JP5574813B2 - Manufacturing method of titanium oxide-based fine particles, antibacterial / deodorant using the titanium oxide-based fine particles, coating solution for forming antibacterial / deodorant coating, and substrate with antibacterial / deodorant coating - Google Patents

Description

  The present invention relates to a method for producing a titanium oxide fine particle having an ultrafine and uniform particle size distribution, a titanium oxide fine particle obtained by the method, an antibacterial / deodorant containing the titanium oxide fine particle, and an antibacterial / deodorant property. The present invention relates to a coating liquid for forming a coating film and a substrate with an antibacterial / deodorant coating film.

In recent years, there has been a demand for improvement in living environment such as cleanliness, hygiene, safety, and comfort.
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 inorganic oxide particle-based antibacterial agent, deodorant, and antibacterial / deodorant are usually used by kneading fine particle powder into resin or fiber, or using it as a base material in paint or ink. Apply and use. Alternatively, it is molded and used as a filter medium.
However, when an inorganic oxide particle-based antibacterial agent or deodorant is applied to a substrate to form a thin film, the adhesion to the substrate, flatness of the film surface, transparency, durability, etc. There was a problem.
Conventionally, a binder component is used to form and use a film on a substrate. However, when a conventionally known binder component is used, there is a problem that antibacterial performance and deodorizing performance cannot be sufficiently exhibited.

  The applicant of the present application discloses a coating solution for forming a film containing peroxopolytitanic acid dissolved in water and / or an organic solvent as a matrix component in Japanese Patent Application Laid-Open No. 07-286114 (Patent Document 5). However, after that, it has been found that a film formed using this coating liquid for forming a film can decompose without odor components such as ammonia by decomposing odor components.

However, even when a thin film containing an inorganic oxide particle-based antibacterial agent or deodorant using such peroxopolytitanic acid as a matrix component is formed, the stability of the coating solution becomes insufficient, and the resulting thin film May have insufficient adhesion to the base material, transparency and surface flatness, and cracks may occur, and in addition, antibacterial performance and deodorization performance were not sufficient.

Recently, in living spaces, public facilities, medical facilities, nursing homes, car interiors, etc., in addition to antibacterial, antifungal, algal, antiviral, antiallergen, insect pest repellent, formaldehyde contained in building materials, cigarette smoking Therefore, there is a need for an antibacterial and deodorant transparent thin film that removes harmful substances such as acetaldehyde and has a deodorizing performance against ammonia generated in a toilet, etc., and does not impair the aesthetics. Moreover, an antibacterial and deodorant that can further improve the above performance and can be maintained over a long period of time is demanded.
Further, when crystalline titanium oxide is used as the antibacterial / deodorant, discoloration or performance is deteriorated when it is used in contact with an organic base material, fiber or the like, and there is a limitation in use and usage.

  As a method for producing titanium oxide-based fine particles, for example, JP-A 63-17221 (Patent Document 6), JP-A 62-235215 (Patent Document 7), JP-A 7-286114 (Patent Document) 8), variously disclosed in Japanese Patent Application Laid-Open No. 2008-44826 (Patent Document 9), etc., but the particle size is small, the particle size distribution is uniform, and amorphous titanium oxide fine particles are not disclosed.

As a result of intensive studies, the present inventors have used ammonia for the hydrolysis (neutralization) of titanium compounds in the preparation of titanium oxide-based fine particles, and when the addition rate of ammonia is performed within a predetermined speed range at a temperature lower than room temperature, Fine titanium oxide hydrate is obtained. When this is dissolved in hydrogen peroxide and heat-treated as necessary, amorphous titanium oxide fine particles having an average particle size of 10 nm or less and a uniform particle size distribution are obtained. It was found that it can be obtained in high yield.
In addition, a dispersion in which the above titanium oxide fine particles containing antibacterial and deodorant metal components are dispersed in an aqueous solution of a titanium chelate compound is stable for a long time without gelation, and the thin film obtained by applying this dispersion is transparent. Thus, the present invention has been completed by finding that it has excellent adhesion to the substrate.

JP-A-6-80527 JP-A-3-275627 Japanese Patent Laid-Open No. 1-283204 JP 2005-318999 A JP 07-286114 A JP-A-63-17221 Japanese Patent Laid-Open No. 62-235215 JP 7-286114 A JP 2008-44826 A

Since the titanium oxide-based fine particles are ultrafine particles, the present invention can carry a large amount of antibacterial / deodorant components, and even if it is fine, it does not agglomerate stably and is suitably used as an antibacterial / deodorant. Production method of titanium oxide fine particles that can be obtained, titanium oxide fine particles obtained, antibacterial / deodorant using the titanium oxide fine particles, antibacterial / deodorant coating film forming liquid, It aims at providing the base material with a deodorizing coating film.

The method for producing titanium oxide-based fine particles of the present invention is characterized by comprising the following steps (a) to (e).
(A) A step of preparing an aqueous titanium compound solution having a concentration of 0.5 to 20% by weight as TiO ₂ .
(B) When the number of moles of titanium compound as TiO ₂ (M _TiO2 ) is 1, while maintaining the temperature of the aqueous titanium compound solution in the range of 0 to 30 ° C., the number of moles of ammonia in the aqueous ammonia solution (M _NH3 ) is in the range of 1 to 10, and an aqueous ammonia solution is added at a rate of 1 to 10 hours / 1 mole (M _NH3 ) to prepare titanium oxide hydrate.
(C) A step of washing titanium oxide hydrate.
(D) To a titanium oxide hydrate dispersion having a concentration of 0.1 to 10% by weight as TiO ₂ , hydrogen peroxide water is _{added to the} number of moles (M _TiO2 ) of titanium oxide hydrate as TiO _2. A step of adding at a molar ratio (M _H2O2 ) / (M _TiO2 ) to the molar number of hydrogen oxide (M _H2O2 ) in the range of 1 to 10 and dissolving at a temperature of 10 to 100 ° C.
(E) A step of removing hydrogen peroxide while stirring at a temperature of 30 to 100 ° C. and aging.

Following the step (e), the following step (f) is preferably performed.
(F) A step of adding silica sol and / or zirconia sol to 0.1 to 15% by weight with respect to TiO ₂ .
Following the step (f), the following step (g) is preferably performed.
(G) A step of aging at a temperature of 30 to 80 ° C.
The titanium oxide-based fine particles are preferably amorphous.

The titanium oxide-based fine particles of the present invention have an average particle diameter (D) in the range of 3 to 10 nm, and the number ratio of titanium oxide-based fine particles having a particle diameter of average particle diameter (D) ± 2 nm is 70% or more. It is characterized by that.
The titanium oxide-based fine particles of the present invention are obtained by any one of the above production methods.

The antibacterial / deodorant of the present invention is a titanium oxide-based fine particle containing an antibacterial / deodorant component in the range of 0.1 to 25% by weight in terms of oxide, and has an average particle diameter (D) of 3 to 10 nm. In this range, the number ratio of titanium oxide fine particles having an average particle diameter (D) ± 2 nm is 70% or more.
The antibacterial / deodorant component is preferably one or more components selected from silver, copper, zinc, tin, cobalt, nickel, and manganese.
The titanium oxide-based fine particles preferably contain silica and / or zirconia in the range of 0.1 to 15% by weight with respect to TiO ₂ .
The titanium oxide-based fine particles are preferably amorphous.
The antibacterial / deodorant described above is preferably dispersed in an aqueous dispersion medium containing a fragrance compound.

The coating liquid for forming an antibacterial / deodorant coating film of the present invention comprises any one of the above antibacterial / deodorant agents.
This antibacterial / deodorant coating film-forming coating solution preferably contains a water-soluble metal chelate compound, the water-soluble metal chelate compound is preferably a titanium chelate compound, and the titanium chelate compound is a titanium lactate ammonium salt. It is preferable that

This coating solution for forming an antibacterial / deodorant coating film has a total solid content of 0.01 to 20% by weight, and the concentration of the antibacterial / deodorant as a solid content is 0.005 to 19. The concentration of the water-soluble metal chelate compound as TiO ₂ is in the range of 0.0001 to 10.0% by weight, the weight of the antibacterial / deodorant (W _a ) and the water-soluble metal. The weight ratio (W _b ) / (W _a ) of the weight (W _b ) of the chelate compound as TiO ₂ is preferably in the range of 0.005 to 1.0.

The substrate with an antibacterial / deodorant coating film of the present invention comprises a substrate and an antibacterial / deodorant coating film formed on the substrate, and the antibacterial / deodorant coating film is any of the above. It is an antibacterial / deodorant coating film formed using the coating solution for forming an antibacterial / deodorant coating film described above.
The content of the antibacterial / deodorant as a solid content in the antibacterial / deodorant coating is in the range of 50 to 99.5% by weight, and the content of the water-soluble metal chelate compound as TiO ₂ is 0.00. It is preferably in the range of 5 to 50% by weight.

According to the present invention, since the titanium oxide fine particles have a small particle size, a large amount of antibacterial / deodorant components can be supported, and even if fine, titanium oxide fine particles that are stable and do not aggregate are produced. be able to. Further, the titanium oxide-based fine particles can be produced with high yield. Furthermore, the antibacterial / deodorant using the titanium oxide-based fine particles is excellent in antibacterial performance and deodorization performance, and also has a discoloration-inhibiting effect with respect to discolorable antibacterial / deodorant components. The antibacterial / deodorant of the present invention is suitable as a coating liquid for forming an antibacterial / deodorant coating film and a substrate with an antibacterial / deodorant coating film.

