Functional fiber structure

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 a durable deodorant, antibacterial, antifungal and antifouling function and an excellent water repellent function, which have not been conventionally provided. In particular, in terms of deodorant properties, it is a woven fabric that has an unprecedented odor prevention effect on the woven fabric. More specifically, the present invention can be widely applied to applications such as clothing, sheet materials, umbrella fabrics and shoes.

【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 with deodorant, antibacterial, antifungal, antifouling, and water repellent treatments have been put into practical use in each field of clothing, food and housing. ing. In particular, in the field of clothing, various deodorant, antibacterial, antifouling, and water-repellent 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, antifungal and antifouling treatments, it is kneaded into the raw yarn, treated in the spinning process, and treated during and after dyeing. However, in this method, in order to perform processing that satisfies deodorant, antibacterial, antifungal, 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. Zinc oxide deodorant itself is basic, Mechirumerukaputa a malodor acidic emissions, but converted into odorless substances to neutralize the like hydrogen sulfide, is powerless against malodor neutral. 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.

【0005】

On the other hand, deodorants using physical adsorption such as activated carbon and silica are also known. These collect the malodorous components in the deodorant and reduce the concentration of the surroundings, but since the malodorous components are only collected in the deodorant and are not decomposed, the total amount of the malodorous components does not decrease. Therefore, a deodorant utilizing physical adsorption is 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 the odorous components in the air by decomposing or adsorbing, but the deodorized fiber fabric rather adsorbs the 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 fabrics that have not been deodorized are often more effective in preventing odors.

【0008】

It can be expected that if the titanium oxide photocatalytic semiconductor is fixed to the fiber, functions such as deodorization, antibacterial, antifungal and antifouling can be obtained, but some kind of binder resin is required to fix the titanium oxide photocatalytic semiconductor 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 photocatalytic semiconductor. , There was a problem such as a foul odor.

【0009】

Further, the fiber itself to which the titanium oxide photocatalytic semiconductor is applied may deteriorate, and problems such as coloring, a decrease in strength, and generation of a decomposition product having a low molecular weight may cause a bad odor. The technique of using it to impart functions such as deodorization has not yet been put into practical use. Conventionally, as an example in which a titanium oxide photocatalytic semiconductor 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 oxidation.

【0010】

[Problems to be Solved by the Invention]

The present invention solves the above-mentioned conventional problems, and is a fiber having excellent deodorizing, antibacterial, antifungal and antifouling functions and excellent water repellent function, which is not discolored or deteriorated during use and is durable. The purpose is to provide a structure.

【0011】

[Means for solving problems]

One aspect of the fiber structure of the present invention has at least one layer selected from the group consisting of a non-crystalline titanium peroxide particle layer, a zeolite layer and an alkyl silicate layer on the surface of the fiber, and the layer of the fiber structure. It is a fiber structure having a photocatalytic semiconductor on its surface and being provided with a water repellent.

【0012】

Another aspect of the fiber structure of the present invention is a fiber structure having a microencapsulated photocatalytic semiconductor on the surface of the fiber and to which a water repellent is applied.

【0013】

Yet another aspect of the present invention is clothing, sheet materials, umbrella fabrics or shoes made of any of the above fibrous structures.

【0014】

BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, the surface of the fiber includes, and is not limited to, the surface of each single fiber constituting the fiber, the surface of the fiber bundle, or the surface of one surface of the fiber structure. ..

【0015】

Such a water repellent can be used without particular limitation. For example, fluorine-based compounds, silicone-based compounds, paraffin-based compounds, ethyleneurea-based compounds, zirconium-based compounds, and methylolamide-based compounds can be used, but among them, they have various functions such as oil repellency in addition to water repellency. It is preferable to use a fluorine-based compound.

【0016】

The amount of the water repellent attached is preferably 0.1% owf or more with respect to the fiber structure in terms of water repellency and the effects of other functions, and is preferably 30% owf or less from the viewpoint of preventing rough hardening of the texture. 2-20% owf is more preferred.

