JP2000265364A - Antifouling fiber fabric and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifouling fiber fabric capable of improving blackened sticking stains in the field of interiors such as curtains and the likes. SOLUTION: In this antifouling fiber fabric, specifically at least one species of photocatalyst semiconductor particles having a UV absorption in 50-400 nm wave length are fixed to the fiber surface in 0.5-20 wt.% based on the weight of the fiber fabric by a silane coupling agent. The antifouling fiber fabric is obtained by soaking the fiber fabric in an aqueous solution containing the photocatalyst semiconductor particles and the silane coupling agent and, after removing the excess liquid, fixing the photocatalyst semiconductor particles on the fiber surface by heat treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber fabric having antifouling properties and a method for producing the same. More specifically, the present invention relates to an antifouling fiber cloth in which photocatalytic semiconductor fine particles are fixed to the fiber surface, and particularly to an antifouling fiber cloth which is effective for preventing dark spots such as curtains and the like, and a method for producing the same.

[0002]

2. Description of the Related Art In the field of interiors such as carpets and curtains, general clothing, and interior materials for automobiles, many antifouling treatments for various living dirt such as dust, dirt, mud, water and oil have been studied. As the application technique, conventionally, a method of applying a silicon-based compound or a fluorine-based compound exhibiting water repellency to a cloth surface by a pad method, a spray method, an exhaustion method, or a hydrophilizing agent made of polyalkylene glycol or a derivative thereof. There is known a method of providing the fiber surface. For synthetic fibers, there is also known a method of producing a conductive yarn at the stage of a raw yarn for the purpose of preventing adhesion of dirt in the atmosphere due to static electricity, and interweaving or knitting the yarn with a fabric. However, among the stains, particularly the darkened stains often seen in curtains and the like are presumed to be caused by the adhesion of carbonaceous substances floating in the air, and it is not sufficient to prevent the darkened stains even with the above-described technology. However, no satisfactory technology has been established, and there is still a great demand for this technique.

In recent years, contamination prevention using a photocatalytic semiconductor has been actively performed. A photocatalytic semiconductor is a substance that exhibits a photocatalytic function when irradiated with light having a wavelength having energy equal to or greater than its band cap. When these substances are irradiated with light having a wavelength having energy equal to or greater than the band cap, electrons are generated in the conduction band and holes are generated in the valence band by photoexcitation. Among the electron-hole pairs generated by these light irradiations, the high reducing power of the electrons and the high oxidizing power of the holes are used for the decomposition of organic substances and the decomposition of water. Methods for preventing contamination using these properties are being studied.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an antifouling fiber cloth which can improve the stains caused by blackening in the interior field such as curtains.

[0005]

In order to achieve the above object, the antifouling fabric of the present invention has the following constitution.

That is, at least one kind of photocatalytic semiconductor fine particles having an ultraviolet absorption having a wavelength of 50 to 400 nm is fixed on the fiber surface by a silane coupling agent in an amount of 0.5 to 20% by weight based on the weight of the fiber cloth. is there.

Further, in the method for producing an antifouling fiber cloth according to the present invention, the fiber cloth is immersed in an aqueous solution containing fine particles of a photocatalytic semiconductor and a silane coupling agent, excess liquid is removed, and then heat treatment is performed. It fixes fine particles on the fiber surface.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS There are various types of stains on textiles, such as water-based stains and oil-based stains. The stains of particular interest in the present invention are those that gradually become dark during long-term use, such as white or light-colored curtains. It comes out (black stain adheres).

The fiber fabric referred to in the present invention may be any of a woven or knitted structure made of synthetic fibers, semi-synthetic fibers, natural fibers, etc., but is particularly useful for a fabric structure made of polyester fibers. Most effective. Further, the polyester fiber is not particularly limited, but those having a main repeating component of polyethylene terephthalate, polybutylene terephthalate, or ethylene terephthalate unit (specifically, 90 mol% or more of the repeating unit), and a main repeating component of butylene terephthalate unit Fibers (specifically, 90 mol% or more of the repeating units) can be preferably used. Among them, polyester fibers composed of a polyester having an ethylene terephthalate unit of 90 mol% or more as a repeating component are preferable, and polyester fibers composed of a polyester having an ethylene terephthalate unit of 95 mol% or more as a repeating component are more preferable. It is more preferable that the polyester fiber is a polyester fiber composed of a polyester containing ethylene terephthalate units as a repeating component of 100 mol% (that is, polyethylene terephthalate). The cross-sectional form of these polyester fibers may be round or irregular.

