JP2011026154A - Anatase type titanium dioxide particles and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide anatase type titanium dioxide particles containing zirconium oxide and having excellent crystallinity, and a method for producing the same. <P>SOLUTION: The anatase type titanium dioxide particles comprise titanium dioxide and zirconium oxide and has a zirconium oxide content in a range of 1-30 wt.% and a crystallite diameter in a range of 15-50 nm, wherein an average maximum particle width (W<SB>M</SB>) is in a range of 2-50 nm and an average particle length (L) is in a range of 10-500 nm. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to anatase-type titanium oxide particles containing zirconium oxide and excellent in crystallinity, and a method for producing the same.

  Titanium oxide particles and titanium oxide-based composite oxide particles have a wide range of uses utilizing their chemical characteristics. For example, titanium oxide particles and titanium oxide-based composite oxide particles are used as a redox catalyst or carrier because they have an appropriate binding force with oxygen and have acid resistance. In addition, it is used as a surface coating agent for cosmetic materials or plastic materials using ultraviolet shielding power, an antireflection coating material using high refraction, and an antistatic material using conductivity. Furthermore, these effects are combined and used for functional hard coat materials, environmental catalysts using photocatalytic action, antibacterial agents, antifouling agents, super hydrophilic coatings, and the like.

Further, in recent years, titanium oxide has been suitably used as a so-called photoelectric conversion material that converts light energy into electric energy because it has a high band gap.
Moreover, it has come to be used also for secondary batteries such as lithium batteries, hydrogen storage materials, proton conductive materials, and the like.

As described above, titanium oxide and titanium oxide composite oxides are used in many applications, and in any case, titanium oxide and titanium oxide composite oxides are required to have many functions.
For example, when titanium oxide is used as a catalyst, not only activity for the main reaction but also selectivity, mechanical strength, heat resistance, acid resistance, or durability are required. In addition, when titanium oxide is used as a cosmetic, not only an ultraviolet shielding effect but also smoothness, texture, transparency, and the like are required.
Further, when titanium oxide is used as a coating material, in addition to transparency and a high refractive index, further excellent film forming properties, adhesion, film hardness, mechanical film strength, wear resistance, and the like are required.

However, when using conventional titanium oxide particles as a dispersion, or when used by dispersing in a coating solution to form a film, the dispersibility and stability are insufficient, and the film formability, adhesion, film hardness, In some cases, there were problems in mechanical film strength, wear resistance, and the like.
Moreover, the obtained film may have a problem in light resistance and weather resistance.

For this reason, the applicant of the present application has proposed particles in which titanium oxide particles are coated with zirconium oxide and silicon oxide, and particles in which composite oxide particles of titanium and silicon are coated with zirconium oxide, silicon oxide, aluminum oxide, or the like. (Patent Document 1: JP-A-8-48940).
However, the coated particles are excellent in dispersibility and weatherability is improved, but there is a problem that the refractive index is greatly reduced.

The applicant of the present invention is an inorganic oxide fine particle composed of a metal component and an inorganic oxide other than the metal component, and the inorganic oxide comprises titanium oxide and silica and / or zirconia. An antibacterial deodorant in which the titanium oxide is crystalline titanium oxide is disclosed (Patent Document 2: JP 2005-318999 A).
In this case, the particles are produced by adding hydrogen peroxide to orthotitanic acid gel and / or sol to obtain an aqueous solution of peroxotitanic acid, adding an aqueous solution of a metal component and a silicon 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 then, if necessary, a silicon compound and / or a zirconium compound is added, followed by hydrothermal treatment at 120 to 280 ° C.
However, the crystalline titanium oxide obtained by this method has a crystallite diameter of about 10 nm and low crystallinity, and the photocatalytic performance, photoelectric conversion performance, etc. may be insufficient.

  Under these circumstances, the present inventors conducted further research and as a result, mixed titania gel (hydrated titanium oxide) and zirconia gel (hydrated zirconium oxide), and dissolved the mixed gel in hydrogen peroxide. Then, it was found that anatase-type titanium oxide particles containing zirconium oxide and having a large crystallite size and excellent crystallinity can be obtained by adding tetramethylammonium hydroxide (TMAH) to this and hydrothermally treating it. It came to complete.

JP-A-8-48940 JP 2005-318999 A

  The present invention is excellent in dispersibility, dispersion stability, and weather resistance, and is useful as a catalyst, a catalyst carrier, an adsorbent, a photocatalyst, a cosmetic material, an optical material, a photoelectric conversion material, and the like, as well as a proton conductive material and a fuel cell electrolyte. An object of the present invention is to provide anatase-type titanium oxide particles that can be used for a film, other conductive materials, and the like, and a method for producing the same.

The anatase-type titanium oxide particles of the present invention are composed of titanium oxide and zirconium oxide, the content of zirconium oxide is in the range of 1 to 30% by weight, and the crystallite diameter is in the range of 15 to 50 nm. The average particle maximum width (W _M ) is in the range of 2 to 50 nm and the average particle length (L) is in the range of 10 to 500 nm.

