JP4980204B2 - Method for producing titanium oxide-based deodorant - Google Patents

Description

  The present invention relates to a method for producing a titanium oxide-based deodorant in which a small amount of iron oxide is supported on titanium oxide-based particles.

  Titanium oxide particles have a wide range of uses that utilize their chemical properties. For example, they have an appropriate binding force with oxygen and have acid resistance, so that they can be used for oxidation-reduction catalysts or carriers, cosmetic materials or plastic materials that use ultraviolet shielding properties. It is used as a surface coating agent, an antireflection coating material utilizing high refraction, and an antistatic material utilizing conductivity. In addition, these effects are used in combination as a functional material, and further used in antibacterial agents, antifouling agents, superhydrophilic coatings and the like using photocatalytic action.

  In recent years, “bad odor” has been highlighted as an environmental problem, but as a source of bad odor, the emphasis has shifted from a conventional factory to a place of life. These malodors are mainly caused by decay and decomposition of organic substances such as animals and plants. For example, basic components such as ammonia and amines, and acidic components such as hydrogen sulfide and mercaptans are considered as causative substances.

In the Japanese Patent Application Laid-Open No. 2004-250239 (Patent Document 1), when a specific sol is used, monodispersed tubular titanium oxide particles can be obtained in a high yield without firing the raw material at a high temperature. It discloses that tubular titanium oxide particles excellent in deodorizing performance and oxidation catalyst performance can be obtained when a metal salt such as platinum or palladium is supported thereon and subjected to reduction treatment.
However, the deodorant carrying such a metal component is extremely expensive, and even if the metal is recovered as necessary, there is a problem in economy.

The present inventors have disclosed in JP-A-2005-318999 (Patent Document 2) that titanium oxide colloidal particles containing zinc oxide have a deodorizing function.
However, in recent years, further improvement in deodorizing performance is required, and a deodorant effective for a wide range of odor components is required.

Furthermore, the present inventors disclosed in Japanese Patent Application Laid-Open No. 2007-130267 (Patent Document 3) as a deodorant composed of tubular titanium oxide particles that exhibit high deodorizing performance without carrying an expensive metal. And at least one oxide selected from SiO ₂ , ZrO ₂ , ZnO, Al ₂ O ₃ , CeO ₂ , Y ₂ O ₃ , Nd ₂ O ₃ , WO ₃ , Fe ₂ O ₃ , or Sb ₂ O ₅ . Specific tubular titanium oxide particles consisting of:

JP 2004-250239 A JP 2005-318999 A JP 2007-130267 A

As a result of extensive research, the present inventors have found that deodorization performance is significantly improved when a small amount of iron oxide is supported on titanium oxide particles using a ferric nitrate aqueous solution in the presence of an ion exchange resin. Thus, the present invention has been completed.
That is, an object of the present invention is to provide a method for producing a titanium oxide-based deodorant having a high deodorizing performance.

The method for producing a titanium oxide-based deodorant of the present invention comprises mixing an aqueous ferric nitrate solution with a dispersion of titanium oxide-based particles in the presence of an ion exchange resin, thereby adding iron oxide to the titanium oxide-based particles. ₂ O ₃ is supported in the range of 0.01 to 5% by weight.
Moreover, the manufacturing method of the titanium oxide type deodorant of this invention is characterized by drying and heat-processing the dispersion liquid which mixed the said ferric nitrate aqueous solution.

The shape of the titanium oxide-based particles is preferably granular or tubular.
The titanium oxide-based particles are preferably composite particles composed of titanium oxide and an inorganic oxide other than titanium oxide.
The inorganic oxide other than titanium oxide is preferably one or more selected from silica, zirconia and zinc oxide.
The silica and / or zirconia is preferably contained in an amount of 0.1 to 30% by weight as SiO ₂ and / or ZrO ₂ .
The zinc oxide is preferably contained in an amount of 0.1 to 15% by weight as ZnO.
It is preferable that titanium oxide colloidal particles having an average particle diameter in the range of 2 to 300 nm are supported on the titanium oxide-based particles.

According to the present invention, a small amount of iron oxide is supported on titanium oxide-based particles, and a deodorant having high deodorizing performance can be produced. This titanium oxide-based deodorant is excellent in the ability to decompose a wide range of odor components, and as a result, has a very high deodorizing performance.

