JP2012096133A - Deodorizing rutile type titanium oxide fine particle, coating liquid for forming deodorizing coating film containing the fine particle, and substrate with deodorizing coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide deodorizing rutile type titanium oxide fine particles which can decompose odor components, such as VOC and ammonia, under visible light irradiation.SOLUTION: The deodorizing rutile type titanium oxide fine particles have an average particle width (W) within a range of 2-50 nm, an average length (L) within a range of 2-500 nm, and an aspect ratio (L)/(W) within a range of 1-10. The particle contains iron as a deodorizing component within a range of 0.01-2 wt.%, calculated as FeO. The titanium oxide fine particle further contains antimicrobial deodorizing metal components, such as silver, copper, and zinc, within a range of 0.1-20 wt.%, calculated as an oxide.

Description

  The present invention relates to deodorant rutile titanium oxide fine particles capable of decomposing odorous components such as volatile organic compounds (VOC) and ammonia under visible light irradiation, a coating solution for forming a deodorant coating film containing the fine particles, and The present invention relates to a substrate with a deodorant coating film formed using the coating solution.

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 has applied an antibacterial agent in which an antibacterial metal component is adhered to inorganic oxide colloidal particles (Patent Document 1: Japanese Patent Laid-Open No. 6-80527) or a metal ion having antibacterial properties to magnesium aluminate metasilicate. An antibacterial agent subjected to ion exchange (Patent Document 2: JP-A-3-275627) is disclosed.
For the purpose of improving the durability of the antibacterial effect and the stability of the antibacterial substance, an antibacterial composition in which an antibacterial metal ion is supported on zeolite or aluminosilicate is also known (Patent Document 3: JP-A-1-283204). Issue gazette).

  The applicant of the present application is an inorganic oxide fine particle composed of a metal component and an inorganic oxide other than the metal component, and the inorganic oxide includes titanium oxide and silica and / or zirconia. An antibacterial deodorant in which the titanium oxide is crystalline titanium oxide is disclosed (Patent Document 4: Japanese Patent Application Laid-Open No. 2005-318999). 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 applicant of the present application is that N-doped tubular titanium oxide particles having excellent conductivity, photocatalytic performance, visible light absorption ability, chemical resistance, and the like, and an aqueous dispersion of titanium oxide particles in the presence of an alkali metal hydroxide. A method for producing N-doped tubular titanium oxide particles that are subjected to a reduction treatment in the presence of ammonia, amine, etc. after hydrothermal treatment is disclosed (Patent Document 5: JP-A-2004-35362).
However, the N-doped tubular titanium oxide particles do not necessarily have sufficient visible light absorption (shielding) performance, and have problems in photocatalytic activity and durability.

Patent Document 6 (Japanese Patent Application Laid-Open No. 2001-205103) discloses a photocatalyst that is a titanium compound doped with nitrogen atoms or sulfur atoms between lattices of a titanium oxide crystal, and a charge separation material is supported on the surface thereof. Is disclosed.
This photocatalyst is exemplified by a sputtering method. In nitrogen doping, a TiO ₂ target is set in a vacuum chamber, N ₂ gas and Ar gas are introduced, and sputtering is performed in N ₂ and Ar plasma. An N-doped titanium oxide film is obtained by heat treatment (annealing) in a nitrogen atmosphere. In addition, in sulfur doping, a method is described in which Ti, TiO ₂ or TiS (titanium sulfide) is used as a target, sputtering is performed in SO ₂ + O ₂ + Ar gas, and heat treatment is performed. However, in any case, a large amount of oxygen defects are generated simultaneously with doping, and this defect becomes a recombination center. Therefore, there is a problem that when the doping concentration is increased, the catalytic activity is greatly reduced.

  In addition, a sulfur-containing metal oxide useful as a photooxidation catalyst and a method for producing the same are also disclosed (Patent Document 7: Japanese Patent Application Laid-Open No. 2004-143032). However, this photo-oxidation catalyst also has an amorphous metal oxide, and the photocatalytic activity is not always sufficient.

Further, the applicant of the present application disclosed in Patent Document 8 (Japanese Patent Application Laid-Open No. 08-230950) that tubular titanium oxide particles doped with N and / or S, particularly tubular titanium oxide particles doped with N and / or S are further added. It is disclosed that anatase-type tubular titanium oxide particles carrying iron oxide exhibit high photooxidation catalytic activity under visible light irradiation.
However, N and / or S-doped tubular titanium oxide particles and N and / or S-doped tubular titanium oxide particles containing iron oxide have a long production process of tubular titanium oxide particles and are not economical, and in addition, sulfur compounds and nitrogen compounds. Has a strong odor and needs attention to safety, requires these treatment facilities, and has an economic problem. Further, when the titanium oxide is anatase type, the photocatalytic activity is high and the light resistance may be a problem depending on the application.

  In recent years, in residential spaces, public facilities, medical facilities, nursing homes, car interiors, etc., removal of harmful substances such as formaldehyde contained in building materials, acetaldehyde generated during tobacco smoking, and ammonia deodorizing performance in toilets, etc. In addition, antibacterial performance such as antibacterial, antifungal, antialgae, anti-well virus, antiallergen, pest repellent is required, and high deodorizing performance and antibacterial performance under irradiation of natural light including visible light or artificial light source Is required.

  As a result of intensive studies, the present inventors have found that the average particle size is in a specific range, the rutile-type titanium oxide fine particles supporting a small amount of iron oxide are excellent in deodorizing performance, and excellent in weather resistance. It came to be completed.

JP-A-6-80527 JP-A-3-275627 Japanese Patent Laid-Open No. 1-283204 JP 2005-318999 A JP 2004-35362 A JP 2001-205103 A JP 2004-143032 A Japanese Patent Laid-Open No. 08-230950

  The present invention relates to deodorant rutile titanium oxide fine particles capable of decomposing odorous components such as volatile organic compounds (VOC) and ammonia under visible light irradiation, a coating solution for forming a deodorant coating film containing the fine particles, and It aims at providing the base material with a deodorizing coating film excellent in the weather resistance formed using this coating liquid.

The deodorant rutile-type titanium oxide fine particles according to the present invention have an average particle width (W) in the range of 2 to 50 nm, an average length (L) in the range of 2 to 500 nm, and an aspect ratio (L) / (W) is in the range of 1 to 10, and iron is contained as a deodorizing component in a range of 0.01 to ₂ % by weight in terms of Fe ₂ O ₃ .
Furthermore, it is preferable to contain an antibacterial / deodorant metal component in the range of 0.1 to 20% by weight in terms of oxide.
The antibacterial / deodorant metal component is preferably one or more metal components selected from silver, copper, zinc, tin, cobalt, nickel, and manganese.

