofilament 50 cm ×
The same treatment as in Example 1 was performed on 50 cm to obtain an antibacterial fiber. Further, similarly to the first embodiment, the washing operation is performed three times.
Repeated 0 times.
【００４０】実施例３ ナイロン・ポリウレタンからなるパンティストッキング
５０ｃｍ×５０ｃｍに対して、実施例１と同様の処理を
行い、抗菌性繊維を得た。また、実施例１と同様に、洗
濯操作を３０回繰り返した。 Example 3 An antibacterial fiber was obtained by performing the same treatment as in Example 1 on a panty hose 50 cm × 50 cm made of nylon / polyurethane. The washing operation was repeated 30 times in the same manner as in Example 1.
【００４１】実施例４ 製造例２で得たコロイド溶液（Ｂ）の５００ｇに５００
ｍｌの純水を添加して、０．５重量％のコロイド溶液を
調製した。この溶液を６０℃に加温し、溶液中に５０ｃ
ｍ×５０ｃｍの綿ガーゼを入れ、３０分間浸漬した。そ
の後、ガーゼを純水にてすすぎ洗いし、６０℃で乾燥し
て抗菌性繊維を得た。 Example 4 500 g of the colloid solution (B) obtained in Production Example 2
A 0.5% by weight colloid solution was prepared by adding ml of pure water. This solution is heated to 60 ° C., and 50 c
A cotton gauze of mx 50 cm was put and immersed for 30 minutes. Thereafter, the gauze was rinsed with pure water and dried at 60 ° C. to obtain an antibacterial fiber.
【００４２】更に、このガーゼを洗剤（ハイトップ、花
王石鹸（株）製）を使用して１０分間洗濯し、その後、
１Ｌの水道水で５分間の水洗いを行った。これらの操作
を３０回繰り返した。Further, the gauze was washed for 10 minutes using a detergent (High Top, manufactured by Kao Soap Co., Ltd.), and thereafter,
Washing was performed with 1 L of tap water for 5 minutes. These operations were repeated 30 times.
【００４３】比較例１ 製造例３で得たゼオライト系抗菌剤（Ｃ）の５．０ｇを
１．０Ｌの純水に添加し、０．５重量％スラリーを調製
した。このスラリーを６０℃に加温し、スラリー中に５
０ｃｍ×５０ｃｍの綿ガーゼを入れ、３０分間浸漬し
た。その後、ガーゼを純水にてすすぎ洗いし、６０℃で
乾燥して抗菌性繊維を得た。また、実施例１と同様に、
洗濯操作を３０回繰り返した。 Comparative Example 1 5.0 g of the zeolite-based antibacterial agent (C) obtained in Production Example 3 was added to 1.0 L of pure water to prepare a 0.5% by weight slurry. This slurry was heated to 60 ° C., and 5
A cotton gauze of 0 cm × 50 cm was put and immersed for 30 minutes. Thereafter, the gauze was rinsed with pure water and dried at 60 ° C. to obtain an antibacterial fiber. Further, similarly to the first embodiment,
The washing operation was repeated 30 times.
【００４４】実施例５ 洗濯機の中に４０Ｌの水、洗剤（ハイトップ、花王石鹸
（株）製）１カップ、約４ｋｇの作業着（長袖ジャンパ
ー、クラボウ製）を入れて、丸洗いをした。すすぎ操作
において、製造例１で得たコロイド溶液（Ａ）の５０ｇ
を添加し、すすぎ洗いをした。その後、脱水し、天日干
を行い、抗菌処理衣類を得た。 Example 5 A washing machine was charged with 40 L of water, 1 cup of detergent (Hi-Top, manufactured by Kao Soap Co., Ltd.), and about 4 kg of work clothes (long-sleeved jumper, manufactured by Kurabo Industries), and washed in a round. In the rinsing operation, 50 g of the colloid solution (A) obtained in Production Example 1
Was added and rinsed. After that, it was dehydrated and dried in the sun to obtain antibacterial clothing.