[Production method of titanium oxide-based fine particles]
Below, the manufacturing method of the titanium oxide type microparticles | fine-particles based on this invention is demonstrated first.
The method for producing titanium oxide-based fine particles according to the present invention is characterized by comprising the following steps (a) to (e).
(A) A step of preparing an aqueous titanium compound solution having a concentration of 0.5 to 20% by weight as TiO ₂ .
(B) When the number of moles of titanium compound as TiO ₂ (M _TiO2 ) is 1, while maintaining the temperature of the aqueous titanium compound solution in the range of 0 to 30 ° C., the number of moles of ammonia in the aqueous ammonia solution (M _NH3 ) is in the range of 1 to 10, and an aqueous ammonia solution is added at a rate of 1 to 10 hours / 1 mole (M _NH3 ) to prepare titanium oxide hydrate.
(C) A step of washing titanium oxide hydrate.
(D) To a titanium oxide hydrate dispersion having a concentration of 0.1 to 10% by weight as TiO ₂ , hydrogen peroxide water is _{added to the} number of moles (M _TiO2 ) of titanium oxide hydrate as TiO _2. A step of adding at a molar ratio (M _H2O2 ) / (M _TiO2 ) with a mole number of hydrogen oxide (M _H2O2 ) in the range of 2 to 10 and dissolving at a temperature of 10 to 100 ° C.
(E) A step of removing hydrogen peroxide while stirring at a temperature of 30 to 100 ° C. and aging.

Hereinafter, each process is demonstrated in order.
Step (a)
An aqueous titanium compound solution having a concentration of 0.5 to 20% by weight as TiO ₂ is prepared.
As the titanium compound, a conventionally known titanium compound can be used, and for example, a titanium compound such as titanium chloride, titanium sulfate, titanyl sulfate, and organic acid titanium can be used.
The concentration of the titanium compound aqueous solution is preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight as TiO ₂ .
When the concentration of the titanium compound aqueous solution is less than 0.5% by weight as TiO ₂ , the yield may be lowered, and the productivity and economy may be lowered.
When the concentration of the titanium compound aqueous solution exceeds 20% by weight as TiO ₂ , the titanium oxide hydrate (gel) produced in the step (b) becomes a lump, and the particle diameter of the finally obtained titanium oxide fine particles May become too large, or the particle size distribution may be non-uniform.

Step (b)
While maintaining the temperature of the titanium compound aqueous solution in the range of 0 to 30 ° C., when the number of moles of titanium compound as TiO ₂ (M _TiO2 ) is 1, the number of moles of ammonia in the aqueous ammonia solution (M _NH3 ) is An aqueous ammonia solution is added at a rate of 1 to 10 hours / 1 mole (M _NH3 ) to prepare titanium oxide hydrate.
First, it is preferable to adjust and maintain the temperature of the titanium compound aqueous solution in the range of 0 to 30 ° C., more preferably 0 to 20 ° C.
When the temperature of the titanium compound aqueous solution exceeds 30 ° C., the primary particles of the titanium oxide hydrate (gel) to be produced increase, and the particle size of the finally obtained titanium oxide-based fine particles increases and the particle size distribution is not good. It may be uniform.
When the temperature of the titanium compound aqueous solution is less than 0 ° C., the primary particles of the titanium oxide hydrate (gel) to be produced are not further reduced, and the particle size distribution of the finally obtained titanium oxide fine particles is Furthermore, it does not become uniform.

Then, an aqueous ammonia solution is added to the titanium compound aqueous solution for hydrolysis (neutralization). When the number of moles of titanium compound as TiO ₂ (M _TiO2 ) is 1, the number of moles of ammonia in the aqueous ammonia solution to be added. (M _NH3 ) is preferably in the range of 1 to 10, more preferably 2 to 5.
When the number of moles of ammonia (M _NH3 ) is less than 1, the titanium compound may be insufficiently hydrolyzed, and the primary particles of the titanium oxide hydrate (gel) to be produced become larger and finally obtained. In some cases, the average particle size of the titanium oxide-based fine particles is larger than 10 nm, and the particle size distribution is not uniform, resulting in a decrease in yield.
Even if the number of moles of ammonia (M _NH3 ) exceeds 10, the primary particles of titanium oxide-based fine particles that are finally obtained are not further reduced in the primary particles of titanium oxide hydrate (gel). The diameter is not further reduced, and the particle size distribution of the finally obtained titanium oxide fine particles is not further uniformed.

Further, when the titanium compound is hydrolyzed to 1 mole as TiO ₂ , the addition rate of ammonia is in the range of 1 to 10 hours / 1 mole (M _NH3 ), and further 2 to 8 hours / 1 mole (M _NH3 ). It is preferable that it exists in.
When the addition rate of ammonia is less than 1 hour / 1 mole (M _NH3 ), the primary particles of titanium oxide hydrate (gel) to be produced become large and the hydrogen peroxide solubility in step (d) decreases. In some cases, the yield of the titanium oxide-based fine particles may decrease, and the particle diameter distribution of the finally obtained titanium oxide-based fine particles may increase and the particle size distribution may become non-uniform.
When the rate of addition of ammonia exceeds 10 hours / mole (M _NH3 ), the primary particles of titanium oxide hydrate (gel) that are produced are small, but large secondary particles are produced. The particle size distribution of the titanium oxide-based fine particles may be non-uniform.

  In the present invention, other basic compounds such as aqueous sodium hydroxide and sodium carbonate can be used in place of ammonia, but ammonia may be used even if it remains in the finally obtained titanium oxide-based fine particles. Can be easily removed, and the antibacterial / deodorant performance is not hindered.

Step (c)
Next, the titanium oxide hydrate (gel) is washed.
The washing method is not particularly limited as long as anions derived from the titanium compound in the titanium oxide hydrate (gel) can be removed, and conventionally known methods can be employed. For example, a method of pouring sufficient pure water, a method of pouring dilute ammonia water, and the like can be mentioned.
It is preferable that impurities (anions, etc.) in the titanium oxide hydrate (gel) after washing is 1% by weight or less, more preferably 0.1% by weight or less in the solid content (TiO ₂ ). When there are many such impurities, the amount of undissolved substances in hydrogen peroxide increases and the yield may decrease, and aggregated particles may be generated in the finally obtained titanium oxide-based fine particles.

Step (d)
Next, a washed titanium oxide hydrate dispersion having a concentration of TiO _{2 in} the range of 0.1 to 10% by weight, preferably 0.2 to 5% by weight is prepared.
When the concentration of the titanium oxide hydrate dispersion is less than 0.1% by weight as the solid content (TiO ₂ ), there is a problem that production efficiency, yield, and economy are lowered.
When the concentration of the titanium oxide hydrate dispersion exceeds 10% by weight as the solid content (TiO ₂ ), it takes a long time to dissolve, depending on the molar ratio of hydrogen peroxide to titanium oxide and the melting temperature described later. Or the dissolution may be insufficient, which causes a problem that the yield of the titanium oxide fine particles is lowered. Furthermore, the particle size distribution of the obtained titanium oxide-based fine particles may be non-uniform.

Titanium oxide hydrate dispersion liquid density adjustment, the molar ratio of the moles of the TiO ₂ of the titanium oxide hydrate (M _TiO2) the moles of hydrogen peroxide _{(M H2O2) (M H2O2)} / (M Hydrogen peroxide water is added so that _TiO2 ) is in the range of 2 to 10, more preferably 3 to 8.
When the molar ratio (M _H2O2 ) / (M _TiO2 ) is less than 2, although depending on the dissolution temperature, it may take time or undissolved titanium oxide hydrate may remain.

Even when the molar ratio (M _H2O2 ) / (M _TiO2 ) exceeds 10, further dissolution does not proceed, undissolved titanium oxide hydrate is reduced, and the yield of titanium oxide fine particles is improved. In addition, the amount of hydrogen peroxide becomes excessive, and the amount of hydrogen peroxide to be removed in the step (e) described later increases, which is not desirable from the viewpoint of economy.

It is preferable that the temperature at the time of melt | dissolution exists in the range of 10-100 degreeC, Furthermore, 30-80 degreeC.
When the dissolution temperature is less than 10 ° C., it may take time for dissolution or unreacted titanium oxide hydrate may remain, and the yield of titanium oxide-based fine particles may be insufficient.
If the melting temperature exceeds 100 ° C., the resulting titanium oxide fine particles may have an excessively large particle size or a non-uniform particle size distribution.
The dissolution time varies depending on the temperature, but refers to the time when the aqueous peroxotitanic acid solution formed after starting dissolution and once yellowing becomes transparent, usually 0.5 to 12 hours.

Step (e)
The dispersion is aged by removing hydrogen peroxide while stirring at a temperature of 30 to 100 ° C., further 40 to 80 ° C.
If the temperature at this time is less than 30 ° C., it may take time to remove hydrogen peroxide, the aging effect may be insufficient, and the particle size distribution of the resulting titanium oxide-based fine particles may be uneven.
If the temperature at this time exceeds 100 ° C., the resulting titanium oxide-based fine particles may aggregate, and ultrafine, monodispersed titanium oxide-based fine particles or particles having a uniform particle size distribution may not be obtained. In addition, crystallization proceeds from amorphous, anatase-type titanium oxide increases, and light resistance and weather resistance may be insufficient depending on applications.
The aging time in the step (e) is a time after the time when the aqueous peroxotitanic acid solution generated after the dissolution in the step (d) starts to turn yellow once becomes transparent.
The processing time at this time is usually 0.5 to 12 hours.

  As described above, the titanium oxide-based fine particles (first titanium oxide-based fine particles) according to the present invention can be obtained. In the present invention, following the step (e), the following step (f) is necessary. Accordingly, by performing the step (g), titanium oxide-based fine particles (second titanium oxide-based fine particles) are obtained.

Step (f)
Silica sol and / or zirconia sol is added in an amount of 0.1 to 15% by weight, preferably 0.2 to 10% by weight, based on TiO ₂ of the first titanium oxide fine particles.
Conventionally known silica sol and zirconia sol can be used as the silica sol and zirconia sol, but the average particle diameter is preferably in the range of 1 to 100 nm.
When the average particle diameter is less than 1 nm, the resulting titanium oxide-based fine particles may agglomerate. When the average particle diameter exceeds 100 nm, the effect of adding a silica component and a zirconia component described below may be insufficient.

When the addition amount of silica sol and / or zirconia sol is less than 0.1% by weight with respect to TiO ₂ , when silica sol is used, the effect of improving the stability of the titanium oxide-based fine particle dispersion becomes insufficient, and light resistance In some cases, the effect of improving weather resistance may not be sufficiently obtained. When zirconia sol is used, the effect of improving the stability of the titanium oxide fine particle dispersion is insufficient, and the effect of improving light resistance and weather resistance is also insufficient. In some cases, it cannot be obtained sufficiently, and depending on the type of antibacterial component, the effect of suppressing discoloration may not be obtained.
If the added amount of silica sol and / or zirconia sol exceeds 15% by weight with respect to TiO ₂ , the stability improvement effect, light resistance and weather resistance improvement effect will be insufficient, and this will carry antibacterial and deodorant components. When used with antibacterial / deodorant, the antibacterial / deodorant performance may be insufficient.

