JP2021055249A - Antibacterial-antifungal fiber structure and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antibacterial / antifungal fiber structure which is provided with an antibacterial / antifungal agent with high utilization efficiency and has excellent antibacterial / antifungal properties.
SOLUTION: The antibacterial / antifungal agent (A) composed of a pyridine-based antibacterial / antifungal agent and a salting out agent (B) composed of an inorganic compound are contained in the fiber of the fiber structure. The agent (A) is fixed together with the salting-out agent (B).
[Selection diagram] None

Description

The present invention relates to an antibacterial / antifungal fiber structure having excellent washing durability and a method for producing the same.

In recent years, due to heightened awareness of hygiene and health, many textile products around us, such as clothing, towels, and bedding, have been given antibacterial and antifungal properties. However, since many antibacterial and antifungal agents are difficult to chemically bond with fibers, many textile products to which antibacterial and antifungal properties have been imparted use antibacterial and antifungal agents as fibers using a binder such as resin. It is merely coated on the surface and attached. Therefore, when the above-mentioned textile products are repeatedly washed, the antibacterial / antifungal agent easily falls off from the fiber surface, and there is a problem that the antibacterial / antifungal performance is deteriorated each time the washing is performed. As for synthetic fibers, some are spun by kneading antibacterial and antifungal agents into the fibers themselves, but antibacterial agents that can withstand such kneading and spinning temperatures (300 ° C or higher in the case of polyester) are available. Inorganic antibacterial agents, which are extremely few and have high heat resistance, do not bleed when encapsulated in synthetic fibers, so that there is a problem that sufficient antibacterial and antifungal performance cannot be obtained.

By the way, polyester fiber has excellent heat resistance, and processing such as dyeing treatment is widely performed by high-pressure high-temperature processing or normal-pressure high-temperature processing (so-called baking processing). For example, a polyester fiber product is immersed in a dispersion of a pyridine-based antibacterial / antifungal agent and heat-treated at a high temperature of 90 to 160 ° C. under normal pressure or pressure to loosen the dense amorphous region of the polyester. Therefore, a technique has been proposed in which a pyridine-based antibacterial / antifungal agent is permeated and fixed in the generated gap to impart antibacterial / antifungal performance having excellent washing durability (see Patent Document 1).

Further, when the obtained antibacterial property is insufficient, it has been proposed to use an antibacterial auxiliary agent having a synergistic effect with a pyridine-based antibacterial agent as described in Patent Documents 2 and 3 below. In particular, in Patent Document 2, an antibacterial synergistic effect is obtained by using at least one antibacterial auxiliary agent selected from a carboxylic acid compound, a phenol compound and a urea compound in a fiber structure together with a pyridine antibacterial agent. Is proposed to get. That is, when a pyridine-based antibacterial agent is heat-penetrated into a polyester fiber at a temperature of 130 ° C., the utilization efficiency of the pyridine-based antibacterial agent is actually as low as about 30%. By blending 0.01% by weight (100 mg / kg) or more of the antibacterial auxiliary agent in order to improve the efficacy, the synergistic effect of the antibacterial property of the pyridine antibacterial agent and the antibacterial auxiliary agent is realized. is there.

The above-mentioned "utilization efficiency" is the ratio of the amount of the pyridine-based antibacterial / antifungal agent permeated and fixed in the synthetic fiber to the amount of the total pyridine-based antibacterial / antifungal agent in the processing liquid. , The purpose is to exclude those that are only attached to the fiber surface. The fixed antibacterial / antifungal agent can be identified by removing the portion adhering to the surface by washing or the like and then analyzing the fixed agent.

Further, in Patent Document 2, the processing of single fibers such as acrylic fibers and nylon fibers having low heat resistance at suitable temperatures is verified, but the utilization efficiency of pyridine-based antibacterial agents for synthetic fibers in general is high. No improvement has been verified, and it does not claim the effect of promoting the immobilization of the pyridine antibacterial agent inside the fiber. In addition, although a surfactant and a solvent are used in the examples, the purpose is to disperse and solubilize the antibacterial auxiliary agent in water, the effect of improving the utilization efficiency by the combined use, and the pyridine system inside the fiber. The effect of promoting the immobilization of the antibacterial agent has not been verified at all.

On the other hand, Non-Patent Document 1 below reports on the improvement of the dye diffusion rate in polyester fibers using phenylphenol. However, the conventional studies have targeted dyes synthesized so as to have a high affinity for polyester fibers, and verification has been made for pyridine-based antibacterial and antifungal agents having a low affinity for polyester fibers. Furthermore, the verification of the effect of improving utilization efficiency by the combined use with an auxiliary agent or the like is insufficient.

Japanese Unexamined Patent Publication No. 2000-8275 JP-A-2007-126778 Special Table No. 10-509171

Journal of the Japanese Society of Chemistry, 1972, pp. 127-132

As described above, according to Patent Documents 1 and 2, etc., it is possible to effectively apply an antibacterial agent to a textile product made of 100% polyester fiber at a high temperature of 90 to 160 ° C. The actual utilization efficiency of the antibacterial agent is still about 30%, and the actual situation is that after processing, the waste liquid of the processing liquid containing 70% of the antibacterial agent that has not been fixed is discharged. Therefore, in view of recent environmental problems, it is an important issue to reduce the amount of antibacterial agent discarded to reduce the environmental load. Also, from the viewpoint of cost, it is required to improve the utilization efficiency of antibacterial agents and reduce the amount of waste.

Incidentally, FIG. 2 shows the utilization efficiency of ZPT (contained in the processing liquid) when a pyridine-based antibacterial / antifungal agent (specifically, zinc pyrithione, so-called ZPT) is fixed to polyester fibers at a predetermined concentration by submerged processing. It is explanatory drawing about the ratio (%) of ZPT fixed in a fiber in the amount of ZPT.

In the pie chart shown on the left side of FIG. 2, P is the utilization efficiency of ZPT fixed in the fiber by, for example, in-liquid processing at 130 ° C. (in this example, the amount of ZPT fixed in the fiber ÷ processing liquid). The amount of ZPT in the inside) is shown, the ratio is about 30%, and the remaining about 70% (the portion indicated by Q in the figure) is discarded together with the residual liquid of the processing liquid. Therefore, it can be seen that most of the ZPT used in the processing liquid is discarded without being used.

Therefore, as shown in the pie chart shown on the right side of FIG. 2, if the utilization efficiency in the liquid (the portion indicated by P in the figure) can be improved to, for example, 70%, ZPT discharged to the environment. It is possible to reduce the amount of ZPT, and even if the concentration of the processing liquid is halved, the same amount of ZPT fixed can be obtained, so that the cost can be reduced. Therefore, its realization is strongly required.

The present invention has been made in order to meet such a problem, and is obtained by realizing high utilization efficiency of an antibacterial / antifungal agent even in in-liquid processing, for example, and is environmentally friendly and inexpensive. Moreover, it provides an antibacterial / antifungal fiber structure having excellent washing durability and a method for producing the same.

In order to meet the above problems, the present invention is a synthetic fiber structure containing an antibacterial / antifungal agent (A) and a salting agent (B), wherein the antibacterial / antifungal agent (A) is pyridine-based. It is an antibacterial / antifungal agent, the salting agent (B) is an inorganic compound, and the antibacterial / antifungal agent (A) is contained in the fibers of the synthetic fiber structure together with the salting agent (B). The first gist is the fixed antibacterial and antifungal fiber structure.

Further, in the present invention, in particular, the content of the antibacterial / antifungal agent (A) is 200 to 20000 mg / kg with respect to the total amount of the fiber structure, and the content of the salting out agent (B) is particularly high. However, the second gist is an antibacterial / antifungal fiber structure that is 1 to 10000 mg / kg based on the total amount of the fiber structure.

The present invention is a synthetic fiber structure containing an antibacterial / antifungal agent (A), a salting agent (B), and an antibacterial / antifungal agent fixing aid (C). The antifungal agent (A) is a pyridine-based antibacterial / antifungal agent, the salting agent (B) is an inorganic compound, and the antibacterial / antifungal agent fixing aid (C) is the following first group ( It is at least one compound selected from the group consisting of c1), the second group (c2) and the third group (c3), and the antibacterial / antifungal agent (A) is contained in the fibers of the synthetic fiber structure. The third gist is an antibacterial / antifungal fiber structure fixed together with the above-mentioned salt-forming agent (B) and the above-mentioned antibacterial / antifungal agent fixing aid (C).
(C1) The first group consisting of a surfactant.
(C2) The second group composed of an organic solvent.
(C3) The third group consisting of aromatic compounds.