【００４５】比較例２ 製造例３で得たゼオライト系抗菌剤（Ｃ）の１．０ｇを
１．０Ｌの純水に添加し、０．１重量％スラリーを調製
した。実施例５と同様の方法で作業着を処理したとこ
ろ、水は白濁した。 Comparative Example 2 1.0 g of the zeolite-based antibacterial agent ( C ) obtained in Production Example 3 was added to 1.0 L of pure water to prepare a 0.1% by weight slurry. When the work clothes were treated in the same manner as in Example 5 , the water became cloudy.
【００４６】実施例６ 〔抗菌力試験〕実施例１〜５および比較例１〜２で得た
抗菌性繊維（実施例１〜４と比較例１については、洗濯
しないものと洗濯を３０回行ったものの双方）について
抗菌力試験を行った。大腸菌および黄色葡萄状球菌を生
理食塩水中に懸濁させ、２００ｍｌの三角フラスコにこ
の溶液２０ｍｌと抗菌性繊維０．５ｇを採り、１６０回
／ｍｉｎのシェイクを行った。この処理溶液から０．１
ｍｌをシャーレ上に採取し、２８℃で２４時間放置後、
生菌数を測定して式１により死滅率を求めた。結果を表
１に示す。 Example 6 [Antibacterial Test] The antibacterial fibers obtained in Examples 1 to 5 and Comparative Examples 1 and 2 (Examples 1 to 4 and Comparative Example 1 were not washed and washed 30 times. Were tested for antimicrobial activity. Escherichia coli and Staphylococcus aureus were suspended in physiological saline, and 20 ml of this solution and 0.5 g of antibacterial fiber were placed in a 200 ml Erlenmeyer flask and shaken at 160 times / min. 0.1%
ml on a Petri dish and left at 28 ° C for 24 hours.
The number of viable bacteria was measured, and the mortality was determined by equation 1. Table 1 shows the results.
【００４７】[0047]
【式１】死滅率（％）＝１００×（初期生菌数−２４時
間後の生菌数）／初期生菌数Formula 1: Death rate (%) = 100 × (initial viable cell count−viable cell count after 24 hours) / initial viable cell count
【００４８】[0048]
【表１】 死滅率（％） 30回処理死滅率（％） 大腸菌 葡萄状球菌 大腸菌 葡萄状球菌 実施例１ 100 100 98.2 100 実施例２ 96.1 97.5 95.4 98.0 実施例３ 90.3 95.9 88.9 94.1 実施例４ 99.8 100 82.5 87.8 実施例５ 98.6 100 − − 比較例１ 66.8 68.3 18.3 21.2 比較例２ 35.9 38.2 − −Table 1 Kill rate (% ) 30 times treatment Kill rate (% ) E. coli staphylococcus E. coli E. staphylococci Example 1 100 100 98.2 100 Example 2 96.1 97.5 95.4 98.0 Example 3 90.3 95.9 88.9 94.1 Example 4 99.8 100 82.5 87.8 Example 5 98.6 100--Comparative Example 1 66.8 68.3 18.3 21.2 Comparative Example 2 35.9 38.2--
【００４９】[0049]
【発明の効果】本発明の抗菌性繊維は、平均粒子径が５
００ｎｍ以下の抗菌性を有する微粒子が均一且つ強固に
繊維に付着しており、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、次のような
各種の用途に有用である。即ち、本発明の抗菌性繊維を
利用した製品として、例えば、衣料用として靴下、下着
類、おむつ、洋服地、スポーツウェアなど、家庭用とし
てカーテン、シーツ、カーペット、壁布、絨毯、包装紙
など、医療用としてシーツ、枕カバー、包帯、ティシ
ュ、紙おむつ、抗菌紙など、フィルター用としてエアー
フィルター、脱臭フィルター、防毒マスクなど、紙材と
して壁紙、障子紙、襖紙などが挙げられる。The antibacterial fiber of the present invention has an average particle size of 5
Fine particles having an antibacterial property of 00 nm or less are uniformly and firmly attached to the fiber, and have a long-term antibacterial effect and antifungal
The deodorant effect can be maintained. Furthermore, since the physical properties and texture of the fiber itself are not impaired at all, it is useful for the following various uses. That is, as a product using the antibacterial fiber of the present invention, for example, socks, underwear, diapers, clothes, sportswear, etc. for clothing, curtains, sheets, carpets, wall cloths, carpets, wrapping paper, etc. for home use Sheets, pillow covers, bandages, tissues, disposable diapers, antibacterial paper, etc. for medical use, air filters, deodorizing filters, gas masks, etc. for filters, and wallpaper, shoji paper, fusuma paper, etc. as paper materials.
