JP2001040574A - Functional fiber fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a functional fiber fabric which contains organic fibers, can widely be applied to clothes, interior articles such as curtains, sanitary materials, and so on, and has a deodorizing function and an antibacterial function, by adhering titanium dioxide photocatalyst to a fiber fabric with a cellulosic binder, or the like. SOLUTION: This functional fiber fabric is obtained by adhering titanium dioxide catalyst to a fiber fabric by the use of a cellulosic binder (preferably crosslinked) and/or a polysaccharide binder. The fiber fabric preferably comprises cellulose fibers or flame-resistant polyester fibers which contain phosphate ester-based units or is treated with a phosphate ester-based flame- resisting agent. Synthetic fibers such as polyester fibers, nylon fibers or acrylic fibers, regenerated cellulosic fibers such as rayon fibers, natural fibers such as cotton or wool, can be considered as the fibers for forming the fiber fabric.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a functional fiber fabric. The present invention relates to a functional fiber fabric containing organic fibers, which has a deodorant and antibacterial function and can be widely applied particularly to clothing, interiors such as curtains, and sanitary materials.

[0002]

2. Description of the Related Art When a titanium oxide photocatalyst is fixed to the surface of an organic polymer material, there is a problem that the titanium oxide photocatalyst deteriorates the binder resin and easily falls off. It is generally known that there is a problem of decomposing, but there is also a problem that the low molecular weight substance generated from the organic polymer material itself or the binder resin becomes a odor causing substance due to the oxidative decomposition power of the photocatalyst. We have found something. In the case of producing a fiber material having deodorizing performance using a photocatalyst, if the fiber itself or a binder resin for fixing the photocatalyst is decomposed to generate an odor, the value as a deodorant fiber is completely lost. In particular, since fiber materials are used in living spaces, even if the photocatalyst-processed fibers have the effect of decomposing harmful substances such as tobacco odor and formalin, there is no practicality at all if there is a problem of generating another bad odor. become.

In fixing a titanium oxide photocatalyst to the surface of an organic polymer material, the following method is generally used, and its purpose is to prevent the photocatalyst from falling off due to decomposition of a binder resin. For example, when coating the surface of a polyester film with a titanium oxide photocatalyst,
A two-step coating method has been proposed in which an inorganic undercoat made of silicon oxide sol is performed, and then a silicon oxide binder and a titanium oxide photocatalyst are coated. A method has also been proposed in which a siloxane-based polymer is used as an undercoat agent, and the siloxane-based polymer and a titanium oxide photocatalyst are coated thereon. Chemicals used in such a two-stage coating method are commercially available from Nippon Soda Co., Ltd. and Ishihara Sangyo Co., Ltd.

[0004] However, the present inventors have found that even with such a two-stage processed film, the problem of generating an offensive odor upon irradiation with ultraviolet rays has not been solved. That is, it was confirmed that when a polyester film coated with a photocatalyst was placed in a glass container and irradiated with an ultraviolet lamp for several hours in a sealed state, there was a problem that a considerably irritating odor was generated. As the undercoat or the binder of the titanium oxide photocatalyst, inorganic resins such as silicon oxide, siloxane-based resins, and fluororesins that are not easily deteriorated by heat are generally used, but the above problems are not always satisfactory.

A method for immobilizing such a photocatalyst on the surface of a substrate is described in Industrial Materials, vol. 45, no. 10,62
Pp. 66. Of course, if the fiber which has been photocatalyzed by the above two-stage processing method is used in a closed room, a bad smell is generated and the method is not practical. If the titanium oxide photocatalyst is fixed to the fiber, it can be deodorized, antibacterial,
It is expected that a fabric having a function such as antifouling can be obtained. However, even if a technique such as a binder resin or a two-stage processing method described in patent literature or general literature is used,
Solving the problem of odor generation is not easy. When applied to fibers, when the titanium oxide photocatalyst is fixed, a low molecular weight product is generated from the fiber base and the binder resin, a dyeing aid such as a dye or a surfactant by ultraviolet irradiation, and often produces a bad smell, In the case of producing deodorant fibers, for example, the fiber material emits offensive odor against the purpose. Further, since fiber materials are often used in human living spaces, the generation of bad odors creates an unpleasant environment and is not practical at all.

Although a two-stage treatment method in which a photocatalyst is adhered after protectively coating the surface of the fiber is generally desirable,
The above problem remains. Further, since the production process is complicated in the two-stage treatment method, it is desirable to solve the above-mentioned problems such as the generation of offensive odor by the one-stage treatment method.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a photocatalyst-treated fabric, which is a functional material having excellent deodorant properties and antibacterial properties which prevent the generation of malodor due to the decomposition of the binder resin and the fibers themselves. It is an object to provide a fiber fabric, desirably by a one-stage processing method.

