JP2998584B2 - Antibacterial fiber or fiber product and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antimicrobial fiber material in which fine particles of an antimicrobial metal or metal compound are firmly fixed on the fiber surface.

[0002]

2. Description of the Related Art Conventionally, an organic polymer material having antibacterial properties is obtained by kneading an organic polymer material with an antibacterial agent having a metal or metal ion supported on an inorganic carrier (for example, Japanese Patent Application Laid-Open No.
254412, JP-A-4-300302,
JP-A-4-321628). Alternatively, there is an organic polymer material in which an aqueous metal or metal compound sol is impregnated at a high concentration (for example, JP-A-64-68478).

[0003]

In a conventional synthetic fiber, an antibacterial powder in which silver ions are immobilized on an inorganic ion exchanger having a diameter of 0.5 μm is mixed with a raw material, which is then melted and spun to obtain an antibacterial fiber. The way to get is taken. In the case of natural fibers or regenerated fibers, kneading-type antibacterial treatment like synthetic fibers is impossible. By blending the above synthetic fiber antibacterial fiber and natural fiber, it is possible to impart antibacterial properties to some extent, but it cannot be applied to 100% natural fiber. Therefore, to impart antibacterial properties to natural or regenerated fibers,
Surface treatment such as applying an antibacterial agent is required. Generally, antibacterial agents are roughly classified into organic antibacterial agents and inorganic antibacterial agents. Many organic antibacterial agents have safety problems. Further, when the heat treatment in the fiber production process is performed at a temperature higher than the thermal decomposition temperature or the boiling point of the organic antibacterial agent, it is not practical. In recent years, silver ion-based inorganic ion exchangers with good thermal stability have been put on the market.
The limit is about μm. When the inorganic ion exchanger is used, it is inevitable that the texture of the fiber is impaired. Furthermore, it cannot be said that it is sufficient to uniformly disperse the particles during coating. Further, the color may be changed by light depending on use conditions. An object of the present invention is to solve the above problems, that is, by using antimicrobial metal or metal compound fine particles having a particle diameter of 500 nm or less, the fine particles are uniformly distributed, and the antimicrobial metal Alternatively, it has been found that the amount of the metal compound used can be minimized, and at the same time, an antibacterial fiber or a fiber product in which the fine particles are firmly retained by a high molecular polymer which does not inhibit the antibacterial activity can be obtained.

[0004]

Means for Solving the Problems The present invention has a particle diameter of 500 nm.
A fiber or a fiber product having antibacterial properties characterized by holding a polymer containing fine particles of a metal or a metal compound having antibacterial properties, and a particle size of 500
Drying after immersing the fiber or fiber product in a precursor of a high molecular polymer containing fine particles of a metal or a metal compound having antimicrobial properties of nm or less, or drying after spraying the precursor on the fiber or fiber product And a method for producing a fiber or a fiber product having antibacterial properties.

The metal or metal compound fine particles having antibacterial properties according to the present invention have a particle diameter of 500 nm or less, preferably 2 nm or less.
100 nm or less, more preferably 100 nm ~ 0.5 nm is used, examples of metals, metal compounds include silver, copper, silver halide, silver oxide, silver sulfide, copper oxide, cuprous oxide, copper sulfide and the like And one or more of these mixed fine particles are used. When the particle size of the fine particles having antibacterial properties exceeds 500 nm, the number of fine particles per surface area of the fiber or the fiber product decreases, and the antibacterial properties decrease.

[0006] The fiber used in the present invention may be any kind of natural fiber, regenerated fiber, synthetic fiber and the like. Specifically, natural fibers include cotton, kapok, flax, hemp, ramie, jute, manila hemp, sisal hemp, and the like. Palm, areca, wool, alpaca, cashmere, mohair, silk and the like.
Rayon, cupra, and the like are examples of the regenerated fiber. Examples of the synthetic fibers include nylon, polyester, acrylic, acetate, and polypropylene. In addition, a fiber product refers to a woven fabric, a knitted fabric, a nonwoven fabric, or the like containing at least one kind of these fibers.

