JPH07243180A - Manufacturing method of antibacterial fiber - Google Patents

Abstract

PURPOSE:To obtain an antimicrobial fiber excellent in antimicrobial property and also having good washing resistance in a post processing method not using a binder resin by forming a carrying layer having antimicrobial property by contact treatment of a fiber with an aqueous dispersion of an inorganic antimicrobial agent under specific conditions. CONSTITUTION:In forming an inorganic carrying layer having antimicrobial property by bringing a fiber such as a raw material fiber consisting of a natural fiber or a synthetic fiber, an intermediate fiber product, a final fiber product into contact with an aqueous dispersion of an inorganic antimicrobial agent having <=1mum particle diameter (e.g. silver, copper or zinc), formation of the layer is carried out under contact treating conditions comprising a condition heating at 50-95 deg.C under <=630Torr reduced pressure or a condition heating at 50-40 deg.C under pressure condition higher by >=0.1atm than atmospheric pressure to provide the objective antimicrobial fiber free from taste, odor and toxicity, having high safety and capable of retaining long-term effect without impairing touch feeling of the fiber in post processing not using a binder resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for imparting durable antibacterial properties to fibers (raw fibers, intermediate fiber products, final fiber products) without changing the texture.

[0002]

2. Description of the Related Art Natural fibers and synthetic fibers are used for clothing, bedding,
Although it is widely used for industrial materials and the like, recently, there is an increasing demand for fibers having antibacterial properties. Because the risk of nosocomial infection due to MRSA (methicillin-resistant Staphylococcus aureus) in hospitals is now a social problem, and once going out, contact with an unspecified number of people is expected. This is because the clothes and personal items used are safe and hygienic if they have antibacterial properties. Therefore, various methods for imparting antibacterial properties to fibers have been proposed.

<Internal addition method> As a method of imparting antibacterial properties to fibers, a method of kneading an organic or inorganic antibacterial agent into a spinning raw material at the production stage of synthetic fibers is adopted. This is the so-called internal addition method. Examples of applications relating to this method include the following.

JP-A-4-228608 discloses a method in which a copper-substituted antibacterial zeolite is added at a stage before the polymerization of the polymer is completed, and a water-soluble copper compound is added to the polymer before spinning, followed by spinning. It is shown.

Japanese Unexamined Patent Publication (Kokai) No. 3-84066 discloses a method in which an inorganic or organic composite particle carrying an antibacterial metal or an oxide thereof is contained in a resin and the resin composition is subjected to melt spinning. ing.

Japanese Unexamined Patent Publication (Kokai) No. 2-225402 describes that wet-spinning is carried out by adding and mixing a titanium oxide fine particle having a metal having an antibacterial action to the surface of the spinning solution.

Japanese Unexamined Patent Publication (Kokai) No. 3-205436 discloses that a resin composition containing antibacterial zeolite particles is melt-spun.

JP-A-4-321623 discloses that silver colloid or silver particles are used as an antibacterial agent in the form of a colloidal liquid, in the form of a fine powder or in the form of being supported on an adsorbent such as zeolite, and its antibacterial effect. It has been shown to incorporate agents into fibers to form antimicrobial fibers.

<Post-Processing Method Using Binder Resin> Another method of imparting antibacterial properties to fibers is a method of attaching a coating agent containing an antibacterial agent and a binder resin to the fibers. Examples of applications relating to this method include the following.

Japanese Unexamined Patent Publication (Kokai) No. 3 mentioned above in the "internal addition method".
JP-A-205436 also describes that the fiber surface can be coated with a resin composition containing antibacterial zeolite particles.

Japanese Unexamined Patent Publication (Kokai) No. 4-194074 discloses a method of processing a fabric by mixing a fine powder in which an antibacterial metal ion is supported on a carrier composed of zeolite and mica with a liquid adhesive such as an acrylic emulsion. Has been done.

Japanese Unexamined Patent Publication No. 4-255767 discloses (a)
Synthetic resin emulsion, (b) colloidal or particulate metal oxide, silica gel or zeolite, (c) antibacterial metal complex ion and water (d) a coating composition containing as a main component, There is also a description of processing the composition into fibers or cloth.