Hereinafter, the best embodiment is described about the manufacturing method of the titanium oxide type deodorizer which concerns on this invention.
In the method for producing a titanium oxide-based deodorant according to the present invention, an aqueous solution of ferric nitrate is mixed with a dispersion of titanium oxide-based particles in the presence of an ion exchange resin, whereby iron oxide is added to the titanium oxide-based particles. Fe ₂ O ₃ is supported in the range of 0.01 to 5% by weight.

Titanium oxide-based particles In the present invention, the titanium oxide-based particles mean composite particles composed of titanium oxide and inorganic oxides other than titanium oxide in addition to titanium oxide particles.
Further, the titanium oxide-based particles include granular particles and tubular particles. Furthermore, it is preferable that the titanium oxide-based particles are crystalline because they are excellent in deodorizing performance, and anatase-type titanium oxide is particularly preferable.

The granular titanium oxide-based particles preferably have an average particle diameter in the range of 2 nm to 3 μm, more preferably 5 nm to 2 μm.
It is difficult to obtain granular titanium oxide-based particles having an average particle diameter of less than 2 nm, and even if they can, they are easily aggregated. In addition, iron oxide loading described later becomes uneven, and the resulting deodorant becomes an aggregate, resulting in insufficient performance and limited applications.
When the average particle diameter of the granular titanium oxide-based particles exceeds 3 μm, the effective external surface area becomes small, and the deodorizing performance may be insufficient.
The average particle diameter of the present invention can be obtained as an average value obtained by photographing a transmission electron micrograph (TEM), measuring the particle diameter of 100 particles.

In the case of tubular titanium oxide-based particles, the average tube outer diameter (D _out ) is in the range of 5 to 40 nm, more preferably 10 to 20 nm, and the average tube inner diameter (D _in ) is 4 to 20 nm, further 5 to 15 nm. The average tube thickness is in the range of 0.5 to 10 nm, more preferably in the range of 1 to 5 nm, the average length (L _p ) is in the range of 50 to 1000 nm, further in the range of 100 to 500 nm, and the aspect ratio (L _p ) / (D _out ) is preferably in the range of 10 to 200, more preferably 15 to 100.

Tubular titanium oxide particles having an average tube outer diameter (D _out ) of less than 5 nm are difficult to obtain, and those having an average tube outer diameter (D _out ) of more than 40 nm are difficult to obtain. Even in such a case, the average inner diameter of the tube may be increased, and the voids may increase so that the deodorizing performance may be insufficient.
When the average length (L _p ) is less than 50 nm, the crystallinity may be insufficient, and the deodorizing performance may be insufficient. It is difficult to obtain a material having an average length (L _p ) exceeding 1000 nm. Even if it is obtained, as will be described later, when kneaded into a resin or attached to a fiber or the like, the moldability or Adhesion may be insufficient.

The above average tube outer diameter (D _out ), average tube inner diameter (D _in ), average length (L _p ), etc. are taken through a transmission electron micrograph, and each value is measured for 100 particles. Asking. Further, the average tube inner diameter (D _in ) can be obtained from a line forming a boundary of contrast recognized inside the line for obtaining the outer diameter.
Such tubular titanium oxide-based particles can be produced by the method disclosed in Patent Document 1 (Japanese Patent Laid-Open No. 2004-250239) or a method based thereon.

  Next, silica, zinc oxide, zirconia, etc. are mentioned as inorganic oxides other than the titanium oxide which comprises the said titanium oxide composite particle.

Zinc oxide is preferably contained in an amount of 0.1 to 15% by weight, more preferably 0.2 to 10% by weight, as ZnO. When the content of ZnO is less than 0.1% by weight, the effect of improving the deodorizing performance may not be sufficiently obtained. When the content exceeds 15% by weight, the crystallinity of the titanium oxide-based particles is insufficient and sufficient. Deodorant performance may not be obtained.
Composite titanium oxide particles containing zinc oxide can be produced according to the method described in Japanese Patent Application Laid-Open No. 2005-318999 (Patent Document 2) or Japanese Patent Application Laid-Open No. 2004-250239 (Patent Document 1).

  That is, hydrogen peroxide is added to orthotitanic acid gel and / or sol to obtain a peroxotitanic acid aqueous solution, zinc compound is added, and heat treatment is performed at 50 ° C. or higher to prepare an inorganic oxide fine particle precursor dispersion. Then, after adding a silicon compound and / or a zirconium compound as necessary, it can be obtained by hydrothermal treatment at 120 to 280 ° C.

