Glass composition for imparting antibacterial property, antibacterial composite material, and antibacterial fiber

【0001】

[Technical field to which the invention belongs]

The present invention relates to glass compositions for imparting antibacterial properties, antibacterial composite materials and antibacterial fibers.

【0002】

[Conventional technology]

The four seasons of Japan (Japan) are an environment in which bacteria can easily grow. Especially in summer, when the temperature and humidity are high during the rainy season, the growth of microorganisms becomes active. Therefore, they often suffer from heat rash, athlete's foot, bedsores and unpleasant odors. With the diversification of lifestyles, textile products having a microbial control function such as suppressing or sterilizing harmful microorganisms that propagate under clothes, so-called antibacterial and deodorant processed textile products, have become widespread.

【0003】

For example, there are antibacterial fiber products in which silver-supported zirconium phosphate, zeolite, soluble glass, etc. are composited with fibers. In particular, soluble glass is a general term for glass whose composition has been adjusted in consideration of the physical and chemical properties of the glass so as to have a controlled melting rate, and silver, copper, zinc compounds, etc. having antibacterial properties are used. It is known that the contained glass can elute the silver, copper, and zinc ions at a predetermined constant rate over an arbitrary period of several hours to several years. Then, the eluted silver, copper, and zinc ions are adsorbed on the cell wall of bacteria and microorganisms and concentrated inside the cells, and the so-called oligogenic action inhibits the growth of bacteria and microorganisms and exerts an antibacterial action. is there.

【0004】

[Problems to be Solved by the Invention]

When producing such an antibacterial fiber, first, the above-mentioned inorganic antibacterial agent is compounded with a chemical fiber material, an antibacterial composite material such as a masterbatch (temporary molded body) is prepared, and then the antibacterial composite material is spun. To produce antibacterial fibers. However, the above-mentioned inorganic antibacterial agent is dissolved by acid and alkali treatment (for example, alkali weight loss for polyester fiber, acid dyeing, raw material dissolution step of caustic soda for rayon, etc.) associated with the fiber manufacturing or processing process, and its antibacterial effect is exhibited. Problems such as deterioration may occur. In addition, discoloration due to silver may occur, which is not preferable in terms of the appearance of the product. Due to these problems, an inorganic antibacterial agent having durability against the above-mentioned acid and alkali treatments and an antibacterial composite material in which the inorganic antibacterial agent is composited with chemical fibers have been desired. Further, an antibacterial fiber which is made by spinning an antibacterial composite material and has high fiber strength and antibacterial property has been desired.

【0005】

An object of the present invention is a glass composition for imparting antibacterial properties having high durability, which is less likely to cause problems such as discoloration and melting in the fiber manufacturing and processing processes, and an antibacterial composite material obtained by compounding the glass composition with chemical fibers. It is to provide an antibacterial fiber having high fiber strength and antibacterial property by spinning an antibacterial composite material.

【0006】

[Means for solving problems]

In order to solve the above problems, the glass composition for imparting antibacterial properties of the present invention is P.₂O₅30-60 mol%, K₂O, Na₂O, Li₂5 to 35 mol% of one or more selected from O, 5 to 35 mol% of one or more selected from MgO, CaO, ZnO, Al₂O₃4 ~ 20mol%, La₂O₃, Y₂O₃In a glass composition containing 0.01 to 5 mol% of one or two selected from Ag₂It is characterized by containing 0.1 to 5.0% by weight of O.

【0007】

The glass composition having the above constitution is generally a soluble glass, and from the antibacterial property-imparting glass composition containing such a soluble glass, Ag contained in the glass composition (soluble glass) The component is eluted at a predetermined constant rate over an arbitrary period, and the Ag component makes the antibacterial fiber highly antibacterial. In the glass composition for imparting antibacterial properties of the present invention, Al is contained in the glass composition as a component for improving acid resistance, alkali resistance and water resistance.₂O₃4 ~ 20mol%, La₂O₃, Y₂O₃Since 0.01 to 5 mol% of one or two selected from the above is contained, the antibacterial property-imparting glass composition imparts acid resistance, alkali resistance and water resistance while imparting an antibacterial effect to chemical fibers. For example, the antibacterial fiber in which the antibacterial property-imparting glass composition is composited exhibits high durability against acid or alkali treatment associated with the manufacturing and processing steps thereof.