【0017】

Such a water repellent may be deteriorated and its durability may be deteriorated when it is processed by itself, and finally its water repellency and other functions may be deteriorated. It is preferable to use a cross-linking agent in combination. As the cross-linking agent, at least one of a melamine-based resin, a blocked isocyanate-based compound (polymerization), an imine-based resin, and the like can be used. The blending amount of the cross-linking agent is preferably 0.01 to 20% owf, more preferably 0.01 to 20% owf, with respect to the fiber structure. The water repellent may further contain a binder resin, and acrylic resin, urethane resin, silicone resin and the like can be used.

【0018】

Post-processing such as padding, dipping method, spraying method, coating method and the like can be adopted as the applying method when treating the fiber structure with the treatment liquid containing the water repellent, and these are applied. The method will also include heat treatment. The heat treatment referred to here means a dry heat treatment or a wet heat treatment. Moist heat treatment includes steam treatment. For the steam treatment, normal pressure saturated steam treatment, heating steam treatment, high pressure steam treatment and the like can be adopted. The temperature of the dry heat treatment or the wet heat treatment is preferably about 100 to 200 ° C. If the heat treatment temperature is less than 100 ° C, the durability of water repellency tends to be insufficient, while if it exceeds 200 ° C, the fiber structure tends to yellow. In addition, other processing agents such as a softening agent, a water absorbing agent, an antistatic agent, and a hard finishing agent may be added to the treatment liquid.

【0019】

The fiber structure referred to in the present invention is synthetic regardless of its structure and shape as long as it contains fibers such as woven fabrics, knitted fabrics, and non-woven fabrics, as well as strips, strings, and threads. It includes fibers, natural fibers such as cotton, wool and silk, or semi-synthetic fibers such as rayon and tencel.

【0020】

From the viewpoint of functionality, the fiber structure of the present invention is preferably composed mainly of polyester fibers, preferably composed of 50% by weight or more by weight, more preferably 70% by weight or more, and 100% by weight. Is even more preferable.

【0021】

Further, the polyester fiber preferably contains inert titanium oxide. The inactive titanium oxide used here refers to titanium oxide used as a matting agent in the production of polyester-based synthetic fibers, and is inactive with respect to light of a specific wavelength without being particularly excited by ultraviolet rays. It is titanium oxide. By adding this inert titanium oxide to the polyester fiber, the inorganicity is enhanced by adding the inorganic titanium oxide to the 100% organic polyester fiber, and the photocatalytic semiconductor used in the upper layer It has the function of reducing the effect of redox action on polyester fibers. This inert titanium oxide is added at the time of polymerization of the polyester fiber, and the particle size is preferably 1.0 μm or less from the viewpoint of yarn-making property and yarn physical characteristics. The amount of the inert titanium oxide added is preferably 0.3 to 5% by weight from the viewpoint of yarn-making property and yarn physical characteristics. More preferably, it is in the range of 0.5 to 4% by weight.

【0022】

In the present invention, polyester fibers having a modified cross section and having a modified cross section coefficient of 1.2 to 2 are preferably used. More preferably, it is in the range of 1.3 to 1.8. The deformed cross-section coefficient referred to here is a value obtained by dividing the outer circumference of the deformed cross-section yarn by the outer circumference of a perfect circular cross-section yarn having the same cross-sectional area. The larger the value, the larger the surface area per yarn weight, and the larger the area where the photocatalytic semiconductor can exist, so that the effect of the present invention is increased.

【0023】

Polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate and the like are generally used as polyester fibers. Further, as the third component, isophthalic acid, 5-sulfoisophthalic acid, metoxypolyoxyethylene glycol and the like may be copolymerized.