The coating solution for forming a deodorant coating film according to the present invention is characterized in that the deodorant rutile type titanium oxide fine particles described above are dispersed in a dispersion medium.
The dispersion medium is preferably an aqueous dispersion medium containing a water-soluble metal chelate compound.
The water-soluble metal chelate compound is preferably a titanium chelate compound.
The titanium chelate compound is preferably a titanium lactate ammonium salt.

The total solid content concentration is in the range of 0.01 to 20% by weight, and the concentration of the deodorant rutile-type titanium oxide fine particles as the solid content is in the range of 0.005 to 19.9% by weight. The concentration of the metal chelate compound as TiO ₂ is in the range of 0.0001 to 10.0% by weight, the weight (W _a ) of the deodorant rutile titanium oxide fine particles and the weight of the water-soluble metal chelate compound as TiO _2. the weight ratio of _{(W b) (W b)} / (W a) is preferably in the range of 0.005 to 1.0.

The substrate with a deodorizing coating film according to the present invention comprises a substrate and a deodorizing coating film formed on the substrate, and the deodorizing coating film according to any one of the above It is a deodorant coating film formed using a coating liquid for forming a coating film.
The content of the deodorant rutile-type titanium oxide fine particles in the deodorant coating film as a solid content is in the range of 50 to 100% by weight, and the content of the water-soluble metal chelate compound as TiO ₂ is 0 to 50. It is preferably in the range of wt%.

By using the deodorant rutile-type titanium oxide fine particles of the present invention, a coating for forming a deodorant coating that can efficiently decompose odorous components such as volatile organic compounds (VOC) and ammonia under irradiation with visible light. A liquid can be obtained.
By applying the coating solution for forming a deodorant coating film of the present invention to various substrates, a substrate with a deodorant coating film having excellent weather resistance can be obtained.

[Deodorant rutile type titanium oxide fine particles]
The deodorant rutile-type titanium oxide fine particles according to the present invention have an average particle width (W) in the range of 2 to 50 nm, an average length (L) in the range of 2 to 500 nm, and an aspect ratio (L) / (W) is in the range of 1 to 10, and iron is contained as a deodorizing component in a range of 0.01 to ₂ % by weight in terms of Fe ₂ O ₃ .

Rutile type titanium oxide fine particles In the present invention, rutile type titanium oxide fine particles are used as a carrier for a deodorant component.
Rutile-type titanium oxide fine particles have lower photocatalytic activity of the carrier itself and superior weather resistance than anatase-type titanium oxide fine particles and anatase-type tubular titanium oxide fine particles. Moreover, it is extremely cheap compared with anatase type tubular titanium oxide fine particles.

  The rutile-type titanium oxide fine particles used in the present invention are prepared by dissolving a hydrated titanium oxide gel or sol disclosed in JP-A-2-255532 filed by the applicant of the present application with hydrogen peroxide. It can be obtained by hydrothermal treatment in the presence of an aqueous stannic acid solution that is a tin compound dealkalized with an ion exchange resin.

As another method, titanium alkoxide and hydrogen peroxide disclosed in Japanese Patent Application Laid-Open No. 2009-179521 by the applicant of the present application are converted into the number of moles (M _HP ) of hydrogen peroxide as H ₂ O ₂ and titanium alkoxide. after the number of moles of the TiO ₂ (M _Ti) molar ratio of _{(M HP) / (M Ti} ) is reacted in the range of 2 to 50 can be obtained by a method of hydrothermal treatment at 100 to 350 ° C. . Furthermore, a mixed aqueous solution of a titanium compound and a tin compound disclosed in Japanese Patent Application Laid-Open No. 2009-227519 by the applicant of the present application is prepared, hydrolyzed by adding an NH ₄ OH aqueous solution, the gel is washed, hydrogen peroxide Of hydrogen peroxide as H ₂ O ₂ (M _HP ) and the molar ratio of the total number of moles of titanium compound and tin compound ((M _Ti ) + (M _S )) (M _HP ) / ( (M _Ti ) + (M _S )) is added and dissolved so as to be in the range of 2 to 50, and then hydrothermally treated at 100 to 350 ° C.

In any of the above methods, rutile-type titanium oxide fine particles can be obtained without firing at a high temperature.
The obtained rutile-type titanium oxide fine particles are substantially the same as the deodorant rutile-type titanium oxide fine particles described later, the average particle width (W) is in the range of 2 to 50 nm, and the average length (L) is 2 to 500 nm. The aspect ratio (L) / (W) is in the range of 1 to 10.

As the deodorant component , iron oxide is supported. Although the content of iron oxide varies depending on the loading method, it is preferably in the range of 0.01 to ₂ % by weight, more preferably 0.02 to 1.5% by weight in terms of Fe ₂ O ₃ .
When the content of iron oxide is less than 0.01% by weight in terms of Fe ₂ O ₃ , trapping of generated electrons is insufficient and reverse reaction occurs, resulting in insufficient photoactivity and insufficient deodorization performance. It may become.
If the iron oxide content exceeds 2% by weight in terms of Fe ₂ O ₃ , the generated electrons are trapped too much, attracting holes, and the deodorizing performance may be lower than when no iron oxide is supported. is there.

Method for producing deodorant rutile type titanium oxide fine particles As a method for producing deodorant rutile type titanium oxide fine particles, there are no particular restrictions as long as deodorant rutile type titanium oxide fine particles having sufficient deodorizing performance and weather resistance are obtained. However, it can be produced according to the method disclosed in, for example, Patent Document 8 (Japanese Patent Laid-Open No. 08-230950).
Specifically, the first method for producing deodorant rutile type titanium oxide fine particles is a dispersion of rutile type titanium oxide fine particles obtained without firing at a high temperature as described above, in the presence of an ion exchange resin. It is preferable to mix a ferric nitrate aqueous solution and then heat-treat as necessary.

The concentration of the rutile-type titanium oxide fine particle dispersion is not particularly limited as long as the ion exchange resin described later can be dispersed and the dispersion can be uniformly stirred, but the solid content ranges from 1 to 30% by weight, and more preferably from 2 to 20% by weight. It is preferable that it exists in.
If the concentration of the rutile-type titanium oxide fine particle dispersion is less than 1% by weight as the solid content, the productivity is lowered, and if it exceeds 30% by weight, the iron oxide is not uniformly supported. The effect of reducing and improving the deodorant performance may not be obtained sufficiently.