The high-molecular polymer in the present invention may be natural or synthetic. There is no particular limitation as long as the antibacterial activity of the fine particles is not inhibited and the texture of the fiber is not reduced. For example, as thermosetting resins, phenolic resins, epoxy resins, unsaturated polyester resins, alkyd resins, urea resins, melamine resins, urethane resins, silicone resins,
There are diallyl phthalate resin and the like, and as thermoplastic resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyolefin such as polyvinylidene chloride, and polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, polymethyl methacrylate, polyacrylamide, polyacrylamide Examples include ether, polyacrylonitrile, polyfluoroethylene, polyether, polycarbonate, nylon, polyimide, polyamide, polysulfone, ABS resin, and AS resin. Further, a combination of these thermoplastic polymers and thermosetting polymers may be used, or a copolymer having a main chain of the above-mentioned polymer as a component may be used. The precursor of a high molecular polymer is a liquid medium, and is an aqueous emulsion (high molecular polymer dispersion), an aqueous solution containing a water-soluble high polymer, and a non-aqueous emulsion (high polymer dispersion). And a non-aqueous solution containing a high molecular polymer soluble in a non-aqueous solvent.

[0008] The concentration of the high polymer in the precursor is 0.0
It is from 0.01 to 40% by weight, preferably from 0.001 to 10% by weight. The optimum concentration is selected depending on the method and amount of holding the high-molecular polymer on the fiber or fiber product, but if it exceeds 40% by weight, uniform holding becomes difficult. The amount of the antimicrobial fine particles to be mixed with the precursor is 1 to 20,00 by weight ratio with respect to the polymer.
0 ppm, preferably 1 to 5,000 ppm. If it exceeds 20,000 ppm, the fine particles will be agglomerated and the antibacterial property will be saturated, and the economic efficiency will be poor.

Various methods can be adopted as the manufacturing method of the present invention. For example, a dipping method in which fibers or textile products are immersed in a precursor of a high molecular polymer containing antimicrobial fine particles, dried, and optionally subjected to a heat treatment, or a high molecular polymer containing antimicrobial fine particles in fibers or fiber products It can be manufactured by combining existing manufacturing methods such as a spraying method in which the precursor is sprayed, dried and then heat-treated as necessary.

The amount of the retained antimicrobial fine particles is 0.1 to 400 ppm, preferably 0.1 to 10 ppm by weight based on the weight of the fiber or fiber product.
It is 0 ppm. If the retained amount exceeds 400 ppm, the fine particles will be agglomerated and the antibacterial properties will be saturated, resulting in poor economic efficiency. The holding amount of the high molecular weight polymer is selected in the range of 0.01 to 20% by weight based on the weight of the fiber or the fiber product. The high molecular weight polymer has a function of firmly fixing the antibacterial fine particles to the surface of the fiber or the fiber product. However, if the holding amount exceeds 20% by weight, the feeling of the fiber or the fiber product may be impaired, which is not preferable.

In the present invention, a precursor of a high molecular polymer containing fine particles of a metal or a metal compound having antibacterial properties can be prepared as follows. In the case of an aqueous emulsion or aqueous solution, it is prepared by mixing an aqueous emulsion or aqueous solution of a polymer with an aqueous dispersion of fine particles of a metal or metal compound having antibacterial properties. The aqueous dispersion of the fine particles is prepared by a known method. For example, this can be carried out by applying the description in New Chemical Chemistry, Vol. 18, edited by The Chemical Society of Japan, Interfaces and Colloids, pp. 319-340 (published by Maruzensha, 1977). In the case of a non-aqueous emulsion or non-aqueous solution, it is prepared by mixing a non-aqueous dispersion of fine particles of a metal or a metal compound having antibacterial properties with a non-aqueous emulsion or non-aqueous solution of a polymer.

The non-aqueous emulsion of the high-molecular polymer or the non-aqueous liquid as a medium for the non-aqueous solution is not particularly limited, but is usually an aromatic hydrocarbon solvent such as benzene, toluene and xylene, and carbon tetrachloride and chloroform. Chlorinated hydrocarbon solvents, aliphatic or alicyclic hydrocarbon solvents such as normal hexane and cyclohexane, alcohols such as ethanol, diethyl ether, methyl isobutyl ketone, and ethyl acetate, ethers, ketones, esters, etc. No. The aqueous emulsion or the non-aqueous emulsion is prepared by a known method. For example, it can be carried out by applying the description in Polymer Colloid, edited by the Society of Polymer Science, pages 1 to 32 (published by Kyoritsu Shuppan, 1989).

The preparation of the non-aqueous dispersion of the metal or metal compound fine particles having antibacterial properties of the present invention is disclosed in Japanese Patent Application Laid-Open No. 5-27171.
It is convenient to use a non-aqueous dispersion in which the fine particles of the metal or metal compound are dispersed in a non-aqueous liquid described in JP-A No. 8 (1993). The non-aqueous dispersion is prepared by bringing an aqueous dispersion of fine particles of a metal or a metal compound into contact with a non-aqueous liquid which is phase-separated from water in the presence of a surfactant, and before and / or after the contact, It is obtained by adding a water-soluble organic acid salt, moving the fine particles from the aqueous dispersion into the non-aqueous liquid, and separating the non-aqueous dispersion from the two-phase mixture. By repeating the above operation using the thus obtained non-aqueous dispersion, a non-aqueous dispersion having a high concentration of metal or metal fine particles can be prepared.