【0008】

The acid or alkali treatment associated with the production and processing of chemical fibers includes weight loss processing (for example, for alkali weight loss, a 4% caustic soda aqueous solution is immersed for 40 minutes at 98 ° C) and dyeing treatment (for example, hydrogen). (Depending on an acid having an ion concentration index of 4 or less) and the like can be exemplified. The antibacterial fiber in which the glass composition for imparting antibacterial property of the present invention is compounded exhibits high durability against such post-processing, and exhibits high antibacterial property even after post-processing.

【0009】

Next, the critical meaning (limited effect) of each component contained in the antibacterial glass composition of the present invention will be described below.

【0010】

P₂O₅Is the main component of glass formation in glass compositions (soluble glass). P in glass composition₂O₅If the content of is less than 30 mol%, it may be difficult to vitrify the soluble glass. Also, P₂O₅If the content of the glass exceeds 60 mol%, the water resistance of the glass may decrease. In addition, P₂O₅The content of is preferably 35 to 60 mol%, more preferably 40 to 54 mol%.

【0011】

K₂O, Na₂O, Li₂One or more selected from O is a component that promotes vitrification and facilitates elution of silver, which is an antibacterial component. If the content of this component is less than 5 mol%, it may be difficult to vitrify the soluble glass. If the content of this component exceeds 35 mol%, the dissolution rate of the glass composition (soluble glass) in water becomes high, and the water resistance of the soluble glass may decrease. The content of this component is preferably 10 to 30 mol%, more preferably 15 to 25 mol%.

【0012】

One or more selected from MgO, CaO, and ZnO is a component for improving the water resistance of glass. If the content of this component is less than 5 mol%, the water resistance of the glass may decrease. If it exceeds 35 mol%, the acid resistance and alkali resistance of the soluble glass may decrease. The content of this component is preferably 10 to 30 mol%, more preferably 10 to 25 mol%.

【0013】

Al₂O₃Is a component for improving the water resistance, acid resistance and alkali resistance of glass. Al₂O₃If the content of is less than 4 mol%, the water resistance, acid resistance and alkali resistance of the soluble glass may decrease. Al₂O₃If the content of is more than 20 mol%, vitrification may be difficult. In addition, Al₂O₃The content of is preferably 4 to 15 mol%, more preferably 6 to 12 mol%.

【0014】

La₂O₃, Y₂O₃One or two selected from are components for improving the water resistance, acid resistance and alkali resistance of glass. Difficult to vitrify and sufficient Al₂O₃Is added when it is not possible to add and it is necessary to further improve the durability against acidic and alkaline treatments. If this content is less than 0.01 mol%, water resistance, acid resistance and alkali resistance may decrease. If the content of this component exceeds 5 mol%, it may be difficult to vitrify the soluble glass. The content of this component is preferably 0.1 to 3 mol%, more preferably 1 to 3 mol%.

【0015】

To such a glass composition, in the present invention, Ag₂O is contained in an amount of 0.1 to 5.0% by weight, and this Ag component is the main component exhibiting an antibacterial effect. Ag for glass composition₂If the O content is less than 0.1% by weight, the antibacterial effect of the antibacterial property-imparting glass composition may decrease. Also, Ag₂If the O content exceeds 5.0% by weight, the antibacterial fiber may be discolored. In addition, Ag for a glass composition₂The O content is preferably 0.1 to 3.0% by weight, more preferably 0.3 to 2.6% by weight.

【0016】

The glass composition for imparting antibacterial properties having the above-mentioned structure is preferably finely pulverized into a particle form and composited with a chemical fiber. In that case, the average particle size is preferably 0.1 to 5 μm. If the average particle size is less than 0.1 μm, it may be difficult to produce the particles, and when the particles are composited with the above fibers, uneven distribution may occur and the composite may not be uniform, so that the antibacterial property imparting effect is reduced. In some cases, the performance of the fiber itself may be reduced, especially in its uneven distribution region. Further, when the average particle size exceeds 5 μm, it may be difficult to produce fibers due to thread breakage or the like, or the obtained antibacterial fibers may cause poor appearance. The average particle size is preferably 0.2 to 2 μm.