【0024】

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 alkyl silicate layer on the surface of the fiber to which the water repellent agent is applied. This layer is an intermediate layer that protects the fiber structure from oxidative decomposition of the photocatalytic semiconductor. Here, the surface of the fiber includes, and is not limited to, the surface of each single fiber constituting the fiber, the surface of the fiber bundle, or the surface of one surface of the fiber structure.

【0025】

Specifically, titanium peroxide or peroxotitanic acid, or a non-crystalline (amorphous) titanium peroxide particle layer containing a metal oxide other than titanium, a zeolite layer, and an alkyl silicate layer are used as intermediate layers.

【0026】

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

【0027】

Next, the zeolite layer can be formed by itself, 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.

【0028】

Such a silicone resin is a condensation-crosslinked resin belonging to the classification of silicone resin or silicone varnish, and is obtained by condensing a condensation-crosslinked resin such as tetraethoxysilane or methyltrimethoxysilane alone or by condensing several kinds of formulations. .. 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.

【0029】

Further, as the fluororesin, vinyl ether and / or vinyl ester and a fluoroolefin polymerizable compound are preferably used because they have very excellent properties. Polyvinyl fluoride, polyvinyl tetrafluoroethylene, ethylene tetrafluoroethylene-perfluoroalkyl vinyl ester, vinyl ester-fluoroolefin and the like are preferable because they are less decomposed and deteriorated. Unlike acrylic resins, urethane resins, and epoxy resins, which are usually used as binder resins, such silicone-based resins and fluorine-based resins contain almost no hydrocarbon groups that 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 FC bonds, and a small amount of methyl groups and phenyl groups are contained as hydrocarbons in the terminal groups and side chains.

【0030】

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

【0031】

[(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. Such alkyl groups are straight or branched saturated alkyls such as methyl, ethyl, propyl and isopropyl.

【0032】

The alkyl silicate may be a mixture of one or two kinds, but one having a methyl group is preferable in order to enhance the inorganic property. These compounds easily undergo a dehydration reaction in the presence of heat to form a polysiloxane film. Alkyl silicate may be commercially available, and 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.

【0033】

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.

【0034】

The fiber structure of the present invention has a photocatalytic semiconductor on the surface of the above-mentioned intermediate layer.

【0035】

The photocatalytic semiconductor has a property of being excited by ultraviolet rays and oxidatively decomposing an organic substance by a strong oxidizing force, and specifically, a semiconductor having a crystalline structure called anatase type or rutile type. One example of utilizing the characteristics of this photocatalytic semiconductor is deodorant property. Many processing technologies with deodorant functions have been introduced so far, but as shown in the "conventional technology" column, only a specific odor is deodorized, and the odor remains, persistence, and durability. There was a problem of poor sex. However, photocatalytic semiconductors deodorize tobacco odors and sweat odors, which have been difficult until now, in a well-balanced manner, and also oxidatively decompose the odors, so that an unprecedented excellent effect of preventing odors can be obtained. It has also been confirmed that it has an antifouling effect that decomposes and removes colored substances such as tobacco tar. Furthermore, photocatalytic semiconductors have bactericidal activity against MRSA bacteria, Escherichia coli, Staphylococcus aureus, etc. due to their oxidizing power. If the particle size of the photocatalytic semiconductor is too large or the specific surface area is small, the decomposition rate of organic substances, especially bacteria, will decrease. Therefore, the particle size is 1 to 20 nm and the specific surface area is 100 to 300 m.²It is preferably / g.

