JP3003473B2 - Antibacterial organic polymer material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial organic polymer material.

[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 in which a metal or a metal ion is carried 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 impregnated with an aqueous metal or metal compound sol (for example, JP-A-64-68478).

[0003]

However, the above-mentioned antibacterial organic polymer material has the following problems. First, in the case where an antibacterial agent in which a metal or a metal ion is carried on an inorganic carrier is kneaded with an organic polymer material, the feel such as the touch due to the inorganic carrier changes during kneading of the antibacterial agent as compared with a case where it is not kneaded. Not only does the organic polymer material lose its texture and other properties, but it is difficult to use the antimicrobial agent efficiently because the antimicrobial agent is present inside the material other than the surface of the organic material exhibiting antimicrobial properties. In the case of this antibacterial agent, the metal ion carrying amount is 0.5 to 3 wt% with respect to the inorganic carrier, and since the antibacterial agent is generally blended with various polymer materials at about 1 wt%,
The mixing ratio of metal ions to the polymer material is 0.005 to
It is about 0.03 wt%. In addition, when an aqueous polymer or metal compound sol is impregnated into an organic polymer material, the surface of the fine particles is coated with a surfactant or the like to be used, and there is a problem that the antibacterial properties inherent to the fine particles cannot be sufficiently exhibited.

[0004] An object of the present invention is to solve the above-mentioned problems, that is, a metal or metal compound fine particle having an antibacterial activity, which is not substantially covered with a surfactant, is formed of an organic polymer material. An object of the present invention is to provide an antibacterial organic polymer material fixed to a surface.

[0005]

Means for Solving the Problems The present inventors contact a dispersion liquid in which fine particles of a metal or a metal compound having an antibacterial action are dispersed in a non-aqueous solvent incompatible with water, with various organic polymer materials. By fixing the fine particles to the surface of the organic polymer material in a state not substantially covered with a surfactant,
The present inventors have found that an antibacterial organic polymer material having a sufficient antibacterial effect and antibacterial durability can be provided, and have completed the present invention.
As a means for fixing the fine particles on the surface of the organic polymer material, there is a method by the present inventors (Japanese Patent Application No. Hei.
No. 60834, Japanese Patent Application No. 5-135691).

The antibacterial metal or metal compound used in the present invention includes silver, copper, zinc,
Examples thereof include cuprous oxide and zinc oxide. In addition, there is no limitation on adopting one or more of these. The metal or metal compound particles have a particle size of 1 to 10
It is in the range of 00 nm. More preferably, it is in the range of 1 to 30 nm. The amount of the fine particles supported on the organic polymer material is in the range of 0.001 to 5% by weight based on the organic polymer material.

The non-aqueous solvent used as the dispersion in the present invention is not particularly limited as long as the organic polymer material is not altered. For example, xylene, toluene, benzene and the like are used as aromatic solvents, and carbon tetrachloride and chloroform are used as chlorinated solvents. Examples of the hydrocarbon-based solvent include various non-aqueous solvents such as cyclohexane and normal hexane.

Various methods are employed for producing the fine particles dispersed in a non-aqueous liquid which is phase-separated from water used in the present invention. For example, a metal is heated and evaporated in helium at 10 to 50 Torr, a metal vapor is introduced with argon gas, a non-aqueous liquid vapor is mixed in the middle, and this mixture is condensed in a liquid nitrogen cooling trap, and then heated and melted. A method of forming a dispersion liquid (evaporation method in gas), a method of reacting a metal or a metal compound in a gaseous state with oxygen or the like in a vacuum (gas phase reaction method),
When dispersing the obtained fine particles in a non-aqueous solvent, or when making a reverse micelle microemulsion in a non-aqueous liquid containing a small amount of water using an oil-soluble surfactant, a trace amount of microemulsion particles are contained in the microemulsion particles. Water is taken in,
Since microemulsion particles are dispersed in a large amount of non-aqueous liquid that separates with water, a method of dissolving a noble metal salt in this trace water and adding a reducing agent to form a dispersion (microemulsion method) Etc. are known.

