JP2000355872A - Photocatalyst-containing fiber-treating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photocatalyst-containing fiber-treating agent having antimicrobial properties, deodorant properties and flexibility by allowing photocatalytic fine particles to be carried between layers of a smectite. SOLUTION: This photocatalyst-containing fiber-treating agent is obtained by mixing a suspension containing a smectite such as a limitless layer-expansive clayey mineral having crystalline three-layer structure, e.g. montmorillonite, and having 0.1-15 μm average particle diameter, and a cationic organic compound such as lauryltrimethylammonium chloride, with photocatalytic fine particles comprising a combination of one or more kinds selected from titanium oxide, zinc oxide and tungsten oxide, and having 0.001-0.3 μm, preferably 0.003-0.2 primary particle diameters to allow the photocatalytic fine particles to be carried between layers of the smectite.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to the antibacterial properties of photocatalysts,
While combining deodorant properties and smectite flexibility,
The present invention relates to a novel photocatalyst-containing fiber treating agent that does not cause fiber deterioration.

[0002]

2. Description of the Related Art Hitherto, as a method of imparting flexibility to fibers, a method of attaching montmorillonite, which is a smectite-based clay mineral, has been proposed (Japanese Patent Laid-Open No. 5-26).
3359, JP-A-7-189115).

[0003] In recent years, environmental pollution has been highlighted as a social problem, and awareness of human living environments, particularly unpleasant odors and bacterial infections, has been increasing. Therefore, a material containing a photocatalyst has been attracting attention as a material having deodorant properties and antibacterial properties. In this photocatalyst, electrons and holes are generated on the surface by ultraviolet irradiation, and active oxygen having strong oxidizing power is generated from surrounding water and oxygen, and organic substances and microorganisms are decomposed by the action of the generated active oxygen. It exhibits deodorant properties and antibacterial properties.

As such deodorizing and antibacterial methods using a photocatalyst, for example, Japanese Patent Application Laid-Open Nos. 2-280818 and 3-94814 have been reported.

[0005]

However, the above-mentioned deodorizing and antibacterial methods using a photocatalyst irradiate ultraviolet rays to a ceramic carrying the photocatalyst, and this photocatalyst is exposed to an organic substance such as fiber. However, there is a problem in that the fibers themselves are deteriorated due to the characteristics of the photocatalyst itself, that is, the characteristics of decomposing organic substances. Therefore, it has been difficult to attach the photocatalyst to the fiber so far.

The present invention has been made to solve the above-mentioned problems, and to provide a photocatalyst-containing fiber treating agent capable of simultaneously exhibiting the characteristics of a photocatalyst and the characteristics of a smectite while suppressing the deterioration of the fibers when the fibers are attached to the fibers. Aim.

[0007]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a photocatalyst-containing fiber treating agent comprising photocatalyst fine particles carried between smectite layers is obtained. It has been found that excellent properties such as flexibility, antibacterial property and deodorant property can be imparted without causing fiber deterioration even when attached to fibers.

That is, when a photocatalyst-containing fiber treating agent in which photocatalyst fine particles are supported between smectite layers is attached to fibers by a method such as mixing photocatalyst fine particles into a suspension containing smectite and a cationic organic compound. Since the fiber is not directly in contact with the photocatalyst fine particles, the fiber can be prevented from deteriorating, while the photocatalytic action works effectively by irradiation with ultraviolet light, and at the same time, excellent properties such as antibacterial properties and deodorant properties can be imparted. The present inventors have found that smectite can impart excellent flexibility, and have accomplished the present invention.

Hereinafter, the present invention will be described in more detail. The photocatalyst-containing fiber treating agent of the present invention has photocatalyst fine particles carried between layers of smectite.

Here, the smectite is an unrestricted layer-expandable clay mineral having a crystalline three-layer structure, such as montmorillonite, beidellite, nontronite, saponite, hectorite, and stevensite. Among these, montmorillonite is preferred. The average particle size of this smectite is usually 0.1 to 15 μm.
m.

The above-mentioned photocatalyst fine particles are substances that generate electrons and holes on the surface thereof when irradiated with ultraviolet rays, and generate active oxygen having strong oxidizing power from surrounding water and oxygen. Specifically, Se, Ge, Si, Ti, Zn, Cu, A
1, Sn, Ga, In, P, As, Sb, C, Cd,
S, Te, Ni, Fe, Co, Ag, Mo, Sr, W,
Compounds such as oxides such as Cr, Ba and Pb, which are insoluble in water, may be mentioned. Among these, titanium oxide,
It is preferable to use one selected from zinc oxide and tungsten oxide alone or in combination of two or more.

The photocatalyst fine particles have a primary particle diameter of 0.001 to 0.3 μm, preferably 0.003 to 0.3 μm.
The range is 2 μm. If the primary particle diameter of the photocatalyst fine particles is too large, the function of the photocatalyst may be difficult to be exhibited.

The photocatalyst-containing fiber treating agent of the present invention can be obtained by mixing photocatalyst fine particles with a suspension containing smectite and a cationic organic compound. According to this method, the cationic organic compound first penetrates between the smectite layers, and then the cationic organic compound between the smectite layers is replaced with the photocatalytic fine particles, and the photocatalytic fine particles are supported between the smectite layers. is there.