As the ion exchange resin, a conventionally known anion exchange resin can be used to remove the nitrate radical of ferric nitrate.
The amount of the ion exchange resin used can be varied depending on the ion exchange capacity of the ion exchange resin and the amount of ferric nitrate used, but it is preferable that the amount of nitrate radicals be removed substantially.
Although ferric nitrate is used, ferrous nitrate can also be used, and ferric sulfate and ferric chloride can also be used. However, although the reason is not clear, ferric nitrate can be suitably used because it is most excellent in deodorizing performance improvement effect. Further, ferric nitrate and other salts may be used in combination.

The amount of ferric nitrate used is such that the iron oxide content in the rutile-type titanium oxide fine particles carrying iron oxide finally obtained is 0.01 to ₂ % by weight as Fe ₂ O ₃ , and further 0.02 to It is used so as to be in the range of 1.5% by weight.
Next, after adding the ferric nitrate aqueous solution, stirring is continued if necessary, and then a dispersion of rutile-type titanium oxide particles carrying iron oxide can be obtained by separating the ion exchange resin. The obtained iron oxide-supported rutile-type titanium oxide fine particle dispersion can be used as it is, but it can be concentrated or diluted as necessary. It can be further dried and further heat-treated as necessary to form a powder, and further, the powder can be used as a molded body.

At this time, the drying temperature is not particularly limited as long as moisture can be substantially removed, but is preferably in the range of 80 to 250 ° C, more preferably 95 to 200 ° C.
The heating temperature at the time of heat treatment according to necessity is generally in the range of 200 to 650 ° C, and further 300 to 600 ° C. When the heating temperature is less than 200 ° C., decomposition and desorption of nitrate radicals are insufficient, and a sufficient deodorizing performance improvement effect may not be obtained. When the heating temperature exceeds 650 ° C., iron oxide, which is a deodorant metal component, grows, the rutile titanium oxide fine particles agglomerate strongly, and pulverization is required, or sufficient deodorization performance may not be obtained. is there.

The second method for producing deodorant rutile-type titanium oxide fine particles includes the above-described rutile-type titanium oxide fine particle powder obtained by drying the rutile-type titanium oxide fine particle dispersion obtained without firing at a high temperature as described above. It is preferable to absorb an aqueous iron compound solution, preferably an aqueous ferric nitrate solution, then dry and heat-treat as necessary.
The amount of the ferric nitrate aqueous solution when the rutile type titanium oxide fine particles, which are powders, are absorbed depends on the average particle size of the rutile type titanium oxide fine particles. It is preferable that the aqueous solution of ferric nitrate is uniformly absorbed and becomes a paste. At this time, the concentration of the rutile-type titanium oxide fine particles in the paste-like mixture is about 25 to 60% by weight as a solid content.

If the concentration of the rutile type titanium oxide fine particles in the paste-like mixture is less than 25% by weight as a solid content, the total amount of iron oxide may not be supported, and if it exceeds 60% by weight, it is uniform to the rutile type titanium oxide fine particles. In some cases, iron oxide may not be supported, and the deodorizing performance may be insufficient.
The amount of ferric nitrate used is such that the iron oxide content in the rutile-type titanium oxide fine particles carrying iron oxide finally obtained is 0.01 to ₂ % by weight as Fe ₂ O ₃ , and further 0.02 to It is used so as to be in the range of 1.5% by weight.

Next, the paste-like mixture is dried. There is no restriction | limiting in particular in the drying method, A conventionally well-known method is employable. Although there will be no restriction | limiting in particular if a drying temperature can remove a water | moisture content substantially, It is preferable that it exists in the range of 80-250 degreeC, Furthermore, 95-200 degreeC.
Next, heat treatment is performed as necessary, but the heating temperature is generally in the range of 200 to 650 ° C., more preferably 300 to 600 ° C. When the heating temperature is less than 200 ° C., decomposition and desorption of nitrate radicals are insufficient, and a sufficient deodorizing performance improvement effect may not be obtained. When the heating temperature exceeds 650 ° C., iron oxide, which is a deodorant metal component, grows, the rutile titanium oxide fine particles agglomerate strongly, and pulverization is required, or sufficient deodorization performance may not be obtained. is there.

Antibacterial / deodorant metal component In the present invention, the antibacterial / deodorant metal component preferably further contains one or more selected from silver, copper, zinc, tin, cobalt, nickel, and manganese as the antibacterial / deodorant metal component. Among these, silver or zinc is preferable because both antibacterial performance and deodorization performance are excellent. In particular, in the case of zinc, since it does not change color at all, it can be preferably used.
Such antibacterial / deodorant components may be present in any form of compounds such as ions, oxides, hydroxides or mixtures thereof. From the viewpoint of antibacterial properties, the ion form is preferable, and if it is an oxide, an antibacterial / deodorant coating film having excellent deodorizing properties can be obtained.

In addition, the antibacterial / deodorant metal component is preferably present in the surface layer of the deodorant rutile type titanium oxide fine particles or distributed relatively uniformly to the inside of the deodorant rutile type titanium oxide fine particles.
As a method for supporting the antibacterial / deodorant metal component on the deodorant rutile-type titanium oxide fine particles, for example, it can be supported according to the method disclosed in Patent Document 4 (Japanese Patent Laid-Open No. 2005-318999).
Specifically, for example, a method of adding an aqueous metal salt solution of an antibacterial / deodorant metal component to a dispersion in which deodorant rutile-type 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. Use of an ammine complex salt aqueous solution reduces the stability of the deodorant rutile-type titanium oxide fine particle dispersion and prevents it from gelling and is stable for a long period of time, as well as antibacterial and deodorant performance. A substrate with a deodorant coating film excellent in the above can be obtained.
The application of the coating solution for forming a deodorant coating film with reduced stability or gelation may be limited, and the antibacterial performance and deodorization performance may be insufficient.
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 addition to the above-described method, a conventionally known impregnation method or the like may be employed depending on the application and usage.
The content of the antibacterial / deodorant metal component is preferably 0.1 to 20% by weight, more preferably 0.2 to 15% by weight in terms of oxide.
When the content of the antibacterial / deodorant metal component is less than 0.1% by weight in terms of oxide, it is difficult to obtain sufficient antibacterial / deodorant performance.
When the content of the antibacterial / deodorant metal component is more than 20% by weight in terms of oxide, the deodorant performance and antibacterial performance are not further improved, but the antibacterial / deodorant metal component aggregates rather. Therefore, these performances may be reduced.

Deodorant rutile titanium oxide fine particles have an average particle width (W) in the range of 2 to 50 nm, an average length (L) in the range of 2 to 500 nm, and an aspect ratio (L) / (W) of 1. It is preferable that it exists in the range of -10.
It is difficult to obtain particles having an average particle width (W) of less than 2 nm. When the average particle width (W) exceeds 50 nm, the average length (L) described later also becomes long, and the dispersion, coating solution, etc. Since it settles easily when using it, there is a limitation in use. A more preferable average particle width (W) is in the range of 5 to 30 nm.

