JP4658813B2 - Antibacterial fibers, woven or knitted fabrics, non-woven fabrics, wallpaper, and insulation - Google Patents
Antibacterial fibers, woven or knitted fabrics, non-woven fabrics, wallpaper, and insulation Download PDFInfo
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- JP4658813B2 JP4658813B2 JP2006008083A JP2006008083A JP4658813B2 JP 4658813 B2 JP4658813 B2 JP 4658813B2 JP 2006008083 A JP2006008083 A JP 2006008083A JP 2006008083 A JP2006008083 A JP 2006008083A JP 4658813 B2 JP4658813 B2 JP 4658813B2
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- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Landscapes
- Knitting Of Fabric (AREA)
- Artificial Filaments (AREA)
- Woven Fabrics (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は、有機系抗菌剤および無機系抗菌剤を含有して繊維形状に成形された抗菌性繊維、さらにはこの抗菌性繊維を含む織布または編布、不織布、壁紙および断熱材に関する。 The present invention relates to an antibacterial fiber formed into a fiber shape containing an organic antibacterial agent and an inorganic antibacterial agent, and further relates to a woven or knitted fabric, a nonwoven fabric, a wallpaper, and a heat insulating material containing the antibacterial fiber.
細菌などの原核生物、カビ、酵母などの真核生物、さらには藻類などの微生物を除去や忌避する抗菌性組成物として、各微生物に対して２種類以上の薬剤を組み合わせることで、相乗効果が得られることが知られている。すなわち、２種類以上の薬剤を併用することで、抗菌スペクトルが拡大したり、最小生育阻止濃度（ＭＩＣ値：Minimum Inhibitory Concentrationの略）（ｐｐｍ）が各薬剤を単独使用する場合に比して減少したりするといった相乗効果を奏する。そして、異なる種類の薬剤を併用する方法として、有機系抗菌剤および無機系抗菌剤を用いる構成が知られている（例えば、特許文献１参照）。 As an antibacterial composition that removes or repels prokaryotes such as bacteria, eukaryotes such as fungi and yeast, and microorganisms such as algae, a synergistic effect can be obtained by combining two or more drugs against each microorganism. It is known to be obtained. In other words, by using two or more drugs together, the antibacterial spectrum is expanded, and the minimum growth inhibitory concentration (MIC value: Abbreviation for Minimum Inhibitory Concentration) (ppm) is reduced compared to when each drug is used alone. There is a synergistic effect. And the structure using an organic type antimicrobial agent and an inorganic type antimicrobial agent is known as a method of using together a different kind of chemical | medical agent (for example, refer patent document 1).
この特許文献１に記載のものは、銀、銅、亜鉛などの金属成分と、この金属成分以外の無機酸化物とからなり抗菌・防黴・防藻性作用を有する無機酸化物微粒子と、チアゾール系化合物およびイミダゾール系化合物のうちの少なくともいずれか一方の有機系抗菌・防黴・防藻剤と、を含有している。そして、無機酸化物微粒子は、分散性や被処理物の表面色調などに及ぼす影響により、平均粒子径を５００ｎｍ以下としている。また、無機酸化物微粒子の含有量は、併用する効果のために０．００１重量％以上としている。 The thing of this patent document 1 consists of inorganic oxide microparticles | fine-particles which consist of metal components, such as silver, copper, and zinc, and inorganic oxides other than this metal component, and have antibacterial / antifungal / algaeproof action, and thiazole And an organic antibacterial / antifungal / algae-proofing agent of at least one of the organic compound and the imidazole compound. The inorganic oxide fine particles have an average particle size of 500 nm or less due to the influence on the dispersibility, the surface color tone of the object to be processed, and the like. Further, the content of the inorganic oxide fine particles is set to 0.001% by weight or more for the effect of combined use.
ところで、抗菌性組成物は、生活環境中に使用されるものであることから、例えば、被処理物に抗菌性組成物を塗布するなどの際に皮膚に付着したり、抗菌性組成物を塗布あるいは含有した成形体に利用者が接触したりしても、かぶれるなどの人体に影響がない薬剤を用いる必要がある。また、抗菌性組成物を塗布あるいは含有した成形体を例えば焼却処理する際に、ダイオキシンなどの有害物質が発生しない薬剤を用いる必要がある。 By the way, since the antibacterial composition is used in the living environment, for example, when the antibacterial composition is applied to the object to be treated, it adheres to the skin or the antibacterial composition is applied. Or it is necessary to use the chemical | medical agent which does not have influence on the human body, such as a rash, even if a user contacts the containing molded object. In addition, when a molded body on which an antibacterial composition is applied or contained, for example, is incinerated, it is necessary to use a chemical that does not generate harmful substances such as dioxin.
一方、抗菌性組成物を調製する際や抗菌性組成物を含有する成形体を成形する際などの製造工程において、混合する際の容器や成形時の金型など、製造設備の腐食を生じさせない薬剤が望ましい。すなわち、製造設備に耐腐食性の材料を用いるなど、製造設備に特別な装置が必要となって製造設備の構築性が低下したりコストが増大したりするなどの不都合が生じない薬剤を対象とすることが望ましい。 On the other hand, in the manufacturing process such as when preparing an antibacterial composition or when molding a molded article containing the antibacterial composition, it does not cause corrosion of manufacturing equipment such as containers for mixing and molds for molding. Drugs are desirable. In other words, it is intended for drugs that do not cause inconveniences such as the use of a corrosion-resistant material for the manufacturing equipment, which requires special equipment in the manufacturing equipment, and the construction efficiency of the manufacturing equipment is reduced or the cost is increased. It is desirable to do.
しかしながら、上述した特許文献１に記載のような従来の有機系および無機系を併用して効果を得る抗菌性組成物は、組み合わせによって十分な相乗効果が発揮できず、限られた微生物にのみしか相乗効果が得られない。すなわち、抗菌スペクトルを大きく拡大できない。さらには、抗菌スペクトルが拡大する抗菌性を発揮させるためには、ＭＩＣ値が増大、すなわち添加量が増大し、効率的な抗菌作用が得られないとともに、添加量の増大による成形体の成形性が困難となるなどの不都合も生じるおそれがある。また、２−（ｎ−オクチル）−４−イソチアゾール−３−オン（略称ＯＩＴ）、１，２−ベンツイソチアゾリン−３−オン（略称ＢＩＴ）などのアレルギ性物質も用いられている。 However, the antibacterial composition which obtains an effect by using a combination of the conventional organic and inorganic systems as described in Patent Document 1 described above cannot exhibit a sufficient synergistic effect by the combination, and is limited to only limited microorganisms. A synergistic effect cannot be obtained. That is, the antibacterial spectrum cannot be greatly expanded. Furthermore, in order to exhibit antibacterial properties with an expanded antibacterial spectrum, the MIC value is increased, that is, the amount added is increased, an efficient antibacterial action cannot be obtained, and the moldability of the molded product due to the increased amount added Inconveniences such as difficulty may occur. In addition, allergenic substances such as 2- (n-octyl) -4-isothiazol-3-one (abbreviation OIT) and 1,2-benzisothiazolin-3-one (abbreviation BIT) are also used.
本発明の目的は、抗菌作用が発揮される微生物の種類が多く効率的な抗菌作用が得られ人体や環境に影響のない抗菌性繊維、織布または編布、不織布、壁紙、および、断熱材を提供する。 An object of the present invention is to provide antibacterial fibers, woven fabrics or knitted fabrics, non-woven fabrics, wallpaper, and heat insulating materials that have many types of microorganisms that exhibit antibacterial effects and have an effective antibacterial effect and do not affect the human body or the environment. I will provide a.
本発明に記載の抗菌性繊維は、高分子材料と、イミダゾール系の有機系抗菌剤から選ばれた少なくとも２種、および無機系抗菌剤を含有する抗菌性組成物と、を含有した原料が、紡糸されたことを特徴とする。
この発明では、高分子材料に少なくとも２種のイミダゾール系の有機系抗菌剤と、無機系抗菌剤とを併用して含有させた繊維である。
このことにより、抗菌スペクトルを広げるために化学的に異種な抗菌剤を用いるという従来の公知知見からは全く予想できないイミダゾール系単一の有機系抗菌剤の組み合わせと、さらに無機系抗菌剤とを組み合わせるにより、著しく広い抗菌スペクトルを達成でき、かつ皮膚刺激性が認められず、人体や環境に影響がない本発明の抗菌性組成物を含有させることで、適宜紡糸した繊維に、皮膚刺激性が陰性で安全性が高く、人体や環境に影響が極めて少なく、かつ、相乗効果による低い最小育成素子濃度（ＭＩＣ値）でも格段に広い抗菌スペクトルが得られ、効率よく高い抗菌作用を発現させることができる。
なお、本発明において、「抗菌性（抗菌効果）」とは、真菌や細菌などの菌類の生育や繁殖を阻止するといった抗菌効果そのものに加え、防カビ・抗カビ効果や、防藻効果といったものも含むものである。
The antibacterial fiber according to the present invention includes an antibacterial composition containing a polymer material, at least two types selected from imidazole-based organic antibacterial agents, and an inorganic antibacterial agent, It is characterized by being spun.
In the present invention, the fiber contains at least two kinds of imidazole organic antibacterial agents and inorganic antibacterial agents in combination in the polymer material.
As a result, a combination of a single organic imidazole antibacterial agent that cannot be predicted from the conventional knowledge of using chemically different antibacterial agents to broaden the antibacterial spectrum, and an inorganic antibacterial agent By using the antibacterial composition of the present invention, which can achieve a remarkably wide antibacterial spectrum, has no skin irritation, and does not affect the human body or the environment, the fiber that is spun appropriately has negative skin irritation. High safety, very little impact on human body and environment, and a very wide antibacterial spectrum can be obtained even with a low minimum growth element concentration (MIC value) due to a synergistic effect, and a high antibacterial effect can be expressed efficiently. .
In the present invention, “antibacterial effect (antibacterial effect)” refers to an antibacterial / antifungal effect, an antialgal effect, in addition to the antibacterial effect itself such as inhibiting the growth and reproduction of fungi such as fungi and bacteria. Is also included.
そして、高分子材料中に抗菌性組成物を０．０１質量％以上１０．０質量％以下で含有されたことが好ましい。抗菌性組成物の含有量を０．０１質量％以上１０．０質量％以下とすることで、例えば強度や外観などの特性を損なうことなく顕著な抗菌性を発揮する成形体として提供できる。
ここで、抗菌性組成物の含有量が０．０１質量％より少なくなると、少ないＭＩＣ値での抗菌スペクトルの拡大が得られにくくなり、十分な抗菌性を発揮できなくなるおそれがある。一方、抗菌性組成物の含有量が１０．０質量％より多くなると、成形体の特性が損なわれたり、成形時における作業性が低下したりするなどの不都合を生じるおそれがある。したがって、抗菌性組成物の含有量を０．０１質量％以上１０．０質量％以下とすることが好ましい。特に、０．０５質量％以上２質量％以下とすることが好ましい。
And it is preferable to contain 0.01 to 10.0 mass% of antibacterial compositions in the polymeric material. By setting the content of the antibacterial composition to 0.01% by mass or more and 10.0% by mass or less, for example, it can be provided as a molded product that exhibits remarkable antibacterial properties without impairing properties such as strength and appearance.
Here, when the content of the antibacterial composition is less than 0.01% by mass, it is difficult to obtain an expansion of the antibacterial spectrum with a small MIC value, and there is a possibility that sufficient antibacterial properties cannot be exhibited. On the other hand, when the content of the antibacterial composition is more than 10.0% by mass, there is a possibility that the characteristics of the molded body are impaired or the workability at the time of molding is deteriorated. Therefore, the content of the antibacterial composition is preferably 0.01% by mass or more and 10.0% by mass or less. In particular, it is preferably 0.05% by mass or more and 2% by mass or less.
さらに、繊維全質量に対して無機系抗菌剤が０．５質量％未満の割合で含有される状態に抗菌性組成物を含有し、社団法人繊維評価技術協議会で規定された殺菌活性値（一般用途）を、以下の条件としていることが好ましい。
ｌｏｇ（Ａ／Ｃ）≧０
Ａ：接種直後の標準布の菌数
Ｃ：１８時間培養後の加工布の生菌数
菌種：黄色ブドウ球菌と肺炎桿菌
本発明では、成形体中に本発明の抗菌性組成物を配合したときに、その成形体中に含まれる無機系抗菌剤が０．５質量％未満であっても、社団法人繊維評価技術協議会で規定された殺菌活性値がｌｏｇ（Ａ／Ｃ）≧０を満たし、広い抗菌スペクトルを示し低いＭＩＣ値の抗菌効果を発揮する。
特に、無機系抗菌剤が０．０３質量％以上、好ましくは０．１質量％以上とすることで、この抗菌効果が良好に発揮される。このような抗菌性組成物が低濃度でも、本発明の抗菌性組成物は、従来の抗菌性組成物では到底得られない広い抗菌スペクトルを示し低いＭＩＣ値の優れた抗菌効果を示す。
Furthermore, the antibacterial composition is contained in a state in which the inorganic antibacterial agent is contained at a ratio of less than 0.5% by mass with respect to the total mass of the fiber, and the bactericidal activity value defined by the Fiber Evaluation Technology Council ( The general conditions are preferably set as follows.
log (A / C) ≧ 0
A: Bacteria count of standard cloth immediately after inoculation C: Viable count of processed cloth after 18 hours of cultivation Bacterial species: Staphylococcus aureus and Klebsiella pneumoniae In the present invention, the antibacterial composition of the present invention was blended in the molded body Sometimes, even if the inorganic antibacterial agent contained in the molded body is less than 0.5% by mass, the bactericidal activity value defined by the Fiber Evaluation Technology Council is log (A / C) ≧ 0. Satisfies and exhibits a broad antibacterial spectrum and exhibits an antibacterial effect with a low MIC value.
