JP2000119955A - Antibacterial and antifungus fiber structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fiber structure excellent in antibacterial properties, antifungus properties and industrial washability, and useful for clothes or the like by attaching an amorphous titanium peroxide particle layer or the like on the surface of fiber, and further attaching a photocatalytic semiconductor on the surface of the attached particle layer. SOLUTION: This fiber structure includes a synthetic fiber (e.g. polyester- based fiber) having an attached and/or impregnated antimicrobial agent having 200-700 molecular weight, 0.3-1.4 value of inorganicity/organicity and <=2 μm average particle diameter, and comprising a nitrile-based compound, a pyridine- based compound or the like. The synthetic fiber also has one or more layers selected from an amorphous titanium peroxide particle layer, a zeolite layer and an alkyl silicate layer, formed on the surface of the fiber, and further having a photocatalytic semiconductor such as TiO2 and ZnO, preferably a microcapsulated photocatalytic semiconductor, on the surface of the obtained layer. Preferably, the photocatalytic semiconductor has 1-200 nm particle diameter, and 100-300 m2/g specific surface area, and attached to the fiber structure so as to be 0.03-15 wt.%.

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 and antifungal properties.

[0002]

2. Description of the Related Art Conventionally, fiber structures provided with antibacterial properties have been widely used for various kinds of clothing, interlining, lining, bedding products, interior products and the like. These fiber structures not only have excellent antibacterial properties, but also have a considerable level of durability in water washing at home due to various contrivances.

On the other hand, in recent years, infection in hospitals due to methicillin-resistant Staphylococcus aureus (hereinafter referred to as "MRSA") has become a problem. In addition, many patients have significantly reduced resistance, other than bacteria such as MRSA,
There is also the problem of hospital-acquired molds with milder effects on the human body. As a countermeasure, it is necessary to impart antibacterial properties and antifungal properties to white coats, covers, sheets, curtains and the like.

By the way, for the antibacterial treatment of the fiber, a method of kneading an inorganic antibacterial agent such as silver, copper or zinc at the spinning stage of the synthetic fiber and a method of spraying or padding an organic antibacterial agent such as a quaternary ammonium salt are used. Post-processing methods of processing and applying have been employed.

The former method is excellent in washing durability, but cannot be processed into products such as cloth. In addition, since the antibacterial agent precipitates as crystals on the surface of the spinneret at the spinning stage, yarn breakage, fusion and the like occur, and the productivity is significantly reduced. Further, since the antibacterial agent is uniformly dispersed in the yarn, it is necessary to knead the antibacterial agent in a large amount.

In the latter case, although there is an advantage that a product such as cloth can be subjected to antibacterial processing, it is inferior in terms of antibacterial washing durability.

Further, in both cases of the former and the latter, some of them can impart some antifungal properties in addition to antibacterial properties.
Since mold has strong resistance to drugs, there is a problem that sufficient performance cannot be obtained as compared with antibacterial properties.

On the other hand, if the titanium oxide photocatalyst is fixed to the fiber, it is expected that an antibacterial and antifungal fiber can be obtained.

However, a binder resin for fixing the titanium oxide photocatalyst to the fiber is required, and in the case of an acrylic or urethane binder resin conventionally used, the organic hydrocarbon constituting the resin is strongly oxidized by the titanium oxide photocatalyst. It is decomposed by dissolving power and is colored or discolored.

Further, the fiber itself provided with the titanium oxide photocatalyst may deteriorate, causing problems such as coloring, discoloration, and deterioration in strength. Therefore, an antibacterial / antifungal fiber structure using the titanium oxide photocatalyst has been put into practical use. Not been. Until now, examples of the use of titanium oxide photocatalysts include those fixed on the surface of inorganic substances such as ceramics and glass, but none on the surface of organic substances.

Further, since the antibacterial and antifungal properties of the titanium oxide photocatalyst are slow-acting, sufficient antifungal properties can be obtained against fungi having a low growth rate, but bacteria having a high growth rate compared to fungi can be obtained. However, sufficient antibacterial properties cannot be obtained.

[0012]

SUMMARY OF THE INVENTION In view of the background of the prior art, an object of the present invention is to provide a fiber structure having excellent antibacterial and antifungal properties.

[0013]

The present invention employs the following means to solve the above-mentioned problems.

