JP2000303357A - Antibacterial fibrous structural material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fibrous structural material having an antibacterial property excellent in industrial washing resistance and also a shape-stabilizing capacity such as a wrinkle resistance and shrink resistance. SOLUTION: This fibrous structural material consists of a cellulose-based fiber and a synthetic fiber having >=0.1 m2 surface 1 g of the fibrous structural material, in which the cellulose-based fiber is modified by cross-linking in 1-4 range cross-linking index defined by the following equation, and the synthetic fiber contains a pyridine-based anti-bacterial agent having 200-700 molecular weight, inorganic/organic value = 0.3-1.4 and <=2 μm mean particle diameter. Cross-linking index = (A-B) Where, A: The moisture-absorbing ratio (%) of the fibrous structural material at 30 deg.C temperature and 90 %RH after the modification by cross-linking. B: The moisture-absorbing ratio (%) of the fibrous structural material at 20 deg.C temperature and 65 %RH after the modification by cross-linking.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fibrous structure having excellent antibacterial properties which is excellent in form stability and industrial washing durability.

[0002]

2. Description of the Related Art Hitherto, fiber structures imparted with antibacterial properties have been widely used in various kinds of clothing, interlining, lining, bedding products, interior products and the like. In particular, in recent years, hospital infections caused by methicillin-resistant Staphylococcus aureus (hereinafter referred to as "MRSA") have become a problem. It is desired to do.

[0003] However, in these applications, usually 60 to 85
Since industrial washing at a temperature of ° C. is repeated many times, those having sufficient durability are hardly obtained by the prior art. Further, when they contain cellulosic fibers, there has been a problem that the form stability after washing is poor.

Conventionally, antibacterial treatments include kneading inorganic antibacterial agents such as silver, copper, or zinc during the spinning of synthetic fibers, and spraying or padding organic antibacterial agents such as quaternary ammonium salts. The post-processing method of applying as a main component has been mainly employed. The former case is excellent in terms of washing durability, but cannot be processed on a fabric such as a knitted fabric. In addition, since the antibacterial agent precipitates as crystals on the surface of the spinneret at the spinning stage, there is a problem in yarn production such as frequent yarn breakage. On the other hand, in the latter case, although there is an advantage that antibacterial processing can be performed on the fabric, antibacterial washing durability is inferior.

[0005] In these applications, cellulosic fibers have been preferably used because of their high water absorption and good touch, but on the other hand, they are more likely to wrinkle than synthetic fiber structures and shrink by washing. There is a drawback of doing so, and a solution is desired.

[0006]

SUMMARY OF THE INVENTION In view of this background, the present invention has an antibacterial property having excellent industrial washing durability, and
It is an object of the present invention to provide a fibrous structure having form stability such as wrinkle resistance and shrink resistance.

[0007]

One aspect of the antibacterial fiber structure of the present invention is a fiber structure comprising cellulosic fibers and synthetic fibers having a surface area of 0.1 m ² or more per gram of the fiber structure. The cellulosic fiber is cross-linked modified with a cross-linking index defined by the following formula in the range of 1 to 4, and the synthetic fiber has a molecular weight of 200 to 700 and an inorganic / organic value = An antibacterial fiber structure comprising a pyridine-based antibacterial agent having a particle diameter of 0.3 to 1.4 and an average particle diameter of 2 μm or less.

Crosslinking index = (AB) where: A: moisture absorption (%) of the fiber structure after crosslinking modification in an atmosphere of a temperature of 30 ° C. and a relative humidity of 90% RH.

B: Moisture absorption (%) of the fibrous structure after crosslinking modification in an atmosphere of a temperature of 20 ° C. and a relative humidity of 65% RH.

[0010] Another embodiment of the antibacterial fiber structure of the present invention comprises:
What is claimed is: 1. A fiber structure comprising a cellulose fiber and a synthetic fiber having a single fiber fineness of 8 denier or less, wherein the cellulose fiber is crosslinked and modified in a crosslinking index defined by the following formula in the range of 1 to 4. And the synthetic fiber has a molecular weight of 200 to 7
00, inorganic / organic value = 0.3-1.4, average particle size 2
An antibacterial fiber structure containing a pyridine antibacterial agent having a particle size of not more than μm.