In particular, when the inorganic antibacterial agent is 0.03% by mass or more, preferably 0.1% by mass or more, this antibacterial effect is exhibited well. Even when such an antibacterial composition has a low concentration, the antibacterial composition of the present invention exhibits a broad antibacterial spectrum that cannot be obtained by conventional antibacterial compositions, and exhibits an excellent antibacterial effect with a low MIC value.
本発明の抗菌性繊維を構成する繊維としては、無機系高分子材料、有機系高分子材料、それらの混合物のいずれかから成る繊維が問題なく使用できる。例えば無機系高分子材料からなる繊維の一例としては、ガラス繊維、炭素繊維、セラミック繊維、バサルトファイバーなどが挙げられる。有機系高分子材料からなる繊維の例としては、合成繊維、再生繊維、天然繊維などが挙げられる。そして、本発明では、前記有機系高分子材料が、熱可塑性樹脂でることが好ましい。
本発明では、高分子材料として例えばポリプロピレン、ポリエチレンなどのポリオレフィン、ナイロンなどのポリアミド、ポリエチレンテレフタレートやポリブチレンテレフタレートなどのポリエステルなどの熱可塑性樹脂を用い、溶融紡糸により繊維形状に成形することから、一般的な各種溶融紡糸方法にて、効率よく高い抗菌作用を発現する繊維が容易に得られる。
繊維の形状としては、通常の単独繊維や、海・島構造の繊維、芯鞘構造の繊維、２以上の成分が積層した繊維などの複合繊維のいずれのタイプでもよい。複合繊維にする場合、前記抗菌性組成物は芯と鞘どちらに入れてもよく、両方とも入れてもよい。また、芯または鞘部の片方に前記抗菌性組成物を、残り一方に帯電防止剤や、遠赤外線効果のある鉱石など、保温性物質、キシリトールなどの涼感性物質、などを入れて複合繊維とするなどしてもよい。
As the fiber constituting the antibacterial fiber of the present invention, a fiber composed of any one of an inorganic polymer material, an organic polymer material, and a mixture thereof can be used without any problem. For example, glass fibers, carbon fibers, ceramic fibers, basalt fibers, and the like are examples of fibers made of inorganic polymer materials. Examples of fibers made of organic polymer materials include synthetic fibers, regenerated fibers, and natural fibers. In the present invention, the organic polymer material is preferably a thermoplastic resin.
In the present invention, for example, a thermoplastic material such as polyolefin such as polypropylene or polyethylene, polyamide such as nylon, polyester such as polyethylene terephthalate or polybutylene terephthalate, and the like is formed into a fiber shape by melt spinning. Various types of melt spinning methods can easily obtain fibers that exhibit high antibacterial activity efficiently.
The shape of the fiber may be any type of a normal single fiber, a fiber having a sea / island structure, a fiber having a core-sheath structure, or a composite fiber such as a fiber in which two or more components are laminated. When making a composite fiber, the antibacterial composition may be placed in either the core or the sheath, or both. In addition, the antibacterial composition is put on one side of the core or the sheath, and the other side is put an antistatic agent, an ore having a far-infrared effect, a heat-retaining substance, a cool-sensitive substance such as xylitol, etc. You may do it.
また、本発明の抗菌性繊維は、前記高分子材料および抗菌性組成物が溶剤中に溶解または分散している溶液を用いて、公知の湿式紡糸法で製造した湿式繊維でもよい。
本発明では、湿式紡糸法の繊維に用いる前記高分子材料は、溶剤に溶解するものであれば特に制限はないが、好ましくは、セルロースと、セルロース系エステルと、ポリアクリロニトリルと、エチレンとビニルアルコールの共重合体と、のうちの少なくともいずれかを主骨格とするポリマであり、湿式紡糸された構成とすることが好ましい。
本発明では、一般的な各種湿式紡糸方法にて、効率よく高い抗菌作用を発現する繊維が容易に得られる。
The antibacterial fiber of the present invention may be a wet fiber manufactured by a known wet spinning method using a solution in which the polymer material and the antibacterial composition are dissolved or dispersed in a solvent.
In the present invention, the polymer material used for the fiber of the wet spinning method is not particularly limited as long as it is soluble in a solvent, but preferably cellulose, cellulose ester, polyacrylonitrile, ethylene and vinyl alcohol. It is preferable that the polymer has a main skeleton of at least one of these copolymers and is a wet-spun structure.
In the present invention, fibers that exhibit high antibacterial activity efficiently can be easily obtained by various general wet spinning methods.
そして、本発明では、溶融紡糸、湿式紡糸などの周知の方法で紡糸されて得られた繊維や、その繊維の集合体（不織布、布帛、わたなど）に前記抗菌性組成物が含浸されたものも含まれる。
本発明では、紡糸されて得られた繊維に、さらに抗菌性組成物を含浸させるので、溶融紡糸法や湿式紡糸法などで繊維を製造し難い場合でも、本願の抗菌性繊維を得ることができる。例えば、ガラス繊維やバサルトファイバーなどのように湿式紡糸ができず、溶融紡糸は、前記抗菌性組成物の少なくとも有機系抗菌剤の耐熱温度を著しく超える温度でしかできない繊維にも抗菌性を簡単に付与することができる。また、高分子材料と混合する抗菌性組成物の配合割合を低減させることができることから、紡糸時における繊維の切断などの不都合を防止でき、製造効率の向上が容易に得られる。
In the present invention, fibers obtained by spinning by a known method such as melt spinning and wet spinning, and aggregates of the fibers (nonwoven fabric, fabric, cotton, etc.) are impregnated with the antibacterial composition. Is also included.
In the present invention, since the fiber obtained by spinning is further impregnated with the antibacterial composition, the antibacterial fiber of the present application can be obtained even when it is difficult to produce the fiber by a melt spinning method or a wet spinning method. . For example, anti-bacterial properties can be easily applied to fibers such as glass fibers and basalt fibers, which cannot be wet-spun and melt spinning can only be performed at temperatures significantly exceeding the heat resistance temperature of at least the organic anti-bacterial agent of the anti-bacterial composition. Can be granted. In addition, since the blending ratio of the antibacterial composition mixed with the polymer material can be reduced, inconveniences such as fiber cutting during spinning can be prevented, and an improvement in production efficiency can be easily obtained.
また、本発明では、前記抗菌性組成物は、１μｍ以下の平均粒径に粒度調整された構成とすることが好ましい。
本発明では、抗菌性組成物として、１μｍ以下の平均粒径に粒度調整しておくことで、高分子材料に対する分散性が向上するとともに、紡糸時の滑動性や繊維の表面の平滑性、紡糸安定性（紡糸時に糸切れし難い）が得られる。また、抗菌性組成物が繊維中、繊維表面に良分散することで、安定した高い抗菌作用を繊維に発揮させることが容易に得られる。
In the present invention, it is preferable that the antibacterial composition has a particle size adjusted to an average particle size of 1 μm or less.
In the present invention, by adjusting the particle size to an average particle size of 1 μm or less as the antibacterial composition, dispersibility in the polymer material is improved, and the slidability at the time of spinning, the smoothness of the fiber surface, spinning Stability (hard to break during spinning) is obtained. In addition, when the antibacterial composition is well dispersed on the fiber surface in the fiber, it is possible to easily obtain a stable and high antibacterial effect on the fiber.
本発明に記載の抗菌性繊維は、高分子材料と、無機系抗菌剤とを含有した原料が紡糸された紡糸繊維に、イミダゾール系の有機系抗菌剤から選ばれた少なくとも２種が含浸されたことを特徴とする。
この発明では、高分子材料に無機系抗菌剤を含有させた原料を紡糸して得られた紡糸繊維に、少なくとも２種のイミダゾール系の有機系抗菌剤を含浸させる、繊維中に少なくとも２種のイミダゾール系の有機系抗菌剤と、無機系抗菌剤とを併用して含有させる。
このことにより、高分子材料を基材として、抗菌スペクトルを広げるために化学的に異種な抗菌剤を用いるという従来の公知知見からは全く予想できないイミダゾール系単一の有機系抗菌剤の組み合わせにより、著しく広い抗菌スペクトルを達成でき、かつ皮膚刺激性が陰性で安全性が高く、人体や環境に影響が極めて少ない本発明の抗菌性組成物を含有させることで、適宜紡糸した繊維に、皮膚刺激性が陰性で安全性が高く、人体や環境に影響が極めて少なく、かつ、相乗効果による低い最小育成素子濃度（ＭＩＣ値）でも格段に広い抗菌スペクトルが得られ、効率よく高い抗菌作用を発現させることができる。
In the antibacterial fiber according to the present invention, a spun fiber obtained by spinning a raw material containing a polymer material and an inorganic antibacterial agent is impregnated with at least two kinds selected from imidazole organic antibacterial agents. It is characterized by that.
In the present invention, at least two kinds of imidazole organic antibacterial agents are impregnated into a spun fiber obtained by spinning a raw material containing a polymer material containing an inorganic antibacterial agent. An imidazole organic antibacterial agent and an inorganic antibacterial agent are used in combination.
As a result of the combination of a single organic imidazole antibacterial agent that cannot be predicted from the conventional known knowledge that a chemically different antibacterial agent is used to broaden the antibacterial spectrum using a polymer material as a base material, By including the antibacterial composition of the present invention, which can achieve a remarkably broad antibacterial spectrum, has negative skin irritation, high safety, and extremely little influence on the human body and the environment, the skin irritation is appropriately added to the spun fiber. Negative, high safety, very little impact on the human body and environment, and a much broader antibacterial spectrum can be obtained even with a low minimum growth element concentration (MIC value) due to a synergistic effect, so that a high antibacterial effect can be expressed efficiently. Can do.
そして、本発明では、前記無機系抗菌剤は、１μｍ以下の平均粒径に粒度調整された構成とすることが好ましい。
本発明では、無機系抗菌剤として、１μｍ以下の平均粒径に粒度調整しておくことで、有機系抗菌剤に比して混ざりにくい高分子材料に対する分散性が向上するとともに、紡糸時の滑動性や繊維の表面の平滑性が得られるなど、良好な無機系抗菌剤の含有状態が容易に得られる。したがって、安定した高い抗菌作用を繊維に発揮させることが容易に得られる。
In the present invention, the inorganic antibacterial agent is preferably configured to have a particle size adjusted to an average particle size of 1 μm or less.
In the present invention, as an inorganic antibacterial agent, by adjusting the particle size to an average particle size of 1 μm or less, dispersibility to a polymer material that is difficult to mix as compared with an organic antibacterial agent is improved, and sliding during spinning Good inorganic antibacterial content can be easily obtained, for example, the property and the smoothness of the fiber surface can be obtained. Therefore, it is possible to easily obtain a stable and high antibacterial effect on the fiber.
また、本発明では、前記イミダゾール系の有機系抗菌剤から選ばれた２種は、ベンゾイミダゾール環にチアゾリル基を有するものと、ベンゾイミダゾール環にカーバメート基を有するものとである。
本発明では、イミダゾール系の有機系抗菌剤として、ベンゾイミダゾール環にチアゾリル基を有するものとカーバメート基を有するものとの２種、特に２種のみを併用することで、同一のイミダゾール系でも、人体や環境に影響がなく、かつ、相乗効果による低いＭＩＣ値でも格段に広い抗菌スペクトルが得られるという抗菌作用が容易に得られ、特にこれらの併用により顕著な抗菌性が得られる。
なお、ベンゾイミダゾール環にチアゾリル基を有するものは、２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールであり、前記ベンゾイミダゾール環にカーバメート基を有するものは、２−ベンゾイミダゾールカルバミン酸メチルであることが好ましい。これらベンゾイミダゾール環にチアゾリル基を有する２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールと、カーバメート基を有する２−ベンゾイミダゾールカルバミン酸メチルとの２種を併用することで、特に併用による相乗効果にて顕著な抗菌性が得られる。さらに、これら２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールと、２−ベンゾイミダゾールカルバミン酸メチルとは、比較的に製造しやすく入手が容易で、既に利用されている材料で安全性が認められたものであることから、容易に利用できる。
Further, in the present invention, two selected from organic antibacterial agent of the imidazole system, and having a benzimidazole ring thiazolyl group, Ru der to those having a carbamate group on a benzimidazole ring.
