Fiber structure having functional property

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

[Technical field to which the invention belongs]

The present invention relates to a fiber structure having excellent functionality that simultaneously satisfies non-conventional durable deodorant, antibacterial, antifungal and antifouling functions. In particular, in terms of deodorant properties, it is a fiber structure having an unprecedented odor prevention effect on the fiber structure. More specifically, the present invention can be widely applied to interior materials such as clothing, curtains, wall coverings, seat materials, bedding, and interior materials such as automobiles.

【0002】

[Conventional technology]

In recent years, awareness of health and hygiene has increased along with the improvement of the standard of living of the people, and products and technologies that have been subjected to deodorant, antibacterial, antifungal and antifouling treatments have been put into practical use in each field of clothing, food and housing. In particular, in the field of clothing, various deodorant, antibacterial, and antifouling processing technologies have been developed for wearing. In addition, it is being developed for other uses including interiors.

【0003】

For example, when the fiber is subjected to deodorant, antibacterial and antifouling treatments, it is kneaded into the raw yarn, applied in the spinning process, and applied during and after dyeing. However, in this method, in order to perform processing that satisfies deodorant, antibacterial, and antifouling properties on the entire fiber, it is necessary to add a large amount of processing agent, which may reduce productivity. In addition, the texture may become hard due to the increased amount of adhesion, or the color may become white and the appearance may be deteriorated depending on the processing agent.

【0004】

Further, the deodorants used for these are mainly those having a neutralizing action or the like except for a small part, and cannot exhibit a long-lasting deodorizing function. For example, acidic titanium oxide, aluminum sulfate, etc. are effective in deodorizing basic ammonia and the like, but are ineffective against neutral malodor. In addition, zinc oxide, whose deodorant itself is basic, is ineffective against neutral malodors even if it neutralizes acidic malodors such as methyl mercaptan and hydrogen sulfide to turn them into odorless substances. Further, the deodorizing method using these acids and bases by a neutralizing action cannot exert its effect when the deodorant itself is saturated, and the function is restored only after a treatment such as washing. Therefore, these deodorants have a limited ability to treat malodors and cannot exert any effect on basic or acidic substances.

【0005】

In addition, deodorants that utilize physical adsorption of activated carbon, silica, and the like are also known. These collect malodorous components in a deodorant and reduce the concentration of the surroundings, but they do not reduce the total amount of malodorous components, so they are not an essential solution. Ideally, it is necessary to decompose the malodorous component into a completely odorless component, and very few chemical substances that perform such an action are known. For example, there is iron / phthalocyanine, and this substance that enzymatically oxidatively decomposes is used by kneading it into rayon fiber. For example, it is used for futon cotton, and it has been confirmed that this deodorizes ammonia. Has been done. It is also known that hydrogen sulfide is oxidized to sulfur, mercaptan to disulfide, aldehyde to carboxylic acid, and amine to ketone and ammonia. However, some of these decomposition products have an odor, and these chemicals are not effective against all malodors. That is, it is not effective in removing the odor of tobacco and sweat.

【0006】

In addition, it is said that the combined malodor, for example, the combustion gas of cigarettes, contains thousands of components, and it was difficult to deodorize all of them. Furthermore, there is no effective deodorant for isovaleric acid, which is the main component of humans, and the odor component of the axillary odor is a mixture of several types of lower fatty acids, making it difficult to completely deodorize them. Met.

【0007】

Such deodorant processing can remove or reduce odorous components in the air by decomposing or adsorbing, but the deodorized fiber structure rather adsorbs odorous components or changes to other components by decomposition. However, strange odorous components may be generated on the contrary, and therefore it is not possible to completely remove the odorous components at this time. Rather, fiber structures that have not been deodorized are often more effective in preventing odors.

【0008】

In addition, if the titanium oxide photocatalyst is fixed to the fiber, it can be expected that functions such as deodorization, antibacterial, antifungal and antifouling can be obtained, but some kind of binder resin is required to fix the titanium oxide photocatalyst to the fiber. Since the acrylic resin and urethane resin binder resins that have been used in the past are resins that contain organic hydrocarbons, the binder resin decomposes and becomes colored due to the strong oxidative decomposition power of the titanium oxide photocatalyst. There were problems such as a foul odor.