【0017】

For the measurement of the average particle size, for example, a laser diffraction type particle size meter can be used. In this case, in the measurement by the laser diffraction type particle size meter, there is no big difference between the diffraction behavior of the incident laser light due to the aggregated particles and the diffraction behavior due to the isolated primary particles. It is indistinguishable from each other whether it is the particle size of what is present or the particle size of the agglomerated secondary particles. Therefore, the average particle size measured by this method is a value that reflects the average particle size of the secondary particles including the isolated primary particles that have not agglomerated in a broad sense.

【0018】

An antibacterial composite material is produced by compounding glass for imparting antibacterial properties with a fiber material. In this case, the composite amount is preferably 0.01 to 50% by weight. If the composite amount is less than 0.01% by weight, the antibacterial effect of the antibacterial fiber produced from the antibacterial composite material may decrease. When the fiber material is a thermoplastic polymer material (nylon (polyamide), polyester, polyethylene, polypropylene, etc.), a masterbatch (temporary molded product) can be prepared. In this case, if the composite amount exceeds 50% by weight, the antibacterial property-imparting glass may be unevenly distributed in the antibacterial composite material, and the composite may not be uniform. The performance of itself may deteriorate especially in the uneven distribution area.

【0019】

The composite amount of the antibacterial glass composition in the antibacterial fiber is preferably 0.01 to 5.0% by weight. The antibacterial fiber of the present invention can be produced by diluting the antibacterial composite material, and therefore, it is possible to produce an antibacterial fiber in which the composite amount of the antibacterial glass composition is lower than that of the antibacterial composite material. it can. If the composite amount is less than 0.01% by weight, the antibacterial effect of the antibacterial fiber may decrease, and if it exceeds 5.0% by weight, the fiber strength decreases or the antibacterial fiber has a poor appearance. In addition to causing it, there may be problems that increase costs.

【0020】

Needless to say, the composite of the antibacterial property-imparting glass with the chemical fiber gives a preferable result when the above-mentioned average particle size and the composite amount with the chemical fiber are satisfied at the same time. Specifically, for example, when the average particle size of the glass composition for imparting antibacterial properties is 0.1 to 5 μm and the composite amount with chemical fibers is 0.01 to 50% by weight, fibers having high antibacterial properties and fiber strength can be obtained. Obtainable.

【0021】

The material of the fiber to which the present invention can be applied is not particularly limited as long as it is a chemical fiber, but for example, the following can be exemplified (for synthetic fibers, in order to specify the material of the fiber substrate, the material of the fiber substrate can be specified. Commercially available products of the corresponding fiber materials have been exemplified. Therefore, it is natural that it does not mean that the fibers of the present invention in which the antibacterial property-imparting glass composition is composited are commercially available under these trade names). ..

【0022】

-Recycled fiber: viscose rayon, tencel, chitin, collagen fiber, polynosic, cupra rayon, organic solvent method cellulose fiber, etc. -Semi-synthetic fibers: acetate, triacetate, promix, etc. -Synthetic fiber: Polypropylene fiber (trade name: nylon, amylan, glylon, etc.) Polypropylene fiber (trade name: terylene, decron, tetron, ester, siluk, etc.) Polyacrylic fiber (trade name: auron, cresslan, exlan, etc.) Bonnell, Acrylan, Canecaron, Casimilon, Trelon, Sylvaron, Finel, etc.) Viniron (Polyvinyl alcohol-based fiber) Polypropylene-based fiber (Product name: Pyrene, Melacron (above, polypropylene-based), Pyrene E (polypropylene-based), etc.) Polyurethane (spandex) ) Fibers (trade names: Lycra, Pyrene, Spandel, Espa, Oberon, Neoron, etc.) Among them, polyester fibers, polyamide fibers, polyacrylic fibers, polypropylene fibers, vinylon, polyurethane fibers, biscous rayon, Polypropylene, cupralayon, organic solvent method cellulose fiber, acetate, triacetate, and promix are preferable, and particularly high antibacterial performance and high antibacterial durability are exhibited against these fibers.