Japanese Unexamined Patent Publication No. 4-349836 discloses (A)
Copper or copper oxide powder, (B) metal zeolite, (C)
An antifouling marine product in which a surface of a core material made of a synthetic or natural fiber bundle is coated with a thermoplastic resin containing an organic antibacterial agent having a decomposition temperature of 200 ° C. or higher is disclosed.

<Post-Processing Method Not Using Binder Resin> Still another method of imparting antibacterial properties to the fibers is a method of treating the fibers with an antibacterial agent treatment liquid containing no binder resin. Examples of applications relating to this method include the following.

In JP-A-59-30963, sterilization is carried out by contact heating an aqueous dispersion of powder of metallic copper, metallic silver or an oxide thereof with a fiber to adhere the metallic compound powder to the fiber. Sex fibers are shown. According to this method
It is also described that the metal compound firmly adheres to the fiber without using an adhesive component such as a resin. However, as the metal compound powder, it is preferable to use a powder having a small particle size corresponding to colloidal particles.

Japanese Examined Patent Publication No. 3-45142 (Japanese Patent Laid-Open No. 2-45142)
160972), the fiber is swollen with an organic solvent or an aqueous solvent, and then immersed in a treatment aqueous solution in which ceramic porous fine particles are mixed, and the immersed treatment solution is heated and pressed to expand the fiber. Production of ceramic-containing fiber in which the fine particles are injected into the prepared fiber hole and then the fine particles are solid-dissolved in a treatment solution in which an antibacterial agent (quaternary ammonium salt, organic nitrogen compound, chitosan, etc.) is dissolved. The method is shown.

[0017]

Among the methods for imparting antibacterial properties to fibers, the internal addition method in which the antibacterial agent is added to the spinning raw material at the fiber manufacturing stage has no effect on the antibacterial agent contained in the resin. Not only that, but most of the antibacterial agents near the surface of the resin cannot exert a sufficient antibacterial effect due to resin coating, and the heat history of the resin in which the antibacterial agent is dispersed due to pre-kneading is likely to cause coloration. If the particles are thin and the antimicrobial particles are relatively large, or if the antimicrobial particles are not well dispersed,
There is a risk of yarn breakage in the melt spinning stage, and when many antibacterial agents are added for the purpose of enhancing the antibacterial effect, the physical properties of the fiber are easily impaired and the fiber becomes opaque. When the amount of the agent added is small, there is a problem that the antibacterial effect is not sufficiently exhibited.

Among the methods for imparting antibacterial properties to fibers, the post-processing method using a binder resin is that the antibacterial agent is covered with the resin and a sufficient antibacterial effect cannot be expected, and the original feeling of the fiber is impaired. However, depending on the type of binder resin, there are problems such as difficulty in washing resistance.

Among the methods for imparting antibacterial properties to the fibers, the post-processing method which does not use a binder resin has a problem that it lacks an adhesive component and thus lacks a fixing force to the fibers and generally lacks washing resistance. There is a point. JP-A-59-3096
If the particle size of the inorganic antibacterial agent is reduced to the colloidal region as in the invention of Japanese Patent No. 3, the adhesive force will appear, but there is still room for improvement. JP-A-59-30963 discloses that it is desirable to maintain the pH of the bath solution acidic in order to stop the adsorption rate of the metal particles to the fiber in the heating method in a bath. Such an acidic region causes dissolution and loss of the antibacterial metal.

In Japanese Patent Publication No. 3-45142, the fine particles are injected into the fiber holes by heating and pressurizing the treatment solution to expand the holes of the fibers, and then the organic antibacterial agent is added to the fine particles. It has been shown that it is carried by humans, but the process is complicated and the antibacterial property is intended to be exerted by an organic antibacterial agent, so people usually wear it in terms of toxicity. There are problems such as not being suitable for clothing applications, having a narrow antibacterial spectrum, and easily losing an organic antibacterial agent by washing. Further, since the ceramic particles used in the invention of this publication are in the form of an oxide gel having no functional group on the particle surface, it is necessary to keep the bath liquid alkaline as described in the examples thereof. Is required to be converted into a hydrosol, and the system must be made alkaline as described above. That is, the invention of this publication discloses that an inorganic substance carrying an antibacterial metal (which may dissolve a metal component in an alkaline region) is supported. It means that it cannot be applied to antibacterial agents.