【0009】

Further, the fiber itself to which the titanium oxide photocatalyst is applied deteriorates, and problems such as coloring, a decrease in strength, and generation of a low molecular weight decomposition product may cause a bad odor. Therefore, the titanium oxide photocatalyst is used for the fiber material. Techniques for imparting functions such as deodorization have not yet been put into practical use. Conventionally, as an example in which a titanium oxide photocatalyst is used, even if it is fixed to the surface of an inorganic substance such as ceramic or glass, there is no one fixed to the surface of an organic substance. The reason is that inorganic substances are not decomposed by the strong oxidizing power of the titanium oxide photocatalyst.

【0010】

[Problems to be Solved by the Invention]

In view of the problems of the prior art, the present invention provides a fiber structure having excellent functions, which does not discolor or deteriorate during use and simultaneously satisfies long-lasting deodorant, antibacterial, antifungal and antifouling properties. It is intended to be provided.

【0011】

[Means for solving problems]

The present invention employs the following means in order to solve such a problem. That is, the fiber structure of the present invention has a titanium peroxide particle layer or a zeolite layer, a layer fixed to zeolite with a silicone-based or fluorine-based resin, or an alkyl silicate as an intermediate layer on the fiber surface. It is characterized by having a layer and further having a layer of a composite oxide composed of titanium and silicon on the upper layer thereof.

【0012】

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention has diligently studied a fibrous structure having excellent functions that simultaneously satisfies the above-mentioned problems, that is, deodorization, antibacterial, antifungal and antifouling properties, and from titanium and silicon on the specific intermediate layer. When a composite layer composed of a layer of composite oxide was provided on the fiber surface, it was surprisingly found that such a problem could be solved at once.

【0013】

Synthetic fibers and natural fibers can be used as the fibers constituting the fiber structure of the present invention, and the fibers are not particularly limited, but are preferably composed of fibers containing 50% by weight or more of polyester fibers. Here, as the polyester fiber, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate and the like are preferably used. Further, as the polyester constituting the polyester fiber, a copolymer of a third component can also be used, and as the third component, isophthalic acid, 5-sulfoisophthalic acid, and metoxypolyoxyethylene glycol can be used. It is preferably used by copolymerizing such as. The functionality of the present invention exhibits an excellent improving effect when the fiber structure is composed of fibers containing 50% by weight or more, more preferably 100% of polyester fibers. The fibers used as the fibers constituting the fiber fabric of the present invention include, for example, synthetic fibers such as polyamide and polyacrylic, semi-synthetic fibers such as acetate and rayon, and natural fibers such as wool, silk, cotton and hemp. May be included.

【0014】

The fiber structure referred to in the present invention may have any structure and shape as long as it is an object including a fiber structure, such as a cloth-like material, a strip-like material, a string-like material, and a thread-like material. However, preferably, a cloth-like material mainly composed of synthetic fibers, that is, a material containing a knitted fabric or a non-woven fabric is used. That is, the fiber structure of the present invention includes a composite material containing such a fiber structure.

【0015】

In the present invention, the polyester fiber may contain inert titanium oxide. The inert titanium oxide is titanium oxide that is inactive without being excited by light of a specific wavelength, particularly preferably ultraviolet rays, and preferably titanium oxide that is used as a matting agent in the production of polyester-based synthetic fibers. used. By adding such inactive titanium oxide, the inorganic nature is enhanced by adding the inorganic titanium oxide to the 100% organic polyester fiber, and the redox action of the photocatalytic semiconductor used in the upper layer is exerted. This is caused by the action of reducing the influence on the polyester fiber. The inert titanium oxide can be added at the time of polymerization of the polyester fiber, and has an average particle size in the range of preferably 0.1 to 0.7 μm, more preferably 0.2 to 0.4 μm in terms of yarn-making property and yarn physical characteristics. Is good.