【0036】

When a photocatalytic semiconductor is irradiated with light, the photocatalytic semiconductor is excited and decomposes harmful substances by oxidation and reduction actions, and exhibits deodorizing, antibacterial, antifungal and antifouling effects. The photocatalytic semiconductor used in the present invention includes a composite oxide of titanium and silicon, TiO.₂, ZnO, SrTiO₃, CdS, CdO, CaP, InP, In₂O₃, CaAs, BaTiO₃, K₂NbO₃, Fe₂O₃, Ta₂O₅, WO₃, SbO₂, Bi₂O₃, NiO, Cu₂O, SiC, SiO₂, MoS₂, MoS₃, InPb, RuO₂, CeO₂Etc., and single or a combination of two or more of these photocatalytic semiconductors can be used. In particular, titanium oxide, which has a high photocatalytic action, is chemically stable, and is harmless, is more preferable. Titanium oxide also includes titanium hydroxide-containing hydrated titanium oxide, titanium hydroxide, metatitanic acid, and orthotitanic acid. Among them, titanium oxide having an anatase-type crystal form has excellent photocatalytic activity, and its preferable particle size is 1 to 20 nm. The particle size of a photocatalytic semiconductor such as titanium oxide is calculated from the price range of the peak obtained by powder X-ray analysis using the following Scheller's formula.

【0037】

Lc = 0.9λ / (W cosθ) (Lc is the particle size (nm), λ is the wavelength of the X-ray (nm), W is the half width of the peak (rad), and θ is the angle of the peak position.) Further, the photocatalytic semiconductor such as titanium oxide may contain other metals such as iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver, gold and platinum, or compounds of other metals, particularly zinc oxide. Titanium oxide carrying zinc hydroxide and / or zinc hydroxide is more preferable because it has both the ability to adsorb harmful substances and the ability to decompose due to photocatalytic action.

【0038】

The amount of the photocatalytic semiconductor attached to the fiber fabric is preferably in the range of 0.03 to 15% by weight in view of the balance between functionality and texture. More preferably, it is 0.05 to 10% by weight.

【0039】

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

【0040】

As described above, the fiber to which the water repellent is applied is used as a fiber structure such as a cloth, an intermediate layer is formed therein, and then a photocatalytic semiconductor is applied.

【0041】

When the titanium peroxide particle layer is used, the intermediate layer is formed after impregnating the fiber structure with a treatment liquid containing titanium peroxide showing properties during the change from the sol state to the gel state. , Squeeze with a mangle roll and fix at a temperature of 200 ° C or less. Alternatively, the titanium peroxide layer can be formed by adjusting this treatment liquid to an appropriate viscosity, applying it with a knife coater, a gravure roll coater, or the like, and then fixing it at a temperature of 200 ° C. or less.

【0042】

In the case of a zeolite layer, it can be formed by forming a vapor phase film on the fiber structure and fusing the zeolite fine particles by the PVA method.

【0043】

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

【0044】

In the case of an alkyl silicate layer, first add alcohol, hydrochloric acid, sulfuric acid, nitric acid, etc. to the aqueous solution of alkyl silicate to make the reaction more stable, and adjust the pH to 2 to 4, and make this solution well. Stir. Then, 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, it can be formed by adjusting this aqueous solution to an appropriate viscosity, applying it with a knife coater, a gravure roll coater, or the like, and then fixing it at a temperature of 200 ° C. or less.

【0045】

In addition, another aspect of the fiber structure of the present invention is to have a microencapsulated photocatalytic semiconductor on the surface of the fiber without using the above-mentioned intermediate layer.

【0046】

The microencapsulated photocatalytic semiconductor referred to here is a spherical substance having no or little photocatalytic action as a shell and a photocatalytic semiconductor as a nucleus. Further, it is more preferable that the shell has micropores. Further, the present invention shows a spherical substance in which fine particles of a photocatalytic semiconductor and fine particles of an inorganic substance having a larger mixing ratio and no or less photocatalytic action are mixed and contain a photocatalyst. The particle size of the microcapsules is preferably 0.1 to 10 μm. By using the microencapsulated photocatalytic semiconductor, since the photocatalyst semiconductor and the binder are not in direct contact with each other, it is possible to prevent the binder resin from being deteriorated by the strong oxidizing power of the photocatalyst semiconductor.

【0047】

If the photocatalytic semiconductor is directly adhered (mixed) with a highly organic polyurethane resin or the like, the problem of oxidative decomposition occurs as described above. This problem does not occur when microencapsulated photocatalytic semiconductors are used.