The method for producing anatase-type titanium oxide particles of the present invention is characterized by comprising the following steps (a) to (e).
(A) Step of mixing acid or base in a mixed aqueous solution of titanium compound and zirconium compound and hydrolyzing (b) Washing hydrolyzed gel (c) Adding hydrogen peroxide to hydrolyzed gel (E) a step of hydrothermally treating the dissolved solution at 100 to 300 ° C.

Following the step (c), the following step (d) is preferably performed.
(D) A quaternary alkylammonium compound (TAA) having a number of moles of quaternary alkylammonium compound (TAA) (M _AR ), a number of moles of TiO ₂ (M _T ) and a number of moles of ZrO ₂ (M _Z ) The step of adding so that the molar ratio (M _AR ) / (M _T + M _Z ) with the total number of moles is in the range of 0.05 to 5.

The molar ratio (M _T ) / (M _Z ) of the number of moles (M _T ) of the titanium compound as TiO ₂ and the number of moles (M _Z ) of the zirconium compound as ZrO ₂ in the step (a) is 4 to 100. It is preferable that it exists in the range.
The H ₂ O ₂ / (TiO ₂ + ZrO ₂ ) weight ratio in the step (c) is preferably in the range of 1-40.

The present invention is excellent in crystallinity in spite of containing zirconium oxide, and excellent in dispersibility, dispersion stability, light resistance, etc., compared to titanium oxide particles made of only titanium oxide because it contains zirconium oxide, and a catalyst. It is possible to provide anatase-type titanium oxide particles useful as a catalyst carrier, an adsorbent, a photocatalyst, a cosmetic material, an optical material, a photoelectric conversion material, a proton conductive material, an electrolyte membrane for a fuel cell, and the like, and a method for producing the same.

2 is a TEM photograph (magnification 250,000 times) of anatase titanium oxide particles (1) obtained in Example 1. FIG.

Anatase type titanium oxide particles The anatase type titanium oxide particles according to the present invention are composed of titanium oxide and zirconium oxide, and the content of zirconium oxide is in the range of 1 to 30% by weight.
The zirconium oxide content in the anatase-type titanium oxide particles is preferably in the range of 1 to 30% by weight, more preferably 2 to 20% by weight.
When the content of zirconium oxide is less than 1% by weight, dispersibility and dispersion stability may be insufficient, and weather resistance may be a problem depending on applications.
When the content of zirconium oxide exceeds 30% by weight, the crystallite diameter becomes less than 15 nm, crystallinity is insufficient, and photocatalytic performance, photoelectric conversion performance, and the like may be insufficient.

The crystallite size of the anatase-type titanium oxide particles is preferably in the range of 15 to 50 nm, more preferably 20 to 50 nm.
When the crystallite size of the anatase-type titanium oxide particles is less than 15 nm, the crystallinity is insufficient and the photocatalytic performance, the photoelectric conversion performance, etc. may be insufficient.
It is difficult to obtain anatase-type titanium oxide particles having a crystallite diameter exceeding 50 nm.
As a method for measuring the crystallite size of the anatase-type titanium oxide particles of the present invention, a general method of calculating from the half width of the peak where 2θ in X-ray diffraction is about = 25 ° can be employed.

The shape of the anatase-type titanium oxide particles of the present invention is rod-shaped, with a thick central portion, a thin tip, and a substantially circular cross section.
The average maximum particle width (W _M ) is preferably in the range of 2 to 50 nm, more preferably 5 to 40 nm.
Those having an average maximum particle width (W _M ) of less than 2 nm are not produced by the method of the present invention described later. May be insufficient.
Those having an average particle maximum width (W _M ) exceeding 50 nm are also difficult to obtain by the method of the present invention.

The average particle length (L) is preferably in the range of 10 to 500 nm, more preferably 20 to 300 nm.
What the average particle length (L) is outside the above range is difficult to obtain by the method of the present invention.
If the average particle length (L) is in the above range, the anatase-type titanium oxide particles tend to be arranged in an orderly manner without being entangled with each other, and such anatase-type titanium oxide particles do not aggregate in the dispersion. When the film is formed, it is possible to obtain a film that is dense and excellent in strength and has transparency and excellent in photocatalytic performance, photoelectric conversion performance, and the like.
The average particle maximum width (W _M ) and average particle length (L) of the present invention are obtained by taking a transmission electron micrograph (TEM), measuring each value for 100 particles, and obtaining the average value.

Method for producing anatase type titanium oxide particles The method for producing anatase type titanium oxide particles according to the present invention is preferably characterized by comprising the following steps (a) to (e).

Step (a)
Hydrolysis is performed by mixing an acid, base, or water with a mixed aqueous solution of a titanium compound and a zirconium compound.
Examples of the titanium compound include titanium salts such as titanium chloride, titanium sulfate, titanium hydride, and titanyl sulfate, and titanium alkoxides such as titanium tetraalkoxide, titanium tetraethoxide, and titanium tetraisopropoxide.
Zirconium compounds include zirconium chloride, zirconium oxychloride (zirconyl chloride), zirconium sulfate, zirconyl sulfate and the like, as well as zirconium alkoxide.