Under such a background, the present invention has excellent antibacterial properties and has a wide antibacterial spectrum, even though the post-processing method using no binder resin is adopted.
It is an object of the present invention to provide a method for producing an antibacterial fiber having high safety and extremely good wash resistance.

[0022]

According to the method for producing an antibacterial fiber of the present invention, the fiber is contacted with an aqueous dispersion of an inorganic antibacterial agent, washed with water and dried to form an inorganic antibacterial agent on the surface of the fiber. In forming the inorganic antibacterial agent-supporting layer by permeation of the aqueous dispersion, a binder resin is not used as the inorganic antibacterial agent aqueous dispersion, and the contact treatment is performed under heating conditions and under emergency pressure conditions. It is characterized by carrying out.

The present invention will be described in detail below.

<Target Fibers> As the fibers to be imparted with antibacterial property, any of raw material fibers, intermediate fiber products and final fiber products are used.

Among the final textile products, examples of textile products to be used for hospital use include undergarments (sleepwear, sleepwear, etc.) worn by patients such as lab coats, surgical clothing and masks worn by doctors and nurses in the hospital. Pajamas, socks, etc.), equipment (masks, supporters, diapers, diaper covers, towels, etc.), bedding (blankets, bed spreads, sheets, towels, bedding covers, futon side, batting, etc.), hospital equipment ( Curtains, chair covers, bench covers, carpets, etc.).

Examples of textile products that are generally useful in the final textile product include general clothing (blouses, skirts, shirts, pants, dresses, sweaters, cardigans, underwear, working, aprons, socks, stockings, Pantyhose, tabi, kimono,
Interlining, band interlining, etc.), personal items (handkerchiefs, scarves, hats, gloves, watch bands, bags, carrying bags, school bags, shoes, footwear, insoles, etc.), interior items (blinds, curtains, carpets, etc.), table cloths ,
Mats, toiletries, car seat covers, etc.),
Daily miscellaneous goods (towels, towels, mops, tents, sleeping bags, stuffed animals, filters, brushes, etc.) are included.

Although the antibacterial property can be imparted to the fiber even at the final fiber product stage after sewing, the material, thread,
If the antibacterial treatment is performed at the stage of the intermediate fiber product such as cotton, the post-process can be easily performed, and the process can be performed at the stage of the raw material fiber. If the antibacterial property is given at the stage of yarn, cotton, etc., it is possible to mix and weave with untreated fibers, so that the economic effect is further increased.

As the material constituting the fibers, both fibers belonging to natural fibers and synthetic fibers are used (including semi-synthetic fibers and recycled fibers). Examples of the natural fibers include cotton, Manila hemp, jute, flax, kozo, mitsumata, wool and silk. Examples of the semi-synthetic fiber or recycled fiber include rayon, cupra and acetate. As synthetic fibers, polyvinyl alcohol-based, polyamide-based, polyvinylidene chloride-based, polyvinyl chloride-based, polyester-based, polyacrylonitrile-based,
Examples include polyolefin-based, polyurethane-based, fluororesin-based, and polyclar-based.

<Inorganic Antibacterial Agent and Its Aqueous Dispersion> The inorganic antibacterial agent comprises inorganic fine particles or inorganic ion exchanger fine particles, and silver, copper, zinc, mercury, lead, bismuth, cadmium and chromium. An inorganic antibacterial agent carrying at least one antibacterial metal selected from the group, particularly silver, copper or zinc is used. By supporting these antibacterial metals alone or in combination of two or more,
Design to suit the purpose of use, and enable synergistic effects.

As the antibacterial metal carrier, synthetic zeolite, natural zeolite, silica alumina magnesium, zirconium phosphate, double phosphate + calcium phosphate, phosphate, calcium phosphate, silica gel, Powdered carriers such as calcium silicate-based carriers are used, and these are also commercially available.

In addition, the antibacterial inorganic oxide colloidal solution described in Japanese Patent Application No. 5-198894 previously proposed by one of the present applicants has a transparency in which ultrafine particles are dispersed, It can be suitably used for the purpose of producing antibacterial fibers.