It is difficult to obtain a product having an average length (L) of less than 2 nm. If the average length (L) exceeds 500 nm, it tends to settle down when used in a dispersion, a coating solution or the like, so that its use is limited. A more preferable average length (L) is in the range of 5 to 300 nm.
Further, the aspect ratio (L) / (W) never becomes less than 1, and it is difficult to obtain an aspect ratio (L) / (W) exceeding 10.
In the present invention, the average particle width (W) and average particle length (L) were measured by taking transmission electron micrographs, obtaining the particle width and particle length of 50 particles, and showing the average values.
The deodorant rutile type titanium oxide fine particles described above can be used after being surface-treated with a silane coupling agent or the like, if necessary.

[Coating solution for forming deodorant coating film]
Next, the coating liquid for forming a deodorant coating film according to the present invention will be described.
The coating solution for forming a deodorant coating film according to the present invention is characterized in that the deodorant rutile type titanium oxide fine particles described above are dispersed in a dispersion medium.

Deodorant rutile type titanium oxide fine particles As the deodorant rutile type titanium oxide fine particles, the aforementioned deodorant rutile type titanium oxide fine particles are used.

Water-soluble metal chelate compound The coating solution for forming a deodorant coating film of the present invention preferably contains a water-soluble metal chelate compound dissolved in an aqueous dispersion medium.
Examples of the water-soluble metal chelate compound used in the present invention include water-soluble metal chelate compounds whose 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 stable even when used in a coating solution for forming a deodorant coating, and the deodorant coating obtained by applying this is a substrate. It has excellent adhesion, transparency, flatness of the coating film surface, and excellent antibacterial / deodorant performance.

Aqueous dispersion medium The aqueous dispersion medium used in the present invention is preferably water or a mixed dispersion medium of water and alcohol.
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 concentration of the water-soluble metal chelate compound in the deodorant coating film-forming coating solution 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 in water-soluble metal chelate compound of the deodorizing coating film-forming coating liquid is less than 0.0001 wt%, stability of the coating solution, adhesion to a substrate, transparency and the like is It may be insufficient.
When the concentration of the TiO ₂ in water-soluble metal chelate compound of the deodorizing coating film-forming coating liquid is more than 10% by weight, without the stability of the coating liquid is further improved, resulting deodorant coating Since the content of the deodorant rutile type titanium oxide fine particles in the inside is lowered, the antibacterial / deodorant performance may be insufficient.

Weight ratio of weight (W _a ) as solid content of deodorant rutile-type titanium oxide fine particles in coating liquid for forming deodorant coating film to weight (W _b ) as TiO ₂ of water-soluble metal chelate compound (W _b ) / (W _a ) 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 liquid is not further improved, and the deodorant rutile type titanium oxide fine particles in the obtained deodorant coating film. In some cases, the antibacterial / deodorizing performance may be insufficient due to a decrease in the content of.
Furthermore, the coating liquid for forming a deodorant coating film 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.

The total solid concentration of the coating solution for forming a deodorant coating film is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight.
When the total solid content is less than 0.01% by weight, the film thickness of the deodorant coating film obtained by coating becomes thin, the antibacterial / deodorant performance becomes insufficient, and the film strength is insufficient. When the substrate surface has irregularities, the surface flatness may be insufficient.
When 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 deodorant coating film to the substrate, the surface flatness, Transparency, durability, crack suppression, etc. may be reduced, and antibacterial performance and deodorization performance may be insufficient.

The concentration of the deodorant rutile-type titanium oxide fine particles in the coating liquid for forming the deodorant coating film may be in the range of 0.005 to 19.9% by weight, further 0.1 to 10% by weight as the solid content. preferable.
When the concentration of the deodorant rutile-type titanium oxide fine particles in the coating liquid for forming a deodorant coating film is less than 0.005% by weight, antibacterial / deodorant performance may be insufficient.
When the concentration of the deodorant rutile-type titanium oxide fine particles in the coating liquid for forming a deodorant coating exceeds 19.9% by weight as a solid content, the water-soluble metal chelate compound is limited. In some cases, the stability, adhesion to the substrate, transparency, and the like are lowered, resulting in insufficient film strength.

[Substrate with deodorant coating]
Below, the base material with a deodorizing coating film which concerns on this invention is demonstrated.
The substrate with a deodorizing coating film according to the present invention comprises a substrate and a deodorizing coating film formed on the substrate, and the deodorizing coating film according to any one of the above It is a deodorant coating film formed using a coating liquid for forming a coating film.

Examples of the base material include base materials such as glass, metal, resin, ceramic, wood, and inorganic oxide.
The content of the deodorant rutile-type titanium oxide fine particles in the deodorant coating film as a solid content is in the range of 50 to 100% by weight, and the content of the water-soluble metal chelate compound as TiO ₂ is 0 to 50. It is preferably in the range of wt%.

The content of the deodorant rutile-type titanium oxide fine particles in the deodorant coating film as a solid content is preferably in the range of 50 to 100% by weight, more preferably 60 to 96% by weight.
If the content of the deodorant rutile-type titanium oxide fine particles in the deodorant coating film is less than 50% by weight, the antibacterial / deodorant performance may be insufficient.

When the deodorant coating film contains a water-soluble metal chelate compound, the content of the water-soluble metal chelate compound in the deodorant coating film as TiO ₂ is 50% by weight or less, more preferably in the range of 4 to 40% by weight. Preferably there is.
When the content of the water-soluble metal chelate compound in the deodorant coating film as TiO ₂ is small, adhesion to the substrate, transparency, surface flatness, film strength, etc. may be insufficient.
If the content of water-soluble metal chelate compound in the deodorant coating as TiO ₂ exceeds 50% by weight, antibacterial and deodorant performance is insufficient due to the low content of deodorant rutile titanium oxide fine particles. It may become.

The film thickness of the deodorant coating is preferably 50 μm or less, more preferably 20 μm or less.
Even if the film thickness of the deodorant coating film exceeds 50 μm, the antibacterial / deodorant performance is not further improved, and the use may be limited because the coating film is cracked or the transparency is lowered. .
The lower limit of the film thickness of the deodorant coating film is not particularly limited as long as the deodorant performance is obtained, and the deodorant rutile type titanium oxide fine particles may be scattered on the substrate. .
When the coating liquid for forming a deodorant coating film contains a water-soluble metal chelate compound, the film thickness of the deodorant coating film is preferably 0.1 μm or more. In this case, when the film thickness of the deodorant coating is less than 0.1 μm, the antibacterial / deodorant performance may be insufficient, and the high antibacterial / deodorant performance may not be maintained over a long period of time. .