【0023】

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described with reference to the drawings. The antibacterial property-imparting glass composition 10 used in this embodiment is P.₂O₅30-60 mol%, K₂O, Na₂O, Li₂5 to 35 mol% of one or more selected from O, 5 to 35 mol% of one or more selected from MgO, CaO, ZnO, Al₂O₃4 ~ 20mol%, La₂O₃, Y₂O₃In a glass composition containing 0.01 to 5 mol% of one or two selected from Ag₂It is composed of 0.1 to 5.0% by weight of O. Further, the antibacterial property-imparting glass composition 10 in the present embodiment is in the form of particles, and the average particle size thereof is 0.1 to 5 μm. Further, such a glass composition 10 for imparting antibacterial properties is composited at a ratio of 0.01 to 5.0% by weight with respect to the fiber substrate 16.

【0024】

FIG. 1 is an enlarged schematic view for explaining an outline of the antibacterial fiber of the present invention. In the antibacterial fiber 200 shown in FIG. 1, the antibacterial property-imparting glass composition 10 is dispersed and composited with respect to the fiber substrate 16 in the form of particles. Such a compounding mode is particularly effective when the particles are compounded with chemical fibers. That is, the fibers of the above-described embodiment can be easily obtained by blending the particles in the spinning stock solution to be the fiber substrate 16 and spinning the particles. FIG. 2 shows an example of the melt spinning method, which is effective when the fiber substrate 16 is a thermoplastic polymer material (nylon (polyamide), polyester, polyethylene, polypropylene, etc.). That is, a masterbatch (temporary molded product), which is an antibacterial composite material, is melted to prepare a melt-spun stock solution, which is extruded into a cooling medium such as air or water, cooled and solidified into fibers. ..

【0025】

A masterbatch for spinning can be produced, for example, as follows. That is, as shown in FIG. 3A, the antibacterial property-imparting glass composition 10 as described above is an antibacterial agent different from the antibacterial property-imparting glass composition 10 alone or as necessary. Along with fillers, colorants such as pigments and dyes, dispersants, etc., it is blended and kneaded in a polymer material (a thermoplastic resin is used in this embodiment) 41 to be a substrate to form a compound 531. To do. The compound 531 can be made into masterbatch particles 32 by molding into granules such as pellets. The masterbatch particles 32 have a size of, for example, about 0.1 to 10 mm (for example, about 1 to 4 mm) in terms of diameter in terms of spheres. The shape of the masterbatch particles 32 is not particularly limited, but as shown in FIG. 3 (b), for example, the softened compound is extruded into a strand shape and cut into a predetermined length to form a columnar shape. Particles in the form (eg, columnar) can be obtained. Note that FIGS. 3 (c) and 3 (d) show another example of the shape of the masterbatch particles 32, the former being spherical (for example, can be manufactured by molding) and the latter being flake-shaped (for example). It can be manufactured by crushing and sizing the sheet-like material), but it is not limited to this.

【0026】

As shown in FIG. 4A, the masterbatch particle 32 may be used alone for spinning, but as shown in FIG. 4B, the masterbatch particle 32 may be used as a polymer substrate. By blending an appropriate amount of diluted polymer material particles 40 made of polymer materials of the same material or different materials, fibers having a composite particle content lower than that in the masterbatch particles 32 can be produced. For example, 0.01 to 5% by weight of fibers can be produced by setting the content of the antibacterial property-imparting glass composition in the masterbatch particles 32 to 0.01 to 50% by weight and diluting by the above method.

【0027】

On the other hand, FIG. 5 shows some other examples of the spinning method. Fig. 5 (a) shows an example of the wet spinning method. The raw material is dissolved or dispersed in a solvent to prepare a spinning stock solution, which is extruded from a nozzle into a coagulation bath to remove the solvent and form a fiber. It is a method of playing back. This method is effective when the fiber substrate is, for example, rayon, acrylic, vinylon, or the like. Fig. 5 (b) shows an example of the dry spinning method, which is similar to the wet method in that the undiluted spinning solution is extruded into a heated gas (air, etc.) and the solvent is evaporated to regenerate it into a fiber shape. is there. This method is effective when the fiber substrate is, for example, acetate, vinylon, polyether urethane, or the like. Fig. 5 (c) shows an example of the dry-wet spinning method. By first passing the spinning stock solution through the voids filled with gas, the orientation state of the molecular chains is controlled, and the solvent is removed in the liquid bath. It is a method of regenerating into fibers.