[0008]

SUMMARY OF THE INVENTION The present invention provides a functional fiber fabric in which a titanium oxide photocatalyst is fixed to a fiber fabric with a cellulosic binder and / or a polysaccharide binder.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In general, the fibers constituting a fiber cloth to which a titanium oxide photocatalyst is adhered by post-processing include:
For example, synthetic fibers such as polyester, nylon, and acrylic, regenerated cellulose fibers such as rayon, and natural fibers such as cotton and wool are conceivable. When a titanium oxide photocatalyst is fixed to a synthetic fiber such as polyester using a resin binder, odor may be generated due to decomposition of the fiber itself and the binder resin, which may be a practical problem,
It has been found that when the photocatalyst is fixed using a binder made of a cellulose-based binder or a polysaccharide, the above-mentioned problem is largely solved, and a fabric excellent in functions such as deodorization and antibacterial can be obtained.

When a titanium oxide photocatalyst is adhered to a cellulosic fiber or paper such as rayon, cotton or wood pulp using a cellulosic binder or a polysaccharide binder, the same processing is applied to synthetic fibers. It has been found that the odor due to decomposition is further reduced, and a fiber cloth having more excellent deodorizing and antibacterial functions can be obtained.

In the present invention, as the above-mentioned fiber cloth,
A fabric made of flameproof polyester fiber may be used,
Thereby, it is possible to provide a fiber cloth having both a flameproofing property, a deodorizing property, and a photocatalytic function such as antibacterial property. Here, the flame-resistant polyester fiber is a polyester obtained by copolymerizing a phosphate ester compound, that is, a polyester fiber containing a phosphate ester compound unit, and a polyester obtained by kneading a phosphate ester-based flame retardant or by post-processing. Say fiber. Specific product names of the phosphoric ester compound copolymerized polyester include Heim manufactured by Toyobo Co., Ltd. and Trevira CS manufactured by Hoechst. Examples of the phosphoric ester compound used for such copolymerization include the existing Chemical Substance Reference No. 5-3777.

Further, as a phosphate ester-based post-processing flame retardant, there is a cyclic aliphatic phosphonate oligomer having the existing Chemical Substance Reference No. 2-1961, and Meisei Chemical Industry Co., Ltd.
The trade name K-19A of manufacture is known. This flameproofing agent is fixed to the fiber by padding the fiber fabric to be treated as an aqueous solution of several percent or less, drying, and heat setting at 190 to 200 ° C. Excessive agent that does not adhere is preferably removed by washing under alkaline conditions. As another method for obtaining a flame-resistant polyester, for example, it is conceivable to use an aqueous dispersion of hexabromocyclododecane and carry out flame-proof treatment with a liquid jet dyeing machine or a thermosol method. When a system binder or a polysaccharide binder is attached, it tends to burn and is not suitable for this purpose.

As described above, when a binder made of a cellulosic binder or a polysaccharide is used as a binder for attaching the titanium oxide photocatalyst to the fiber cloth,
Although it is not clear why the problem of malodor generation due to decomposition is greatly reduced, it has been found that the odor due to decomposition of the cellulosic fiber itself by the titanium oxide photocatalyst is small. Furthermore, the cellulosic binder was considered to have a low odor due to decomposition, and it was confirmed that there was little problem of malodor generation. When a titanium oxide photocatalyst is attached to an organic polymer material, silicon oxide sol, silicon resin, fluororesin, etc. are used as an undercoat agent or a binder resin. It has been found that the odor is low.

Fiber fabrics useful in the present invention include synthetic fibers such as polyester, nylon and acrylic; cellulose fibers such as cotton, hemp and wood pulp; regenerated cellulose fibers such as rayon; cellulose acetate fibers such as triacetate; wool; And the like, or organic fibers obtained by blending or blending them, and further, these organic fibers may contain inorganic fibers or the like. Preferably, it is made of cellulose fibers such as cellulose fibers, regenerated cellulose fibers, and cellulose acetate fibers. In addition, those fabrics are woven fabrics,
It may be in any form such as a knit or a non-woven fabric. If necessary, these fabrics may be colored with a disperse dye, an acid dye, a direct dye, a reactive dye, a pigment, or the like.

The titanium oxide photocatalyst useful in the present invention generally has a particle size of 1 micron or less and is in the form of an acidic or alkaline aqueous dispersion, powder or the like. Also, apatite surface treatment as titanium oxide surface treatment,
It is also possible to use a material which has been treated so as not to decompose the material when it comes into contact with an organic substance such as silica surface treatment. The amount of the titanium oxide photocatalyst attached to the fiber cloth was 0.4 g.
/ M ² or more.