In a mixed aqueous solution of a titanium compound and a zirconium compound, the molar ratio (M _T ) / (M _Z ) between the number of moles of titanium compound as TiO ₂ (M _T ) and the number of moles of zirconium compound as ZrO ₂ (M _Z ). ) Is preferably in the range of 4 to 100, more preferably 6 to 75.
When the molar ratio (M _T ) / (M _Z ) is less than 4, the content of zirconia in the resulting anatase-type titanium oxide particles is too large, crystallization is insufficient, and the crystallite diameter is less than 15 nm. Performance, photoelectric conversion performance, etc. may become insufficient.
When the molar ratio (M _T ) / (M _Z ) exceeds 100, the crystallinity is excellent, but the zirconia content is low, so the dispersibility and dispersion stability are insufficient, and the weather resistance is insufficient. There is.

The concentration of the mixed aqueous solution is not particularly limited as long as the titanium compound and the zirconium compound are dissolved, but is preferably in the range of 1 to 30% by weight, more preferably 2 to 20% by weight as an oxide.
When the concentration is less than 1% by weight, the yield, productivity, etc. are low and there is a problem of economy. When the concentration exceeds 30% by weight, the viscosity of the gel when hydrolyzed is high, and titania and zirconia The anatase-type titanium oxide particles with high crystallinity may not be obtained due to non-uniform mixing of the particles, and particles having a particle size deviating from the shapes described later may be obtained, or aggregated particles may be obtained. However, there is a problem in using it for forming a film or as an optical material, and there is a problem that its application and usage are limited.

In order to hydrolyze (hereinafter sometimes referred to as neutralization) a mixed aqueous solution of a titanium compound and a zirconium compound, the mixed aqueous solution and an acid or base, or water are mixed, depending on the compound used.
Although the temperature at the time of mixing does not have a restriction | limiting in particular, Usually, it carries out at normal temperature. Moreover, it is preferable that pH at this time exists in the range of 8-11 in general and also 8.5-10.

After hydrolysis, the resulting gel can be aged as needed. By aging, the neutralization reaction is completed, and the composite of titanium and zirconium proceeds. The resulting anatase-type titanium oxide particles have a large crystallite diameter and tend to improve crystallinity.
For aging, the produced gel may be stirred or allowed to stand at approximately 30 to 60 ° C. for 0.5 to 12 hours.
In addition, although the said method is recommended in this invention, as another method, a titanium compound is hydrolyzed, a zirconium compound is hydrolyzed separately, and this can also be mixed and used.

Step (b)
The hydrolyzate gel is then washed. Salt or alcohol generated by washing is removed.
The washing method is not particularly limited as long as the generated salt, alcohol or the like can be removed, and a conventionally known method can be adopted.
For example, the produced gel dispersion (sometimes referred to as a slurry) is filtered and washed with pure water or dilute aqueous ammonia.

The concentration of the slurry after washing is adjusted so that the concentration of the gel as an oxide (TiO ₂ + ZrO ₂ ) is 0.1 to 5% by weight, preferably 0.2 to 4% by weight.
When the concentration of the slurry is less than 0.1% by weight as an oxide, the concentration of the titanium oxide / zirconium oxide solution obtained in the step (c) is low and there is a problem that the production efficiency is lowered.
When the concentration of the slurry exceeds 5% by weight as an oxide, in step (c), the viscosity becomes high, the hydrogen peroxide dissolution rate decreases, or a gel is formed, resulting in a uniform hydrogen peroxide solution (peroxotitanium).・ Zirconium solution) may not be obtained, and the final anatase-type titanium oxide may have a non-uniform shape and particle size distribution, a small crystallite size, and insufficient crystallinity. .

Step (c)
Next, hydrogen peroxide is added and the hydrolyzate gel is dissolved at 30-100 ° C.
The amount of hydrogen peroxide used is not particularly limited as long as the gel dissolves, but the weight ratio of the weight of hydrogen peroxide (H ₂ O ₂ ) to the weight of the gel oxide (TiO ₂ + ZrO ₂ ) is 1. It is preferable that it exists in the range of -40, Furthermore, 2-30.
When the weight ratio of H ₂ O ₂ / (TiO ₂ + ZrO ₂ ) is less than 1, it may not be completely dissolved, and the final crystallinity of the anatase-type titanium oxide may be insufficient.
Even if the weight ratio of H ₂ O ₂ / (TiO ₂ + ZrO ₂ ) exceeds 40, the solubility is not further improved, and unreacted hydrogen peroxide remains in the system, which is not economical.
If hydrogen peroxide remains after the gel is dissolved, it may be recovered or allowed to escape after dissolution.

The temperature at the time of dissolution varies depending on the amount of hydrogen peroxide used, but is preferably in the range of 30 to 100 ° C, more preferably 50 to 80 ° C.
When the temperature at the time of dissolution is less than 30 ° C., it may not be completely dissolved, and it takes a long time to dissolve.
When the melting temperature exceeds 100 ° C., low-crystalline anose-type titanium oxide particles are produced, and even if a predetermined quaternary alkylammonium compound is added in step (d), the crystallinity becomes insufficient. There is.
In addition, although melt | dissolution time changes also with temperature, it is 0.5 to 12 hours normally.

