Fiber fabric having deodorizing, antimicrobial and stain-proof functions and its production

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

[Technical field to which the invention belongs]

The present invention relates to a fiber fabric having deodorant, antibacterial and antifouling functions and a method for producing the same. In particular, the present invention relates to a fabric containing organic fibers having deodorant, antibacterial and antifouling functions, which can be widely applied to interior materials such as clothing and curtains, and sanitary materials, and a method for producing the same.

【0002】

[Conventional technology]

It has long been expected that if a titanium oxide photocatalyst is fixed to a fiber, a fabric having functions such as deodorization, antibacterial action, and antifouling can be obtained due to its oxidative decomposition ability, and the titanium oxide photocatalyst is fixed on glass or ceramic by baking. It is known that a titanium oxide photocatalyst is kneaded into a resin before spinning and the titanium oxide photocatalyst is immobilized on a synthetic fiber.

【0003】

However, although there is no problem when the photocatalyst is immobilized on the surface of an inorganic substance such as the surface of ceramics or glass that does not decompose due to the oxidation of the titanium oxide photocatalyst, the titanium oxide photocatalyst is applied to the organic fibers used for interiors and clothing. When fixed, the strong oxidative decomposition power of the titanium oxide photocatalyst decomposes fiber treatment agents such as fibers, dyes, and surfactants, and the generation of low molecular weight decomposition products produces a foul odor. There was a problem contrary to the function that should be possessed, which was the biggest obstacle to practical use.

【0004】

In addition, various methods for immobilizing the titanium oxide photocatalyst on organic fibers have been studied. For example, a resin that is not easily oxidatively decomposed by the titanium oxide photocatalyst is used as a binder for immobilization of the titanium oxide photocatalyst. However, even for binders that are not easily oxidatively decomposed, if the resin contains organic substances such as hydrocarbons, the fibers are decomposed by the strong oxidizing power of the titanium oxide photocatalyst to some extent, and a foul odor is generated. Although the decrease in the strength of the fabric and the loss of titanium oxide due to the deterioration of the organic fiber fabric have been improved, the effect of suppressing the generation of foul odor is not sufficient, and further improvement is desired. The current situation.

【0005】

[Problems to be Solved by the Invention]

The present invention provides a woven fabric containing organic fibers on which a titanium oxide photocatalyst is immobilized, which has an antibacterial and antifouling function in addition to an extremely excellent deodorizing function that eliminates the above-mentioned problem of bad odor. I am aiming.

【0006】

[Means for solving problems]

In order to solve the above problems, the present invention provides a fiber fabric containing organic fibers in which a titanium oxide photocatalyst is immobilized on organic fibers coated with a melamine resin. The present invention also provides a method for producing a fiber fabric, which comprises applying a melamine resin to a fabric containing organic fibers and then applying a silicon oxide-containing sol solution containing a titanium oxide photocatalyst.

【0007】

BEST MODE FOR CARRYING OUT THE INVENTION

Examples of the organic fiber used in the present invention include synthetic fibers such as polyester fibers, polyamide fibers and acrylic fibers, regenerated / semi-synthetic fibers such as rayon and triacetate, and natural fibers such as cotton, wool and silk. Examples of the fabric containing organic fibers include woven fabrics, knitted fabrics, non-woven fabrics, etc., which are composed of the above-mentioned organic fibers alone or in combination with two or more kinds of fibers of the same type or different types or inorganic fibers other than organic fibers. Further, the fabric containing the organic fiber may be one that has been subjected to ordinary dyeing or printing.

【0008】

Further, the titanium oxide photocatalyst used in the present invention is titanium oxide capable of decomposing organic substances by exercising redox ability by being excited by light irradiation, particularly ultraviolet irradiation, and is titanium dioxide or lower order. Those in an oxidized state are preferable, and anatase-type, rutile-type, and frucite-type crystal types can be used. The particle size of 500 nm or less, particularly 50 nm or less, is preferable from the viewpoint of high photocatalytic activity.