In the present invention, the titanium oxide photocatalyst is fixed to a fiber cloth with a cellulose binder and / or a polysaccharide binder. Examples of the cellulose-based binder useful in the present invention include, but are not limited to, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, and methylcellulose.

Examples of the polysaccharide binder include sodium alginate, locus bean gum,
Guar gum, starch and the like can be used, but are not limited thereto. The ratio of the cellulose-based binder or polysaccharide binder to the titanium oxide photocatalyst is desirably 100% or less by weight, and the smaller the ratio, the more the function of the titanium oxide photocatalyst can be exhibited. That is, when the amount of the binder exceeds the amount of the titanium oxide photocatalyst, the photocatalyst is buried in the binder, and the probability of exposure to ultraviolet rays is reduced, and the function is reduced.

[0018] In view of the use of the fabric, without washing
When it does not come into contact with water, the titanium oxide photocatalyst may be fixed only with a cellulose-based binder or a polysaccharide binder, but when washed, these binders alone dissolve and fall off, so a crosslinking treatment is performed. Is good.
Examples of the crosslinking agent include water-soluble or water-dispersible isocyanates that react with hydroxyl groups, and epoxy compounds, aziridine compounds, oxazoline compounds, and carbodiimide compounds that react with carboxyl groups. The proportion of these crosslinking agents is 50% or less by weight based on the weight of the cellulosic binder or polysaccharide binder.
Further use does not contribute to crosslinking.

An example of a process for processing a fabric is performed according to the following procedure. The fiber cloth is immersed in an aqueous treatment liquid containing a titanium oxide photocatalyst, a cellulose-based binder and / or a polysaccharide binder and, if necessary, a crosslinking agent, and then squeezed with, for example, a mangle roll, if necessary, at 70 to 150 ° C.
And heat treatment at 150 to 200 ° C. within several minutes to complete the reaction (pad-cure method).

Alternatively, a coating method using a gravure coater or the like, or a spraying method can also be used. Further, silver zeolite fine particles or zinc oxide fine particles may be used in combination with a treatment liquid for a fiber cloth containing a titanium oxide photocatalyst, a binder, and a crosslinking agent for the purpose of enhancing functions such as antibacterial and deodorant. Further, in order to remove the uncrosslinked binder and to improve that the texture of the fiber fabric is too hard, water, hot water, using an aqueous solution such as acetic acid, wash the fiber fabric, and dry Good.

From the viewpoint of productivity, it is preferable to use a one-step treatment method. However, after providing the protective layer, the titanium oxide photocatalyst may be fixed with a cellulose-based and / or polysaccharide binder.

[0022]

The present invention will be further described below with reference to examples. In the following examples, "%" indicates% by weight. Example 1 A plain woven fabric (100 g / m ^{2 in} weight) made of 100% cotton was dyed light blue using a reactive dye and used in the test.

The following treatment liquid containing a photocatalyst was prepared. Apatite-coated titanium oxide photocatalyst aqueous dispersion 3.5% (Showa Denko, solid content 25%) Cellogen PR 1.0% (Daiichi Kogyo Seiyaku, carboxymethyl cellulose) WS-500 0.2% (Nippon Shokubai, Oxazoline-based crosslinking agent) Water is added to 100%.

Next, the fabric was immersed in the treatment liquid, squeezed to 80% with a mangle roll, and dried with a dryer at 130 ° C. for 3 minutes. Then, it heat-set at 170 degreeC for 1 minute using the pin tenter. 10 cm to determine the odor due to decomposition of the resulting functional fiber fabric
The square sample was placed in a 300 ml Erlenmeyer flask, stoppered, placed 30 cm under a 20 W black light, and left for 4 hours.

Next, the stopper was removed, and the odor in the Erlenmeyer flask was determined. Further, when a sample was further taken out and the odor of the functional fiber fabric was determined, the odor was 2 and all had no problem. The degradability of sweat odor of this functional fiber fabric was evaluated by the following procedure. A 0.005% isopropyl alcohol solution of isovaleric acid was prepared.

The functional fiber cloth was sampled in a size of 5 × 10 cm, and 25 μl of the above solution was dropped on the entire surface of the cloth. Then, after being left under a fluorescent lamp for 2 hours, the odor was judged by smell. For comparison, the same evaluation was performed on an unprocessed cloth. Table 1 shows the results. The untreated fabric had a strong sweat odor, while the photocatalyst-treated fabric had almost no odor.