Further, in the present invention, in particular, the content of the antibacterial / antifungal agent (A) is 200 to 20000 mg / kg with respect to the total amount of the fiber structure, and the content of the salinizer (B) is particularly high. However, the content of the antibacterial / antifungal agent fixing aid (C) is 1 to 10000 mg / kg based on the total amount of the fiber structure, and the content of the antibacterial / antifungal agent (C) is 1 to 500 mg / kg based on the total amount of the fiber structure. The fourth gist is the sex fiber structure.

Further, among these, the fifth gist of the present invention is, in particular, an antibacterial / antifungal fiber structure in which the antibacterial / antifungal agent (A) is a pyridine-based metal complex.

In the present invention, among these, in particular, the salt salting agent (B) is an ammonium salt, an alkali metal salt, an alkaline earth metal salt, a group IIb metal salt, a group III metal salt and a group VII. The sixth gist is an antibacterial / antifungal fiber structure which is at least one inorganic salt selected from the group consisting of metal salts, and among them, the salt salting agent (B) is selected from alkali metal salts. The seventh gist is an antibacterial / antifungal fiber structure which is at least one inorganic salt.

Further, in the present invention, among them, in particular, among the antibacterial / antifungal agent fixing aids (C), the first group (c1) is represented by the following formulas (1) and (2). The eighth gist is an antibacterial / antifungal fiber structure containing at least one of the surfactants, and among the antibacterial / antifungal agent fixing aids (C), the third group (c3) is as follows. The ninth gist is an antibacterial / antifungal fiber structure containing at least one selected from the aromatic compounds represented by the formulas (3) to (6).

Further, in the present invention, among them, the antibacterial / antifungal agent fixing aid (C) is composed of the first group (c1), the second group (c2) and the third group (c3). The tenth gist is an antibacterial / antifungal fiber structure containing at least two compounds selected from the group, and the antibacterial / antifungal agent fixing aid (C) is selected from the first group (c1). The eleventh gist is an antibacterial / antifungal fiber structure containing at least one compound to be used and at least one compound selected from the second group (c2).

Further, in the present invention, among them, in particular, the antibacterial / antifungal agent fixing aid (C) is at least one compound selected from the first group (c1) and the third group (c3). The twelfth gist is an antibacterial / antifungal fiber structure containing at least one compound selected from), and the antibacterial / antifungal agent fixing aid (C) is from the second group (c2). The thirteenth gist is an antibacterial / antifungal fiber structure containing at least one compound selected and at least one compound selected from the third group (c3), and the antibacterial / antifungal agent fixation. The auxiliary agent (C) is selected from at least one compound selected from the first group (c1), at least one compound selected from the second group (c2), and the third group (c3). The 14th gist is an antibacterial / antifungal fiber structure containing at least one compound.

The present invention is a method for obtaining an antibacterial / antifungal fiber structure by subjecting a synthetic fiber structure to an antibacterial / antifungal treatment, wherein the following antibacterial / antifungal agent (A) and a salting agent (B) are obtained. ), And the process of bringing the processing liquid into contact with the synthetic fiber structure and heating at 70 to 150 ° C. for 10 to 120 minutes in the fiber of the synthetic fiber structure. The fifteenth gist is a method for producing an antibacterial / antifungal fiber structure including a processing step of fixing the antibacterial / antifungal agent (A) together with the salinization agent (B).
(A) An antibacterial / antifungal agent composed of a pyridine-based antibacterial / antifungal agent.
(B) A salting-out agent composed of an inorganic compound.

Further, in the present invention, in particular, in the above-mentioned processing liquid, the content of the antibacterial / antifungal agent (A) is 0.001 to 0.2% by weight based on the total amount of the processing liquid, and the above-mentioned salt. The 16th gist is a method for producing an antibacterial / antifungal fiber structure in which the content of the salting-out agent (B) is 0.1 to 30% by weight based on the total amount of the processing liquid.

Further, the present invention is a method for obtaining an antibacterial / antifungal fiber structure by subjecting a synthetic fiber structure to an antibacterial / antifungal treatment, wherein the following antibacterial / antifungal agent (A) and a salting agent (B) are obtained. ) And the step of preparing the processing liquid containing the antibacterial / antifungal agent fixing auxiliary agent (C), and the above-mentioned processing liquid and the synthetic fiber structure are brought into contact with each other and heated at 70 to 150 ° C. for 10 to 120 minutes. Thereby, a processing step of fixing the antibacterial / antifungal agent (A) in the fibers of the synthetic fiber structure together with the salinizing agent (B) and the antibacterial / antifungal agent fixing auxiliary agent (C) is performed. The 17th gist is a method for producing an antibacterial / antifungal fiber structure provided.
(A) An antibacterial / antifungal agent composed of a pyridine-based antibacterial / antifungal agent.
(B) A salting-out agent composed of an inorganic compound.
(C) An antibacterial / antifungal agent-fixing aid comprising at least one compound selected from the following groups consisting of the first group (c1), the second group (c2) and the third group (c3).
(C1) The first group consisting of a surfactant.
(C2) The second group composed of an organic solvent.
(C3) The third group consisting of aromatic compounds.

In the present invention, in particular, in the processing liquid, the content of the antibacterial / antifungal agent (A) is 0.001 to 0.2% by weight based on the total amount of the processing liquid, and the salt The content of the salting-out agent (B) is 0.1 to 30% by weight based on the total amount of the processing liquid, and the content of the antibacterial / antifungal agent fixing aid (C) is 0.01 based on the total amount of the processing liquid. The 18th gist is a method for producing an antibacterial / antifungal fiber structure of ~ 1% by weight.

Further, in the present invention, among them, in particular, the synthetic fiber structure contains at least polyester fiber, and the processing step puts the processing liquid and the synthetic fiber structure in a sealed container and puts the synthetic fiber structure in the liquid. The 19th gist is a method for producing an antibacterial / antifungal fiber structure, which is a step of heating at 100 ° C. or higher and lower than 150 ° C. for 10 minutes or more and less than 120 minutes under pressure, and the synthetic fiber structure does not contain polyester fiber. The antibacterial / antifungal fiber structure is a step in which the synthetic fiber structure is put into a processing liquid and heated in the liquid under normal pressure at 70 ° C. or higher and lower than 100 ° C. for 10 minutes or more and less than 120 minutes. The 20th gist is the manufacturing method of.

That is, in the antibacterial / antifungal fiber structure of the present invention, whether an inorganic compound is used as the salting out agent (B) together with the pyridine-based antibacterial / antifungal agent which is the antibacterial / antifungal agent (A). Further, as an antibacterial / antifungal agent fixing auxiliary agent (C), a first group (c1) composed of a surfactant, a second group (c2) composed of an organic solvent, and a third group composed of an aromatic compound. Whether at least one compound selected from the group (c3) is used and the antibacterial / antifungal agent (A) is fixed together with the salting out agent (B) in the fibers of the synthetic fiber structure. Or, it is fixed together with the salting-out agent (B) and the antibacterial / antifungal agent fixing aid (C).

Here, synthetic fibers such as polyester fibers generally have the property that the movement of the chain molecules of the polymer increases above the glass transition point and the gaps in the non-crystalline region widen. The higher the temperature, the higher the movement of the chain molecules, and the easier it is for the gaps in the non-crystalline region to widen. For this reason, in general, when dyes, antibacterial agents, etc. are permeated into synthetic fibers by normal pressure high temperature processing or high pressure processing, the dyes are used under high temperature heating conditions above the glass transition point as much as possible within the range where the fibers are not damaged by heat. And antibacterial agents are infiltrated. However, the utilization efficiency (also referred to as exhaustion rate) of antibacterial agents and the like for synthetic fibers is not satisfactory at present.

Therefore, in the present invention, the salting-out agent (B) can be used alone, or the salting-out agent (B) and a specific antibacterial / antifungal agent fixing aid (C) can be used in combination to obtain synthetic fibers. The permeation of the antibacterial / antifungal agent (A) is enhanced, and the utilization efficiency of the antibacterial / antifungal agent can be enhanced.

More specifically, the salting-out agent (B) suppresses the water solubility of the antibacterial / antifungal agent (A) in the processing liquid and changes the partition coefficient between the water and the synthetic resin which is a fiber. It acts, and by that action, it has the effect of promoting the penetration of antibacterial agents and the like dispersed in the processing liquid into the synthetic resin which is a fiber.

The salting-out agent (B) has a sufficient effect of improving the utilization efficiency of the antibacterial / antifungal agent (A), but in order to obtain the effect, the antibacterial / antifungal agent (A) can be obtained. It tends to require a large amount of salting out agent (B) relative to the amount. Therefore, even if the utilization efficiency of the antibacterial / antifungal agent (A) is improved, there is a possibility that a large amount of the salting out agent (B) must be discarded, which is not preferable from the viewpoint of environment and cost. ..