【0016】

The amount of the inert titanium oxide added is preferably 0.3 to 5% by weight, more preferably 0.5 to 4% by weight, based on the weight of the fiber. If it is less than 0.3% by weight, the polyester fiber is easily decomposed by the photocatalytic semiconductor, and the photocatalytic function and the physical properties of the fiber structure cannot be maintained with good durability. On the other hand, if it exceeds 5% by weight, it is not possible to obtain a product having satisfactory yarn-making properties and yarn physical characteristics.

【0017】

The deformed cross-sectional coefficient of the polyester fiber in the present invention is a comparison between the outer peripheral length of the deformed cross-section yarn and the outer peripheral length of the round cross-section yarn having the same cross-sectional area as the perfect circular cross-section yarn, in other words, at the same denier. Specifically, it is expressed by the value obtained by dividing the outer circumference of the deformed cross-section yarn by the outer circumference of the perfect circular cross-section yarn. The larger this value is, the larger the surface area per yarn weight is, and the larger the area of the optical semiconductor layer is, so that the functionality of the present invention is increased accordingly. As the modified cross-sectional coefficient, those in the range of preferably 1.2 to 2, more preferably 1.3 to 1.8 are preferably used. If it is less than 1.2, it is close to a circular cross section, and the effect of functionality cannot be expected so much. Further, those exceeding 2 are at a level where it is difficult to form a cross-sectional shape in the spinning of polyester fibers, which is not preferable from the viewpoint of productivity.

【0018】

In the present invention, the photocatalyst has a property of being excited by ultraviolet rays and oxidatively decomposing an organic substance by a strong oxidizing force, and specifically, a photocatalyst having a crystal type structure called anatase type or rutile type.

【0019】

The present invention has focused on the fact that such a photocatalyst has deodorant properties, decomposing and removing properties for colored substances (antifouling properties), and bactericidal properties (antibacterial properties, antifungal properties), and has made use of this by imparting it to a fiber structure. It is a thing.

【0020】

For example, many processing technologies with deodorant functions have been introduced so far, but conventional deodorant technologies deodorize only a specific odor, leaving odors or lacking sustainability and durability. There was a problem.

【0021】

However, the photocatalyst of the present invention deodorizes tobacco odors and sweat odors, which have been difficult so far, in a well-balanced manner, and also has a function of oxidatively decomposing such odors. It also achieves excellent effects. Further, since it has a function of decomposing and removing colored substances such as tobacco tar, it is possible to achieve an antifouling effect on the colored substances. Furthermore, since the photocatalyst of the present invention has a bactericidal activity against MRSA bacteria, Escherichia coli, Staphylococcus aureus, etc. due to its oxidizing power, it is possible to achieve antibacterial and antifungal treatment effects.

【0022】

If the particle size of such a photocatalyst is too large or the specific surface area is too small, the decomposition rate of organic substances, particularly bacteria, tends to decrease. In addition, the deodorizing reaction is considered to undergo a process in which the malodorous component is adsorbed on the catalyst and then undergoes ultraviolet oxidative decomposition, and it is considered that the good or bad adsorption of the malodorous component greatly affects the deodorizing efficiency. The diameter is 20 nm or less, and the specific surface area is 100 to 300 m.²Those with / g are preferably used. If the amount of the photocatalyst adhering to the fiber structure is too small, the decomposition rate of organic substances such as malodorous components will decrease and sufficient performance will not be obtained, or if it is too large, the fiber fabric will deteriorate due to the photocatalyst. Since the texture becomes hardened and impractical, the amount of the photocatalyst attached to the fiber structure is preferably 0.1 to 30% by weight.

【0023】

As such a photocatalyst, a composite oxide of titanium and silicon is used. As such a composite oxide, for example, a catalyst produced by the method described in Japanese Patent Publication No. 5-55184 can be used. In general, a binary composite oxide composed of titanium and silicon is known as a solid acid and has a composition, as is also known by, for example, Kozo Tabe (Catalyst, Vol. 17, No. 3, p. 72, 1975). Each of them exhibits remarkable acidity not found in a single oxide and has a high surface area. That is, it is recognized that the composite oxide of titanium and silicon is not simply a mixture of titanium oxide and silicon oxide, but its unique characteristics are exhibited by forming a so-called dual oxide of titanium and silicon. It can be done. Furthermore, as a result of analysis by X-ray diffraction, the above composite oxide has an amorphous or nearly amorphous microstructure. The ratio of titanium to silicon is preferably in the range of 20 to 95 mol% of titanium oxide and 5 to 80 mol% of silicon oxide in terms of oxide. As a preferable method for producing a composite oxide of titanium and silicon, titanium tetrachloride is mixed with silica sol, and aqueous ammonia is added dropwise thereto to form a precipitate. The precipitate is filtered, washed, and dried, and then 300 to 650. Bake at ° C. Compared with the generally known titanium oxide photocatalyst, it is excellent in oxidative decomposition characteristics of organic substances, and has the characteristics of being excellent in antibacterial, deodorant, odor prevention, and antifouling properties as described above. ..