【0009】

In the present invention, first, it is considered that the above-mentioned organic fiber is protected from oxidative decomposition by a titanium oxide photocatalyst and the generation of an unpleasant odor is suppressed, and a method and a material thereof are investigated. Also found that coating the fibers with an excellent melamine resin is extremely effective. As the melamine resin, preferably, methylol melamine produced by adding formaldehyde to melamine under alkaline conditions is used, and this methylol melamine is attached to organic fibers and then crosslinked by a condensation reaction to form a dense three-dimensional network. A melamine resin film is formed in the form of organic fibers.

【0010】

More specifically, the methylol melamine is preferably trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine and a mixture thereof, or a condensate thereof. The amount of the melamine resin that coats the organic fibers is preferably 0.1% by weight or more, preferably 1 to 5% by weight, based on the weight of the organic fibers.

【0011】

Next, when immobilizing a titanium oxide photocatalyst on an organic fiber coated with a melamine resin, a binder capable of withstanding the oxidative decomposition was searched for, and it was found that it is preferable to use silica oxide as a binder. An example of using this silicon oxide as a binder is described in JP-A-10-1879. However, in the present invention, it is significant to fix the photocatalyst on the organic fiber coated with the melamine resin with a binder composed of a sol solution of sodium oxide, and the object of the present invention can be achieved without the melamine resin film. Can't.

【0012】

Preferably, nitric acid oxide is used as a sol solution, for example, a lower alkoxysilane having 1 to 4 carbon atoms such as tetraethoxysilane or an oligomer thereof and a part in which an alkoxy group is replaced with a halogen is used as a lower alcohol. / Obtained by hydrolysis with nitric acid or hydrochloric acid in a mixed solvent of water. From this sodium oxide sol solution, an almost inorganic film can be obtained by heat treatment at 200 ° C. or lower, which is performed in the treatment of general organic fibers. The mixing ratio of the titanium oxide photocatalyst and the silicon oxide is preferably in the range of 20 to 95:80 to 5 by weight. If the ratio of the titanium oxide photocatalyst is too low, the ratio of the titanium oxide photocatalyst covered with the silicon oxide film increases, and the contact between the titanium oxide photocatalyst and the outside air is hindered, making it difficult to exert the effect, and this ratio is high. If it is too much, the titanium oxide photocatalyst cannot be sufficiently fixed and easily falls off, which is not preferable.

【0013】

Further, if the amount of the titanium oxide photocatalyst adhering to the organic fiber is too small, the decomposition rate of the malodor becomes slow, which may be impractical. If the amount of adhesion is too large, the texture of the fabric becomes hard, which is not preferable. The amount of titanium oxide photocatalyst attached to organic fibers is 0.01 to 10 g / m.²Is preferably in the range of 0.05 to 2 g / m²The range of is more preferred.

【0014】

Next, a method for producing a fiber fabric having deodorant, antibacterial and antifouling functions of the present invention will be described. First, the organic fibers are coated with a melamine resin. As a method thereof, a solution containing methylol melamine can be applied to the fabric containing organic fibers by a knife coater, a gravure coater, a spray or the like, but in order to uniformly adhere to the entire fabric, the solution containing methylol melamine is applied to the organic fibers. After impregnating the fabric containing the above, a method of squeezing with a mangle roll is preferable.

【0015】

Next, a melamine resin film is formed by a condensation reaction using a known method such as dry heat treatment or wet heat treatment. Particularly preferable methods of the condensation reaction are wet heat treatment in saturated water vapor at 100 ° C., dielectric heat treatment of microwaves, or cold batch in a wet state at room temperature as a method capable of uniformly and evenly coating the fibers in the fabric. There is a method in which the fibers are coated with a uniform melamine resin by cross-linking by a method such as treatment. When cross-linked by dry heat treatment, the melamine resin migrates due to heat, the coating on the fibers becomes uneven, and the resin is biased in the fabric, which may cause the texture to harden or whiten. Therefore, the quality of the obtained fabric may be deteriorated, and the effect of protecting the organic fiber from the oxidative decomposition of the titanium oxide photocatalyst may be reduced.