Crosslinking index = (AB) where: A: moisture absorption (%) of the fiber structure after crosslinking modification in an atmosphere of a temperature of 30 ° C. and a relative humidity of 90% RH.

B: Moisture absorption (%) of the fibrous structure after crosslinking modification in an atmosphere of a temperature of 20 ° C. and a relative humidity of 65% RH.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The cellulosic fibers referred to in the present invention include natural cellulose fibers such as cotton, hemp and pulp, and regenerated cellulose fibers such as viscose rayon.

Further, in the present invention, the cellulosic fibers are those which have been cross-linked and modified by a cross-linking agent. The cross-linking agent referred to here reacts with a hydroxyl group in the cellulose molecule constituting the cellulosic fiber, particularly a wrinkle at the time of washing, and a hydroxyl group in an amorphous region which causes shrinkage. A compound capable of forming crosslinks, specifically, formaldehyde, dimethylol ethylene urea, dimethylol triazone, dimethylol urone, dimethylol glyoxal monourein, dimethylol propylene urea, and these methylols Examples thereof include cellulose-reactive resins such as those obtained by methoxylation or ethoxylation of a part or all of the groups, polycarboxylic acids, isocyanates, and the like. Among these crosslinking agents, formaldehyde or a compound represented by the following general formula [I] is preferably used in order to more efficiently and effectively modify the crosslinking of the cellulosic fiber.

[0015]

Embedded image

Here, R ₁ and R ₂ are —H, an alkyl group having 1 to 4 carbon atoms, or a same or different group of —CH ₂ OR ₇ , R ₃ , R ₄ , R ₅ , R ₆ is -H or -OR
₈ , the same or different groups, R ₇ and R _{8 each} represent-
The degree of modification of the same or different base cellulosic fibers which are either H or an alkyl group having 1 to 4 carbon atoms is required to have a crosslinking index defined by the following formula in the range of 1 to 4. And preferably in the range of 2 to 3.5. Such a crosslinking index, the temperature of the cellulosic fiber after crosslinking modification 30 ℃,
Under the relative humidity 90% RH atmosphere, the moisture absorption value
This is calculated by subtracting the value of the moisture absorption rate in an atmosphere of 65 ° C. and a relative humidity of 65% RH, and is an index for knowing how much the cellulosic fiber has been crosslinked and modified. That is, this utilizes the fact that the hydroxyl group in the cellulose molecule is blocked by the crosslinking modification, and as a result, the value of the moisture absorption rate decreases. The smaller the index, the greater the degree of cross-linking modification, and the larger the index, the smaller the degree of cross-linking modification. Generally, raw cotton and hemp are about 4-5.

Crosslinking index = (AB) where A: moisture absorption (%) of the fiber structure after crosslinking modification in an atmosphere of a temperature of 30 ° C. and a relative humidity of 90% RH.

B: Moisture absorption (%) of the fibrous structure after crosslinking modification at a temperature of 20 ° C. and a relative humidity of 65% RH.

If the crosslinking index is less than 1, crosslinking is excessively formed, and the strength and flexibility of the fabric are reduced, and although the form stability is good, it is not practical. On the other hand, when the crosslinking index is larger than 4, the crosslinking modification of the cellulose fiber is not sufficient, and the required level of form stability such as wrinkle resistance and shrink resistance cannot be imparted. When considering the balance between the strength, flexibility and form stability of the fabric, the crosslinking index is preferably in the range of 2 to 3.5.

As a method for applying the crosslinking agent to the cellulosic fiber, various means can be applied. Specifically, a method for applying the crosslinking agent in a gaseous state, a padding method, a dipping method, a spray method, a printing method, and the like. Method, coating method, gravure processing method, foam processing method and the like. Among them, when the cross-linking agent is formaldehyde, the method of applying in the form of gas is used. In the case of isocyanates, etc., the padding method is preferably used.