Step (g)
Then, aging is performed at a temperature of 30 to 80 ° C, preferably 40 to 60 ° C.
When the aging temperature is less than 30 ° C., the aging effects such as improvement in particle dispersibility, improvement in stability, and uniform particle diameter may not be obtained sufficiently.
When the ripening temperature exceeds 80 ° C., particle growth may occur and the particle diameter may become too large, and depending on the temperature and time, anatase crystallization may not be obtained and sufficient weather resistance may not be obtained.
At this time, the aging time varies depending on the temperature, but is generally 1 to 24 hours.

The titanium oxide-based fine particles (first and second titanium oxide-based fine particles) thus obtained have an average particle diameter (D) in the range of 3 to 10 nm and an average particle diameter (D) of ± 2 nm. It is preferable that the number ratio of the titanium oxide-based fine particles having 70 is 70% or more, and the titanium oxide-based fine particles are preferably amorphous.

The average particle diameter (D) is preferably in the range of 3 to 10 nm, more preferably 5 to 8 nm.
When the average particle diameter (D) is less than 3 nm, the dispersion may have insufficient stability, and may be agglomerated when used in a coating solution described below, and the strength of the resulting coating film, Transparency, antibacterial / deodorant performance may be insufficient.
If the average particle diameter (D) exceeds 10 nm, the effect of improving the content per unit weight of the antibacterial and deodorant components in a state of being uniformly highly dispersed may not be obtained, because the external surface area of the particles becomes small, Sufficient antibacterial / deodorant performance may not be obtained.

Regarding the particle size distribution, the number ratio of the titanium oxide-based fine particles having an average particle size (D) ± 2 nm is preferably 70% or more, and more preferably 80% or more.
When the number ratio of the titanium oxide fine particles having an average particle diameter (D) of ± 2 nm is less than 70%, the dispersion and the coating liquid tend to be insufficiently stable, depending on the application and usage. The strength, transparency, antibacterial and deodorizing performance of the resulting coating film may be insufficient.

In the present invention, the average particle size is obtained by photographing a transmission electron microscope (Hitachi H-800, manufactured by Hitachi High-Tech Co., Ltd.) of titanium oxide-based fine particles, measuring the particle size of 100 particles, and calculating the average value. Can be sought.
In addition, the particle size distribution is obtained by obtaining a distribution curve of the particle size and determining the number ratio of particles having an average particle size (D) ± 2 nm.

  The titanium oxide-based fine particles are preferably amorphous. The titanium oxide-based fine particles can be used even if they are crystalline, but are preferably amorphous from the viewpoint of light resistance and weather resistance. More specifically, crystalline titanium oxide-based fine particles have high antibacterial and deodorant performance, but have problems with light resistance. On the other hand, amorphous titanium oxide-based fine particles are uniform and have a small particle size in the present application. The content of the antibacterial / deodorant can be increased, and for this reason, there are no problems in light resistance and weather resistance, and titanium oxide fine particles having excellent antibacterial / deodorant performance can be obtained.

[Antimicrobial / deodorant]
Next, the antibacterial / deodorant will be described.
The first antibacterial / deodorant according to the present invention is titanium oxide-based fine particles containing an antibacterial / deodorant component in the range of 0.1 to 25% by weight in terms of oxide, and has an average particle diameter (D). Is in the range of 3 to 10 nm, and the number ratio of titanium oxide fine particles having an average particle diameter (D) ± 2 nm is 70% or more.
The titanium oxide fine particles are used as the titanium oxide fine particles.

The content of the antibacterial / deodorant component in the first antibacterial / deodorant is in the range of 0.1 to 25% by weight, more preferably 1 to 20% by weight, in terms of oxide, with respect to the titanium oxide fine particles. Preferably there is.
When the content of the antibacterial / deodorant component is less than 0.1% by weight, it is difficult to obtain sufficient antibacterial / deodorant performance.
If the content of the antibacterial / deodorant component is more than 25% by weight, the deodorant performance and antibacterial performance will not be further improved, but rather the performance will decrease due to aggregation of the antibacterial / deodorant component. There is a case.

The antibacterial / deodorant component is preferably one or more 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 and deodorant components may be present in any form of compounds such as ions, oxides, hydroxides or mixtures thereof. From the viewpoint of antibacterial properties, ionic form is preferable, and if it is an oxide, an antibacterial / deodorant excellent in deodorizing properties can be obtained.
In addition, the antibacterial / deodorant component is preferably 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.

In the antibacterial / deodorant of the present invention, the titanium oxide fine particles preferably contain silica and / or zirconia in the range of 0.1 to 15% by weight with respect to TiO ₂ as described above.
The titanium oxide fine particles are preferably amorphous.

The second antibacterial / deodorant according to the present invention is characterized in that the antibacterial / deodorant is dispersed in an aqueous dispersion medium containing a fragrance compound.
The aqueous dispersion medium is not particularly limited as long as the antibacterial / deodorant can be uniformly and stably dispersed, and usually water, a mixed dispersion medium of water and alcohols is preferable.
As alcohols, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, butanol, etc., higher alcohols, polyhydric alcohols, aromatic alcohols and the like are used. Moreover, you may add additives other than alcohol as needed.
The concentration of the antibacterial / deodorant in the aqueous dispersion medium varies depending on the application, but is in the range of 0.01 to 10% by weight, preferably 0.1 to 5% by weight as the solid content.

  As the fragrance compound, the fragrance compound disclosed in JP-A No. 2004-180979 can be suitably used. Specifically, 2,4,6-trimethyl-2-phenyl-1,3-dioxane, 2-ethyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-butene -1-ol, methylnonylacetaldehyde, benzyl alcohol, 3-methyl-5-phenylpentan-1-ol and the like can be suitably used.

The blending amount of such a fragrance compound varies depending on the type, use, and usage of the fragrance compound, but is usually in the range of 0.001 to 2% by weight, more preferably 0.01 to 1% by weight.
When a fragrance compound is included in such a range, the fragrance does not change over time, has a masking power against off-flavors, has a stable fragrance over a long period of time, and has a continuous antibacterial / deodorant. An antibacterial / deodorant having performance is obtained.

As a method of supporting the antibacterial / deodorant component in the above-mentioned first antibacterial / deodorant on the titanium oxide-based fine particles, for example, the method disclosed in Japanese Patent Application Laid-Open No. 2005-318999 (Patent Document 4) is adopted. Can do.
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. When an aqueous solution of an ammine complex salt is used, an antibacterial / deodorant coating film having stable antibacterial / deodorant performance over a long period of time can be produced without reducing the stability of the titanium oxide-based fine particle dispersion or gelling. The antibacterial deodorant with reduced stability and the gelled antibacterial deodorant may have limited applications or may have insufficient antibacterial and deodorant performance.
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 the preparation of the antibacterial deodorant by the above-described method, the concentration of the titanium oxide-based fine particle dispersion using water as a dispersion medium is 5% by weight or less, preferably 0.5% by weight to 3% by weight as an oxide. It is preferable that it exists in the range.
The addition amount of the metal salt aqueous solution of the antibacterial / deodorant component is such that the content of the antibacterial / deodorant component is 0.1 to 25% by weight, preferably 1 to 20% by weight as an oxide with respect to the titanium oxide fine particles. Add to be.
The titanium oxide fine particle dispersion liquid carrying the antibacterial / deodorant 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.

[Coating liquid for forming antibacterial and deodorant coating films]
Next, the coating solution for forming an antibacterial / deodorant coating film will be specifically described.
The coating solution for forming an antibacterial / deodorant coating film according to the present invention contains the antibacterial / deodorant, and particularly in an aqueous dispersion medium in which the antibacterial / deodorant contains a water-soluble metal chelate compound. It is characterized by being dispersed.

Antibacterial / deodorant The above-mentioned antibacterial / deodorant is used as the antibacterial / deodorant.
Aqueous Dispersion Medium As the aqueous dispersion medium used in the present invention, water and a mixed dispersion medium of water and alcohol are preferable.
Examples of the alcohol include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, butanol and the like.
In the case of a mixed dispersion medium, the mixing ratio is not particularly limited, but it is generally preferable that the ratio of water is 10% by weight or more.

The total solid concentration of the coating solution for forming an antibacterial / deodorant coating film is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight.
When the total solid content concentration is less than 0.01% by weight, the antibacterial / deodorant coating film obtained by coating becomes thinner, resulting in insufficient antibacterial / deodorant performance and increased film strength. If the surface of the base material is insufficient, the surface flatness may be insufficient.

If the total solid content exceeds 20% by weight, the stability of the coating solution becomes insufficient, the coating property is lowered, the adhesion of the resulting antibacterial / deodorant coating film to the substrate, and the surface is flat. In addition, the antibacterial performance and deodorizing performance may be insufficient while the properties, transparency, durability, crack suppression, etc. are reduced.
The concentration of the antibacterial / deodorant in the coating solution for forming the antibacterial / deodorant coating film is preferably in the range of 0.005 to 19.9% by weight, more preferably 0.1 to 10% by weight as the solid content. .
If the concentration of the antibacterial / deodorant in the coating solution for forming the antibacterial / deodorant coating is less than 0.005% by weight as the solid content, the antibacterial / deodorant performance may be insufficient.
When the concentration of the antibacterial / deodorant in the coating liquid for forming the antibacterial / deodorant coating exceeds 19.9% by weight as a solid content, the water-soluble metal chelate compound is limited. In some cases, stability, adhesion to a substrate, transparency, and the like are lowered, resulting in insufficient film strength.