One embodiment of the fibrous structure of the present invention comprises a synthetic fiber to which an antibacterial agent has been attached and / or exhausted, and a layer of amorphous titanium peroxide particles on the surface of the fiber.
The fiber structure has at least one layer selected from the group consisting of a zeolite layer and an alkyl silicate layer, and further has a photocatalytic semiconductor on the surface of the layer.

Another embodiment of the fibrous structure of the present invention comprises a synthetic fiber to which an antimicrobial agent has been attached and / or has been exhausted, and having a microencapsulated photocatalytic semiconductor on the surface of the fiber. It is a characteristic fiber structure.

Still another embodiment of the present invention is a garment, a sock, a shoe, an air filter, a curtain, a floor sheet, or a bedding constituted by the fiber structure.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The fibrous structure of the present invention comprises a synthetic fiber to which an antibacterial agent has been adhered or exhausted.

The antimicrobial agent referred to here is not particularly limited, and any ordinary antimicrobial agent can be used. Fiber structures having antibacterial and antifungal properties are often used for hospitals because of their properties. In this case, industrial washing at 60 to 85 ° C. is usually repeated many times, so that it is extremely preferable to have industrial washing durability. In order to improve industrial washing durability, the molecular weight is preferably 200 to 700, more preferably 30.
0-500, inorganic / organic value = 0.3-1.
4, an antibacterial agent having an average particle diameter of 2 μm or less, more preferably 1 μm or less, more preferably 0.5 to 1.2, further preferably 0.7 to 0.9. Is preferred.

When the molecular weight is less than 200, adhesion or exhaustion to synthetic fibers occurs, but sufficient industrial washing durability cannot be obtained. On the other hand, when the molecular weight exceeds 700, adhesion or exhaustion to synthetic fibers hardly occurs. Become.

On the other hand, if the inorganic / organic value is less than 0.3, the organic property becomes too strong, and if it exceeds 1.4, the inorganic property becomes too strong. Has low affinity for synthetic fibers and is less likely to be attached to or exhausted from synthetic fibers, resulting in poor durability in industrial washing. The inorganic / organic values referred to here are values that treat the polarities of various organic compounds devised organically by Minoru Fujita (“Reorganized Chemical Experiments-Organic Chemistry”, Minoru Fujita, Minoru Fujita, Kawade Shobo ( Published September 15, 1951), pp. 511-525),
One carbon (C) is defined as organic 20, and the values of the inorganic and organic properties of the various polar groups are determined as shown in Table 1, and the sum of the inorganic values and the organic value is calculated and the ratio between the two is determined. Value. For example, the calculated inorganic / organic value of polyethylene terephthalate is 0.83.

[0021]

[Table 1] On the other hand, if the average particle size exceeds 2 μm, it is difficult for the synthetic fibers to adhere to and / or be exhausted from the synthetic fibers, and when formed into a working liquid, the particles tend to sediment, resulting in a lack of liquid stability.

Preferred antibacterial agents for obtaining a fiber structure excellent in industrial washing durability include, for example, 2,4,5,6.
-Tetrachloroisophthalonitrile, 5-chloro-2,
Nitrile compounds such as 4,6-trifluoroisophthalonitrile, 2-chloro-6-trichloromethylpyridine,
2-chloro-4-trichloromethyl-6-methoxypyridine, 2-chloro-4-trichloromethyl-6- (2-
Furylmethoxy) pyridine, di (4-chlorophenyl)
Pyridyl methanol, 2,3,5,6-tetrachloro-
4-methylsulfonylpyridine, 2,3,5-trichloro-4- (n-propylsulfonyl) pyridine, 2
Pyridine compounds such as -pyridylthiol-1-oxide zinc, di (2-pyridylthiol-1-oxide),
N-florodichloromethylthiophthalimide, N-trichloromethylthiophthalimide, N-1,1,2,2-
Tetrachloroethylthiotetrahydrophthalimide, N
-Trichloromethylthiotetrahydrophthalimide, N
-Trichloromethylthio-N- (phenyl) methylsulfamide, N-trichloromethylthio-N- (4-chlorophenyl) methylsulfamide, N- (1-fluoro-
1,1,2,2-tetrachloroethylthio) -N- (phenyl) methylsulfamide, N- (1,1-difluoro-1,2,2-trichloroethylthio) -N- (phenyl) methylsulfamide , N, N-dimethyl-N'-phenyl-N '-(fluorodichloromethylthio) sulfamide, N, N-dichlorofluoromethylthio-N'-phenylsulfamide, N, N-dimethyl-N'-(p Haloalkylthio compounds such as -tolyl) -N '-(florodichloromethylthio) sulfamide, 1-diiodomethylsulfonyl-4-methylbenzene, 1-diiodomethylsulfonyl-4-chlorobenzene, 3-iodo-
2-propargylbutylcarbamic acid, 4-chlorophenyl-3-iodopropargylformal, 3-ethoxycarbonyloxy-1-bromo-1,2-diiodo-
Organic iodo compounds such as 1-propene and 2,3,3-triiodoallyl alcohol; 2- (n-octyl) -4
-Isothiazolin-3-one, 4,5-dichloro-2-
Cyclohexyl-4-isothiazolin-3-one, 2-
(4-thiocyanomethylthio) benzthiazole, 2-
Thiazole compounds such as zinc mercaptobenzthiazole and benzimidazoles such as 1H-2-thiocyanomethylthiobenzimidazole, 2- (4-thiazolyl) -1H-benzimidazole and 2- (2-chlorophenyl) -1H-benzimidazole. System compounds.