Step (d)
In the present invention, following step (c), the quaternary alkyl ammonium compound (TAA) is converted into the number of moles (M _AR ) of the quaternary alkyl ammonium compound (TAA), the number of moles of TiO ₂ (M _T ) and ZrO _2. it is preferred that the molar ratio of the total number of moles of the number of moles _{(M Z) (M AR)} / (M T + M Z) is added to a range of 0.05 to 5.
Examples of the quaternary alkylammonium compound used in the present invention include tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide.

The amount of quaternary alkylammonium compound used is the total number of moles of quaternary alkylammonium compound (TAA) (M _AR ), the number of moles of TiO ₂ (M _T ), and the number of moles of ZrO ₂ (M _Z ). The molar ratio (M _AR ) / (M _T + M _Z ) is preferably 0.05 to 5, more preferably 0.1 to 4.
When the molar ratio is less than 0.05, the crystal diameter of the obtained anatase-type titanium oxide particles is small, crystallinity is insufficient, and photocatalytic performance, photoelectric conversion performance, and the like may be insufficient.
When the molar ratio exceeds 5, there is a problem that the crystallinity is not further improved, small particles are mixed, and the economical efficiency is lowered.

Step (e)
Next, the dissolved solution in step (c) or the TAA-added dissolved solution in step (d) is hydrothermally treated at 100 to 300 ° C., preferably 120 to 250 ° C.
When the hydrothermal treatment temperature is less than 100 ° C., anatase-type titanium oxide particles having a small crystallite diameter and low crystallinity may be produced, and brookite-type titanium oxide may be produced.
Even if the hydrothermal treatment temperature exceeds 300 ° C., the crystallite size is further increased, there is a problem that the crystallinity is not improved and the economic efficiency is lowered. Further, when the concentration at this time is high, aggregated anatase-type titanium oxide particles may be generated.
The hydrothermal treatment time varies depending on the temperature, and it is sufficient that the anatase-type titanium oxide particles described above can be obtained, and is approximately 1 to 48 hours.

The anatase-type titanium oxide particles obtained in this way can be used after being washed, dried and fired as necessary.
The washing method is not particularly limited as long as the quaternary alkyl ammonium compound can be reduced, and a conventionally known method can be adopted. When the particle size of the particles is large, a filtration washing method can be adopted, and when the particle size is small, an ultrafiltration membrane method can be adopted.
Specifically, when reducing the quaternary alkylammonium compound, after washing the anatase-type titanium oxide particle dispersion after hydrothermal treatment, it is again made into a dispersion and neutralized by adding an acid thereto, followed by filtration washing or What is necessary is just to perform ultrafiltration washing.

The drying is not particularly limited as long as it can be adjusted to a desired water content (including crystal water) according to the purpose of use, and a conventionally known method can be adopted.
Firing is performed when the quaternary alkylammonium compound remaining in the anatase-type titanium oxide particles is reduced or removed, but is usually fired at 300 to 700 ° C.
When the firing temperature is less than 300 ° C., the quaternary alkyl ammonium compound may not be removed, and when it exceeds 700 ° C., crystal transformation may occur in the rutile type.

The anatase-type titanium oxide particles thus obtained are composed of titanium oxide and zirconium oxide, the zirconium oxide content is in the range of 1 to 30% by weight, and the crystallite diameter is in the range of 15 to 50 nm. It is a rod-like particle having a thick central portion and a thin tip, and has an average maximum particle width (W _M ) in the range of 2 to 50 nm and an average particle length (L) in the range of 10 to 500 nm.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.

[Example 1]
Preparation of Anatase Type Titanium Oxide Particles (1) A mixed aqueous solution was prepared by adding 85 g of zirconium oxychloride octahydrate to 1865 g of a titanium tetrachloride aqueous solution having a concentration of 13.9% by weight as TiO ₂ . The molar ratio M _T / M _{Z at} this time is 12.28.
Subsequently, while stirring 6048.9 g of an aqueous ammonia solution having a concentration of 4% by weight prepared at a temperature of 40 ° C., 1950 g of the mixed aqueous solution was added thereto to neutralize it, thereby preparing a TiO ₂ .ZrO ₂ hydrogel slurry.

Subsequently, after aging at 45 ° C. for 1 hour, the mixture was filtered and washed with sufficient warm water. The concentration of the washed gel was 9% by weight as TiO ₂ .ZrO ₂ .
Next, 638.9 g of the washing gel was diluted with 2236.1 g of pure water, 704.1 g of a hydrogen peroxide solution having a concentration of 35% by weight was added, dissolved by heating at 80 ° C. for 1 hour, and an oxide concentration of 1.6 A weight percent aqueous peroxotitanium / zirconium solution was prepared. In this case, hydrogen peroxide (H ₂ O ₂₎ weight ratio of oxides of the weight and the gel (TiO ₂ + ZrO ₂₎ of _{H 2 O 2 / (TiO 2} + ZrO 2) was 4.28.