The photocatalyst semiconductor fine particles used in the present invention are titanium oxide, tungsten oxide, strontium titanate, which can absorb light in the ultraviolet region having a wavelength of 50 to 400 nm.
Zinc oxide and the like can be used, and among them, titanium oxide is preferable because it is inexpensive and easily available.

The particle size of titanium oxide is 100 nm or less, preferably 50 nm or less, and more preferably 20 nm. 1
Those having a thickness of more than 00 nm have disadvantages such as poor water dispersibility of titanium oxide, poor binding durability, and insufficient blackening adhesion preventing performance. When the particle size is 20 nm or less, a material having extremely excellent water dispersibility, binding durability, and anti-darkening adhesion performance can be obtained.

The amount of titanium oxide particles for providing sufficient blackening adhesion preventing performance is 0.5 to the weight of the fiber cloth.
~ 20% by weight is required, and 1.5%
~ 10% by weight is preferred. If it is less than 0.5% by weight, the effect of preventing darkening is insufficient, and if it exceeds 20% by weight, the effect of preventing darkening is sufficient, but the texture of the fabric becomes hard.

In the present invention, as the silane coupling agent, those commonly used as an adhesive between an organic substance and an inorganic substance can be used. Examples of the hydrolyzable group bonded to silicon of the silane coupling agent include an alkoxy group, a halogen, and an acetoxy group, but an alkoxy group that is most easily used is usually preferred. Examples of the organic functional group include an amino group, a methacryl group, a vinyl group, an epoxy group, and a mercapto group. Among them, a silane coupling agent having a vinyl group or an epoxy group functional group is preferable in terms of adhesiveness. . Specifically, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2
-Aminoethyl) aminopropylmethyldimethoxysilane, aminosilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, γ-glycidoxy Propyltrimethoxysilane, γ
-Mercaptopropyltrimethoxysilane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ -Chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and the like.

The silane coupling agent is used in the form of an aqueous solution. If the solubility in water is poor, acetic acid is added to adjust the pH to a weakly acidic one to promote the hydrolyzability of the alkoxysilane. You can improve your sex. This addition of acetic acid is effective for the stability of silanol in the aqueous solution, and also has the effect of delaying the formation of a water-insoluble siloxane polymer.

The amount used depends on the surface morphology and surface area of the photocatalytic conductive particles such as titanium oxide.
An aqueous solution of 0.5 to 3.0% by weight is preferred, and an aqueous solution of 0.5 to 3.0% by weight is preferred. If it is less than 0.2% by weight, it is not possible to bind (fix) titanium oxide to such an extent that the effect of preventing adhesion of dirt according to the present invention can be sufficiently exhibited. Further, even when the amount exceeds 5.0% by weight, a large difference is not found in the binding amount (fixed amount) of titanium oxide, resulting in wasteful use.

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

As described above, the fiber cloth is immersed in the aqueous solution (treatment liquid) containing the photocatalytic semiconductor fine particles and the silane coupling agent, and after removing the excess liquid, the residual water adhering to the cloth is removed. A dipping method or a spraying method can be adopted as a method for applying the treatment liquid to the cloth. When the immersion method is adopted, excess liquid may be removed by mangle. The method of removing residual moisture adhering to the fabric,
Both the immersion method and the spray method can be performed by drying with a hot air drier. The hot air temperature in this case is not particularly limited, but is 100 ° C. to 1 ° C. in the sense that moisture is efficiently removed in a short time.
It is preferable to carry out the drying treatment in the range of 50 ° C.

[0018]

The present invention will be described more specifically below with reference to examples. The performance evaluation in the examples was performed by the following method. <Dark stain adhesion prevention property> 0.2 g of a dry contaminant having the following composition and three test samples of 10 x 10 cm were collected in a polyethylene bag, sealed in a state containing air, and put in a box of a pilling tester. For 30 minutes. Thereafter, the test sample was taken out, and the stain by the dry contaminant was graded on a gray scale. The L value was measured using a spectrometer CM-3700d manufactured by Minolta Co., Ltd. and compared. [Dry contaminant composition] Product name Composition (% by weight) Viscosity (fine powder Shigaraki viscosity) 55.0 Portland cement (JIS R5210) 17.0 Silica gel (JIS K8885) 17.0 Ferric oxide (Reagent CP grade) 0.50 n-decane (Reagent EP class) 8.75 Car phone rack (Tamagawa car phone rack) 1.75 <Washing test> Home washing machine VH-3410 (Toshiba Corporation)
0.2% by weight of a weak alkaline detergent "Zab" (registered trademark, manufactured by Kao Corporation) at a temperature of 40 ° C. ± 2 ° C.
After treating at 1:30 for 5 minutes, drainage and dehydration are performed, and rinsing for 2 minutes is repeated twice while overflowing.
This was made one wash, and repeated five times.