As the synthetic fiber used in the present invention, a fiber made of a fiber-forming polymer such as polyester, acrylic and nylon can be used. Among the synthetic fibers, polyester is preferable because it can provide a fiber structure having the most excellent antibacterial and antifungal properties in industrial washing durability.

The fiber structure referred to in the present invention is not limited to fabrics such as woven fabrics, knitted fabrics or non-woven fabrics, and may be of any structure and shape as long as the fabrics include fibers such as strips, cords, and threads. In addition to synthetic fibers, natural fibers such as cotton, wool and silk, or semi-synthetic fibers such as rayon and Tencel may be combined.

Among such fiber structures, 1 g of the fiber structure
A synthetic fiber having a surface area of 0.1 m ² or more is preferable because the antibacterial agent is easily attached or exhausted. Those having a surface area of 0.15 m ² or more are more preferable.

The method of applying the antibacterial agent to the fiber structure is, for example, immersing the fibrous structure in a liquid containing the antibacterial agent using a liquid jet dyeing machine or the like, and applying 10 to 90 to 160 ° C. under normal pressure or pressure. ~ 12
0 min, more preferably 20-60 at 120-135 ° C
Heat for a minute. At this time, if necessary, a disperse dye or a dispersible fluorescent brightener may be added to the liquid. In such a method, after the treatment in the liquid, the content is 160 to 200
15 seconds to 5 minutes at ℃, more preferably 170 to 190 ℃
For 30 seconds to 2 minutes. Thereby, the antibacterial agent can be diffused from the fiber surface to the inside to improve the washing durability. Under the heating condition of less than 160 ° C, the effect of the dry heat treatment is not obtained. In the case of the condition exceeding 200 ° C, yellowing and embrittlement of the fiber material, sublimation or thermal decomposition of the dye or antibacterial agent, and increase of energy consumption are required. Is not preferred.

As another method of applying the antibacterial agent, after impregnating the fibrous structure with a liquid containing the antibacterial agent in a padding bath or the like, a tenter or the like at 160 to 200 ° C. for 30 seconds to 10 minutes is more preferable. Can be manufactured by subjecting at least one kind of heat treatment selected from dry heat treatment and wet heat treatment at 170 to 190 ° C. for 2 to 5 minutes.

The fiber surface of the fiber structure of the present invention has at least one layer selected from the group consisting of an amorphous titanium peroxide particle layer, a zeolite layer and an alkylsilicate layer, and further has a photocatalytic semiconductor thereon. .

Here, the fiber surface includes, but is not limited to, the surface of a single fiber constituting the fiber structure, the surface of a yarn, or the surface of one surface of the fiber structure.

In the present invention, the photocatalytic semiconductor has a property of decomposing organic substances by a strong oxidation / reduction reaction caused by ultraviolet excitation, and specifically has a crystal structure called anatase type or rutile type. A thing. Among the oxidation and reduction reactions, antibacterial properties and antifungal properties can be imparted, particularly by the action of oxidative decomposition. Among such photocatalytic semiconductors, titanium oxide having an anatase crystal form is preferably used because of its excellent photocatalytic activity.

The present invention has a photocatalytic semiconductor on the fiber surface of a fibrous structure made of synthetic fibers to which an antibacterial agent has been applied, and is excellent against bacteria having a faster growth rate than mold due to the action of the antibacterial agent. In addition to its antibacterial properties, it has excellent antifungal properties against fungi, which have a slow growth rate but are more resistant than bacteria due to the photocatalytic semiconductor.