Silica from 0.1 to 30 wt% as SiO _2, and more preferably in the range of 1 to 20 wt%. When the content of silica is less than 0.1% by weight, although depending on the content of zirconia, stability may be insufficient or agglomeration may occur, and there are limitations on applications and usage. Even if the content of silica exceeds 30% by weight, the stability is not further improved, and at the same time as the crystallinity of titanium oxide is lowered, the deodorization performance tends to be lowered by the content being lowered.
By including silica, stability is improved, and composite titanium oxide particles in the coating liquid for forming a composite titanium oxide particle dispersion or coating film are highly dispersed, and the resulting coating film has adhesion to the substrate. Excellent transparency.

Moreover, the effect similar to a silica is acquired also by including a zirconia.
Zirconia is preferably in the range of 0 to 30% by weight, more preferably 1 to 20% by weight as ZrO ₂ .
The composite titanium oxide particles containing silica and / or zirconia are obtained by adding hydrogen peroxide to an orthotitanic acid gel and / or sol to obtain a peroxotitanic acid aqueous solution, adding a silicate compound and / or a zirconium compound, The inorganic oxide fine particle precursor dispersion is prepared by heat treatment at a temperature of not lower than ° C., and after adding a zinc compound, it can be obtained by hydrothermal treatment at 120 to 280 ° C.
When silica and zirconia are included, the total is preferably in the range of 0.1 to 30% by weight, more preferably 1 to 20% by weight. Further, when zinc oxide is included, the total of silica, zirconia and zinc oxide is preferably in the range of 0.1 to 30% by weight, more preferably 1 to 20% by weight.

In view of improving the deodorizing performance, it is preferable that the titanium oxide-based particles of the present invention carry titanium oxide colloidal particles having an average particle diameter of 2 to 300 nm, preferably 5 to 200 nm.
In this case, the average particle diameter of the granular titanium oxide-based particles is preferably 5 times or more the average particle diameter of the titanium oxide colloidal particles. If the average particle size is less than 5 times the average particle size of the titanium oxide colloidal particles, it will be difficult to support, and even if it can be supported, it will have the same deodorizing performance as a simple mixture, and the effect of sufficiently improving the deodorizing performance May not be obtained.
Therefore, the average particle diameter of the granular titanium oxide-based particles on which the titanium oxide colloid particles are supported is preferably in the range of 10 nm to 3 μm, particularly 25 nm to 2 μm.

As for the tubular titanium oxide-based particles, it is preferable to support the titanium oxide colloidal particles in order to improve the deodorizing performance. In this case, the average tube outer diameter (D _out ) of the tubular titanium oxide-based particles is preferably 5 times or more the average particle diameter of the titanium oxide colloidal particles as in the case of the granular titanium oxide-based particles.

Titanium oxide-based particle dispersion The concentration of the titanium oxide-based particle dispersion is not particularly limited as long as the ion-exchange resin described below can be dispersed and the dispersion can be uniformly stirred. Is preferably in the range of 2 to 20% by weight.
When the concentration of the dispersion is less than 1% by weight as an oxide, productivity decreases, and when it exceeds 30% by weight, the deodorant finally obtained may aggregate.

Ion Exchange Resin As the ion exchange resin of the present invention, an anion exchange resin is used to remove the nitrate radical of ferric nitrate. The amount of ion exchange resin used varies 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.

Ferric nitrate Although ferric nitrate is used in the present invention, 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 is preferable because it has the best deodorizing performance. Furthermore, in the present invention, ferric nitrate and other salts may be mixed and used.
The amount of ferric nitrate used is such that the content of iron oxide in the deodorant finally obtained is in the range of 0.01 to 5% by weight, more preferably 0.02 to 2% by weight as Fe ₂ O _3. To use.
When the amount of Fe ₂ O ₃ supported is less than 0.01% by weight, the effect of improving the deodorizing performance may not be sufficiently obtained. When the amount exceeds 5% by weight, the reason is not necessarily clear. The deodorizing performance may be lower than when it is not supported.

  After adding the ferric nitrate aqueous solution, stirring is continued as necessary, and then the ion exchange resin is separated to obtain a deodorant dispersion. The obtained deodorant dispersion can be used as it is, but can be concentrated or diluted as necessary.

Drying / heating treatment The deodorant dispersion liquid may be dried and further heat-treated as necessary to obtain a deodorant powder. Moreover, after apply | coating a deodorizer dispersion liquid to various base materials etc., it can also be used after heat-processing as needed.
There is no particular limitation on the drying method, and a conventionally known method can be employed.