【0024】

In the present invention, it is necessary to use a specific intermediate layer in order to fix the photocatalyst on the fiber surface. That is, the photocatalyst of the present invention, that is, the composite oxide of titanium and silicon, has a strong oxidizing power, and the organic matter is decomposed by irradiation with ultraviolet rays, and the resin such as the fiber structure and the binder is decomposed and colored. Sometimes. For example, when urethane resin, acrylic resin, etc. coexist with a photocatalyst and are irradiated with ultraviolet rays, coloring and odor are 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, and generation of odor due to oxidation of the photocatalyst peculiar to the organic resin. In the present invention, it has been found that a specific inorganic intermediate layer is optimal as such an intermediate layer.

【0025】

The inorganic intermediate layer referred to in the present invention includes, for example, the formation of a non-crystalline (amorphous) titanium peroxide particle layer containing titanium peroxide, peroxotitanic acid, or a metal oxide other than titanium, or an inorganic porous zeolite. An alkyl silicate layer or the like is preferably used. By using such an inorganic intermediate layer as a protective layer, decomposition by a photocatalyst can be prevented.

【0026】

Since the above-mentioned amorphous titanium peroxide particles are in an amorphous state at room temperature, they are in a form that has not been crystallized to anatase-type titanium oxide, that is, they do not have a function as a photocatalyst. It is in a state. Since the titanium peroxide particles in the amorphous state have a high film-forming property, they have an advantage that a uniform thin film can be easily formed.

【0027】

The amorphous titanium peroxide is Titanium tetrachloride TiCl.₄Titanium hydroxide Ti (OH) by adding alkali hydroxide to a titanium salt aqueous solution such as₄The titanium hydroxide is washed, separated, and then treated with hydrogen peroxide solution.

【0028】

Next, the intermediate layer can be formed by zeolite alone, but more preferably, a more durable intermediate layer can be formed by using a silicone-based or fluorine-based resin as the binder for fixing the zeolite. it can. Zeolites in which precious metals such as gold, platinum, silver and palladium are supported in the range of 0.01 to 5% by weight can also be used. As a result, the deodorant effect can be expected to be further improved, and when silver is used, the antibacterial effect is further improved.

【0029】

Further, as the silicone resin, a condensation-crosslinked resin belonging to the classification of silicone resin or silicone varnish can be used, and such a resin may be a single or several kinds of condensation-crosslinked resins such as tetraethoxysilane and methyltrimethoxysilane. It can be obtained by condensing the formulation of. These form a resin with a three-dimensional structure, and are the most excellent in heat resistance and chemical resistance among silicone resins. Further, when the silicon oxide sol obtained by hydrolyzing tetraisopropoxysilane or tetraethoxysilane with a strong acid in an alcohol / water mixed solvent is dried, a glassy film is formed. The film obtained by such a sol / gel method is close to an inorganic substance, which is more preferable for the present invention.

【0030】

Further, as the fluorine-based resin, vinyl ether and / or vinyl ester and a fluoroolefin polymerizable compound have very excellent properties and are preferably used. For example, polyvinyl fluoride, polyvinyl tetrafluoroethylene, ethylene tetrafluoroethylene-perfluoroalkyl vinyl ester, vinyl ester-fluoroolefin and the like are preferably used because they are less decomposed and deteriorated.