Therefore, by using the salting-out agent (B) and the antibacterial / antifungal agent fixing aid (C) in combination, the antibacterial / antifungal agent (B) can be suppressed while suppressing the blending amount of the salting-out agent (B). Since the high utilization efficiency of A) can be achieved, a more preferable effect can be obtained.

When the surfactant of (c1) is used as the antibacterial / antifungal agent fixing aid (C), the fiber surface of the pyridine antibacterial / antifungal agent is changed by changing the fiber surface energy with the surfactant. Antibacterial due to the effect of increasing the affinity for the fiber and selectively increasing the presence probability of the pyridine antibacterial / antifungal agent near the fiber surface and the effect of leading the pyridine antibacterial / antifungal agent into the synthetic fiber.・ Assists the penetration of antifungal agents.

Further, when the organic solvent of (c2) is used as the antibacterial / antifungal agent fixing aid (C), the dissolution concentration of the poorly water-soluble pyridine-based antibacterial / antifungal agent in the processing liquid is increased. Due to its effect, it exerts the effect of promoting the permeation rate of pyridine antibacterial and antifungal agents.

Further, when the aromatic compound of (c3) is used as the antibacterial / antifungal agent fixing auxiliary agent (C), these compounds permeate the polyester fiber to form a chain molecule in the non-crystalline region. By activating the movement and widening the gaps in the non-crystalline region, it has the effect of promoting the permeation rate of antibacterial agents and the like.

Therefore, the antibacterial / antifungal fiber structure of the present invention has achieved high utilization efficiency of the antibacterial / antifungal agent (A) as compared with the original in-liquid processing, and is an antibacterial / antifungal agent for the environment. The emission of (A) is suppressed, the product cost is reduced, and the product has excellent antibacterial and antifungal properties.

In particular, in the present invention, as the antibacterial / antifungal agent (A), methicillin-resistant enterococci (so-called MRSA) and vancomycin-resistant enterococci (VRE) are sufficiently antibacterial against more drug-resistant bacteria. Because of the use of pyridine-based antibacterial and antifungal agents, it is best to apply this fiber structure to a variety of linen supply supplies such as surgical gowns, nursing gowns, and sheets in hospitals and facilities. The antibacterial and antifungal fiber structure of the present invention can maintain its excellent antibacterial and antifungal properties even after repeated industrial washing.

In the present invention in which the salting out agent (B) is used alone with respect to the antibacterial / antifungal agent (A), the content of the antibacterial / antifungal agent (A) is particularly high with respect to the total amount of the fiber structure. When the content of the salting-out agent (B) is 200 to 20000 mg / kg and the content of the salting-out agent (B) is 1 to 10000 mg / kg with respect to the total amount of the fiber structure, particularly excellent antibacterial / antifungal properties and washing durability are exhibited. Therefore, it is suitable.

Further, in the present invention in which the salt-forming agent (B) and the antibacterial / antifungal agent fixing aid (C) are used in combination with the antibacterial / antifungal agent (A), particularly, the antibacterial / antifungal agent (A). ) Is 200 to 20000 mg / kg with respect to the total amount of the fiber structure, and the content of the salinizer (B) is 1 to 10000 mg / kg with respect to the total amount of the fiber structure. The content of the fungicide fixing aid (C) of 1 to 500 mg / kg with respect to the total amount of the fiber structure is particularly suitable because it exhibits more excellent antibacterial / antifungal properties and washing durability. Is.

Among the present inventions, those in which the antibacterial / antifungal agent (A) is a pyridine-based metal complex are particularly methicillin-resistant staphylococci (so-called MRSA) and vancomycin-resistant enterococci (VRE). It is suitable because it exhibits excellent antibacterial properties against bacteria with stronger drug resistance.

In the present invention, the salting-out agent (B) is particularly derived from ammonium salt, alkali metal salt, alkaline earth metal salt, Group IIb metal salt, Group III metal salt and Group VII metal salt. At least one inorganic salt selected from the group, and in particular, one in which the salting-out agent (B) is at least one inorganic salt selected from alkali metal salts. , The antibacterial / antifungal agent (A) is suitable because it improves the utilization efficiency.

Further, in the present invention, in particular, among the antibacterial / antifungal agent fixing aids (C), the first group (c1) is two types represented by the above formulas (1) and (2). Among those containing at least one of the surfactants and the antibacterial / antifungal agent fixing aid (C), the third group (c3) is represented by the above formulas (3) to (6). Those containing at least one of the four types of aromatic compounds are suitable because the utilization efficiency of the antibacterial / antifungal agent (A) is further improved.

Then, among the present inventions, in particular, the antibacterial / antifungal agent fixing aid (C) is selected from the group consisting of the first group (c1), the second group (c2) and the third group (c3). Those containing at least two compounds to be prepared, or those containing at least one compound selected from the first group (c1) and at least one compound selected from the second group (c2). It is suitable because the utilization efficiency of the antibacterial / antifungal agent (A) is further improved.

Further, in the present invention, in particular, the antibacterial / antifungal agent fixing aid (C) is selected from at least one compound selected from the first group (c1) and the third group (c3). Those containing at least one compound selected from the above, or those containing at least one compound selected from the second group (c2) and at least one compound selected from the third group (c3). , It is preferable because the utilization efficiency of the antibacterial / antifungal agent (A) is further improved.

Further, in the present invention, in particular, the antibacterial / antifungal agent fixing aid (C) is selected from at least one compound selected from the first group (c1) and the second group (c2). A compound containing at least one compound to be used and at least one compound selected from the third group (c3) is suitable because the utilization efficiency of the antibacterial / antifungal agent (A) is further improved. ..

Further, according to the method for producing an antibacterial / antifungal fiber structure of the present invention, the antibacterial / antifungal agent can be fixed in the fiber of the synthetic fiber structure with high utilization efficiency as compared with the conventional method. The antibacterial / antifungal agent fixing aid (A) discharged to the environment can be significantly reduced. Therefore, it is possible to provide a synthetic fiber structure which is excellent in terms of both environment and cost and has excellent antibacterial and antifungal properties.

Among the above-mentioned production methods, in particular, in the above-mentioned processing liquid, the content of the antibacterial / antifungal agent (A) is 0.001 to 0.2% by weight with respect to the total amount of the processing liquid, and the above-mentioned salting-out agent. When the content of (B) is 0.1 to 30% by weight with respect to the total amount of the processing liquid, the utilization efficiency of the antibacterial / antifungal agent (A) can be further improved, which is preferable.

Further, among the above-mentioned production methods, in particular, in the above-mentioned processing liquid, the content of the antibacterial / antifungal agent (A) is 0.001 to 0.2% by weight based on the total amount of the processing liquid, and the above-mentioned salting-out agent. The content of (B) is 0.1 to 30% by weight with respect to the total amount of the processing liquid, and the content of the antibacterial / antifungal agent fixing aid (C) is 0.01 to 1 with respect to the total amount of the processing liquid. The one by weight% is suitable because the utilization efficiency of the antibacterial / antifungal agent (A) can be further improved.

Here, in these production methods, the range of preferable content of each component with respect to the processing liquid is large because the bath ratio (ratio of the amount of fiber structure and the amount of processing liquid) set at the time of processing greatly varies depending on the processing conditions. It is due to doing. For example, when processing using the latest dyeing machine, the bath ratio is usually 1: 5 (the amount of processing liquid is 5 tons with respect to the weight of the fiber structure of 1 ton), whereas the conventional general dyeing machine is used. In the case of processing, for example, the bath ratio may be 1:30 (the amount of processing liquid is 30 tons with respect to the weight of the fiber structure of 1 ton), and the content of each component changes significantly.

Among the above-mentioned production methods, in particular, the above-mentioned fiber structure contains at least polyester fiber, and the above-mentioned processing step puts a processing liquid and a fiber structure in a sealed container and pressurizes in the liquid at 100 ° C. The process of heating at a temperature of 150 ° C. or higher for 10 minutes or more and less than 120 minutes is an excellent antibacterial / antibacterial process with significantly higher utilization efficiency than conventional polyester fibers, which is desirable to be pressurized and subjected to high pressure treatment. It is suitable because it can impart moldiness.

Further, among the above-mentioned manufacturing methods, in particular, the above-mentioned fiber structure does not contain polyester fiber, and in the above-mentioned processing step, the fiber structure is put into a processing liquid, and the temperature is 70 ° C. or more and less than 100 ° C. under normal pressure in the liquid. In the process of heating for 10 minutes or more and less than 120 minutes, it is not necessary to perform a treatment exceeding 100 ° C. as for polyester fibers, and the utilization efficiency is significantly higher than before, and excellent antibacterial and antifungal properties are obtained. It can be imparted and is suitable.

It is a schematic explanatory drawing which shows an example of the manufacturing method of the antibacterial and antifungal fiber structure of this invention. It is explanatory drawing for demonstrating the subject of this invention.