In the present invention, as an imidazole-based organic antibacterial agent, a combination of two types, one having a thiazolyl group on a benzimidazole ring, and one having a carbamate group, in particular only two types, can be used in the same imidazole system. In addition, the antibacterial action that a remarkably broad antibacterial spectrum can be obtained even with a low MIC value due to a synergistic effect can be easily obtained, and remarkable antibacterial properties can be obtained particularly by the combined use thereof.
In addition, what has a thiazolyl group in a benzimidazole ring is 2- (4-thiazolyl) -1H-benzimidazole, and what has a carbamate group in the said benzimidazole ring is methyl 2-benzimidazole carbamate Is preferred. By using two kinds of 2- (4-thiazolyl) -1H-benzimidazole having a thiazolyl group in these benzimidazole rings and methyl 2-benzimidazole carbamate having a carbamate group, particularly in combination with the synergistic effect. Outstanding antibacterial properties. Furthermore, these 2- (4-thiazolyl) -1H-benzimidazoles and methyl 2-benzimidazole carbamate are relatively easy to produce and readily available, and safety has been recognized in the materials already used. Therefore, it can be used easily.
また、本発明では、前記無機系抗菌剤は、銀系抗菌剤と酸化亜鉛とのうちの少なくともいずれか一方であることが好ましい。
本発明では、無機系抗菌剤として、銀系抗菌剤と酸化亜鉛とのうちの少なくともいずれか一方を用いるので、顕著な抗菌性が容易に得られる。そして、銀系抗菌剤と酸化亜鉛とを併用することにより、銀系抗菌剤および酸化亜鉛自体による抗菌作用とともに、これら同一の無機系抗菌剤でも併用することで抗菌作用の相乗効果も得られ、より顕著な抗菌性が容易に得られる。
なお、銀系抗菌剤は、銀を担持したジルコニウムまたはその塩あるいはゼオライトであることが好ましい。銀系抗菌剤として銀を担持したジルコニウムまたはその塩あるいはゼオライトを用いることで、貴金属である銀が抗菌作用を発揮する必要最小限の量となり、効率よく無機系抗菌剤による抗菌作用が得られるとともに有機系抗菌剤との抗菌作用の相乗効果が得られ、コストの低減も容易に図れる。
また、無機系抗菌剤としては、銀を担持したジルコニウムまたはその塩あるいはゼオライトと酸化亜鉛との配合割合が、質量比で１：１〜１：１０であることが好ましい。銀を担持したジルコニウムまたはその塩あるいはゼオライトと、酸化亜鉛とを併用することで、同一の無機系抗菌剤でも併用による抗菌作用の相乗効果が得られ、より顕著な抗菌性が得られる。さらに、無機系抗菌剤自体による抗菌作用と、無機系抗菌剤の併用による抗菌作用の相乗効果と、有機系抗菌剤との抗菌作用の相乗効果とが損なわれることなく、貴金属である銀の使用量が低減し、コストの低減がより容易に図れる。そして、銀を担持したジルコニウムまたはその塩あるいはゼオライトと酸化亜鉛との配合割合が、質量比で１：１〜１：１０であることから、抗菌性が損なわれることなく適切に銀の使用量が低減する。
ここで、銀を担持したジルコニウムまたはその塩あるいはゼオライトと酸化亜鉛との配合割合が、質量比で１：１より酸化亜鉛が少なくなると、銀の使用量の低減による十分なコストの低減が得られにくくなる。また、銀の酸化による変色が問題となるおそれもある。一方、質量比で１：１０より酸化亜鉛が多くなると、銀による十分な抗菌作用が得られにくくなるおそれがある。したがって、銀を担持したジルコニウムまたはその塩あるいはゼオライトと酸化亜鉛との配合割合を質量比で１：１〜１：１０とすることが好ましい。
さらに、イミダゾール系の有機系抗菌剤と無機系抗菌剤との配合割合は、質量比で１：１〜５：１であることが好ましい。イミダゾール系の有機系抗菌剤と無機系抗菌剤との配合割合を、質量比で１：１〜５：１とすることで、有機系抗菌剤や無機系抗菌剤自体の抗菌作用とともに、有機系抗菌剤と無機系抗菌剤との併用による顕著な抗菌作用の相乗効果が適切に得られる。
ここで、有機系抗菌剤と無機系抗菌剤との配合割合が、質量比で１：１より有機系抗菌剤が少なくなると、少ないＭＩＣ値での抗菌スペクトルの拡大が得られなくなるおそれがある。一方、質量比で５：１より有機系抗菌剤が多くなると、無機系抗菌剤に比して初期抗菌性能が遅く抗菌性能の持続性が低減しやすい有機系抗菌剤の割合が多くなり、使用当初から長期間に亘って安定した顕著な抗菌性が得られなくなるおそれがある。したがって、ベンゾイミダゾール系の有機系抗菌剤と無機系抗菌剤との配合割合を、質量比で１：１〜５：１とすることが好ましい。
In the present invention, the inorganic antibacterial agent is preferably at least one of a silver antibacterial agent and zinc oxide.
In this invention, since at least any one of a silver type antibacterial agent and a zinc oxide is used as an inorganic type antibacterial agent, remarkable antibacterial property is easily obtained. And by using silver antibacterial agent and zinc oxide together, together with the antibacterial action by silver antibacterial agent and zinc oxide itself, the synergistic effect of antibacterial action can also be obtained by using these same inorganic antibacterial agents together, More remarkable antibacterial properties can be easily obtained.
The silver antibacterial agent is preferably zirconium carrying silver or a salt thereof or zeolite. By using silver or its salt or zeolite supporting silver as the silver antibacterial agent, the noble metal silver is the minimum necessary amount to exert the antibacterial action, and the antibacterial action by the inorganic antibacterial agent can be obtained efficiently. The synergistic effect of the antibacterial action with the organic antibacterial agent is obtained, and the cost can be easily reduced.
Moreover, as an inorganic type antibacterial agent, it is preferable that the compounding ratio of zirconium carrying silver or a salt thereof or zeolite and zinc oxide is 1: 1 to 1:10 by mass ratio. By using together silver-supported zirconium or a salt thereof or zeolite and zinc oxide, a synergistic effect of antibacterial action by the combined use can be obtained even with the same inorganic antibacterial agent, and more remarkable antibacterial properties can be obtained. Furthermore, the use of silver, a precious metal, without compromising the synergistic effect of the antibacterial effect of the inorganic antibacterial agent itself, the antibacterial effect of the combined use of the inorganic antibacterial agent, and the antibacterial effect of the organic antibacterial agent The amount is reduced and the cost can be reduced more easily. And since the compounding ratio of the zirconium which supported silver, its salt or zeolite, and zinc oxide is 1: 1-1: 10 by mass ratio, the usage-amount of silver is appropriately used, without impairing antibacterial property. Reduce.
Here, when the amount of zirconium supported on silver or a salt thereof or zeolite and zinc oxide is less than 1: 1 in terms of mass ratio, sufficient cost reduction can be obtained by reducing the amount of silver used. It becomes difficult. In addition, discoloration due to silver oxidation may be a problem. On the other hand, when zinc oxide is more than 1:10 by mass ratio, it may be difficult to obtain a sufficient antibacterial action due to silver. Therefore, it is preferable that the mixing ratio of zirconium carrying silver or a salt thereof or zeolite and zinc oxide is 1: 1 to 1:10 by mass ratio.
Furthermore, the blending ratio of the imidazole organic antibacterial agent and the inorganic antibacterial agent is preferably 1: 1 to 5: 1 by mass ratio. By combining the imidazole organic antibacterial agent and the inorganic antibacterial agent in a mass ratio of 1: 1 to 5: 1, the organic antibacterial agent or the inorganic antibacterial agent itself has an antibacterial action as well as an organic antibacterial agent. The synergistic effect of the remarkable antibacterial action by combined use of an antibacterial agent and an inorganic antibacterial agent is appropriately obtained.
Here, if the organic antibacterial agent and the inorganic antibacterial agent are mixed in an organic antibacterial agent with a mass ratio of less than 1: 1, the antibacterial spectrum may not be expanded with a small MIC value. On the other hand, when the amount of organic antibacterial agent is larger than 5: 1 by mass ratio, the proportion of organic antibacterial agents that are slow in initial antibacterial performance and easy to reduce the durability of antibacterial performance is higher than that of inorganic antibacterial agents. There is a risk that stable antibacterial properties that are stable over a long period from the beginning cannot be obtained. Therefore, it is preferable that the blending ratio of the benzimidazole organic antibacterial agent and the inorganic antibacterial agent is 1: 1 to 5: 1 by mass ratio.
本発明に記載の織布または編布は、本発明の抗菌性繊維が織り込まれたことを特徴とする。
本発明では、上述した本発明の抗菌性繊維を織り込んでいる。
このことにより、例えばエプロン、布巾、病院制服、家具張地、カーテン、カーペットなど、人体の接触が多い箇所に適用できるとともに、壁紙などのようにシート状に形成して貼り付けるなどすることで抗菌性を発現できない構造物などでも、効率よく高い抗菌作用を付与できる。
The woven or knitted fabric described in the present invention is characterized in that the antibacterial fiber of the present invention is woven.
In the present invention, the antibacterial fiber of the present invention described above is woven.
As a result, it can be applied to places with a lot of human contact, such as apron, cloth, hospital uniform, furniture upholstery, curtains, carpets, etc., and antibacterial by forming and sticking it into a sheet like wallpaper Even a structure or the like that cannot exhibit the property can efficiently impart a high antibacterial effect.
本発明に記載の不織布は、本発明の抗菌性繊維を有したことを特徴とする。
本発明では、上述した本発明の抗菌性繊維を有している。
このことにより、例えば家具張地やカーペットなど、人体の接触が多い箇所に適用できるとともに、壁紙などのようにシート状に形成して貼り付けるなどすることで抗菌性を発現できない構造物などでも、効率よく高い抗菌作用を付与できる。さらには、織り込む必要がなく、布状物としての製造性の向上が容易に得られ、抗菌性繊維の歩留まりの有効利用によるコストの低減も容易に得られる。
The nonwoven fabric described in the present invention has the antibacterial fiber of the present invention .
In this invention, it has the antimicrobial fiber of this invention mentioned above.
As a result, it can be applied to places where there is much contact with the human body, such as furniture upholstery and carpets, and even structures that cannot exhibit antibacterial properties by being formed and pasted into a sheet like wallpaper, etc. High antibacterial action can be imparted efficiently. Furthermore, it is not necessary to weave, and it is possible to easily improve the manufacturability as a cloth-like product, and it is also easy to reduce the cost by effectively using the yield of antibacterial fibers.
本発明に記載の壁紙は、本発明の織布または編布、および本発明の不織布のうちの少なくともいずれか一方と、フィルムまたはシートと、が積層されたことを特徴とする。
本発明では、上述した発明の抗菌性繊維を有する織布または編布や不織布の少なくともいずれか一方と、フィルムまたはシートとを積層して構成している。
このことにより、人体の接触が多い箇所で、また建造物の外物との温度差で生じる水滴や湿度などによりカビなどの発生しやすい利用形態でも、良好にカビなどの発生を防止でき、良好な居住空間の提供が容易に得られる。特に、表面側にフィルムやシートが被覆する状態に構成することで、刺激に敏感な人体への影響も防止できる。
The wallpaper described in the present invention is characterized in that at least one of the woven or knitted fabric of the present invention and the nonwoven fabric of the present invention and a film or sheet are laminated.
In the present invention, at least one of a woven fabric, a knitted fabric or a nonwoven fabric having the antibacterial fiber of the above-described invention and a film or a sheet are laminated.
This makes it possible to prevent the occurrence of mold, etc., even in usage forms that tend to generate mold due to water drops or humidity generated due to temperature differences from the outside of the building, and where there is a lot of human contact. Providing a comfortable living space. In particular, by configuring the surface side to be covered with a film or sheet, it is possible to prevent the human body sensitive to stimulation.
本発明に記載の断熱材は、本発明の抗菌性繊維の集合体からなることを特徴とする。
本発明では、上述した本発明の抗菌性繊維を、例えばガラスウールのような綿状の集合体としている。
このことにより、例えば建材の断熱材として利用され温度差で生じやすい水滴などによりカビなどの発生しやすい利用形態でも、良好にカビなどの発生を防止でき、良好な居住空間の提供が容易に得られる。
なお、繊維間や吹き付けるために被吹き付け物との接着のためなど、結合材や接着剤などを適宜混合して断熱材として利用することを除外するものではない。
The heat insulating material described in the present invention is characterized by comprising the aggregate of antibacterial fibers of the present invention .
