JP2009298614A - Titanium oxide-based particles and its producing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide titanium oxide particles which have a low or controlled refractive index and are spherical. <P>SOLUTION: The titanium oxide-based particles consist of a silica-based hollow microparticle and a titanium oxide coating layer on the hollow microparticle surface, and its average particle diameter is in the range of 5-100 nm and its refractive index is in the range of 1.30-2.00. The method for producing the titanium oxide-based particles comprises the following processes (a)-(c); (a) a process of depositing a titanium compound hydrolysate on the surface of a silica-based hollow microparticle by hydrolyzing in adding a titanium compound aqueous solution or a titanium compound aqueous solution and an acid or an alkali to a liquid in which silica-based hollow microparticles are dispersed, (b) a process of adding a hydrogen peroxide aqueous solution to the liquid in which the silica-based hollow microparticles on the surfaces of which the titanium compound hydrolysate is deposited are dispersed so as to control a molar ratio (M<SB>HP</SB>)/(M<SB>Ti</SB>) between a mole number (M<SB>HP</SB>) as H<SB>2</SB>O<SB>2</SB>of the hydrogen peroxide aqueous solution and a mole number (M<SB>Ti</SB>) as TiO<SB>2</SB>of the titanium compound hydrolysate to be 2-50, and (c) a process of hydrothermally treating the dispersion liquid at 80-350°C. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a low refractive index titanium oxide-based particle and a method for producing the same.

  Conventionally, various uses using the chemical properties of titanium oxide particles are known. For example, a catalyst material such as a redox catalyst, a catalyst carrier material, a photocatalyst material for a solar cell semiconductor film or NOx removal, etc., as a high refractive index material, a filler for a hard coat film of an eyeglass lens, an antireflection film, etc. In addition to fillers for high refractive index films for base materials, it is used as a material for cosmetics as an ultraviolet shielding material.

  However, there is a need for titanium oxide that suppresses photocatalytic activity or does not have photocatalytic activity from the viewpoints of light resistance, weather resistance, etc., even if the refractive index is high. For this reason, the inventors of the present application tried to dope with alkali or alkaline earth element or coat with silica or the like, but it was difficult to completely suppress the photocatalytic activity, and there was a problem that the refractive index was lowered. there were.

  In addition, since titanium oxide has hydrophilicity and photocatalytic activity, it is expected to prevent or remove dirt. For example, it is expected to be used for building materials and displays used outdoors. However, since titanium oxide has a high refractive index, it has a glare and has a problem in that its use outdoors is limited. In addition, when used as a filler for a high refractive index film provided in the lower layer of the antireflection film, it is necessary to adjust the refractive index of the high refractive index film by the refractive index of the base material and the refractive index of the antireflection film. The refractive index and content of the titanium oxide particles were adjusted by the refractive index of the matrix. In these applications, titanium oxide particles that are spherical and have a low refractive index or an adjusted refractive index have been demanded.

  Furthermore, in the field of cosmetics, titanium oxide particles are used as an ultraviolet shielding material. However, since the refractive index of titanium oxide itself is high, it may be accompanied by glare and white floating phenomenon, and therefore the refractive index is low. Alternatively, there is a need for titanium oxide particles having an adjusted refractive index.

Furthermore, when the titanium oxide particles are crystalline, rod-like particles having an aspect ratio of approximately 2 or more are obtained. When such rod-like particles are used as a filler for a high refractive index film, the adhesion to the substrate is obtained. May be insufficient, the particles may not be densely packed, resulting in insufficient film strength, and insufficient photocatalytic performance. Furthermore, when used in cosmetics, there is a problem that the touch is accompanied by a foreign body sensation. For this reason, the present applicant has proposed spherical titanium oxide particles obtained by precipitating titanium hydroxide on the surface of the inorganic oxide fine particles. (Patent Document 1, Japanese Patent Application Laid-Open No. 2003-12324)
JP 2003-12324 A

There has been a demand for spherical titanium oxide particles having a low refractive index or a refractive index adjusted as described above.
In addition, in the method described in Patent Document 1, although spherical titanium oxide-based particles can be obtained, when titanium oxide particles having a desired low refractive index cannot be obtained, or when the particle diameter is small, the obtained titanium oxide particles are There are problems such as aggregation and difficulty in forming a uniform coating layer.