【００５０】また、本発明の抗菌性繊維を無機繊維とし
たものにあっては、含有される微粒子が結合剤としても
作用するため、無機繊維製品の機械的強度を向上させる
ことができるという効果も有している。Further, in the case where the antibacterial fiber of the present invention is made of inorganic fiber, the fine particles contained also act as a binder, so that the mechanical strength of the inorganic fiber product can be improved. Also have.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ // Ｄ０６Ｍ 101:00 (56)参考文献 特開 平４−21615（ＪＰ，Ａ) 特開 平３−275627（ＪＰ，Ａ) 特開 昭62−215506（ＪＰ，Ａ) 特開 平３−205436（ＪＰ，Ａ) 特開 平４−255767（ＪＰ，Ａ) 特開 平５−132309（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) D06M 11/00 - 11/84 Continuation of the front page (51) Int.Cl. 7 Identification symbol FI // D06M 101: 00 (56) References JP-A-4-21615 (JP, A) JP-A-3-275627 (JP, A) JP 62-215506 (JP, A) JP-A-3-205436 (JP, A) JP-A-4-255767 (JP, A) JP-A 5-132309 (JP, A) (58) Fields studied (Int .Cl. 7 , DB name) D06M 11/00-11/84
Claims (2)
の無機酸化物とから構成され、平均粒子径が５００ｎｍ
以下の微粒子が分散してなる抗菌性無機酸化物コロイド
溶液と、繊維を接触させて得られる抗菌性繊維であっ
て、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性繊維。1. An antibacterial metal component and an inorganic oxide other than the antibacterial metal component, and having an average particle diameter of 500 nm.
Antibacterial inorganic oxide colloid comprising the following fine particles dispersed
Antibacterial fiber obtained by contacting the solution with the fiber
The weight of the antibacterial metal component in the colloid solution is A,
Antibacterial metal released by ultracentrifugation of colloid solution
Antibacterial gold represented by B / A, where B is the weight of the component
When the value of the binding strength index (I) of the genus component is 1.0 × 10 −3 or less
Antibacterial fiber, characterized in that there.
項１記載の抗菌性繊維。2. The method according to claim 1, wherein the fine particles are an inorganic composite oxide.
Item 7. The antibacterial fiber according to Item 1 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27776993A JP3197126B2 (en) | 1993-10-08 | 1993-10-08 | Antibacterial fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27776993A JP3197126B2 (en) | 1993-10-08 | 1993-10-08 | Antibacterial fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07109674A JPH07109674A (en) | 1995-04-25 |
| JP3197126B2 true JP3197126B2 (en) | 2001-08-13 |
Family
ID=17588075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27776993A Expired - Lifetime JP3197126B2 (en) | 1993-10-08 | 1993-10-08 | Antibacterial fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3197126B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000178870A (en) * | 1998-12-18 | 2000-06-27 | Catalysts & Chem Ind Co Ltd | Antimicrobially processing method for textile product |
| US20040178135A1 (en) * | 2003-03-13 | 2004-09-16 | Beplate Douglas K. | Filtering device incorporating nanoparticles |
| JP2009108448A (en) * | 2007-10-31 | 2009-05-21 | Jgc Catalysts & Chemicals Ltd | Deodorizing and antimicrobial fiber |
-
1993
- 1993-10-08 JP JP27776993A patent/JP3197126B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07109674A (en) | 1995-04-25 |
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