Next, a mode for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

First, the antibacterial / antifungal fiber structure of the present invention (hereinafter, may be simply referred to as “fiber structure”) is a synthesis containing an antibacterial / antifungal agent (A) and a salinizer (B). It is a fiber structure or a synthetic fiber structure containing the antibacterial / antifungal agent (A), a salting agent (B), and an antibacterial / antifungal agent fixing aid (C).

The above-mentioned "synthetic fiber structure" is a fiber structure made of synthetic fibers such as polyester fiber, polyamide fiber, acrylic fiber, and polyurethane fiber, and even if it is made of one kind of fiber, it is composed of a plurality of kinds of fibers. It may be a blended product, a blended fiber product, a mixed woven product, a mixed knitted product, or the like.

The "synthetic fiber structure" targeted by the present invention does not have to be composed of 100% synthetic fibers, and may contain synthetic fibers in a proportion of 20% by weight or more based on the total weight of the fibers. For example, the remaining fibers may be semi-synthetic fibers such as cellulose and acetate, and non-synthetic fibers such as natural fibers such as silk, cotton, wool and hemp. By mixing 20% by weight or more of synthetic fibers containing an antibacterial / antifungal agent (A), if sufficient antibacterial / antifungal properties are imparted as a whole, excellent antibacterial / antifungal properties will be exhibited. Is.

The thickness of the synthetic fiber depends on the type of the fiber, but in the case of polyester fiber, the average single yarn fineness is 0.1, for example, in order to apply antibacterial / antifungal agent treatment. It is preferably ~ 100 dtex, and more preferably 0.5 to 50 dtex.

When the synthetic fiber is a synthetic fiber such as polyurethane, polyamide, acrylic, polyethylene, polypropylene, etc. other than the polyester fiber, the thickness thereof is, for example, the average single yarn thereof for antibacterial / antifungal treatment. The fineness is preferably 0.1 to 1000 dtex, and more preferably 1 to 500 dtex.

In the present invention, various forms such as yarn, knitted fabric, woven fabric, and non-woven fabric can be mentioned as the form of the "fiber structure". Specific products include, for example, various clothing, socks, tights, sportswear, outdoor products, bedding, rugs, curtains, indoor cloths, sanitary goods such as bandages, gauze, and masks. In particular, since the fiber structure of the present invention has antibacterial and antifungal properties with excellent washing durability, linen supply supplies (surgical gowns and surgical gowns) that are repeatedly used for industrial washing in medical facilities and nursing care facilities. It is preferably applied to white coats, nightwear, sheets, etc.).

Further, as the antibacterial / antifungal agent (A) used in the present invention, a pyridine-based antibacterial / antifungal agent having excellent antibacterial / antifungal performance and high safety to the human body is used. As such a pyridine-based antibacterial / antifungal agent, for example, a pyridine-based metal complex represented by the following formula (7) is preferably used. That is, as described above, the pyridine-based metal complex exhibits excellent antibacterial properties against more drug-resistant bacteria such as methicillin-resistant staphylococci (so-called MRSA) and vancomycin-resistant enterococci (VRE). is there. As described in Patent Document 1, the pyridine-based metal complex is easy to be fixed to the polyester-based fiber because the organic value / inorganic value is close to that of the polyester fiber. Therefore, it is particularly suitable when applied to polyester fibers.

More specifically, as the pyridine-based metal complex, in the following formula (7), bis (2-pyridylthio) copper-1,1'-dioxide (hereinafter, "" Bis (2-pyridylthio) zinc-1,1'-dioxide (hereinafter referred to as "pyrythion zinc") in which "M" is Zn, and bis (2-pyridylthio) in which "M" is Fe. ) Iron-1,1'-dioxide (hereinafter referred to as "pyrythion iron") and the like. These may be used alone or in combination of two or more. However, since the solution of pyrithione iron turns purple, it is preferable to use it in applications where coloring is not a problem. And, it is particularly preferable to use pyrithion zinc, which is white, in that it can be used without causing a problem of coloring.

Since the pyridine-based metal complex is hardly soluble in water or an organic solvent and has a very high specific gravity, the average particle size is 0 in order to maintain a stable suspension state during antibacterial and antifungal treatment processing. .1 to 0.7 μm is preferable, and 0.3 to 0.5 μm is particularly preferable. Then, it is preferable that the pyridine metal complex having a particle size of 2 μm or more is pulverized so as to be 5% by weight or less, preferably 3% by weight or less, and more preferably 1% by weight or less based on the total pyridine metal complex. is there.

The average particle size of the pyridine-based metal complex is determined as a median diameter corresponding to a cumulative total of 50% in the particle size distribution measured using a laser diffraction particle size distribution measuring device in accordance with JIS R1629.

Further, the salting-out agent (B) used in the present invention suppresses the water solubility of the antibacterial / antifungal agent (A) in the processing liquid and changes the partition coefficient between water and the synthetic resin which is a fiber. This action has the effect of promoting the penetration of antibacterial agents and the like dispersed in the processing liquid into the synthetic resin which is a fiber.

Then, due to the effect of the salting-out agent (B) or the synergistic effect of the salting-out agent (B) and the antibacterial / antifungal agent fixing aid (C) described later, in the present invention, it is processed in liquid. However, the utilization efficiency of the antibacterial / antifungal agent (A) for fibers can be improved.

An inorganic compound is used as the salting-out agent (B). And more specifically, for example, ammonium salts such as ammonium sulfate and ammonium chloride: alkali metal salts such as potassium sulfate, sodium sulfate, potassium chloride, sodium chloride and sodium nitrate: calcium chloride, barium chloride, magnesium chloride, magnesium sulfate. Alkaline earth metal salts such as calcium sulfate and strontium chloride: Group IIb metal salts such as zinc chloride and zinc nitrate: Group III metal salts such as aluminum sulfate and aluminum chloride: ferric nitrate, ferric chloride, etc. Examples thereof include inorganic salts such as Group VII metal salts. These may be used alone or in combination of two or more. Moreover, you may use these double salts.

Among the salting-out agents (B), neutral salts are preferable from the viewpoint of effectiveness and handleability, and in particular, alkali metal salts such as potassium sulfate, sodium sulfate, potassium chloride, sodium chloride, and sodium nitrate are used. It is preferable to use, and in particular, sodium sulfate and potassium sulfate are preferably used.

Further, in selecting the salting-out agent (B), when the pH fluctuates due to the addition of the salting-out agent (B), the pH is more preferably 4.5 to 8.0. It is preferable to select a combination of two or more salting out agents (B) so as to have a pH of 5.5 to 7.0.

Further, in the present invention, the antibacterial / antifungal agent fixing aid (C) that can be used together with the salting out agent (B) includes the following first group (c1), second group (c2) and third group. At least one compound selected from the group consisting of group (c3) can be mentioned.
(C1) The first group consisting of a surfactant.
(C2) The second group composed of an organic solvent.
(C3) The third group consisting of aromatic compounds.

As the surfactant of the first group (c1), a nonionic surfactant and an anionic surfactant are usually used. Examples of the nonionic surfactant include ester-type nonionic surfactants such as glycerin laurate and sorbitan fatty acid ester, ether-type nonionic surfactants such as polyoxyalkylene alkyl ether and polyoxyalkylene alkyl phenyl ether, and polyoxy. Ester ether type nonionic surfactants such as alkylene sorbitan fatty acid ester, alkanolamide type nonionic surfactants such as steaic acid diethanolamide, alkyl glycoside type nonionic surfactants such as octyl glucoside, higher alcohol type nonionic surfactants such as cetanol Examples include ionic surfactants. In addition, examples of the anionic surfactant include anionic surfactants such as alkylbenzene sulfonate. These may be used alone or in combination of two or more.

When these surfactants are used, by changing the fiber surface energy with the surfactant, the affinity of the pyridine-based antibacterial / antifungal agent on the fiber surface is increased, and the pyridine-based antibacterial / antifungal agent is selectively used. The existence probability of the agent (A) near the fiber surface can be increased. Then, the surfactant together with the antibacterial / antifungal agent (A) permeates into the non-crystalline region of the fiber, and exerts an effect of assisting the permeation of the antibacterial / antifungal agent (A).

Among the above surfactants, it is particularly preferable to use an ether type nonionic surfactant from the viewpoint of the effect of fixing the antibacterial / antifungal agent (A) to the fiber, and among them, the following formula (1) or It is optimal to use at least one of the two types of nonionic surfactants shown in (2).

In the compounds of the above formulas (1) and (2), the values of the number of carbon atoms in the alkyl group and the number of repetitions n of the oxyalkylene are appropriately adjusted in order to adjust the HLB value of the nonionic surfactant to a preferable value. Will be done. Incidentally, the HLB value of the nonionic surfactant is preferably set to 6 to 19, and particularly 8 to 18 in terms of the effect of fixing the antibacterial / antifungal agent (A) to the fiber. Is more preferable.