If the particle diameter of the photocatalytic semiconductor is too large or the specific surface area is too small, the decomposition rate against mold tends to decrease.
m and a specific surface area of 100 to 300 m ² / g are preferably used. The particle diameter of such a photocatalytic semiconductor is determined from the half width of the peak obtained by powder X-ray diffraction using the following Scherrer's formula.

Lc = 0.9λ / (W · cos θ) where Lc: particle diameter (nm), λ: wavelength of X-ray (nm), W: half width of peak (rad), θ: peak position angle.

If the amount of the photocatalyst semiconductor attached to the fiber structure is too small, the decomposition rate of mold is reduced and sufficient performance cannot be obtained. Therefore, the amount is preferably 0.03% by weight or more. If the content is too large, the fiber fabric is deteriorated by the photocatalytic semiconductor or the texture is hardened and becomes impractical. Therefore, the content is preferably 15% by weight or less. More preferably, it is in the range of 0.05 to 10% by weight.

The photocatalytic semiconductor is excited by light and decomposes bacteria and mold by oxidation / reduction. Such substances include TiO ₂ , ZnO, SrTiO ₃ , Cd
S, CdO, CaP, InP, In ₂ O ₃ , CaAs, B
aTiO ₃ , K ₂ NbO ₃ , Fe ₂ O ₃ , Ta ₂ O ₅ , WO ₃ ,
SbO ₂ , Bi ₂ O ₃ , NiO, Cu ₂ O, SiC, SiO
₂ , at least one selected from the group consisting of MoS ₂ , MoS ₃ , InPb, RuO ₂ , CeO _2, and a composite oxide composed of titanium and silicon can be used. Titanium oxide-based compounds that have high photocatalysis, are chemically stable, and are harmless are more preferred. As such a titanium oxide-based compound, in addition to titanium oxide, at least one selected from hydrous titanium oxide, hydrated titanium oxide, titanium hydroxide, metatitanic acid and orthotitanic acid can be used.

For the purpose of improving antibacterial and antifungal properties and imparting deodorant properties, in addition to such photocatalytic semiconductors, iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver, gold, platinum, etc. Or a compound of another metal such as zinc oxide or zinc hydroxide.

In the present invention, in order to fix the photocatalyst semiconductor on the fiber surface, it is necessary to provide another layer between the fiber and the photocatalyst semiconductor layer or to microencapsulate the photocatalyst semiconductor. That is, the photocatalytic semiconductor of the present invention has a strong redox power,
Decomposition of an organic substance occurs by irradiation of ultraviolet rays, and a resin such as a fibrous structure or a binder may be decomposed or colored. For example, when urethane resin or acrylic resin is irradiated with ultraviolet light in the presence of a photocatalyst, coloring or odor is generated due to decomposition of organic substances. As described above, in order to attach the photocatalyst to the fiber structure, it is necessary to use an intermediate layer for preventing decomposition, coloring, or generation of odor of the photocatalyst specific to the organic resin due to oxidation.

In the present invention, as the intermediate layer, an amorphous (amorphous) titanium peroxide particle layer containing titanium oxide or peroxotitanic acid or a metal oxide other than titanium, a zeolite layer, an alkylsilicate layer Is used. By using such an intermediate layer as a so-called protective layer, it is possible to prevent the synthetic fiber from being decomposed by the photocatalyst.

Since the above-mentioned amorphous titanium peroxide particles are in an amorphous state at normal temperature, they are not crystallized to anatase type titanium oxide and have no function as a photocatalyst. . Since the titanium peroxide particles in the amorphous state have high film-forming properties, there is an advantage that a uniform thin film can be easily formed. Such an amorphous titanium peroxide is added to an aqueous solution of a titanium salt such as titanium tetrachloride TiCl ₄ ,
After adding alkali hydroxide to obtain titanium hydroxide Ti (OH) ₄ , the titanium hydroxide is washed, separated and treated with hydrogen peroxide solution.

Next, the zeolite layer can be formed alone, but more preferably, a silicone-based or fluorine-based resin is used as a zeolite fixing binder to form a more durable intermediate layer. .