Recently, a method of preparing a dispersion of noble metal fine particles by transferring a noble metal salt from an aqueous solution to a non-aqueous liquid phase using an extractant and reducing the same with a reducing agent added to the aqueous phase (extraction method) Law) has also been attempted.

A particularly preferred method is one of the present inventors.
The following method according to the invention of a human being can be mentioned (Japanese Patent Application No. 4-358518). That is, in the presence of a surfactant, an aqueous dispersion of metal fine particles and / or metal compound fine particles is brought into contact with a non-aqueous liquid that separates from water, and before and / or after the contact, a water-soluble inorganic acid salt and / or A water-soluble organic acid salt is added to move the fine particles from the aqueous dispersion into the non-aqueous liquid, and the non-aqueous dispersion can be isolated from the two-phase mixture.
According to this method, a large amount or high concentration of a non-aqueous dispersion of metal or metal compound fine particles can be easily prepared by a simple operation without requiring a special device.

The particle size of the fine particles dispersed in the non-aqueous dispersion thus obtained is substantially the same as the particle size in the aqueous dispersion used, and is in the range of 1 nm to 1 μm. More preferably, it is in the range of 1 nm to 30 nm. The concentration of the fine particles uniformly dispersed is about 0.05 to 500 mmol / l.

Examples of the organic polymer material used in the present invention include natural polymer materials such as cellulose and starch, and synthetic polymer materials such as polystyrene, nylon and polyacetal. Examples of the cellulose include natural polymer substances such as cotton, flax, jute, wool, and silk; regenerated polymer substances such as rayon and cupra; and semi-synthetic polymer substances such as acetate. Since a non-aqueous solvent is used, a water-soluble substance such as soluble starch and hydroxypropylcellulose can also be used as a carrier. The shape of the carrier is not particularly limited, and includes a film shape, a powder shape, a whisker shape, a fiber shape, a fabric shape, a honeycomb shape, and the like.
Any of a porous body and a non-porous body may be used. The present invention is applicable to a mixture, a composite, and a molded article of one or more of these.

[0013]

Next, the present invention will be described specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. The metal or metal compound fine particle dispersion was prepared according to Japanese Patent Application No. 4-358518. The specific mode is as follows.

A predetermined amount of the aqueous dispersion of fine particles is collected, and a surfactant is added to the aqueous dispersion in an amount of 0.01 to 5% by weight, preferably 0.05 to 0.5% by weight, based on the amount of water in the aqueous dispersion. Add so that it becomes. A non-aqueous liquid having a volume of 0.01 to 50 times, preferably 0.05 to 10 times the volume of the aqueous dispersion is added thereto, and the mixture is added for 15 minutes to
The non-aqueous liquid is dispersed and emulsified in an aqueous dispersion (or vice versa) by mixing and stirring for 8 hours, preferably 2 to 6 hours. 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 surface activity is added to the aqueous dispersion in an amount of 0.005 to 30%.
%, Preferably 0.01 to 15% by weight, and the mixture is stirred for 30 seconds to 30 minutes, preferably 1 to 2 minutes. Thereby, substantially all of the metal fine particles move from the aqueous phase to the non-aqueous liquid phase. After that, when the mixture is left standing for 2 hours to 2 days, an aqueous phase in which fine particles are not dispersed and a non-aqueous liquid phase in which 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.

The aqueous dispersion of fine particles is prepared by applying a well-known method, for example, the method described in The Chemical Society of Japan, New Experimental Chemistry, Vol. 18, Interfaces and Colloids, pp. 319-340, Maruzen, 1977. Can be. The concentration of the fine particles in the aqueous dispersion is from 0.005 to 100 mmol / l, usually from 0.02 to 70 mmol / l, but the higher the concentration, the more preferable.