【0016】

Further, the above-mentioned cross-linking reaction is often carried out in the presence of a catalyst, and the catalyst may be added to a solution containing methylolmelamine. Examples of such catalysts include aliphatic carboxylic acids such as formic acid and acetic acid, saturated dicarboxylic acids such as acrylic acid, oxycarboxylic acids such as malic acid and tartaric acid, aminocarboxylic acids such as glutamic acid, unsaturated dicarboxylic acids such as maleic acid, and phthalates. Examples thereof include aromatic dicarboxylic acids such as acids and their organic acid salts such as ammonium, sodium and potassium or acidic organic salts such as amino hydrochlorides. In addition to organic salts, inorganic salts such as sulfuric acid, persulfuric acid, hydrochloric acid, phosphoric acid, nitric acid ammonium, sodium, magnesium and aluminum, and double salts thereof can be mentioned.

【0017】

These catalysts are preferably used in a solution containing methylolmelamine at a concentration of 0.01 to 10% by weight. Furthermore, it is preferable to use a surfactant in combination with a solution containing methylolmelamine in order to improve permeability and solution stability. Next, a sol solution of silicon oxide containing a titanium oxide photocatalyst is applied to the fabric containing the organic fibers coated with the melamine resin. As the method, a method of impregnating the sol solution with the cloth and then squeezing it with a mangle roll, or a method of adjusting the viscosity to an appropriate level and applying it with a knife coater, a gravure coater, a spray or the like can be used. After coating, it is dried at a temperature of about 50 to 150 ° C to form a film, and the titanium oxide photocatalyst is immobilized. Further, heat treatment at 200 ° C. or lower may be performed in order to improve the film strength and the adhesive strength.

【0018】

The sol solution of zinc oxide containing a titanium oxide photocatalyst contains fine particles for matting, pigments for coloring, and known deodorants such as silica gel, acidic clay, and activated charcoal for improving the efficiency of deodorizing and antibacterial functions. It may contain a odorant, a known antibacterial agent, and other additives for imparting a specific function, for example, zinc oxide for obtaining an ultraviolet shielding effect.

【0019】

[Example]

Hereinafter, the present invention will be further described based on examples. The ultraviolet intensity in the examples was measured by conveniently using Minolta's UV RADIO METERUM-1 (maximum absorption wavelength 367 nm). The wavelength of ultraviolet rays used to obtain the effects of the present invention is not particularly limited. Example 1 Metsuke 180g / m made of polyester filament²The satin woven fabric of No. 1 was dyed in beige at 130 ° C. with a disperse dye by a high-pressure dyeing machine, and used as a fiber cloth. As a treatment for protecting the organic fiber, a treatment of coating with a melamine resin was carried out as follows.

【0020】

Formulation solution 1 Sumitex Resin MC 10.00% by weight (Sumitomo Chemical Co., Ltd. Hexamethylol melamine condensate solid content 80 weight%) Malic acid 0.50% by weight Emargen 909 0.15% by weight (Nonionic surfactant manufactured by Kao Corporation Solid content 100% by weight) Water 89.35% by weight The above-mentioned compounding solution 1 was prepared, the fiber cloth was dipped in the fiber cloth, the pick-up was squeezed to 60% with a mangle roll, and then treated in saturated steam at 100 ° C. for 10 minutes. Then, it was reduced-washed with hydrosulfite and soda ash, washed with water, dried at 120 ° C., and heat-treated at 170 ° C. for 30 seconds to obtain an organic fiber cloth coated with a melamine resin. The amount of melamine resin adhered was 4.8% by weight.