Water-soluble metal chelate compound Examples of the water-soluble metal chelate compound used in the present invention include water-soluble metal chelate compounds in which the metal is Ti, Al, Zr, Si or the like. Among these, a water-soluble titanium chelate compound in which the metal is Ti does not deteriorate the antibacterial / deodorant performance and can be preferably used.
Examples of the water-soluble titanium chelate compound include water-soluble titanium lactate ammonium salt, titanium diisopropoxybis (triethanolamine), titanium lactate and the like.
These water-soluble titanium chelate compounds are stable in the solution itself, but are also stable when used in an antibacterial / deodorant coating film-forming coating solution. The film is excellent in adhesion to the substrate, transparency, flatness of the coating film surface, and excellent in antibacterial and deodorizing performance.

The concentration of the water-soluble metal chelate compound in the coating solution for forming the antibacterial / deodorant coating film as TiO ₂ is preferably in the range of 0.0001 to 10% by weight, more preferably 0.0005 to 8% by weight.
If the concentration of the TiO ₂ antibacterial and deodorant coating the coating liquid for forming a water-soluble metal chelate compound in is less than 0.0001 wt%, stability of the coating solution, adhesion to a substrate, transparent May be insufficient.
When the concentration of the TiO ₂ antibacterial and deodorant coating the coating liquid for forming a water-soluble metal chelate compound in more than 10% by weight, without the stability of the coating liquid is further improved, resulting Antibacterial and anti Since the content of titanium oxide-based fine particles in the odorous coating film decreases, the antibacterial / deodorant performance may be insufficient.

Weight (W _a ) as solid content of antibacterial / deodorant (titanium oxide fine particles containing antibacterial / deodorant components) in coating liquid for forming antibacterial / deodorant coating film and TiO _{2 of} water-soluble metal chelate compound The weight ratio (W _b ) / (W _a ) of the weight (W _b ) is preferably in the range of 0.005 to 1.0, more preferably 0.01 to 0.5.
When the weight ratio (W _b ) / (W _a ) is less than 0.005, the amount of the water-soluble metal chelate compound decreases, the stability of the coating solution, the adhesion to the substrate, the transparency, the surface flatness, etc. May decrease or the film strength may be insufficient.
When the weight ratio (W _b ) / (W _a ) exceeds 1.0, the stability of the coating solution is not further improved, and the antibacterial / deodorant agent in the resulting antibacterial / deodorant coating is not improved. Since content falls, antibacterial and deodorizing performance may become inadequate.

  Furthermore, the antibacterial and deodorant coating film-forming coating liquid 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 a compounding agent in paints and inks.

[Base material with antibacterial and deodorant coating]
Next, the substrate with an antibacterial / deodorant coating film according to the present invention will be described.
The substrate with antibacterial / deodorant coating film according to the present invention comprises a substrate and an antibacterial / deodorant coating film formed on the substrate, and the antibacterial / deodorant coating film comprises the antibacterial / deodorant coating film. It is characterized by being an antibacterial / deodorant coating film formed using a coating liquid for forming a deodorant coating film.

Examples of the base material include base materials such as glass, metal, resin, ceramic, wood, various fibers, and inorganic oxides.
Moreover, after forming an antibacterial and deodorant coating film on one surface of an adhesive resin film or the like, another substrate can be attached and used.

The content of the antibacterial / deodorant as a solid content in the antibacterial / deodorant coating is preferably in the range of 50 to 99.5% by weight, more preferably 60 to 96% by weight.
If the content of the antibacterial / deodorant as a solid content in the antibacterial / deodorant coating is less than 50% by weight, the antibacterial / deodorant performance may be insufficient.
The antibacterial / deodorant coating content in the solid content of the antibacterial / deodorant exceeds 99.5% by weight, and the antibacterial / deodorant performance is not further improved. Transparency, surface flatness, film strength, etc. may be insufficient.

The content of the water-soluble metal chelate compound in the antibacterial / deodorant coating film as TiO ₂ is preferably 0.5 to 50% by weight, more preferably 4 to 40% by weight.
When the content of water-soluble metal chelate compound in the antibacterial / deodorant coating as TiO ₂ is less than 0.5% by weight, adhesion to the substrate, transparency, surface flatness, film strength, etc. It may be insufficient.
If the content of water-soluble metal chelate compound in the antibacterial / deodorant coating as TiO ₂ exceeds 50% by weight, the antibacterial / deodorant performance is insufficient due to the low content of antibacterial / deodorant. There is a case.

The film thickness of the antibacterial / deodorant coating film is preferably in the range of 0.1 to 50 μm, more preferably 0.1 to 20 μm.
When the film thickness of the antibacterial / deodorant coating film is less than 0.1 μm, the antibacterial / deodorant performance may be insufficient, and the high antibacterial / deodorant performance cannot be maintained over a long period of time. There is.
Even if the film thickness of the antibacterial / deodorant coating film exceeds 50 μm, the antibacterial / deodorant performance will not be further improved, cracks will be generated in the coating film, or the use will be limited due to a decrease in transparency. There is.

  Such a substrate with an antibacterial / deodorant coating film is a known method such as a dipping method, a spray method, a spinner method, a roll coat method, a bar coater method, etc. It can be manufactured by applying to the above-mentioned substrate, drying, and further heat-treating as necessary.

Antibacterials and deodorants of the present invention, fungi to be antibacterial in the antibacterial and deodorant coatings include fungi such as Staphylococcus aureus, Streptococcus, Escherichia coli, Pseudomonas aeruginosa, Proteus, Neisseria pneumoniae, Bacillus subtilis, etc. Examples include black mold, black mold, and white mold, viruses include influenza virus, adenovirus, and norovirus, and 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 coating film of the present invention is particularly useful in places where antibacterial performance and deodorization performance are required in residential spaces, public facilities, medical facilities, nursing homes, automobile interiors, and the like.

[Example 1]
Preparation of Titanium Oxide Fine Particle (1) Dispersion A 1600 g aqueous solution of titanyl sulfate having a concentration of 5.0% by weight was prepared as TiO ₂ and adjusted to a temperature of 15 ° C. (Process (a))
Subsequently, while maintaining the temperature at 15 ° C., 360 g of ammonia water having a concentration of 15% by weight was added over 1 hour to prepare a titanium oxide hydrate gel slurry. At this time, the molar ratio (M _NH3 ) / (M _TiO2 ) = 3.2, and the addition time was 3.2 hours / mole (M _NH3 ). (Process (b))
Next, the titanium oxide hydrate gel slurry was filtered and washed with 8000 g of hot water at 60 ° C. (Process (c))

Next, using the washed titanium oxide hydrate gel slurry, a hydrated titanium oxide hydrate dispersion having a concentration of 1% by weight and 2000 g as TiO ₂ was prepared, and 140 g of hydrogen peroxide solution having a concentration of 35% by weight was added thereto. And dissolved at 50 ° C. for 1 hour.
At this time, the molar ratio (M _H2O2 ) / (M _TiO2 ) = 5.8. (Process (d))
Subsequently, the mixture was aged for 1 hour while removing hydrogen peroxide while stirring at a temperature of 80 ° C. (Process (e))

Subsequently, using pure water, it was washed by an ultrafiltration membrane method to obtain a dispersion of titanium oxide fine particles (1) having a concentration of 1% by weight as TiO ₂ . The average particle size, particle size distribution, crystallinity, and yield of the titanium oxide fine particles (1) were measured, and the results are shown in the table.
Here, the yield, the solid content of the resulting titanium oxide-based fine particles (1) (TiO ₂₎ weight the use of titanium oxide (TiO ₂₎ was determined by dividing the weight.

The crystallinity was measured by an X-ray analysis spectrum and evaluated according to the following criteria.
High X-ray analysis peak: S (High crystallinity)
Medium X-ray analysis peak: M (medium crystallinity)
X-ray analysis peak is low: W (low crystallinity)
X-ray analysis peak is hardly recognized: Am (Amorphous)

Preparation of Antibacterial / Deodorant Titanium Oxide Fine Particles (1) Dispersion A titanium ammonium fine particle (1) dispersion having a concentration of 1% by weight as TiO ₂ was added to a silver ammonium solution (silver oxide, 0. 9 g of pure water was added to 89.1 g, and a solution prepared by adding 15% ammonia solution and 13.5 g in 1 hour) was added to the titanium oxide fine particle (1) dispersion, and aged at 95 ° C. for 4 hours. By washing with 5000 g of pure water by an ultrafiltration membrane method, an antibacterial / deodorant titanium oxide fine particle (1) dispersion having a solid content concentration of 1.5% by weight was prepared.
The average particle size, particle size distribution, and crystallinity of the antibacterial / deodorant titanium oxide fine particles (1) were measured, and the results are shown in the table.

Preparation of coating solution (1-1) for antibacterial / deodorant coating film formation Antibacterial / deodorant titanium oxide fine particles (1) 10% by weight in 89.5 parts by weight of ion-exchanged water with a solid concentration of 1.5% by weight After mixing and fully dispersing, a titanium lactate ammonium salt solution (manufactured by Matsumoto Fine Chemical Co., Ltd .: Olga Tix TC-300, 42% by weight of titanium lactate ammonium salt, 20% by weight of water as a water-soluble metal chelate compound. 0.5% by weight, isopropyl alcohol 38% by weight, TiO ₂ concentration 10.0% by weight), and a solid content concentration 0.2% by weight antibacterial / deodorant coating forming liquid ( 1) was prepared.

The stability of the antibacterial / deodorant coating solution (1) was evaluated by the following method.
Stability evaluation In a closed glass container, the sample was allowed to stand at 50 ° C. for 1 week and then visually confirmed.
No gelation: ◎
Gelation, thin cloudiness: ○
Gelation, cloudiness separation: △
Gelation, cloudy precipitation: ×

Preparation of antibacterial / deodorant coating liquid (1-2) coating solution 90 parts by weight of ion-exchanged water 10 parts by weight of antibacterial / deodorant titanium oxide fine particles (1) having a solid content of 1.5% by weight Blended and sufficiently dispersed, a coating solution (1-2) for forming an antibacterial / deodorant coating film having a solid content concentration of 0.15% by weight was prepared.
The stability of the antibacterial / deodorant coating solution (1-2) is shown in the table.

