JPH11100771A - Fiber structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fiber structure excellent in anti-staining, deodorizing and antimicrobial properties and useful for wall-decorating materials, curtains and the like by forming a coating film produced from an amino resin on the surfaces of the fibers and further forming a coating film containing photocatalyst particles. SOLUTION: This fiber structure is obtained by forming a coating film (thickness is preferably 0.05-20 μm) produced from an amino resin comprising the polymer of a monomer of the formula (R1-R6 are each H, OH, OCn H2n-1 , CH2 OH, CONH2 or the like) on the surfaces of fibers such as polyester fibers or polyamide fibers and further forming a coating film containing photocatalyst particles (particle diameter is preferably <=20 nm, and adhesion amount is preferably >=1% based on the weight of the fibers) comprising one or more kinds of metal oxides selected from TiO2 , ZnO2 , SnO2 , SrTiO3 , WO3 , Bi2 O3 , and Fe2 O3 on the surface of the coated film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a fiber having excellent antifouling property by photocatalytic reaction while maintaining physical and chemical properties of the fiber.
An object of the present invention is to provide a fiber structure having deodorant properties and antibacterial properties.

[0002]

2. Description of the Related Art Fiber structures such as fiber cloths are widely used for clothing and industrial use. Regardless of clothing or industrial use,
Various methods have been proposed to improve the antifouling property, deodorant property, antibacterial property and the like according to each use environment. For example, to improve the antifouling property, a method of treating with a water and oil repellent composed of a fluorine-based compound or a silicon-based compound or a method of treating with a hydrophilic compound containing a polyethylene glycol component has been proposed. A possible contaminant is determined, and furthermore, when washing or the like is carried out, there is a problem that the compound falls off and the antifouling performance decreases. As a method of imparting deodorizing performance, a method of physically adsorbing malodor with activated carbon or porous silica, etc., is to adsorb a part of malodor components in the atmosphere and lower the atmospheric concentration, and if saturation adsorption is reached There is no deodorant function. For example, basic zinc oxide neutralizes acidic malodors such as hydrogen sulfide and methyl mercaptan, and acidic aluminum sulfate neutralizes basic malodor ammonia. It is well known that deodorizing by deodorizing.However, such a method has a problem that when the deodorant is saturated, the deodorizing function is lost and the neutral odor cannot be completely deodorized. is there. A preferred deodorizing method is to decompose malodorous components into odorless components. For example, iron / phthalocyanine is a deodorant that oxidizes and decomposes ammonia, but has little effect on other malodorous components. At present, all methods have a problem in deodorizing ability.

[0003] Antibacterial properties include those in which silver, copper, etc. are carried on ceramics and various organic compounds are used as bactericides and repellents. May have safety issues.

[0004] As described above, there are many problems in imparting independent performances of antifouling property, deodorant property and antibacterial property, and it is extremely difficult to provide these three functions at the same time. It is.

In recent years, techniques for imparting functions such as antifouling properties, deodorizing properties, antibacterial properties, etc. by utilizing the oxidation / reduction reactions of optical semiconductors represented by titanium oxide have been proposed, and various organic impurities and NOx have been proposed. It has been demonstrated that some inorganic compounds such as SOx gas can be decomposed, and products obtained by sintering titanium oxide on the surface of an inorganic base such as ceramics and glass have been commercialized. When this method is performed on an organic substrate, there is a serious problem that the substrate itself is decomposed together with the action of antifouling property, deodorant property, antibacterial property and the like, so that it is difficult to adopt. In order to solve this problem, it has been proposed to form a light-corrosion resistant material such as aluminum or silicon compound between the substrate and titanium oxide. ,
There is a problem in adhesion at the interface between the fiber and the titanium layer.

[0006]

SUMMARY OF THE INVENTION In view of the above situation, the present invention provides a fiber structure having excellent antifouling, deodorizing and antibacterial properties by photocatalytic reaction while maintaining the physical and chemical properties of the fiber. It will not be provided.

[0007]

The present invention adopts the following means to solve the above-mentioned problems.
That is, the fiber structure of the present invention is characterized in that an amino resin coating is formed on a fiber surface, and a coating containing photocatalyst particles is further formed on the coating surface.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides an excellent antifouling property without changing the physical and chemical properties of fibers by a photocatalytic reaction.
After extensive studies on fiber structures that impart photocatalytic properties such as deodorant and antibacterial properties, it was found that an object can be achieved by forming a crosslinked film of an amino resin, such as melamine resin, between the fiber surface and the photocatalytic film. Things.