【0021】

Next, the following compounding solution 2 was prepared, and 125 mesh gravure roll was used on one side of the obtained organic fiber cloth, and 8 g / m.²Was applied and dried at 120 ° C. Further, it was cured at 170 ° C. for 30 seconds to obtain a cloth on which the titanium oxide photocatalyst was fixed. Formulation 2 ST-K03 50.0% by weight (Titanium oxide photocatalyst silicon oxide sol compound solution manufactured by Ishihara Techno Co., Ltd.) (Titanium oxide photocatalyst particle size 7 nm solid content 5% by weight) (Silicon oxide solid content 5% by weight) Isopropyl alcohol 20.0% by weight Water 30.0% by weight The amount of titanium oxide photocatalyst attached is 0.2 g / m with respect to the fiber fabric.²Met. Comparative example 1 Using the same dyed fiber cloth used in Example 1, the compounding solution 2 was applied in the same manner as in Example 1 without protection treatment with a melamine resin to obtain a cloth to which a titanium oxide photocatalyst was fixed. Comparative example 2 Using the same dyed fiber cloth used in Example 1, as a treatment liquid for fiber protection, use the following compounding solution 3 instead of compounding solution 1, soak the organic fiber cloth in it, and pick up 60% with a mangle roll. After squeezing to, the cloth was dried at 120 ° C for 5 minutes and cured at 170 ° C for 3 minutes, and the compounding solution 2 was applied in the same manner as in Example 1 to fix the titanium oxide photocatalyst. A fabric was obtained.

【0022】

Formulation 3 Corcourt N-103X 100.0% by weight (Alcohol-based silicon oxide sol solution manufactured by Corcote Co., Ltd.) (Chinese oxide solid content 10% by weight) Using each of the fiber fabrics to which the titanium oxide photocatalysts of Example 1, Comparative Example 1 and Comparative Example 2 were fixed, the degree of odor generation when irradiated with ultraviolet rays was evaluated as follows.

【0023】

Each fiber cloth (10 cm × 10 cm) was placed in a separate Erlenmeyer flask of 300 mL, sealed tightly, and irradiated with ultraviolet rays on the surface coated with the titanium oxide photocatalyst at a distance of 30 cm under a 20 W ultraviolet lamp. The ultraviolet intensity on the fabric at this time is 0.8 mW / cm.²Met. After irradiation for 5 hours, the stopper was opened and the odor in the flask was evaluated by olfaction. The results of the judgment by the 6-step odor intensity display method are shown below.

【0024】

Textile fabric Odor strength Example 1 1 Comparative Example 1 4 ~ 5 Comparative example 2 3 6-step odor intensity display method 0: Odorless 1: Finally perceptible odor 2: A weak odor that you can tell what the odor is 3: Easily perceptible odor 4: Strong smell 5: Strong odor In Example 1, there is only an odor that is not noticeable, whereas in Comparative Example 1 without melamine resin protection, an acid-based malodor that is considered to be due to oxidative decomposition of organic fibers is strong, and in Comparative Example 2, organic fibers also have a strong odor. It was insufficient as a protective material and generated an odor that could be easily perceived.

【0025】

In addition, the following experiments were conducted to investigate the deodorizing effect on tobacco odor. Using the cloth to which the titanium oxide photocatalyst of Example 1 was fixed, a curtain with a width of 3.0 m and a length of 1.8 m was created, and the 8 tatami room (width 3.6 m x depth 3.6 m x height 2.7 m) facing south The window was hung with the surface coated with the titanium oxide photocatalyst facing the sunlight. As a control cloth, a cloth to which the titanium oxide photocatalyst was not fixed was used to prepare a curtain in the same manner, and the cloth was hung in another room under the same conditions. After burning 10 cigarettes at the same time in the center of each room, the air in the room was circulated by a small fan and kept closed during the day. The results of having 20 people (10 men and 10 women) perform olfactory evaluation of the odor in each room after 5 hours are shown below. The UV intensity on the curtain surface exposed to sunlight at this time is 0.5 to 0.8 mW / cm.²Met.

【0026】

Odor intensity 5 4 3 2 1 Example 10 0 people 6 people 13 people 1 person Control cloth 1 person 10 people 9 people 0 people 0 people A clear deodorizing effect on tobacco odor was observed in the curtain made of the fiber cloth to which the titanium oxide photocatalyst of Example 1 was fixed. Example 2 Metsuke 110g / m made of polyester spun yarn²The plain woven fabric of No. 1 was dyed in a fluorescent white color at 130 ° C. with a disperse dye by a high-pressure dyeing machine, and used as a fiber cloth.