In the heat treatment, the heating temperature is preferably 200 to 500 ° C, more preferably 250 to 450 ° C. If the heating temperature is less than 200 ° C., sufficient deodorizing performance may not be obtained depending on the usage. If the temperature exceeds 500 ° C., the supported iron oxide may be aggregated, or the deodorizing performance may be insufficient, or depending on the powder particles, the powder may be strongly aggregated, requiring pulverization, and the application may be limited.
Hereinafter, although an example explains, the present invention is not limited by these examples.

Preparation of deodorant (1) Titanium oxide colloidal particle dispersion (manufactured by Catalyst Kasei Kogyo Co., Ltd .: ATOMYBALL- (TZ-R), ZnO content 1.0 wt%, SiO ₂ content 1.39 wt%, Anatase type, average particle diameter 10 nm, solid content concentration 10% by weight) 1000 g of ion exchange resin (Mitsubishi Chemical Corporation: SA20A) 1000 g is mixed, and this is mixed with nitric acid with a concentration of 1% by weight as Fe ₂ O ₃ . After adding 20 g of a 2 iron aqueous solution and stirring for 1 hour, the ion exchange resin was separated and concentrated with an ultra-thin film to prepare 2000 g of a deodorant (1) dispersion having a concentration of 10% by weight as an oxide. The Fe ₂ O ₃ content in the deodorant (1) is shown in the table.

Deodorization test (1)
0.5 g of deodorant (1) powder obtained by drying the deodorant (1) dispersion was placed in a 1.5 L vinyl tetrapack, and then a test odor gas was enclosed. After standing at room temperature for 1 hour, the concentration of residual odor gas was measured with a detector tube (manufactured by Gastec Co., Ltd.).
As the odor gas, ammonia (concentration 100 ppm), hydrogen sulfide (concentration 28 ppm), formaldehyde (concentration 14 ppm) was used, and a detection tube dedicated to each odor gas was used. The results are shown in the table.

Deodorization test (2)
Put 0.25g of deodorant (1) powder obtained by drying the deodorant (1) dispersion into a screw tube (4ml in internal volume), then add 1ml of isopropyl alcohol (IPA), sunlight (clear weather) The amount of acetone produced was measured with a gas chromatograph mass spectrometer (manufactured by JEOL Ltd .: JMF AX505) when irradiated for 5 hours with the assumption of daytime in the day and when irradiated with ultraviolet light (black light, 360 nm) for 5 hours. The results are shown in Table 1.

Preparation of Deodorant (2) In Example 1, except that 10 g of a ferric nitrate aqueous solution having a concentration of 1% by weight as Fe ₂ O ₃ was added, the concentration of 10% by weight as an oxide was eliminated. An odorant (2) dispersion was prepared. The Fe ₂ O ₃ content in the deodorant (2) is shown in the table.
Subsequently, a deodorization test (1) and a deodorization test (2) were carried out, and the results are shown in the table.

Preparation of deodorant (3) In Example 1, except that 40 g of a ferric nitrate aqueous solution having a concentration of 1% by weight as Fe ₂ O ₃ was added, the concentration of 10% by weight as an oxide was eliminated. An odorant (3) dispersion was prepared. The Fe ₂ O ₃ content in the deodorant (3) is shown in the table.
Subsequently, a deodorization test (1) and a deodorization test (2) were carried out, and the results are shown in the table.

Preparation of deodorant (4) In Example 1, titanium colloidal particle dispersion (manufactured by Catalyst Kasei Kogyo Co., Ltd .: TZR, ZnO content 0.5% by weight, SiO ₂ content 1.39% by weight, anatase A deodorant (4) dispersion having a total concentration of 10% by weight as an oxide was prepared in the same manner except that 2000 g of a mold, an average particle diameter of 10 nm, and a solid content of 10% by weight were used. The Fe ₂ O ₃ content in the deodorant (4) is shown in the table.
Subsequently, a deodorization test (1) and a deodorization test (2) were carried out, and the results are shown in the table.

In example 1 deodorant (5), titanium oxide colloidal particle dispersion (Catalysts & Chemicals Industries Co., Ltd.: TZR1.5, ZnO content of 1.5 wt%, SiO ₂ content of 1.39 wt% A deodorant (5) dispersion having a total concentration of 10 wt% as an oxide was prepared in the same manner except that 2000 g of anatase type, average particle diameter of 10 nm, solid content concentration of 10 wt% was used. The Fe ₂ O ₃ content in the deodorant (5) is shown in the table.
Subsequently, a deodorization test (1) and a deodorization test (2) were carried out, and the results are shown in the table.

