JP2013047396A - Dispersion liquid of titanium oxide-based antibacterial/deodorizing agent, and fiber and fabric having titanium oxide-based antibacterial/deodorizing agent applied thereon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dispersion liquid of an antibacterial/deodorizing agent, which has antibacterial performance and also can decompose an acidic and basic odorous component.SOLUTION: The dispersion liquid of the antibacterial/deodorizing agent is produced by dispersing titanium oxide-based particulates that carry an antibacterial/deodorant metal component and acidic substance absorptive particulates in water. A concentration (C) of the titanium oxide-based particulate that carries the antibacterial/deodorant metal component is in a range of 0.01-20 wt.%, a concentration (C) of the acidic substance absorptive particulate is in a range of 0.001-10 wt.%, and (C)/(C) that is a ratio of the concentration (C) to the concentration (C) is in a range of 0.01-2.

Description

  The present invention carries an antibacterial / deodorant dispersion and an antibacterial / deodorant capable of decomposing acidic odor components and basic odor components such as volatile organic compounds (VOC) and ammonia in combination with antibacterial performance. It relates to antibacterial and deodorant fibers and fabrics.

In recent years, improvement of living environment such as cleanliness, hygiene, safety, and comfort has been demanded.
Conventionally, an antibacterial composition in which a metal component such as silver, copper, or zinc having antibacterial properties is supported on a powder of silica gel, composite oxide, titanium oxide, or colloidal particles is known.

For example, the applicant of the present application ionizes an antibacterial agent in which an antibacterial metal component is attached to inorganic oxide colloidal particles (Japanese Patent Laid-Open No. 6-80527: Patent Document 1) or metal ions having antibacterial properties in magnesium metasilicate aluminate. An exchanged antibacterial agent (JP-A-3-275627: Patent Document 2) is disclosed.
An antibacterial composition in which an antibacterial metal ion is supported on zeolite or aluminosilicate for the purpose of improving the durability of the antibacterial effect and the stability of the antibacterial substance is also known (Japanese Patent Laid-Open No. 1-283204: Patent). Reference 3).

  The applicant of the present invention is an inorganic oxide fine particle composed of a metal component and an inorganic oxide other than the metal component, and the inorganic oxide comprises titanium oxide and silica and / or zirconia. An antibacterial deodorant in which the titanium oxide is crystalline titanium oxide is disclosed (Japanese Patent Laid-Open No. 2005-318999: Patent Document 4). It is disclosed that this antibacterial deodorant has a deodorizing performance due to decomposition of a volatile organic compound (VOC) in addition to the antibacterial performance.

  The above-mentioned antibacterial deodorant containing the crystalline titanium oxide of the present applicant has excellent antibacterial performance and deodorization performance, but depending on the metal component, the antibacterial performance is high but the deodorization performance is insufficient. There was a case. For this reason, when it changed to the metal component excellent in deodorizing performance, there existed a problem that antibacterial performance became inadequate.

  Furthermore, in recent years, clothing, underwear, etc. having antibacterial performance and deodorizing performance have been demanded, and excellent in deodorizing performance of basic odor components such as ammonia, but deodorizing performance of acidic odor components such as acetic acid. May be insufficient or vice versa, and the basic odor component and the acidic odor component may not be deodorized to the extent that they can be satisfied simultaneously.

  As a result of diligent study, the inventors of the present invention have greatly improved the deodorization rate of acidic odor components and the adhesion to fibers when alumina fine particles are mixed with antibacterial and deodorant metal component-supported titanium oxide fine particles. The inventors have found that the antibacterial / deodorant performance can be maintained over a long period of time without lowering, and have completed the present invention.

JP-A-6-80527 JP-A-3-275627 Japanese Patent Laid-Open No. 1-283204 JP 2005-318999 A

  The present invention provides an antibacterial / deodorant dispersion capable of decomposing acidic and basic odor components together with antibacterial performance, and an antibacterial / deodorant fiber and cloth carrying the antibacterial / deodorant. It is aimed.

The titanium oxide antibacterial / deodorant dispersion according to the present invention is characterized in that antibacterial / deodorant metal component-supported titanium oxide fine particles and acidic substance-adsorbing fine particles are dispersed in water.
The concentration (C _T ) of the antibacterial / deodorant metal component-supported titanium oxide fine particles is in the range of 0.01 to 20% by weight, and the concentration (C _A ) of the acidic substance-adsorbing fine particles is 0.001 to 10% by weight. It is preferable that the ratio (C _A ) / (C _T ) between the concentration (C _A ) and the concentration (C _T ) is in the range of 0.01 to 2.

The acidic substance-adsorbing fine particles are preferably alkali-containing silica fine particles.
The acidic substance-adsorbing fine particles are preferably alumina fine particles.
The antibacterial / deodorant metal component is preferably at least one selected from silver, copper, zinc, tin, cobalt, nickel, and manganese.
The average particle size of the antibacterial / deodorant metal component-supported titanium oxide-based fine particles is preferably in the range of 2 to 50 nm.

The amount of the antibacterial / deodorant metal component supported is preferably in the range of 0.1 to 20% by weight as a metal in the antibacterial / deodorant metal component-supported titanium oxide fine particles.
The titanium oxide-based fine particles are preferably amorphous.
The titanium oxide-based fine particles preferably contain silica and / or zirconia, and the content of silica and / or zirconia in the titanium oxide-based fine particles is preferably in the range of 1 to 20% by weight as an oxide.

The antibacterial / deodorant fiber or cloth according to the present invention is characterized in that any one of the above-described titanium oxide antibacterial / deodorant dispersions is applied.
The amount of the titanium oxide antibacterial / deodorant dispersion applied is preferably in the range of 0.01 to 2% by weight as the solid content of the titanium oxide antibacterial / deodorant.

According to the present invention, an antibacterial / deodorant dispersion capable of decomposing an acidic odor component and a basic odor component together with antibacterial performance, and an antibacterial / deodorant fiber and fabric carrying the antibacterial / deodorant Can be provided.

First, the titanium oxide antibacterial / deodorant dispersion according to the present invention will be described.
[Titanium oxide antibacterial / deodorant dispersion]
The titanium oxide antibacterial / deodorant dispersion according to the present invention is characterized in that antibacterial / deodorant metal component-supported titanium oxide fine particles and acidic substance-adsorbing fine particles are dispersed in water.

Antibacterial / deodorant metal component-supported titanium oxide fine particles In the antibacterial / deodorant metal component-supported titanium oxide fine particles of the present invention, antibacterial / deodorant metal components are supported on titanium oxide fine particles.
The titanium oxide fine particles used in the present invention include titanium oxide fine particles and titanium oxide fine particles containing oxides other than titanium oxide. Examples of the oxides other than titanium oxide include silica and / or zirconia.
At this time, the content of titanium oxide in the titanium oxide-based fine particles is preferably 50% by weight or more, and more preferably in the range of 70 to 95% by weight.
When the content of titanium oxide in the titanium oxide fine particles is less than 50% by weight, sufficient antibacterial performance and deodorizing performance may not be obtained.