【0027】

In the same manner as in Example 1, the compounding solution 1 was used to obtain a fiber cloth protected by a melamine resin. Next, the following compounding solution 4 was prepared as a sol solution of silicon oxide, and the compounding solution 5 containing a titanium oxide photocatalyst was prepared using this. The obtained fiber cloth was dipped in this, squeezed to 50% pickup with a mangle roll, and then dried at 120 ° C. for 3 minutes. Further, it was cured at 170 ° C. for 1 minute to obtain a fabric on which a titanium oxide photocatalyst was fixed.

【0028】

Formulation 4 Tetraethoxysilane 20.0% by weight Ethyl alcohol 40.0% by weight Water 39.8% by weight Concentrated nitric acid 0.2% by weight The hydrolysis was completed by leaving it for 24 hours.

【0029】

Formulation 5 Formulation 4 8.0% by weight STS-01 1.0 weight% (Titanium oxide photocatalytic solution manufactured by Ishihara Techno Co., Ltd.) (Titanium oxide photocatalyst particle size 7nm solid content 30% by weight) Water 91.0% by weight Comparative example 3 Using the same fiber cloth protected by the same melamine resin as in Example 2, the compounding solution 6 was prepared as a compounding solution containing the titanium oxide photocatalyst instead of the compounding solution 5, and a cloth to which the titanium oxide photocatalyst was fixed was obtained by the same method. It was.

【0030】

Formulation 6 BY22-826 4.0% by weight (Made by Toray Dow Corning Silicone Co., Ltd. Silicone aqueous emulsion solid content 45% by weight) STS-01 1.0 weight% (Titanium oxide photocatalytic solution manufactured by Ishihara Techno Co., Ltd.) Water 95.0% by weight The results of evaluating the degree of odor generation when irradiated with ultraviolet rays using each fiber fabric to which the titanium oxide photocatalysts of Example 2 and Comparative Example 3 are fixed are shown below in the same manner as in Example 1.

【0031】

Textile fabric Odor strength Example 2 1 Comparative Example 3 3 ~ 4 In Example 2, there was only an unpleasant odor, whereas in Comparative Example 3, an acid-based malodor, which was considered to be due to oxidative decomposition of the organic component in the silicone resin, was strongly generated.

【0032】

Next, in order to investigate the deodorizing effect of isovaleric acid, which is one of the causative substances of the unpleasant odor of sweat, on the organic fiber cloth to which the titanium oxide photocatalyst of Example 2 was fixed, the following test was conducted. .. The organic fiber cloth (10 cm × 10 cm) obtained in Example 2 is placed in a 300 mL Erlenmeyer flask, isovaleric acid is injected, the stopper is sealed, and a titanium oxide photocatalyst is applied at a distance of 30 cm under a 20 W ultraviolet lamp. The surface was irradiated with ultraviolet rays. As a control cloth, a cloth to which the titanium oxide photocatalyst was not fixed was used and irradiated in the same manner. The ultraviolet intensity on the fabric at this time is 0.8 mW / cm.²Met.

【0033】

The results of measuring the residual concentration of isovaleric acid with a gas detector tube after irradiation for 1 hour are shown below. Isovaleric acid Initial concentration 1 hour later Odor intensity Example 2 2.0ppm <0.05ppm 1 Control fabric 2.0ppm 1.8ppm 5 In Example 2, the value was below the detection limit of the gas detector tube, and even in the olfactory evaluation of the odor in the Erlenmeyer flask, almost no odor was felt with respect to the intense odor of the control cloth.

【0034】

Further, the antibacterial property was tested on the fiber cloth to which the titanium oxide photocatalyst of Example 2 was fixed as follows. The antibacterial property was evaluated by the bacterial count measurement method specified by the Textile Product Sanitary Processing Council. Staphylococcus aureus was used as the bacterial species, and the culture was carried out under 30 cm under a 20 W fluorescent lamp. As a control cloth, a cloth to which the titanium oxide photocatalyst was not fixed was used in the same manner. The results are shown below. The difference in the increase / decrease in the number of bacteria is 1.6 or more.