Preparation of Deodorant (6) In Example 1, a titanium oxide colloidal particle dispersion (manufactured by Catalytic Chemical Industry Co., Ltd .: PW-1010, TiO ₂ content 8.4 wt%, SiO ₂ content 1.59 wt% %, Anatase type, average particle size 10 nm, solid content concentration 10% by weight) was used in the same manner to prepare a deodorant (6) dispersion having a total concentration of 10% by weight as an oxide. The Fe ₂ O ₃ content in the deodorant (6) is shown in the table.
Subsequently, a deodorization test (1) and a deodorization test (2) were carried out, and the results are shown in the table.

Preparation of Deodorant (7) In Example 1, titanium oxide particle dispersion (manufactured by Catalyst Chemical Industry Co., Ltd .: PW-6010, TiO ₂ content 8.4 wt%, SiO ₂ content 1.59 wt% A deodorant (7) dispersion having a total concentration of 10% by weight as an oxide was prepared in the same manner except that 2000 g of anatase type, average particle diameter of 60 nm, solid content of 10% by weight was used. The Fe ₂ O ₃ content in the deodorant (7) is shown in the table.
Subsequently, a deodorization test (1) and a deodorization test (2) were carried out, and the results are shown in the table.

Preparation of deodorant (8) Titanium oxide particle dispersion (manufactured by Catalyst Kasei Kogyo Co., Ltd .: PW-6010, TiO ₂ content 9.2 wt%, SiO ₂ content 0.69 wt%, ZnO content 0 1% by weight, anatase type, average particle diameter 60 nm, solid content concentration 10% by weight) and titanium oxide colloidal particle dispersion (manufactured by Catalyst Chemical Industries, Ltd .: ATOMYBALL- (TZ-R), ZnO content 0% by weight, anatase type, average particle size 10 nm, solid content concentration 10% by weight) 200 g, and hydrothermally treated in an autoclave at 160 ° C. for 2 hours to support colloidal particles having a solid content concentration of 11% by weight. A titanium oxide particle dispersion was prepared.
This was mixed with 1000 g of an ion exchange resin (Mitsubishi Chemical Corporation: SA20A), then 22 g of a ferric nitrate aqueous solution having a concentration of 1% by weight as Fe ₂ O ₃ was added, and the mixture was stirred for 1 hour. The exchange resin was separated and concentrated with an ultrafiltration membrane to prepare a deodorant (8) dispersion having a total concentration of 10% by weight as an oxide. The Fe ₂ O ₃ content in the deodorant (8) is shown in the table.
Subsequently, a deodorization test (1) and a deodorization test (2) were carried out, and the results are shown in the table.

Preparation of deodorant (9) A titanium chloride aqueous solution was diluted with pure water to prepare a titanium chloride aqueous solution having a concentration of 5% by weight as TiO ₂ . This aqueous solution was neutralized and hydrolyzed by adding it to 15% by weight ammonia water whose temperature was adjusted to 5 ° C. The pH after addition of the aqueous titanium chloride solution was 10.5. Subsequently, the produced gel was washed by filtration to obtain an orthotitanic acid gel having a concentration of 9% by weight as TiO ₂ .
After 100 g of this orthotitanic acid gel was dispersed in 2900 g of pure water, 800 g of hydrogen peroxide having a concentration of 35% by weight was added and heated at 85 ° C. for 3 hours with stirring to prepare a peroxotitanic acid aqueous solution. The concentration of the resulting aqueous peroxotitanic acid solution as TiO ₂ was 0.5% by weight.

Next, the mixture was heated at 95 ° C. for 10 hours to obtain a titanium oxide particle dispersion, and tetramethylammonium hydroxide (MW = 149.2) was added to the titanium oxide particle dispersion so that the molar ratio to TiO ₂ in the dispersion was 0.016. ) Was added. The pH of the dispersion at this time was 11. Next, hydrothermal treatment was performed at 230 ° C. for 5 hours to prepare a titanium oxide particle dispersion. The average particle diameter of the titanium oxide particles was 30 nm.