The decomposition temperatures of these inorganic antibacterial agents differ somewhat depending on the constitutional components and the structure. However, since the heat-resistant temperatures of all of them are 600 ° C. or higher, they do not deteriorate at the temperature of ordinary steam ironing. Suitable as an antibacterial agent for fibers.

In some cases, the organic antibacterial agent exerts a strong inhibitory effect on a specific bacterium or mold.
Many of them are not suitable for the purpose of the present invention, because they often lack decomposition stability and fixability, are difficult to stay on the fiber surface for a long time, and are often toxic to the human body.

In order to form an inorganic antibacterial agent-supporting layer by permeating an inorganic antibacterial agent aqueous dispersion on the surface of a fiber, first, an aqueous dispersion of inorganic antibacterial agent fine particles is prepared. This aqueous dispersion is in the neutral range (pH 7 ± 1, especially 7 ± 0.5).

The concentration of the aqueous dispersion is important for the density of the inorganic antibacterial agent impregnated in the fiber, but from the viewpoint of the washing operation and the feeling after the treatment, it is at most 3% by weight or less, usually 2.
It is preferably not more than 1% by weight, particularly preferably not more than 1% by weight.
The lower limit is about 0.01% by weight.

If necessary, a surfactant or a swelling agent may be added for the purpose of promoting the suspension stability of the above-mentioned aqueous dispersion or permeation into the fiber surface, but the antibacterial fiber after treatment is adversely affected. However, it is not recommended to add it unless it is an inorganic antibacterial agent having poor dispersibility.

Addition of a particle fixing agent such as a protective colloid and a resin for forming a film for the purpose of strengthening the fixing of the antibacterial agent fine particles to the fiber surface may impair the antibacterial effect and the feel of the fiber. It should be avoided in the invention. However, merely adding a nominal amount does not depart from the scope of the present invention.

The particle size of the inorganic antibacterial agent in the aqueous dispersion of the inorganic antibacterial agent is 1 μm or less, preferably 0.7 μm, from the viewpoint of the permeability of the fine pores on the fiber surface and the stability of the dispersion.
It is particularly desirable that the thickness be less than 0.5 μm. The lower limit is often set to about 3 nm, but even if the particle size is larger than the colloidal region (for example, 50 nm or more), a necessary and sufficient amount of particles can be supported in the present invention. It is also one of Since commercially available inorganic antibacterial agents often have a particle size of several μm or more, in such a case, they are pulverized (usually pulverized) before use. Since the antibacterial inorganic oxide colloidal solution described above is a stable dispersion of ultrafine particles, it can be used as it is in the method of the present invention.

<Treatment Method> In the present invention, the contact treatment between the fiber and the aqueous dispersion of the inorganic antibacterial agent is carried out under heating conditions and under emergency pressure conditions. "Emergency pressure" means not normal pressure, that is, reduced pressure or increased pressure. By adopting such conditions, the inorganic antibacterial agent can be made to penetrate into the fiber surface and deep inside the surface.

One of the preferable conditions is that the above contact treatment is carried out under the heating condition of a temperature of 50 to 95 ° C. (preferably 55 to 90 ° C.) and 630 Torr or less (preferably 530 Torr).
The following) is performed under reduced pressure conditions. If the degree of pressure reduction is too high, the temperature of the system cannot be increased in relation to the saturated vapor pressure of water, and therefore the degree of pressure reduction is limited to about 90 Torr. The higher the temperature is, the more effective it is. However, since heating the fiber beyond the allowable limit may deteriorate the fiber, the temperature condition and the pressure reducing condition are set in consideration of the softening point of the fiber.

Another preferable condition is that the above contact treatment is carried out at a temperature of 50 to 140 ° C. (preferably 55 to 120).
It is carried out under a heating condition of (° C.) and a pressure higher than atmospheric pressure by at least 0.1 atm (preferably at least 0.2 atm). Since it is not preferable in terms of equipment and safety that the pressure is too high, it is usually desirable to keep the pressure up to about 3 atmospheres higher than the atmospheric pressure. The higher the temperature is, the more effective it is. However, as described above, heating above the allowable limit may deteriorate the fiber. Therefore, the temperature condition is set in consideration of the softening point of the fiber.