In the present invention, the above-described antibacterial fiber of the present invention is a cotton-like aggregate such as glass wool.
This makes it possible to prevent the occurrence of mold and the like, and to provide a good living space easily even in usage forms that tend to generate mold due to, for example, water droplets that are easily used due to temperature differences and are used as heat insulating materials for building materials. It is done.
In addition, it does not exclude using as a heat insulating material by appropriately mixing a binder, an adhesive, or the like, for bonding between fibers or bonding with an object to be sprayed.
以下、本発明の抗菌性成形体に係る一実施の形態について説明する。
なお、本実施の形態では、本発明の抗菌性繊維を含有する抗菌性布状物を例示して説明するが、本発明の抗菌性繊維としては、織布や不織布などの布状物への利用形態に限らず、例えば壁紙のようなシート状物としたり、ガラスウールなどのような綿状の集合体として断熱材に利用したりするなど、繊維を利用するいずれのものに適用できる。また、あらかじめ本発明における抗菌性組成物を含有する状態で紡糸した抗菌性繊維に限らず、例えば紡糸した繊維に本発明の抗菌性組成物を含浸させたり、本発明の抗菌性組成物における有機系抗菌剤または無機系抗菌剤のいずれか一方を含有する状態で紡糸した繊維に、いずれか他方を含浸させたりするなどしてもよい。
Hereinafter, an embodiment according to the antibacterial molded article of the present invention will be described.
In this embodiment, the antibacterial cloth containing the antibacterial fiber of the present invention is exemplified and described. However, the antibacterial fiber of the present invention is applied to a cloth-like object such as a woven fabric or a non-woven fabric. The present invention is not limited to the form of use, and can be applied to any material that uses fibers, for example, a sheet-like material such as wallpaper, or a heat-insulating material as a cotton-like aggregate such as glass wool. The antibacterial fiber spun in advance in a state containing the antibacterial composition of the present invention is not limited to, for example, the spun fiber impregnated with the antibacterial composition of the present invention, or the organic in the antibacterial composition of the present invention. A fiber spun in a state containing either one of an antibacterial agent or an inorganic antibacterial agent may be impregnated with one of the other.
〔抗菌性布状物の構成〕
抗菌性布状物は、特に適用制限はないが、例えば、微生物である菌類（真菌類、細菌類、藻類など）が繁殖しやすい環境に使われる部品や部位、具体的には、壁紙やハウスラップなどの建材、衣料品、食品包装材など、各種用途に直接、あるいは粘着テープなどのように粘着層を設けて接着あるいは貼着、または粘着層を設けずに単に挾持するなどして利用できる。
この抗菌性布状物は、例えば、溶融紡糸、乾式紡糸、湿式紡糸など、公知の紡糸方法を用いて得られた抗菌性繊維を、一部あるいは全部に織り込んだ織布や、一部あるいは全部に利用した不織布である。
そして、抗菌性布状物を構成する抗菌性繊維は、高分子材料と、イミダゾール系の有機系抗菌剤から選ばれた少なくとも２種、および無機系抗菌剤を含有する抗菌性組成物と、を含有する。
[Configuration of antibacterial cloth]
There are no particular restrictions on the application of antibacterial cloths, but for example, parts and parts used in environments where fungi (fungi, bacteria, algae, etc.) that are microorganisms are likely to propagate, specifically, wallpaper and houses. Can be used directly in various applications such as wrapping materials, clothing, food packaging materials, etc., or by sticking or sticking with an adhesive layer such as an adhesive tape, or simply holding it without an adhesive layer .
This antibacterial cloth is, for example, a woven cloth in which antibacterial fibers obtained by using a known spinning method such as melt spinning, dry spinning, and wet spinning are partially or wholly woven, or partly or wholly. Nonwoven fabric used for
And the antibacterial fiber which comprises an antibacterial cloth is an antibacterial composition containing a polymer material, at least two kinds selected from imidazole organic antibacterial agents, and an inorganic antibacterial agent. contains.
高分子材料としては、例えば溶融紡糸する場合にはポリプロピレン、ポリエチレンなどのポリオレフィン、ナイロンなどのポリアミド、ポリエチレンテレフタレート、ポリブチレンテレフタレートなどのポリエステルなどの熱可塑性樹脂、乾式紡糸する場合には、溶剤に溶解するものであれば特に制限はないが、好ましくは、セルロースと、セルロース系エステルと、ポリアクリロニトリルと、エチレンとビニルアルコールの共重合体と、のうちの少なくともいずれかを主骨格とするポリマなどが例示できる。
また、壁紙のように抗菌性布状物にさらにフィルムやシートなどを積層する多層構造とした場合における表層側に設けられる層として用いられる材料としては、樹脂材料や木皮あるいは紙など、特に制限はないが、例えばポリエチレン系樹脂、ポリプロピレン系樹脂、ポリウレタン系樹脂、ポリカーボネート系樹脂、ポリスチレン系樹脂、ポリエチレンテレフタレートなどのポリエステル系樹脂、ナイロン（ポリアミド）系樹脂、アクリル樹脂、ポリ塩化ビニル樹脂、アクリロニトリル−ブタジエン−スチレン（Acrylonitorile-Butadiene-Styrene：ＡＢＳ）樹脂などの樹脂材料の一種を単独で、または二種以上を組み合わせて使用することができる。
なお、高分子材料や多層構造における表面側の層の樹脂材料として結晶性樹脂であれば、結晶化度が比較的に低い樹脂材料を用いることが好ましい。すなわち、結晶化度が低い樹脂材料の方が、樹脂材料中に存在する抗菌性組成物や表面側の層を介して下層の抗菌性組成物を含有する抗菌性布状物による抗菌作用が発揮されやすくなるためである。
Polymer materials include, for example, polypropylene such as polypropylene and polyethylene for melt spinning, polyamide such as nylon, thermoplastic resins such as polyester such as polyethylene terephthalate and polybutylene terephthalate, and dissolved in a solvent for dry spinning. There is no particular limitation as long as it is, but preferably a polymer having a main skeleton of at least one of cellulose, cellulose ester, polyacrylonitrile, and a copolymer of ethylene and vinyl alcohol, and the like. It can be illustrated.
In addition, as a material used as a layer provided on the surface side in the case of a multilayer structure in which a film or sheet is further laminated on an antibacterial cloth like wallpaper, resin material, bark, paper, etc. are not particularly limited For example, polyethylene resin, polypropylene resin, polyurethane resin, polycarbonate resin, polystyrene resin, polyester resin such as polyethylene terephthalate, nylon (polyamide) resin, acrylic resin, polyvinyl chloride resin, acrylonitrile-butadiene -One kind of resin materials such as styrene (Acrylonitorile-Butadiene-Styrene: ABS) resin can be used alone or in combination of two or more kinds.
Note that a resin material having a relatively low degree of crystallinity is preferably used as long as it is a crystalline resin as a polymer material or a resin material for a surface layer in a multilayer structure. In other words, the resin material having a low crystallinity exhibits the antibacterial effect of the antibacterial composition existing in the resin material or the antibacterial cloth containing the antibacterial composition of the lower layer through the surface side layer. It is because it becomes easy to be done.
抗菌性組成物は、イミダゾール系の有機系抗菌剤のみから選ばれた２種と、無機系抗菌剤と、を含有、特にイミダゾール系の有機系抗菌剤のみから選ばれた２種と、無機系抗菌剤と、のみからなるものが好ましい。
この抗菌性組成物は、表１ないし表６に示す微生物である菌類（真菌類、細菌類、藻類など）に対して、低いＭＩＣ値でも抗菌効果を奏し格段に広い抗菌スペクトルを示す。
すなわち、ＭＩＣ値を５０ｐｐｍ以下と厳しいレベルとしても、真菌類２１４種、細菌類１３１種、藻類２７種（現時点で確認済み）を示す。なお、表１ないし表３に真菌類、表４および表５に細菌類、表６に藻類を示す。
なお、表１ないし表６において、実施例１は、後述する実施例１で用いた抗菌組成物の、Ａはチアベンダゾールとカルベンダジムとが１：１で混合された抗菌性組成物、Ｂは銀担持リン酸ジルコニウム（東亞合成社製 商品名 ノバロン）と酸化亜鉛（関東化学株式会社試薬）が１８：８２で混合された抗菌性組成物のＭＩＣ値のデータである。また、表１ないし表６において、比較例における空白部分は、抗菌効果が認められなかったことを意味する。
The antibacterial composition contains two types selected from only imidazole-based organic antibacterial agents and inorganic antibacterial agents, and in particular, two types selected from only imidazole-based organic antibacterial agents, and inorganic What consists only of an antibacterial agent is preferable.
This antibacterial composition exhibits an antibacterial effect against fungi (fungi, bacteria, algae, etc.), which are microorganisms shown in Tables 1 to 6, even at low MIC values, and exhibits a significantly broad antibacterial spectrum.
That is, even when the MIC value is a severe level of 50 ppm or less, 214 species of fungi, 131 species of bacteria, and 27 species of algae (confirmed at present) are shown. Tables 1 to 3 show fungi, Tables 4 and 5 show bacteria, and Table 6 shows algae.
In Tables 1 to 6, Example 1 is an antibacterial composition used in Example 1 described later, A is an antibacterial composition in which thiabendazole and carbendazim are mixed at 1: 1, and B is silver. It is the data of the MIC value of the antibacterial composition in which the supported zirconium phosphate (trade name NOVALON, manufactured by Toagosei Co., Ltd.) and zinc oxide (Kanto Chemical Co., Ltd. reagent) were mixed at 18:82. In Tables 1 to 6, a blank portion in the comparative example means that the antibacterial effect was not recognized.
イミダゾール系の有機系抗菌剤としては、例えばベンゾイミダゾールカルバミン酸化合物、イオウ原子含有ベンゾイミダゾール化合物、ベンゾイミダゾールの環式化合物誘導体などが例示できる。 Examples of imidazole organic antibacterial agents include benzimidazole carbamic acid compounds, sulfur atom-containing benzimidazole compounds, and cyclic compound derivatives of benzimidazoles.
ベンゾイミダゾールカルバミン酸化合物としては、１Ｈ−２−ベンゾイミダゾールカルバミン酸メチル、１−ブチルカルバモイル−２−ベンゾイミダゾールカルバミン酸メチル、６−ベンゾイル−１Ｈ−２−ベンゾイミダゾールカルバミン酸メチル、６−（２−チオフェンカルボニル）−１Ｈ−２−ベンゾイミダゾールカルバミン酸メチルなどが例示できる。
イオウ原子含有ベンゾイミダゾール化合物としては、１Ｈ−２−チオシアノメチルチオベンゾイミダゾール、１−ジメチルアミノスルフォニル−２−シアノ−４−ブロモ−６−トリフロロメチルベンゾイミダゾールなどが例示できる。
ベンゾイミダゾールの環式化合物誘導体としては、２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾール、２−（２−クロロフェニル）−１Ｈ−ベンゾイミダゾール、２−（１−（３，５−ジメチルピラゾリル））−１Ｈ−ベンゾイミダゾール、２−（２−フリル）−１Ｈ−ベンゾイミダゾールなどが例示できる。
Examples of the benzimidazole carbamate compound include methyl 1H-2-benzimidazole carbamate, methyl 1-butylcarbamoyl-2-benzimidazole carbamate, methyl 6-benzoyl-1H-2-benzimidazole carbamate, 6- (2- Examples include thiophenecarbonyl) -1H-2-benzimidazole carbamate methyl.
Examples of the sulfur atom-containing benzimidazole compound include 1H-2-thiocyanomethylthiobenzimidazole and 1-dimethylaminosulfonyl-2-cyano-4-bromo-6-trifluoromethylbenzimidazole.
As cyclic compound derivatives of benzimidazole, 2- (4-thiazolyl) -1H-benzimidazole, 2- (2-chlorophenyl) -1H-benzimidazole, 2- (1- (3,5-dimethylpyrazolyl)) Examples thereof include -1H-benzimidazole and 2- (2-furyl) -1H-benzimidazole.