  As a result of intensive investigations in view of the above problems, the present inventors coated titanium oxide with peroxotitanic acid on the surface of spherical silica-based hollow fine particles, and hydrothermally treated in the presence of alkali as necessary. It was found that colloidal region titanium oxide fine particles having a refractive index of 1.3 to 2.0, a low refractive index that was not conceivable with conventional titanium oxide, and whose photocatalytic activity was adjusted, were obtained, and the present invention was completed. .

The configuration of the present invention is as follows.
[1] A silica-based hollow fine particle and a titanium oxide coating layer on the surface of the hollow fine particle,
The average particle size is in the range of 5 to 100 nm,
A titanium oxide-based particle having a refractive index in the range of 1.30 to 2.00.
[2] The silica-based hollow fine particles have an average particle diameter in the range of 3 to 100 nm and a refractive index of 1.
[1] Titanium oxide-based particles in the range of 15 to 1.40.
[3] The average thickness of the titanium oxide coating layer is in the range of 0.1 to 20 nm (however, the thickness of the coating layer does not exceed 1/2 of the average particle diameter). Titanium oxide particles.

[4] The titanium oxide particles according to any one of [1] to [3], wherein the spherical coefficient represented by the following formula (1) of the titanium oxide particles is in the range of 0.5 to 1.
Spherical coefficient = (D _S ) / (D _L ) (1)
(However, (D _L ) is the longest average particle diameter, (D _S ) is the midpoint of the longest diameter and the average short diameter perpendicular to the longest diameter)
[5] The titanium oxide particles according to [1] to [4], wherein the titanium oxide coating layer is one or more types of titanium oxide selected from anatase type, rutile type, and brookite type.

[6] The titanium oxide-based particles according to [1] to [5], which are surface-treated with an organosilicon compound represented by the following formula (1) or a hydrolyzate thereof.
_{R n -SiX 4-n (1} )
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms or a silanol group) , Halogen, hydrogen, n: an integer of 0 to 3)
[7] A method for producing titanium oxide-based particles comprising the following steps (a) to (c).
(A) A step of hydrolyzing a silica-based hollow fine particle dispersion while adding a titanium compound aqueous solution or a titanium compound aqueous solution and an acid or alkali to precipitate a titanium compound hydrolyzate on the surface of the silica-based hollow fine particles.
(B) In a silica-based hollow fine particle dispersion having a titanium compound hydrolyzate deposited on the surface, the number of moles of hydrogen peroxide as H ₂ O ₂ (M _HP ) and the mole of titanium compound hydrolyzate as TiO ₂ the number (M _Ti) molar ratio of _{(M HP) / (M Ti} ) is the step of adding a hydrogen peroxide solution to be in the range of 2 to 50.
(C) A step of hydrothermally treating the dispersion at 80 to 350 ° C.

[8] A method for producing titanium oxide-based particles comprising the following steps (ab) to (c).
(Ab) A step of adding a peroxotitanic acid aqueous solution to the silica-based hollow fine particle dispersion.
(C) A step of hydrothermally treating the dispersion at 80 to 350 ° C.
[9] The method for producing titanium oxide-based particles according to [6] or [7], wherein the following step (d) is performed after the step (c).
(D) A step of hydrothermally treating the dispersion adjusted to pH 7.5 to 13.5 at 80 to 350 ° C.
[10] The method for producing titanium oxide-based particles according to [6] to [8], wherein the average particle diameter is in the range of 5 to 500 nm and the refractive index is in the range of 1.3 to 2.0.

According to the present invention, it is spherical and has an average particle diameter in the range of 5 to 500 nm and a refractive index of 1.
A titanium oxide-based particle having a low refractive index in the range of 30 to 2.00 and a method for producing the same can be provided.

  Such titanium oxide-based particles have a photocatalytic activity while having a low refractive index, which has not been considered in conventional titanium oxide, and have a moderately photocatalytic activity while having a low refractive index, Since it has a shielding ability and can be adjusted to a desired refractive index, it also has a characteristic of a film, and is useful as a film compounding agent, a compounding agent for adjusting the refractive index, a cosmetic compounding agent and the like.