Preparation of base material with antibacterial / deodorant coating film (1-1) 0.105mm thick industrial pure aluminum plate is degreased, causticized, thoroughly washed with water and dried on the surface of aluminum base The coating solution (1-1) for forming an antibacterial / deodorant coating film was applied by a bar coater method so as to have a film thickness of about 10 μm, and dried at 120 ° C. for 2 minutes. Subsequently, it was heat-treated at 200 ° C. for 2 minutes to prepare an antibacterial / deodorant-coated substrate (1-1).
For the obtained substrate (1-1) with antibacterial / deodorant coating film, the film thickness, adhesion, surface flatness, antibacterial performance and deodorization performance were evaluated, and the results are shown in the table. Evaluation methods and evaluation criteria are shown below.

Preparation of base material with antibacterial / deodorant coating film (1-2) Degreased 0.105mm thick industrial aluminum plate, caustic treatment, thoroughly washed with water and dried on aluminum substrate surface The antibacterial / deodorant coating film forming liquid (1-2) was applied by a bar coater method so as to have a film thickness of about 10 μm, and dried at 120 ° C. for 2 minutes. Subsequently, it heat-processed at 200 degreeC for 2 minute (s), and produced the base material (1-2) with an antibacterial and deodorant coating film.
The obtained substrate (1-2) with antibacterial / deodorant coating film was evaluated for film thickness, adhesion, surface flatness, antibacterial performance, and deodorization performance, and the results are shown in the table.

The cross section of the film cut perpendicular to the film thickness was observed and measured by observation with a scanning electron microscope.

Adhesion
In accordance with the basic eye test based on JIS K 5400, the surface of the substrate with antibacterial and deodorant coating film (1) is made with 11 parallel scratches with a knife at intervals of 1 mm in length and width, and 100 squares are made. Adhering cellophane tape (registered trademark) to this, and then separating the cellophane tape (registered trademark), the film does not peel off, and the number of cells remaining is classified into the following four stages Evaluated.
Number of remaining squares: ◎
93-99 remaining squares: ○
Number of remaining squares: 85-92:
Number of remaining squares: 84 or less: ×

The average roughness of the surface was evaluated with a flat stylus type surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd .: Surfcom).

Antibacterial performance
In accordance with JIS Z2801, after inoculating bacterial suspension, 0.4 ml on the antibacterial and deodorant coated substrate (1), covering it with a covering film, and covering, 35 ± 1 ° C, After standing at RH90 or more for 24 hours, the bacterial suspension was recovered, the number of viable bacteria was measured, and the antibacterial performance was evaluated by the bactericidal activity value of the following formula (1). The results are shown in the table.
Staphylococcus aureus, Escherichia coli, and MRSA are used as test bacteria. Meat extract (3 g / L) + peptone (10 g / L) + sodium chloride (5 g / L) is multiplied by 100 as nutrients for the bacterial suspension. A diluted one was used.
Bactericidal activity value = Log (number of inoculated bacteria)-Log (number of viable test pieces) (1)

Deodorant performance
Test odor (1) : Acetaldehyde (initial concentration: 60 ppm)
Test method: A specimen (10 cm × 10 cm) is placed in a 1 L tedlar bag, 1 L of odor is added, and then left at room temperature under ultraviolet irradiation (1.0 mW / cm ² ). After 24 hours, residual odor concentration (deodorization rate) and carbon dioxide concentration (ppm) were measured with a detector tube.

Test odor (2,3) : Hydrogen sulfide (initial concentration: 4 ppm), ammonia (initial concentration: 100 ppm)
Test method: Put a sample (10 cm × 10 cm) in a 5 L Tedlar bag, add 3 L of odor, and leave it at room temperature under fluorescent light irradiation. After 2 hours, the residual odor concentration (deodorization rate) was measured with a detector tube.

[Example 2]
Preparation of Titanium Oxide Fine Particle (2) Dispersion A titanium oxide fine particle (1) dispersion having a solid content (TiO ₂ ) concentration of 1% by weight and 1626 g was prepared in the same manner as in Example 1, and silica sol (JGC) Catalyst Chemical Co., Ltd. product: SN-350, average particle diameter 7 nm, SiO ₂ concentration 16.7 wt%) was mixed and aged at 80 ° C. for 1 hour to obtain titanium oxide fine particles having a solid content concentration of 1 wt% ( 2) A dispersion was prepared.
The average particle size, particle size distribution, crystallinity, and yield of the titanium oxide fine particles (2) are shown in the table. The composition of the titanium oxide fine particles (2) had a TiO ₂ concentration of 85.2% by weight and a SiO ₂ concentration of 14.8% by weight.

Preparation of antibacterial and deodorant titanium oxide fine particles (2) dispersion A solid content concentration of 1.5 was obtained in the same manner as in Example 1 except that a titanium oxide fine particle (2) dispersion having a solid concentration of 1% by weight was used. A weight percent antibacterial / deodorant titanium oxide fine particle (2) dispersion was prepared.
The average particle size, particle size distribution, and crystallinity of the antibacterial / deodorant titanium oxide fine particles (2) were measured, and the results are shown in the table. The composition of the antibacterial and deodorant titanium oxide fine particles (2) had a TiO ₂ concentration of 81.4% by weight, a SiO ₂ concentration of 14.1% by weight, and an Ag ₂ O concentration of 4.5% by weight.

Preparation of antibacterial / deodorant coating film-forming coating solution (2) In preparation of the antibacterial / deodorant coating film-forming coating solution (1-1) of Example 1, an antibacterial agent having a solid content of 1.5% by weight was prepared. A coating solution (2) for forming an antibacterial / deodorant coating film was prepared in the same manner except that the deodorant titanium oxide fine particle (2) dispersion was used.
The stability of the antibacterial / deodorant coating solution (2) was evaluated, and the results are shown in the table.

Preparation of base material with antibacterial / deodorant coating film (2) In preparation of base material with antibacterial / deodorant coating film (1-1) of Example 1, an antibacterial / deodorant coating film coating solution ( A substrate (2) with an antibacterial / deodorant coating was prepared in the same manner except that 2) was used.
The obtained substrate (2) with antibacterial / deodorant coating film was evaluated for film thickness, adhesion, surface flatness, antibacterial performance, and deodorization performance, and the results are shown in the table.

[Example 3]
Preparation of Titanium Oxide Fine Particle (3) Dispersion 1600 g of a titanyl sulfate aqueous solution having a concentration of 5.0% by weight was prepared as TiO ₂ and adjusted to a temperature of 5 ° C. (Process (a))
Subsequently, while maintaining the temperature at 5 ° C., 360 g of ammonia water having a concentration of 15% by weight was added over 1 hour to prepare a titanium oxide hydrate gel slurry. At this time, the molar ratio (M _NH3 ) / (M _TiO2 ) = 3.2, and the addition time was 3.2 hours / mole (M _NH3 ). (Process (b))
Next, the titanium oxide hydrate gel slurry was filtered and washed with 8000 g of hot water at 60 ° C. (Process (c))
Thereafter, in the same manner as in Example 1, a dispersion of titanium oxide fine particles (3) having a concentration of 1% by weight as TiO ₂ was obtained. The average particle size, particle size distribution, crystallinity, and yield of the titanium oxide fine particles (3) are shown in the table.

Preparation of antibacterial and deodorant titanium oxide fine particles (3) dispersion A solid content concentration of 1.5 was obtained in the same manner as in Example 1 except that a titanium oxide fine particle (3) dispersion having a solid concentration of 1% by weight was used. A weight percent antibacterial and deodorant titanium oxide fine particle (3) dispersion was prepared.
The average particle size, particle size distribution, and crystallinity of the antibacterial / deodorant titanium oxide fine particles (3) were analyzed, and the results are shown in the table.

Preparation of antibacterial / deodorant coating film-forming coating solution (3) In the preparation of antibacterial / deodorant coating film-forming coating solution (1-1) in Example 1, an antibacterial agent having a solid content of 1.5% by weight was prepared. A coating solution (3) for forming an antibacterial / deodorant coating film was prepared in the same manner except that the deodorant titanium oxide fine particle (3) dispersion was used.
The stability of the antibacterial / deodorant coating solution (3) was evaluated, and the results are shown in the table.

Preparation of substrate with antibacterial / deodorant coating film (3) In preparation of substrate (1-1) with antibacterial / deodorant coating film of Example 1, coating liquid for forming antibacterial / deodorant coating film (1-1) A substrate (3) with an antibacterial / deodorant coating film was prepared in the same manner except that 3) was used.
The obtained substrate (3) with antibacterial / deodorant coating film was evaluated for film thickness, adhesion, surface flatness, antibacterial performance, and deodorization performance, and the results are shown in the table.

[Example 4]
Preparation of Titanium Oxide Fine Particle (4) Dispersion 1600 g of a titanyl sulfate aqueous solution having a concentration of 5.0% by weight was prepared as TiO ₂ and adjusted to a temperature of 25 ° C. (Process (a))
Subsequently, while maintaining the temperature at 25 ° C., 360 g of ammonia water having a concentration of 15% by weight was added over 1 hour to prepare a titanium oxide hydrate gel slurry. At this time, the molar ratio (M _NH3 ) / (M _TiO2 ) = 3.2, and the addition time was 3.2 hours / mole (M _NH3 ). (Process (b))
Next, the titanium oxide hydrate gel slurry was filtered and washed with 8000 g of hot water at 60 ° C. (Process (c))
Thereafter, in the same manner as in Example 1, a dispersion of titanium oxide fine particles (4) having a concentration of 1% by weight as TiO ₂ was obtained. The average particle size, particle size distribution, crystallinity, and yield of the titanium oxide fine particles (4) are shown in the table.

Preparation of antibacterial and deodorant titanium oxide fine particles (4) dispersion The solid content concentration of 1.5 was the same as in Example 1 except that the titanium oxide fine particle (4) dispersion having a solid concentration of 1% by weight was used. A weight percent antibacterial / deodorant titanium oxide fine particle (4) dispersion was prepared.
The average particle size, particle size distribution, and crystallinity of the antibacterial / deodorant titanium oxide fine particles (4) were analyzed, and the results are shown in the table.