【0028】

[Example]

Hereinafter, examples of the present invention will be described. P₂O₅, K₂O, Na₂O, Li₂O, MgO, CaO, ZnO, Al₂O₃, La₂O₃, Y₂O₃Was mixed so as to have each composition ratio (mol%) shown in Table 1, and then Ag₂O was mixed at each weight ratio (% by weight) shown in Table 1, and this was melted in an electric furnace at 1300 to 1400 ° C. for 1 hour. Then, it was taken out from an electric furnace, poured onto a carbon plate, and allowed to cool. Then, it is finely pulverized using a roll crusher and a ball mill so that the average particle size is 2 μm, and A and B, which are glass compositions for imparting antibacterial properties belonging to the present invention, and samples C and D as comparative examples are obtained. It was.

【0029】

[table 1]<img file="JP2005022916A_D0001.tif" /> 【0030】

After adding the antibacterial property-imparting glass composition A to the polyester resin and preparing a masterbatch as an antibacterial composite material with a twin-screw extruder so that the content is 20% by weight, the final concentration is 1% by weight. 120 denier / 36 filament polyester fiber was prepared by spinning and drawing by a conventional method. It was immersed in a 4% caustic soda aqueous solution at 98 ° C. for 40 minutes to reduce the amount of alkali. In this way, Example 1 which is an antibacterial fiber belonging to the present invention was obtained.

【0031】

Polyester fibers were prepared under the same conditions as in Example 1 except that the glass composition B for imparting antibacterial properties was added, and used as Example 2 which is an antibacterial fiber belonging to the present invention.

【0032】

To a solution of N-methylmorpholin-N-oxide in which cellulose is dissolved, 1% by weight of glass composition B for imparting antibacterial properties is added based on the weight of cellulose, and the mixture is uniformly dispersed by stirring, and then wet spinning 120. A denier / 36 filament cellulose fiber was prepared and used as Example 3 which is an antibacterial fiber belonging to the present invention.

【0033】

Polyester fibers were prepared under the same conditions as in Example 1 except that the glass composition C for imparting antibacterial properties was added, and used as Comparative Example 1. In addition, cellulose fibers were prepared under the same conditions as in Example 3 except that the glass composition D for imparting antibacterial properties was added, and used as Comparative Example 2.

【0034】

The antibacterial effects of the examples and comparative examples obtained as described above were evaluated as follows. First, Examples 1 to 3 and Comparative Examples 1 and 2 (antibacterial test samples) and fibrous samples (standard samples) that do not contain each of the antibacterial agents A to D are prepared, and JIS L is used as a pretreatment for the antibacterial test. 0217 Washing was performed under the washing conditions specified in No. 103. That is, a washing liquid kept at 40 ° C was prepared, and an antibacterial test sample, a standard sample, and a load cloth were added to the washing liquid so that the bath ratio was 1:30, and the operation was started. After processing for 5 minutes, stop operation, dehydrate each sample and load cloth with a dehydrator, rinse for 2 minutes, dehydrate again to make one wash. This was done a total of 10 times.

【0035】

After that, an antibacterial test based on JIS L 1902: 2002 was conducted. A bacterial solution containing Staphylococcus aureus is added dropwise to the above antibacterial test sample, and after culturing at 37 ° C for 18 hours, the bacterial solution is washed out and the viable cell count is counted by a 10-fold dilution method. did.

【0036】

On the other hand, based on JIS L 1902: 2002, a bacterial solution containing Staphylococcus aureus was added dropwise to a standard sample, and after culturing at 37 ° C for 18 hours, the bacterial solution was washed out and subjected to a 10-fold dilution method by a pour plate culture method. The viable cell count was counted. The antibacterial property evaluation is performed when the viable cell count for the standard sample containing each antibacterial agent A to D is X and the viable cell count for the antibacterial test sample containing each antibacterial agent A to D is Y. When the common logarithmic value of / Y was 2.2 or more, it was evaluated as , and when it was less than 2.2, it was evaluated as ×. The common logarithmic value of X / Y is defined as the bacteriostatic activity value in JIS L 1902: 2002, and is a product that has undergone antibacterial deodorant processing (processing aimed at suppressing the growth of bacteria and deodorizing effect). Used for evaluation of. The results are shown in Table 2.