Hereinafter, the titanium oxide particles according to the present invention will be specifically described.
[Titanium oxide particles]
The titanium oxide-based particles according to the present invention are formed by coating silica-based hollow fine particles with titanium oxide, the average particle diameter is in the range of 5 to 500 nm, and the refractive index is in the range of 1.30 to 2.00. It is characterized by. The “titanium oxide-based” of the present invention does not consist of titanium oxide alone but includes a silica component.

Silica-based hollow fine particles The silica-based hollow fine particles used in the present invention preferably have an average particle size of 3 to 100 nm, more preferably 5 to 80 nm.

  In the first place, it is difficult to obtain a silica-based hollow fine particle having a size less than the lower limit of the above range, and even if it is obtained, the refractive index cannot be sufficiently lowered. Even so, it is difficult to obtain titanium oxide particles having a low refractive index.

When the silica-based hollow fine particles have an average particle diameter in the above range, a transparent film having excellent transparency can be obtained.
The refractive index of the silica-based hollow fine particles used in the present invention is 1.15 to 1.40, preferably 1.15 to 1.35. When silica-based hollow fine particles in this refractive index range are used, desired low refractive index titanium oxide-based particles can be prepared. It is difficult to obtain silica-based hollow fine particles having a refractive index below the lower limit of the above range, and those having a refractive index exceeding the above range have little significance in using silica-based hollow fine particles, or substantially silica. It becomes difficult to obtain titanium oxide-based particles that are solid solid particles and have a desired low refractive index.

  The refractive index of the hollow silica fine particles is reduced by increasing the amount of the hollow portion due to the ratio of the hollow portions constituting the hollow fine particles and the outer shell layer, and the refractive index decreases if the outer shell layer portion is increased. Get higher.

The ratio (T _s / D _p ) of the thickness (T _s ) of the outer shell layer to the average particle diameter (D _p ) should be in the range of 1/20 to 1/5, preferably 1/20 to 1/10. desirable.
The shape of the silica-based hollow fine particles is usually a spherical shape. This spherical shape preferably has a spherical coefficient in the range of 0.5 to 1 described later. This spherical coefficient is maintained even when a titanium oxide coating layer described later is formed, or further improves the sphericity. There is a case. In addition, in a method other than the manufacturing method described later, agglomeration or titanium oxide does not selectively precipitate on the surface, and titanium oxide fine particles may be generated separately.

  As the silica-based hollow fine particles used in the present invention, silica-based hollow fine particles disclosed in Japanese Patent Application Laid-Open Nos. 2001-233611 and 2003-192994 filed by the applicant of the present application can be suitably employed.

Titanium oxide coating layer In the present invention, a titanium oxide coating layer made of titanium oxide is formed on the surface of the silica-based hollow fine particles. The average thickness of the titanium oxide coating layer is 0.1 to 100 nm, preferably 0.5 to 15 nm.

Within this range, titanium oxide-based fine particles having a lower refractive index than conventional titanium oxide-based fine particles can be obtained.
When the average thickness of the titanium oxide coating layer is thin, the photocatalytic activity and the ultraviolet shielding effect may be insufficient. When the average thickness of the titanium oxide coating layer is too thick, the average particle size of the silica-based hollow fine particles is small. In some cases, the refractive index of the obtained particles is not sufficiently low, and when the titanium oxide coating layer is thickened, fine particles made of titanium oxide are generated separately from the coating layer and do not form the coating layer. Particles may increase.

  The refractive index of the titanium oxide-based particles can be adjusted by appropriately changing the ratio between the thickness of the titanium oxide coating layer and the average particle diameter of the silica-based hollow fine particles, and the ratio (thickness of titanium oxide coating layer / oxidation) If the average particle diameter (titanium-based particles) is reduced, the refractive index is decreased, and if the ratio is increased, the refractive index is increased.

Moreover, the thickness of the titanium oxide coating layer is desirably in the range of about 1/20 to 1/4, preferably 1/10 to 1/6, of the average particle diameter of the titanium oxide-based particles. If it is in this range, a low refractive index can be achieved with sufficient photocatalytic activity, ultraviolet shielding performance and the like.
The method for forming such a coating layer is as shown in the manufacturing method described later.

Characteristics of Titanium Oxide-Based Particles The average particle diameter of the titanium oxide-based particles of the present invention is preferably 5 to 100 nm, more preferably 10 to 80 nm.