The fiber structure of the present invention includes polyester fiber, polyamide fiber, polyacrylonitrile fiber, polypropylene fiber, polyethylene fiber, polyvinyl chloride fiber, fluorine fiber, aramid fiber, sulfone fiber. Synthetic fibers such as fibers, semi-synthetic fibers such as rayon and acetate, natural fibers such as cotton, wool, silk, hemp, glass fibers, carbon fibers, ceramic fibers, etc. Non-woven fabric, thread, rope, string and the like. Such fibers may contain various additives commonly used for improving productivity and properties in the production and processing steps of the raw yarn. For example, a heat stabilizer, an antioxidant, a light stabilizer, a flame retardant, an antistatic agent, a plasticizer, a thickener, a coloring agent, a leveling agent, an antibacterial agent, a fungicide, and the like can be contained. INDUSTRIAL APPLICABILITY The present invention is particularly effective for fibers made of an organic polymer that is easily degraded by a photocatalytic reaction.

[0010] The amino resin coating on the fiber surface of the present invention,
Although a known amino resin can be used, a polymer (condensate) containing a melamine compound represented by the following formula as a monomer is preferably used.

[0011]

Embedded image In the method for forming a coating film of an amino resin, for example, a melamine resin, of the present invention, an aqueous solution or a solvent solution of the resin is applied to a fibrous structure, and heat treatment is performed. More specifically, in the case of using an aqueous solution, the resin is preferably 0.05 to
The melamine resin solid content is preferably 0.1 to 15% by weight with respect to the fiber weight on the fiber using a 20% by weight aqueous solution,
More preferably, it is applied so as to be 0.5 to 10% by weight. As a method of application, for example, a method of immersing the fiber structure in an aqueous solution and squeezing with a mangle or the like, or a method of applying a required amount with a knife coater or a spray, can be adopted,
There is no particular limitation. After the application, a heat treatment is performed for the condensation, and the condensation reaction of the present invention preferably uses a catalyst. Examples of such a catalyst include acetic acid, formic acid, acrylic acid, malic acid, tartaric acid, glutamic acid, maleic acid, and phthalic acid. Acids, sulfuric acid, persulfuric acid, hydrochloric acid, phosphoric acid and the like, and ammonium salts, sodium salts, magnesium salts and the like thereof, and one or more of these are used. Among them, ammonium persulfate and potassium persulfate can be preferably used. The amount of the catalyst used is preferably 0.001 to 1% by weight based on the amount of the melamine resin used.

The heat treatment for the polymerization (condensation) of the amino resin is preferably carried out at a temperature of 50 to 180 ° C., for 0.1 minute.
The heat treatment is performed for a period of up to 30 minutes. Such a heat treatment can exert the effects of the present invention by any of the dry heat treatment and the steam heat treatment, but the steam heat treatment is particularly preferable because a uniform film is easily formed on the fiber surface and the texture after the film formation is flexible. Such a steaming heat treatment is a saturated steam or a superheated steam having a temperature of 80 ° C. or more, preferably a saturated steam of 100 to 130 ° C. and a superheated steam of 110 to 160 ° C., and performs treatment for several seconds to several minutes. After such heat treatment, unreacted amino resin (melamine resin) or catalyst may be removed by washing with hot water or water as necessary.

The thickness of such an amino resin, for example, a melamine resin coating is preferably 0.02 μm or more, and more preferably 0.05 to 20 μm.

The photocatalyst of the present invention is a photocatalyst that is excited by light to generate electron / hole pairs, the generated electrons reduce surface oxygen to generate superoxide ions, and the holes oxidize surface hydroxyl groups to form water. It generates acid radicals and decomposes substances by redox reaction of these active species. For example, TiO ₂ , ZnO, SnO ₂ , SrTiO excited by ultraviolet rays
₃ , metal oxides such as WO ₃ , Bi ₂ O ₃ , and Fe ₂ O ₃ , and at least one of them is used. Among them, titanium oxide is particularly preferable because it is chemically stable, harmless, and inexpensive. Titanium oxide includes anatase type and rutile type, and anatase type is preferable because of high reactivity.

The method of forming a photocatalyst film according to the present invention comprises, for example, dispersing photocatalyst particles in an aqueous resin or a solvent resin,
It can be attached by a known method such as an immersion method, a coating method, and a spray method. As the type of the water-based resin and the solvent-based resin used here, a silicon-based resin, an acrylic silicon-based resin, a fluorine-based resin, a melamine-based resin, an epoxy-based resin, and the like can be used.

The smaller the particle size of the photocatalyst of the present invention is, the higher the activity is.
m or less. The attached amount of the particles is 0.05 or more, preferably 1% or more based on the weight of the fiber.

In the present invention, a metal such as platinum, palladium, silver, copper, or zinc can be doped to enhance the activity of the photocatalytic reaction or the antibacterial action.

[0018]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. The performance values shown in Examples and Comparative Examples were measured by the following methods. (Tensile strength retention of woven fabric decomposed yarn) 6 at 63 ° C with an ultraviolet irradiation device (SUV-W-13, manufactured by Iwasaki Electric Co., Ltd.)
After treating for a time, the tensile strength of the warp-decomposed yarn of the woven fabric was measured based on JIS-L-1017, and the tenacity retention rate with respect to those not irradiated with ultraviolet rays was calculated.