  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 produced by applying to the above-mentioned substrate, drying, and further curing by heat treatment if necessary.

As odor components to be deodorized in the deodorant coating film of the present invention, eight legal malodorous substances (hydrogen sulfide, methyl mercaptan, methyl sulfide, dimethyl disulfide, ammonia, trimethylamine, acetaldehyde, styrene), hydrocarbons, Examples include ketones, aldehydes, alcohols, esters, nitrogen compounds, sulfur compounds, and lower fatty acids.
Antibacterial fungi include Staphylococcus aureus, Streptococcus, Escherichia coli, Pseudomonas aeruginosa, Proteus, Neisseria pneumoniae, Bacillus subtilis, etc. As fungi, black mold, black mold, white mold, etc. Examples of algae such as viruses, adenoviruses and noroviruses include chlorella.
The deodorant coating film of the present invention is irradiated with natural light or artificial light source including visible light, particularly in places where deodorant performance and antibacterial performance are required in living spaces, public facilities, medical facilities, nursing homes, automobile interiors, etc. Useful below.

[Example 1]
Preparation of deodorant rutile-type titanium oxide fine particles (1) 6.3 g of 63 wt% nitric acid was added to an aqueous hydrogen peroxide solution obtained by diluting 1425 g of 35 wt% hydrogen peroxide water with 7122 g of pure water. To this, 143 g of tetraisopropyl titanate was added to obtain a yellowish brown peroxotitanic acid aqueous solution.
Then, the peroxotitanic acid aqueous solution was aged at 90 ° C. for 2 hours and at 95 ° C. for 12 hours. The solution was initially yellowish brown, but became a milky white transparent liquid (colloidal liquid) after aging.
Subsequently, 3.2 g of nitric acid having a concentration of 63 wt% was added to the transparent liquid (colloidal liquid), and hydrothermal treatment (heating) was performed at 180 ° C. for 16 hours to prepare a rutile type titanium oxide fine particle (1) dispersion.
The obtained rutile type titanium oxide fine particle (1) dispersion was washed by an ultrafiltration membrane method and then concentrated to obtain a deodorant rutile type titanium oxide fine particle (1) dispersion sol.

  For the dried rutile-type titanium oxide fine particles (1), the average particle width (W) and average particle length (L) were measured, the specific surface area was measured by the BET method, and the X-ray diffraction method (manufactured by Rigaku Corporation: LAD-IIC) The crystal form was measured with a mold, Cu tube, 35 kV, 12.5 mA), and the results are shown in the table.

Next, 80 g of rutile-type titanium oxide fine particles (1) dispersion sol (solid content 10 wt%) was dispersed in 720 g of water and stirred sufficiently, and then mixed with 5 g of anion exchange resin (Mitsubishi Chemical Corporation: SA20A). Then, after adjusting the temperature to 50 ° C., 8 g of ferric nitrate aqueous solution having a concentration of 0.1% by weight as Fe ₂ O ₃ was added, stirred for 2 hours, and then aged at 95 ° C. for 1 hour. The ion exchange resin was separated, and a deodorant rutile-type titanium oxide fine particle (1) dispersion carrying iron oxide having a solid content concentration of 10% by weight was obtained by an ultrafiltration membrane method. The amount of iron oxide supported is shown in the table.

Preparation of coating liquid (1) for forming deodorant coating film Deodorant rutile type titanium oxide fine particles (10) 10 parts by weight of dispersion containing iron oxide having a solid content of 10% by weight in 85 parts by weight of ion exchange water Was mixed and sufficiently dispersed, and then a titanium lactate ammonium salt solution (manufactured by Matsumoto Fine Chemical Co., Ltd .: Olga Tix TC-300, titanium lactate ammonium salt 42% by weight, water 20% by weight as a water-soluble metal chelate compound. 5 parts by weight of isopropyl alcohol, 38% by weight of isopropyl alcohol and 10.0% by weight of TiO ₂ ) was added to prepare a coating solution (1) for forming a deodorant coating film having a solid content of 1.5% by weight. .

Preparation of base material with deodorant coating (1) Anti-bacterial / deodorant surface of 0.15mm thick industrial aluminum plate, degreased, causticized, thoroughly washed with water and dried The coating solution (1) for forming a conductive 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, the base material (1) with a deodorizing coating film was created by heat-processing at 200 degreeC for 2 minute (s).
About the obtained base material (1) with a deodorant coating film, film thickness, adhesiveness, 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.

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 coated substrate (1) is made with a knife with 11 parallel scratches at 1 mm vertical and horizontal intervals to make 100 squares, and cellophane tape ( Adhesion was evaluated by classifying the number of squares remaining after the cellophane tape (registered trademark) was peeled off, after the cellophane tape (registered trademark) was peeled off. The results are shown in Table 1.
98 or more remaining cells: ◎
93-97 remaining squares: ○
Number of remaining squares: 85-92:
Number of remaining squares: 84 or less: ×

Surface flatness An average surface roughness (μm) was evaluated with a stylus type surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd .: Surfcom).

Deodorant performance
Test odor (1) : Acetaldehyde (initial concentration: 60 ppm)
Test method: A specimen (10 cm × 10 cm) was placed in a 1 L Tedlar bag, and after adding 1 L of odor, it was left at room temperature under fluorescent light irradiation (illuminance: 4 klux). After 24 hours, the deodorization rate was determined from the residual odor concentration measured with the detector tube, and the carbon dioxide generation amount (ppm) was measured.

Test odor (2,3) : Hydrogen sulfide (initial concentration: 4 ppm), ammonia (initial concentration: 100 ppm)
Test method: A specimen (10 cm × 10 cm) was placed in a 5 L Tedlar bag, and after adding 3 L of odor, it was allowed to stand at room temperature under fluorescent light irradiation (illuminance: 400 lux). The deodorization rate was determined from the residual odor concentration measured with the detector tube after 2 hours.

Antibacterial performance
In accordance with JIS Z2801, after inoculating bacterial suspension, 0.4 ml on the antibacterial / deodorant coated substrate (1), covering it with a covering film and covering it, 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 Table 2.
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)

[Example 2]
Preparation of Deodorant Rutile Type Titanium Oxide Fine Particles (2) Deodorant rutile type in the same manner as in Example 1 except that 4 g of ferric nitrate aqueous solution having a concentration of 0.1% by weight as Fe ₂ O ₃ was added. A titanium oxide fine particle (2) dispersion was obtained.
Preparation of coating solution (2) for forming a deodorant coating film In Example 1, an anti-deodorant rutile type titanium oxide fine particle (2) dispersion was used, except that a solid content concentration of 1.5% by weight was used. A coating liquid (2) for forming an odorous coating film was prepared.