Next, the peroxotitanium / zirconium aqueous solution was diluted to 1% by weight as TiO ₂ / ZrO ₂ , and 160 g of this aqueous solution was hydrothermally treated at 150 ° C. for 10 hours, filtered, washed, and then dried at 120 ° C. for 10 hours. Thus, anatase titanium oxide particles (1) were prepared.
The obtained anatase titanium oxide particles (1) were measured for crystal form and crystallite diameter by X-ray diffraction, ZrO ₂ content was determined by chemical analysis, TEM was measured, and average particle maximum width (W _M ), The average particle length (L) was measured, and the results are shown in the table.

[Example 2]
Preparation of Anatase Type Titanium Oxide Particles (2) A mixed aqueous solution was prepared by adding 21.3 g of zirconium oxychloride octahydrate to 1766.2 g of titanium tetrachloride aqueous solution having a concentration of 14.7% by weight as TiO ₂ . The molar ratio M _T / M _{Z at} this time is 48.98.
Next, while stirring 5544.9 g of a 4 wt% aqueous ammonia solution prepared at a temperature of 40 ° C., 1787.5 g of a mixed aqueous solution was added thereto and neutralized to prepare a TiO ₂ / ZrO ₂ hydrogel slurry.

Subsequently, after aging at 45 ° C. for 1 hour, the mixture was filtered and washed with sufficient warm water. The concentration of the washed gel was 9% by weight as TiO ₂ .ZrO ₂ .
Next, 638.9 g of the washing gel was diluted with 2236.1 g of pure water, 704.1 g of a hydrogen peroxide solution having a concentration of 35% by weight was added, dissolved by heating at 80 ° C. for 1 hour, and an oxide concentration of 1.6 A weight percent aqueous peroxotitanium / zirconium solution was prepared. In this case, hydrogen peroxide (H ₂ O ₂₎ weight ratio of oxides of the weight and the gel (TiO ₂ + ZrO ₂₎ of _{H 2 O 2 / (TiO 2} + ZrO 2) was 4.28.

Next, the peroxotitanium / zirconium aqueous solution was diluted to 1% by weight as TiO ₂ / ZrO ₂ , and 160 g of this aqueous solution was hydrothermally treated at 150 ° C. for 10 hours, filtered, washed, and then dried at 120 ° C. for 10 hours. Thus, anatase titanium oxide particles (2) were prepared.
The obtained anatase titanium oxide particles (2), by X-ray diffraction, the crystalline form, the crystallite size, measured to obtain the ZrO ₂ content by chemical analysis to measure TEM, the average particle maximum width (W _M ), The average particle length (L) was measured, and the results are shown in the table.

[Example 3]
Preparation of Anatase Type Titanium Oxide Particles (2) A mixed aqueous solution was prepared by adding 170 g of zirconium oxychloride octahydrate to 19996.6 g of a titanium tetrachloride aqueous solution having a concentration of 13.0 wt% as TiO ₂ . The molar ratio M _T / M _{Z at} this time is 6.15.
Next, while stirring 6721.0 g of a 4 wt% aqueous ammonia solution prepared at a temperature of 40 ° C., 2166.6 g of a mixed aqueous solution was added thereto and neutralized to prepare a TiO ₂ / ZrO ₂ hydrogel slurry.

Subsequently, after aging at 45 ° C. for 1 hour, the mixture was filtered and washed with sufficient warm water. The concentration of the washed gel was 9% by weight as TiO ₂ .ZrO ₂ .
Next, 638.9 g of the washing gel was diluted with 2236.1 g of pure water, 704.1 g of a hydrogen peroxide solution having a concentration of 35% by weight was added, dissolved by heating at 80 ° C. for 1 hour, and an oxide concentration of 1.6 A weight percent aqueous peroxotitanium / zirconium solution was prepared. In this case, hydrogen peroxide (H ₂ O ₂₎ weight ratio of oxides of the weight and the gel (TiO ₂ + ZrO ₂₎ of _{H 2 O 2 / (TiO 2} + ZrO 2) was 4.28.

Next, the peroxotitanium / zirconium aqueous solution was diluted to 1% by weight as TiO ₂ / ZrO ₂ , and 160 g of this aqueous solution was hydrothermally treated at 150 ° C. for 10 hours, filtered, washed, and then dried at 120 ° C. for 10 hours. Thus, anatase titanium oxide particles (3) were prepared.
The obtained anatase titanium oxide particles (3), by X-ray diffraction, the crystalline form, the crystallite size, measured to obtain the ZrO ₂ content by chemical analysis to measure TEM, the average particle maximum width (W _M ), The average particle length (L) was measured, and the results are shown in the table.