そして、イミダゾール系の有機抗菌剤としては、イミダゾール系の有機系抗菌剤のみから選ばれた少なくとも２種のみを併用する。同一のイミダゾール系でも、異なる２種を併用することにより、微生物に対して抗菌作用の相乗効果が得られ、特に、ベンゾイミダゾール環にチアゾリル基を有するものと、ベンゾイミダゾール環にカーバメート基を有するものと、を使用することが、顕著な相乗効果が得られることから好ましい。
チアゾリル基としては、例えば２−チアゾリル、４−チアゾリル、５−チアゾリルなどが例示できる。また、カーバメート基としては、このカーバメート基における炭化水素基が、例えば、メチル、エチル、ｎ−２プロピル、ｉｓｏ−プロピル、などのアルキル基が好ましく、特にメチル基あるいはエチル基を有するものが特に好ましい。
具体的には、チアゾリル基を有するものとして、２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾール（チアベンダゾール：Thiabendazole(ＴＢＺ)）などが例示できる。また、カーバメート基を有するものとして、メチル−２−ベンゾイミダゾールカルバミン酸メチル（カルベンダジム：Carbendazim(ＢＣＭ)）、エチル−２−ベンゾイミダゾールカルバミン酸メチルなどが例示できる。特に、２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールと、２−ベンゾイミダゾールカルバミン酸メチルとは、熱的安定性が比較的に高く、特に樹脂成形体として利用することが容易であり、また例えばグレープフルーツやオレンジ、バナナなどの防かび剤（食品添加物）としても既に利用され、人体への影響が比較的に小さい材料として確認されたものであることから、特に好ましい。
And as an imidazole type organic antibacterial agent, only at least 2 sorts chosen only from an imidazole type organic antibacterial agent are used together. Even in the same imidazole system, by using two different types together, a synergistic effect of antibacterial action against microorganisms can be obtained, especially those having a thiazolyl group in the benzimidazole ring and those having a carbamate group in the benzimidazole ring Is preferable because a remarkable synergistic effect is obtained.
Examples of the thiazolyl group include 2-thiazolyl, 4-thiazolyl, 5-thiazolyl and the like. Further, as the carbamate group, the hydrocarbon group in the carbamate group is preferably an alkyl group such as methyl, ethyl, n-2 propyl, iso-propyl, etc., and particularly preferably has a methyl group or an ethyl group. .
Specifically, 2- (4-thiazolyl) -1H-benzimidazole (thiabendazole (TBZ)) and the like can be exemplified as those having a thiazolyl group. Examples of those having a carbamate group include methyl methyl-2-benzimidazole carbamate (Carbendazim (BCM)), methyl ethyl-2-benzimidazole carbamate and the like. In particular, 2- (4-thiazolyl) -1H-benzimidazole and methyl 2-benzimidazole carbamate have relatively high thermal stability, and are particularly easy to use as a resin molded body. For example, it is particularly preferable because it has already been used as a fungicide (food additive) such as grapefruit, orange and banana, and has been confirmed as a material having a relatively small influence on the human body.
そして、これらイミダゾール系の有機系抗菌剤はハロゲンを含まないため、抗菌性組成物や抗菌性成形体を例えば焼却処理した場合であってもダイオキシンなどの有害物質が生成せず、環境への影響がなく好ましい。また、抗菌性組成物を樹脂材料に含有させて成形する場合に成形金型などの製造ラインにおける金属部品を腐食するなどの不都合が生じず、製造設備に特別な材料を用いた装置が不要で製造設備の簡略化や製造性の向上、装置コストの低減なども容易に得ることができるので好ましい。
また、これらイミダゾール系の有機系抗菌剤は実質的に水に不溶であるため、例えば雨露に曝されるなどの使用条件でも流れ落ちて長期間安定した抗菌性を提供できなくなるなどの不都合がない。さらに、水に分散質の基材と良好に混合されて抗菌性を有したエマルジョンとして提供することが容易となり、汎用性の向上も容易に図ることができる。
And since these imidazole-based organic antibacterial agents do not contain halogen, no harmful substances such as dioxin are generated even when the antibacterial composition or antibacterial molded body is incinerated, for example, and this has an impact on the environment. This is preferable. In addition, when an antibacterial composition is contained in a resin material and molded, there is no inconvenience such as corrosion of metal parts in a production line such as a molding die, and no equipment using a special material is required for production equipment. Simplification of manufacturing equipment, improvement in manufacturability, reduction in apparatus cost, and the like can be easily obtained, which is preferable.
In addition, since these imidazole organic antibacterial agents are substantially insoluble in water, there is no inconvenience such as being unable to provide stable antibacterial properties for a long period of time even under use conditions such as exposure to rain. Furthermore, it becomes easy to provide an emulsion having antibacterial properties by being well mixed with a dispersoid base material in water, and versatility can be easily improved.
一方、無機系抗菌剤としては、亜酸化銅、銅粉、チオシアン酸銅、炭酸銅、塩化銅、硫酸銅、酸化亜鉛、硫酸亜鉛、硫酸ニッケル、銅−ニッケル合金などの無機金属化合物や、リン酸ジルコニウム、金属を担持したゼオライト、またはその塩であるリン酸ジルコニウムなどを使用することができる。特に、金属として銀または銅を担持したリン酸ジルコニウムが好ましく、より好ましくは抗菌性の高い銀系抗菌剤である銀を担持したリン酸ジルコニウムを使用する。なお、銀系抗菌剤としては、担持した形態に限らず、金属単体の銀なども対象とすることができる。
銀や銅といった金属を担持したリン酸ジルコニウムやゼオライトは、人体への安全性に優れ、抗菌速度も速く抗菌性能に優れているとともに、リン酸ジルコニウムやゼオライトに貴金属である銀を担持させることによるコストの低減などが得られるために好ましい。
特に、銀担持リン酸ジルコニウムやゼオライトを利用する場合、酸化亜鉛を併用することがより好ましい。銀担持リン酸ジルコニウムと酸化亜鉛との併用により、銀担持リン酸ジルコニウム自体および酸化亜鉛自体の抗菌作用とともに、同一の無機系である無機系抗菌剤でも併用による抗菌作用の相乗効果が得られ、より顕著な抗菌性が得られることから好ましい。さらに、酸化亜鉛との併用により、銀担持リン酸ジルコニウムやゼオライトの含有量を低減でき、貴金属である銀の使用量の低減によりコストの低減も容易に得られるので好ましい。また、銀の酸化による変色を抑えることもできる。
On the other hand, inorganic antibacterial agents include cuprous oxide, copper powder, copper thiocyanate, copper carbonate, copper chloride, copper sulfate, zinc oxide, zinc sulfate, nickel sulfate, copper-nickel alloy and other inorganic metal compounds, phosphorus Zirconate acid, metal-supported zeolite, or zirconium phosphate which is a salt thereof can be used. In particular, zirconium phosphate supporting silver or copper as a metal is preferable, and more preferably, zirconium phosphate supporting silver which is a silver antibacterial agent having high antibacterial properties is used. The silver antibacterial agent is not limited to the supported form, and silver as a single metal can also be targeted.
Zirconium phosphate and zeolite supporting metals such as silver and copper have excellent safety to human body, fast antibacterial speed and excellent antibacterial performance, and by supporting silver which is noble metal on zirconium phosphate and zeolite This is preferable because cost reduction can be obtained.
In particular, when silver-supported zirconium phosphate or zeolite is used, it is more preferable to use zinc oxide in combination. With the combination of silver-supported zirconium phosphate and zinc oxide, the antibacterial action of silver-supported zirconium phosphate itself and zinc oxide itself, as well as the synergistic effect of the antibacterial action of the combined inorganic antibacterial agent, It is preferable because more remarkable antibacterial properties can be obtained. Furthermore, the combined use with zinc oxide is preferable because the content of silver-supported zirconium phosphate and zeolite can be reduced, and the reduction in cost can be easily obtained by reducing the amount of silver used as a noble metal. Moreover, the discoloration by silver oxidation can also be suppressed.
そして、抗菌性組成物は、イミダゾール系の有機系抗菌剤と無機系抗菌剤との配合割合を、質量比で１：１〜５：１、特に２：１とすることが好ましい。
ここで、有機系抗菌剤と無機系抗菌剤との配合割合が質量比で１：１より有機系抗菌剤が少なくなると、少ないＭＩＣ値での抗菌スペクトルの拡大が得られなくなるおそれがある。一方、質量比で５：１より有機系抗菌剤が多くなると、無機系抗菌剤に比して初期抗菌性能が遅くなるおそれがある。このことから、ベンゾイミダゾール系の有機系抗菌剤と無機系抗菌剤との配合割合を、質量比で１：１〜５：１とし、有機系抗菌剤や無機系抗菌剤自体の抗菌作用とともに、有機系抗菌剤と無機系抗菌剤との併用による顕著な抗菌作用の相乗効果を適切に発揮させることが好ましい。
In the antibacterial composition, the mixing ratio of the imidazole organic antibacterial agent and the inorganic antibacterial agent is preferably 1: 1 to 5: 1, particularly 2: 1 in terms of mass ratio.
Here, if the organic antibacterial agent and the inorganic antibacterial agent are mixed at a mass ratio of less than 1: 1, the antibacterial spectrum may not be expanded with a small MIC value. On the other hand, when the organic antibacterial agent is more than 5: 1 by mass ratio, the initial antibacterial performance may be delayed as compared with the inorganic antibacterial agent. From this, the blending ratio of the benzimidazole organic antibacterial agent and the inorganic antibacterial agent is 1: 1 to 5: 1 by mass ratio, together with the antibacterial action of the organic antibacterial agent and the inorganic antibacterial agent itself, It is preferable to appropriately exhibit a synergistic effect of remarkable antibacterial action by the combined use of an organic antibacterial agent and an inorganic antibacterial agent.
また、イミダゾール系の有機系抗菌剤として、２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールと、２−ベンゾイミダゾールカルバミン酸メチルとを併用する場合、これらの配合割合を質量比で１：１〜５：１とすることが好ましい。
ここで、２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールと、２−ベンゾイミダゾールカルバミン酸メチルとの配合割合が質量比で１：１より２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールが少なくなる、あるいは５：１より２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールが多くなると、低いＭＩＣ値で抗菌作用を示す抗菌スペクトルの数が減少、すなわち抗菌性組成物の添加量が増大するおそれがある。このことから、２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールと、２−ベンゾイミダゾールカルバミン酸メチルとの配合割合を質量比で１：１〜５：１とすることが好ましい。
In addition, when 2- (4-thiazolyl) -1H-benzimidazole and methyl 2-benzimidazole carbamate are used in combination as an imidazole-based organic antibacterial agent, the mixing ratio thereof is 1: 1 to 1 by mass ratio. 5: 1 is preferable.
Here, the mixing ratio of 2- (4-thiazolyl) -1H-benzimidazole and methyl 2-benzimidazole carbamate is less than 1: 1 by mass ratio of 2- (4-thiazolyl) -1H-benzimidazole. Or when the amount of 2- (4-thiazolyl) -1H-benzimidazole is larger than 5: 1, the number of antibacterial spectra exhibiting antibacterial activity at a low MIC value may be decreased, that is, the amount of the antibacterial composition added may be increased. There is. From this, it is preferable that the mixing ratio of 2- (4-thiazolyl) -1H-benzimidazole and methyl 2-benzimidazole carbamate is 1: 1 to 5: 1.
さらに、無機系抗菌剤として、銀を担持したリン酸ジルコニウムやゼオライトと酸化亜鉛とを併用する場合、これらの配合割合を質量比で好ましくは１：１〜１：１０、より好ましくは約１：２とする。
ここで、銀担持リン酸ジルコニウムやゼオライトと酸化亜鉛との配合割合が質量比で１：１より酸化亜鉛が少なくなると、貴金属である銀の使用量の低減による十分なコストの低減が得られにくくなる。また、銀の酸化による変色のおそれも考えられる。一方、質量比で１：１０より酸化亜鉛が多くなると、銀による十分な抗菌作用が得られにくくなって、抗菌性組成物の添加量が増大するおそれがある。このことから、銀担持リン酸ジルコニウムやゼオライトと酸化亜鉛との配合割合を質量比で１：１〜１：１０として、併用による顕著な抗菌作用の相乗効果を適切に発揮させることが好ましい。
Furthermore, when silver phosphate-supported silver phosphate or zeolite and zinc oxide are used in combination as an inorganic antibacterial agent, the mixing ratio thereof is preferably 1: 1 to 1:10, more preferably about 1: 2.
Here, when the mixing ratio of silver-supported zirconium phosphate or zeolite and zinc oxide is less than 1: 1 by mass ratio, it is difficult to obtain a sufficient cost reduction due to a reduction in the amount of silver used as a noble metal. Become. There is also a possibility of discoloration due to silver oxidation. On the other hand, when the zinc oxide is more than 1:10 by mass ratio, it is difficult to obtain a sufficient antibacterial action by silver, and the addition amount of the antibacterial composition may increase. For this reason, it is preferable that the compounding ratio of silver-supported zirconium phosphate or zeolite and zinc oxide is 1: 1 to 1:10 by mass ratio to appropriately exhibit a synergistic effect of remarkable antibacterial action by the combined use.