【0031】

The difference between such silicone-based resins and fluorine-based resins and commonly used acrylic resins, urethane resins, epoxy resins, etc. is that they contain almost no hydrocarbon groups that are easily decomposed by the action of heat or chemicals, and the silicone-based resins are Si. -O-bonds and fluororesins are mainly composed of FC bonds, and the terminal groups and side chains contain a small amount of methyl groups and phenyl periods as hydrocarbons.

【0032】

The alkyl silicate used in the present invention is represented by the following general formula.

【0033】

[(R₁O)₃-Si-O]_n-R₂-OH In the formula, R₁, R₂Is a saturated alkyl group having straight or branched carbons 1 to 4, and n means an integer of 1 or more.

【0034】

Such alkyl groups are straight or branched saturated alkyls such as methyl, ethyl, propyl and isopropyl. These alkyl silicates may be a mixture of one or two types, but those having a methyl group are preferably used in order to enhance the inorganicity. These compounds easily undergo a dehydration reaction in the presence of heat to form a polysiloxane film.

【0035】

Commercially available alkyl silicates may be used, for example, CLG-520, 550, 590 (manufactured by Kyoeisha Chemical Co., Ltd.), MKC silicate MS-51, 56 (manufactured by Mitsubishi Chemical Corporation), etc. Can be used. These alkyl silicates are water-soluble, and when the fiber structure is impregnated with these aqueous solutions, squeezed with a mangle roll, and treated at 200 ° C. or lower, a thin film is formed on the fiber surface.

【0036】

Such an alkyl silicate can be directly attached to the surface of the fiber structure, but may be attached by a binder of a silicone-based resin or a fluorine-based resin. As described above, these binders are excellent in heat resistance, light resistance, and chemical resistance, and also have excellent durability against the oxidizing power of the photocatalytic semiconductor.

【0037】

Next, the method for producing the fiber structure of the present invention will be described. First, as a treatment method when the titanium peroxide particle layer is used as the intermediate layer, the fiber structure is impregnated with a treatment liquid containing titanium peroxide showing properties while changing the state from the sol state to the gel state. After that, squeeze it with a mangle roll and fix it at a temperature of 200 ° C or less. Alternatively, a fiber structure having a titanium peroxide layer (intermediate layer) is formed by adjusting this treatment liquid to an appropriate viscosity, applying it with a knife coater or a gravure roll coater, and then fixing it at a temperature of 200 ° C. or less. Is obtained.

【0038】

Further, by forming a vapor phase film on the fiber structure by the PVA method and fusing the zeolite fine particles, a fiber structure having a layer of zeolite fine particles can be obtained.

【0039】

After impregnating the fiber structure in a treatment liquid containing zeolite fine particles and a water-soluble silicone-based resin or fluorine-based resin, it is squeezed with a mangle roll and fixed at a temperature of 200 ° C. or lower. Alternatively, by adjusting this aqueous solution to an appropriate viscosity, applying it with a knife coater or gravure roll coater, and then fixing it at a temperature of 200 ° C or less, a zeolite fine particle layer fixed with a silicone-based or fluorine-based resin ( A fiber structure having an intermediate layer) is obtained.

【0040】

To make the reaction more stable, add alcohol, hydrochloric acid, sulfuric acid, nitric acid, etc. to the aqueous solution of alkyl silicate to adjust the pH to 2-4. Then stir this solution well. After impregnating the fiber structure with this solution, it is squeezed with a mangle roll and fixed at a temperature of 200 ° C. or less. Alternatively, a fiber structure having an alkyl silicate layer (medium-sized layer) is formed by adjusting this aqueous solution to an appropriate viscosity, applying it with a knife coater or a gravure roll coater, and then fixing it at a temperature of 200 ° C. or less. Is obtained.

【0041】

The fiber structure obtained by the above method is impregnated with an aqueous dispersion of a composite oxide of titanium and silicon, and a pad-dry-cure step is performed, so that the photocatalyst can be fixed to the fiber.

【0042】

Further, it can also be fixed by mixing a silicone-based or fluorine-based resin with an aqueous dispersion of a composite oxide of titanium and silicon.