As the organic solvent of the second group (c2), a solvent having low volatility is desirable, and specifically, a low volatility organic solvent having a boiling point of 100 ° C. or higher is used. More preferably, one having a boiling point of 120 ° C. or higher is used. An organic solvent having a boiling point of less than 100 ° C. may cause pressure abnormality depending on the processing conditions, which is not preferable. On the other hand, those having a boiling point of 100 ° C. or higher are less likely to cause pressure abnormality. Examples of such a low volatility organic solvent include butanol (boiling point 117.7 ° C.), butyl acetate (boiling point 126.6 ° C.), propylene glycol monoethyl ether (boiling point 132.2 ° C.), and propylene glycol (boiling point 132.2 ° C.). 187.4 ° C.), dimethyl sulfoxide (DMSO, boiling point 189 ° C.), N-methyl-2-pyrrolidone (NMP, boiling point 202 ° C.), 1,3-butylene glycol (boiling point 204 ° C.), etc. Alternatively, two or more types may be used in combination. These organic solvents have the effect of enhancing the permeability of the antibacterial / antifungal agent (A) and the motility of other antibacterial / antifungal agent fixing aids (C) used in combination.

On the other hand, the aromatic compounds of the third group (c3) include monosubstituted aromatic monocyclic compounds such as toluene and benzoic acid, and disubstituted aromatic monocycles such as xylene, salicylic acid, methyl salicylate, and guaiacol (methoxyphenol). Examples thereof include ring compounds, aromatic polycyclic compounds such as phenyl salicylate and o-phenylphenol, and fused ring compounds such as naphthalene and anthracene, and these may be used alone or in combination of two or more.

These aromatic compounds have the effect of activating the movement of chain molecules in the non-crystalline region by penetrating into the fiber and promoting the permeation rate of antibacterial agents and the like by widening the gaps in the non-crystalline region of the fiber. ..

Among the above aromatic compounds, it is most suitable to use at least one of four kinds of aromatic compounds represented by the following formulas (3) to (6) in particular from the viewpoint of effect.

In the compounds of the above formulas (3) to (6), if the carbon number of the substituent introduced into the aromatic ring is too small, it may volatilize before permeating into the fiber, and if it is too large, it does not permeate into the fiber. Since there is a risk, the one having a carbon number in the range of 1 to 10 is usually preferable, and the one having a carbon number in the range of 1 to 5 is more preferable.

More specifically, examples of the compound represented by the above chemical formula (3) include ^{benzoic acid in which R 4} is a hydrogen atom, ^{methyl benzoate in which R 4} is a methyl group, and benzoic acid in which R ⁴ is an ethyl group. Examples thereof include ethyl, ^{butyl benzoate in which R 4} is a butyl group, and ^{octyl benzoate in which R 4} is an octyl group.

Examples of the compound represented by the chemical formula (4) include ^{methyl paraoxybenzoate in which R 5} is a methyl group, ^{ethyl paraoxybenzoate in which R 5} is an ethyl group, and ^{butyl paraoxybenzoate in which R 5} is a butyl group. , ^{Octyl paraoxybenzoate in which R 5} is an octyl group and the like.

Further, as specific compounds represented by the above chemical formula (5), for example, R ^{6 in} the formula is a phenyl group such as p-phenylphenol or o-phenylphenol, and R ⁶ is a benzyl group. Benzylphenol and the like such as certain o-benzylphenol can be mentioned. Further, as a specific compound represented by the above chemical formula (6), for example, ^{an alkoxyphenol such as pentyloxyphenol in which R 7} is a pentyl group and the like can be mentioned.

As described above, the antibacterial / antifungal agent fixing aid (C) that can be used in the present invention includes the surfactant of the first group (c1), the organic solvent of the second group (c2), and the third group (c3). ) Is at least one compound selected from the group consisting of aromatic compounds, and any one of them may be used alone, but at least two compounds are selected from the whole of the above three groups and used in combination. This is preferable because it can increase the permeation and fixation amount of the antibacterial / antifungal agent (A).

Then, as the antibacterial / antifungal agent fixing aid (C), it is better to select at least three compounds from the whole of the above three groups and use them in combination to obtain the permeation-fixing amount of the antibacterial / antifungal agent (A). It is more preferable because it can be further increased.

Further, as the antibacterial / antifungal agent fixing aid (C), it is selected from at least one compound selected from the surfactant of the first group (c1) and the organic solvent of the second group (c2). It is more preferable to use it in combination with at least one compound in terms of effect.

Further, as the antibacterial / antifungal agent fixing aid (C), at least one compound selected from the surfactant of the first group (c1) and an aromatic compound of the third group (c3) are selected. It is more preferable to use it in combination with at least one compound to be used in terms of effect.

Further, as the antibacterial / antifungal agent fixing aid (C), it is selected from at least one compound selected from the organic solvent of the second group (c2) and the aromatic compound of the third group (c3). It is more preferable to use it in combination with at least one compound in terms of effect.

Then, in particular, as the antibacterial / antifungal agent fixing aid (C), at least one compound selected from the surfactant of the first group (c1) and the organic solvent of the second group (c2) are selected. It is preferable to further use at least one compound to be used in combination with at least one compound selected from the aromatic compounds of the third group (c3) from the viewpoint of obtaining particularly excellent effects.

The antibacterial / antifungal fiber structure of the present invention uses the antibacterial / antifungal agent (A) and the salting out agent (B), or uses the antibacterial / antifungal agent fixing aid (C). ) Can be further used to produce, for example, as follows. That is, first, an aqueous suspension containing the antibacterial / antifungal agent (A) is first crushed and stirred by a pulverizing means such as a ball mill or a hammer mill in the presence of water. Alternatively, a dispersion liquid consisting of an aqueous emulsion is obtained. Then, the dispersion liquid and the salting-out agent (B) are mixed and diluted at the time of processing to prepare a processing liquid.

When the antibacterial / antifungal agent fixing aid (C) is used, the antibacterial / antifungal agent fixing auxiliary agent (C) is also added when preparing the dispersion liquid of the antibacterial / antifungal agent (A). It can be uniformly dispersed and mixed. Alternatively, the antibacterial / antifungal agent (A) is made into an aqueous suspension in the same manner as above, and the salting out agent (B) and the antibacterial / antifungal agent fixing aid (C) are combined with an aqueous emulsion or an aqueous solution. It is made into a solubilized liquid and made into two liquids to be mixed and used at the time of processing. For convenience, these liquids are referred to as "preparation liquids for processing", and those finally prepared as processing liquids for use in the processing treatment are referred to as "processing liquids".

Then, using the above-mentioned preparatory liquid for processing, for example, as shown in FIG. 1, the processing treatment of the antibacterial / antifungal agent on the fiber structure can be performed under high pressure using the sealed container 10. In this case, first, the lid of the sealed container 10 is opened, a processing liquid is prepared in the container 10 in the same manner as described above, and then the fiber structure 2 is charged. Then, after the lid is closed and sealed, the inside of the container 10 is heated to pressurize the container 10 to obtain the desired antibacterial and antifungal fiber structure (referred to as "high pressure processing"). As the sealed container 10, various high-pressure dyeing machines such as a liquid flow dyeing machine and a cheese dyeing machine can be used.

When the fiber structure is treated under such a high pressure, the pressure during the treatment is usually 0.5 to 4 kg / cm ² (49), although it depends on the type of fiber and the form of the fiber structure. It is preferable to set the condition of ~ 392 kPa) (gauge pressure). If the pressure is too high, no further effect may be obtained. Conversely, if the pressure is too low, some fibers may have insufficient antibacterial and antifungal properties unless the time is lengthened, resulting in insufficient efficiency. It is not preferable because it is lowered.

Further, the processing temperature in the present invention is usually in the range of 70 to 150 ° C. regardless of whether the processing is performed under normal pressure or high pressure. Further, the processing time is usually preferably set to 10 to 120 minutes.

That is, if the processing temperature is lower than 70 ° C, the permeation and fixation amount of the antibacterial / antifungal agent (A) may be too small and the antibacterial / antifungal property may be insufficient, and if it is higher than 150 ° C, the pressure is high. There is a risk of becoming too dangerous. Further, if the processing time is less than 10 minutes, heat may not be sufficiently transferred to the synthetic fiber and the antibacterial / antifungal agent (A) may not sufficiently penetrate into the synthetic fiber. There is no change in utilization efficiency even if it is applied, which is not preferable.