そして、抗菌性布状物の抗菌性繊維は、抗菌性組成物を０．０１質量％以上１０．０質量％以下で含有することが好ましく、０．０５質量％以上２．０質量％以下で含有することが特に好ましい。
ここで、抗菌性組成物の含有量が０．０１質量％より少なくなると、十分な抗菌性を発揮できなくなるおそれがある。一方、抗菌性組成物の含有量を１０．０質量％より多くしても、抗菌性能はほとんど変化がない一方、例えば抗菌性繊維の強度が低下したり、表面の平滑性などの外観が損なわれるなどの特性に影響を及ぼしたり、紡糸時における作業性や紡糸性などが低下したりするなどの不都合を生じるおそれがある。このように、必要最小限の含有量で十分な抗菌性を発揮させつつ、抗菌性組成物の含有量の増大によるコストの増大を抑えるため、抗菌性組成物の含有量を０．０１質量％以上１０．０質量％以下にすることが好ましい。
The antibacterial fiber of the antibacterial cloth preferably contains the antibacterial composition at 0.01% by mass or more and 10.0% by mass or less, and 0.05% by mass or more and 2.0% by mass or less. It is particularly preferable to contain it.
Here, if the content of the antibacterial composition is less than 0.01% by mass, sufficient antibacterial properties may not be exhibited. On the other hand, even if the content of the antibacterial composition is more than 10.0% by mass, the antibacterial performance is hardly changed. On the other hand, for example, the strength of the antibacterial fiber is reduced or the appearance such as the smoothness of the surface is impaired. There is a risk of inconveniences such as influencing the properties such as squeezing and the like, and the workability and spinnability during spinning are lowered. Thus, in order to suppress the increase in cost due to the increase in the content of the antibacterial composition while exhibiting sufficient antibacterial properties with the minimum necessary content, the content of the antibacterial composition is 0.01% by mass. It is preferable to set it to 10.0 mass% or less.
〔実施の形態の作用効果〕
この抗菌性布状物を構成する本発明の抗菌性繊維では、ハロゲン基を有さず皮膚刺激性が認められない少なくとも２種のイミダゾール系の有機系抗菌剤と、無機系抗菌剤とを併用した抗菌性組成物を含有している。このことにより、有機系抗菌剤と無機系抗菌剤との併用による相乗効果に加え、同一のイミダゾール系でも２種の有機系抗菌剤、特に２種のみを併用することによる相乗効果を得ることができる。
このため、この抗菌性組成物を含有する抗菌性繊維では、高分子材料を基材として、抗菌スペクトルを広げるために化学的に異種な抗菌剤を用いるという従来の公知知見からは全く予想できないイミダゾール系単一の有機系抗菌剤の組み合わせにより、著しく広い抗菌スペクトルを達成でき、かつ皮膚刺激性が陰性で安全性が高く、人体や環境に影響が極めて少ない本発明の抗菌性組成物を含有させることで、適宜紡糸した繊維に、皮膚刺激性が陰性で安全性が高く、人体や環境に影響が極めて少なく、かつ、相乗効果による低い最小育成素子濃度（ＭＩＣ値）でも格段に広い抗菌スペクトルが得られ、効率よく高い抗菌作用を発現させることができる。
[Effects of Embodiment]
In the antibacterial fiber of the present invention constituting the antibacterial cloth, at least two kinds of imidazole organic antibacterial agents which do not have a halogen group and do not have skin irritation are used in combination with an inorganic antibacterial agent Containing an antibacterial composition. As a result, in addition to the synergistic effect by the combined use of the organic antibacterial agent and the inorganic antibacterial agent, it is possible to obtain a synergistic effect by using only two types of organic antibacterial agents, particularly two types, even in the same imidazole type. it can.
For this reason, in the antibacterial fiber containing this antibacterial composition, an imidazole that cannot be predicted from the conventional knowledge that a chemically different antibacterial agent is used to broaden the antibacterial spectrum, using a polymer material as a base material. The antibacterial composition of the present invention can be contained by combining a single organic antibacterial agent with a significantly broad antibacterial spectrum, negative skin irritation, high safety, and extremely low impact on the human body and environment. As a result, the fiber that has been spun as appropriate has a negative skin irritation, high safety, very little impact on the human body and the environment, and a significantly broader antibacterial spectrum even at a low minimum growth element concentration (MIC value) due to a synergistic effect. It is obtained and a high antibacterial action can be expressed efficiently.
そして、抗菌性組成物のイミダゾール系の有機系抗菌剤として、ベンゾイミダゾール環にチアゾリル基を有するものとカーバメート基を有するものとの２種を併用するので、同一のイミダゾール系でも、皮膚刺激性が陰性で安全性が高く、人体や環境に影響が極めて少なく、かつ、相乗効果による低いＭＩＣ値でも格段に広い抗菌スペクトルが得られるという抗菌作用が容易に得られ、特にこれらの併用により顕著な抗菌性が得られる。
特に、ベンゾイミダゾール環にチアゾリル基を有する２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールと、カーバメート基を有する２−ベンゾイミダゾールカルバミン酸メチルとの２種を併用するので、併用による相乗効果にて顕著な抗菌性を発揮できる。さらに、これら２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールおよび２−ベンゾイミダゾールカルバミン酸メチルは、比較的に製造しやすく入手が容易で、既に利用されている材料で安全性が認められたものであることから、容易に利用でき、汎用性を向上できる。
And as an imidazole type organic antibacterial agent of the antibacterial composition, since two types of those having a thiazolyl group on the benzimidazole ring and those having a carbamate group are used in combination, skin irritation can be achieved even with the same imidazole type. Antibacterial action that is negative and highly safe, has very little effect on the human body and the environment, and can obtain a much broader antibacterial spectrum even with a low MIC value due to a synergistic effect. Sex is obtained.
In particular, since two types of 2- (4-thiazolyl) -1H-benzimidazole having a thiazolyl group in the benzimidazole ring and methyl 2-benzimidazole carbamate having a carbamate group are used in combination, Can exhibit remarkable antibacterial properties. Furthermore, these 2- (4-thiazolyl) -1H-benzimidazole and methyl 2-benzimidazole carbamate are relatively easy to produce and readily available, and have been confirmed to be safe from materials that have already been used. Therefore, it can be easily used and versatility can be improved.
また、無機系抗菌剤として、イミダゾール系の有機系抗菌剤との相乗効果が得られる銀担持リン酸ジルコニウムと酸化亜鉛とのうちの少なくともいずれか一方を用いるので、顕著な抗菌性が容易に得られる。特に、銀担持リン酸ジルコニウムと酸化亜鉛とを併用することにより、銀担持リン酸ジルコニウム自体および酸化亜鉛自体による抗菌作用とともに、これら同一系である無機系抗菌剤でも、併用することで抗菌作用の相乗効果も得られ、より顕著な抗菌性を発揮できる。また、銀担持リン酸ジルコニウムと酸化亜鉛との併用により、抗菌性を損なうことなく、貴金属である銀の使用量を低減でき、コストをより容易に低減できる。
さらに、高い抗菌性を示す銀の使用形態として、リン酸ジルコニウムに銀を担持させた形態としている。このため、必要最小限の量で貴金属である銀による抗菌作用を発揮でき、無機系抗菌剤による抗菌作用および有機系抗菌剤との抗菌作用の相乗効果を効率よく発揮でき、コストをより容易に低減できる。
In addition, as the antibacterial agent, at least one of silver-supported zirconium phosphate and zinc oxide, which provides a synergistic effect with the imidazole organic antibacterial agent, is used, so that remarkable antibacterial properties can be easily obtained. It is done. In particular, when silver-supported zirconium phosphate and zinc oxide are used in combination, the antibacterial effect of silver-supported zirconium phosphate itself and zinc oxide itself, as well as these inorganic antibacterial agents, which are the same system, can be used together. A synergistic effect is also obtained, and more remarkable antibacterial properties can be exhibited. In addition, the combined use of silver-supported zirconium phosphate and zinc oxide makes it possible to reduce the amount of silver used as a noble metal without impairing antibacterial properties, and to reduce costs more easily.
Furthermore, as a usage form of silver exhibiting high antibacterial properties, a form in which silver is supported on zirconium phosphate is used. For this reason, the antibacterial effect of silver, which is a noble metal, can be exerted in the minimum necessary amount, and the synergistic effect of the antibacterial effect of an inorganic antibacterial agent and the antibacterial effect of an organic antibacterial agent can be efficiently exhibited, making cost easier Can be reduced.
そして、抗菌性組成物としては、１μｍ以下の平均粒径に粒度調整したものを用いる。
このことにより、高分子材料に対する分散性が向上するとともに、紡糸時の滑動性などの良好な紡糸性や繊維の表面の平滑性が得られるなど、良好な抗菌性組成物の含有状態が容易に得られる。したがって、表面の平滑性の向上による織り込み作業性も良好で、歩留まりの向上が得られるとともに、安定した高い抗菌作用を繊維に発揮させることが容易に得られる。
また、抗菌性組成物を０．０１質量％以上１０．０質量％以下で含有されたことが好ましい。抗菌性組成物の含有量を０．０１質量％以上１０．０質量％以下とすることで、例えば強度や外観などの特性を損なうことなく顕著な抗菌性を発揮する成形体として提供できる。
And as an antibacterial composition, what adjusted the particle size to the average particle diameter of 1 micrometer or less is used.
As a result, the dispersibility of the polymer material is improved, and a good antibacterial composition is easily contained, such as good spinning properties such as slidability during spinning and smoothness of the fiber surface. can get. Therefore, weaving workability by improving the smoothness of the surface is good, the yield is improved, and it is easy to obtain a stable and high antibacterial effect on the fiber.
The antibacterial composition is preferably contained in an amount of 0.01% by mass or more and 10.0% by mass or less. By setting the content of the antibacterial composition to 0.01% by mass or more and 10.0% by mass or less, for example, it can be provided as a molded product that exhibits remarkable antibacterial properties without impairing properties such as strength and appearance.
そして、高分子材料として、熱可塑性樹脂を用い、一般的な各種溶融紡糸方法にて、効率よく高い抗菌作用を発現する繊維が容易に得られる。
また、高分子材料として、例えば、セルロースと、セルロース系エステルと、アクリロニトリルと、エチレンとビニルアルコールの共重合体と、のうちの少なくともいずれかを主骨格とするポリマを用い、一般的な各種湿式紡糸方法にて、効率よく高い抗菌作用を発現する繊維が容易に得られる。
Then, a thermoplastic resin is used as the polymer material, and fibers that exhibit high antibacterial activity efficiently can be easily obtained by various general melt spinning methods.
In addition, as a polymer material, for example, a polymer having a main skeleton of at least one of cellulose, cellulose ester, acrylonitrile, and a copolymer of ethylene and vinyl alcohol is used, and various kinds of general wet materials are used. With the spinning method, a fiber that efficiently exhibits a high antibacterial action can be easily obtained.
そして、本発明の抗菌性繊維を織り込んだ織布または編布、抗菌性繊維が含まれる不織布とすることで、例えばエプロン、布巾、病院制服、家具張地、カーテン、カーペットなど、人体の接触が多い箇所に適用できるとともに、壁紙などのようにシート状に形成して貼り付けるなどすることで抗菌性を発現できない構造物などでも、効率よく高い抗菌作用を付与できる。 And, by using a woven or knitted fabric in which the antibacterial fiber of the present invention is woven, and a non-woven fabric containing the antibacterial fiber, contact with the human body such as an apron, a cloth, a hospital uniform, a furniture tension fabric, a curtain, a carpet, etc. In addition to being applicable to many places, it is possible to efficiently impart a high antibacterial action even to a structure that cannot exhibit antibacterial properties by forming and sticking it into a sheet shape such as wallpaper.
〔実施の形態の変形例〕
なお、以上に説明した態様は、本発明の一態様を示したものであって、本発明は、前記した実施形態に限定されるものではなく、本発明の目的および効果を達成できる範囲内での変形や改良が、本発明の内容に含まれるものであることはいうまでもない。また、本発明を実施する際における具体的な構造および形状などは、本発明の目的および効果を達成できる範囲内において、他の構造や形状などとしても問題はない。
[Modification of Embodiment]
The aspect described above shows one aspect of the present invention, and the present invention is not limited to the above-described embodiment, and within the scope of achieving the objects and effects of the present invention. Needless to say, the modifications and improvements are included in the contents of the present invention. In addition, the specific structure and shape in carrying out the present invention may be used as other structures and shapes within the scope of achieving the object and effect of the present invention.
すなわち、本発明の抗菌性繊維を布状物とした抗菌性布状物について例示したが、上述したように、織布や不織布などの布状物としての利用形態に限らず、例えば壁紙のようなシート状物としたり、ガラスウールなどのような綿状の集合体として断熱材に利用したりするなど、繊維を利用可能ないずれの利用形態に適用できる。具体的には、衝撃吸収材（靴の中敷きなど）、繊維強化プラスチック（Fiber Reinforced Plastic：ＦＲＰ）などのように各種成形体の強度向上のためのガラスファイバのような繊維物、など、生活用品から建材、業務用など各種用途に利用できる。
なお、断熱材として、単に抗菌性繊維のみの集合体として構成したものに限らず、抗菌性繊維間や吹き付けるために被吹き付け物との接着のためなど、結合材や接着剤などを適宜混合して断熱材として利用してもよい。
That is, although the antibacterial cloth-like material in which the antibacterial fiber of the present invention is used as a cloth-like material has been exemplified, as described above, the present invention is not limited to the form of use as a cloth-like material such as a woven fabric or a non-woven fabric. It can be applied to any form of utilization in which fibers can be used, such as a sheet-like material or a heat-insulating material as a cotton-like aggregate such as glass wool. Specifically, household items such as shock absorbers (shoe insoles, etc.), fiber products such as glass fibers for improving the strength of various molded products such as fiber reinforced plastic (FRP), etc. Can be used for various purposes such as building materials and commercial use.