As such a silicone resin, a condensation-crosslinking resin belonging to the class of silicone resin or silicone varnish can be used.
Condensation-crosslinkable resins such as tetraethoxysilane and methyltrimethoxysilane can be obtained alone or by condensing several kinds of blends. These form a resin having a three-dimensional structure, and are the most excellent in heat resistance and chemical resistance among silicone resins. When a sol of silicon oxide obtained by hydrolysis of tetraisopropoxysilane or tetraethoxysilane with a strong acid in a mixed solvent of alcohol and water is dried, a vitreous film is formed. The film obtained by such a sol / gel method is close to an inorganic material, and is more preferable for the present invention.

As the fluorine-based resin, vinyl ether and / or vinyl ester and a fluoroolefin polymerizable compound are preferably used because they have excellent properties. Polyvinyl fluoride, polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkylvinyl ester, vinyl ester-fluoroolefin, and the like are preferably used because they are less decomposed and deteriorated.

Unlike the commonly used acrylic resin, urethane resin and epoxy resin, these silicone resins and fluorine resins contain almost no hydrocarbon groups which are easily decomposed by the action of heat or chemicals. Silicone-based resins are mainly composed of Si—O bonds, and fluorine-based resins are mainly composed of F—C bonds, and only a small amount of a methyl group or phenyl group is contained as a hydrocarbon in a terminal group or a side chain.

Next, the alkyl silicate referred to in the present invention is represented by the following general formula.

[(R ₁ O) ₃ —Si—O] _n —R ₂ —OH In the formula, R ₁ and R ₂ are linear or branched saturated alkyl groups having 1 to 4 carbon atoms; Represents an integer of 1 or more. Such alkyl groups are methyl, ethyl, propyl,
It is a linear or branched saturated alkyl such as isopropyl.

The alkyl silicate may be one kind or a mixture of two kinds, but preferably has a methyl group in order to increase the inorganicity. These compounds readily undergo a dehydration reaction in the presence of heat to form a polysiloxane coating. As the alkyl silicate, commercially available ones may be used, for example, CLG-520, 550, 590
(Manufactured by Kyoeisha Chemical Co., Ltd.), MKC silicate MS-5
1, 56 (manufactured by Mitsubishi Chemical Corporation) and the like can be used. These alkyl silicates are water-soluble, and when a fiber structure is impregnated with the aqueous solution, squeezed with a mangle roll and treated at 200 ° C. or lower, a thin film is formed on the fiber surface.

The alkyl silicate can be directly adhered on the surface of the fibrous structure, but may be adhered by a binder of silicone resin or fluorine resin. These binders, as described above,
It has excellent heat resistance, light resistance, and chemical resistance, and has excellent durability against the oxidizing power of the photocatalytic semiconductor.

Next, a method for producing the fiber structure of the present invention will be described.

As described above, a synthetic fiber to which an antibacterial agent has been applied or exhausted is used to form a fibrous structure, on which an intermediate layer is formed, and then a photocatalytic semiconductor is applied.

In the case of using a titanium peroxide particle layer, the intermediate layer is formed by impregnating the fiber structure with a treatment liquid containing titanium peroxide, which is in the process of changing from a sol state to a gel state. After squeezing with mangle roll, 200
Fix at a temperature below ° C. Alternatively, a titanium peroxide layer can be formed by adjusting the treatment liquid to an appropriate viscosity, applying the treatment liquid to a fiber structure using a knife coater, a gravure roll coater, or the like, and then fixing the treatment liquid at a temperature of 200 ° C. or less.

In the case of a zeolite layer, it can be formed by fusing a gas phase coating of zeolite fine particles to a fiber structure by a PVA method.

In the case of a zeolite fine particle layer fixed with a silicone-based or fluorine-based resin, the fibrous structure is impregnated with a treatment liquid containing zeolite fine particles and a water-soluble silicone-based or fluorine-based resin. And squeezed with a mangle roll and fixed at a temperature of 200 ° C. or less. Alternatively, the aqueous solution can be formed by adjusting the aqueous solution to an appropriate viscosity, applying the solution to a fiber structure using a knife coater, a gravure roll coater, or the like, and then fixing the solution at a temperature of 200 ° C. or less.

In the case of an alkyl silicate layer, first, an alcohol and hydrochloric acid, sulfuric acid, nitric acid, etc. are added to an aqueous solution of the alkyl silicate in order to make the reaction more stable.
The pH is brought to 2-4 and the solution is stirred well. Then
After the fiber structure is impregnated with this solution, it is squeezed with a mangle roll and fixed at a temperature of 200 ° C. or less. Alternatively, this aqueous solution is adjusted to an appropriate viscosity and applied to the fiber structure using a knife coater or a gravure roll coater.
It can be formed by fixing at a temperature of 00 ° C. or less.