By including silica, the stability of the titanium oxide-based fine particle dispersion is improved, and the light resistance and weather resistance tend to be improved. In addition, the inclusion of zirconia improves the stability of the titanium oxide-based fine particle dispersion and also tends to improve the light resistance and weather resistance. Discoloration can be suppressed depending on the type of antibacterial component.
The titanium oxide-based fine particles described above can be obtained according to the methods disclosed in Japanese Patent Application Laid-Open Nos. 63-185820 and 2005-318999 (Patent Document 4) by the applicant of the present application.

The titanium oxide-based fine particles preferably have an average particle diameter in the range of about 2 to 50 nm, more preferably 5 to 40 nm.
When the average particle diameter of the titanium oxide-based fine particles is less than 2 nm, the titanium oxide-based fine particles tend to agglomerate, and the antibacterial / deodorant metal component-supported titanium oxide-based fine particles described later are supported on a fiber or cloth. In some cases, the adhesion is insufficient, the particles are likely to fall off with use, and the deodorant performance and antibacterial performance may be insufficient.
Even if the average particle diameter of the titanium oxide fine particles exceeds 50 nm, the adhesion to the fiber or cloth may be insufficient, and the deodorizing performance and antibacterial performance may be insufficient due to a decrease in the effective external surface area of the particles. .

The titanium oxide-based fine particles are preferably amorphous.
If the titanium oxide fine particles are amorphous, the reason is not clear, but the antibacterial and deodorant properties are particularly excellent in deodorizing performance compared to the case of using crystalline titanium oxide fine particles such as anatase type and rutile type. Metal component-supported titanium oxide-based fine particles can be obtained.
Amorphous titanium oxide-based fine particles can be obtained according to the methods disclosed in JP-A-63-185820, JP-A-2005-318999, etc. filed by the applicant of the present application. The important point is that the amorphous titanium oxide-based fine particles are not crystallized. For example, it varies depending on the titanium oxide content of the titanium oxide-based fine particles, the average particle diameter, etc. It is preferable to perform the treatment at a low temperature for a short time.

The antibacterial / deodorant metal component preferably includes one or more antibacterial / deodorant metal components selected from silver, copper, zinc, tin, cobalt, nickel, and manganese. Among these, silver or zinc is preferable because both antibacterial performance and deodorization performance are excellent. In particular, in the case of zinc, since it does not change color at all, it can be preferably used.
Such antibacterial / deodorant metal components may be present in any form of compounds such as ions, oxides, hydroxides or mixtures thereof. From the viewpoint of antibacterial properties, the form of ions is preferable. If it is an oxide, titanium oxide-based fine particles carrying antibacterial and deodorant metal components excellent in deodorizing properties can be obtained.

Further, it is preferable that the antibacterial / deodorant metal component is present on the surface layer of the titanium oxide-based fine particles or is relatively uniformly distributed to the inside of the titanium oxide-based fine particles.
As a method for supporting the antibacterial / deodorant metal component on the titanium oxide-based fine particles, for example, the method disclosed in JP-A-2005-318999 can be employed.
Specifically, for example, a method of adding an aqueous metal salt solution of an antibacterial / deodorant component to a dispersion in which titanium oxide fine particles having a negative charge are dispersed may be mentioned.

The metal salt aqueous solution is preferably an ammine complex salt aqueous solution. Producing antibacterial and deodorant metal component-supported titanium oxide fine particles with stable antibacterial and deodorant performance for a long time without lowering the stability of the titanium oxide fine particle dispersion or gelling when using an ammine complex salt aqueous solution can do.
As a suitable aqueous solution of ammine complex salt, for example, an aqueous solution of ammine complex salt such as zinc, silver or copper can be prepared by dissolving zinc oxide, silver oxide or copper oxide in ammonia water.

In preparation of the antibacterial and deodorant metal component-supported titanium oxide fine particle dispersion by the above-described method, the concentration of the titanium oxide fine particle dispersion using water as a dispersion medium is 5% by weight or less as an oxide, preferably , Preferably in the range of 0.5 wt% to 3 wt%.
The titanium oxide fine particle dispersion carrying an antibacterial / deodorant metal component using water as a dispersion medium obtained by the above-described method is adjusted to a desired concentration using a known method, for example, an ultrafiltration membrane. The

The content of the antibacterial / deodorant metal component-supported titanium oxide fine particles in the antibacterial / deodorant metal component-supported titanium oxide fine particles is preferably 0.1 to 20% by weight, more preferably 1 to 15% by weight as an oxide. .
When the content of the antibacterial / deodorant metal component is less than 0.1% by weight, it is difficult to obtain sufficient antibacterial / deodorant performance.
If the content of the antibacterial / deodorant metal component is more than 20% by weight, the deodorant performance and antibacterial performance will not be further improved. May decrease.

Acidic substance adsorbing fine particles The titanium oxide antibacterial / deodorant dispersion of the present invention contains acidic substance adsorbing fine particles.
The acidic substance-adsorbing fine particles are not particularly limited as long as odor components described below, particularly acidic substances can be adsorbed. In the present invention, alkali-containing silica fine particles and / or alumina fine particles are preferably used.

Alkali-containing silica fine particles As alkali-containing silica fine particles, silica sol containing alkali is preferable.
The alkali content in the alkali-containing silica fine particles is preferably 0.1 to 30% by weight, more preferably 10.0 to 25% by weight as M ₂ O (M: alkali metal).
If the alkali content in the alkali-containing silica fine particles is less than 0.1% by weight as M ₂ O, the deodorizing performance of the acidic odor component may be insufficient because of the low adsorption amount of the acidic odor component.
When the alkali content in the alkali-containing silica fine particles exceeds 30% by weight as M ₂ O, the stability of the titanium oxide antibacterial / deodorant dispersion is insufficient or the antibacterial performance is insufficient. There is.

The average particle size of the alkali-containing silica fine particles is preferably about the same or smaller than the antibacterial / deodorant metal component-supported titanium oxide-based fine particles, and is preferably in the range of 2 to 50 nm, more preferably 5 to 40 nm.
If the average particle size of the alkali-containing silica fine particles is less than 2 nm, the stability of the titanium oxide antibacterial / deodorant dispersion may be insufficient, and if it exceeds 50 nm, the amount of adsorption of the acidic odor component is insufficient. For this reason, the deodorizing performance of the acidic odor component may be insufficient.
Such alkali-containing silica fine particles can be produced by a conventionally known silica sol production method, and if necessary, the alkali content can be adjusted by treating the silica sol containing an alkali with a cation exchange resin or the like. it can.

As alumina fine particles, conventionally known alumina fine particles can be used. In the present invention, alumina hydrate fine particles, particularly pseudo boehmite alumina hydrate fine particles are preferred.
Pseudoboehmite alumina hydrate (Al ₂ O ₃ .nH ₂ O, n = 0.5 to 2.5) is a kind of crystalline alumina hydrate, usually a fiber in which fibrous primary particles are bundled Secondary particles.
The shape, size, etc. of the alumina hydrate fine particles are not particularly limited, but the following are preferably used.