【0048】

Since the fiber structure of the present invention has deodorant, antibacterial, antifungal and antifouling functions and excellent water repellent function, deodorant, antibacterial, antifungal and antifouling by a conventional method using this fiber structure. It can be used as clothing, sheet material, umbrella cloth, and shoes, which have excellent stain function.

【0049】

[Example]

Next, the present invention will be described in more detail with reference to examples.

【0050】

The following methods were used for quality evaluation in the examples, and the results are summarized in Table 1.

【0051】

For washing, use the automatic reversing swirl type electric washing machine VH-3410 (manufactured by Toshiba Corporation) with a commercial detergent of 0.2%, a temperature of 40 ± 2 ° C, and a bath ratio of 1:50 for 5 minutes with strong reversal. After that, the operation of draining and rinsing for 2 minutes while overflowing was repeated twice, and this was regarded as one washing.

【0052】

(1) Deodorant rate (evaluation of deodorant property by detector tube method) Ammonia gas was placed in a 500 ml container containing 10 g of the sample so that the initial concentration was 200 ppm, and the mixture was sealed. After leaving for 1 hour, the residual ammonia concentration was measured with a gas detector tube.

【0053】

The residual gas concentration was measured by the same method after 200 ppm-1 hour of acetaldehyde and 60 ppm-3 hours of methyl mercaptan.

【0054】

(2) Tobacco deodorant (odor evaluation of deodorant against tobacco odor) A 500 ml glass Erlenmeyer flask was placed with the entrance facing down, and a smoking cigarette was placed directly under the entrance for 5 seconds, then the Erlenmeyer flask was quickly laid down, 3 g of the sample was added, and the sample was 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.

【0055】

5: Strong odor, 4: Strong odor, 3: Easy to detect, 2: Weak odor to understand what the odor is, 1: Finally perceptible, 0: Odorless (3) Antibacterial A unified test method was adopted as the evaluation method, and a clinical isolate of Staphylococcus aureus was used as the test cell. 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.

【0056】

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.

【0057】

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.

【0058】

(4) Antifouling property 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 air at 20 ° C x 65% RH (make it about 10 liters) and secure it with a rubber band.

【0059】

[table 1]

<img file="JP2000119958A_D0001.tif" />Step 2: Place the polyethylene bag from step 1 in the ICI tester box and rotate for 1 hour. Then take out the sample.

【0060】

Step 3: Wash the treated sample once under standard washing conditions. Repeat steps 1 to 3 two more times.

【0061】

Step 4: As described above, measure the L value of the sample in which the contaminants are attached and washed 10 times and the untreated sample with a colorimeter, and calculate the L value.

【0062】

(5) Water repellency Measured according to JIS L 1092 (spray method).

【0063】

Example 1 For women's blouses, the warp yarn contains 3.0% by weight of inert titanium oxide, and the Y-shaped cross-section yarn with a deformed cross-section coefficient of 1.4 is 75 denier 96 filament polyester yarn, and the weft yarn contains 3.0% by weight of inert titanium oxide. Using polyester yarn with 100 denier 48 filaments of Y-shaped cross-section yarn with a cross-section coefficient of 1.4, a raw machine with a woven structure of 2/3 twill, a warp density of 170 yarns / inch, and a weft yarn density of 98 yarns / inch was created under normal conditions. , Smelting, drying, intermediate set, and dyeing.

【0064】

Next, Titanium tetrachloride TiCl₄Titanium hydroxide Ti (OH) after adding a 5% solution of sodium hydroxide NaOH to the 30% solution of₄Got This was treated with 25% hydrogen peroxide solution to obtain an amorphous titanium peroxide sol. This titanium peroxide sol was adjusted to 0.5% by weight. The cloth was dipped in this liquid and squeezed with a mangle. The squeezing ratio at this time was 90% with respect to the cloth. After that, it was dried at 120 ° C. and weighed, and the amount of titanium peroxide adhered was calculated. As a result, it was 0.45% by weight based on the fiber fabric.