In order to apply the photocatalyst semiconductor to such an intermediate layer, the fiber structure is impregnated with an aqueous dispersion of the photocatalyst semiconductor or a solution in which a silicone-based or fluorine-based resin is mixed, followed by drying and fixing. (Pad-dry-cure) process. Alternatively, it can be applied by adjusting the solution to an appropriate viscosity, applying the solution to the fiber structure using a knife coater, a gravure roll coater, or the like, and then fixing the solution at a temperature of 200 ° C. or less.

In the present invention, the photocatalyst semiconductor may be microencapsulated. Here, the microencapsulated photocatalytic semiconductor is a spherical substance in which an inorganic substance having no or little photocatalytic action is a shell and the photocatalytic semiconductor is a nucleus, and the shell has micropores. preferable. Further, this also includes a spherical substance containing a photocatalyst in which fine particles of a photocatalytic semiconductor and fine particles of an inorganic substance having a higher mixing ratio than that and having no or little photocatalysis are mixed. The particle size of the microcapsules is preferably from 0.1 to 10 μm. By using the microencapsulated photocatalyst semiconductor, since the photocatalyst semiconductor and the binder are not in direct contact, it is possible to prevent the binder resin from deteriorating due to the strong oxidizing power of the photocatalyst semiconductor without providing the above-mentioned intermediate layer. Can be.

Since the fibrous structure of the present invention has excellent antibacterial and antifungal properties, clothes, socks, shoes,
It can be an air filter, curtain, floor sheet or bedding.

[0057]

EXAMPLES In the examples, "%" and "part" mean "% by weight" unless otherwise specified.

The quality evaluation in the examples was performed according to 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 aqueous hydrogen peroxide (35% industrial)
/ 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) Evaluation method of antibacterial activity The evaluation method used was a unified test method, and the test cells used were MRSA bacteria (IID1677). The test method is as follows. A bouillon suspension of the above test bacteria is poured into a sterile sample cloth, and the number of viable bacteria after culturing at 37 ° C. for 18 hours in a closed container is measured. According to the standards of

Under the condition of log (B / A)> 1.5,
g (A / C) was defined as a bactericidal activity value, and 0 or more was defined 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 method for mold resistance The evaluation method is a mold resistance test JIS Z 2911.6.
2.2 Wet method is used, and the test mold is Asperg
illus niger (FERM S-1), Pen
icillium citrinum (FERM S-
5), Chaetomium globosum (FE
RM S-11) and Myrothecium ve
rucuria (FERM S-13), and a JIS inorganic salt agar medium was used as a medium. The evaluation was based on the following criteria.

1: On the sample piece, the hyphal growth part is observed over one third of the total area.

2: The hyphal growth portion is observed on the sample within 1/3 of the total area.

3: No hyphal growth was observed on the sample.

As a test cloth, 150 denier-48 filaments of polyethylene terephthalate filament fiber ("Tetron" (registered trademark) manufactured by Toray Industries, Inc.) were woven by a water jet loom to obtain a plain woven fabric having a basis weight of 200 g / m ² . Was used. The fiber surface area per g of the fiber structure is 0.16 m ² / g.

Example 1 (1) Addition of antibacterial agent 2-chloro-4-trichloromethyl-6- as an antibacterial agent
50 g of (2-furylmethoxy) pyridine (molecular weight: 329, inorganic / organic value: 0.73), 20 g of formalin condensate of naphthalenesulfonic acid, and 30 g of sodium ligninsulfonate are slurried with 300 g of water, and then glass Wet grinding process using beads,
A colloidal composition having an average particle size of 1 μm was obtained. next,
Using a high-pressure dyeing tester, 1% owf of an antibacterial agent colloided by the above method, and a disperse dye Sumikaron Re
d E-RPD (Sumitomo Chemical Co., Ltd.) 0.5% ow
f, the test cloth was immersed in a solution having a bath ratio of 1:10 and a pH of 5,
After treating at 0 ° C. for 60 minutes, it was washed with water and dried.

(2) Formation of Intermediate Layer A 5% solution of sodium hydroxide NaOH was added to a 30% solution of titanium tetrachloride TiCl ₄ and allowed to stand for a while to obtain titanium hydroxide Ti (OH) ₄ . This was treated with 25% aqueous hydrogen peroxide to obtain an amorphous titanium peroxide sol.
This titanium peroxide sol was adjusted to 0.5%. The cloth obtained in the above (1) was immersed in this liquid and squeezed at a squeezing ratio of 90% using a mangle. Thereafter, drying was performed at 120 ° C.
The weight of the obtained dough was measured to calculate the amount of the titanium peroxide sol attached, and as a result, it was 0.45% based on the dough.