Titanium oxide particle dispersion liquid, a KOH aqueous solution 70g of concentration 40 wt%, TiO ₂ molar number (T _M) and the number of moles of alkali metal hydroxide (A _M) and the molar ratio of (A _M) / (T _M ) was added to 10 and hydrothermally treated at 150 ° C. for 2 hours.
The obtained particles were sufficiently washed with pure water. At this time, the residual amount of K ₂ O was 0.9% by weight. After washing with pure water, an aqueous dispersion of tubular titanium oxide particles (concentration of 5% by weight as TiO ₂ ) was added, and the same amount of cation exchange resin and anion exchange resin as tubular titanium oxide particles were added thereto. The resulting solution was purified at 60 ° C. for 24 hours to remove alkali or the like.
Subsequently, it baked at 300 degreeC for 1 hour, and the tubular titanium oxide particle was prepared.
A TEM photograph of the obtained tubular titanium oxide particles was taken to obtain an average particle length (L), an average tube outer diameter (D _out ), and an average tube inner diameter (D _in ), and the results are shown in the table.

Subsequently, 2000 g of a tubular titanium oxide particle dispersion (solid content concentration: 10% by weight) was prepared, and 1000 g of an ion exchange resin (manufactured by Mitsubishi Chemical Corporation: SA20A) was mixed therewith, and then Fe ₂ O ₃ was used. After adding 20 g of ferric nitrate aqueous solution with a concentration of 1% by weight and stirring for 1 hour, the ion exchange resin was separated and concentrated on the outer membrane to give a deodorant with a total concentration of 10% by weight (9 ) A dispersion was prepared. The Fe ₂ O ₃ content in the deodorant (9) is shown in the table.
Subsequently, a deodorization test (1) and a deodorization test (2) were carried out, and the results are shown in the table.

Preparation of deodorant (10) 2000 g of tubular titanium oxide particle dispersion (solid content concentration: 10% by weight) prepared in the same manner as in Example 9 and titanium oxide colloidal particle dispersion (manufactured by Catalyst Kasei Kogyo Co., Ltd .: ATOMYBALL- (TZ-R), SiO ₂ content 1.39% by weight, ZnO content 1.0% by weight, anatase type, average particle size 10 nm, solid content concentration 10% by weight) and 200 g are mixed and 160 by an autoclave. A tubular titanium oxide particle dispersion carrying titanium oxide colloid particles having a solid content of 11% by weight was prepared by hydrothermal treatment at 2 ° C. for 2 hours. This was mixed with 1000 g of an ion exchange resin (Mitsubishi Chemical Corporation: SA20A), then 22 g of a ferric nitrate aqueous solution having a concentration of 1% by weight as Fe ₂ O ₃ was added, and the mixture was stirred for 1 hour. The exchange resin was separated and concentrated with an ultra-membrane to prepare a deodorant (10) dispersion having a total concentration of 10% by weight as an oxide. The Fe ₂ O ₃ content in the deodorant (10) is shown in the table.
Subsequently, a deodorization test (1) and a deodorization test (2) were carried out, and the results are shown in the table.

Preparation of deodorant (11) Titanium oxide colloidal particle dispersion (manufactured by Catalyst Kasei Kogyo Co., Ltd .: HPW-10R, anatase type, average particle size 10 nm, solid content concentration 10% by weight) to 2000 g of ion exchange resin (Mitsubishi Chemical) (Product: SA20A) 1000 g was mixed, 20 g of ferric nitrate aqueous solution having a concentration of 1% by weight as Fe ₂ O ₃ was added thereto, stirred for 1 hour, and then the ion exchange resin was separated. Concentrated with a membrane, 2000 g of a deodorant (11) dispersion having a concentration of 10% by weight as an oxide was prepared. The Fe ₂ O ₃ content in the deodorant (11) is shown in the table.
Subsequently, a deodorization test (1) and a deodorization test (2) were carried out, and the results are shown in the table.

Preparation of Deodorant (12) A titanium chloride aqueous solution was diluted with pure water to prepare 180 g of a titanium chloride aqueous solution having a concentration of 5% by weight as TiO ₂ . Separately, a zinc chloride aqueous solution was diluted with pure water to prepare 20 g of a zinc chloride aqueous solution having a concentration of 5% by weight as ZnO and mixed with the titanium chloride aqueous solution.
This mixed aqueous solution was neutralized and hydrolyzed by adding it to ammonia water having a concentration of 15% by weight adjusted to 5 ° C. The pH after addition of the mixed aqueous solution was 10.5. Subsequently, the produced gel was washed by filtration to obtain a gel having a concentration of 9% by weight as TiO ₂ · ZnO.
After 100 g of this gel was dispersed in 2900 g of pure water, 800 g of hydrogen peroxide having a concentration of 35% by weight was added and dissolved by heating at 85 ° C. for 3 hours while stirring. The concentration of the resulting solution as TiO ₂ · ZnO was 0.5% by weight.