Example 1 Commercially available 6,6-nylon long fiber (thickness: 15 denier) 2
7 g together with 100 ml of a silver colloidal cyclohexane dispersion having a silver concentration of 0.25 mmol / l and an average particle diameter of 8 nm
The flask was placed in a 0 ml flask and stirred with a magnetic stirrer for 10 minutes. The silver fine particle dispersion having a yellow color became colorless and transparent after stirring and was white.
Nylon filaments are colored pale yellow and silver particles are 6,6
-Adsorbed on nylon long fibers. Next, the 6,6-nylon filaments were taken out of the flask, washed with cyclohexane, and air-dried. A portion of the 6,6-nylon long fiber was collected, and the metal silver adsorbed in a 10% aqueous nitric acid solution was ionized with silver and measured by ICP emission analysis.
-Adsorption amount of fine silver particles to nylon filament is 0.01 wt%
Met.

Example 2 100 ml of ion-exchanged water to which 0.1 g of sodium oleate (special grade of reagent manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a surfactant using the silver-fixed 6,6-nylon filament obtained in Example 1 as a surfactant. When the mixture was vigorously stirred for 1 hour in a 300 ml flask, no change in the coloring of the 6,6-nylon filament was observed. On the other hand, ion-exchanged water was colorless and transparent. The concentration of silver fine particles in the ion-exchanged water was measured by ICP emission spectroscopy. As a result, the concentration of silver fine particles was 0.2 mg / l or less, and desorption of silver fine particles once adsorbed on 6,6-nylon filaments by adding a surfactant. Was rarely observed. Next, the 6,6-nylon filament was taken out of the flask,
After washing with ion-exchanged water, it was air-dried. The same surfactant-containing ion-exchanged water treatment was repeated 40 times. A portion of the 6,6-nylon filament was collected, and silver metal ion adsorbed in a 10% nitric acid aqueous solution was ionized with silver and measured by ICP emission analysis. As a result, silver fine particles on the 6,6-nylon filament were measured. The amount of adsorption was 0.01 wt%. From this, it became clear that 6,6-nylon filaments adsorbing the silver fine particles had excellent washing durability.

Example 3 A commercially available cotton fabric (20 g) was subjected to a zinc oxide concentration of 0.25 mmol.
The mixture was placed in a 300 ml flask together with 100 ml of a zinc oxide colloidal cyclohexane dispersion having an average particle size of 12 nm / l and stirred with a magnetic stirrer for 10 minutes. The white zinc oxide fine particle cyclohexane dispersion became colorless and transparent after stirring, and the zinc oxide fine particles were adsorbed on the cotton fabric. Next, the cotton fabric was taken out of the flask, washed with cyclohexane, and air-dried. A part of the cotton cloth was collected and measured by X-ray fluorescence analysis. As a result, the amount of zinc oxide fine particles adsorbed on the cotton cloth was 0.01 w
t%.

Example 4 The cotton cloth adhered to zinc oxide obtained in Example 3 was added to 0.1 g of sodium oleate (reagent grade, manufactured by Tokyo Chemical Industry Co., Ltd.) as a surfactant in 100 ml of ion-exchanged water.
When vigorously stirred for 1 hour in a 0 ml flask, the ion-exchanged water was colorless and transparent. As a result of measuring the concentration of zinc oxide fine particles in the ion-exchanged water by fluorescent X-ray analysis,
The concentration of the zinc oxide fine particles was 0.2 mg / l or less, and almost no desorption of the zinc oxide fine particles once adsorbed on the cotton fabric by the addition of the surfactant was observed. Next, the cotton fabric was taken out of the flask, washed with ion-exchanged water, and air-dried. The same surfactant-containing ion-exchanged water treatment was repeated 40 times. A part of the cotton fabric was collected and measured by X-ray fluorescence analysis. As a result, the amount of zinc oxide fine particles adsorbed on the cotton fabric was 0.01 wt%. From this, it was clarified that the cotton fabric adsorbing the zinc oxide fine particles had excellent washing durability.