Preparation of base material with deodorant coating film (2) In Example 1, the base material with deodorant coating film (2) was prepared in the same manner except that the coating liquid for forming a deodorant coating film (2) was used. Created.
The obtained substrate (2) with a 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 deodorant rutile type titanium oxide fine particles (3) In Example 1, deodorant rutile type was the same except that 40 g of ferric nitrate aqueous solution having a concentration of 0.1 wt% as Fe ₂ O ₃ was added. A titanium oxide fine particle (3) dispersion was obtained.
Preparation of coating liquid (3) for deodorant coating film formation In Example 1, a deodorant rutile type titanium oxide fine particle (3) dispersion was used except that a solid content concentration of 1.5% by weight was used. A coating liquid (3) for forming an odorous coating film was prepared.

Preparation of base material with deodorant coating film (3) In Example 1, the base material with deodorant coating film (3) was prepared in the same manner as in Example 1, except that the coating liquid for forming a deodorant coating film (3) was used. Created.
The obtained substrate (3) with a 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 Deodorant Rutile Type Titanium Oxide Fine Particles (4 ) 80 g of rutile type titanium oxide fine particle (1) dispersion sol (solid content 10 wt%) prepared in the same manner as in Example 1 is dispersed in 720 g of water. On the other hand, 39.6 g of water was added to 0.4 g of silver oxide, 6 g of 15% ammonia was added and stirred, dissolved, and then added to the rutile-type titanium oxide fine particle (1) dispersed sol at 95 ° C. for 4 hours. After aging, washing with 100 times the solid content of water by the ultrafiltration membrane method, and concentrating, a rutile-type titanium oxide fine particle (4) -dispersed sol carrying Ag ₂ O was obtained.

Next, 80 g of rutile-type titanium oxide fine particles (4) dispersion sol (solid content 10% by weight) was dispersed in 720 g of water and stirred sufficiently, and then mixed with 5 g of an anion exchange resin (Mitsubishi Chemical Corporation: SA20A). Then, after adjusting the temperature to 50 ° C., 8 g of ferric nitrate aqueous solution having a concentration of 0.1% by weight as Fe ₂ O ₃ was added, stirred for 2 hours, and then aged at 95 ° C. for 1 hour. Then, the ion exchange resin was separated, and a deodorant rutile type titanium oxide fine particle (4) dispersion carrying iron oxide having a solid concentration of 10% by weight was obtained by an ultrafiltration membrane method.

Preparation of coating solution (4) for forming a deodorant coating film In Example 1, an odor eliminating solution having a solid content of 1.5% by weight was used except that the deodorant rutile type titanium oxide fine particle (4) dispersion was used. A coating liquid (4) for forming an odorous coating film was prepared.

Preparation of base material with deodorant coating film (4) In Example 1, the base material with deodorant coating film (4) was prepared in the same manner except that the coating liquid for forming a deodorant coating film (4) was used. Created.
About the obtained base material (4) with a deodorant coating film, a film thickness, adhesiveness, surface flatness, antibacterial performance, and deodorizing performance were evaluated, and a result is shown to a table | surface.

[Example 5]
Preparation of deodorant rutile type titanium oxide fine particles (5) 6.3 g of 63 wt% nitric acid was added to hydrogen peroxide aqueous solution obtained by diluting 1425 g of hydrogen peroxide water of 35 wt% with pure water 7122 g. 143 g of isopropyl titanate was added to obtain a yellowish brown peroxotitanic acid aqueous solution.
800 g of a peroxotitanic acid aqueous solution (solid content: 1%) was heated to 50 ° C., and the pH was adjusted to 9.0 with 15% ammonia. Meanwhile, 79.2 g of water is added to 2.92 g of zinc nitrate and dissolved by stirring. Zinc nitrate solution is added to peroxotitanic acid aqueous solution (solid content 1%) over 1 hour, and at the same time, anion exchange resin (Diaion SA20A manufactured by Mitsubishi Chemical Corporation) is kept at a pH of 9.0. Added. After completion of the addition, the ion exchange resin was separated.

Then, the peroxotitanic acid aqueous solution was aged at 90 ° C. for 2 hours and at 95 ° C. for 12 hours. The solution was initially yellowish brown, but became a milky white transparent liquid (colloidal liquid) after aging.
Subsequently, 3.2 g of nitric acid having a concentration of 63 wt% was added to the transparent liquid (colloid liquid), and hydrothermal treatment (heating) was performed at 180 ° C. for 16 hours to prepare a rutile type titanium oxide fine particle (5) dispersion.
The obtained zinc-supported rutile type titanium oxide fine particle (5) dispersion was washed by an ultrafiltration membrane method and then concentrated to obtain a zinc-supported rutile type titanium oxide fine particle (5) dispersion sol.

Next, 80 g of rutile-type titanium oxide fine particles (5) dispersion sol (solid content 10 wt%) was dispersed in 720 g of water and stirred sufficiently, and then mixed with 5 g of an anion exchange resin (Mitsubishi Chemical Corporation: SA20A). Then, after adjusting the temperature to 50 ° C., 8 g of ferric nitrate aqueous solution having a concentration of 0.1% by weight as Fe ₂ O ₃ was added, stirred for 2 hours, and then aged at 95 ° C. for 1 hour. Then, the ion exchange resin was separated, and a deodorant rutile type titanium oxide fine particle (5) dispersion carrying iron oxide having a solid concentration of 10% by weight was obtained by an ultrafiltration membrane method.

Preparation of coating liquid (5) for forming deodorant coating film In Example 1, a liquid with a solid content concentration of 1.5% by weight was obtained in the same manner except that the deodorant rutile type titanium oxide fine particle (5) dispersion was used. A coating liquid (5) for forming an odorous coating film was prepared.

Preparation of base material with deodorant coating film (5) In Example 1, the base material with deodorant coating film (5) was prepared in the same manner except that the coating liquid for deodorant coating film formation (5) was used. Created.
The obtained substrate (5) with a 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 coating solution (6) for forming deodorant coating film In Example 1, titanium lactate ammonium salt solution (manufactured by Matsumoto Fine Chemical Co., Ltd .: ORGATICS TC-300, titanium lactate ammonium salt 42 wt%, water 20 wt% 2.5 parts by weight of isopropyl alcohol 38% by weight, TiO ₂ concentration 10.0% by weight) to obtain a coating solution (6) for forming a deodorant coating film having a solid content concentration of 1.25% by weight. Prepared.