Further, in the present invention, particularly when the fiber structure contains at least polyester fiber, the processing liquid and the fiber structure are placed in a sealed container as described above, and the temperature is 100 ° C. or higher under pressure in the liquid. By performing a processing process including a step of heating at a temperature of less than 150 ° C. for 10 minutes or more and less than 120 minutes, it is possible to impart excellent antibacterial and antifungal properties with significantly higher utilization efficiency than before, which is preferable. .. Among them, the processing temperature is more preferably 120 to 140 ° C., and the processing time is more preferably 20 to 100 minutes.

On the other hand, in the present invention, in particular, when the fiber structure does not contain polyester fibers, the processing step involves putting the fiber structure in a processing liquid and under normal pressure in the liquid at 70 ° C. or higher and 100 ° C. By performing the processing process including the step of heating for less than 10 minutes or more and less than 120 minutes, it is possible to impart excellent antibacterial and antifungal properties with significantly higher utilization efficiency than before, which is preferable.

In the production method of the present invention, the content of each drug (A) and (B) or (A), (B) and (C) contained in the finally obtained fiber structure is antibacterial. The concentration of the processing liquid is adjusted so as to be in a preferable range sufficient for exhibiting antifungal properties. Even if the concentration of the processing liquid is the same as the conventional concentration, the antibacterial / antifungal agent (A) can be used more efficiently for the fibers, so that the antibacterial / antifungal agent (A) is immobilized on the fibers after the processing. Since the amount of the antibacterial / antifungal agent (A) that is discarded without being discarded is significantly reduced, the material cost can be suppressed and the environmental load due to the waste is reduced. This is also a great effect of the present invention.

Incidentally, in the production method of the present invention, the content of the antibacterial / antifungal agent (A), the salting out agent (B), and the antibacterial / antifungal agent fixing aid (C) in the processing liquid used for the processing treatment is, for example, The following adjustments are preferable in terms of effect. That is, the content of the antibacterial / antifungal agent (A) is preferably 0.001 to 0.2% by weight based on the total amount of the processing liquid, and the content of the salting out agent (B) is the processing liquid. The content is preferably 0.1 to 30% by weight based on the total amount, and the content of the antibacterial / antifungal agent fixing aid (C) is preferably 0.01 to 1% by weight based on the total amount of the processing liquid. ..

In the production method of the present invention, the bath ratio at the time of processing is appropriately set depending on the material and form of the fiber, the type of processing apparatus used, and the like, but usually, the bath ratio is 1: 5 to 1:30. It is preferable to set the condition of 1: 5 to 1:20, and more preferably to the condition of a bath ratio of 1: 5 to 1:20. This is because the smaller the amount of the processing liquid, the higher the concentration of the components can be blended, and the higher the utilization efficiency can be obtained.

As already described, when the antibacterial / antifungal agent fixing aid (C) is used together with the salting out agent (B), the salting out agent (A) against the antibacterial / antifungal agent (A) due to the synergistic effect of both. Even if the blending ratio of B) is reduced, an excellent effect of improving utilization efficiency can be obtained, which is preferable.

Further, in the production method of the present invention, a processing liquid containing an antibacterial / antifungal agent (A) and a salting-out agent (B), or an antibacterial / antifungal agent fixing aid (C) together with the above (A) and (B). In preparing the processing liquid containing the above, in order to keep the processing preparation liquid for that purpose stable for a long period of time and improve the fixation rate of the antibacterial / antifungal agent (A) to the fibers, the pH of the processing preparation liquid should be adjusted. Usually, it is preferable to adjust the pH between 4 and 10, preferably between 5.5 and 8.5, and more preferably between 6 and 8. If the processing preparation liquid is on the alkaline side of the above range, an acid such as acetic acid, hydrochloric acid, or phosphoric acid is added, and if it is on the acidic side, an alkali such as sodium hydroxide or sodium hydroxide is added. do it. The above-mentioned "acid" or "alkali" is different from the salting-out agent (B) of the present invention, and the two are distinguished from each other.

Then, any additive can be further added to the processing preparation liquid or the processing liquid, if necessary. For example, an organic solvent (different from the organic solvent used as an antibacterial / antifungal agent fixing aid (C), for example, a highly volatile organic solvent having a boiling point of less than 100 ° C.), a thickener, an antifreeze agent, etc. Examples thereof include antifouling agents, softeners, flame retardants, flame retardants, insect repellents, antistatic agents, UV blocking agents and the like.

Examples of the organic solvent (highly volatile organic solvent) include alcohols having a boiling point of less than 100 ° C. These are used to solubilize sparingly soluble components in water, but do not volatilize and remain in the final product.

Further, examples of the thickener include sodium polyacrylate, carboxymethyl cellulose, polyvinyl alcohol, starch acetate and the like, and examples of the antifreeze agent include glycerin and potassium acetate.

The antibacterial / antifungal fiber structure of the present invention thus obtained is the effect of the salting out agent (B), or the salting out agent (B) and the antibacterial / antifungal agent fixing aid (C). Due to the synergistic effect, the affinity of the fiber surface for the antibacterial / antifungal agent (A) is improved, the permeability into the fiber is promoted, or the movement of the chain molecule in the non-crystalline region of the fiber is increased to increase the voids. As a result, the antibacterial / antifungal agent (A) is efficiently permeated, and high utilization efficiency that could not be obtained in the past is achieved. Moreover, since the antibacterial / antifungal agent (A) is firmly permeated and fixed in the fiber, the antibacterial / antifungal agent (A) is unlikely to fall off even after repeated washing. Therefore, according to this antibacterial / antifungal fiber structure, antibacterial / antifungal properties can be satisfactorily exhibited for a long period of time.

The content of the antibacterial / antifungal agent (A) in the antibacterial / antifungal fiber structure of the present invention depends on the form of the fiber structure and the treatment temperature, but in order to obtain practical antibacterial / antifungal performance. In the finished stage of the product, that is, in the unused state, it is usually preferably 200 to 20000 mg / kg based on the total amount of the fiber structure, and more preferably 400 to 4000 mg / kg. ..

The content of the salting-out agent (B) used together with the antibacterial / antifungal agent (A) depends on the form of the fiber structure and the treatment temperature, but it is in the finished stage as a product, that is, in an unused state. In general, it is preferably 1 to 10000 mg / kg, more preferably 1 to 1000 mg / kg, and even more preferably 1 to 100 mg / kg with respect to the total amount of the fiber structure. is there.

The content of the antibacterial / antifungal agent fixing aid (C) that can be used together with the antibacterial / antifungal agent (A) depends on the form of the fiber structure and the treatment temperature, but is finished as a product. In the step, i.e., unused state, it is usually preferred to be 1-500 mg / kg relative to the total amount of fibrous structure. When the compound of the first group (c1) is used, the content thereof is preferably 1 to 100 mg / kg and more preferably 1 to 50 mg / kg with respect to the total amount of the fiber structure. Suitable. When the compounds of the second group (c2) and the third group (c3) are used, the content thereof is preferably 10 to 500 mg / kg with respect to the total amount of the fiber structure, and 10 to 10 More preferably, it is 100 mg / kg.

As described above, even if the same antibacterial / antifungal agent fixing aid (C) is used, there is a difference in the suitable content between the first group (c1) and the second group (c2) and the third group (c3). The reason is that the compounds of the first group (c1) work mainly outside the fiber and enter and exit the fiber as a leader of the antibacterial / antifungal agent (A), so that the compound is active in the fiber at a relatively low concentration. On the other hand, the compounds of the second group (c2) and the third group (c3) are fixed in the fiber at a relatively high concentration because they contribute to the motility and swelling of the fiber by entering the fiber. This is because it is easy.

Next, examples of the present invention will be described together with comparative examples. However, the present invention is not limited to the following examples.

First, pyrithion zinc is prepared as the antibacterial / antifungal agent (A), and as shown below, a processing preparation liquid X (aqueous suspension) containing only the antibacterial / antifungal agent (A) in a dispersed manner is prepared. Prepared. Further, a processing preparation liquid Y (aqueous solution or emulsion) containing only the antibacterial / antifungal agent fixing aid (C) was prepared as shown below. Then, the processing preparation liquid X and the processing preparation liquid Y were appropriately diluted with water and used as a processing liquid for permeating and fixing pyrithion zinc in the fibers.