The non-aqueous liquid phase-separated from water used in the present invention is not particularly limited, but is usually an aromatic hydrocarbon solvent such as benzene, toluene and xylene, carbon tetrachloride,
Chlorinated hydrocarbon solvents such as chloroform, normal hexane, aliphatic or alicyclic hydrocarbon solvents such as cyclohexane, ethers such as diethyl ether, methyl isobutyl ketone, and ethyl acetate, ketones, and esters are preferably used. Can be

The non-aqueous dispersion of the metal or metal compound fine particles having antibacterial properties is specifically produced as follows. A predetermined amount of the metal or metal compound fine particle aqueous dispersion is sampled, and a surfactant is added thereto to the amount of water in the aqueous dispersion,
It is added in an amount of 0.01 to 5% by weight, preferably 0.05 to 0.5% by weight. To this is added a non-aqueous liquid of 0.01 to 50 times, preferably 0.05 to 10 times the volume of the aqueous dispersion, and 15 minutes to 8 hours,
The mixture is stirred for preferably 2 to 6 hours, and the non-aqueous liquid is dispersed in the aqueous dispersion (or vice versa) and emulsified. in this case,
It is desirable to keep the temperature constant in the range of 0 to 90 ° C, preferably 20 to 60 ° C. Thereafter, the water-soluble inorganic acid salt and / or the water-soluble organic acid salt having substantially no surfactant effect is added in an amount of 0.005 to 30% by weight, preferably 0.1 to 30% by weight, based on the amount of water in the aqueous dispersion.
It is added so as to have a concentration of 01 to 15% by weight, and the mixture is stirred for 30 seconds to 30 minutes, preferably for 1 to 2 minutes. Thereby, substantially all of the metal or metal compound fine particles move from the aqueous phase to the non-aqueous liquid phase. After that, if left for 2 hours to 2 days, the aqueous phase in which the fine particles are not dispersed and the non-aqueous liquid phase in which the fine particles are dispersed are separated into upper and lower two phases. Thereby, a non-aqueous liquid in which fine particles are dispersed can be easily obtained.

Examples of the water-soluble inorganic acid salt and / or water-soluble organic acid salt used in this method include water-soluble ammonium, lithium, sodium, potassium, magnesium, calcium, strontium, barium, aluminum, lanthanum and the like. Sulfate, halide, acetate, nitrate, carbonate, citrate, tartrate and the like.

[0017]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1 Aqueous dispersion of silver fine particles having a silver concentration of 0.16 wt% and a silver average particle diameter of 8 nm
0.19 g of a self-crosslinking acrylic copolymer aqueous emulsion (manufactured by Hoechst Gosei KK, Movinyl 963, solid content concentration
In addition to 6.52 g of water and 293.29 g of water, 300 g of a coating solution (acrylic copolymer concentration 1 wt%, silver concentration in solids 100 ppm) was prepared. 100% cotton pile cotton fabric 10g
Was immersed in the coating solution at room temperature for 5 minutes, and the coating solution excessively adhered was removed with a roller. After air-drying the fabric for 8 hours, heated in a dryer at 150 ° C for 2 minutes,
Cooled slowly. The weight increase of the fabric was 0.2 wt%. The feel of the cotton fabric was similar to the original fabric. When the cloth was observed with an electron microscope, the average particle size was 8 near the surface of the cloth.
The silver fine particles of nm were uniformly dispersed. The weight ratio of silver to cotton fabric was measured by X-ray fluorescence analysis. The weight ratio of the silver fine particles to the cotton fabric was 0.2 ppm. The fabric was subjected to an antibacterial test by a shake flask method. Place the sample and test bacteria (Staphylococcus aureu) in a closed container.
s IFO12732), and the mixture was shaken at 150 times / minute for 90 minutes. The number of viable cells after the shaking was counted, and the reduction rate (%) of the number of cells relative to the number of cells in the added suspension was determined. I asked. Table 1 shows the results. Excellent antibacterial properties were confirmed. After washing 10 times,
The sample was again subjected to an antibacterial test by the shake flask method. Table 1 shows the results. Even after 10 washes, excellent antibacterial properties were confirmed.