Examples of the cationic organic compound include organic compounds having a cationic group such as an ammonium group, a sulfonium group, and a phosphonium group, and a cationic surfactant represented by the following general formula (1) is particularly preferable.

[0015]

Embedded image

In the formula (1), R ¹ is a linear or branched saturated or unsaturated aliphatic hydrocarbon group which may be substituted with a hydroxyl group having 10 to 24 carbon atoms, for example, substituted with a hydroxyl group. Represents an optionally substituted alkyl or alkenyl group. In addition, the alkyl group and the alkenyl group may be a mixed alkyl group and a mixed alkenyl group.

R ² , R ³ , and R ⁴ are the same or different linear or branched saturated or unsaturated aliphatic groups which may be substituted with the same hydroxyl group having 10 to 24 carbon atoms as R ^1. A hydrocarbon group, a substituent represented by the following general formula (2),
Alternatively, it represents an alkyl group having 1 to 3 carbon atoms (eg, a methyl group or an ethyl group).

[0018]

Embedded image (However, in the formula, m is an integer of 1 to 5, and Y is a hydrogen atom or a methyl group.)

In the above formula (1), X ^- represents a halide ion such as a fluorine ion, a chloride ion and a bromide ion, a hydroxide ion, or glycolic acid, acetic acid, tartaric acid, propionic acid, lactic acid, citric acid, salicylic acid, It represents an organic acid anion such as succinic acid, malic acid, butyric acid, p-toluenesulfonic acid, higher fatty acid, L or DL-pyrrolidone carboxylic acid, acidic amino acid, and pyroglutamic acid.

Such cationic surfactants include:
Lauryltrimethylammonium chloride, myristyltrimethylammonium chloride, palmityltrimethylammonium chloride and the like can be mentioned.

The dispersion medium for preparing the above suspension is not particularly limited, and various ones can be used. Preferably, water is used. The mixing ratio of the three components (water, smectite and cationic organic compound) in this suspension was water: smectite = 100: 1 to 1: 3 by weight.
More preferably, water: smectite = 100: 1 to 1: 1.
And smectite: cationic organic compound = 10
0: 0.1 to 1:10, more preferably smectite:
Cationic organic compound = 100: 0.5 to 1: 3.

The pH of the suspension is not particularly limited, but the pH can be adjusted using ammonia water, hydrochloric acid, or the like in order to efficiently carry the photocatalyst fine particles between smectite layers.

The photocatalyst fine particles are added while stirring the above suspension. In this case, the photocatalyst fine particles may be in the form of a fine powder or a slurry dispersed in water or the like. The amount of the photocatalyst fine particles added to the suspension is 0.01 to 70% by weight, preferably 0.02 to 50% by weight, more preferably 0.1 to 5% by weight, based on the photocatalyst content in the smectite containing the photocatalyst.
0% by weight, more preferably 0.2 to 30% by weight.
If the content of the photocatalyst is too small, the performance of the photocatalyst may not be sufficiently exhibited. On the other hand, if the content exceeds 70% by weight, the improvement of the photocatalytic effect is difficult to be obtained, which may be economically disadvantageous.

The mixing of the suspension and the photocatalyst fine particles can be carried out at normal temperature and normal pressure.
It is also possible to carry out under pressure or under reduced pressure, or under heating or cooling. The mixing time is not particularly limited, and is usually about one hour.

The photocatalyst-containing smectite thus obtained is separated and collected by a solid-liquid separation operation such as filtration and centrifugation, and the collected cake can be dried as it is to obtain a product. Further, after washing with water or alcohol, the product can be naturally dried or dried by heating to obtain a product. Smectite containing photocatalyst (fiber treating agent containing photocatalyst)
Has an average particle size of 0.1 to 15 μm, preferably 0.2 to 1 μm.
0 μm.

The method for attaching the photocatalyst-containing fiber treatment agent (photocatalyst-containing smectite) in which the photocatalyst fine particles of the present invention are supported between smectite layers is not particularly limited. For example, the fiber treatment agent is previously added to water. It is possible to adopt a method in which the fibers are put into the place where they are dispersed, and immersed or stirred. Further, when washing with a detergent, a method of adding a fiber treatment agent together and adhering to fibers may be adopted. In any of the methods, the conditions such as the processing time are not particularly limited, and commonly used conditions can be appropriately adopted.

The photocatalyst-containing fiber treating agent of the present invention is capable of imparting excellent flexibility, deodorant property and antibacterial property to the fiber without deteriorating the fiber itself by an ordinary simple method. There are no particular restrictions on the fibers and textile products, for example, shirts, underwear, sheets, bedding and bedding,
It can be suitably used for various fiber products such as towels.

[0028]

According to the photocatalyst-containing fiber treating agent of the present invention, the properties of photocatalyst and smectite can be simultaneously exhibited, and excellent properties such as flexibility, deodorant property, antibacterial property and the like are obtained without deteriorating the fiber. , And fiber products treated with this fiber treatment agent are extremely useful as materials for improving living environments.