The primary particles of the pseudo boehmite alumina hydrate fine particles have an average length (L ₁ ) of preferably ₁ to 20 nm, more preferably 2 to 15 nm, and an average width (W ₁ ) of 0.5. It is preferably in the range of -10 nm, more preferably 1-8 nm. At this time, the ratio of length to diameter (L ₁ ) / (W ₁ ) (sometimes referred to as aspect ratio) is preferably in the range of 2-40. The size of the primary particles can be determined by taking a transmission electron micrograph (TEM) of fine particles of alumina hydrate, measuring the width and length of 100 particles, and calculating the average value of each.

The size of the secondary particles of the alumina hydrate fine particles is preferably in the range of 2 to 500 nm, more preferably 5 to 300 nm.
If the size of the secondary particles of the alumina hydrate fine particles is within the above range, the amount of adsorption of the acidic odor component is high without inhibiting the stability of the titanium oxide antibacterial / deodorant dispersion, and the acidic odor component It is possible to obtain a titanium oxide antibacterial / deodorant dispersion having excellent deodorizing performance.
In the present invention, the size of the secondary particles was measured with a laser method particle size distribution analyzer (manufactured by HORIBA Ltd .: LA-950v2).

The concentration (C _T ) of the antibacterial / deodorant metal component-supported titanium oxide fine particles in the titanium oxide antibacterial / deodorant dispersion is 0.01 to 20% by weight, more preferably 0.1 to 10% by weight as a solid content. % Is preferable.
When the concentration (C _T ) of the titanium oxide-based fine particles supporting the antibacterial / deodorant metal component in the titanium oxide-based antibacterial / deodorant dispersion is less than 0.01% by weight as the solid content, the antibacterial / deodorant described later Antibacterial / deodorant metal component-supported titanium oxide fine particles are applied in a small amount, depending on the amount of antibacterial / deodorant metal component supported, but antibacterial / deodorant performance is insufficient It may become.

When the concentration (C _T ) of the antibacterial / deodorant metal component-supported titanium oxide fine particles in the titanium oxide antibacterial / deodorant dispersion exceeds 20% by weight as a solid content, the antibacterial / deodorant fibers described later or Stabilization of the titanium oxide antibacterial / deodorant dispersion without increasing the antibacterial and deodorant performance, even though the amount of antibacterial / deodorant metal component-supported titanium oxide fine particles increases when the fabric is manufactured If a dispersion with low stability is used, the uniformity of coating may be reduced or adhesion may be insufficient, and particles may easily fall off with use, deodorizing performance, Antibacterial performance may not be maintained for a long time.

Next, the concentration (C _A ) of the acidic substance-adsorbing fine particles in the titanium oxide antibacterial / deodorant dispersion is in the range of 0.001 to 10% by weight, further 0.01 to 8% by weight as the solid content. It is preferable that it exists in.
When the concentration (C _A ) of the acidic substance-adsorbing fine particles is less than 0.001% by weight as the solid content, although the antibacterial performance is obtained, the adsorption performance of the acidic odor component is insufficient, and the deodorization performance of the acidic odor component is low. It may be insufficient.
When the concentration (C _A ) of the acidic substance-adsorbing fine particles exceeds 10% by weight as the solid content, the stability of the titanium oxide antibacterial / deodorant dispersion becomes insufficient, and it is applied to a fiber or cloth and supported. In addition, the uniformity of coating may be reduced or adhesion may be insufficient, and particles may easily fall off during use, resulting in insufficient deodorant performance and antibacterial performance.

Further, the weight ratio (C _A ) / (C _T ) as the solid content of the concentration (C _A ) and the concentration (C _T ) is in the range of 0.01 to 2, more preferably 0.05 to 0.5. Preferably there is.
When the ratio (C _A ) / (C _T ) is less than 0.01, the acidic odor component is decomposed, but the acidic odor component is not sufficiently adsorbed. May be sufficient.
Even when the ratio (C _A ) / (C _T ) exceeds 2, although the amount of adsorption of the acidic odor component is sufficient, the decomposition performance of the acidic odor component is insufficient, and as a result, the deodorization performance is insufficient. In addition, the stability of the titanium oxide antibacterial / deodorant dispersion is reduced, and as described above, the uniformity of coating is reduced or the adhesion is insufficient, and the particles are reduced with use. It is easy to drop off and the deodorant performance and antibacterial performance may be insufficient.

The concentration of the titanium oxide antibacterial / deodorant dispersion is preferably 0.011 to 30% by weight, more preferably 0.11 to 18% by weight as the total solid content.
In the present invention, alkali-containing silica fine particles and alumina fine particles can be used separately as the acidic substance-adsorbing fine particles, or they can be mixed and used.
When used in combination, the total concentration of the titanium oxide antibacterial / deodorant dispersion is preferably about 10% by weight or less from the viewpoint of stability.
In the titanium oxide antibacterial / deodorant dispersion, water is mainly used as a dispersion medium, but a mixed dispersion medium of water and alcohol can be used as necessary.

Furthermore, the titanium oxide antibacterial / deodorant dispersion of the present invention may contain other components. Examples of other components include pigments, dispersants, surfactants, and the like, as well as components that are usually used as compounding agents in paints and inks.
The titanium oxide antibacterial / deodorant dispersion described above is applied to fibers and fabrics by a known method such as dipping, spraying, spinner, roll coating, bar coater, etc., dried, and if necessary Antibacterial / deodorant fibers and fabrics can be produced by fixing by heat treatment.

Next, the antibacterial / deodorant fibers and cloth according to the present invention will be described.
[Antimicrobial / deodorant fibers and fabrics]
The antibacterial / deodorant fiber and cloth according to the present invention are characterized by applying any of the above-described titanium oxide antibacterial / deodorant dispersions.

Conventionally known fibers such as natural fibers and synthetic fibers can be used as the fibers and fabric fibers.
Examples of natural fibers include cotton, hemp, linen, wool, silk, cashmere, asbestos, and glass fiber.
Examples of synthetic fibers include nylon, vinylon, polyester, acrylic, polyolefin, polyurethane, and the like.
Moreover, the cloth using the said fiber is mentioned as a cloth.
Antibacterial and deodorant fibers and fabrics are coated with titanium oxide antibacterial and deodorant dispersions by well-known methods such as dipping, spraying, spinner, roll coating, bar coater, etc., and dried. It can manufacture by making it adhere by heat processing as needed.

The attached amount (W _T ) of the antibacterial / deodorant fibers and the antibacterial / deodorant metal component-supported titanium oxide fine particles in the cloth is 0.01 to 2% by weight as a solid content, and further 0.05 to 1%. It is preferably in the range of 5% by weight.
Further, the adhesion amount (W _A ) of the antibacterial / deodorant fiber and the acidic substance adsorbing component in the cloth is a solid content of the weight ratio of the antibacterial / deodorant metal component-supported titanium oxide fine particles (W _A ) / ( W _T ) is preferably in the range of 0.01 to 2, more preferably 0.05 to 0.5.