Note that the heat insulating material is not limited to a structure composed of only antibacterial fibers, but may be appropriately mixed with binders, adhesives, etc., for bonding between antibacterial fibers and sprayed objects for spraying. It may be used as a heat insulating material.
また、高分子材料に抗菌性組成物を適宜混合して成形する構成を例示したが、例えばポリエチレンなどの紡糸した化学繊維や綿糸などの各種繊維に、抗菌性組成物を含浸させてもよい。さらには、本発明の抗菌性組成物における有機系抗菌剤または無機系抗菌剤のいずれか一方を含有する状態で紡糸した繊維に、菌性組成物における有機系抗菌剤または無機系抗菌剤のいずれか他方を含浸させたり、本発明の抗菌性組成物における有機系抗菌剤におけるイミダゾール系の有機系抗菌剤から選ばれた少なくとも２種のうちのいずれかをあらかじめ含有させて紡糸した後に残りの有機系抗菌剤を含浸させたりするなとしてもよい。特に抗菌性組成物を１μｍ以下の平均粒径に粒度調整したものを用いることで、ポリエチレンなどにも抗菌性組成物が容易に浸透でき、あらかじめ混合して成形する抗菌性成形体と同等の機能を発揮できる。
ここで、抗菌性組成物の溶液として、水や有機溶剤など、抗菌性組成物を分散あるいは溶解可能ないずれの溶媒を利用できる。
なお、含浸させる方法としては、例えば刷毛塗りやロール塗り、スプレー塗布などの塗布や、いわゆるどぶ付けなどによる浸漬、さらには減圧下による浸漬、ナイフコーティングやスプレーコーティング、グラビアコーティング、フローコーティング、ダイコーティング、コンマコーティングなどの各種コーティング手段、あるいは、スクリーン印刷、パッド印刷、オフセット印刷、インクジェット印刷などの各種印刷などにより、抗菌性組成物の溶液を繊維の表面に付着させる各種方法が利用できる。
Moreover, although the structure which mixes and shape | molds an antibacterial composition suitably with a polymeric material was illustrated, you may impregnate antibacterial compositions, for example in various fibers, such as spun chemical fiber and cotton yarn, such as polyethylene. Furthermore, any of the organic antibacterial agent or the inorganic antibacterial agent in the fungal composition is applied to the fiber spun in the state containing either the organic antibacterial agent or the inorganic antibacterial agent in the antibacterial composition of the present invention. The remaining organic material is impregnated with the other, or is pre-spun with at least one of at least two selected from imidazole organic antibacterial agents in the organic antibacterial agent of the antibacterial composition of the present invention. It may not be impregnated with an antibacterial agent. In particular, by using an antibacterial composition whose particle size is adjusted to an average particle size of 1 μm or less, the antibacterial composition can easily penetrate into polyethylene and the like, and has the same function as an antibacterial molded body that is premixed and molded. Can be demonstrated.
Here, any solvent that can disperse or dissolve the antibacterial composition, such as water or an organic solvent, can be used as the solution of the antibacterial composition.
In addition, as impregnation methods, for example, brush coating, roll coating, spray coating, etc., soaking by soaking, soaking under reduced pressure, knife coating or spray coating, gravure coating, flow coating, die coating Various methods for attaching the antibacterial composition solution to the fiber surface by various coating means such as comma coating or various printing methods such as screen printing, pad printing, offset printing, and inkjet printing can be used.
また、イミダゾール系の有機系抗菌剤としては、２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールと、２−ベンゾイミダゾールカルバミン酸メチルとに限らず、上述した各種ベンゾイミダゾール系の組成物を組み合わせた構成として適用することができる。
さらに、各配合割合についても、利用部位や用途などに対応して適宜設定することができる。
In addition, the imidazole organic antibacterial agent is not limited to 2- (4-thiazolyl) -1H-benzimidazole and methyl 2-benzimidazole carbamate, and the above-described various benzimidazole compositions are combined. It can be applied as a configuration.
Furthermore, each blending ratio can also be set as appropriate in accordance with the use site and application.
さらには、前記抗菌性組成物と他の機能付与材、例えば撥水剤、ＳＲ加工剤、柔軟剤、天然有機物を併用しても構わない。天然有機物としては、蛋白質（およびその分解物）系ではシルクやコラーゲン、ケラチン、羽毛、セリシン、卵殻膜、アミノ酸、多糖類系ではキチン、キトサン、茶葉、コンドロイチン、ヒアルロン酸などが挙げられる。他に、ビタミン、ポリフェノールなどの生理活性物質でもよい。特に、シルクや卵殻膜といったプロテイン加工との併用は、本願の優れた抗菌性に加え、肌の保湿性を向上させる効果も期待できる。 Furthermore, you may use together the said antibacterial composition and another function provision material, for example, a water repellent, SR processing agent, a softening agent, and a natural organic substance. Examples of natural organic substances include silk, collagen, keratin, feathers, feathers, sericin, eggshell membranes, amino acids, and polysaccharides such as chitin, chitosan, tea leaves, chondroitin, and hyaluronic acid. In addition, physiologically active substances such as vitamins and polyphenols may be used. In particular, combined use with protein processing such as silk and eggshell membranes can be expected to improve skin moisture retention in addition to the excellent antibacterial properties of the present application.
その他、本発明の実施における具体的な構造および形状などは、本発明の目的を達成できる範囲で他の構造等としてもよい。 In addition, the specific structure, shape, and the like in the implementation of the present invention may be other structures as long as the object of the present invention can be achieved.
［実施例１、比較例１〜４］
以下、実施例および比較例などを挙げて、本発明をより具体的に説明するが、本発明は実施例などの内容に何ら限定されるものではない。
[Example 1, Comparative Examples 1 to 4]
EXAMPLES Hereinafter, although an Example, a comparative example, etc. are given and this invention is demonstrated more concretely, this invention is not limited to the content, such as an Example, at all.
〔実験１〕
（湿式紡糸繊維）
本発明の抗菌性繊維として、湿式紡糸により繊維状に成形した湿式紡糸繊維について、各成分で調製して、抗菌作用を確認した。
[Experiment 1]
(Wet spinning fiber)
As antibacterial fibers of the present invention, wet-spun fibers formed into fibers by wet spinning were prepared with each component, and antibacterial action was confirmed.
（試料）
分散剤としてのアニオン性界面活性剤（第一工業製薬株式会社社製）を３％濃度となるように添加した水に、イミダゾール系の有機系抗菌剤としてチアベンダゾールおよびカルベンダジム（関東化学株式会社より試薬として購入）、無機系抗菌剤として銀担持リン酸ジルコニウムおよび酸化亜鉛を、それぞれ３３：３３：６：２８の割合として調製された抗菌性組成物を、２．５質量％になるように添加し、アジホモミキサ（プライミクス株式会社製、商品名；Ｔ．Ｋ．ロボミックス）により、平均粒子径０．８μｍ以下（測定機；マイクロトラック ＭＴ３３００、日機装株式会社）になるように攪拌混合し、抗菌組成物水分散液を調製した。
一方、液体状の硫酸銅五水和物５ｇを２８％アンモニア水５０ｍｌおよび２Ｍ水酸化ナトリウム水溶液２０ｍｌに溶解させ、攪拌しつつ脱脂綿２．５ｇを徐々に加えて溶解させて高分子材料の主剤を調製した。この主剤に、さらに２８％アンモニア水と、抗菌組成物水分散液０．２５ｇとを添加し、十分に攪拌し、セルロース水溶液である基材を調製した。
そして、基材を注射器に充填し、２Ｍ希硫酸水溶液２リットル中に静かに押し出し、抗菌性繊維のセルロース繊維を作製した。この作製したセルロース繊維を水道水で十分に洗浄して水分を落とし、６０℃で一晩乾燥した後、ケント紙に隙間無く巻き取り、実施例１の試験片とした。本方法で作製した糸中の抗菌組成物は、固形分比で約０．２５％である。
また、比較例１として実施例１に抗菌性組成物を添加せずに作製したもの、比較例２として実施例１の抗菌性組成物に代えて実施例１のチアベンダゾールを用いて作製したもの、比較例３として実施例１の抗菌性組成物に代えて実施例１のカルベンダジムを用いて作製したもの、比較例４として実施例１の抗菌性組成物に代えて実施例１の銀担持リン酸ジルコニウムと酸化亜鉛とを１８：８２の割合とした無機系抗菌剤を用いて作製したものを用いた。
(sample)
Thiabendazole and carbendazim (from Kanto Chemical Co., Inc.) as imidazole-based organic antibacterial agents in water added with an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd.) as a dispersant to a concentration of 3% Purchased as a reagent), silver-supported zirconium phosphate and zinc oxide as inorganic antibacterial agents, added in an antibacterial composition prepared at a ratio of 33: 33: 6: 28, respectively, to 2.5% by mass Then, the mixture was stirred and mixed with an azimuth homomixer (trade name: TK Robotics, manufactured by Primix Co., Ltd.) so that the average particle size was 0.8 μm or less (measuring instrument: Microtrac MT3300, Nikkiso Co., Ltd.), and antibacterial composition A water dispersion was prepared.
On the other hand, 5 g of liquid copper sulfate pentahydrate was dissolved in 50 ml of 28% aqueous ammonia and 20 ml of 2M aqueous sodium hydroxide solution, and 2.5 g of absorbent cotton was gradually added and dissolved while stirring to obtain the main component of the polymer material. Prepared. To this main ingredient, 28% ammonia water and 0.25 g of an antibacterial composition aqueous dispersion were further added and stirred sufficiently to prepare a base material which was an aqueous cellulose solution.
Then, the base material was filled into a syringe and gently extruded into 2 liters of 2M dilute sulfuric acid aqueous solution to produce cellulose fibers as antibacterial fibers. The produced cellulose fiber was sufficiently washed with tap water to remove moisture, dried at 60 ° C. overnight, and wound up on a Kent paper without a gap to obtain a test piece of Example 1. The antibacterial composition in the yarn produced by this method has a solid content ratio of about 0.25%.
Moreover, what was produced without adding an antibacterial composition to Example 1 as Comparative Example 1, and what was produced using thiabendazole of Example 1 instead of the antibacterial composition of Example 1 as Comparative Example 2. Comparative Example 3 was prepared using carbendazim of Example 1 instead of the antibacterial composition of Example 1, and Comparative Example 4 was silver-supported phosphorus of Example 1 instead of the antibacterial composition of Example 1. What was produced using the inorganic type antibacterial agent which made the zirconium acid and zinc oxide the ratio of 18:82 was used.
（評価方法）
（１）無機塩培地の調製
表７に示す無機塩培地を調製し、これを１２１℃で２０分間オートクレーブ殺菌後、苛性ソーダ水溶液（ＮａＯＨ水溶液）によりｐＨが６．０〜６．５となるように調整した。
(Evaluation methods)
(1) Preparation of inorganic salt medium An inorganic salt medium shown in Table 7 was prepared, and after autoclaving at 121 ° C. for 20 minutes, the pH was adjusted to 6.0 to 6.5 with an aqueous caustic soda solution (NaOH aqueous solution). It was adjusted.
（２）混合胞子液の調製
以下の表８に示した菌株（７７混合菌種）からなるカビの胞子を減菌水に懸濁させ、ろ過して濃度が約１×１０6ｃｅｌｌ／ｍｌの混合胞子液を調製した。なお、胞子の懸濁には、ラウリル硫酸ナトリウムを用いて分散を行うようにした。
(2) Preparation of mixed spore solution Mold spores composed of the strains (77 mixed bacterial species) shown in Table 8 below are suspended in sterilized water and filtered to a concentration of about 1 × 10 6 cells / ml. A mixed spore solution was prepared. The spore suspension was dispersed using sodium lauryl sulfate.
（３）評価の方法
（１）で調製した無機塩培地に（２）で調製した混合胞子液をまいた後、その上からあらかじめ作製した試験片を乗せ、それぞれを載せた後、温度を２８℃、湿度を８５％ＲＨ以上とした状態で２８日間カビを培養させた。そして、カビの生育状況を目視で確認し、表９に示す判定基準を用いて評価した。その結果を表１０に示す。
(3) Evaluation method After the mixed spore solution prepared in (2) is sprinkled on the inorganic salt medium prepared in (1), a test piece prepared in advance is placed on the medium, and after placing each, the temperature is 28 Mold was cultivated for 28 days in a state where the temperature and humidity were 85% RH or higher. And the growth condition of mold | fungi was confirmed visually and it evaluated using the criteria shown in Table 9. The results are shown in Table 10.