[Example 4]
Preparation of Anatase Type Titanium Oxide Particles (4) A 1% by weight peroxotitanium / zirconium aqueous solution was prepared as TiO ₂ .ZrO ₂ in the same manner as in Example 1, and a 25% by weight concentration tetramethylammonium hydroxide (TMAH) was prepared. ) 1.6 g of aqueous solution was mixed (molar ratio M _AR / M _T + M _Z = 0.23), then hydrothermally treated at 150 ° C. for 10 hours, filtered, washed, dried at 120 ° C. for 10 hours and anatase Titanium oxide particles (4) were prepared.
The obtained anatase titanium oxide particles (4), by X-ray diffraction, the crystalline form, the crystallite size, measured to obtain the ZrO ₂ content by chemical analysis to measure TEM, the average particle maximum width (W _M ), The average particle length (L) was measured, and the results are shown in the table.

[Example 5]
Preparation of Anatase Type Titanium Oxide Particles (5) In the same manner as in Example 1, a 1% by weight peroxotitanium / zirconium aqueous solution was prepared as TiO ₂ .ZrO ₂ , and 25% by weight tetramethylammonium hydroxide (TMAH) was prepared. ) 0.1 g of aqueous solution was mixed (molar ratio M _AR / M _T + M _Z = 0.014), then hydrothermally treated at 150 ° C. for 10 hours, filtered, washed, dried at 120 ° C. for 10 hours and anatase Titanium oxide particles (5) were prepared.
The obtained anatase titanium oxide particles (5) were measured for crystal form and crystallite diameter by X-ray diffraction, ZrO ₂ content was determined by chemical analysis, TEM was measured, and average particle maximum width (W _M ), The average particle length (L) was measured, and the results are shown in the table.

[Example 6]
Preparation of Anatase Type Titanium Oxide Particles (6) In the same manner as in Example 1, a 1% by weight peroxotitanium / zirconium aqueous solution was prepared as TiO ₂ .ZrO ₂ , and 25% by weight tetramethylammonium hydroxide (TMAH) was prepared. ) 3.2 g of aqueous solution was mixed (molar ratio M _AR / M _T + M _Z = 0.46), then hydrothermally treated at 150 ° C. for 10 hours, filtered, washed, dried at 120 ° C. for 10 hours and anatase Titanium oxide particles (6) were prepared.
The obtained anatase titanium oxide particles (6), by X-ray diffraction, the crystalline form, the crystallite size, measured to obtain the ZrO ₂ content by chemical analysis to measure TEM, the average particle maximum width (W _M ), The average particle length (L) was measured, and the results are shown in the table.

[Example 7]
Preparation of anatase type titanium oxide particles (7) Anatase titanium oxide particles (7) were prepared in the same manner as in Example 4 except that hydrothermal treatment was performed at 120 ° C for 10 hours.
The obtained anatase titanium oxide particles (7) were measured for crystal form and crystallite diameter by X-ray diffraction, ZrO ₂ content was determined by chemical analysis, TEM was measured, and average particle maximum width (W _M ), The average particle length (L) was measured, and the results are shown in the table.

[Example 8]
Preparation of anatase type titanium oxide particles (8) Anatase titanium oxide particles (8) were prepared in the same manner as in Example 4 except that hydrothermal treatment was performed at 180 ° C for 10 hours.
The obtained anatase titanium oxide particles (8) were measured for crystal form and crystallite diameter by X-ray diffraction, ZrO ₂ content was determined by chemical analysis, TEM was measured, and average particle maximum width (W _M ), The average particle length (L) was measured, and the results are shown in the table.

[Example 9]
Preparation of Anatase Type Titanium Oxide Particles (9) 93.8 g of zirconium sulfate was added to 1856.2 g of titanyl sulfate having a concentration of 14.0% by weight as TiO ₂ to prepare a mixed aqueous solution. The molar ratio M _T / M _{Z at} this time is 12.49.
Subsequently, while stirring 6048.9 g of an aqueous ammonia solution having a concentration of 4% by weight prepared at a temperature of 40 ° C., 1950 g of the mixed aqueous solution was added thereto to neutralize it, thereby preparing a TiO ₂ .ZrO ₂ hydrogel slurry.

Subsequently, after aging at 45 ° C. for 1 hour, the mixture was filtered and washed with sufficient warm water. The concentration of the washed gel was 9% by weight as TiO ₂ .ZrO ₂ .
Next, 638.9 g of the washing gel was diluted with 2236.1 g of pure water, 704.1 g of a hydrogen peroxide solution having a concentration of 35% by weight was added, dissolved by heating at 80 ° C. for 1 hour, and an oxide concentration of 1.6 A weight percent aqueous peroxotitanium / zirconium solution was prepared. In this case, hydrogen peroxide (H ₂ O ₂₎ weight ratio of oxides of the weight and the gel (TiO ₂ + ZrO ₂₎ of _{H 2 O 2 / (TiO 2} + ZrO 2) was 4.28.