Comparative Example 1 Commercially available silver-based antibacterial agent having a silver concentration of 3.8 wt% and an average particle diameter of 800 nm.
0.38 g of a self-crosslinking acrylic polymer aqueous emulsion (manufactured by Hoechst Gosei Co., Ltd., Movinyl 9) as in Example 1
63) Coating liquid 30 in addition to 293.10 g of water with 6.52 g
0g (acrylic copolymer concentration 1wt%, silver concentration in solids 4
272 ppm). After 10 g of 100% cotton pile cotton fabric as in Example 1 was immersed in the coating solution with stirring at room temperature for 5 minutes, the excessive coating solution was removed with a roller. The fabric was air-dried for 8 hours, then heated at 150 ° C. for 2 minutes in a dryer, and gradually cooled. The weight increase of the fabric was 0.21 wt%. The feel of the cotton fabric was similar to the original fabric. When the cloth was observed with an electron microscope, silver antibacterial agents having an average particle diameter of 800 nm were sparsely dispersed near the surface of the cloth. The weight ratio of silver to cotton fabric was measured by X-ray fluorescence analysis. The weight ratio of silver to cotton fabric was 9 ppm. The fabric was subjected to an antibacterial test by a shake flask method in the same manner as in Example 1. Table 1 shows the results. Antimicrobial properties were hardly confirmed.

Comparative Example 2 A coating liquid (300 g) was prepared in the same manner as in Example 1 except that an aqueous emulsion of a self-crosslinking acrylic polymer (manufactured by Hoechst Gosei KK, Movinyl 963) was not used. After 10 g of 100% cotton pile cotton fabric as in Example 1 was immersed in the coating solution for 5 minutes at room temperature, the excessive coating solution was removed with a roller. The fabric was air-dried for 8 hours, heated at 150 ° C. for 2 minutes in a dryer, and gradually cooled. The feel of the cotton fabric was similar to the original fabric. When the cloth was observed with an electron microscope, the average particle size was 8 near the surface of the cloth.
The silver fine particles of nm were uniformly dispersed. The weight ratio of silver to cotton fabric was measured by X-ray fluorescence analysis. The weight ratio of the silver fine particles to the cotton fabric was 0.2 ppm. The fabric was subjected to an antibacterial test by a shake flask method in the same manner as in Example 1.
Table 1 shows the results. Excellent antibacterial properties were confirmed. After washing 10 times, it was again subjected to the antibacterial test by the shake flask method. Table 1 shows the results. After washing 10 times, no antibacterial property was confirmed.

Example 2 0.19 g of a silver fine particle xylene dispersion having a silver concentration of 0.20 wt% and a silver average particle diameter of 8 nm was mixed with 3 g of an acrylic resin in 293.29 g of xylene.
And 300 g of a coating liquid (acrylic resin concentration: 1 wt%, silver concentration in solid content: 126 ppm) was prepared by sufficiently stirring and mixing. 10 g of 100% wool yarn (extremely thick) was immersed in the coating solution for 5 minutes at room temperature, and then treated with a centrifuge at 300 rpm for 1 minute to remove the excessively adhered coating solution. The yarn was air-dried for 8 hours and then subjected to a reduced pressure treatment with an aspirator. The weight increase of the wool was 0.08 wt%. The yarn is
There was no shrinkage and the hand was similar to the original yarn. Observation of the wool with an electron microscope revealed that silver fine particles having an average particle diameter of 8 nm were uniformly dispersed near the surface of the wool. The weight ratio of silver to wool was measured by fluorescent X-ray analysis. The weight ratio of the silver fine particles to the wool was 0.1 ppm. The wool was subjected to an antibacterial test by the shake flask method in the same manner as in Example 1. Table 1 shows the results. Excellent antibacterial properties were confirmed.
After washing 10 times, it was again subjected to the antibacterial test by the shake flask method. Table 1 shows the results. Even after 10 washes, excellent antibacterial properties were confirmed.