(3) Addition of photocatalytic semiconductor Titanium dioxide having photocatalytic function (manufactured by Ishihara Sangyo Co., Ltd.)
ST-01) and pure water so that the solid content of a silicone resin (Toray Silicone SD-8000, manufactured by Dow Corning Silicone Toray Co., Ltd.) becomes 4.0%. A slurry was prepared by suspending. The dough obtained in the above (2) was immersed in the prepared solution, and squeezed at a squeezing ratio of 90% using a mangle. Thereafter, drying was performed at 120 ° C. The weight of the obtained dough was measured to calculate the amount of titanium dioxide attached thereto, and as a result, it was 0.09% based on the dough.

Table 2 shows the evaluation results of the antibacterial property and the antifungal property of this fiber structure.

Example 2 An intermediate layer was processed in the same manner as in Example 1 except that the intermediate layer was formed by fusing a gas phase coating of zeolite fine particles to the cloth by the PVA method. Table 2 shows the evaluation results of the antibacterial property and the antifungal property of this fiber structure.

Example 3 Processing was performed in the same manner as in Example 1 except that the formation of the intermediate layer was performed by fixing zeolite fine particles with a silicone resin. Table 2 shows the evaluation results of the antibacterial property and the antifungal property of this fiber structure.

The prescription for forming the intermediate layer is as follows.

After preparing a treatment liquid having the following composition, the dough is immersed in this preparation liquid, and a squeezing ratio of 90% is determined using a mangle.
And squeezed. Then, after drying at 100 ° C. for 1 minute, 19
Heat treatment was performed at 5 ° C. for 30 seconds.

Zeolite fine particles 20 parts Toray Silicone SD-8000 (manufactured by Toray Tow Corning Silicone Co., Ltd.) 20 parts Methanol 25 parts Pure water 32 parts 0.5N hydrochloric acid 3 parts Example 4 In forming an intermediate layer, a fluorine-based material was used. Processing was performed in the same manner as in Example 1 except that zeolite fine particles were fixed with a resin. Table 2 shows the evaluation results of the antibacterial property and the antifungal property of this fiber structure.

The prescription for forming the intermediate layer is as follows.

After preparing a treatment liquid having the following composition, the dough is immersed in this preparation liquid, and the squeezing ratio is 90% using a mangle.
And squeezed. Then, after drying at 100 ° C. for 1 minute, 19
Heat treatment was performed at 5 ° C. for 30 seconds.

Zeolite fine particles 20 parts Lumiflon LF200C (manufactured by Asahi Glass Co., Ltd.) 20 parts Isocyanate-based curing agent 4 parts Toluene 56 parts Example 5 In the formation of the intermediate layer, the same procedure as in Example 1 was carried out except for the formation of alkyl silicate. Processed to. Table 2 shows the evaluation results of the antibacterial property and the antifungal property of this fiber structure.

The prescription for forming the intermediate layer is as follows.

After preparing a treatment liquid having the following composition, the dough is immersed in this preparation liquid, and a squeezing ratio of 90% is determined using a mangle.
And squeezed. Then, after drying at 100 ° C. for 1 minute, 19
Heat treatment was performed at 5 ° C. for 30 seconds.

Methyl silicate CLG-520 (manufactured by Kyoeisha Chemical Co., Ltd.) 20.5 parts Methanol 8.5 parts Pure water 70.0 parts Sulfuric acid (20%) 1.0 part Comparative Example 1 In the process of Example 1, Those to which only an antibacterial agent was applied (one in which the formation of the intermediate layer and the photocatalytic semiconductor were not applied) were subjected to evaluation. Table 2 shows the evaluation results of the antibacterial property and the antifungal property of this fiber structure.

COMPARATIVE EXAMPLE 2 In the process of Example 1, an intermediate layer was formed and a photocatalytic semiconductor was only applied (an antibacterial agent was not applied). Table 2 shows the evaluation results of the antibacterial property and the antifungal property of this fiber structure.

Example 6 After the antibacterial agent was applied in the step of Example 1 (1), a microencapsulated photocatalytic semiconductor was applied in combination with a melamine resin without providing an intermediate layer. Antibacterial properties of this fiber structure,
Table 2 shows the evaluation results of the antifungal property.