【0065】

Next, a composite oxide of titanium and silicon with photocatalytic functionality (SX-T1: manufactured by Nippon Catalyst Co., Ltd.) was added in an amount of 0.5% by weight and a silicone resin BY22-826 (manufactured by Toray Dow Corning Silicone Co., Ltd.). ) Was suspended in pure water to a concentration of 4.0% by weight to prepare a slurry. The cloth was dipped in this adjusting liquid and squeezed with a mangle. At this time, the squeezing ratio was 90% with respect to the cloth. After that, it was dried at 120 ° C. and weighed, and the amount of the composite oxide of titanium and silicon was calculated. As a result, it was 0.5% by weight with respect to the fiber fabric.

【0066】

Next, a treatment liquid having the following composition was applied by a padding method. At this time, the drawing ratio was 90%, and after dry heat treatment at 130 ° C × 20 minutes, dry heat treatment was performed at 170 ° C × 3 minutes.

【0067】

Water repellent: Asahi Guard AG-930 (manufactured by Asahi Glass Co., Ltd.) 10% Cross-linking agent: Sumitex Resin M-3 (manufactured by Sumitomo Chemical Co., Ltd.) 3% Catalyst: Sumitex Accelerator ACX (manufactured by Sumitomo Chemical Co., Ltd.) 1% The above% means% owf after drying. The cross-linking agent is a melamine resin.

【0068】

Example 2 For women's blouses, the warp yarn contains 3.0% by weight of inert titanium oxide and the cross-sectional shape is round 75 denier 96 filament polyester yarn, and the weft yarn contains 3.0% by weight of inert titanium oxide and the cross-sectional shape is round. A woven fabric was prepared with the same weaving structure as in Example 1 using 100 denier 48 filament polyester yarn, and the weaving density at that time was almost the same as that in Example 1. Next, refining, drying, intermediate setting, and dyeing were performed under the same conditions as in Example 1. Next, a fiber fabric having a titanium peroxide particle layer as an intermediate layer under the same processing agent and processing conditions as in Example 1 and a layer of a composite oxide of titanium and silicon having photocatalytic functionality on the upper layer was prepared. did. At this time, the amount of the composite oxide of titanium and silicon adhered was 0.5% by weight, which was the same as in Example 1. Further, water repellent treatment was performed under the same conditions as in Example 1. Example 3 Using the dyed woven fabric used in Example 1, zeolite fine particles were vapor-phase coated on the fiber fabric by the PVD method and fused. Next, a fiber fabric having a layer of a composite oxide of titanium and silicon having the same photocatalytic functionality as in Example 1 was prepared. At this time, the amount of the composite oxide of titanium and silicon adhered was 0.5% by weight, which was the same as in Example 1. Further, water repellent treatment was performed under the same conditions as in Example 1. Example 4 Using the dyed woven fabric used in Example 2, a fiber fabric was prepared by using the same processing agent and processing method as in Example 3 for the intermediate layer and the upper layer portion. At this time, the amount of the composite oxide of titanium and silicon adhered was 0.5% by weight, which was the same as in Example 1. Further, water repellent treatment was performed under the same conditions as in Example 1.