【0043】

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples. First, the following method was used for the quality evaluation in the examples. (Washing) Using the automatic reversing swirl type electric washing machine VH-3410 (manufactured by Toshiba Corporation), wash with commercially available detergent 0.2%, temperature 40 ± 2 ° C, bath ratio 1:50 for 5 minutes with strong reversal, and then wash. The operation of rinsing for 2 minutes while draining and overflowing was repeated twice, and this was regarded as one washing. (Evaluation of deodorant property by detector tube method) Ammonia gas was put into a 500 ml container containing 10 g of the sample so that the initial concentration was 200 ppm, sealed, left for 1 hour, and then the residual ammonia concentration was measured with a gas detector tube. ..

【0044】

Acetaldehyde 200ppm-1 hour later in a similar manner. Methyl mercaptan 60ppm-The residual gas concentration after 3 hours was measured. (Evaluation of deodorant olfaction against cigarette odor) Place a 500 ml glass Erlenmeyer flask with the entrance down, place a smoking cigarette directly under the entrance for 5 seconds, and then quickly lay the Erlenmeyer flask sideways to sample 3 g. Was put in and sealed with a glass stopper. After leaving for 1 hour, the glass stopper was opened, and 10 people were sensory-evaluated by smelling the residual odor. The odor at that time was evaluated by the following evaluation points, and the average value was calculated.

【0045】

5: Strong smell 4: Strong smell 3: Easy to detect 2: A weak odor that tells you what the odor is 1: Odorless (Antibacterial evaluation method) A unified test method was adopted as the evaluation method, and a clinical isolate of Staphylococcus aureus was used as the test cells. The test method was as follows: the above test bacteria were poured into a sterilized test cloth, the viable cell count after culturing for 18 hours was measured, the bacterial count relative to the cultured bacterial count was determined, and the following criteria were followed. Under the condition of log (B / A)> 1.5, log (B / C) was defined as the difference in the increase / decrease in the number of bacteria, and 2.2 or more was regarded as acceptable.

【0046】

However, A represents the number of bacteria dispersed and recovered immediately after inoculation of the unprocessed product, B represents the number of bacteria dispersed and recovered after culturing the unprocessed product for 18 hours, and C represents the number of bacteria dispersed and recovered after culturing the processed product for 18 hours. (Anti-fouling evaluation method) Step 1: Put 0.2 g of the contaminant shown in Table 1, a sample of 10 cm in length and 16 cm in width, and one rubber tube for ICI pilling, which has been dried at 100 ° C for 2 hours in a polyethylene bag (20 liters). Inflate the bag with 20 ° C x 65% RH air (make it about 10 liters) and secure it with a rubber band.

【0047】

[table 1]

<img file="JP2000110064A_D0001.tif" />【0048】

Step 2: Place the polyethylene bag from step 1 in the ICI tester box and rotate for 1 hour. Then take out the sample. Step 3: Wash the treated sample once under standard washing conditions. Repeat steps 1 to 3 two more times. Step 4: As described above, measure the L value of the sample in which the contaminants have been attached and washed 10 times and the untreated sample with a colorimeter, and calculate the L value. Example 1 A fiber fabric containing 0.35% by weight of inert titanium oxide having an average particle size of 0.3 μm, having a flat cross-sectional shape and having a deformed cross-sectional coefficient of 1.5, consisting of 65% by weight of polyester and 35% by weight of cotton, is produced under normal processing conditions. Smelting, drying, intermediate setting and dyeing were performed.

【0049】

Next, Titanium tetrachloride TiCl₄To the 30% by weight solution of the above, add a 5% by weight solution of sodium hydroxide NaOH, leave it for a while, and then titanium hydroxide Ti (OH).₄Got This was treated with 25% by weight hydrogen peroxide solution to obtain an amorphous titanium peroxide sol. Soak the dyed fiber fabric in it, squeeze it with a mangle roll at 80% by weight, dry it at 120 ° C for 2 minutes, and then heat it at 190 ° C for 1 minute to make non-crystalline titanium peroxide particles on the fiber surface. A fiber fabric having a layer was obtained.