[0085] Incidentally, as a photocatalyst semiconductor microencapsulated, was used the TiO ₂ forms a porous SiO ₂ is contained (content). The prescription for the application is as follows.

After preparing a treatment liquid having the following composition, the dough is immersed in this preparation liquid, and the squeezing rate is 90% using a mangle.
And squeezed. After drying at 100 ° C. for 1 minute,
Heat treatment was performed at 0 ° C. for 30 seconds.

Microencapsulated photocatalytic semiconductor (diameter: about 5 μm, manufactured by Suzuki Yushi Kogyo Co., Ltd.) 0.1 part Sumitex Resin M-3 (manufactured by Sumitomo Chemical Co., Ltd.) 10.0 parts Sumitex Accelerator ACX ( Catalyst, manufactured by Sumitomo Chemical Co., Ltd.) 0.3 parts Pure water 89.6 parts

[Table 2] As is clear from Table 2, Examples 1 to 6 are Comparative Examples 1 and
Compared to No. 2, it has sufficient antibacterial and antifungal properties before washing and after 50 times of industrial washing.

[0088]

According to the present invention, a fibrous structure having excellent antibacterial and antifungal properties can be provided.

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Claims (19)

[Claims] Claims: 1. A synthetic fiber comprising an antimicrobial agent deposited and / or exhausted thereon, comprising, on the surface of the fiber, an amorphous titanium peroxide particle layer, a zeolite layer and an alkyl silicate layer. A fibrous structure having at least one selected layer and further having a photocatalytic semiconductor on the surface of the layer. 2. A fibrous structure comprising a synthetic fiber to which an antibacterial agent is attached and / or exhausted, and having a microencapsulated photocatalytic semiconductor on the surface of the fiber. 3. The antibacterial agent having a molecular weight of 200 to 700,
The fiber structure according to claim 1 or 2, wherein the inorganic / organic value is in the range of 0.3 to 1.4 and the average particle size is 2 µm or less. 4. The antimicrobial agent is at least one selected from the group consisting of nitrile compounds, pyridine compounds, haloalkylthio compounds, organic iodine compounds, thiazole compounds and benzimidazole compounds. The fibrous structure according to any one of claims 1 to 3. 5. The fiber structure according to claim 1, wherein the surface area of the synthetic fiber is 0.1 m ² or more per 1 g of the fiber structure. 6. The fiber structure according to claim 1, wherein said synthetic fiber is a polyester fiber. 7. The photocatalytic semiconductor is composed of TiO ₂ , ZnO, S
rTiO ₃ , CdS, CdO, CaP, InP, In ₂ O
_{3, CaAs, BaTiO 3, K} 2 NbO 3, Fe 2 O 3, T
a ₂ O ₅ , WO ₃ , SbO ₂ , Bi ₂ O ₃ , NiO, Cu
₂ O, SiC, SiO ₂ , MoS ₂ , MoS ₃ , InPb,
RuO _2, CeO ₂ and fiber structure according to claim 1 is at least one selected from the group consisting of a composite oxide comprising titanium and silicon. 8. The fiber structure according to claim 1, wherein said photocatalytic semiconductor is a titanium oxide-based compound. 9. The fiber structure according to claim 1, wherein said photocatalytic semiconductor has an anatase type crystal form. 10. The photocatalytic semiconductor has a particle diameter of 1 to 200 n.
m, the specific surface area is 100 to 300 m ² / g.
10. The fibrous structure according to any one of 9. 11. The fiber structure according to claim 1, wherein the photocatalytic semiconductor is attached to the fiber structure in an amount of 0.03 to 15% by weight. 12. The fiber structure according to claim 1, wherein the photocatalytic semiconductor layer is formed by fixing the photocatalytic semiconductor with a silicone-based or fluorine-based resin. 13. A garment using the fibrous structure according to any one of claims 1 to 12. 14. A sock comprising the fibrous structure according to any one of claims 1 to 12. 15. A shoe comprising the fibrous structure according to any one of claims 1 to 12. 16. An air filter using the fibrous structure according to any one of claims 1 to 12. 17. A curtain comprising the fibrous structure according to any one of claims 1 to 12. 18. A floor sheet comprising the fibrous structure according to any one of claims 1 to 12. 19. A bedding comprising the fibrous structure according to any one of claims 1 to 12.