【0069】

Example 5 Using the dyed woven fabric used in Example 1, as an intermediate layer in which zeolite fine particles are fixed with a silicone resin. BY22-826 (manufactured by Toray Dow Corning Silicone Co., Ltd.) 20% by weight Zeolite fine particles 20% by weight Water 60% by weight After preparing the treatment liquid, the fiber fabric was impregnated with the treatment liquid, squeezed with a mangle roll, dried at 100 ° C for 1 minute, and then heat-treated at 195 ° C for 30 seconds. Next, a fiber fabric having a layer of a composite oxide of titanium and silicon having the same photocatalytic functionality as in Example 1 was prepared. At this time, the amount of the composite oxide of titanium and silicon adhered was 0.5% by weight, which was the same as in Example 1. Further, water repellent treatment was performed under the same conditions as in Example 1. Example 6 Using the dyed woven fabric used in Example 1, as an intermediate layer in which zeolite fine particles are fixed with a fluororesin. Lumiflon LF200C (manufactured by Asahi Glass Co., Ltd.) 20% by weight Isocyanate-based curing agent 4% by weight Zeolite fine particles 20% by weight Toluene 56% by weight After preparing the treatment liquid, the fiber fabric was impregnated with the treatment liquid, squeezed with a mangle roll, dried at 100 ° C for 1 minute, and then heat-treated at 195 ° C for 30 seconds. Next, a fiber fabric having a layer of a composite oxide of titanium and silicon having the same photocatalytic functionality as in Example 1 was prepared. At this time, the amount of the composite oxide of titanium and silicon adhered was 0.5% by weight, which was the same as in Example 1. Further, water repellent treatment was performed under the same conditions as in Example 1.

【0070】

Example 7 Using the dyed woven fabric used in Example 1, as the formation of an intermediate layer of alkyl silicate. 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% by weight After preparing the treatment liquid, the fiber fabric was impregnated with the treatment liquid, squeezed with a mangle roll, dried at 100 ° C for 1 minute, and then heat-treated at 195 ° C for 30 seconds. Next, a fiber fabric having a layer of a composite oxide of titanium and silicon having the same photocatalytic functionality as in Example 1 was prepared. At this time, the amount of the composite oxide of titanium and silicon adhered was 0.5% by weight, which was the same as in Example 1. Further, water repellent treatment was performed under the same conditions as in Example 1. Example 8 Using the dyed woven fabric used in Example 2, a fiber fabric was prepared by using the same processing agent and processing method as in Example 7 for the intermediate layer and the upper layer portion. At this time, the amount of the composite oxide of titanium and silicon adhered was 0.5% by weight, which was the same as in Example 1. Further, water repellent treatment was performed under the same conditions as in Example 1.

【0071】

Example 9 For women's blouses, Y-shaped cross-sectional yarn 75 denier 96 filament polyester yarn that does not contain inert titanium oxide in the warp and has a deformed cross-sectional coefficient of 1.4, and polyester yarn that does not contain inert titanium oxide in the weft and has a deformed cross-sectional coefficient of 1.4. Using 100 denier 48 filament polyester yarn of Y-shaped cross section, a raw machine with a woven structure of 2/3 twill, a warp density of 170 yarns / inch, and a weft yarn density of 98 yarns / inch was created, and scoured and dried under normal conditions. , Intermediate set, and dyeing. Next, a fiber fabric was prepared by using the same processing agent and processing method as in Example 1 for the intermediate layer and the upper layer portion. At this time, the amount of the composite oxide of titanium and silicon adhered was 0.5% by weight, which was the same as in Example 1. Further, water repellent treatment was performed under the same conditions as in Example 1.

【0072】

Example 10 Using the dyed woven fabric used in Example 9, a fiber fabric was prepared by using the same processing agent and processing method as in Example 3 for the intermediate layer and the upper layer portion. At this time, the amount of the composite oxide of titanium and silicon adhered was 0.5% by weight, which was the same as in Example 1. Further, water repellent treatment was performed under the same conditions as in Example 1.

【0073】

Example 11 Using the dyed woven fabric used in Example 9, a fiber fabric was prepared by using the same processing agent and processing method as in Example 5 for the intermediate layer and the upper layer portion. At this time, the amount of the composite oxide of titanium and silicon adhered was 0.5% by weight, which was the same as in Example 1. Further, water repellent treatment was performed under the same conditions as in Example 1.