In carrying out the crosslinking modification of the cellulosic fibers, it is also preferable to use a catalyst in combination with a catalyst for the purpose of accelerating the reaction of the crosslinking agent. Specifically, organic acids, organic amine salts, magnesium chloride, nitric acid and the like are used. Metal salts such as zinc, zinc borofluoride, magnesium nitrate, and zinc chloride can be used.

As a method for modifying the cross-linking of the cellulosic fiber with a cross-linking agent, a usual cross-linking and modifying method can be applied. Specifically, the fiber structure in the state of a sewn product is treated with formaldehyde. A method of vapor-phase treatment, a post-curing method of applying the cross-linking agent to the fibrous structure in the state of the fabric, sewing, and then performing a heat treatment, a method of applying the cross-linking agent to the fibrous structure in the state of the fabric , And a pre-curing method in which heat treatment is performed until the heat treatment, but the present invention is not limited thereto. The heat treatment temperature is 80 to 220.
C. It is preferable that the heat treatment is performed in the range of 120 to 200C.

The synthetic fibers used in the present invention include polyester fibers such as polyethylene terephthalate and polybretine terephthalate, acrylic fibers, and polyamide fibers such as nylon 6 and nylon 66. As the fiber structure of the present invention, yarn, woven fabric, non-woven fabric, or the like can be used. Among such synthetic fibers, polyester fibers can provide a fiber structure having the most excellent antibacterial industrial washing durability.

In the present invention, the synthetic fibers are preferably colored from the viewpoint of imparting antibacterial properties without impairing the coloring properties. Here, being colored means that the synthetic fiber contains a colored substance such as a disperse dye, an acid dye, a cationic dye, and a fluorescent brightener.

Among such fibrous structures, those used in the present invention
The fiber structure that can be used is synthetic fiber per gram of the fiber structure.
0.1m surface area^TwoOr single fiber of fiber structure
Having a degree of 8 denier or less, preferably having a surface area of
0.15m^TwoOr a single fiber fineness of 4 denier or less
Things. Antibacterial agent adheres to or exhausts synthetic fibers
The application depends on the surface area of the fiber or the fineness of the fiber
So the surface area is 0.1m ^TwoFiber or monofilament fineness
However, fibers with a denier of 8 deniers or less have high industrial washing durability.
An antimicrobial fiber structure having the same can be obtained. In addition,
When combining several types of synthetic fibers and even natural fibers
The same effect can be obtained.

In the fiber structure of the present invention, the above-mentioned cellulosic fiber and synthetic fiber must be mixed by blending, blending, blending, blending and the like.
Silk or the like may be mixed. From the viewpoint of securing effective form stability performance, it is preferable that the cellulosic fiber is contained in a fiber weight range of 10 to 90 wt%.

In the present invention, the synthetic fiber has a molecular weight of 20.
0 to 700, inorganic / organic value = 0.3 to 1.4
And a pyridine-based antibacterial agent having an average particle size of 2 μm or less.

Such a pyridine-based antibacterial agent firmly adheres to, or is absorbed and diffused into, synthetic fibers. This is because the three requirements of a specific molecular weight, inorganic / organic value and average particle size are brought close to the conditions close to those of a disperse dye that exhausts and diffuses inside the fiber, thereby exhibiting the same behavior as a disperse dye. Conceivable. When these conditions are not satisfied, the antibacterial agent does not firmly adhere to the synthetic fibers or does not absorb or diffuse, and sufficient industrial washing durability cannot be obtained.

When the molecular weight is less than 200, the antibacterial agent adheres to, or is absorbed and diffused into the synthetic fibers, but the washing durability is low. On the other hand, when the molecular weight exceeds 700, the antibacterial agent does not adhere or exhaust to the synthetic fibers. Preferably, the molecular weight of the antimicrobial agent is between 300 and 500.