Preparation of antibacterial / deodorant coating film-forming coating solution (4) In preparation of the antibacterial / deodorant coating film-forming coating solution (1-1) of Example 1, an antibacterial agent having a solid content of 1.5% by weight was prepared. A coating solution (4) for forming an antibacterial / deodorant coating film was prepared in the same manner except that the deodorant titanium oxide fine particle (4) dispersion was used.
The stability of the antibacterial / deodorant coating solution (4) was evaluated and the results are shown in the table.

Preparation of base material with antibacterial / deodorant coating film (4) In preparation of base material with antibacterial / deodorant coating film (1-1) of Example 1, coating liquid for forming antibacterial / deodorant coating film (1-1) A substrate (4) with an antibacterial / deodorant coating was prepared in the same manner except that 4) was used.
The obtained substrate (4) with antibacterial / deodorant coating film was evaluated for film thickness, adhesion, surface flatness, antibacterial performance, and deodorization performance, and the results are shown in the table.

[Example 5]
Preparation of Titanium Oxide Fine Particle (5) Dispersion A 8000 g aqueous solution of titanyl sulfate having a concentration of 1.0% by weight was prepared as TiO ₂ and adjusted to a temperature of 10 ° C. (Process (a))
Next, while maintaining the temperature at 10 ° C., 360 g of 15% by weight ammonia water was added over 1 hour to prepare a titanium oxide hydrate gel slurry. At this time, the molar ratio (M _NH3 ) / (M _TiO2 ) = 3.2, and the addition time was 3.2 hours / mole (M _NH3 ). (Process (b))
Next, the titanium oxide hydrate gel slurry was filtered and washed with 8000 g of hot water at 60 ° C. (Process (c))
Thereafter, in the same manner as in Example 1, a dispersion of titanium oxide fine particles (5) having a concentration of 1% by weight as TiO ₂ was obtained. The average particle size, particle size distribution, crystallinity, and yield of the titanium oxide fine particles (5) are shown in the table.

Preparation of antibacterial and deodorant titanium oxide fine particles (5) dispersion The solid content concentration of 1.5 was the same as in Example 1 except that the titanium oxide fine particle (5) dispersion having a solid concentration of 1% by weight was used. A weight percent antibacterial / deodorant titanium oxide fine particle (5) dispersion was prepared.
The average particle size, particle size distribution, and crystallinity of the antibacterial / deodorant titanium oxide fine particles (5) were analyzed, and the results are shown in the table.

Preparation of antibacterial / deodorant coating film-forming coating solution (5) In preparation of the antibacterial / deodorant coating film-forming coating solution (1-1) of Example 1, an antibacterial agent having a solid content of 1.5% by weight was prepared. A coating solution (5) for forming an antibacterial / deodorant coating film was prepared in the same manner except that the deodorant titanium oxide fine particles (5) dispersion was used.
The stability of the antibacterial / deodorant coating solution (5) was evaluated, and the results are shown in the table.

Preparation of base material with antibacterial / deodorant coating film (5) In preparation of the base material with antibacterial / deodorant coating film (1-1) of Example 1, an antibacterial / deodorant coating film forming liquid ( A substrate (5) with an antibacterial / deodorant coating film was prepared in the same manner except that 5) was used.
The obtained substrate (5) with antibacterial / deodorant coating film was evaluated for film thickness, adhesion, surface flatness, antibacterial performance, and deodorization performance, and the results are shown in the table.

[Example 6]
Preparation of Titanium Oxide Fine Particle (6) Dispersion A 530 g titanyl sulfate aqueous solution having a concentration of 15% by weight was prepared as TiO ₂ and adjusted to a temperature of 10 ° C. (Process (a))
Next, while maintaining the temperature at 10 ° C., 360 g of 15% by weight ammonia water was added over 1 hour to prepare a titanium oxide hydrate gel slurry. At this time, the molar ratio (M _NH3 ) / (M _TiO2 ) = 3.2, and the addition time was 3.2 hours / mole (M _NH3 ). (Process (b))
Next, the titanium oxide hydrate gel slurry was filtered and washed with 8000 g of hot water at 60 ° C. (Process (c))
Thereafter, in the same manner as in Example 1, a dispersion of titanium oxide fine particles (6) having a concentration of 1% by weight as TiO ₂ was obtained. The average particle size, particle size distribution, crystallinity, and yield of the titanium oxide fine particles (6) are shown in the table.

Preparation of antibacterial and deodorant titanium oxide fine particle (6) dispersion The solid content concentration was 1.5 in the same manner as in Example 1 except that the titanium oxide fine particle (6) dispersion having a solid concentration of 1% by weight was used. A weight percent antibacterial / deodorant titanium oxide fine particle (6) dispersion was prepared.
The average particle size, particle size distribution, and crystallinity of the antibacterial / deodorant titanium oxide fine particles (6) were analyzed, and the results are shown in the table.

Preparation of antibacterial / deodorant coating film-forming coating solution (6) In preparation of the antibacterial / deodorant coating film-forming coating solution (1-1) of Example 1, an antibacterial agent having a solid content of 1.5% by weight was prepared. A coating solution (6) for forming an antibacterial / deodorant coating film was prepared in the same manner except that the deodorant titanium oxide fine particle (6) dispersion was used.
The stability of the antibacterial / deodorant coating solution (6) was evaluated, and the results are shown in the table.

Preparation of base material with antibacterial / deodorant coating film (6) In preparation of base material with antibacterial / deodorant coating film (1-1) of Example 1, coating liquid for forming antibacterial / deodorant coating film (1-1) A substrate (6) with an antibacterial / deodorant coating film was prepared in the same manner except that 6) was used.
The obtained substrate (6) with antibacterial / deodorant coating film was evaluated for film thickness, adhesion, surface flatness, antibacterial performance, and deodorization performance, and the results are shown in the table.

[Example 7]
Preparation of Titanium Oxide Fine Particle (7) Dispersion 1600 g of a titanyl sulfate aqueous solution having a concentration of 5.0% by weight was prepared as TiO ₂ and adjusted to a temperature of 15 ° C. (Process (a))
Subsequently, while maintaining the temperature at 15 ° C., 360 g of ammonia water having a concentration of 15% by weight was added over 1 hour to prepare a titanium oxide hydrate gel slurry. At this time, the molar ratio (M _NH3 ) / (M _TiO2 ) = 3.2, and the addition time was 3.2 hours / mol (M _NH3 ). (Process (b))
Next, the titanium oxide hydrate gel slurry was filtered and washed with 8000 g of hot water at 60 ° C. (Process (c))

Then, using the washed titanium oxide hydrate gel slurry, a hydrated titanium oxide hydrate dispersion having a concentration of 1% by weight and 2,000 g as TiO ₂ was prepared, and 48.5 g of hydrogen peroxide water having a concentration of 35% by weight was prepared. And dissolved at 50 ° C. for 1 hour.
At this time, the molar ratio (M _H2O2 ) / (M _TiO2 ) = 2.0. (Process (d))
Subsequently, the mixture was aged for 1 hour while removing hydrogen peroxide while stirring at a temperature of 80 ° C. (Process (e))
Subsequently, using pure water, it was washed by an ultrafiltration membrane method to obtain a dispersion of titanium oxide fine particles (7) having a concentration of 1% by weight as TiO ₂ . The average particle size, particle size distribution, crystallinity, and yield of the titanium oxide fine particles (7) are shown in the table.

Preparation of Antibacterial and Deodorant Titanium Oxide Fine Particles (7) Dispersion A solid content concentration of 1.5 was the same as in Example 1 except that a titanium oxide fine particle (7) dispersion having a solid content concentration of 1% by weight was used. A weight percent antibacterial / deodorant titanium oxide fine particle (7) dispersion was prepared.
The average particle size, particle size distribution, and crystallinity of the antibacterial / deodorant titanium oxide fine particles (7) were analyzed, and the results are shown in the table.

Preparation of antibacterial / deodorant coating film-forming coating solution (7) In preparation of the antibacterial / deodorant coating film-forming coating solution (1-1) of Example 1, an antibacterial agent having a solid content of 1.5% by weight was prepared. A coating solution (7) for forming an antibacterial / deodorant coating film was prepared in the same manner except that the deodorant titanium oxide fine particle (7) dispersion was used.
The stability of the antibacterial / deodorant coating solution (7) was evaluated, and the results are shown in the table.

Preparation of base material with antibacterial / deodorant coating film (7) In preparation of base material with antibacterial / deodorant coating film (1-1) of Example 1, an antibacterial / deodorant coating film forming liquid ( A substrate (7) with an antibacterial / deodorant coating was prepared in the same manner except that 7) was used.
The obtained substrate (7) with antibacterial / deodorant coating film was evaluated for film thickness, adhesion, surface flatness, antibacterial performance, and deodorization performance, and the results are shown in the table.

[Example 8]
Preparation of Titanium Oxide Fine Particle (8) Dispersion 1600 g of a titanyl sulfate aqueous solution having a concentration of 5.0% by weight was prepared as TiO ₂ and adjusted to a temperature of 15 ° C. (Process (a))
Subsequently, while maintaining the temperature at 15 ° C., 360 g of ammonia water having a concentration of 15% by weight was added over 1 hour to prepare a titanium oxide hydrate gel slurry. At this time, the molar ratio (M _NH3 ) / (M _TiO2 ) = 3.2, and the addition time was 3.2 hours / mol (M _NH3 ). (Process (b))
Next, the titanium oxide hydrate gel slurry was filtered and washed with 8000 g of hot water at 60 ° C. (Process (c))

Next, using the washed titanium oxide hydrate gel slurry, a hydrated titanium oxide hydrate dispersion having a concentration of 1% by weight and 2,000 g as TiO ₂ was prepared, and 220 g of hydrogen peroxide solution having a concentration of 35% by weight was added thereto. And dissolved at 50 ° C. for 1 hour.
At this time, the molar ratio (M _H2O2 ) / (M _TiO2 ) = 9.0. (Process (d))
Subsequently, the mixture was aged for 1 hour while removing hydrogen peroxide while stirring at a temperature of 80 ° C. (Process (e))
Subsequently, using pure water, it was washed by an ultrafiltration membrane method to obtain a dispersion of titanium oxide fine particles (8) having a concentration of 1% by weight as TiO ₂ . The average particle size, particle size distribution, crystallinity, and yield of the titanium oxide fine particles (8) are shown in the table.