Next, the mixture is heated at 95 ° C. for 10 hours to obtain a titanium oxide / zinc oxide composite particle dispersion, and tetramethylammonium hydroxide (MW = 149.2) is added to the titanium oxide / zinc oxide composite particle dispersion to adjust the pH of the dispersion. Was set to 11. Subsequently, hydrothermal treatment was performed at 230 ° C. for 5 hours to prepare a titanium oxide / zinc oxide composite particle dispersion. The dispersion was washed with an ultrafiltration membrane and then concentrated to obtain a dispersion having a concentration of 10% by weight as TiO ₂ · ZnO. The average particle size of the titanium oxide / zinc oxide composite particles was 20 nm.

1000 g of ion exchange resin (Mitsubishi Chemical Corporation: SA20A) 1000 g is mixed with 2000 g of titanium oxide / zinc oxide composite particle dispersion, and 20 g of ferric nitrate aqueous solution having a concentration of 1 wt% as Fe ₂ O ₃ is added thereto. Then, after stirring for 1 hour, the ion exchange resin was separated and concentrated with an ultrafiltration membrane to prepare 2000 g of a deodorant (12) dispersion having a concentration of 10% by weight as an oxide. The Fe ₂ O ₃ content in the deodorant (12) is shown in the table.
Subsequently, a deodorization test (1) and a deodorization test (2) were carried out, and the results are shown in the table.

Comparative Example 1

Preparation of deodorant (R1) Titanium oxide colloidal particle dispersion (manufactured by Catalyst Kasei Kogyo Co., Ltd .: ATOMYBALL- (TZ-R), ZnO content 7.6% by weight, anatase type, average particle size 10 nm, solid content A deodorizer (R1) was prepared by drying 500 g of 10% by weight) at 120 ° C. for 2 hours and then baking at 400 ° C. for 1 hour.
Subsequently, a deodorization test (1) and a deodorization test (2) were carried out, and the results are shown in the table.

Comparative Example 2

Preparation of deodorant (R2) Titanium oxide colloidal particle dispersion (manufactured by Catalyst Kasei Kogyo Co., Ltd .: PW-1010, TiO ₂ content 8.4 wt%, anatase type, average particle size 10 nm, solid content concentration 10 wt% %) Was dried at 120 ° C. for 2 hours and then calcined at 400 ° C. for 1 hour to prepare a deodorant (R2).
Subsequently, a deodorization test (1) and a deodorization test (2) were carried out, and the results are shown in the table.

Comparative Example 3

Preparation of deodorant (R3) Titanium oxide particle dispersion (manufactured by Catalyst Kasei Kogyo Co., Ltd .: PW-6010, TiO ₂ content 8.4 wt%, anatase type, average particle size 60 nm, solid content concentration 10 wt% ) 500 g was dried at 120 ° C. for 2 hours, and then calcined at 400 ° C. for 1 hour to prepare a deodorant (R3).
Subsequently, a deodorization test (1) and a deodorization test (2) were carried out, and the results are shown in the table.

Comparative Example 4

Preparation of deodorant (R4 ) 500 g of a tubular titanium oxide particle dispersion (TiO ₂ content 9.9 wt%, anatase type, solid content concentration 10 wt%) obtained in Example 9 before supporting Fe ₂ O ₃ Was dried at 120 ° C. for 2 hours and then calcined at 400 ° C. for 1 hour to prepare a deodorant (R4).
Subsequently, a deodorization test (1) and a deodorization test (2) were carried out, and the results are shown in the table.

Comparative Example 5

Preparation of deodorant (R5) Titanium oxide particle dispersion (manufactured by Catalyst Kasei Kogyo Co., Ltd .: PW-6010, TiO ₂ content 8.4 wt%, anatase type, average particle diameter 60 nm, solid content concentration 10 wt% ) Was dried to obtain a powder of titanium oxide particles. To 200 g of the powder of titanium oxide particles, 200 g of a ferric nitrate aqueous solution having a concentration of 0.1% by weight as Fe ₂ O ₃ was added and mixed uniformly. At this time, the solid content concentration was 50% by weight, and it was in the form of a paste.
Next, after drying at 120 ° C. for 2 hours, the lump was crushed and then calcined at 400 ° C. for 1 hour to prepare a deodorant (R5). The Fe ₂ O ₃ content in the deodorant (R5) is shown in the table.
Subsequently, a deodorization test (1) and a deodorization test (2) were carried out, and the results are shown in the table.