Next, the "inorganic / organic value" used in the present invention.
Is a value that organically treats the polarity of various organic compounds devised by Minoru Fujita [Referred to Chemical Experiments-Organic Chemistry-Kawade Shobo (1971)]. The value is obtained by determining the values of the inorganic and organic properties of various polar groups as shown in Table 1, obtaining the sum of the inorganic values and the sum of the organic values, and taking the ratio between the two.

[0031]

[Table 1]

In this organic concept, for example, when the inorganic / organic value of polyethylene terephthalate is calculated, it is 0.7,
The present invention focuses on the affinity between a synthetic fiber and an antibacterial agent based on the value calculated in the organic concept, and attaches an antibacterial agent having an inorganic / organic value within a predetermined range to the synthetic fiber. Or they are exhausted and diffused.

When the inorganic / organic value is less than 0.3, the organic property becomes too strong. On the other hand, when it exceeds 1.4, the inorganic property becomes too strong. Difficult to spread. The inorganic / organic value is preferably from 0.35 to 1.3, more preferably from 0.4 to 1.2.

For example, 2,3,5,6-tetrachloro-
In the case of 4-hydroxypyridine, one benzene nucleus,-
One 4 Cl group, one -OH group, inorganic value for containing one -NR ₂ group becomes 265. Further, the organic value is 180 since it contains five C (carbon) and four -Cl groups, and the inorganic value / organic value becomes 1.47. Since 2-pyridylthiol-1-oxide zinc is present as a chelate complex and zinc and sulfur are considered to have a covalent bond in terms of electronegativity, the inorganic value of this compound is 85, and the organic value is 85. Is 190, and the inorganic value / organic value can be calculated as 0.45. On the other hand, in sodium 2-pyridylthiol-1-oxide which is the same pyridine antibacterial agent, sodium and sulfur have an electronegativity difference of 1.6 or more, and this bond becomes an ionic bond. In this case, sodium is converted into a light metal salt. Since it works, the inorganic value can be calculated to be 585 and the organic value can be calculated to be 190, and the inorganic value / organic value is 3.0, so that the affinity with the polyester is deteriorated.

In the present invention, among these antibacterial agents, those having an average particle size of 2 μm or less are used. If the average particle size exceeds 2 μm, it becomes difficult to adhere or exhaust to the synthetic fiber, and when the solution is processed, sedimentation of particles occurs.
It shows a tendency to lack the stability of the liquid. Preferably, the average particle size of the antimicrobial agent is 1 μm or less.

As such antibacterial agents, 2-chloro-6-trichloromethylpyridine, 2-chloro-4-trichloromethyl-6-methoxypyridine, 2-chloro-4-trichloromethyl-6- (2-furylmethoxy) pyridine ,
Di (4-chlorophenyl) pyridylmethanol, 2,
Pyridine compounds such as 3,5-trichloro-4- (n-propylsulfonyl) pyridine, zinc 2-pyridylthiol-1-oxide, and di (2-pyridylthiol-1-oxide) can be used. Among them, in particular, 2-pyridylthiol-1-oxide zinc has a good affinity with the fiber, and is firmly attached to and exhausted from the fiber, so that it has good washing durability, and the target bacterial species showing an effect including MRSA. Is preferred in terms of the size of

Further, the fiber structure of the present invention can be prepared by using a washing liquid mixed with a surfactant and subjecting to an SEK (Fiber Product New Function Evaluation Council) even after industrial washing at 80 ° C. for 12 minutes / times × 50 times. )), Those having a bacteriostatic activity value of 2.2 or more are preferable. More preferably, using a washing solution mixed with a surfactant, even after an industrial washing treatment at 85 ° C. for 15 minutes / times × 50 times, the bacteria control method defined by the SEK (Fiber Product New Function Evaluation Council) (unified) Test method)
Having a bacteriostatic activity value of 2.2 or more.