(Contaminant decomposability) An aqueous ink (red ink manufactured by Pilot Corporation) was diluted with water to a concentration of 10%,
A line was drawn on the surface of the woven fabric with a writing brush, air-dried, and exposed to sunlight to measure the time required for the ink to dissolve and discolor.

(Stainability) The sample was exposed to a 45-degree exposure table specified in JIS-A-1410 for 60 days to evaluate the stainability. A sample with little dirt was indicated by 、, a sample with many stains was indicated by ×, and a middle was indicated by Δ.

(Deodorizing property) 80 μl of 0.3% ammonia water is placed in a 500 cc quartz glass container capable of transmitting ultraviolet rays.
A sample of 5 cm × 5 cm is dropped into the container, sealed, and irradiated with a germicidal lamp at a UV intensity of 5 mw / cm ² from a distance of 7 cm from the sample, and 30 minutes later, remains in 100 cc of the container. The amount of ammonia was measured using a gas detection tube (manufactured by Gastech), and the removal rate with respect to the ammonia concentration at the start was calculated.

(Antibacterial activity) Staphylococcus aureus (St)
aphylococcus aureus 12732) was added thereto, and the number of viable cells after culturing at 37 ° C. for 18 hours in a closed vessel was measured to obtain an increase / decrease value with respect to the number of inoculated cells. The UV intensity during culture was 0.8 mw / cm ²
And those without irradiation with an ultraviolet lamp were evaluated.

Examples 1 to 7 and Comparative Examples 1 to 4 A twill fabric is woven using a 75-denier, 36-filament, false-twisted polyester fiber yarn (manufactured by Toray Industries, Inc.) as a warp and a weft, according to a conventional method. After scouring at 98 ° C, drying at 130 ° C and heat setting at 190 ° C, a woven fabric having a warp density of 125 yarns / inch and a weft density of 108 yarns / inch was obtained. This fabric was treated by the following method, and the performance was evaluated. The results are shown in Table 1.

(First Layer Treatment) Sumitex Resin M-3
The woven fabric was immersed in a treatment liquid prepared by adding water to 6 g (trimethylol melamine manufactured by Sumitomo Chemical Co., Ltd.) and 0.5 g of ammonium persulfate to make the total amount 100 g.
It was squeezed with a mangle so that the wet pickup became 100%. Subsequently, treatment was performed in saturated steam at 103 ° C. for 5 minutes, washed with hot water at 50 ° C., and dried at 130 ° C. to coat the fiber surface with a uniform polymer of melamine resin.

(Second layer treatment) Aqueous dispersion of titanium oxide (Ishihara Sangyo Co., Ltd., particle system 20 nm, solid content 40%) 5
The woven fabric subjected to the first layer treatment was immersed in a liquid made up to 100 g by adding 0 g of water, squeezed with a mangle so that the wet pickup became 100%, and dried at 130 ° C.

From Table 1, it can be seen that the fiber according to the present invention is a fiber structure having a small decrease in the physical properties of the fiber due to the photocatalyst and having excellent antifouling properties, deodorizing properties and antibacterial properties.

Example 8 The first layer treated product of Example 1 was treated in the second layer with the following solution, and the performance was similarly evaluated. The strength retention was 78%, the decomposition time of contaminants was 3 hours, and the odor was eliminated. 96%.

Titanium oxide aqueous dispersion 20 g (Ishihara Sangyo Co., Ltd., particle system 7 nm, solid content 30%) Sumitex Resin M-3 0.4 g (Sumitomo Chemical Co., Ltd.) Water 89.6 g

[Table 1]

[0029]

【The invention's effect】

Claims (7)

[Claims] 1. A fibrous structure, wherein an amino resin coating is formed on a fiber surface, and a coating containing photocatalyst particles is further formed on the coating surface. 2. The fibrous structure according to claim 1, wherein the amino resin is composed of a monomer polymer represented by the following formula. Embedded image 3. The fiber structure according to claim 1, wherein the photocatalyst particles are metal oxides. 4. The method according to claim 1, wherein the metal oxide is TiO ₂ , ZnO, S
nO ₂ , SrTiO ₃ , WO ₃ , Bi ₂ O ₃ and Fe
At least one kind of claim 3 fiber structure according selected from ₂ O _3. 5. The fiber structure according to claim 3, wherein the photocatalyst particles are titanium oxide. 6. The fiber according to claim 1, wherein the fiber is an organic polymer.
The fiber structure as described in the above. 7. The fibrous structure is used for wall coverings, curtains, carpets, tatami mats, bedding, table cloths, clothing, construction work, seats, canvas, tents, and cool boxes. The fibrous structure according to any one of claims 1 to 6, which is a material used for at least one use for a cover and a flag.