Comparative Example 1 In the same manner as in Example 1, 27 g of 6,6-nylon long fiber (thickness: 15 denier) was prepared by silver concentration of 5 mmol / l and average particle size of 8 n.
20 mg of surfactant (stearyltrimethylammonium chloride) together with 100 ml of an aqueous dispersion of silver fine particles of m
For 3 hours. During the stirring, the 6,6-nylon filaments floated above the aqueous dispersion. The silver fine particle dispersion having a brown color hardly changed in color even after stirring, and the 6,6-nylon filaments were colored pale yellow. Next, the 6,6-nylon filament was taken out of the flask,
After washing with ion-exchanged water, it was air-dried. A part of the 6,6-nylon long fiber was collected, and the metal silver adsorbed in the 10% nitric acid aqueous solution was ionized with silver and measured by ICP emission spectrometry. As a result, silver fine particles on the 6,6-nylon long fiber were measured. The amount of adsorption was 0.05 wt%.

Comparative Example 2 100 ml of ion-exchanged water to which 0.1 g of sodium oleate (reagent grade, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a surfactant using the silver-fixed 6,6-nylon filament obtained in Comparative Example 1 as a surfactant. When the mixture was vigorously stirred for 1 hour, the 6,6-nylon filament changed from pale yellow to white. On the other hand, the ion-exchanged water was colored yellow. As a result of measuring the concentration of silver particles in the ion-exchanged water by ICP emission analysis, the concentration of silver particles was 2
Most of the silver fine particles once adsorbed on 6,6-nylon filaments were desorbed by the addition of a surfactant at 3.7 mg / l. Next, the 6,6-nylon long fiber was taken out of the flask, washed with ion-exchanged water, and air-dried. 6,
-A part of the nylon long fiber was collected, and the metal silver adsorbed in the 10% nitric acid aqueous solution was ionized with silver and measured by ICP emission analysis. 0.01 wt% or less.

Example 5 The antibacterial activity of 6,6-nylon long fibers adsorbed with silver fine particles and cotton cloth adsorbed with zinc oxide fine particles obtained in Examples 1, 2, 3, 4 and Comparative Examples 1 and 2 were used as samples. Was determined. The antibacterial activity was determined by the shake flask method described below. A suspension buffer of the sample and the test bacterium (Staphylococcus aureus 209P) was added to a closed container, and the mixture was shaken at 150 times / minute for 90 minutes, the number of viable cells after shaking was counted, and the added suspension was added. The reduction rate (%) of the bacteria relative to the number of bacteria in the liquid was determined.

[0024]

[Table 1]

As shown in Table 1, in the case of the present invention, the excellent antibacterial power is maintained and the washing durability is also excellent by efficiently fixing the antibacterial fine particles to the surface of the organic polymer material. Was revealed.

On the other hand, when fine particles having antibacterial properties are adhered to the surface of an organic polymer material in the presence of a surfactant in an aqueous system, the surface of the fine particles is covered with the surfactant. It has low antibacterial activity and requires a large amount of fine particles. In addition, washing durability was poor, and it was difficult to maintain antibacterial activity.

[0027]

According to the present invention, an inorganic carrier is not required because a metal or metal compound fine particle having a small particle size and having antibacterial properties is directly adhered to the surface of the organic polymer material. It does not impair the aesthetics such as appearance and feel, and exhibits antibacterial properties efficiently even in a small amount. Further, since the active ingredient is substantially in a metal state or insoluble, it is less susceptible to a chemical change than a metal ion. Therefore, the antibacterial organic polymer material according to the present invention is expected to be used in various fields such as medicine, textiles, construction, and the electronics industry.

Claims (4)

(57) [Claims] 1. A dispersion in which fine particles of a metal or a metal compound having an antibacterial action are dispersed in a non-aqueous solvent incompatible with water.
The by contacting the organic polymeric material, an antimicrobial organic polymer material comprising the fine particles <br/> substantially by fixing in a state which is not covered by the surfactant on the surface of the organic polymeric material. 2. The antibacterial organic polymer material according to claim 1, wherein the metal or metal compound fine particles have a particle size of 1 to 1000 nm. 3. The organic polymer material is cellulose, starch, nylon, polyester, polydivinylbenzene,
The antibacterial organic polymer material according to claim 1 or 2, comprising at least one of polystyrene and polyacetal. 4. The antibacterial according to claim 1, wherein the metal or metal compound fine particles having an antibacterial action are silver, copper, zinc, cuprous oxide or zinc oxide. Organic polymer material.