【0035】

Judgment of acceptance / rejection of increase / decrease in the number of fiber fabrics Example 2 4.32 Passed Control fabric 0.63 failed It was found that the organic fiber cloth on which the titanium oxide photocatalyst of Example 2 was fixed had excellent antibacterial properties under fluorescence irradiation.

【0036】

Further, the organic fiber cloth to which the titanium oxide photocatalyst was fixed obtained in Example 2 was subjected to a decomposition removal test of tobacco tar stain as follows. The organic fiber cloth obtained in Example 2 and the fiber cloth to which the titanium oxide photocatalyst is not fixed as a control cloth are attached to face the side wall in the desiccator having a volume of 2 L, and the cigarette is placed in the center of the desiccator with the lid closed. Was burned to attach the tar to each of them. After 1 hour, it was taken out, hung inside a south-facing windowpane, and exposed to sunlight.

【0037】

UV intensity on fabric 0.5 ~ 0.8mW / cm²When left for a total of one week in the sunlight, the fiber cloth to which the titanium oxide photocatalyst of Example 2 was fixed recovered to almost the original whiteness and had no unpleasant odor. On the other hand, in the control fabric to which the titanium oxide photocatalyst was not fixed, yellowing remained and an unpleasant odor still remained. Example 3 Metsuke made of 100% polyester 200g / m²The surface of the satin fabric for curtains was printed in blue using a disperse dye.

【0038】

The following melamine resin treatment was performed to form a protective layer of organic fibers. Beccamin PMN 10.0% by weight (Made by Dainippon Ink, trimethylolpropane resin solid content 80% by weight) Unica Catalyst A-35 1.0 Weight% (Union Kasei, curing catalyst solid content 35% by weight) Water 89.0% by weight After impregnating the woven fabric with this treatment liquid, the pickup was squeezed to 60%.

【0039】

Next, microwave irradiation was performed in saturated steam at an output of 6 kW for 5 minutes. The fabric was then washed with hot water for 5 minutes, dried with hot air at 120 ° C. and set at 170 ° C. for 30 seconds. The amount of melamine resin attached is 4.8 g / m²Met. A compounding solution 2 containing the same titanium oxide photocatalyst as used in Example 1 was prepared, and a 125 mesh gravure roll was used on the back side of the fiber cloth to 8 g / m.²It was applied and dried at 120 ° C. Further, it was cured at 170 ° C. for 30 seconds to obtain a cloth on which the titanium oxide photocatalyst was fixed.

【0040】

The acetaldehyde degradability of the obtained fabric was evaluated by the following procedure. A cloth having a size of 10 cm × 10 cm is placed in a 300 mL triangular flask, acetaldehyde is added so that the concentration in the flask becomes 70 ppm, the cloth is sealed, and then ultraviolet rays on the cloth are used using black light. It was irradiated with ultraviolet rays having an intensity of 0.8 mW for 3 hours. For comparison, the same test was performed on raw fabrics.

【0041】

As a result, as shown below, the fabric of the present invention showed excellent acetaldehyde decomposing property. Acetaldehyde concentration Unprocessed fabric The fabric of the present invention Initial 70ppm 70ppm After 3 hours 70ppm 25ppm [0042]

[Effect of the invention]

The textile fabric of the present invention does not cause unpleasant feelings when used indoors or near the human body, has excellent deodorant, antibacterial and antifouling functions, and also has various types including washing. It is durable against processing and can be widely applied to interiors such as curtains, sanitary materials, and clothing.

【0043】

Further, according to the present invention, it is possible to deodorize tobacco odor, sweat odor, axillary odor, etc., which have been difficult to deodorize in the past, and also decompose colored substances such as tobacco tar adhering to the cloth to prevent stains. A fabric containing organic fibers, which exerts an effect, has a bactericidal ability against Escherichia coli, Staphylococcus aureus, etc., and has an effect of suppressing a bad odor generated when the bacterium decomposes human metabolites and the like can be obtained.