[0027]

[Table 1]

The determination of the odor was made by a six-step odor intensity display method. Each odor intensity is as follows. 6-step odor intensity display method 0: Odorless 1: Smell that can be sensed at last 2: Smell that can be sensed what is smell 3: Smell that can be easily sensed 4: Strong smell 5: Intense smell Comparative Example 1 Same as Example 1. A cotton cloth was used for the test. However, a silicon oxide sol was used as the binder resin.

Apatite-coated aqueous titanium oxide dispersion 3.5% (Showa Denko, solid content 25%) Colcoat N-103X 10.0% (Colcoat, silicon oxide sol, solid content 10%) %.

This treatment liquid was applied to a woven fabric in the same procedure as in Example 1 to obtain a functional fiber cloth. Further, when the decomposition odor of this fabric was evaluated by the same method as in Example 1, the odor intensity in the flask was 4, and that of the taken-out fabric was 3.5, which was a strong odor, which was a practically problematic level. Met.

Example 2 Spunlace nonwoven fabric consisting of 100% rayon (basis weight 5
0 g / m ² ) was used for the test cloth. The following treatment liquid containing a titanium oxide photocatalyst was prepared. STS-21 10% (Ishihara Sangyo, titanium oxide photocatalyst dispersion, solid content 40%) Cellogen PR 1% (Daiichi Kogyo Seiyaku, carboxymethyl cellulose) CR-5L 0.2% (Dai Nippon Ink, epoxy cross-linking) Agent) Add water to make 100%.

The above treatment solution was applied from one side at a coating amount of 1.5 g / m ² (solid content) using a gravure coater of 40 mesh and dried at 150 ° C. for 2 minutes. In order to determine the odor due to the decomposition of the obtained functional fiber-based fabric, 10
A square cm sample was placed in a 300 ml Erlenmeyer flask, sealed, placed under a 20 W black light at 30 cm, and left for 4 hours.

Next, the stopper was removed, and the odor in the Erlenmeyer flask was determined. Further, when a sample was further taken out and the odor of the functional fiber cloth was judged, the odor intensity was 1.5, and all were odors without any problem. Next, the acetaldehyde decomposability of the functional fiber fabric was evaluated by the following procedure. A 10 cm square sample was placed in a 300 ml Erlenmeyer flask, added so that the acetaldehyde concentration became 300 ppm, and sealed. Then, it was placed 30 cm under a 20 W black light, and the concentration in the flask after 1 hour and 3 hours was measured by a detector tube method.

For comparison, a sample which was not processed with a photocatalyst was also judged. Table 2 shows the results. It can be seen that the obtained functional fiber fabric has excellent acetaldehyde decomposition performance.

[0035]

[Table 2]

Example 3 Cellulose filter paper was used for the test. The following treatment liquid containing a photocatalyst was prepared. Apatite-coated titanium oxide photocatalyst aqueous dispersion 15% (manufactured by Showa Denko, solid content 25%) Metrolose SE 1% (manufactured by Shin-Etsu Chemical, hydroxyethyl methylcellulose) Water is added to 100%.

Next, after the cellulose filter paper was immersed in the treatment liquid, it was dried with a dryer at 130 ° C. for 3 minutes to obtain a functional fiber cloth (processed filter paper). The antibacterial activity of the obtained sample against Staphylococcus aureus was evaluated. 20 during culture
The test was performed in a state where light was applied 30 cm below a W fluorescent lamp. Table 3 shows the results.

The untreated filter paper did not show antibacterial properties, whereas the resulting functional fiber fabric (processed filter paper) showed excellent antibacterial properties.

[0039]

[Table 3]

Example 4 Spun plain woven fabric composed of 100% polyester (having a basis weight of 10)
0 g / m ² ) were dyed beige with a disperse dye. Further, the following treatment liquid containing a photocatalyst was prepared. Kimitsu Argin BL-2 0.5% (Kimitsu Chemical Industry, sodium alginate) Apatite-coated titanium oxide photocatalyst aqueous dispersion 4.0% (Showa Denko, solid content 25%) Carbodilite V-02 0.1% (Nisshinbo) , Polycarbodiimide resin) Water is added to 100%.

Next, the fabric was immersed in the treatment liquid, squeezed to 80% with a mangle roll, and dried with a dryer at 130 ° C. for 3 minutes. Furthermore, it heat-set at 170 degreeC for 30 second using the pin tenter. In order to examine the deodorizing effect of the obtained functional fiber fabric on tobacco odor, the following verification test was performed.