Example 1 Sandet G-29 (manufactured by Sanyo Chemical Co., Ltd.) 0.5 g / l of a twill fabric using 100% polyethylene terephthalate fiber of 75 denier-36 filaments for both warp and weft yarns,
80% in a processing solution containing 1 g / l of sodium hydroxide (30%)
After refining under the conditions of 15 ° C. × 15 minutes, it was dried and dried at 180 ° C.
Intermediate setting is performed under the conditions of ° C x 30 seconds, and the basis weight is 120 g / m.
² test fabrics were obtained.

Next, an aqueous solution was prepared by diluting 100 g of a 30% aqueous dispersion of a photocatalytic semiconductor having an absorption wavelength of 388 nm and a particle diameter of 7 nm with 10 g of γ-glycidoxypropyltrimethoxysilane in 1 liter of water. The woven fabric prepared above is immersed in this aqueous solution, and picked up with a mangle.
%. Thereafter, the mixture was treated in a hot air dryer at 130 ° C. for 5 minutes to evaporate water. Then, add another 40 ° C hot water.
The fabric was washed with hot water for 0 minutes and dried at a temperature of 100 ° C. From the measured weight of the fabric before and after the treatment, the photocatalytic semiconductor fine particles and γ
Glycidoxypropyltrimethoxysilane combined weight was 2.2% by weight of fabric weight.

Next, the intensity of ultraviolet light (260 to
(400 nm) was set to 1.3 mW / cm ² for 3 hours.

The test fabric was evaluated for its ability to prevent dark stains from adhering. As a result, a result was obtained in which the dry stain was less likely to adhere than untreated fabric. Further, after the washing, a test for preventing the adhesion of dark stains was conducted again, and the durability effect of the washing was examined. The result was almost the same as before the washing. The results are shown in Table 1.
Table 2 shows the results of evaluation of the untreated cloth for comparison, in terms of the property of preventing dark stains from adhering.

Example 2 The test fabric obtained in Example 1 was applied to only one side of the test solution obtained in Example 1 by using a spray. When the weight of the fabric immediately after the application was measured, 50 g of the treatment liquid was attached. Thereafter, the mixture was treated in a 130 ° C. hot air dryer for 5 minutes to evaporate water. Then wash with hot water of 40 ° C for 10 minutes
The fabric was dried at a temperature of 00 ° C. From the measured values of the weight of the fabric before and after the treatment, the adhesion amount of the photocatalytic semiconductor fine particles and γ-glycidoxypropyltrimethoxysilane was 1.2% by weight of the weight of the fabric.

Next, the UV intensity (260 to
(400 nm) was set to 1.3 mW / cm ² for 3 hours.

The test fabric was evaluated for its ability to prevent dark stains from adhering. As a result, the treated surface showed less adhesion of the dry contaminant than the untreated fabric, and the non-treated surface had the same degree of adhesion of the dry contaminant as the untreated fabric. Was seen. The results are shown in Table 1.

Comparative Example 1 A test fabric was prepared under the same conditions as in Example 1 except that a treatment solution containing no photocatalytic semiconductor fine particles was used. When the anti-staining property of the darkening stain was evaluated, there was almost no difference from the adhesion of the untreated cloth, and no effect was exhibited. The results are shown in Table 1.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

The fabric obtained according to the present invention has the effect of maintaining the original hue forever without being darkened as in the past, even when used for a long period of time, for example, in the field of curtains. . In addition, it also has an effect of preventing the yellow stain caused by cigarette tar from adhering, and an effect on antibacterial and deodorant.

Claims (3)

[Claims] At least one kind of photocatalytic semiconductor fine particles having an ultraviolet absorption having a wavelength of 50 to 400 nm is coated on the fiber surface by a silane coupling agent, based on the weight of the fiber cloth.
An antifouling fiber cloth fixed at 0.5 to 20% by weight. 2. The antifouling fiber fabric according to claim 1, wherein said photocatalytic semiconductor fine particles are at least one selected from the group consisting of titanium oxide, tungsten oxide, strontium titanate and zinc oxide. 3. The method according to claim 1, wherein the fiber fabric is immersed in an aqueous solution containing the photocatalyst semiconductor fine particles and a silane coupling agent, excess liquid is removed, and heat treatment is performed to fix the photocatalyst semiconductor fine particles on the fiber surface. A method for producing a soiled fiber cloth.