As fungi to be antibacterial in the antibacterial / deodorant fiber of the present invention, Staphylococcus aureus, Streptococcus, Escherichia coli, Pseudomonas aeruginosa, Proteus, Neisseria pneumoniae, Bacillus subtilis, etc. Examples of fungi, white mold, etc. include viruses such as influenza virus, adenovirus, and norovirus, and examples of algae include chlorella.
The odor components that are subject to deodorization include eight legal malodorous substances (hydrogen sulfide, methyl mercaptan, methyl sulfide, dimethyl disulfide, ammonia, trimethylamine, acetaldehyde, styrene), hydrocarbons, ketones, aldehydes, alcohols, Examples include esters, nitrogen compounds, sulfur compounds, and lower fatty acids.

The antibacterial / deodorant fiber or cloth of the present invention is not limited to clothes, underwear, underwear, etc., but also in living spaces, public facilities, medical facilities, nursing homes, car interiors, etc. Is also useful.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

[Example 1]
Preparation of antibacterial and deodorant metal component-supported titanium oxide fine particles (1) dispersion Titanium sulfate was dissolved in water to prepare an aqueous solution containing 1.0% by weight as TiO ₂ . To this solution, 15% by weight of ammonia water is gradually added with stirring to obtain a white slurry liquid, which is filtered through a glass filter, the cake is thoroughly washed with water, and a hydrous titanic acid cake is obtained. Obtained. To 31.4 g of this cake, water and 219.8 g of hydrogen peroxide having a concentration of 33% by weight were added, and then heated at 80 ° C. for 14 hours to obtain a TiO ₂ concentration of 1.0% by weight, pH 8.2, transparent yellowish brown. 3136 g of titanic acid solution was obtained.

Subsequently, the pH was adjusted to 9 with an aqueous ammonia solution having a concentration of 15% by weight. The amount of the aqueous ammonia solution having a concentration of 15% by weight was 4.2 g.
Subsequently, it heated until it became temperature 50 degreeC, and the zinc nitrate aqueous solution which melt | dissolved 12.7 g of zinc nitrate in 335.8 g of pure water was added at 5.8 g / min. During the addition, the pH was maintained in the range of 8.5 to 9.5 while adding an anion exchange resin (Mitsubishi Chemical Corporation: Diaion SA20).
Next, after separating the resin from the dispersion, 34.5 g of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: SN-350, solid content concentration 16.5 wt%) was added and heated at 95 ° C. for 1 hour, Antibacterial and deodorant metal component-supported titanium oxide system consisting of a titanium oxide / silica fine particle (TS-1) dispersion that has been cooled and then concentrated on an ultrafiltration membrane to support zinc with a solid concentration of 10% by weight A fine particle (1) dispersion was obtained.

The amount of ZnO supported in the antibacterial and deodorant metal component-supported titanium oxide fine particles (1) was 8.0% by weight.
The average particle size of the antibacterial / deodorant metal component-supported titanium oxide fine particles (1) was 5 nm as measured with an ultracentrifugal automatic particle size distribution analyzer (CAPA-700). Further, the particles were amorphous by X-ray diffraction.

Preparation of titanium oxide antibacterial / deodorant dispersion (1) Antibacterial / deodorant metal component-supported titanium oxide microparticles (1) with a solid content of 10% by weight Silica sol (JGC) Catalyst Chemical Co., Ltd. product: SI-500, average particle size 7 nm, solid content concentration 10.0 wt%, solid content Na ₂ O content 22.0 wt%) 100 g were mixed and solid content concentration 10.0 A weight percent titanium oxide antibacterial / deodorant dispersion (1) was prepared.

The stability of the titanium oxide antibacterial / deodorant dispersion (1) was evaluated by the following method, and the results are shown in the table.
Stability evaluation In a closed glass container, left at 50 ° C for 1 week, then visually confirmed.
No gelation: ◎
Gelation, thin cloudiness: ○
Gelation, cloudiness separation: △
Gelation, cloudy precipitation: ×

Preparation of antibacterial / deodorant cloth (1) 6.0 g of titanium oxide antibacterial / deodorant dispersion (1) is dispersed in 94 g of pure water, and cloth (cotton polyester blend (T / C): 25 cm x 25 cm) ) 6.25 g was immersed, squeezed with 100% pickup, and then dried at 110 ° C. for 30 minutes to prepare an antibacterial / deodorant cloth (1).
For the antibacterial / deodorant cloth (1), the adhesion, antibacterial performance and deodorant performance of the titanium oxide antibacterial / deodorant were evaluated by the following methods and standards, and the results are shown in the table.

Antibacterial performance
The test was conducted in accordance with JIS L 1902.
Place 0.4 g of antibacterial / deodorant cloth (1) in a vial, and add a bacterial suspension (1/20 concentration of nutrient broth: meat extract (150 mg / L), peptone (250 mg / L), surface activity 0.2 ml of the agent Tween 80 (0.05% by weight) was added dropwise, and after culturing at 37 ° C. for 18 hours, it was washed out and the number of viable bacteria was measured, and Staphylococcus aureus, Escherichia coli, and MRSA were used as test bacteria.
The antibacterial performance is evaluated by the bactericidal activity value of the following formula (1), and the results are shown in the table.
Bactericidal activity value = Log (number of inoculated bacteria)-Log (number of viable test pieces) (1)

Deodorant performance
Deodorization test (1) :
An antibacterial / deodorant cloth (1) (10 cm × 10 cm) was placed in a 5 L Tedlar bag, 3 L of hydrogen sulfide gas having a concentration of 4 ppm was sealed, and a fluorescent lamp was irradiated for 2 hours at room temperature. Next, the residual hydrogen sulfide gas concentration was measured with a detector tube, and the deodorization rate is shown in the table.
Deodorization test (2) :
An antibacterial / deodorant cloth (1) (10 cm × 10 cm) was placed in a 5 L Tedlar bag, 3 L of ammonia gas having a concentration of 100 ppm was sealed, and irradiated with a fluorescent lamp at room temperature for 2 hours. Next, the residual ammonia gas concentration was measured with a detection tube, and the deodorization rate is shown in the table.
Deodorization test (3) :
An antibacterial / deodorant cloth (1) (10 cm × 10 cm) was placed in a 5 L Tedlar bag, 3 L of acetic acid gas having a concentration of 50 ppm was sealed, and irradiated with a fluorescent lamp for 2 hours at room temperature. Next, the residual acetic acid gas concentration was measured with a detector tube, and the deodorization rate is shown in the table.