For the test, adjacent rooms (3.6 m wide)
× depth 3.6 m × height 2.7 m). Ultra-violet light with an intensity of 0.5 to 0.8 mW / cm ^{2 in} clear weather (Minolta U
VRADIOMETE RUM-1 (Maximum absorption wavelength 36
(Measured at 7 nm)). In each room, a curtain having a width of 3.0 m and a length of 1.8 m made of a functional fiber fabric and a raw fabric was hung.

Further, at the same time in the center of each room,
After burning 0 cigarettes, the air in the room was circulated by a small electric fan and kept closed during the day. Five hours later, 20 adults (10 males and 10 females) evaluated the odor of the odor in each room. Table 4 shows the results.

[0044]

[Table 4]

The curtain made of the functional fiber cloth to which the titanium oxide photocatalyst obtained in Example 4 was fixed exhibited a clear deodorizing effect on tobacco odor. Example 5 A satin fabric for curtains composed of 100% polyester fiber was used for the test. For flameproofing, a 4% aqueous solution of a phosphoric ester-based flameproofing agent K-19A manufactured by Meisei Chemical Co., Ltd. was prepared.

After immersing the woven fabric in the solution, the pickup was squeezed to 80% with a mangle roll and dried at 120 ° C. for 3 minutes. Next, using a pin tenter, heat treatment was performed at 195 ° C. for 2 minutes for fixing. The unfixed flameproofing agent was washed with a 1% soda ash solution at 50 ° C. for 10 minutes using a jet dyeing machine, and then washed with water to remove it. Next, it was dried at 120 ° C. for 3 minutes to obtain a flameproofed fabric.

The following solutions were prepared for photocatalytic processing. Apatite-coated titanium oxide aqueous dispersion 4.5% (Showa Denko, solid content 25%) Cellogen PR 0.5% (Daiichi Kogyo Seiyaku, carboxymethyl cellulose) CR-5L 0.2% (Dainippon Ink, Epoxy crosslinking agent) After immersing the woven fabric in this solution, the pickup was squeezed to 80% with a mangle roll and dried at 120 ° C for 3 minutes. Next, heat treatment was performed at 170 ° C. for 2 minutes using a pin tenter. The uncrosslinked binder resin was washed with a 0.5% solution of acetic acid at 50 ° C. for 10 minutes using a jet dyeing machine, and then washed with water to remove it. Next, it was dried at 120 ° C. for 3 minutes to obtain a functional fiber cloth.

Table 5 shows the results of measuring the flame resistance of the obtained functional fiber fabric. The flameproofness of this fabric conformed to the classification of the Japan Flame Retardant Association, which does not require reprocessing after washing (washing with water, dry cleaning) for curtains.

[0049]

[Table 5]

Next, the decomposability of acetaldehyde was evaluated in the same manner as in Example 2. However, the initial concentration of acetaldehyde was 70 ppm. Table 6 shows the evaluation results.
The resulting fabric has the action of decomposing acetaldehyde.

[0051]

[Table 6]

[0052]

According to the present invention, in fixing the titanium oxide photocatalyst to the fiber cloth, a method for suppressing the problem of the generation of offensive odor due to the oxidative decomposition power of the titanium oxide photocatalyst of the fiber cloth and the binder resin, which was a conventional problem. In the use indoors and in the vicinity of the human body, the fiber cloth has excellent deodorizing and antibacterial functions of the titanium oxide photocatalyst, and furthermore has flameproofness when used indoors or near the human body. Can be provided. In addition, this fiber fabric can be widely applied to interiors such as curtains, sanitary materials, clothing, and the like.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) D06M 101: 32 (72) Inventor Keisuke Miyazaki 167 Namahama, Negami-cho, Nomi-gun, Ishikawa Pref. Komatsu Seiren Co., Ltd. Terms (reference) 4L031 AA02 AA18 AB01 AB31 BA09 BA31 CA08 DA16 4L033 AA02 AA07 AB01 AB04 AC05 BA35 CA02 CA05 DA04 DA06 4L035 EE11 EE14 FF05 4L048 AA08 AA13 AA20 AA53 AA56 AB01 BA01 BA02 CA00 DA06 DA01

Claims (4)

[Claims] 1. A functional fiber cloth comprising a titanium oxide photocatalyst fixed to a fiber cloth with a cellulose binder and / or a polysaccharide binder. 2. The functional fiber fabric according to claim 1, wherein the cellulosic binder and / or the polysaccharide binder is crosslinked. 3. The fiber fabric is composed of cellulosic fibers.
The functional fiber fabric according to claim 1. 4. The functional fiber fabric according to claim 1, wherein the fiber fabric contains a phosphate ester compound unit or is made of flame-retardant polyester fibers to which a phosphate ester-based flame retardant has been applied.