Even when the washing treatment conditions are severe, those having a bacteriostatic activity value of 2.2 or more are more preferable. That is, SEK (Textile Product New Function Evaluation Council) is used even after industrial washing treatment at 80 ° C. for 12 minutes / times × 50 times using a washing solution in which a peroxide, a strong alkali agent and a surfactant are mixed.
It is more preferable that the bacteriostatic activity value is 2.2 or more in the bacteriostatic evaluation method (unified test method) defined in the above. Most preferably, SEK (Textile Product New Function Evaluation Council) is used even after industrial washing at 85 ° C. for 15 minutes / times × 50 times using a washing solution in which a peroxide, a strong alkali agent and a surfactant are mixed. The bacteriostatic activity value is 2.2 or more according to the bacteriostatic evaluation method (unified test method) specified in (2).

The washing liquid mixed with a peroxide, a strong alkali agent and a surfactant is, for example, 2 g / l of detergent "Zab" (registered trademark) manufactured by Kao Corporation as a surfactant. Hydrogen peroxide solution (35% industrial use) 3 cc / l
1.5 g / l of sodium percarbonate as a strong alkaline agent,
After weighing each to a predetermined amount, the mixture was charged into a drum dyeing machine filled with water at a bath ratio of 1:20, mixed and adjusted. Thereafter, the temperature of the washing liquid is raised to 85 ° C., and the antibacterial fiber structure of the present invention and the cloth are thrown in and washed for 15 minutes. After draining and dehydrating, overflow water washing is performed for 10 minutes, and finally dehydration is performed, which is defined as one washing.
After repeating this process 50 times, the mixture is dried using a tumbler dryer for 20 minutes, and the bacteriostatic evaluation is performed.

As a method of adhering or exhausting such an antibacterial agent to synthetic fibers, a fiber structure is immersed in a liquid containing an antibacterial agent by a liquid jet dyeing machine or the like, and 90 to 16 under normal pressure or pressure.
0 ° C. for 10 to 120 minutes, more preferably 120 to 13
Heat at 5 ° C. for 20-60 minutes. At this time, if necessary, a disperse dye or a dispersible fluorescent brightener may be added to the liquid.

In this method, it is more preferable that after the treatment in a liquid, a tenter or the like is used at 160 to 200 ° C. for 15 seconds to 5 minutes, more preferably 170 to 190 ° C. for 30 seconds to
A dry heat treatment for 2 minutes can be performed. By such dry heat treatment, the antibacterial agent is diffused from the fiber surface to the inside to be in a state of fiber inner ring distribution, and the washing durability can be improved without impairing the antibacterial property. By changing the treatment conditions, the antimicrobial agent can be controlled to each state of fiber surface adhesion, fiber internal ring distribution, and fiber internal diffusion.

Another method is to attach a liquid containing the antibacterial agent to a fibrous structure by a padding method, a spraying method, or the like, and then use a tenter or the like at 160 to 200 ° C. for 30 seconds to 10 minutes, more preferably 170 to 200 minutes. It can be manufactured by performing at least one kind of heat treatment selected from dry heat treatment and wet heat treatment at 190 ° C. for 1 to 5 minutes.

From the viewpoint of cost and rationalization of the processing steps, the crosslinking agent and the antibacterial agent are simultaneously adhered to the fiber structure by a padding method or a spray method, and then heat-treated at 170 to 190 ° C. for 30 seconds to 5 minutes. Is preferably used, but the method is not limited thereto.

The fibrous structure is excellent in antibacterial properties and morphological stability with industrial washing durability, and is preferably used in the form of a woven fabric or a knitted fabric, and is used for applications such as dress shirts, uniforms, inner socks, interiors, and sports clothing. It is suitable.

[0045]

EXAMPLES The present invention will be described below more specifically with reference to examples.