Adhesive antibacterial / deodorant cloth (1) using a synthetic detergent for washing, water flow is weak, bath ratio is 1:30, washing is at 40 ° C for 5 minutes, and the first rinse is at a temperature of 30 ° C or less for 2 minutes The second rinse was performed at a temperature of 30 ° C. or less for 2 minutes, and this was defined as one cycle.
The washed antibacterial / deodorant cloth (1) is subjected to the deodorization test (3), and the maintenance rate of the deodorant performance after selection is evaluated as adhesion according to the following classification, and the results are shown in the table.
Deodorant performance maintenance rate of 90% or more: ◎
Deodorant performance maintenance rate 50% to less than 90%: ○
Deodorant performance maintenance rate 10% to less than 50%: △
Deodorant performance maintenance rate of less than 10%: ×

[Example 2]
Preparation of Titanium Oxide Antibacterial / Deodorant Dispersion (2) In Example 1, except that 33 g of silica sol was mixed as acidic substance-adsorbing fine particles, the titanium oxide antibacterial antibacterial / A deodorant dispersion (2) was prepared.
The stability of the titanium oxide antibacterial / deodorant dispersion (2) was evaluated, and the results are shown in the table.

Preparation of antibacterial / deodorant cloth (2) An antibacterial / deodorant cloth (2) was prepared in the same manner as in Example 1 except that the titanium oxide antibacterial / deodorant dispersion (2) was used.
For the antibacterial / deodorant cloth (2), the adhesion, antibacterial performance and deodorant performance of the titanium oxide antibacterial / deodorant were evaluated, and the results are shown in the table.

[Example 3]
Preparation of Titanium Oxide Antibacterial / Deodorant Dispersion (3) In Example 1, except that 133 g of silica sol was mixed as acidic substance-adsorbing fine particles, a titanium oxide antibacterial / A deodorant dispersion (3) was prepared.
The stability of the titanium oxide antibacterial / deodorant dispersion (3) was evaluated, and the results are shown in the table.

Preparation of antibacterial / deodorant cloth (3) An antibacterial / deodorant cloth (3) was prepared in the same manner as in Example 1 except that the titanium oxide antibacterial / deodorant dispersion (3) was used.
For the antibacterial / deodorant cloth (3), the adhesion, antibacterial performance and deodorant performance of the titanium oxide antibacterial / deodorant were evaluated, and the results are shown in the table.

[Example 4]
Preparation of Titanium Oxide Antibacterial / Deodorant Dispersion (4) Prepared in the same manner as in Example 1 was added to 100 g of antibacterial / deodorant metal component-supported titanium oxide fine particles (1) dispersion having a solid content concentration of 10% by weight. As the acidic substance-adsorbing fine particles, 13.9 g of alumina hydrate fine particles (manufactured by JGC Catalysts & Chemicals Co., Ltd .: AP-1, Al ₂ O ₃ content 72 wt%, average particle diameter 200 nm) and 86.1 g of water were mixed. Thus, a titanium oxide antibacterial / deodorant dispersion (4) having a solid content of 10.0% by weight was prepared.
The stability of the titanium oxide antibacterial / deodorant dispersion (4) was evaluated, and the results are shown in the table.

Preparation of antibacterial / deodorant cloth (4) An antibacterial / deodorant cloth (4) was prepared in the same manner as in Example 1 except that the titanium oxide antibacterial / deodorant dispersion (4) was used.
For the antibacterial / deodorant cloth (4), the adhesion, antibacterial performance and deodorant performance of the titanium oxide antibacterial / deodorant were evaluated, and the results are shown in the table.

[Example 5]
Preparation of Titanium Oxide Antibacterial / Deodorant Dispersion (5) Preparation of antibacterial / deodorant metal component-supported titanium oxide fine particles (1) having a solid content concentration of 10% by weight prepared in the same manner as in Example 1 As acidic substance adsorbing fine particles, 4.6 g of alumina hydrate fine particles (manufactured by JGC Catalysts & Chemicals Co., Ltd .: AP-1, Al ₂ O ₃ content 72 wt%, average particle size 200 nm) and 28.7 g of water were mixed. Thus, a titanium oxide antibacterial / deodorant dispersion (5) having a solid content of 10.0% by weight was prepared.
The stability of the titanium oxide antibacterial / deodorant dispersion (5) was evaluated, and the results are shown in the table.

Preparation of antibacterial / deodorant cloth (5) An antibacterial / deodorant cloth (5) was prepared in the same manner as in Example 1 except that the titanium oxide antibacterial / deodorant dispersion (5) was used.
For the antibacterial / deodorant cloth (5), the adhesion, antibacterial performance and deodorant performance of the titanium oxide antibacterial / deodorant were evaluated, and the results are shown in the table.

[Example 6]
Preparation of Titanium Oxide Antibacterial / Deodorant Dispersion (6) Preparation of Antibacterial / Deodorant Metal Component-Supported Titanium Oxide Fine Particles (1) Dispersion Prepared as in Example 1 Alumina hydrate fine particles (manufactured by JGC Catalysts & Chemicals Co., Ltd .: AP-1, Al ₂ O ₃ content 72% by weight, average particle size 200 nm) 18.5 g and water 114.8 g are mixed as acidic substance adsorbing fine particles. Thus, a titanium oxide antibacterial / deodorant dispersion (6) having a solid content of 10.0% by weight was prepared.
The stability of the titanium oxide antibacterial / deodorant dispersion (6) was evaluated, and the results are shown in the table.

Preparation of antibacterial / deodorant cloth (6) An antibacterial / deodorant cloth (6) was prepared in the same manner as in Example 1 except that the titanium oxide antibacterial / deodorant dispersion (6) was used.
For the antibacterial / deodorant cloth (6), the adhesion, antibacterial performance and deodorant performance of the titanium oxide antibacterial / deodorant were evaluated, and the results are shown in the table.

[Example 7]
Preparation of Titanium Oxide Antibacterial / Deodorant Dispersion (7) Prepared in the same manner as in Example 1 was added to 100 g of antibacterial / deodorant metal component-supported titanium oxide fine particles (1) dispersion having a solid content concentration of 10% by weight. Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: SI-500, average particle diameter 7 nm, solid content concentration 10.0 wt%, Na ₂ O content 22.0 wt% in solid content) as acidic substance adsorbing fine particles 50 g, 7 g of alumina hydrate fine particles (manufactured by JGC Catalysts & Chemicals Co., Ltd .: AP-1, Al ₂ O ₃ content 72 wt%, average particle diameter 200 nm) and 43 g of water were mixed to obtain a solid content concentration of 10.0 wt%. A titanium oxide antibacterial / deodorant dispersion (7) was prepared.
The stability of the titanium oxide antibacterial / deodorant dispersion (7) was evaluated, and the results are shown in the table.

Preparation of antibacterial / deodorant cloth (7) An antibacterial / deodorant cloth (7) was prepared in the same manner as in Example 1 except that the titanium oxide antibacterial / deodorant dispersion (7) was used.
For the antibacterial / deodorant cloth (7), the adhesion, antibacterial performance and deodorant performance of the titanium oxide antibacterial / deodorant were evaluated, and the results are shown in the table.