Preparation of Antibacterial and Deodorant Titanium Oxide Fine Particles (8) Dispersion A solid content concentration of 1.5 was the same as in Example 1 except that a titanium oxide fine particle (8) dispersion having a solid content concentration of 1% by weight was used. A weight percent antibacterial / deodorant titanium oxide fine particle (8) dispersion was prepared.
The average particle size, particle size distribution, and crystallinity of the antibacterial / deodorant titanium oxide fine particles (8) were analyzed, and the results are shown in the table.

Preparation of antibacterial / deodorant coating film-forming coating solution (8) In preparation of the antibacterial / deodorant coating film-forming coating solution (1-1) of Example 1, an antibacterial agent having a solid content of 1.5% by weight was prepared. A coating solution (8) for forming an antibacterial / deodorant coating film was prepared in the same manner except that the deodorant titanium oxide fine particle (8) dispersion was used.
The stability of the antibacterial / deodorant coating solution (8) was evaluated, and the results are shown in the table.

Preparation of base material with antibacterial / deodorant coating film (8) In preparation of the base material with antibacterial / deodorant coating film (1-1) of Example 1, an antibacterial / deodorant coating film forming liquid ( A substrate (8) with an antibacterial / deodorant coating film was prepared in the same manner except that 8) was used.
The obtained substrate (8) with antibacterial / deodorant coating film was evaluated for film thickness, adhesion, surface flatness, antibacterial performance, and deodorization performance, and the results are shown in the table.

[Example 9]
Preparation of Titanium Oxide Fine Particles (9) Dispersion Titanium oxide fine particles (9) dispersion having a concentration of 1% by weight as TiO _{2 in the same} manner as in Example 1 except that the temperature of step (e) was 50 ° C. Got. The average particle size, particle size distribution, crystallinity, and yield of the titanium oxide fine particles (9) are shown in the table.

Preparation of antibacterial and deodorant titanium oxide fine particle (9) dispersion The solid content concentration of 1.5 was the same as in Example 1 except that the titanium oxide fine particle (9) dispersion having a solid content concentration of 1% by weight was used. A weight percent antibacterial / deodorant titanium oxide fine particle (9) dispersion was prepared.
The average particle size, particle size distribution, and crystallinity of the antibacterial / deodorant titanium oxide fine particles (9) were analyzed, and the results are shown in the table.

Preparation of antibacterial / deodorant coating film-forming coating liquid (9) In preparation of the antibacterial / deodorant coating film-forming coating liquid (1-1) of Example 1, an antibacterial agent having a solid content of 1.5% by weight was prepared. A coating solution (9) for forming an antibacterial / deodorant coating film was prepared in the same manner except that the deodorant titanium oxide fine particle (9) dispersion was used.
The stability of the antibacterial / deodorant coating solution (9) was evaluated, and the results are shown in the table.

Preparation of base material with antibacterial / deodorant coating film (9) In preparation of base material with antibacterial / deodorant coating film (1-1) of Example 1, an antibacterial / deodorant coating film forming liquid ( A substrate (9) with an antibacterial / deodorant coating was prepared in the same manner except that 9) was used.
The obtained substrate (9) with antibacterial / deodorant coating film was evaluated for film thickness, adhesion, surface flatness, antibacterial performance, and deodorization performance, and the results are shown in the table.

[Example 10]
Titanium oxide-based particles (10) concentration of 5.0% by weight of the four except for using titanium chloride aqueous solution 1600g in the same manner as in Example 1 concentration of 1% by weight of titanium oxide fine particles as TiO ₂ Preparation of TiO ₂ dispersion (10) A dispersion was obtained. The average particle size, particle size distribution, crystallinity, and yield of the titanium oxide fine particles (10) are shown in the table.

Preparation of antibacterial and deodorant titanium oxide fine particle (10) dispersion The solid content concentration was 1.5 in the same manner as in Example 1 except that the titanium oxide fine particle (10) dispersion having a solid content concentration of 1% by weight was used. A weight% antibacterial / deodorant titanium oxide fine particle (10) dispersion was prepared.
The average particle size, particle size distribution and crystallinity of the antibacterial / deodorant titanium oxide fine particles (10) were analyzed, and the results are shown in the table.

Preparation of antibacterial / deodorant coating film-forming coating solution (10) In preparation of the antibacterial / deodorant coating film-forming coating solution (1-1) of Example 1, an antibacterial agent having a solid content of 1.5% by weight was prepared. A coating solution (10) for forming an antibacterial / deodorant coating film was prepared in the same manner except that the deodorant titanium oxide fine particle (10) dispersion was used.
The stability of the antibacterial / deodorant coating solution (10) was evaluated and the results are shown in the table.

Preparation of base material with antibacterial / deodorant coating film (10) In preparation of the base material with antibacterial / deodorant coating film (1-1) in Example 1, an antibacterial / deodorant coating film forming liquid ( A substrate (10) with an antibacterial / deodorant coating film was prepared in the same manner except that 10) was used.
The obtained substrate (10) with antibacterial / deodorant coating film was evaluated for film thickness, adhesion, surface flatness, antibacterial performance, and deodorization performance, and the results are shown in the table.

[Example 11]
Preparation of Antibacterial / Deodorant Titanium Oxide Fine Particle (11) Dispersion As in Example 1, an antibacterial / deodorant titanium oxide fine particle (1) dispersion having a solid content concentration of 1.5% by weight was prepared. 0.02 g of 2,4,6-trimethyl-2-phenyl-1,3-dioxane as a fragrance compound was added to 100 g of the dispersion, and antibacterial / deodorant titanium oxide fine particles having a solid content concentration of 1.52% by weight ( 11) A dispersion was prepared.
The antibacterial / deodorant titanium oxide fine particle (11) dispersion gave off a fragrance.

Preparation of antibacterial / deodorant coating film-forming coating solution (11) In preparation of the antibacterial / deodorant coating film-forming coating solution (1-1) of Example 1, an antibacterial agent having a solid content of 1.5% by weight was prepared. A coating solution (11) for forming an antibacterial / deodorant coating film was prepared in the same manner except that the deodorant titanium oxide fine particle (11) dispersion was used.
The stability of the antibacterial / deodorant coating solution (11) was evaluated and the results are shown in the table.

Preparation of base material with antibacterial / deodorant coating film (11) In preparation of the base material with antibacterial / deodorant coating film (1-1) of Example 1, an antibacterial / deodorant coating film forming liquid ( A substrate (11) with an antibacterial / deodorant coating was prepared in the same manner except that 11) was used.
The obtained substrate (11) with antibacterial / deodorant coating film was evaluated for film thickness, adhesion, surface flatness, antibacterial performance, and deodorization performance, and the results are shown in the table.

[Comparative Example 1]
Preparation of Titanium Oxide Fine Particle (R1) Dispersion 1600 g of a titanyl sulfate aqueous solution having a concentration of 5.0% by weight was prepared as TiO ₂ and adjusted to a temperature of 35 ° C. (Process (a))
Next, while maintaining the temperature at 35 ° C., 360 g of ammonia water having a concentration of 15% by weight was added over 1 hour to prepare a titanium oxide hydrate gel slurry. At this time, the molar ratio (M _NH3 ) / (M _TiO2 ) = 3.2, and the addition time was 3.2 hours / mole (M _NH3 ). (Process (b))
Next, the titanium oxide hydrate gel slurry was filtered and washed with 8000 g of hot water at 60 ° C. (Process (c))

Next, using the washed titanium oxide hydrate gel slurry, a hydrated titanium oxide hydrate dispersion having a concentration of 1% by weight and 2000 g as TiO ₂ was prepared, and 140 g of hydrogen peroxide solution having a concentration of 35% by weight was added thereto. And dissolved at 50 ° C. for 1 hour.
At this time, the molar ratio (M _H2O2 ) / (M _TiO2 ) = 5.8. (Process (d))
Subsequently, the mixture was aged for 1 hour while removing hydrogen peroxide while stirring at a temperature of 80 ° C. (Process (e))
Subsequently, using pure water, it was washed by an ultrafiltration membrane method to obtain a dispersion of titanium oxide fine particles (R1) having a concentration of 1% by weight as TiO ₂ . The average particle size, particle size distribution, crystallinity, and yield of the titanium oxide fine particles (R1) are shown in the table.

Preparation of antibacterial and deodorant titanium oxide fine particle (R1) dispersion The solid content concentration was 1.5 in the same manner as in Example 1 except that a titanium oxide fine particle (R1) dispersion having a solid content concentration of 1% by weight was used. A weight percent antibacterial / deodorant titanium oxide fine particle (R1) dispersion was prepared.
The average particle size, particle size distribution, and crystallinity of the antibacterial / deodorant titanium oxide fine particles (R1) were analyzed, and the results are shown in the table.

Preparation of antibacterial / deodorant coating film-forming coating solution (R1) In preparation of the antibacterial / deodorant coating film-forming coating solution (1-2) of Example 1, an antibacterial agent having a solid content of 1.5% by weight was prepared. An antibacterial / deodorant coating solution (R1) was prepared in the same manner except that the deodorant titanium oxide fine particle (R1) dispersion was used.
The stability of the antibacterial / deodorant coating solution (R1) was evaluated, and the results are shown in the table.

Preparation of base material with antibacterial / deodorant coating film (R1) In preparation of the base material with antibacterial / deodorant coating film (1-2) in Example 1, an antibacterial / deodorant coating film forming liquid ( A substrate (R1) with an antibacterial / deodorant coating film was prepared in the same manner except that R1) was used.
The obtained substrate (R1) with antibacterial / deodorant coating film was evaluated for film thickness, adhesion, surface flatness, antibacterial performance, and deodorization performance, and the results are shown in the table.