The quality evaluation in the examples and comparative examples is based on the following method. (1) Washing method Using a drum dyeing machine, 2 g / l of detergent "Zab" (registered trademark) manufactured by Kao Corporation, 3 cc of hydrogen peroxide water (35% industrial use)
/ L, sodium percarbonate 1.5g / l, temperature 85 ± 2
After washing at 15 ° C. and a bath ratio of 1:20 for 15 minutes, drainage, dehydration, and overflow washing were performed for 10 minutes. After washing with water, it was dried for 20 minutes using a tumbler dryer.
This was one wash. (2) Antibacterial test method A unified test method was adopted as the test method, and MRSA clinical isolates were used as test cells. The test was performed by pouring a bouillon suspension of the test bacterium into a sterile sample cloth, and heating at 37 ° C in a closed container.
After 8 hours of culture, the number of viable cells was counted, and the number of cells relative to the number of cultured cells was determined.

Under the condition of log (B / A)> 1.5,
g (B / C) was defined as the difference in the number of bacteria, and 2.2 or more was regarded as a pass level.

Here, A is the number of bacteria recovered and dispersed immediately after inoculation of the unprocessed product, B is the number of bacteria recovered and recovered after 18 hours of culturing of the unprocessed product, and C is the number of bacteria recovered and recovered after culturing the processed product for 18 hours. Represent. (3) Evaluation of anti-wrinkle property The evaluation was based on the AATCC124-19845 step replica method. Grade 5 (good) to grade 1 (poor) (4) Washing shrinkage Measured according to JIS L-1042.

Example 1 First, a colloidal treatment of an antibacterial agent was performed. That is, formalin condensate 2 of 50 g of an antibacterial agent and naphthalenesulfonic acid
0 g and sodium ligninsulfonate 30 g in water 3
Then, the slurry was formed into a slurry together with 00 g, and then subjected to a wet pulverization treatment using glass beads to obtain a colloidal composition having an average particle size of 1 μm. The antibacterial agent used was 2-pyridinethiol-1-oxide zinc. The crosslinking agent is an aqueous solution of dimethylol dihydroxyethylene urea resin (solid content 2).
0%) was used as the catalyst.

As the test cloth, polyethylene terephthalate spun yarn (having a surface area of 0.28 per gram of the fiber structure) was used.
m ² , a single fiber fineness of 1 denier, a fiber length of 38 mm) and a woven fabric (for a basis weight of 185 g / m) using a 45th spun yarn blended so that the ratio of the cotton yarn is 50:50 for the warp and the weft.
² ) was prepared.

The woven fabric was immersed in a working fluid having the composition shown in Table 2 and padded at a squeezing ratio of 80%.
The sample was pre-dried for 2 seconds and then heat-treated at 180 ° C. for 1 minute to prepare a sample. The results are shown in Table 2 together with the evaluation results.

A product exhibiting good form stability and exhibiting excellent antibacterial properties in industrial washing durability was obtained.

Example 2 A 75 denier-72 filament polyethylene terephthalate filament yarn (fiber structure 1) was used as a test cloth.
0.27m ² surface area per g, single fiber fineness 1.04
(Denier) and a 45-count cotton yarn in a 50:50 ratio. The knit was processed under the conditions shown in Example 1 to prepare a sample. The results are shown in Table 2 together with the evaluation results.

A product exhibiting good form stability and exhibiting antibacterial properties having excellent industrial washing durability was obtained.

Example 3 The same fabric as in Example 1 was used as a test cloth. The woven fabric was immersed in a solution having an antibacterial agent of 1% owf, a bath ratio of 1:10 and a pH of 5 using a high-pressure dyeing tester, and treated at 130 ° C. for 60 minutes according to a conventional dyeing process. Thereafter, 100 g / l of an aqueous solution of dimethylol dihydroxyethylene urea resin (solid content: 20%) and 15 g /
Using a working fluid containing 1 under the same conditions as in Example 1,
A sample was prepared. The results are shown in Table 2 together with the evaluation results.

A product having good morphological stability and excellent antibacterial properties in industrial washing durability was obtained.

Comparative Examples 1 and 2 Processing was performed in the same manner as in Example 1 using a working fluid having the composition shown in Table 2 to prepare a sample. The results are shown in Table 2 together with the evaluation results.