  When the average particle diameter of the titanium oxide particles is smaller than the lower limit of the above range, it is difficult to obtain silica-based hollow fine particles themselves, and there is a tendency to aggregate when the titanium oxide particles are coated. When the average particle diameter of the silica exceeds the upper limit of the above range, it takes a long time to produce the silica-based hollow fine particles themselves used for coating, and the surface of the silica-based hollow fine particles when producing thick particles of the titanium oxide coating layer. In some cases, it may be difficult to selectively coat the film, which may cause problems in productivity and economy, and may reduce transparency.

  The refractive index of the titanium oxide-based particles of the present invention is desirably 1.30 to 2.00, preferably 1.30 to 1.80. When the refractive index of the titanium oxide-based particles is smaller than the lower limit of the above range, it may indicate that the amount of titanium oxide coating is small, and sufficient photocatalytic activity, ultraviolet shielding performance, etc. may not be obtained.

When the refractive index of the titanium oxide-based particles is higher than the above range, it is not necessary to have the constitution of the present invention, and it is a mere titanium oxide particle, and is an object of the present invention and does not achieve a low refractive index.
In the present invention, the refractive index of silica-based hollow fine particles and titanium oxide-based particles is measured by the following method.

(1) The particle dispersion is taken in an evaporator and the dispersion medium is evaporated.
(2) This is dried at 120 ° C. to obtain a powder.
(3) A standard refraction liquid having a known refractive index is dropped on a glass plate of a few drops, and the above powder is mixed therewith.
(4) The operation of (3) is performed with various standard refractive liquids, and the refractive index of the standard refractive liquid when the mixed liquid becomes transparent is defined as the refractive index of the particles.
The titanium oxide-based particles according to the present invention desirably have a spherical coefficient represented by the following formula (1) in the range of 0.5 to 1, preferably 0.7 to 1.
Spherical coefficient = (D _S ) / (D _L ) (1)
(However, (D _L ) is the longest average particle diameter, (D _S ) is the midpoint of the longest diameter and the average short diameter perpendicular to the longest diameter)
When the spherical coefficient of the titanium oxide-based particles does not exceed 1 and the spherical coefficient of the titanium oxide-based particles is less than 0.5, a rod-shaped titanium oxide system having an aspect ratio of approximately 2 or more obtained by a conventionally known method Like the particles, if used as a filler or the like, the adhesion with the substrate is insufficient, the particles are not densely packed, the film strength is insufficient, the photocatalytic performance may be insufficient, Furthermore, when used in cosmetics, the touch may be accompanied by a foreign body sensation.

The spherical coefficient of the present invention was obtained by taking a transmission electron micrograph (TEM), measuring the longest diameter (D _L ) and the short diameter (D _S ) perpendicular to the midpoint of the longest diameter for 100 particles, It can be obtained as a ratio of average values. When the same particle was measured three times, substantially the same value was obtained.

The average particle diameter of the titanium oxide-based particles was expressed as ½ of the longest diameter (D _L ) + short diameter (D _S ).
The average particle diameter of the silica-based hollow fine particles used in the present invention can be determined as an average value obtained by taking an electron micrograph and measuring the particle diameter of 100 particles.

  In the titanium oxide particles of the present invention, the titanium oxide coating layer is preferably at least one titanium oxide selected from anatase type, rutile type, and brookite type. When titanium oxide has such a crystal form, it is excellent in photocatalytic activity and ultraviolet shielding performance.

The crystal form is X-ray diffractometry (for example, manufactured by Rigaku Corporation: LAD-IIC type, Cu tube,
35 kV, 12.5 mA).

The titanium oxide-based particles of the present invention are preferably surface-treated with an organosilicon compound represented by the following formula (1) or a hydrolyzate thereof.
_{R n -SiX 4-n (1} )
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms or a silanol group) , Halogen, hydrogen, n: an integer of 0 to 3)

Examples of the organosilicon compound represented by the formula (1) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane. , Methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3- Trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxy Silane, γ-glycidoxymethyltriexisilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltriethoxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxy Silane, γ- (meth) acrylooxypropyltrimethoxysilane, γ- (meth) a Acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyl Triethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriiso Propoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β ( Minoechiru) .gamma.-aminopropyltrimethoxysilane, N- phenyl--γ- aminopropyltrimethoxysilane, .gamma.-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane, and the like.