[Comparative Example 2]
Preparation of Titanium Oxide Fine Particle (R2) Dispersion A titanyl sulfate aqueous solution having a concentration of 0.2% by weight was prepared as TiO ₂ and adjusted to a temperature of 15 ° C. (Process (a))
Subsequently, while maintaining the temperature at 15 ° C., 360 g of ammonia water having a concentration of 15% by weight was added over 1 hour to prepare a titanium oxide hydrate gel slurry. At this time, the molar ratio (M _NH3 ) / (M _TiO2 ) = 3.2, and the addition time was 3.2 hours / mole (M _NH3 ). (Process (b))
Next, the titanium oxide hydrate gel slurry was filtered and washed with 8000 g of hot water at 60 ° C. (Process (c))

Next, using the washed titanium oxide hydrate gel slurry, a hydrated titanium oxide hydrate dispersion having a concentration of 1% by weight and 2000 g as TiO ₂ was prepared, and 140 g of hydrogen peroxide solution having a concentration of 35% by weight was added thereto. And dissolved at 50 ° C. for 1 hour.
At this time, the molar ratio (M _H2O2 ) / (M _TiO2 ) = 5.8. (Process (d))
Subsequently, the mixture was aged for 1 hour while removing hydrogen peroxide while stirring at a temperature of 80 ° C. (Process (e))
Subsequently, using pure water, it was washed by an ultrafiltration membrane method to obtain a titanium oxide fine particle (R2) dispersion having a concentration of 1% by weight as TiO ₂ . The average particle size, particle size distribution, crystallinity, and yield of the titanium oxide fine particles (R2) are shown in the table.

Preparation of antibacterial and deodorant titanium oxide fine particle (R2) dispersion A solid content concentration of 1.5 was obtained in the same manner as in Example 1 except that a titanium oxide fine particle (R2) dispersion having a solid content concentration of 1% by weight was used. A weight percent antibacterial / deodorant titanium oxide fine particle (R2) dispersion was prepared.
The average particle size, particle size distribution, and crystallinity of the antibacterial / deodorant titanium oxide fine particles (R2) were analyzed, and the results are shown in the table.

Preparation of antibacterial / deodorant coating film-forming coating liquid (R2) In the preparation of antibacterial / deodorant coating film-forming coating liquid (1-2) in Example 1, the solid content concentration was 1.5. A coating solution (R2) for forming an antibacterial / deodorant coating film was prepared in the same manner, except that a weight percent antibacterial / deodorant titanium oxide fine particle (R2) dispersion was used.
The stability of the antibacterial / deodorant coating solution (R2) was evaluated and the results are shown in the table.

Preparation of base material with antibacterial / deodorant coating film (R2) In preparation of the base material with antibacterial / deodorant coating film (1-2) in Example 1, an antibacterial / deodorant coating film forming liquid ( A substrate (R2) with an antibacterial / deodorant coating film was prepared in the same manner except that R2) was used.
The obtained base material with antibacterial / deodorant coating film (R2) was evaluated for film thickness, adhesion, surface flatness, antibacterial performance, and deodorization performance, and the results are shown in the table.

[Comparative Example 3]
Preparation of Titanium Oxide Fine Particles (R3) Dispersion 320 g of an aqueous titanyl sulfate solution having a concentration of 25% by weight was prepared as TiO ₂ and adjusted to a temperature of 15 ° C. (Process (a))
Subsequently, while maintaining the temperature at 15 ° C., 360 g of ammonia water having a concentration of 15% by weight was added over 1 hour to prepare a titanium oxide hydrate gel slurry. At this time, the molar ratio (M _NH3 ) / (M _TiO2 ) = 3.2, and the addition time was 3.2 hours / mole (M _NH3 ). (Process (b))
Next, the titanium oxide hydrate gel slurry was filtered and washed with 8000 g of hot water at 60 ° C. (Process (c))

Next, using the washed titanium oxide hydrate gel slurry, a hydrated titanium oxide hydrate dispersion having a concentration of 1% by weight and 2000 g as TiO ₂ was prepared, and 140 g of hydrogen peroxide solution having a concentration of 35% by weight was added thereto. And dissolved at 50 ° C. for 1 hour.
At this time, the molar ratio (M _H2O2 ) / (M _TiO2 ) = 5.8. (Process (d))
Subsequently, the mixture was aged for 1 hour while removing hydrogen peroxide while stirring at a temperature of 80 ° C. (Process (e))
Subsequently, using pure water, it was washed by an ultrafiltration membrane method to obtain a dispersion of titanium oxide fine particles (R3) having a concentration of 1% by weight as TiO ₂ . The average particle size, particle size distribution, crystallinity, and yield of the titanium oxide fine particles (R3) are shown in the table.

Preparation of antibacterial and deodorant titanium oxide fine particle (R3) dispersion A solid content concentration of 1.5 was obtained in the same manner as in Example 1 except that a titanium oxide fine particle (R3) dispersion having a solid content concentration of 1% by weight was used. A weight percent antibacterial / deodorant titanium oxide fine particle (R3) dispersion was prepared.
The average particle size, particle size distribution, and crystallinity of the antibacterial / deodorant titanium oxide fine particles (R3) were analyzed, and the results are shown in the table.

Preparation of antibacterial / deodorant coating film-forming coating liquid (R3) In the preparation of antibacterial / deodorant coating film-forming coating liquid (1-2) in Example 1, the solid content concentration was 1.5. A coating solution (R3) for forming an antibacterial / deodorant coating film was prepared in the same manner except that a weight percent antibacterial / deodorant titanium oxide fine particle (R3) dispersion was used.
The stability of the antibacterial / deodorant coating solution (R3) was evaluated, and the results are shown in the table.

Preparation of base material with antibacterial / deodorant coating film (R3) In preparation of the base material with antibacterial / deodorant coating film (1-2) in Example 1, an antibacterial / deodorant coating film forming liquid ( A substrate (R3) with an antibacterial / deodorant coating was prepared in the same manner except that R3) was used.
The obtained base material with antibacterial / deodorant coating film (R3) was evaluated for film thickness, adhesion, surface flatness, antibacterial performance, and deodorization performance, and the results are shown in the table.

Claims (16)

The manufacturing method of the titanium oxide type microparticles | fine-particles characterized by including the following process (a)-(e).
(A) step of concentration as TiO ₂ to prepare a 0.5 to 20 wt% of the titanium compound aqueous solution.
(B) While maintaining the temperature of the titanium compound aqueous solution in the range of 0 to 30 ° C., when the number of moles of titanium compound as TiO ₂ (M _TiO2 ) is 1, the number of moles of ammonia in the aqueous ammonia solution to be added (M _NH3 ) is in the range of 1 to 10, and an aqueous ammonia solution is added at a rate of 1 to 10 hours / 1 mole (M _NH3 ) to prepare titanium oxide hydrate.
(C) A step of washing titanium oxide hydrate.
(D) To a titanium oxide hydrate dispersion having a concentration of 0.1 to 10% by weight as TiO ₂ , hydrogen peroxide water is _{added to the} number of moles (M _{TiO 2} ) of titanium oxide hydrate as TiO _2. A step of adding at a molar ratio (M _H2O2 ) / (M _TiO2 ) with a mole number of hydrogen oxide (M _H2O2 ) in the range of 1 to 10 and dissolving at a temperature of 10 to 100 ° C.
(E) A step of removing hydrogen peroxide while stirring at a temperature of 30 to 100 ° C. and aging. 2. The method for producing titanium oxide-based fine particles according to claim 1, wherein the following step (f) is performed after the step (e).
(F) A step of adding silica sol and / or zirconia sol to 0.1 to 15% by weight with respect to TiO ₂ . The method for producing titanium oxide-based fine particles according to claim 1 or 2, wherein the following step (g) is performed after the step (f).
(G) A step of aging at a temperature of 30 to 80 ° C.   The method for producing titanium oxide-based fine particles according to any one of claims 1 to 3, wherein the titanium oxide-based fine particles are amorphous.   Titanium oxide fine particles containing an antibacterial / deodorant component in the range of 0.1 to 25% by weight in terms of oxide, the average particle size (D) is in the range of 3 to 10 nm, and the average particle size (D ) An antibacterial / deodorant characterized in that the number ratio of titanium oxide fine particles having a particle diameter of ± 2 nm is 70% or more. The antibacterial / deodorant component according to claim 5 , wherein the antibacterial / deodorant component is one or more components selected from silver, copper, zinc, tin, cobalt, nickel, and manganese. . Antibacterial deodorant according to claim 5 or 6, wherein the titanium oxide-based fine particles containing silica and / or zirconia in the range of 0.1 to 15% by weight with respect to TiO _2. The antibacterial / deodorant according to any one of claims 5 to 7 , wherein the titanium oxide fine particles are amorphous. An antibacterial / deodorant obtained by dispersing the antibacterial / deodorant according to any one of claims 5 to 8 in an aqueous dispersion medium containing a fragrance compound. A coating solution for forming an antibacterial / deodorant coating film, comprising the antibacterial / deodorant agent according to any one of claims 5 to 9 . The coating liquid for forming an antibacterial / deodorant coating film according to claim 10 , comprising a water-soluble metal chelate compound. The coating solution for forming an antibacterial / deodorant coating film according to claim 11 , wherein the water-soluble metal chelate compound is a titanium chelate compound. The coating liquid for forming an antibacterial / deodorant coating film according to claim 12 , wherein the titanium chelate compound is a titanium lactate ammonium salt. The total solid content concentration is in the range of 0.01 to 20% by weight, the concentration of the antibacterial / deodorant as a solid content is in the range of 0.005 to 19.9% by weight, and the water-soluble metal chelate compound The concentration of TiO _{2 in} the range of 0.0001 to 10.0% by weight, the weight of the antibacterial / deodorant (W _a ) and the weight of the water-soluble metal chelate compound as TiO ₂ (W _b ) the ratio _{(W b) / (W a} ) antibacterial and deodorant coating film-forming coating liquid according to any one of claims 11 to 13, characterized in that in the range of 0.005 to 1.0. It consists of a base material and the antibacterial and deodorant coating film formed on the base material, The antibacterial and deodorant coating film formation in any one of Claims 10-14 A base material with an antibacterial / deodorant coating film, characterized by being an antibacterial / deodorant coating film formed using a coating liquid for use. The content of the antibacterial / deodorant as a solid content in the antibacterial / deodorant coating is in the range of 50 to 99.5% by weight, and the content of the water-soluble metal chelate compound as TiO ₂ is 0.00. The substrate with an antibacterial / deodorant coating film according to claim 15 , which is in the range of 5 to 50% by weight.