In any of the above-mentioned methods, the contact treatment time between the fibers and the aqueous dispersion of the inorganic antibacterial agent is about 5 to 60 minutes, but it may be longer or shorter.

After completion of the contact treatment operation, the fibers are taken out from the aqueous dispersion of the inorganic antibacterial agent, washed with water and dried. As a result, an inorganic antibacterial agent-supporting layer is formed on the fiber surface, and excess inorganic antibacterial agent is removed.

Although the thickness of the inorganic antibacterial agent-supporting layer varies somewhat depending on the fiber material, it usually reaches several μm to several tens of μm, and when optimum conditions are adopted, it is several hundred μm.
It also reaches m.

As a practical device satisfying the conditions for forming a support layer of fine particles of inorganic antibacterial agent on a fiber, for example, the following can be used. That is, when the fiber is a monofilament or a twisted yarn, it is possible to use an Overmeier dyeing machine, a cheese dyeing machine, a reflux type yarn dyeing machine, a jet type yarn dyeing machine, etc. , Various jet dyeing machines, wind type dyeing machines, jigger dyeing machines and the like can be used as they are. When the fiber is a sewn fiber product, a small lot product, or raw cotton, a simple drum dyeing machine can be used as it is without any particular improvement. In the case of a long fiber material, continuous operation can be made possible by improving heating of the padding tank of the paddle dyeing machine, adjustment of residence time, and washing process. Regardless of which device is used, the structure is such that depressurization or pressurization is possible.

In the operation for forming the inorganic antibacterial agent-supporting layer on the fiber surface, when the fiber is brought into contact with the aqueous antibacterial agent dispersion, the influence of the mordant is more likely than the problem of reactivity with the dye. Therefore, it is desirable that the fiber is dyed.

[0047]

Function The fiber is crystalline, but it is possible to make a gap in the crystal structure by swelling. The inorganic antibacterial agent aqueous dispersion permeates into the gaps, and the penetration depth thereof is promoted under heating / depressurizing conditions or heating / pressurizing conditions. Therefore, the antibacterial fiber produced by the method of the present invention has an excellent effect that the antibacterial property is hardly reduced even after repeated washing.

The inorganic antibacterial agent used in the present invention is different from the organic antibacterial agent (which exhibits an antibacterial effect by diffusing in the air or a solvent by volatilization or elution) and has a trace amount of water existing in the environment. Easily dissociates to form an antibacterial metal ion and exhibits an antibacterial effect. Therefore, it exerts a non-selective antibacterial action against a wide range of microorganisms. All of these inorganic antibacterial agents are tasteless, odorless, and nontoxic, have high safety, and can maintain their effects for a long period of time.

When the inorganic carrier is zeolite-based or silica-alumina-magnesium-based, a synergistic effect of the "reactive oxygen anion" and the antibacterial metal ion generated by the catalytic action of the antibacterial metal on the surface of the antibacterial agent fine particles is exhibited. Since it has been confirmed that there is no possibility of imparting variability to microorganisms, it is more preferably used.

When the inorganic antibacterial agent is the above-mentioned antibacterial inorganic oxide colloid, since ultrafine particles having transparency are stably dispersed for a long time, it is preferably used for fibers.

The fibers on which the inorganic antibacterial agent-supporting layer is formed have no change in appearance, feel, size, mechanical strength and the like as compared with untreated fibers.

[0052]

EXAMPLES The present invention will be further described with reference to examples. Hereinafter, "%" means% by weight.

Reference Example 1 First, the following tests were carried out in order to compare the antibacterial performance of antibacterial agents of various companies with respect to fibers.

<Preparation of Aqueous Dispersion of Inorganic Antibacterial Agent> Inorganic antibacterial agent (average particle size: 2 μm) in which silver or the like is supported on silica-alumina magnesium carrier, inorganic antibacterial in which silver or the like is supported on zeolite carrier. Antibacterial agents A, B, and C3 obtained by wet pulverizing the agent (average particle size 2 μm) and the inorganic antibacterial agent (average particle size 2 μm) in which silver or the like is carried on a calcium phosphate-based carrier to a particle size of 0.5 μm or less % And water 97%
An inorganic antibacterial agent aqueous dispersion having a composition of was prepared.
The pH of each of these aqueous dispersions was about 7.