  Although the deodorant of the present invention can be used as a deodorant as it is, as disclosed in JP-A-9-299460 filed by the applicant of the present application, (1) application to fibers, (2) resin, Application to rubber, (3) Application to paints, (4) Other bad odors emitted from manufacturing and processing factories of paints, foods, resins, etc. Effective for deodorization. Also, building materials for homes, joinery materials (wallpaper, bags, shoji, tatami, etc.), ceramics (tiles, pottery, magnetism, etc.), leather products (bags, shoes, fur, wallets, regular holders, etc.), wooden products ( Desks, cupboards, chests, floorboards, ceiling boards, interior materials, etc.), paper products (tissue paper, corrugated paper, paper cups, paper plates, etc.), glass products (vases, water tanks, etc.), metal products (sashes, kettles, cars) Deodorizing properties can be imparted to air conditioners, etc. Furthermore, the deodorant of the present invention is also suitable for use in deodorizing water treatment agents such as water purifiers and pool water, cosmetic materials, and cat sand.

Further, it can be mixed with a binder component and formed into an arbitrary shape such as a honeycomb shape, a columnar shape, a plate shape, a sheet shape, a fiber shape, or a film shape. The molding method is not particularly limited, and a conventionally known method can be employed.
As the binder component, can be a conventionally _{known, SiO 2, Al 2 O 3} , TiO 2, ZrO 2, SiO 2 -Al 2 other gel or sol, etc. O ₃ such as kaolinite, bentonite In addition, an organic resin, an inorganic resin, or the like can also be used.

  In particular, the deodorant according to the present invention exhibits high activity even at room temperature, so various odors generated in the living environment, formaldehyde generated from indoor building materials, furniture, etc., acetaldehyde, acetone, toluene, xylene, methyl isobutyl Oxidative decomposition and removal of odorous components or harmful substances in the air such as ketones, ethyl acetate, butyl acetate, di-n-butyl phthalate, ethylbenzene, styrene, paradichlorobenzene, chlorpyrifos, and other organic solvents. It is suitable as a deodorant that can be used.

Claims (8)

The presence of an ion-exchange resin, by mixing the ferric nitrate solution average particle diameter in the dispersion of the particulate titanium oxide particles in the range of 2Nm～3myuemu, iron oxide titanium oxide-based particles Fe ₂ O ₃ , a method for producing a titanium oxide-based deodorant, characterized in that it is supported in a range of 0.01 to 5% by weight. The presence of an ion exchange resin, ferric nitrate aqueous solution Average tube outer diameter (D _out) is 5 to 40 nm, the average pipe inner diameter (D _in) is 4 to 20 nm, the thickness of the average tube 0.5 to 10 nm, average By mixing with a dispersion of tubular titanium oxide particles having a length (L _p ) in the range of 50 to 1000 nm, iron oxide is added to the titanium oxide particles as Fe ₂ O _{3 in an amount} of 0.01 to 5% by weight. A method for producing a titanium oxide-based deodorant , characterized by being carried in a range . The manufacturing method of the titanium oxide type deodorant of Claim 1 or 2 which dries and heat-processes the dispersion liquid which mixed the said ferric nitrate aqueous solution .   The method for producing a titanium oxide-based deodorant according to claim 1, wherein the titanium oxide-based particles are composite particles composed of titanium oxide and an inorganic oxide other than titanium oxide.   The method for producing a titanium oxide-based deodorant according to claim 4, wherein the inorganic oxide other than titanium oxide is one or more selected from silica, zirconia and zinc oxide. Method for producing a deodorizing agent according to claim 5, wherein the silica and / or zirconia are contained 0.1 to 30 wt% as SiO ₂ and / or ZrO _2.   The method for producing a deodorant according to claim 5, wherein the zinc oxide is contained as ZnO in an amount of 0.1 to 15% by weight.   The method for producing a deodorant according to claim 1, wherein the titanium oxide-based particles carry titanium oxide colloidal particles having an average particle diameter in the range of 2 to 300 nm.