[Example 8]
Preparation of antibacterial / deodorant metal component-supported titanium oxide fine particles (2) dispersion Titanium sulfate was dissolved in water to prepare an aqueous solution containing 1.0% by weight as TiO ₂ . To this solution, 15% by weight of ammonia water is gradually added with stirring to obtain a white slurry liquid, which is filtered through a glass filter, the cake is thoroughly washed with water, and a hydrous titanic acid cake is obtained. Obtained. To 31.4 g of this cake, water and 219.8 g of hydrogen peroxide having a concentration of 33% by weight were added, and then heated at 80 ° C. for 14 hours to obtain a TiO ₂ concentration of 1.0% by weight, pH 8.2, transparent yellowish brown. 3136 g of titanic acid solution was obtained.

Subsequently, the pH was adjusted to 9.0 with an aqueous ammonia solution having a concentration of 15% by weight. At this time, the amount of 15% by weight aqueous ammonia solution used was 4.2 g.
Subsequently, it heated until it became temperature 50 degreeC, and the aqueous solution which melt | dissolved 10.6 g of copper nitrate in 335.8 g of pure water was added at 5.8 g / min. During the addition, the pH was maintained in the range of 8.5 to 9.5 while adding an anion exchange resin (Mitsubishi Chemical Corporation: Diaion SA20).
Next, after separating the resin from the dispersion, 34.5 g of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: SN-350, solid content concentration 16.5 wt%) was added and heated at 95 ° C. for 1 hour, Antibacterial and deodorant metal component-supported titanium oxide system consisting of a titanium oxide / silica fine particle (TS-2) dispersion supporting copper with a solid content concentration of 10% by weight after cooling and concentrating with an ultrafiltration membrane A fine particle (2) dispersion was obtained.
The amount of CuO supported in the antibacterial and deodorant metal component-supported titanium oxide fine particles (2) was 8.0% by weight.
The average particle size of the antibacterial / deodorant metal component-supported titanium oxide fine particles (2) was 5 nm. Further, the particles were amorphous by X-ray diffraction.

Preparation of titanium oxide antibacterial / deodorant dispersion (8) Antibacterial / deodorant metal component-supported titanium oxide fine particles (2) with a solid content of 10% by weight Silica sol (JGC) Catalyst Chemical Co., Ltd. product: SI-500, average particle size 7 nm, solid content concentration 10.0 wt%, solid content Na ₂ O content 22.0 wt%) 100 g were mixed and solid content concentration 10.0 A weight percent titanium oxide antibacterial / deodorant dispersion (8) was prepared.
The stability of the titanium oxide antibacterial / deodorant dispersion (8) was evaluated, and the results are shown in the table.

Preparation of antibacterial / deodorant cloth (8) An antibacterial / deodorant cloth (8) was prepared in the same manner as in Example 1 except that the titanium oxide antibacterial / deodorant dispersion (8) was used.
For the antibacterial / deodorant cloth (8), the adhesion, antibacterial performance and deodorant performance of the titanium oxide antibacterial / deodorant were evaluated, and the results are shown in the table.

[Example 9]
Preparation of antibacterial and deodorant metal component-supported titanium oxide fine particles (3) dispersion Titanium sulfate was dissolved in water to prepare an aqueous solution containing 1.0% by weight as TiO ₂ . To this solution, 15% by weight of ammonia water is gradually added with stirring to obtain a white slurry liquid, which is filtered through a glass filter, the cake is thoroughly washed with water, and a hydrous titanic acid cake is obtained. Obtained. To 31.4 g of this cake, water and 219.8 g of hydrogen peroxide having a concentration of 33% by weight were added, and then heated at 80 ° C. for 14 hours to obtain a TiO ₂ concentration of 1.0% by weight, pH 8.2, transparent yellowish brown. 3136 g of titanic acid solution was obtained.

Subsequently, the pH was adjusted to 9.0 with an aqueous ammonia solution having a concentration of 15% by weight. At this time, the amount of 15% by weight aqueous ammonia solution used was 4.2 g.
Subsequently, it heated until it became temperature 50 degreeC, and the aqueous solution which melt | dissolved 12.7 g of zinc nitrate in 335.8 g of pure water was added at 5.8 g / min. During the addition, the pH was maintained in the range of 8.5 to 9.5 while adding an anion exchange resin (Mitsubishi Chemical Corporation: Diaion SA20).
Next, after separating the resin from the dispersion, 34.5 g of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: SN-350, solid content concentration 16.5% by weight) was added and heated at 160 ° C. for 16 hours, Antibacterial / deodorant metal component-supported titanium oxide system consisting of a dispersion of titanium oxide / silica fine particles (TS-3) supporting zinc with a solid concentration of 10% by weight after cooling and concentrating on an ultrafiltration membrane A fine particle (3) dispersion was obtained.
The amount of ZnO supported in the antibacterial and deodorant metal component-supported titanium oxide fine particles (3) was 8.0% by weight.
The average particle diameter of the antibacterial / deodorant metal component-supported titanium oxide fine particles (3) was 10 nm. The particles were anatase by X-ray diffraction.

Preparation of Titanium Oxide Antibacterial / Deodorant Dispersion (9) In Example 1, a solid content concentration of 10 was similarly obtained except that the antibacterial / deodorant metal component-supported titanium oxide fine particles (3) dispersion was used. A 0% by weight titanium oxide antibacterial / deodorant dispersion (9) was prepared.
The stability of the titanium oxide antibacterial / deodorant dispersion (9) was evaluated, and the results are shown in the table.

Preparation of antibacterial / deodorant cloth (9) An antibacterial / deodorant cloth (9) was prepared in the same manner as in Example 1 except that the titanium oxide antibacterial / deodorant dispersion (9) was used.
For the antibacterial / deodorant cloth (9), the adhesion, antibacterial performance and deodorant performance of the titanium oxide antibacterial / deodorant were evaluated, and the results are shown in the table.

[Example 10]
Preparation of antibacterial and deodorant metal component-supported titanium oxide fine particles (4) dispersion Titanium sulfate was dissolved in water to prepare an aqueous solution containing 1.0% by weight as TiO ₂ . To this solution, 15% by weight of ammonia water is gradually added with stirring to obtain a white slurry liquid, which is filtered through a glass filter, the cake is thoroughly washed with water, and a hydrous titanic acid cake is obtained. Obtained. To 31.4 g of this cake, water and 219.8 g of hydrogen peroxide having a concentration of 33% by weight were added, and then heated at 80 ° C. for 14 hours to obtain a TiO ₂ concentration of 1.0% by weight, pH 8.2, transparent yellowish brown. 3136 g of titanic acid solution was obtained.

Subsequently, the pH was adjusted to 9.0 with an aqueous ammonia solution having a concentration of 15% by weight. At this time, the amount of 15% by weight aqueous ammonia solution used was 4.2 g.
Subsequently, it heated until it became temperature 50 degreeC, and the aqueous solution which melt | dissolved 10.6 g of copper nitrate in 335.8 g of pure water was added at 5.8 g / min. During the addition, the pH was maintained in the range of 8.5 to 9.5 while adding an anion exchange resin (Mitsubishi Chemical Corporation: Diaion SA20).
Next, after separating the resin from the dispersion, 34.5 g of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: SN-350, solid content concentration 16.5% by weight) was added and heated at 160 ° C. for 16 hours, Antibacterial and deodorant metal component-supported titanium oxide system consisting of a dispersion of titanium oxide and silica fine particles (TS-4) supporting copper with a solid content concentration of 10% by weight after cooling and concentrating with an ultrafiltration membrane A fine particle (4) dispersion was obtained.
The amount of CuO supported in the antibacterial and deodorant metal component-supported titanium oxide fine particles (4) was 8.0% by weight.
The average particle diameter of the antibacterial / deodorant metal component-supported titanium oxide fine particles (4) was 10 nm. The particles were anatase by X-ray diffraction.