【0074】

Example 12 Using the dyed woven fabric used in Example 9, a fiber fabric was prepared by using the same processing agent and processing method as in Example 6 for the intermediate layer and the upper layer portion. At this time, the amount of the composite oxide of titanium and silicon adhered was 0.5% by weight, which was the same as in Example 1. Further, water repellent treatment was performed under the same conditions as in Example 1.

【0075】

Example 13 Using the dyed woven fabric used in Example 9, a fiber fabric was prepared by using the same processing agent and processing method as in Example 7 for the intermediate layer and the upper layer portion. At this time, the amount of the composite oxide of titanium and silicon adhered was 0.5% by weight, which was the same as in Example 1. Further, water repellent treatment was performed under the same conditions as in Example 1.

【0076】

Example 14 Using the dyed woven fabric used in Example 1, a fiber cloth was prepared in the intermediate layer by the same processing agent and processing method as in Example 5. Furthermore, as the upper layer, porous SiO manufactured by Suzuki Yushi Kogyo Co., Ltd.₂Is TiO₂Prepare a toluene solution consisting of 2% by weight of microcapsules having a diameter of about 5 μm, 20% by weight of fluororesin Lumiflon LF200C (manufactured by Asahi Glass Co., Ltd.), and 4% by weight of isocyanate-based cross-linking agent. A sample was obtained. The amount of the photocatalyst attached at this time was 0.5% by weight. Further, water repellent treatment was performed under the same conditions as in Example 1.

【0077】

Comparative example 1 The dyed fiber fabric used in Example 1 was used for evaluation.

【0078】

Comparative example 2 The dyed fiber fabric used in Example 2 was used for evaluation.

【0079】

Comparative example 3 The dyed fiber fabric used in Example 9 was used for evaluation.

【0080】

Comparative example 4 The dyed fiber fabric used in Example 1 is provided with a titanium peroxide particle layer as an intermediate layer under the same processing agents and processing conditions as in Example 1, and titanium and silicon having photocatalytic functionality are added to the upper layer. A fiber fabric having a layer of composite oxide was prepared. At this time, the amount of the composite oxide of titanium and silicon adhered was 0.5% by weight, which was the same as in Example 1.

【0081】

Comparative example 5 The dyed fiber fabric used in Example 2 is provided with a titanium peroxide particle layer as an intermediate layer under the same processing agents and processing conditions as in Example 1, and titanium and silicon having photocatalytic functionality are added to the upper layer. A fiber fabric having a layer of composite oxide was prepared. At this time, the amount of the composite oxide of titanium and silicon adhered was 0.5% by weight, which was the same as in Example 1.

【0082】

Comparative example 6 The dyed fiber fabric used in Example 9 is provided with a titanium peroxide particle layer as an intermediate layer under the same processing agents and processing conditions as in Example 1, and titanium and silicon having photocatalytic functionality are added to the upper layer. A fiber fabric having a layer of composite oxide was prepared. At this time, the amount of the composite oxide of titanium and silicon adhered was 0.5% by weight, which was the same as in Example 1.

【0083】

Comparative example 7 The dyed fiber fabric used in Example 1 with a water-repellent finish was used for evaluation.

【0084】

Comparative Example 8 The dyed fiber fabric used in Example 2 with a water-repellent finish was used for evaluation.

【0085】

Comparative Example 9 The dyed fiber fabric used in Example 9 with a water-repellent finish was used for evaluation.

【0086】

[Table 2]

<img file="JP2000119958A_D0002.tif" />【0087】

[Effect of the invention]

According to the present invention, a polyester having a water-repellent finish to have a water-repellent function, a specific intermediate layer on the fiber surface that is not easily deteriorated by a photocatalyst, and a photocatalytic semiconductor having a photocatalytic function on the intermediate layer. It is a fiber fabric. The fibrous fabric has a durable deodorant, antibacterial, antifungal and antifouling function and an excellent water repellent function, which have never been seen before. In particular, in terms of deodorant property, there is an effect of preventing the odor of textile fabrics, which has never been seen before.