Preparation of base material with deodorant coating film (6) In Example 1, the base material with deodorant coating film (6) was prepared in the same manner except that the coating liquid for forming a deodorant coating film (6) was used. Created.
About the obtained base material (6) with a deodorant coating film, a film thickness, adhesiveness, surface flatness, antibacterial performance, and deodorizing performance were evaluated, and a result is shown to a table | surface.

[Example 7]
Preparation of coating solution (7) for forming deodorant coating film In Example 1, titanium lactate ammonium salt solution (manufactured by Matsumoto Fine Chemical Co., Ltd .: ORGATICS TC-300, titanium lactate ammonium salt 42% by weight, water 20% by weight , Isopropyl alcohol 38% by weight, TiO ₂ concentration 10.0% by weight) 1.25 parts by weight, and a solid content concentration 1.125% by weight of deodorant coating film forming coating solution (7) Prepared.

Preparation of base material with deodorant coating film (7) In Example 1, the base material with deodorant coating film (7) was prepared in the same manner except that the coating liquid for deodorant coating film formation (7) was used. Created.
About the obtained base material (7) with a deodorant coating film, a film thickness, adhesiveness, surface flatness, antibacterial performance, and deodorizing performance were evaluated, and a result is shown to a table | surface.

[Example 8]
Preparation of coating solution (8) for forming deodorant coating film 90 parts by weight of ion-exchange water and 10 parts by weight of deodorant rutile type titanium oxide fine particles (1) dispersion supporting iron oxide having a solid content of 10% by weight And a coating solution (8) for forming a deodorant coating film having a solid content concentration of 1.0% by weight was prepared.

Preparation of substrate with deodorant coating film (8) In Example 1, the substrate with deodorant coating film (8) was prepared in the same manner except that the coating liquid for deodorant coating film formation (8) was used. Created.
About the obtained base material (8) with a deodorant coating film, a film thickness, adhesiveness, surface flatness, antibacterial performance, and deodorizing performance were evaluated, and a result is shown in a table | surface.

[Comparative Example 1]
Preparation of deodorant anatase type titanium oxide fine particles (R1) Titanium oxide fine particle dispersion (manufactured by JGC Catalysts & Chemicals Co., Ltd .: ATOMYBALL- (TZ-R), average particle size 10 nm, solid content concentration 10.0% by weight, 80 g of antibacterial deodorant component (ZnO) content in solid content, 80% by weight, anatase type) was dispersed in 720 g of water and sufficiently stirred.
Next, 5 g of an anion exchange resin (Mitsubishi Chemical Co., Ltd .: SA20A) was mixed, and the temperature was adjusted to 50 ° C., and then a ferric nitrate aqueous solution having a concentration of 0.1 wt% as Fe ₂ O _3. 8 g was added and stirred for 2 hours, then aged at 95 ° C. for 1 hour, then the ion exchange resin was separated, and deodorant carrying iron oxide with a solid content concentration of 10% by weight by the ultrafiltration membrane method An anatase type titanium oxide fine particle (R1) dispersion was obtained.

Preparation of coating liquid (R1) for forming a deodorant coating film 10 parts by weight of a deodorant anatase type titanium oxide fine particle (R1) dispersion in which iron oxide having a solid content of 10% by weight is supported in 85 parts by weight of ion exchange water. Was mixed and sufficiently dispersed, and then a titanium lactate ammonium salt solution (manufactured by Matsumoto Fine Chemical Co., Ltd .: Olga Tix TC-300, titanium lactate ammonium salt 42% by weight, water 20% by weight as a water-soluble metal chelate compound. 5 parts by weight of isopropyl alcohol (38 wt%, TiO ₂ concentration: 10.0 wt%) was added to prepare a deodorant coating film forming liquid (R1) having a solid content concentration of 1.5 wt%. .

Preparation of base material with deodorant coating film (R1) In Example 1, the base material with deodorant coating film (R1) was prepared in the same manner except that the coating liquid (R1) for forming a deodorant coating film was used. Created.
About the obtained base material (R1) with a deodorant coating film, a film thickness, adhesiveness, surface flatness, antibacterial performance, and deodorizing performance were evaluated, and a result is shown in a table | surface.

[Comparative Example 2]
Preparation of coating solution (R2) for forming a deodorant coating film Deodorizing anatase-type titanium oxide carrying 90% by weight of ion-exchanged water and iron oxide having a solid content concentration of 10% by weight prepared in the same manner as in Comparative Example 1. A coating solution (R2) for forming a deodorant coating film having a solid content concentration of 1.0% by weight was prepared by blending 10 parts by weight of the fine particle (R1) dispersion.

Preparation of base material with deodorant coating film (R2) In Example 1, the base material with deodorant coating film (R2) was prepared in the same manner except that the coating liquid for forming a deodorant coating film (R2) was used. Created.
About the obtained base material (R2) with a deodorant coating film, a film thickness, adhesiveness, surface flatness, antibacterial performance, and deodorization performance were evaluated, and a result is shown in a table | surface.

[Comparative Example 3]
Preparation of deodorant rutile type titanium oxide fine particles (R3) In Example 1, a rutile type titanium oxide fine particle (R3) dispersion having a solid content concentration of 10% by weight was added without adding a ferric nitrate aqueous solution. Obtained.

Preparation of coating liquid (R3) for forming deodorant coating film In 85 parts by weight of ion-exchanged water, 10 parts by weight of a rutile-type titanium oxide fine particle (R3) dispersion having a solid content concentration of 10% by weight is blended and sufficiently dispersed. After that, titanium lactate ammonium salt solution (manufactured by Matsumoto Fine Chemical Co., Ltd .: Orgatics TC-300, titanium lactate ammonium salt 42% by weight, water 20% by weight, isopropyl alcohol 38% by weight, TiO 2 as a water-soluble metal chelate compound. ₂ parts by weight) was added to prepare a deodorant coating film forming solution (R3) having a solid content of 1.5% by weight.

Preparation of base material with deodorant coating film (R3) In Example 1, the base material with deodorant coating film (R3) was prepared in the same manner except that the coating liquid for forming a deodorant coating film (R3) was used. Created.
About the obtained base material (R3) with a deodorant coating film, a film thickness, adhesiveness, surface flatness, antibacterial performance, and deodorizing performance were evaluated, and a result is shown to a table | surface.