Next, the peroxotitanium / zirconium aqueous solution was diluted to 1% by weight as TiO ₂ / ZrO ₂ , and 160 g of this aqueous solution was hydrothermally treated at 150 ° C. for 10 hours, filtered, washed, and then dried at 120 ° C. for 10 hours. Thus, anatase titanium oxide particles (9) were prepared.
The obtained anatase titanium oxide particles (9), by X-ray diffraction, the crystalline form, the crystallite size, measured to obtain the ZrO ₂ content by chemical analysis to measure TEM, the average particle maximum width (W _M ), The average particle length (L) was measured, and the results are shown in the table.

[Comparative Example 1]
Preparation of anatase-type titanium oxide particles (R1) While stirring 5376.8 g of a 4 wt% aqueous ammonia solution prepared at a temperature of 40 ° C., 1733.3 g of a 15 wt% titanium tetrachloride aqueous solution as TiO ₂ was added. Neutralized to prepare a TiO ₂ hydrogel slurry.
Subsequently, after aging at 45 ° C. for 1 hour, the mixture was filtered and washed with sufficient warm water. The concentration of the washed gel was 10% by weight as TiO ₂ .

Next, 2587.5 g of the washing gel slurry was diluted with 10420 g of pure water, 3164 g of a 35 wt% aqueous hydrogen peroxide solution was added, dissolved by heating at 80 ° C. for 1 hour, and dissolved in a peroxo oxide having a concentration of 1.6 wt%. A titanium aqueous solution was prepared. In this case, hydrogen peroxide (H ₂ O ₂₎ an oxide of weight and gel weight ratio H ₂ O ₂ / (TiO ₂₎ of (TiO ₂₎ was 4.28.

Next, the peroxotitanium aqueous solution was diluted with TiO ₂ to a concentration of 1% by weight, and 160 g of this aqueous solution was mixed with 1.6 g of an aqueous solution of 25% by weight of tetramethylammonium hydroxide (TMAH) (molar ratio M _AR / M _T = 0.21) Hydrothermally treated at 150 ° C. for 10 hours, filtered, and dried at 120 ° C. for 10 hours to prepare anatase titanium oxide particles (R1).
The obtained anatase titanium oxide particles (R1) were measured for crystal form and crystallite diameter by X-ray diffraction, ZrO ₂ content was determined by chemical analysis, TEM was measured, and average particle maximum width (W _M ), The average particle length (L) was measured, and the results are shown in the table.

[Comparative Example 2]
Preparation of Anatase Type Titanium Oxide Particles (R2) A mixed aqueous solution of 1743.9 g of a titanium tetrachloride aqueous solution having a concentration of 14.9% by weight and 3.5 g of zirconium oxychloride octahydrate as TiO ₂ was prepared. The molar ratio M _T / M _{Z at} this time is 299.
Next, while stirring 5431.1 g of an aqueous ammonia solution having a concentration of 4% by weight prepared at a temperature of 40 ° C., 1757.7 g of a mixed aqueous solution was added thereto and neutralized to prepare a TiO ₂ .ZrO ₂ hydrogel slurry.

Subsequently, after aging at 45 ° C. for 1 hour, the mixture was filtered and washed with sufficient warm water. The concentration of the washed gel was 9% by weight as TiO ₂ .ZrO ₂ .
Next, 638.9 g of the washing gel was diluted with 2236.1 g of pure water, 704.1 g of a hydrogen peroxide solution having a concentration of 35% by weight was added, dissolved by heating at 80 ° C. for 1 hour, and an oxide concentration of 1.6 A weight percent aqueous peroxotitanium / zirconium solution was prepared. In this case, hydrogen peroxide (H ₂ O ₂₎ weight ratio of oxides of the weight and the gel (TiO ₂ + ZrO ₂₎ of _{H 2 O 2 / (TiO 2} + ZrO 2) was 4.28.

Next, 1.6 g of a 25 wt% tetramethylammonium hydroxide (TMAH) aqueous solution was mixed with 160 g of a peroxotitanium / zirconium aqueous solution (molar ratio M _AR / M _T + M _Z = 0.22) at 150 ° C. for 10 hours. Heat treated, filtered, washed and dried at 120 ° C. for 10 hours to prepare anatase titanium oxide particles (R2).
The obtained anatase titanium oxide particles (R2) were measured for crystal form and crystallite diameter by X-ray diffraction, ZrO ₂ content was determined by chemical analysis, TEM was measured, and average particle maximum width (W _M ), The average particle length (L) was measured, and the results are shown in the table.

[Comparative Example 3]
Preparation of Anatase Type Titanium Oxide Particles (R3) A mixed aqueous solution of 2184.7 g of a titanium tetrachloride aqueous solution having a concentration of 11.9 wt% and 291.5 g of zirconium oxychloride octahydrate was prepared as TiO ₂ . The molar ratio M _T / M _{Z at} this time is 3.59.
Next, while stirring 7681.2 g of an aqueous ammonia solution having a concentration of 4% by weight prepared at a temperature of 40 ° C., 2476.2 g of a mixed aqueous solution was added and neutralized to prepare a TiO ₂ .ZrO ₂ hydrogel slurry.