<Formation of Inorganic Antibacterial Agent-Supporting Layer on Fibers> These inorganic antibacterial agent aqueous dispersions are heated to 80 ° C., and various fiber cloths cut into appropriate sizes are immersed therein. Hold for about 30 minutes. Then, the fiber fabric was taken out, washed with water at room temperature, and then naturally dried under sunlight.

As a result, an inorganic antibacterial agent-supporting layer was formed on the surface of the fiber forming the fabric by permeation fixing of the antibacterial agent aqueous dispersion, and the thickness of the supporting layer reached several μm.

<Evaluation Method of Antibacterial Property> In order to evaluate the antibacterial property of the antibacterial fiber produced above, a test piece (30 mm × 30 mm, about 0.5 g) was produced according to the above.

Staphylococcus aureus (IFO-12732) cultivated in liquid culture at 28 ° C. for 24 hours was used as a test bacterium, and a test was conducted by a shake flask method using sterile physiological saline as a medium. That is, 20
Add the test specimen and 10 ml of the bacterial suspension to a 0 ml Erlenmeyer flask, and add 2
The mixture was shaken at 8 ° C. for 24 hours, the number of viable bacteria was measured, and the mortality was calculated by the following formula. Death rate (%) = 100 x (initial viable cell count – viable cell count after 24 hours)
/ Initial viable cell count

<Test Results of Antibacterial Properties> The test results are shown in Table 1, and no difference in the antibacterial effect due to the difference in the inorganic antibacterial agents was observed, but only Tetoron cloth was made of cotton cloth, nylon cloth and acrylic cloth. It was slightly less effective than the dough.

[0060]

[Table 1] 0 hours after 24 hours after viable cell count number of living bacteria kill rate (number / ml) (cells / ml) (%) Cotton Fabric / untreated ku ^{3.0 × 10 3 2.3 × 10 3} 23.3 Cotton Fabric / antimicrobial agent A (3 %) Treated area 3.0 × 10 ³ 0 100 Cotton fabric / antibacterial agent B (3%) Treated area 3.0 × 10 ³ 0 100 Cotton fabric / antibacterial agent C (3%) Treated area 3.0 × 10 ³ 100 Nylon fabric / not Treatment area 3.0 × 10 ³ 2.8 × 10 ³ 6.7 Nylon fabric / antibacterial agent A (3%) Treatment area 3.0 × 10 ³ 0 100 nylon fabric / antibacterial agent B (3%) Treatment area 3.0 × 10 ³ 0 100 nylon fabric / Antibacterial agent C (3%) treated area 3.0 × 10 ³ 0 100 acrylic fabric / untreated area 3.0 × 10 ³ 2.6 × 10 ³ 13.3 acrylic fabric / antibacterial agent A (3%) treated area 3.0 × 10 ³ 0 100 acrylic fabric / Antibacterial agent B (3%) treated area 3.0 × 10 ³ 0 100 acrylic fabric / Antibacterial agent C (3%) treated area 3.0 × 10 ³ 0 100 Tetoron fabric / untreated area 3.0 × 10 ³ 2.5 × 10 ³ 16.7 Tetron Fabric / antibacterial agent A (3%) treatment area 3.0 × 10 ³ 1.2 × 10 ¹ 99.6 Tetron fabric / antibacterial agent B (3%) treatment area 3.0 × 10 ³ 3.5 × 10 ¹ 98.8 Tetron fabric / Antibacterial agent C (3%) treatment area 3.0 × 10 ³ 2.3 × 10 ¹ 99.2

Reference Example 2 In Reference Example 1, no difference in the antibacterial effect due to the difference in the inorganic antibacterial agents was observed, so this time, the antibacterial agent was limited to one kind, and the effect due to the concentration difference was investigated. That is, an inorganic antibacterial agent aqueous dispersion having a composition of the above antibacterial agent A3% and water 97%, antibacterial agent A2% and water 98%, and antibacterial agent A1% and water 99% was prepared, and Reference Example 1 Was repeated. However, the processing conditions were 95 ° C. × 30 minutes.