Preparation of Titanium Oxide Antibacterial / Deodorant Dispersion (10) In Example 1, the solid content concentration of 10. was changed except that the antibacterial / deodorant metal component-supported titanium oxide fine particles (4) dispersion was used. A 0% by weight titanium oxide antibacterial / deodorant dispersion (10) was prepared.
The stability of the titanium oxide antibacterial / deodorant dispersion (10) was evaluated, and the results are shown in the table.

Preparation of antibacterial / deodorant cloth (10) An antibacterial / deodorant cloth (10) was prepared in the same manner as in Example 1 except that the titanium oxide antibacterial / deodorant dispersion (10) was used.
For the antibacterial / deodorant cloth (10), the adhesion, antibacterial performance and deodorant performance of the titanium oxide antibacterial / deodorant were evaluated, and the results are shown in the table.

[Example 11]
It was prepared 5 wt% of titanium tetrachloride solution as TiO ₂ antibacterial and deodorant metal component carrying a titanium oxide fine particles (5) Preparation of titanium tetrachloride aqueous dispersion was diluted with pure water. This aqueous solution was neutralized and hydrolyzed by adding it to 15% by weight ammonia water whose temperature was adjusted to 5 ° C. The pH after addition of the aqueous titanium tetrachloride solution was 10.5. Subsequently, the produced gel was washed by filtration to obtain an orthotitanic acid gel having a concentration of 10% by weight as TiO ₂ .
After 1000 g of this orthotitanic acid gel was dispersed in 29000 g of pure water, 8000 g of a hydrogen peroxide solution having a concentration of 35% by weight was added to form a peroxotitanic acid aqueous solution, followed by heating at 85 ° C. for 3 hours while stirring. A dispersion of titanium oxide fine particles (T-5) having a concentration of 3.0% by weight as TiO ₂ was prepared.

Separately carrying deodorant antibacterial component 470.9 g of water was added to 29.1 g of zinc nitrate to prepare a zinc nitrate aqueous solution having a concentration of 1.0% by weight.
9.2 kg of a titanium oxide fine particle (T-5) dispersion in which the TiO 2 concentration was diluted to 1.0% by weight was collected in a preparation tank and heated to 50 ° C. while stirring. Next, after adding an aqueous ammonia solution having a concentration of 15% by weight so that the pH of the titanium oxide fine particle (T-5) dispersion becomes 9.0, the aqueous zinc nitrate solution was added at a rate of 10 g / min with a peristaltic pump. did. When the pH of the titanium oxide fine particle (T-5) dispersion began to drop due to the addition of the aqueous zinc nitrate solution, anion exchange resin (Mitsubishi Chemical) was added in small portions so as to maintain the pH at 8.5. This operation was continued until the addition of the aqueous zinc solution was completed. The total amount of anion exchange resin used was 1100 g, and the final pH of the titanium oxide fine particle (T-5) dispersion was 8.4.

After the ion exchange resin was separated from the titanium oxide fine particle (T-5) dispersion, it was then heated at 95 ° C. for 3 hours, cooled, and then with an ultrafiltration membrane device with 200 times water with respect to the TiO 2 weight. After washing, it is concentrated with an ultrafiltration membrane device, and antibacterial and deodorant metal component-supported titanium oxide-based fine particles (T-5) dispersion containing zinc with a solid content concentration of 10% by weight (T-5) 5) A dispersion was obtained. The amount of ZnO supported in the antibacterial and deodorant metal component-supported titanium oxide fine particles (5) was 8.0% by weight.
The average particle size of the antibacterial and deodorant metal component-supported titanium oxide fine particles (5) was 5 nm. Further, the particles were amorphous by X-ray diffraction.

Preparation of Titanium Oxide Antibacterial / Deodorant Dispersion (11) In Example 1, a solid content concentration of 10 was similarly obtained except that the antibacterial / deodorant metal component-supported titanium oxide fine particles (5) dispersion was used. A 0% by weight titanium oxide antibacterial / deodorant dispersion (11) was prepared.
The stability of the titanium oxide antibacterial / deodorant dispersion (11) was evaluated, and the results are shown in the table.
Preparation of antibacterial / deodorant cloth (11) An antibacterial / deodorant cloth (11) was prepared in the same manner as in Example 1 except that the titanium oxide antibacterial / deodorant dispersion (11) was used.
For the antibacterial / deodorant cloth (11), the adhesion, antibacterial performance and deodorant performance of the titanium oxide antibacterial / deodorant were evaluated, and the results are shown in the table.

[Comparative Example 1]
Preparation of Titanium Oxide Antibacterial / Deodorant Dispersion (R1) Prepared in the same manner as in Example 1, antibacterial / deodorant metal component-supported titanium oxide fine particles (1) having a solid concentration of 10% by weight were solidified. A titanium oxide antibacterial / deodorant dispersion (R1) having a concentration of 10.0% by weight was obtained.
The stability of the titanium oxide antibacterial / deodorant dispersion (R1) was evaluated, and the results are shown in the table.

Preparation of antibacterial / deodorant cloth (R1) An antibacterial / deodorant cloth (R1) was prepared in the same manner as in Example 1 except that the titanium oxide antibacterial / deodorant dispersion (R1) was used.
For the antibacterial / deodorant cloth (R1), the adhesion, antibacterial performance and deodorant performance of the titanium oxide antibacterial / deodorant were evaluated, and the results are shown in the table.

[Comparative Example 2]
Preparation of titanium oxide antibacterial / deodorant dispersion (R2) In the same manner as in Example 1, antibacterial / deodorant metal component-supported titanium oxide fine particles (1) having a solid content concentration of 10% by weight were added to 100 g of the dispersion. Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: SI-500, average particle diameter 7 nm, solid content concentration 10.0 wt%, solid content Na ₂ O content 22.0 wt%) 5 g were mixed to prepare a titanium oxide antibacterial / deodorant dispersion (R2) having a solid content of 10.0% by weight.
The stability of the titanium oxide antibacterial / deodorant dispersion (R2) was evaluated, and the results are shown in the table.

Preparation of antibacterial / deodorant cloth (R2) An antibacterial / deodorant cloth (R2) was prepared in the same manner as in Example 1 except that the titanium oxide antibacterial / deodorant dispersion (R2) was used.
The antibacterial / deodorant cloth (R2) was evaluated for the adhesion, antibacterial performance and deodorant performance of the titanium oxide antibacterial / deodorant, and the results are shown in the table.