  When surface-treated with such an organosilicon compound, when blended into a film as a film compounding agent, it can be uniformly dispersed and dispersed in a dispersion medium, binder or matrix, and the film strength, A transparent film excellent in scratch resistance can be obtained.

Moreover, photocatalytic activity can be suppressed or light resistance can be improved, maintaining an ultraviolet-ray shielding capability depending on a use.
The amount ratio of titanium oxide-based particles to the organosilicon compound (weight as the solid content of the organosilicon compound / weight of the titanium oxide-based particles) varies depending on the average particle diameter of the titanium oxide-based particles, but is generally 1.0 or less, preferably Is preferably in the range of 0.3 or less.

  When the weight ratio is small, for example, when blended in a coating solution, the affinity with the matrix forming component is low, the dispersibility in the paint, the stability is insufficient, and the fine particles may aggregate in the paint, A dense transparent film may not be obtained, and adhesion to the substrate, film strength, scratch resistance, and the like may be insufficient.

Even if the weight ratio is too high, dispersibility in the paint is not further improved, and the ratio of titanium oxide in the titanium oxide-based particles is low, so that sufficient ultraviolet light shielding ability may not be obtained. .
Such titanium oxide-based particles according to the present invention can be produced by the following production method.

[Method for producing titanium oxide-based particles]
First, the manufacturing method of the 1st titanium oxide type particle | grains which concern on this invention is demonstrated.

The manufacturing method of the 1st titanium oxide type particle which concerns on this invention consists of the following process (a)-(c).
(A) A step of hydrolyzing a silica-based hollow fine particle dispersion while adding a titanium compound aqueous solution or a titanium compound aqueous solution and an acid or alkali to precipitate a titanium compound hydrolyzate on the surface of the silica-based hollow fine particles.
(B) A step of adding aqueous hydrogen peroxide to a silica-based hollow fine particle dispersion having a titanium compound hydrolyzate deposited on the surface thereof.
(C) A step of hydrothermally treating the dispersion at 80 to 350 ° C.

Step (a)
The silica-based hollow fine particles are as described above.
The titanium compound is not particularly limited as long as it is water-soluble, and specific examples include titanium tetrachloride, titanium trichloride, titanium sulfate, titanyl sulfate, and titanium hydride. Furthermore, titanium alkoxide or a partial hydrolyzate thereof can also be used. As the titanium alkoxide, a titanium alkoxide represented by Ti (OR) ₄ (R: hydrocarbon group) is preferably used. For example, tetraisopropyl titanate, tetranormal butyl titanate, tetra (2-ethylhexyl) titanate, etc. Can be mentioned. Titanium alkoxide may be used as it is or as an alcohol solution.

The silica-based hollow fine particle dispersion is hydrolyzed (hereinafter sometimes referred to as “neutralization”) while adding an aqueous solution of the titanium compound or an aqueous solution of the titanium compound and an acid or an alkali. The solid content concentration of the silica-based hollow fine particle dispersion is desirably 0.01 to 30% by weight, preferably 0.1 to 20% by weight. At this time, it is preferable that the density | concentration of a titanium compound exists in the range of 0.05-30 weight% as solid content, and also 0.1-20 weight%. If the solid content concentration is low, the production efficiency is lowered in addition to requiring an excessively large container. If the solid content concentration is too high, the hydrolysis becomes uneven or the viscosity of the gel is reduced. The gel becomes high, handling of the gel is not easy, and cleaning may be difficult when cleaning as required. If the titanium oxide coating layer is to be thickened, the amount of the titanium compound may be increased within the above range, and if it is to be thinned, the amount of the titanium compound may be decreased within the above range.

  The amount of the titanium compound added is such that the titanium oxide coating layer is in the range of 1/20 to 1/4, preferably 1/10 to 1/6, of the average particle diameter of the resulting titanium oxide particles. The If it exists in this range, the above-mentioned titanium oxide type particle | grains which have a titanium oxide coating layer will be obtained.

  As the acid, in addition to hydrochloric acid, nitric acid, sulfuric acid and the like, an organic acid can be used, and as the alkali, ammonia, organic amine, NaOH, KOH and the like can be used. The pH of the dispersion during hydrolysis is preferably in the range of 8 to 14, more preferably 9 to 13.