[0029]

EXAMPLES The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

A photocatalyst-containing smectite having 1% by weight of photocatalyst fine particles supported between smectite layers was prepared as follows. The smectite used was Montmorillonite (trade name: POLA GEL) manufactured by American Colloid Co., Ltd. having an average particle size of about 5 μm.

Montmorillonite 139.6 in 563 g of water
g and 6.97 g of a cationic surfactant (lauryltrimethylammonium chloride) were added, followed by stirring at room temperature for 1 hour. Thereafter, 1.395 g of titanium oxide (ST-01, average particle size: 7 nm, manufactured by Ishihara Techno Co., Ltd.) was added as photocatalyst fine particles, followed by stirring at room temperature for 1 hour. Next, a solid content is taken out by a centrifugal separator, washed by stirring with isopropyl alcohol (IPA), again taken out by a centrifugal separator, and dried at 80 ° C. to obtain an average particle size of 5 μm.
Montmorillonite containing photocatalyst (containing 1 wt% photocatalyst)
I got

The performance of the obtained photocatalyst-containing montmorillonite was evaluated by the following method.

Example 1 and Comparative Example 1 (1) Deodorizing property 600 ml of 0.2 g of the above-mentioned photocatalyst-containing montmorillonite was used.
And sealed in a vial. 7 in this vial
0 ppm ammonia was added using a syringe, and 0.1 ppm was added.
After irradiating with ultraviolet rays of 5 mW / cm ² for 3 hours, the ammonia gas concentration was measured using a detector tube (Example 1). In addition, a vial containing no photocatalyst-containing montmorillonite was treated in the same manner, and the ammonia gas concentration was measured (Comparative Example 1). Table 1 shows the results.

[0034]

[Table 1]

Example 2, Comparative Example 2 (2) Performance Evaluation on Skin Shirt In the case of treatment with a dispersion suspended in water (treatment with a suspension), a household containing 20 liters of water was used. 6 g of the above-mentioned photocatalyst-containing montmorillonite was added to a two-layer washing machine for use and dispersed by stirring for 5 minutes. Here, three commercially available skin shirts were put and stirred for 5 minutes. After dehydration for 2 minutes, the sample was air-dried under sunlight and conditioned for 24 hours in a thermo-hygrostat at 25 ° C.-60% RH (Example 2). The same treatment was performed using montmorillonite not carrying a photocatalyst (Comparative Example 2).

Example 3 and Comparative Example 3 When washing with a detergent (washing treatment), the detergent (Lion Co., Ltd.) was placed in a household two-layer washing machine filled with 20 liters of water. Top) 17 g and powder 6 g were added, and three commercially available skin shirts were put therein and washed for 5 minutes. Then 2
After dehydration for minutes, air-dried and conditioned for 24 hours in a constant temperature and humidity room at 25 ° C.-60% RH (Example 3). In addition, completely the same treatment was performed using montmorillonite not carrying a photocatalyst (Comparative Example 3).

The treated skin shirts of Examples 2 and 3 and Comparative Examples 2 and 3 were evaluated for the following performance. Table 2 shows the results.

Flexibility The touch feeling by three panelists of each treated skin shirt was evaluated according to the following criteria. ：: Good flexibility ×: No flexibility Deodorant Each treated skin shirt was cut into 10 cm squares and cut into 600
The mixture was sealed in a vial of 100 ml. 70 ppm of ammonia was added to the vial using a syringe,
After irradiation with ultraviolet rays of 0.5 mW / cm ² for 3 hours, the ammonia gas concentration was measured using a detector tube. Antimicrobial properties Each treated skin shirt was left in the air for 24 hours and exposed to sunlight for 3 hours. Then, using a food stamp (standard agar medium for general bacteria, manufactured by Nissui Pharmaceutical Co., Ltd.), the viable bacteria on the skin shirt were collected, and the antibacterial activity was determined based on the following criteria based on the area of the colony after culture. ：: No colonies were generated ×: Colonies were considerably generated Shirt deterioration After repeating the fiber treatment (suspension treatment and washing treatment) of the above-mentioned skin shirt and drying treatment under sunlight 10 times, The degree of damage was evaluated according to the following criteria. ○: No damage ×: Damaged

[0039]

[Table 2]

From the results shown in Tables 1 and 2, the photocatalyst-containing fiber treating agent of the present invention has excellent deodorizing properties, and the fiber product to which the photocatalyst-containing fiber treating agent of the present invention is attached deteriorates. It was confirmed that the resin had good flexibility, deodorant properties, and antibacterial properties without any problem.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toshio Tsunoi 1-3-7, Honjo, Sumida-ku, Tokyo F-term in Lion Corporation (reference) 4G030 BA14 BA32 BA34 CA01 HA05 4L031 AB01 BA20 BA24 DA05 DA12 DA13

Claims (2)

[Claims] 1. A photocatalyst-containing fiber treating agent comprising photocatalyst fine particles carried between smectite layers. 2. The photocatalyst-containing fiber treating agent according to claim 1, which is obtained by mixing photocatalyst fine particles with a suspension containing smectite and a cationic organic compound.