The test results are shown in Table 2, and a sufficient antibacterial effect was recognized even when the concentration of the antibacterial agent aqueous dispersion was 1%. In the treatment area with the 3% aqueous dispersion of the inorganic antibacterial agent, the texture was slightly impaired and the cloth material tended to be slightly harder than the other materials. It was found that the upper limit of the concentration was 3%.

[0063]

[Table 2] 0 hours after 24 hours after viable cell count number of living bacteria kill rate (number / ml) (cells / ml) (%) Cotton Fabric / untreated ku ^{3.5 × 10 3 3.3 × 10 3} 5.7 Cotton Fabric / antimicrobial agent A (3 %) Treated area 3.5 × 10 ³ 0 100 Cotton fabric / antibacterial agent A (2%) Treated area 3.5 × 10 ³ 0 100 Cotton fabric / antibacterial agent A (1%) Treated area 3.5 × 10 ³ 0 100 Nylon fabric / not Treatment area 3.5 × 10 ³ 3.2 × 10 ³ 8.6 Nylon fabric / antibacterial agent A (3%) Treatment area 3.5 × 10 ³ 0 100 nylon fabric / antibacterial agent A (2%) Treatment area 3.5 × 10 ³ 0 100 nylon fabric / Antibacterial agent A (1%) treated area 3.5 × 10 ³ 0 100 acrylic fabric / untreated area 3.5 × 10 ³ 2.9 × 10 ³ 17.1 acrylic fabric / antibacterial agent A (3%) treated area 3.5 × 10 ³ 0 100 acrylic fabric / Antibacterial agent A (2%) treated area 3.5 × 10 ³ 0 100 acrylic fabric / Antibacterial agent A (1%) treated area 3.5 × 10 ³ 0 100 Tetoron fabric / untreated area 3.5 × 10 ³ 3.0 × 10 ³ 14.3 Tetron Fabric / antibacterial agent A (3%) treatment area 3.5 × 10 ³ 0 100 Tetoron fabric / antibacterial agent A (2%) treatment area 3.5 × 10 ³ 0 100 Tetoron fabric / antibacterial agent A (1%) treatment RIKU 3.5 × 10 ³ 0 100

Examples 1 and 2 and Comparative Example 1 It was found from Reference Example 2 that the concentration of the inorganic antibacterial agent aqueous dispersion was sufficient to be 1%. Therefore, from the above antibacterial agent A 1% and water 99%, Using the inorganic antibacterial agent aqueous dispersion having the following composition, the temperature and pressure conditions during treatment were set as follows, and Reference Example 1 was repeated. In each case, after the treatment, the dough was taken out, washed with water at room temperature, and then naturally dried under sunlight. Example 1 The aqueous dispersion was heated to 80 ° C., the dough was immersed therein and kept for 20 minutes, and then the soaked fabric was kept under reduced pressure condition (about 350 Torr) with boiling for 10 minutes. Processed in the state. Example 2 A state in which the aqueous dispersion was heated to 80 ° C., the dough was immersed therein and kept for 20 minutes, and then the dough was kept immersed for 10 minutes under a pressure condition of about 1 atm higher than atmospheric pressure. Processed by. Comparative Example 1 The aqueous dispersion was heated to 80 ° C., and the dough was immersed in the aqueous dispersion for 30 minutes for treatment.

The test results are shown in Table 3, and in all cases, good antibacterial effect was obtained. The viable cell count after 0 hour is 3.3 × 10 ³ cells / ml. The thickness of the carrier layer is several μm in the case of the comparative example, and several tens in the case of Examples 1 and 2.
It seems to have reached μm.

[0066]

[Table 3] Mortality after 24 hours (%) Example 1 Example 2 Comparative Example 1 heating vacuum heating pressurized heated atmospheric pressure cotton fabric / antimicrobial agent A (1%) treated plot 100 100 99.8 nylon fabric / antimicrobial agent A (1%) treated area 100 100 99.6 Acrylic fabric / antibacterial agent A (1%) treated area 100 100 99.6 Tetoron fabric / antibacterial agent A (1%) treated area 100 100 98.8 (Note) For untreated area after 24 hours Death rate is cotton fabric 9.1
%, Nylon fabric 6.1%, acrylic fabric 12.1%, Tetoron fabric 15.2%.