<Preparation of preparation liquid X for processing>
20 parts by weight of pyrithion zinc (manufactured by Lonza Japan, powdered state, particle size of approximately 0.025 mm, sometimes abbreviated as "ZPT"), 3 parts by weight of polyoxyethylene hydrogenated castor oil (dispersant), polyacrylic acid 0.5 parts by weight of sodium (thickening agent), 2 parts by weight of glycerin (antifreeze), and 74.5 parts by weight of water were prepared, charged into a ball mill (using a glass ball), and pulverized. The pH of the liquid at the start of pulverization was 6.5, but the pH after pulverization for 12 hours became 10.5. At this point, acetic acid was added to adjust the pH and the pH was adjusted to 8.0 to give the processing preparation liquid X. The average particle size of pyrithion zinc in the obtained preparation liquid X for processing was 0.4 μm, and the amount of pyrithion zinc having a particle size of 2 μm or more was 0.5% by weight based on the total pyrithion zinc. Further, the concentration of pyrithion zinc in the above-mentioned preparation liquid X for processing was 20% by weight, showing a uniformly dispersed state. A part of the processing preparation liquid X was transferred to a 1-liter container and left for 24 hours, but no extreme separation was observed.

<Preparation of preparation liquid Y for processing>
The salting-out agent (B) shown below was blended so as to have the compositions shown in Tables 1 to 10 below. Further, in the same manner, the antibacterial / antifungal agent fixing aid (C) shown below is blended so as to have the compositions shown in Tables 1 to 10 below, and is a preparatory liquid for processing that can be diluted with water. Y was prepared.

Then, using the above-mentioned preparatory liquids for processing X and Y, a processing liquid having the composition shown in Tables 1 to 10 described later was prepared. The fibers contained in the processing liquid and the fibers constituting the fiber structure (fabric) to be processed are as shown below.

<Salting out agent (B)>
Inorganic salt 1: Sodium sulfate

<Antibacterial / antifungal agent fixing aid (C)>
Group 1 (c1)
Surfactant 1: Polyoxyethylene alkyl ether (EO-added mole 11 HLB 12.8), trade name Blaunon SR-711 (manufactured by Aoki Oil & Fat Industry Co., Ltd.)
Surfactant 2: Polyoxyethylene alkylphenol (EO-added mole 10 HLB13.6), trade name Braunon NK-810 (manufactured by Aoki Yushi Kogyo Co., Ltd.)
Surfactant 3: Polyoxyethylene alkylaminel (EO-added mole 2 HLB 5.1
), Product name Brownon S-202 (manufactured by Aoki Oil & Fat Industry Co., Ltd.)
Surfactant 4: Polyhydric alcohol fatty acid ester (HLB4.3), trade name Blaunon P-80 (manufactured by Aoki Oil & Fat Industry Co., Ltd.)
Group 2 (c2)
Organic solvent 1: 1-methyl-2-pyrrolidone (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
Group 3 (c3)
Aromatic compound 1: Methyl salicylate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
Aromatic compound 2: Benzyl alcohol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
Aromatic compound 3: 2-phenoxyethanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
Aromatic compound 4: Biphenyl (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
Aromatic compound 5: 1-naphthol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
Aromatic compound 6: Hydroxybenzophenone (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
Aromatic compound 7: Benzyl salicylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
Aromatic compound 8: Phenyl salicylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
Aromatic compound 9: Phenyl benzoate (manufactured by Tokyo Chemical Industry Co., Ltd.)
Aromatic compound 10: o-phenylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
Aromatic compound 11: 1-methylnaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.)
Aromatic compound 12: Benzophenone (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
Aromatic compound 13: 2,6-diphenylphenol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)

<Fibers of fiber structures to be processed>
Fiber 1: Polyester fiber

Then, the target antibacterial / antifungal fiber structure was obtained by applying the following processing method using the processing liquid prepared in this manner and the fiber structure (the dough composed of the fiber 1).

<Processing method>
A dyeing machine (MCD-306-2EPT manufactured by Tsujii Dyeing Machine Co., Ltd.) is used as a sealed container, and the processing liquid and the synthetic fiber structure (dough) are put into the processing tank of the dyeing machine (bath ratio 1: 10 to 10). 1: 400), after applying pressure heat treatment under the conditions shown in Tables 1 to 10 below, take it out of the container and wash it with water for 5 minutes overflow in a washing machine to remove excess components on the fiber surface, and then overnight. By air-drying, the desired antibacterial and antifungal fiber structure was obtained.

Then, the following items were analyzed and evaluated according to the procedures described in each item with respect to the example product and the comparative example product obtained by the above processing.

<Analysis of the content of antibacterial / antifungal agent (A)>
After 0.1 g of the obtained treated product (Example product, Comparative example product, the same applies hereinafter) is incinerated, zinc is extracted with hydrochloric acid, and the amount of zinc derived from pyrithion zinc in the fiber is extracted by atomic absorption spectroscopy. Was measured. From this amount of zinc, the pyrithion zinc content was calculated.

<Evaluation of antibacterial properties 1 and 2>
According to the method based on JIS L1902, "Staphylococcus aureus" was used as the test bacterial species in the evaluation of antibacterial property 1, and "Klebsiella pneumoniae" was used as the test bacterial species in the evaluation of antibacterial property 2. Was evaluated using. That is, first, a standard cloth (cotton cloth showing no antibacterial activity) and the obtained treated fiber cloth were inoculated, and the viable cell count of each cloth was measured after culturing at 37 ° C. for 18 to 24 hours. The antibacterial activity value was calculated from the obtained viable cell counts by the calculation shown below.

Antibacterial activity value = (LogCt-LogCo)-(LogTt-LogTo)
Growth value of standard cloth = (LogCt-LogCo)
LogCo: Arithmetic mean common logarithm of the viable cell counts of the three samples immediately after the test bacteria inoculation of the standard cloth LogCt: Arithmetic mean common logarithm of the viable cell counts of the three samples after 18 hours of culture of the standard cloth LogTo: Of the treated fiber dough Arithmetic mean common logarithm of the viable cell counts of the three samples immediately after inoculation of the test bacteria LogTt: Arithmetic mean common logarithm of the viable cell counts of the three samples after 18 hours of culturing the treated fiber dough.

Then, when the antibacterial activity value is equal to or higher than the "proliferation value of standard cloth", "○ (very effective)", and when the antibacterial activity value is less than "growth value of standard cloth" and is "2.2" or more "Δ (valid)" and those having an antibacterial activity value less than "2.2" were designated as "x (invalid)". This evaluation method conformed to the "SEK Mark Textile Product Certification Criteria" of the Textile Evaluation Technology Council. Then, the antibacterial properties 1 and 2 were evaluated in the same manner for the processed products (after washing) washed according to the washing method described later.

<Evaluation of antifungal property>
According to a method conforming to JIS L1921, "Trichophyton mentagophytes" was used as a test bacterial species, and evaluation was performed by measuring the amount of ATP contained in the cells. That is, first, a liquid medium in which spores of the above test bacterial species were suspended was inoculated into the obtained treated product and cultured at 25 ° C. for 42 hours. Then, the amount of ATP after culturing is measured, and the comparison with the same test value (ATP amount) of the untreated cotton fiber is used as the antifungal activity value, and the antifungal activity value is 1000 minutes of the growth value of the untreated cotton fiber. A decrease of "3" or more, which represents 1 of the above, is "○ (very effective)", and a decrease of "2" or more, which also represents 1/100 of the growth value of untreated cotton fiber, and less than "3". The case was set as "△ (valid)". Further, the case where the antifungal activity value was "less than 2" was defined as "x (invalid)". Then, as in the evaluation of antibacterial properties 1 and 2, the antifungal property was evaluated in the same manner for the washed processed product (after washing).

<Washing method>
(General corporate judicial person) Washing was carried out 50 times by a method conforming to the "SEK mark textile product washing method (high temperature accelerated washing)" specified by the Textile Evaluation Technology Council.

<Usage efficiency (%) of antibacterial / antifungal agent (A)>
The pyrithion zinc content of the entire processed dough was calculated from the pyrithion zinc content (mg / kg) obtained by the analysis of the content of the antibacterial / antifungal agent (A), and then the total pyrithion zinc blended in the processing liquid. Utilization efficiency was obtained by dividing by the amount. For example, when 0.6 mg of pyrithion zinc is detected in 1 g of processed cloth, the amount of pyrithion zinc in the total processed cloth (10 kg) is 6 g. When 20 g of pyrithion zinc is blended in 100 kg of the processing liquid, the utilization efficiency is 6 g / 20 g × 100 (%), which is 30%. The amount of zinc pyrithione in the processing liquid can also be measured by titration. That is, the amount of zinc pyrithione may be measured from the titration amount by adding hydrochloric acid to the processing solution to dissolve zinc pyrithione, adding starch, and titrating with an iodine solution.

[Examples 1 to 4, Comparative Example 1]
The target processed product was obtained by processing the fiber structure (fabric made of fiber 1) under the processing conditions shown in Table 1 below. Then, these Examples 1 to 4 products and Comparative Example 1 product were analyzed and evaluated as described above, and the results thereof are also shown in Table 1 below.