（評価結果）
表１０に示すように、２週間培養後では、有機系抗菌剤を用いた比較例２および比較例３は、無機抗菌剤を用いた比較例４より多少の抗菌作用が認められたが、４週間培養後では、比較例１ないし比較例４とも試験片の全面に対して６０％以上でカビが繁殖しており、有機系抗菌剤のみや無機系抗菌剤のみでは十分に防カビ性が認められなかった。一方、本発明の抗菌性繊維である実施例１のものでは、４週間の培養後でもカビの発育は全く見られず、明確に強い防かび性を発揮することが認められた。
(Evaluation results)
As shown in Table 10, after 2 weeks of culture, Comparative Example 2 and Comparative Example 3 using an organic antibacterial agent showed some antibacterial action compared to Comparative Example 4 using an inorganic antibacterial agent. After weekly culture, both Comparative Example 1 and Comparative Example 4 propagated molds in 60% or more of the entire test piece, and organic antibacterial agents alone or inorganic antibacterial agents alone have sufficient antifungal properties. I couldn't. On the other hand, in the case of Example 1 which is the antibacterial fiber of the present invention, no mold growth was observed even after culturing for 4 weeks, and it was confirmed that it clearly exhibited strong antifungal properties.
［実施例２、比較例５〜８］
〔実験２〕
（溶融系紡糸繊維）
本発明の抗菌性繊維として、溶融法紡糸により繊維状に成形した溶融系紡糸繊維について、各成分で調製して、抗菌作用を確認した。
[Example 2, Comparative Examples 5 to 8]
[Experiment 2]
(Melted spinning fiber)
As antibacterial fibers of the present invention, melt-spun fibers formed into fibers by melt spinning were prepared with each component, and antibacterial action was confirmed.
（試料）
イミダゾール系の有機系抗菌剤として実験１で用いたチアベンダゾールおよびカルベンダジムと、無機系抗菌剤として実験１で用いた銀担持リン酸ジルコニウムおよび酸化亜鉛とを、それぞれ３３：３３：６：２８の割合として抗菌性組成物を調製する。
一方、硬化性材料としての熱可塑性樹脂であるメルトフローが１８ｇ／１０分の繊維用ポリプロピレン（出光興産株式会社製 商品名；ＩＤＥＭＩＴＳＵ ＰＰＹ−２０００ＧＶ）に、滑剤としてステアリン酸カルシウムを適宜配合するとともに抗菌性組成物を０．２５質量％となる状態に配合し、ミキサ（プライミクス株式会社製 商品名；Ｔ．Ｋ．ロボミックス）にて攪拌混合し、基材を調製した。
そして、基材を口径６５ｍｍの押出機にて２４０℃で押し出し、ペレットを作製した。このペレットを、直径０．７ｍｍの孔が１９８設けられた紡糸ノズルが装着された口径４０ｍｍの押出機にて２４０℃、空冷しながら巻き取り、紡糸した。紡糸した繊維をケント紙に隙間無く巻き取り、実施例２の試験片とした。
また、比較例５として実施例２に抗菌性組成物を添加せずに作製したもの、比較例６として実施例２の抗菌性組成物に代えて実験１のチアベンダゾールを用いて作製したもの、比較例７として実施例２の抗菌性組成物に代えて実験１のカルベンダジムを用いて作製したもの、比較例８として実施例２の抗菌性組成物に代えて実験１における比較例４の無機系抗菌剤を用いて作製したものを用いた。
(sample)
The ratio of thiabendazole and carbendazim used in Experiment 1 as imidazole-based organic antibacterial agents and silver-supported zirconium phosphate and zinc oxide used in Experiment 1 as inorganic antibacterial agents was 33: 33: 6: 28, respectively. As an antibacterial composition.
On the other hand, a polypropylene resin for fibers (trade name: IDEMISUSU PPY-2000GV, manufactured by Idemitsu Kosan Co., Ltd.), which is a thermoplastic resin as a curable material, has a melt flow of 18 g / 10 min. The composition was blended in a state of 0.25% by mass and stirred and mixed with a mixer (trade name, TK Robotics, manufactured by PRIMIX Corporation) to prepare a substrate.
And the base material was extruded at 240 degreeC with the extruder with a diameter of 65 mm, and the pellet was produced. The pellets were wound and spun while being air-cooled at 240 ° C. in an extruder having a diameter of 40 mm equipped with a spinning nozzle provided with 198 holes having a diameter of 0.7 mm. The spun fiber was wound up on a Kent paper without any gaps to obtain a test piece of Example 2.
Further, Comparative Example 5 was prepared without adding the antibacterial composition to Example 2, and Comparative Example 6 was prepared by using thiabendazole of Experiment 1 instead of the antibacterial composition of Example 2. Example 7 was prepared using carbendazim of Experiment 1 instead of the antimicrobial composition of Example 2, and Comparative Example 8 was an inorganic system of Comparative Example 4 of Experiment 1 instead of the antimicrobial composition of Example 2. What was produced using the antibacterial agent was used.
（評価方法）
上述した実験１の（１）で調製した無機塩培地に（２）で調製した混合胞子液をまいた後、その上からあらかじめ作製した試験片を乗せ、実験１と同様に培養させた。そして、実験１と同様に、表９に示す判定基準を用いて評価した。その結果を表１１に示す。
(Evaluation methods)
After the mixed spore solution prepared in (2) was sprinkled on the inorganic salt medium prepared in (1) of Experiment 1 described above, a test piece prepared in advance was placed thereon and cultured in the same manner as in Experiment 1. And it evaluated using the criterion shown in Table 9 similarly to the experiment 1. FIG. The results are shown in Table 11.
（評価結果）
表１１に示すように、２週間培養後では、有機系抗菌剤を用いた比較例６および比較例７は、無機抗菌剤を用いた比較例８より多少の抗菌作用が認められたが、４週間培養後では、比較例５および比較例８は試験片の全面に対して６０％以上、比較例６は試験片の全面に対して１０％〜３０％、比較例７は試験片の全面に対して３０％〜６０％で菌が繁殖しており、有機系抗菌剤のみや無機系抗菌剤のみでは十分に防カビ性が認められなかった。一方、本発明の抗菌性繊維である実施例２のものでは、４週間の培養後でもカビの発育は全く見られず、明確に強い防かび性を発揮することが認められた。
(Evaluation results)
As shown in Table 11, after two weeks of culture, Comparative Example 6 and Comparative Example 7 using an organic antibacterial agent showed some antibacterial action than Comparative Example 8 using an inorganic antibacterial agent. After weekly culture, Comparative Example 5 and Comparative Example 8 are 60% or more with respect to the entire test piece, Comparative Example 6 is 10% to 30% with respect to the entire test piece, and Comparative Example 7 is on the entire test piece. On the other hand, bacteria propagated in 30% to 60%, and only an organic antibacterial agent or an inorganic antibacterial agent did not exhibit sufficient antifungal properties. On the other hand, in the case of Example 2 which is the antibacterial fiber of the present invention, no mold growth was observed even after 4 weeks of culturing, and it was confirmed that it clearly exhibited strong antifungal properties.
Claims (11)
前記イミダゾール系の有機系抗菌剤から選ばれた２種は、ベンゾイミダゾール環にチアゾリル基を有するものと、ベンゾイミダゾール環にカーバメート基を有するものとである
ことを特徴とした抗菌性繊維。 A raw material containing a polymer material, at least two types selected from imidazole-based organic antibacterial agents, and an antibacterial composition containing an inorganic antibacterial agent, is spun ,
Two kinds selected from the imidazole organic antibacterial agents are those having a thiazolyl group in the benzimidazole ring and those having a carbamate group in the benzimidazole ring.
前記高分子材料は、熱可塑性樹脂であり、
溶融紡糸された
ことを特徴とした抗菌性繊維。 The antibacterial fiber according to claim 1,
The polymer material is a thermoplastic resin,
Antibacterial fiber characterized by melt spinning.
前記高分子材料は、セルロースと、セルロース系エステルと、ポリアクリロニトリルと、エチレンとビニルアルコールの共重合体と、のうちの少なくともいずれかを主骨格とするポリマであり、
湿式紡糸された
ことを特徴とした抗菌性繊維。 The antibacterial fiber according to claim 1,
The polymer material is a polymer having a main skeleton of at least one of cellulose, cellulose ester, polyacrylonitrile, and a copolymer of ethylene and vinyl alcohol,
Antibacterial fiber characterized by wet spinning.
前記抗菌性組成物が含浸された
ことを特徴とした抗菌性繊維。 The antibacterial fiber according to any one of claims 1 to 3,
An antibacterial fiber, which is impregnated with the antibacterial composition.
前記抗菌性組成物は、１μｍ以下の平均粒径に粒度調整された
ことを特徴とした抗菌性繊維。 The antibacterial fiber according to any one of claims 1 to 4,
The antibacterial composition is characterized in that the particle size is adjusted to an average particle size of 1 μm or less.
前記無機系抗菌剤は、１μｍ以下の平均粒径に粒度調整された
ことを特徴とした抗菌性繊維。 The antibacterial fiber according to any one of claims 1 to 5,
The antibacterial fiber, wherein the inorganic antibacterial agent is adjusted to have an average particle size of 1 μm or less.
前記無機系抗菌剤は、銀系抗菌剤と酸化亜鉛とのうちの少なくともいずれか一方である
ことを特徴とした抗菌性繊維。 The antibacterial fiber according to any one of claims 1 to 6 ,
The antibacterial fiber, wherein the inorganic antibacterial agent is at least one of a silver antibacterial agent and zinc oxide.
ことを特徴とした織布または編布。 A woven or knitted fabric in which the antibacterial fiber according to any one of claims 1 to 7 is woven.
ことを特徴とした不織布。 A non-woven fabric comprising the antibacterial fiber according to any one of claims 1 to 7 .
フィルムまたはシートと、が積層された
ことを特徴とした壁紙。 At least one of the woven or knitted fabric according to claim 8 and the nonwoven fabric according to claim 9 ;
Wallpaper characterized by the lamination of film or sheet.
ことを特徴とした断熱材。 A heat insulating material comprising the aggregate of antibacterial fibers according to any one of claims 1 to 7 .
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| US9163335B2 (en) | 2011-09-06 | 2015-10-20 | Honeywell International Inc. | High performance ballistic composites and method of making |
| JP2013184906A (en) * | 2012-03-06 | 2013-09-19 | Idemitsu Technofine Co Ltd | Antibacterial/anti-mold/anti-algae composition, molded article, treating agent and fiber including the same, and treating method using the same |
| CN102644162B (en) * | 2012-05-16 | 2015-03-18 | 常州崇高纳米材料有限公司 | Method for preparing antibacterial non-woven fabrics based on nano-silver monoatomic antibacterial agent |
| JP6108171B2 (en) * | 2013-08-01 | 2017-04-05 | 三菱レイヨン株式会社 | Acrylic composite fiber having antibacterial and deodorant properties and deodorant property, and spun yarn and woven / knitted fabric containing the same |
| CN105593421A (en) * | 2013-09-27 | 2016-05-18 | 可乐丽股份有限公司 | Antibacterial nonwoven sheet, liquid-containing sheet, and face mask |
| CN103774265B (en) * | 2014-02-17 | 2015-12-09 | 北京化工大学 | A kind of anti-bacterial fibre and preparation method thereof |
| AT516414B1 (en) * | 2014-10-28 | 2017-07-15 | Chemiefaser Lenzing Ag | Liquid-soaked non-woven fabric containing zinc oxide-containing cellulose fibers |
| JP6606213B2 (en) * | 2018-03-28 | 2019-11-13 | 俊夫 小室 | Health promoting composition that generates photons and ions |
| KR20210003557A (en) * | 2019-07-02 | 2021-01-12 | 엘지전자 주식회사 | An antibacterial composition, a filter using the same, and appliances with the filter |
| CN112160049A (en) * | 2020-09-12 | 2021-01-01 | 高文灿 | Sun-proof antibacterial textile fabric and preparation method thereof |
| CN113666886B (en) * | 2021-08-26 | 2022-03-29 | 诸暨华海氨纶有限公司 | Antibacterial spandex fiber for diaper and preparation method thereof |
| CN114130123B (en) * | 2021-12-01 | 2023-03-28 | 江苏舒源空调制造有限公司 | Antibacterial and mildewproof air purification material and preparation method thereof |
| CN114481392A (en) * | 2022-01-06 | 2022-05-13 | 西安工程大学 | Nanofiber covered yarn and preparation method thereof, nanofiber covered yarn plied yarn and application thereof |
| CN115819885A (en) * | 2022-12-19 | 2023-03-21 | 广东道生科技股份有限公司 | Antibacterial and tensile polypropylene composite material and preparation method and application thereof |
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