Examples 3 to 4, Comparative Example 2 In order to confirm the wash fastness of the treated cloths obtained in Examples 1 to 2 and Comparative Example 1, no washing, 10 washings,
The antibacterial effect was examined after 30 washings.

The test results are shown in Table 4. In the non-washed area, there was no substantial difference between each other.
In the 30-time washing section, as compared with the treated product under the heated and atmospheric pressure condition (Comparative Example 2), the treated product under the heated and reduced pressure condition (Example 3) and the heated and pressurized condition (Example 4). The product had a significantly superior antibacterial effect.

[0069]

[Table 4] Death rate after 24 hours (%) Non-washing zone 10 times washing zone 30 times washing zone Cotton cloth / untreated area 9.1 − − Cotton cloth / heated and atmospheric pressure treated area 99.8 92.2 68.4 Cotton cloth / heated / depressurized area 100 100 100 Cotton cloth / heated / pressurized area 100 100 100 Nylon cloth / untreated area 6.1 − − Nylon cloth / heated and normal pressure area 99.6 90.0 63.5 Nylon cloth / heated / depressurized area 100 100 100 Nylon cloth / added Warm and pressurized treatment area 100 100 100 Acrylic fabric / Untreated treatment area 12.1 − − Acrylic fabric / Heating and normal pressure treatment area 99.6 89.8 64.4 Acrylic fabric / Heating and depressurization treatment area 100 100 100 Acrylic fabric / Heating and pressure treatment area 100 100 100 Tetoron cloth / untreated area 15.2 − − Tetoron cloth / heated and atmospheric pressure processed area 98.8 85.7 57.0 Tetoron cloth / heated / depressurized area 100 100 100 Tetron cloth / heated / pressurized area 100 100 100

[0070]

The antibacterial fiber obtained by the method of the present invention has excellent antibacterial properties, a broad antibacterial spectrum, high safety, and extremely good washing resistance. In addition, since the post-processing method that does not use a binder resin is adopted, there is no change in the feel of the fiber, and there is no difference in terms of appearance, strength, and odor from the untreated fiber.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Katsuhiro Shiro 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu-shi, Fukuoka Prefecture Catalytic Chemicals Co., Ltd. Wakamatsu Factory (72) Inventor Atsushi Tanaka 13-minato-minato, Wakamatsu-ku, Kitakyushu-shi, Fukuoka 2 catalyst inside Wakamatsu factory

Claims (7)

[Claims] 1. A fiber is brought into contact with an aqueous dispersion of an inorganic antibacterial agent, followed by washing with water and drying to form an inorganic antibacterial agent-supporting layer on the surface of the fiber by permeation of the aqueous dispersion of the inorganic antibacterial agent. In this regard, a method for producing an antibacterial fiber, characterized in that the inorganic antibacterial agent aqueous dispersion which does not contain a binder resin is used, and the contact treatment is carried out under a heating condition and an emergency pressure condition. 2. The method according to claim 1, wherein the contact treatment is carried out under a heating condition of a temperature of 50 to 95 ° C. and under a reduced pressure condition of 630 Torr or less. 3. The production method according to claim 1, wherein the contact treatment is carried out under a heating condition at a temperature of 50 to 140 ° C. and under a pressure condition higher than the atmospheric pressure by at least 0.1 atm. 4. The method according to claim 1, wherein the particle size of the inorganic antibacterial agent in the inorganic antibacterial agent aqueous dispersion is 1 μm or less. 5. The method according to claim 1, wherein the concentration of the inorganic antibacterial agent in the aqueous dispersion of the inorganic antibacterial agent is 3% by weight or less. 6. The method according to claim 1, wherein the inorganic antibacterial agent is an inorganic microparticle, an inorganic ion exchanger microparticle or an inorganic oxide colloidal microparticle on which an antibacterial metal is supported. 7. The method according to claim 1, wherein the fibers are raw fibers made of fibers belonging to natural fibers and synthetic fibers, intermediate fiber products and final fiber products.