From the above results, it can be seen that the products of Examples 1 to 4 are all provided with antibacterial and antifungal properties having excellent washing durability. In particular, the product of Example 4 in which the salting-out agent (B) and the antibacterial / antifungal agent fixing aid (C) are combined has the content of the salting-out agent (B) as can be seen in comparison with the product of Example 1. It can be seen that the utilization efficiency is improved even if the amount is small, and that excellent antibacterial and antifungal properties are imparted more efficiently and without waste. On the other hand, although the product of Comparative Example 1 is provided with antibacterial and antifungal properties, it is found that the utilization efficiency is low and there are problems in terms of environment and cost.

[Examples 5 to 36, Comparative Examples 2 to 7]
The target processed product was obtained by processing the fiber structure (fabric made of fiber 1) under the processing conditions shown in Tables 2 to 10 below. Then, these Examples 5 to 36 products and Comparative Examples 2 to 7 products were analyzed and evaluated as described above, and the results thereof are also shown in Tables 2 to 10 below.

From the above results, under the same processing conditions, the salting-out agent (B) and the antibacterial / antifungal agent fixing aid (C) used in combination were more pyrithione-zinc than those without them. It can be seen that the utilization efficiency is improved, and that excellent antibacterial and antifungal properties are imparted more efficiently and without waste.

The present invention is to be used for a fiber structure made of synthetic fibers, which is provided with antibacterial and antifungal properties by an antibacterial and antifungal agent with high utilization efficiency and whose antibacterial and antifungal properties are excellent in washing durability. Can be done.

Claims (20)

A synthetic fiber structure containing an antibacterial / antifungal agent (A) and a salting out agent (B), wherein the antibacterial / antifungal agent (A) is a pyridine-based antibacterial / antifungal agent, and the salting out The antibacterial agent (B) is an inorganic compound, and the antibacterial / antifungal agent (A) is fixed together with the salting out agent (B) in the fibers of the synthetic fiber structure. Anti-mold fiber structure. The content of the antibacterial / antifungal agent (A) is 200 to 20000 mg / kg with respect to the total amount of the fiber structure, and the content of the salting out agent (B) is 1 to 10000 mg / kg with respect to the total amount of the fiber structure. The antibacterial / antifungal fiber structure according to claim 1, which is kg. A synthetic fiber structure containing an antibacterial / antifungal agent (A), a salting agent (B), and an antibacterial / antifungal agent fixing aid (C), wherein the antibacterial / antifungal agent (A) Is a pyridine-based antibacterial / antifungal agent, the salt-forming agent (B) is an inorganic compound, and the antibacterial / antifungal agent fixing aid (C) is the following first group (c1) and second group. It is at least one compound selected from the group consisting of (c2) and the third group (c3), and the antibacterial / antifungal agent (A) is contained in the fibers of the synthetic fiber structure. An antibacterial / antifungal fiber structure characterized by being fixed together with B) and the antifungal / antifungal agent fixing aid (C).
(C1) The first group consisting of a surfactant.
(C2) The second group composed of an organic solvent.
(C3) The third group consisting of aromatic compounds. The content of the antibacterial / antifungal agent (A) is 200 to 20000 mg / kg with respect to the total amount of the fiber structure, and the content of the salinizer (B) is 1 to 10000 mg / kg with respect to the total amount of the fiber structure. The antibacterial / antifungal fiber structure according to claim 3, wherein the content of the antibacterial / antifungal agent fixing aid (C) is 1 to 500 mg / kg with respect to the total amount of the fiber structure. The antibacterial / antifungal fiber structure according to any one of claims 1 to 4, wherein the antibacterial / antifungal agent (A) is a pyridine-based metal complex. The salting-out agent (B) is at least one inorganic selected from the group consisting of ammonium salts, alkali metal salts, alkaline earth metal salts, Group IIb metal salts, Group III metal salts and Group VII metal salts. The antibacterial / antifungal fiber structure according to any one of claims 1 to 5, which is a salt. The antibacterial / antifungal fiber structure according to claim 6, wherein the salting-out agent (B) is at least one inorganic salt selected from alkali metal salts. 3. Among the antibacterial / antifungal agent fixing aids (C), the first group (c1) contains at least one of the surfactants represented by the following formulas (1) and (2). The antibacterial / antifungal fiber structure according to any one of 7 to 7.

Among the antibacterial / antifungal agent fixing aids (C), the third group (c3) contains at least one selected from aromatic compounds represented by the following formulas (3) to (6). The antibacterial / antifungal fiber structure according to any one of claims 3 to 7.

Claim that the antibacterial / antifungal agent fixing aid (C) contains at least two compounds selected from the group consisting of the first group (c1), the second group (c2) and the third group (c3). Item 3. The antibacterial / antifungal fiber structure according to any one of Items 3 to 7. The antibacterial / antifungal agent fixing aid (C) contains at least one compound selected from the first group (c1) and at least one compound selected from the second group (c2). The antibacterial / antifungal fiber structure according to any one of claims 3 to 7. The antibacterial / antifungal agent fixing aid (C) contains at least one compound selected from the first group (c1) and at least one compound selected from the third group (c3). The antibacterial / antifungal fiber structure according to any one of claims 3 to 7. The antibacterial / antifungal agent fixing aid (C) contains at least one compound selected from the second group (c2) and at least one compound selected from the third group (c3). The antibacterial / antifungal fiber structure according to any one of claims 3 to 7. The antibacterial / antifungal agent fixing aid (C) includes at least one compound selected from the first group (c1), at least one compound selected from the second group (c2), and the first group. The antibacterial / antifungal fiber structure according to any one of claims 3 to 7, which comprises at least one compound selected from the group 3 (c3). A method for obtaining an antibacterial / antifungal fiber structure by subjecting a synthetic fiber structure to an antibacterial / antifungal treatment, which contains the following antibacterial / antifungal agent (A) and a salt-forming agent (B). By bringing the process of preparing the liquid into contact with the processing liquid and the synthetic fiber structure and heating at 70 to 150 ° C. for 10 to 120 minutes, the antibacterial and antifungal components are contained in the fibers of the synthetic fiber structure. A method for producing an antibacterial / antifungal fiber structure, which comprises a processing step of fixing the agent (A) together with the salting agent (B).
(A) An antibacterial / antifungal agent composed of a pyridine-based antibacterial / antifungal agent.
(B) A salting-out agent composed of an inorganic compound. In the processing liquid, the content of the antibacterial / antifungal agent (A) is 0.001 to 0.2% by weight based on the total amount of the processing liquid, and the content of the salting out agent (B) is the processing liquid. The method for producing an antibacterial / antifungal fiber structure according to claim 15, which is 0.1 to 30% by weight based on the total amount. This is a method of obtaining an antibacterial / antifungal fiber structure by subjecting a synthetic fiber structure to an antibacterial / antifungal treatment. The synthetic fiber is prepared by preparing a processing liquid containing the agent fixing aid (C), contacting the processing liquid with the synthetic fiber structure, and heating at 70 to 150 ° C. for 10 to 120 minutes. It is characterized by including a processing step of fixing the antibacterial / antifungal agent (A) in the fiber of the structure together with the salt salting agent (B) and the antibacterial / antifungal agent fixing auxiliary agent (C). A method for manufacturing antibacterial and antifungal fiber structures.
(A) An antibacterial / antifungal agent composed of a pyridine-based antibacterial / antifungal agent.
(B) A salting-out agent composed of an inorganic compound.
(C) An antibacterial / antifungal agent-fixing aid comprising at least one compound selected from the following groups consisting of the first group (c1), the second group (c2) and the third group (c3).
(C1) The first group consisting of a surfactant.
(C2) The second group composed of an organic solvent.
(C3) The third group consisting of aromatic compounds. In the processing liquid, the content of the antibacterial / antifungal agent (A) is 0.001 to 0.2% by weight based on the total amount of the processing liquid, and the content of the salting out agent (B) is the processing liquid. The antibacterial agent according to claim 17, which is 0.1 to 30% by weight based on the total amount, and the content of the antibacterial / antifungal agent fixing aid (C) is 0.01 to 1% by weight based on the total amount of the processing liquid. -Manufacturing method of antifungal fiber structure. The synthetic fiber structure contains at least polyester fiber, and the processing step is to put the processing liquid and the synthetic fiber structure in a sealed container and pressurize in the liquid at 100 ° C. or higher and lower than 150 ° C. for 10 minutes or longer. The method for producing an antibacterial / antifungal fiber structure according to claim 15 or 16, which is a step of heating for less than 120 minutes. The synthetic fiber structure does not contain polyester fiber, and the processing step is to put the synthetic fiber structure in the processing liquid and heat it in the liquid under normal pressure at 70 ° C. or higher and lower than 100 ° C. for 10 minutes or more and less than 120 minutes. The method for producing an antibacterial / antifungal fiber structure according to claim 15 or 16, which is a step of performing the process.

Images