[Comparative Example 4]
Preparation of antibacterial rutile-type titanium oxide fine particles (R4) 6.3 g of 63% by weight nitric acid was added to hydrogen peroxide aqueous solution obtained by diluting 1425 g of 35% by weight hydrogen peroxide water with 7122 g of pure water, and tetraisopropyl was added thereto. 143 g of titanate was added to obtain a yellowish brown peroxotitanic acid aqueous solution.
800 g of a peroxotitanic acid aqueous solution (solid content: 1%) was heated to 50 ° C., and the pH was adjusted to 9.0 with 15% ammonia. Meanwhile, 79.2 g of water is added to 2.92 g of zinc nitrate and dissolved by stirring. Zinc nitrate solution is added to peroxotitanic acid aqueous solution (solid content 1%) over 1 hour, and at the same time, anion exchange resin (Diaion SA20A manufactured by Mitsubishi Chemical Corporation) is kept at a pH of 9.0. Added. After completion of the addition, the ion exchange resin was separated.

Then, the peroxotitanic acid aqueous solution was aged at 90 ° C. for 2 hours and at 95 ° C. for 12 hours. The solution was initially yellowish brown, but became a milky white transparent liquid (colloidal liquid) after aging.
Subsequently, 3.2 g of nitric acid having a concentration of 63 wt% was added to the transparent liquid (colloid liquid), and hydrothermal treatment (heating) was performed at 180 ° C. for 16 hours to prepare a rutile-type titanium oxide fine particle (R4) dispersion.
The obtained zinc-supported rutile-type titanium oxide fine particle (R4) dispersion is washed by an ultrafiltration membrane method and then concentrated to obtain an antibacterial rutile-type titanium oxide fine particle (R4) dispersion having a solid content of 10% by weight. Got.

Preparation of coating liquid (R4) for forming deodorant coating film Into 85 parts by weight of ion-exchanged water, 10 parts by weight of antibacterial rutile titanium oxide fine particle (R4) dispersion with a solid content concentration of 10% by weight is mixed sufficiently. After being dispersed, a titanium lactate ammonium salt solution (manufactured by Matsumoto Fine Chemical Co., Ltd .: Olga Tix TC-300, titanium lactate ammonium salt 42% by weight, water 20% by weight, isopropyl alcohol 38% by weight as a water-soluble metal chelate compound. 5 parts by weight of TiO ₂ as a concentration of 10.0% by weight) was added to prepare a coating solution (R4) for forming a deodorant coating film having a solid content of 1.5% by weight.

Preparation of base material with deodorant coating film (R4) In Example 1, the base material with deodorant coating film (R4) was prepared in the same manner except that the coating liquid for forming a deodorant coating film (R4) was used. Created.
About the obtained base material (R4) with a deodorant coating film, a film thickness, adhesiveness, surface flatness, antibacterial performance, and deodorizing performance were evaluated, and a result is shown to a table | surface.

[Comparative Example 5]
Preparation of Deodorant Rutile Type Titanium Oxide Fine Particles (R5) In Example 1, a solid content concentration of 10% by weight was the same except that 50 g of ferric nitrate aqueous solution having a concentration of 1% by weight as Fe ₂ O ₃ was added. A deodorant rutile-type titanium oxide fine particle (R5) dispersion was obtained. The amount of iron oxide supported is shown in the table.

Preparation of coating liquid (R5) for forming deodorant coating film In 85 parts by weight of ion-exchanged water, 10 parts by weight of an antibacterial rutile titanium oxide fine particle (R5) dispersion having a solid content concentration of 10% by weight is mixed sufficiently. After being dispersed, a titanium lactate ammonium salt solution (manufactured by Matsumoto Fine Chemical Co., Ltd .: Olga Tix TC-300, titanium lactate ammonium salt 42% by weight, water 20% by weight, isopropyl alcohol 38% by weight as a water-soluble metal chelate compound. 5 parts by weight of TiO ₂ as a concentration of 10.0% by weight) was added to prepare a coating solution (R5) for forming a deodorant coating film having a solid content of 1.5% by weight.

Preparation of base material with deodorant coating film (R5) In Example 1, the base material with deodorant coating film (R5) was prepared in the same manner except that the coating liquid for forming a deodorant coating film (R5) was used. Created.
About the obtained base material (R5) with a deodorant coating film, a film thickness, adhesiveness, surface flatness, antibacterial performance, and deodorizing performance were evaluated, and a result is shown to a table | surface.

Claims (10)

The average particle width (W) is in the range of 2 to 50 nm, the average length (L) is in the range of 2 to 500 nm, the aspect ratio (L) / (W) is in the range of 1 to 10, Deodorant rutile type titanium oxide fine particles containing iron as a component in a range of 0.01 to ₂ % by weight in terms of Fe ₂ O ₃ .   The deodorant rutile type titanium oxide fine particle according to claim 1, further comprising an antibacterial / deodorant metal component in an amount of 0.1 to 20% by weight in terms of oxide.   The antibacterial / deodorant metal component is one or more metal components selected from silver, copper, zinc, tin, cobalt, nickel, and manganese. Odorable rutile type titanium oxide fine particles.   A coating solution for forming a deodorant coating film, wherein the deodorant rutile type titanium oxide fine particles according to any one of claims 1 to 3 are dispersed in a dispersion medium.   The coating liquid for forming a deodorant coating film according to claim 4, wherein the dispersion medium is an aqueous dispersion medium containing a water-soluble metal chelate compound.   The coating solution for forming a deodorant coating film according to claim 4 or 5, wherein the water-soluble metal chelate compound is a titanium chelate compound.   The coating solution for forming an antibacterial / deodorant coating film according to any one of claims 4 to 6, 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, and the concentration of the deodorant rutile-type titanium oxide fine particles as the solid content is in the range of 0.005 to 19.9% by weight. The concentration of the metal chelate compound as TiO ₂ is in the range of 0.0001 to 10.0% by weight, and the weight (W _a ) of the deodorant rutile titanium oxide fine particles and the weight of the water-soluble metal chelate compound as TiO _2. (W _b) weight ratio of _{(W b) / (W a} ) deodorant coating film formed of any one of claims 5-7, characterized in that in the range of 0.005 to 1.0 Coating liquid.   It consists of a base material and the deodorizing coating film formed on the base material, and this deodorizing coating film uses the coating liquid for deodorizing coating film formation in any one of Claims 4-8. A substrate with a deodorant coating film, which is a formed deodorant coating film. The content of the deodorant rutile-type titanium oxide fine particles in the deodorant coating film as a solid content is in the range of 50 to 100% by weight, and the content of the water-soluble metal chelate compound as TiO ₂ is 0 to 50. It exists in the range of weight%, The base material with a deodorizing coating film of Claim 9 characterized by the above-mentioned.