Example 3 Silver fine particle dispersion having a silver concentration of 0.16 wt% and a silver average particle diameter of 8 nm
0.38 g of fluororesin aqueous emulsion (Asahigard AG-471, manufactured by Meisei Chemical Co., Ltd., fluororesin concentration 2.3 wt
%) Along with 130.43 g, 169.19 g of water was added to prepare 300 g of a coating solution (acrylic copolymer concentration 1 wt%, silver concentration in solids 200 ppm). After immersing 10 g of 100% cotton plain woven cotton fabric in the coating solution at room temperature for 20 minutes, the coating solution excessively adhered was removed with a roller. The fabric was air-dried for 8 hours, then dried at 120 ° C for 10 minutes, followed by drying for 1 hour.
The mixture was heated at 70 ° C. for 30 seconds and gradually cooled. The weight increase of the fabric is 2wt
%Met. The feel of the cotton fabric was similar to the original fabric. When the cloth was observed with an electron microscope, silver fine particles having an average particle diameter of 8 nm were uniformly dispersed near the surface of the cloth.
The weight ratio of silver to cotton fabric was measured by X-ray fluorescence analysis. The weight ratio of the silver fine particles to the cotton fabric was 4 ppm.
A 5 cm square test piece was obtained from the cotton cloth and subjected to an antibacterial test.
E. coli and S. aureus were suspended in sterile phosphate buffer solution was prepared so that the cell count density of about 10 ⁵ / ml. After 1 ml of each bacterial solution was dropped on the test piece, it was stored at 25 ° C. for 18 hours. After 18 hours, the test bacterial solution on the test piece was washed out with 10 ml of SCDLP medium, and the number of viable bacteria in the wash solution was measured by a pour plate method (35 ° C., 2 days) using SCDLP agar medium.
The results are shown in Table 2. Excellent antibacterial properties were confirmed.

Example 4 5.0 g of a copper oxide fine particle toluene dispersion having a copper oxide concentration of 0.12 wt% and a copper oxide average particle diameter of 200 nm was mixed with polymethyl methacrylate 1
300g of coating liquid in addition to 278.0g of toluene together with 2g
(Poly (methyl methacrylate) concentration: 4 wt%, copper oxide concentration in solid content: 500 ppm) were prepared. 100% hemp plain woven linen cloth 1
After immersing 0 g in the coating solution at room temperature for 5 minutes, the coating solution excessively adhered was removed with a roller.
The linen cloth was air-dried for 8 hours and then subjected to a reduced pressure treatment with an aspirator. The weight increase of the linen fabric was 2.8 wt%. The linen cloth did not shrink and the hand was similar to the original linen cloth. Observation of the linen cloth with an electron microscope revealed that copper oxide fine particles having an average particle diameter of 200 nm were uniformly dispersed near the surface of the linen cloth. The weight ratio of copper oxide to hemp cloth was measured by X-ray fluorescence analysis. The weight ratio of the copper oxide fine particles to the hemp cloth was 14 ppm. The linen cloth was subjected to an antibacterial test by a shake flask method in the same manner as in Example 1. Table 1 shows the results. Excellent antibacterial properties were confirmed. After washing 10 times,
The sample was again subjected to an antibacterial test by the shake flask method. Table 1 shows the results. Even after 10 washes, excellent antibacterial properties were confirmed.

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

According to the present invention, an antimicrobial fine particle having a particle diameter of 500 nm or less is fixed to a surface of various fibers or textile products by using a high molecular polymer as a binder in a small amount.
It is possible to impart antibacterial properties without impairing the aesthetics such as the texture of the fiber. Compared with a conventional antibacterial agent using an inorganic ion exchanger, an inorganic ion exchanger is unnecessary, and only the effective ingredient is blended on the surface as much as possible. Therefore, the antibacterial fiber or textile product according to the present invention,
It is expected to be used in various fields such as medical care, household goods, construction, and the electronics industry.

Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) D06M 11/83

Claims (6)

(57) [Claims] 1. A fiber or a fiber product having antibacterial properties, wherein the fiber or the fiber product has a polymer containing fine particles of metal or metal compound having antibacterial properties with a particle diameter of 500 nm or less. 2. Metal or metal compound fine particles having antibacterial properties are silver, copper, silver halide, silver oxide, silver sulfide, copper oxide,
The fiber or fiber product according to claim 1, which is at least one type of fine particles selected from cuprous oxide and copper sulfide. 3. The holding amount of the metal or metal compound fine particles having antibacterial properties is 0.1 ppm by weight relative to the fiber or fiber product.
The fiber or fiber product according to claim 1 or 2, wherein: 4. The method for producing an antibacterial fiber or a fiber product according to claim 1, wherein the high molecular weight polymer or the metal compound fine particle has an antibacterial property having a particle diameter of 500 nm or less. A production method characterized by dipping a fiber or a fiber product in a precursor and then drying. 5. The method for producing a fiber or a fiber product having antibacterial properties according to any one of claims 1 to 3, wherein the high molecular weight polymer contains fine particles of metal or metal compound having antibacterial properties with a particle diameter of 500 nm or less. A production method characterized in that a precursor is sprayed onto a fiber or a fiber product and then dried. 6. The method according to claim 4, wherein the precursor is selected from an aqueous emulsion, an aqueous solution, a non-aqueous emulsion, and a non-aqueous solution of the polymer.