[Comparative Example 3]
Preparation of Titanium Oxide Antibacterial / Deodorant Dispersion (R3) Prepared in the same manner as in Example 1, antibacterial / deodorant metal component-supported titanium oxide fine particles (1) having a solid concentration of 10% by weight were added to 100 g of the dispersion. 300 g of silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: SI-500, average particle diameter 7 nm, solid content concentration 10.0 wt%, Na ₂ O content 22.0 wt% in solid content) as acidic substance adsorbing fine particles By mixing, a titanium oxide antibacterial / deodorant dispersion (R3) having a solid content concentration of 10.0% by weight was prepared.
The stability of the titanium oxide antibacterial / deodorant dispersion (R3) was evaluated, and the results are shown in the table.

Preparation of antibacterial / deodorant cloth (R3) An antibacterial / deodorant cloth (R3) was prepared in the same manner as in Example 1 except that the titanium oxide antibacterial / deodorant dispersion (R3) was used.
For the antibacterial / deodorant cloth (R3), the adhesion, antibacterial performance and deodorant performance of the titanium oxide antibacterial / deodorant were evaluated, and the results are shown in the table.

[Comparative Example 4]
In accordance with Example 1 of JP2009-209089, a fine crystalline aluminosilicate was prepared.
Preparation of Silica Alumina Hydrogel Slurry (1-1) 5203 g of sodium aluminate aqueous solution (Al ₂ O ₃ concentration 22 wt%, Na ₂ O concentration 17 wt%) was added to 203 g NaOH aqueous solution (NaOH concentration 48 wt%). Stir for 1 hour.
Subsequently, 740 g of No. 3 water glass having a SiO ₂ concentration of 16.2% by weight was added to this over 1 hour. At this time, the temperature was maintained at 30 ° C. Next, after stirring for 30 minutes, the mixture was allowed to stand at 38 ° C. for 12 hours to prepare a silica-alumina hydrogel slurry (1-1).
The oxide molar ratio of the silica-alumina hydrogel slurry (1-1) was Na ₂ O: Al ₂ O ₃ : SiO ₂ : H ₂ O = 16.0: 1.0: 16.0: 332.

Preparation of Silica Alumina Hydrogel Slurry (2-1) Add 500 g of silica alumina hydrogel slurry (1-1) with stirring to 500 g of No. 3 water glass with a SiO ₂ concentration of 24% by weight, and stir for 30 minutes. A slurry (2-1) was prepared. The oxide molar ratio was Na ₂ O: Al ₂ O ₃ : SiO ₂ : H ₂ O = 26.0: 1.0: 48.1: 637.

Subsequently, the silica alumina hydrogel slurry (2-1) was hydrothermally treated at 60 ° C. for 48 hours. Subsequently, the mixture was centrifuged and thoroughly washed with ion exchange water to synthesize colloidal faujasite type zeolite (1). The obtained colloidal faujasite type zeolite (1) had an average primary particle size (D ₁ ) of 60 nm and an average secondary particle size (D ₂ ) of 130 nm.

Preparation of antibacterial / deodorant metal component- supported zeolite fine particles (1) dispersion liquid 10 g of the colloidal faujasite type zeolite (1) which is the NaY type obtained above is dispersed in 100 g of pure water, and the concentration is obtained while stirring. The pH was adjusted to 5.5-6.0 with 10% by weight aqueous nitric acid solution. Separately, 1.8 g of zinc nitrate was dissolved in 100 g of pure water, and a pH adjusted NaY-type zeolite suspension slurry was added with stirring. After the addition, the slurry temperature was adjusted to 60 ° C., stirred for 1 hour, filtered, washed, added with water, and added with ZnO, 8.0 wt% solid content concentration of 10 wt% antibacterial / deodorant metal A component-supported zeolite fine particle (1) dispersion was prepared.

Preparation of zeolite antibacterial / deodorant dispersion (R4) Antibacterial / deodorant metal component-supported zeolite fine particles (1) with a solid concentration of 10% by weight Co., Ltd .: SI-500, average particle size 7 nm, solid content concentration 10.0 wt%, solid content Na ₂ O content 22.0 wt%) 100 g were mixed to obtain a solid content concentration 10.0 wt% A zeolite antibacterial / deodorant dispersion (R4) was prepared.
The stability of the zeolite antibacterial / deodorant dispersion (R4) was evaluated, and the results are shown in the table.

Preparation of antibacterial / deodorant cloth (R4) An antibacterial / deodorant cloth (R4) was prepared in the same manner as in Example 1, except that the zeolite antibacterial / deodorant dispersion (R4) was used.
The antibacterial / deodorant cloth (R4) was evaluated for the adhesion, antibacterial performance, and deodorant performance of the zeolite antibacterial / deodorant, and the results are shown in the table.

Claims (11)

  Antibacterial / deodorant metal component-supported titanium oxide fine particles and acidic substance-adsorbing fine particles dispersed in water. The concentration (C _T ) of the antibacterial / deodorant metal component-supported titanium oxide fine particles is in the range of 0.01 to 20% by weight, and the concentration (C _A ) of the acidic substance-adsorbing fine particles is 0.001 to 10% by weight. The ratio (C _A ) / (C _T ) between the concentration (C _A ) and the concentration (C _T ) is in the range of 0.01 to 2 in the range of 0.01%. Titanium oxide antibacterial and deodorant dispersion.   The titanium oxide antibacterial / deodorant dispersion according to claim 1 or 2, wherein the acidic substance-adsorbing fine particles are alkali-containing silica fine particles.   The titanium oxide antibacterial / deodorant dispersion according to claim 1, wherein the acidic substance-adsorbing fine particles are alumina fine particles.   The antibacterial / deodorant metal component is at least one selected from silver, copper, zinc, tin, cobalt, nickel, and manganese, and the titanium oxide antibacterial according to any one of claims 1 to 4・ Deodorant dispersion.   6. The titanium oxide antibacterial / deodorant dispersion according to claim 1, wherein an average particle size of the antibacterial / deodorant metal component-supported titanium oxide fine particles is in the range of 2 to 50 nm. liquid.   The amount of the antibacterial / deodorant metal component supported is in the range of 0.1 to 20% by weight as an oxide in the antibacterial / deodorant metal component-supported titanium oxide fine particles. The titanium oxide antibacterial / deodorant dispersion according to any one of the above.   The titanium oxide-based antibacterial / deodorant dispersion according to any one of claims 1 to 7, wherein the titanium oxide-based fine particles are amorphous.   The titanium oxide-based fine particles contain silica and / or zirconia, and the content of silica and / or zirconia in the titanium oxide-based fine particles is in the range of 1 to 20% by weight as an oxide. The titanium oxide antibacterial / deodorant dispersion according to any one of 8 above.   An antibacterial / deodorant fiber or cloth obtained by applying the titanium oxide antibacterial / deodorant dispersion according to any one of claims 1 to 9.   The antibacterial / deodorant fiber or cloth according to claim 10, wherein a coating amount of the titanium oxide antibacterial / deodorant is in a range of 0.01 to 2% by weight as a solid content.