【0037】

[Table 2]<img file="JP2005022916A_D0002.tif" /> 【0038】

Furthermore, the bacteriostatic effect of Examples and Comparative Examples was evaluated as follows. First, Examples 1 to 3 and Comparative Examples 1 and 2 (antibacterial test samples) and fibrous samples (standard samples) that do not contain each of the antibacterial agents A to D are prepared, and the Ministry of Health and Welfare Ordinance as a pretreatment for the antibacterial test. Washing was performed under the washing conditions compliant with No. 13.

【0039】

After that, an antibacterial test based on JIS L 1902: 2002 was conducted. A bacterial solution containing Staphylococcus aureus, pneumonia bacillus, and MRSA was added dropwise to the antibacterial test samples (Examples and Comparative Examples) after the above washing, and the cells were cultured at 37 ° C for 18 hours, and then the bacteria. The solution was washed out, and the viable cell count was counted by a mixed plate culture method using a 10-fold dilution method.

【0040】

On the other hand, based on JIS L 1902: 2002, a bacterial solution containing Staphylococcus aureus, Pneumoniae bacillus, and MRSA is added dropwise to a fibrous sample (standard sample) that does not contain each of the antibacterial agents A to D. Immediately after, the number of viable bacteria was counted. For the antibacterial property evaluation, the viable cell count for the standard sample not containing each antibacterial agent A to D is Z, and the viable cell count for the antibacterial test sample (Example and Comparative Example) containing each antibacterial agent A to D. When W was set, the case where the common logarithmic value of Z / W was greater than 0 was evaluated as , and the case where it was 0 or less was evaluated as ×. The common logarithmic value of Z / W is defined as the bactericidal activity value in JIS L 1902: 2002, and is used for evaluation of products that have undergone antibacterial processing (processing aimed at suppressing the growth of bacteria). used. The results are shown in Table 3.

【0041】

[Table 3]<img file="JP2005022916A_D0003.tif" /> 【0042】

As shown in Tables 2 and 3, Examples 1, 2 and 3 belonging to the present invention showed high antibacterial effect and bactericidal effect even after washing. However, Comparative Examples 1 and 2 showed a bacteriostatic activity value of less than 2.2 and a bactericidal activity value of 0 or less. This is because Comparative Example 1 has a high ZnO content (43 mol%), so that acid resistance and alkali resistance are lowered, and antibacterial property is lowered by the alkali weight reduction treatment in the chemical fiber manufacturing process. Comparative example 2 is La₂O₃, Y₂O₃This is because the water resistance, acid resistance, and alkali resistance are lowered because the above is not used.

【0043】

[Effect of the invention]

As described above, the glass composition for imparting antibacterial properties of the present invention can improve water resistance, acid resistance and alkali resistance due to the glass composition, and as a result, in the manufacturing and processing steps of antibacterial fibers. Problems such as discoloration and melting are unlikely to occur. Furthermore, since the particle size of the glass composition for imparting antibacterial properties is appropriate, it is possible to produce fibers that are difficult to cut. Further, since the amount of the glass composition for imparting antibacterial properties added to the chemical fibers is appropriate, the antibacterial fibers can exhibit high antibacterial properties.

[Simple explanation of drawings]

FIG. 1 is an enlarged schematic diagram for explaining an outline of the antibacterial fiber of the present invention.

FIG. 2 is an example of a melt spinning method.

FIG. 3 is a diagram showing a method of manufacturing a masterbatch.

FIG. 4 is a diagram showing a diluted state of a masterbatch.

FIG. 5 is a diagram showing another example of the spinning method.

[Explanation of symbols]

Ten Glass composition for imparting antibacterial properties 16 Fiber substrate 32 Masterbatch particles 33 Extruded softened compound 40 Diluted polymer material particles 41 Polymer material 200 Antibacterial fiber 531 compound