In Comparative Example 1, no antibacterial property was obtained.
It can be seen that Comparative Example 2 did not have any form stability performance such as wrinkle resistance and shrink resistance.

[0059]

[Table 2]

[0060]

According to the present invention, it is possible to provide a fiber structure having antibacterial properties excellent in industrial washing durability, and having form stability performance such as wrinkle resistance and shrink resistance.

Claims (10)

[Claims] 1. A fibrous structure comprising a cellulosic fiber and a synthetic fiber having a surface area of 0.1 m ² or more per 1 g of the fiber structure, wherein the cellulosic fiber has a crosslinking index defined by the following formula: A pyridine-based synthetic fiber which has been crosslinked and modified in the range of 1 to 4 and whose synthetic fiber has a molecular weight of 200 to 700, an inorganic / organic value of 0.3 to 1.4, and an average particle size of 2 μm or less. An antibacterial fiber structure containing an antibacterial agent. Crosslinking index = (AB) where A: moisture absorption (%) of the fiber structure after crosslinking modification in an atmosphere of a temperature of 30 ° C. and a relative humidity of 90% RH. B: Moisture absorption (%) of the fiber structure after crosslinking modification in an atmosphere of a temperature of 20 ° C. and a relative humidity of 65% RH. 2. A fibrous structure comprising a cellulosic fiber and a synthetic fiber having a single fiber fineness of 8 denier or less, wherein the cellulosic fiber has a crosslinked index defined by the following formula in the range of 1 to 4. And the synthetic fiber has a molecular weight of 200 to 700 and an inorganic / organic value of 0.3 to 1.
4. An antibacterial fiber structure comprising a pyridine antibacterial agent having an average particle size of 2 μm or less. Crosslinking index = (AB) where A: moisture absorption (%) of the fiber structure after crosslinking modification in an atmosphere of a temperature of 30 ° C. and a relative humidity of 90% RH. B: Moisture absorption (%) of the fiber structure after crosslinking modification in an atmosphere of a temperature of 20 ° C. and a relative humidity of 65% RH. 3. The method according to claim 1, wherein the pyridine antibacterial agent is 2-chloro-6-.
Trichloromethylpyridine, 2-chloro-4-trichloromethyl-6-methoxypyridine, 2-chloro-4-trichloromethyl-6- (2-furylmethoxy) pyridine, di (4-chlorophenyl) pyridylmethanol,
Being at least one selected from 2,3,5-trichloro-4- (n-propylsulfonyl) pyridine, zinc 2-pyridylthiol-1-oxide, and di (2-pyridylthiol-1-oxide). The antibacterial fiber structure according to claim 1 or 2, wherein 4. The antibacterial fiber structure according to claim 1, wherein the pyridine-based antibacterial agent is zinc 2-pyridylthiol-1-oxide. 5. The cellulose fiber has a crosslinking index of 2-3.
The antibacterial fiber structure according to any one of claims 1 to 4, wherein 6. The composition according to claim 1, further comprising cellulosic fibers in a fiber weight range of 10 to 90% by weight.
The fiber structure according to any one of the above. 7. The antibacterial fiber structure according to claim 1, wherein said cellulosic fiber is cross-linked and modified using formaldehyde as a cross-linking agent. 8. The cellulose-based fiber according to the following general formula [I]:
The antibacterial fiber structure according to any one of claims 1 to 7, wherein the antibacterial fiber structure is crosslinked and modified using a compound represented by the formula (1) as a crosslinking agent. Embedded image Here, R ₁ and R ₂ are —H, an alkyl group having 1 to 4 carbon atoms,
Or the same or different groups is either _{-CH 2 OR 7, R 3,} R 4, R 5, R 6 is -H or one is a same or different groups -OR _8, R _7, R ₈ is the same or different group represented by -H or an alkyl group having 1 to 4 carbon atoms. 9. The antibacterial fiber structure according to claim 1, wherein the antibacterial agent is attached to or exhausted from the synthetic fiber. 10. The antibacterial fiber structure according to claim 1, wherein said synthetic fiber is made of polyester.