【0050】

Next, this fiber cloth is used as a titanium-silicon composite oxide aqueous dispersion (particle size 12 nm, specific surface area 150 m).²/ g, manufactured by Nippon Shokubai Co., Ltd .: Treatment liquid A), squeezed with a mangle roll, dried at 100 ° C for 1 minute, heat-treated at 195 ° C for 30 seconds, and treated with a photocatalyst. Got The amount of the photocatalyst attached was 1.8% by weight with respect to the fiber fabric. The deodorant property, antibacterial property, antifouling property, etc. of this fiber cloth were evaluated, and the results are shown in Table 2. Example 2 Zeolite fine particles were vapor-phase-coated and fused to the dyed fiber fabric of Example 1 by the PVD method. Then, using the treatment liquid A, it was processed in the same manner as in Example 1 to obtain a treatment cloth having a photocatalyst. The amount of the photocatalyst attached was 0.8% by weight with respect to the fiber cloth. The deodorant property, antibacterial property, antifouling property, etc. of this fiber cloth were evaluated, and the results are shown in Table 2. Example 3 In order to form an intermediate layer in which zeolite fine particles are fixed with a silicone resin, the following treatment liquid is prepared, then the dyed fiber cloth of Example 1 is impregnated with the treatment liquid, squeezed with a mangle roll, and 100 ° C. After drying for 1 minute at 195 ° C. for 30 seconds, the treatment cloth A was processed in the same manner as in Example 1 to obtain a treated cloth having a photocatalyst. The amount of the photocatalyst attached was 0.4% by weight with respect to the fiber cloth. The deodorant property, antibacterial property, antifouling property, etc. of this fiber cloth were evaluated, and the results are shown in Table 2.

【0051】

Treatment liquid for intermediate layer Toray Silicone SD8000 (manufactured by Toray Dokoning Silicone Co., Ltd.) 20% by weight 25% by weight of methanol Purified water 32% by weight Hydrochloric acid 3% by weight Zeolite fine particles 20% by weight Example 4 After stirring the following treatment liquid, it was adhered to the surface of the dyed fiber cloth of Example 1 with a gravure roll, and then heat-treated at 185 ° C. for 1 minute. Next, using the treatment liquid A of Example 1, processing treatment was performed in the same manner as in Example 1.

【0052】

Treatment liquid for intermediate layer Methyl silicate CLG-520 (manufactured by Kyoeisha Chemical Co., Ltd.) 20.5% by weight Methanol 8.5% by weight Pure water 70.0% by weight Sulfuric acid (20%) 1.0 weight% The amount of the photocatalyst adhered to the obtained treated cloth having the photocatalyst was 1.6% by weight. The deodorant property, antibacterial property, antifouling property, etc. of this fiber cloth were evaluated, and the results are shown in Table 2. Examples 5-8 Using the fiber fabrics having the respective intermediate layers of Examples 1 to 4, these fabrics were impregnated with the following treatment liquid, squeezed with a mangle roll, dried at 100 ° C for 1 minute, and then dried at 195 ° C for 30 seconds. Heat treatment was performed to obtain treated cloths having four types of photocatalysts. The amount of the photocatalyst attached to these treated fabrics was 1.4% by weight, respectively, with respect to the fiber fabrics. The deodorant property, antibacterial property, antifouling property, etc. of this fiber cloth were evaluated, and the results are shown in Table 2.

【0053】

Photocatalytic treatment liquid Lumiflon LF200C (manufactured by Asahi Glass Co., Ltd.) 16% by weight Isocyanate-based curing agent 4% by weight Titanium-silicon composite oxide aqueous dispersion 30% by weight Toluene 50% by weight Comparative example 1 The fiber cloth used in Example 1 at the time of dyeing was evaluated for deodorant property, antibacterial property, antifouling property, etc., and the results are shown in Table 2.

【0054】

[Table 2]

<img file="JP2000110064A_D0002.tif" />【0055】

As is clear from Table 2, those of Examples 1 to 8 exhibit a well-balanced and excellent level of function in terms of deodorant property, antibacterial property and antifouling property as compared with those of Comparative Examples. It can be seen that it has excellent durability.

【0056】

[Effect of the invention]

According to the present invention, it is possible to provide a fiber structure having durable deodorant, antibacterial, antifungal and antifouling functions which has not been conventionally provided. In particular, in terms of deodorant property, it is possible to achieve an odor prevention effect that has not been obtained by conventional techniques.