Subsequently, after aging at 45 ° C. for 1 hour, the mixture was filtered and washed with sufficient warm water. The concentration of the washed gel was 9% by weight as TiO ₂ .ZrO ₂ .
Next, 638.9 g of the washing gel was diluted with 2236.1 g of pure water, 704.1 g of a hydrogen peroxide solution having a concentration of 35% by weight was added, dissolved by heating at 80 ° C. for 1 hour, and an oxide concentration of 1.6 A weight percent aqueous peroxotitanium / zirconium solution was prepared. In this case, hydrogen peroxide (H ₂ O ₂₎ weight ratio of oxides of the weight and the gel (TiO ₂ + ZrO ₂₎ of _{H 2 O 2 / (TiO 2} + ZrO 2) was 4.28.

Next, 1.6 g of a 25 wt% tetramethylammonium hydroxide (TMAH) aqueous solution was mixed with 160 g of a peroxotitanium / zirconium aqueous solution (molar ratio M _AR / M _T + M _Z = 0.24) at 150 ° C. for 10 hours. Heat treated, filtered, washed and dried at 120 ° C. for 10 hours to prepare anatase titanium oxide particles (R3).
The obtained anatase titanium oxide particles (R3) were measured for crystal form and crystallite diameter by X-ray diffraction, ZrO ₂ content was determined by chemical analysis, TEM was measured, and average particle maximum width (W _M ), The average particle length (L) was measured, and the results are shown in the table.

[Comparative Example 4]
Preparation of anatase-type titanium oxide particles (R4) While stirring 5800 g of a 4 wt% ammonia aqueous solution prepared at a temperature of 40 ° C., 1865 g of 13.9 wt% titanium tetrachloride aqueous solution as TiO ₂ was added and neutralized. A TiO ₂ hydrogel slurry was prepared.
Subsequently, after aging at 45 ° C. for 1 hour, the mixture was filtered and washed with sufficient warm water. The concentration of the washed gel was 9% by weight as TiO ₂ .
Next, 638 g of the washing gel slurry was diluted with 2676 g of pure water, 280 g of a hydrogen peroxide aqueous solution having a concentration of 35% by weight was added, and the solution was heated and dissolved at 80 ° C. for 1 hour to dissolve the peroxotitanium aqueous solution having an oxide concentration of 1.6% by weight. Was prepared. In this case, hydrogen peroxide (H ₂ O ₂₎ an oxide of weight and gel weight ratio H ₂ O ₂ / (TiO ₂₎ of (TiO ₂₎ was 4.

Next, 46.2 g of zirconia sol (manufactured by Daiichi Rare Element Co., Ltd .: AL-7, average particle size 5 nm, solid content concentration 13 wt%) was mixed with 3000 g of peroxotitanium aqueous solution (molar ratio M _T / M _Z was 12.28) Then, 2354 g of pure water was added to dilute to an oxide concentration of 1% by weight. 160 g of this aqueous solution was hydrothermally treated at 150 ° C. for 10 hours, filtered, washed and dried at 120 ° C. for 10 hours. Thus, anatase titanium oxide particles (R4) were prepared.
With respect to the obtained anatase titanium oxide particles (R4), the crystal form and crystallite diameter were measured by X-ray diffraction, and the ZrO ₂ content was determined by chemical analysis. Moreover, when TEM was measured, the particle shape was granular and the average particle diameter was 10 nm.

Claims (5)

Anatase-type titanium oxide particles comprising titanium oxide and zirconium oxide, having a zirconium oxide content in the range of 1 to 30% by weight and a crystallite diameter in the range of 15 to 50 nm, and having an average particle maximum width ( Anatase-type titanium oxide particles, wherein W _M ) is in the range of 2 to 50 nm and the average particle length (L) is in the range of 10 to 500 nm. A method for producing anatase-type titanium oxide particles, comprising the following steps (a) to (e).
(A) Step of mixing acid or base in a mixed aqueous solution of titanium compound and zirconium compound and hydrolyzing (b) Washing hydrolyzed gel (c) Adding hydrogen peroxide to hydrolyzed gel (E) a step of hydrothermally treating the dissolved solution at 100 to 300 ° C. The method for producing anatase-type titanium oxide particles according to claim 2, wherein the following step (d) is performed after the step (c).
(D) A quaternary alkylammonium compound (TAA) having a number of moles of quaternary alkylammonium compound (TAA) (M _AR ), a number of moles of TiO ₂ (M _T ) and a number of moles of ZrO ₂ (M _Z ) The step of adding so that the molar ratio (M _AR ) / (M _T + M _Z ) with the total number of moles is in the range of 0.05 to 5. The molar ratio (M _T ) / (M _Z ) of the number of moles (M _T ) of the titanium compound as TiO ₂ and the number of moles (M _Z ) of the zirconium compound as ZrO ₂ in the step (a) is 4 to 100. The method for producing anatase-type titanium oxide particles according to claim 2 or 3, wherein the method falls within the range. 5. The production of anatase-type titanium oxide particles according to claim 2, wherein the weight ratio of H ₂ O ₂ / (TiO ₂ + ZrO ₂ ) in the step (c) is in the range of 1 to 40. Method.