By this hydrolysis, a hydrolyzate of the titanium compound is precipitated on the surface of the silica hollow fine particles.
In this invention, after hydrolyzing, it can wash | clean as needed. The washing method is not particularly limited as long as the impurity ions in the silica-based hollow fine particles on which the titanium compound hydrolyzate is deposited can be reduced, and a conventionally known method can be employed. For example, after filtering a silica-based hollow fine particle dispersion having a titanium compound hydrolyzate deposited on the surface, it can be washed by applying sufficient water, warm water, dilute ammonia water or the like. Moreover, conventionally well-known methods, such as an ultrafiltration membrane method and an ion exchange resin method, can also be employ | adopted. When washed, titanium oxide-based particles having high crystallinity and excellent photocatalytic performance can be obtained.

The residual amount of impurities such as anions and / or alkalis after washing is preferably 1% by weight or less, more preferably 0.1% by weight or less in the solid content of the titanium oxide particles.
Further, after hydrolysis or washing, aging can be performed as necessary. As aging conditions, it is generally stirred at 30 to 120 ° C. for 0.1 to 24 hours, or left unstirred.
When such aging is performed, the aggregated particles disappear, the thickness of the titanium oxide coating layer becomes uniform, and titanium oxide-based particles having a uniform particle size distribution can be obtained.

Step (b)
Hydrogen peroxide water is added to the silica-based hollow fine particle dispersion on which the titanium compound hydrolyzate of step (a) is deposited, and the concentration of the dispersion is 0.1 to 30% by weight as a solid content, Further, it is preferably in the range of 1 to 20% by weight.

If the solid content concentration is too low, the productivity and production efficiency will decrease, and even if the solid content concentration is too high, it will depend on the amount of hydrogen peroxide to be described later, but the dissolution of the titanium compound hydrolyzate will be uneven. For this reason, the crystallinity of the resulting titanium oxide particles may be insufficient.

The amount of hydrogen peroxide added is the molar ratio (M _HP ) / mole ratio of hydrogen peroxide as H ₂ O ₂ (M _HP ) to the number of moles of titanium compound hydrolyzate as TiO ₂ (M _Ti ) / (M _Ti ) is 2 to 50, more preferably 5
A range of 40 is preferable. If the molar ratio (M _HP ) / (M _Ti ) is too low, the resulting titanium oxide particles may have insufficient crystallinity. Even if the molar ratio (M _HP ) / (M _Ti ) is too high, the dissolution rate of the titanium compound hydrolyzate is not improved and the dissolution becomes more uniform, which is not economical.

By adding hydrogen peroxide solution in this way, the shape factor of the titanium oxide-based particles finally obtained (through step (c)) is improved, and the titanium oxide coating layer becomes dense and crystallized. Excellent titanium oxide particles can be obtained.

Step (c)
Next, the dispersion is hydrothermally treated at 80 to 350 ° C., preferably 80 to 200 ° C. If the hydrothermal treatment temperature is low, densification and crystallization of the coated titanium oxide layer may be insufficient. Even if the hydrothermal treatment temperature is too high, densification and crystallization are not promoted and agglomeration occurs. Titanium oxide-based particles may be obtained.

The hydrothermal treatment time is preferably about 0.1 to 24 hours.
The method for producing titanium oxide-based particles according to the present invention may be the one consisting of the following (ab) to (c) (second production method) instead of the steps (a) to (c).
(Ab) A step of adding a peroxotitanic acid aqueous solution to the silica-based hollow fine particle dispersion.
(C) A step of hydrothermally treating the dispersion at 80 to 350 ° C.

Process (ab)
The silica-based hollow fine particles described above are used as the silica-based hollow fine particles.
Examples of the aqueous solution of peroxotitanic acid include aqueous solutions of peroxotitanic acid obtained by reacting a titanium compound and hydrogen peroxide, or peroxotitanic acid obtained by reacting titanium hydroxide and hydrogen peroxide.

In order to prepare a peroxotitanic acid aqueous solution, for example, a titanium compound, or a mole number (M _HP ) of hydrogen peroxide as H ₂ O _{2 in} reacting a titanium hydroxide with hydrogen peroxide and a titanium compound, moles as TiO ₂ of titanium hydroxide (M _Ti) molar ratio of _{(M HP) / (M Ti} ) is 2
It is possible to employ a conventionally known method of mixing so as to be in the range of 50, preferably 5 to 40, and heating as necessary.

  When peroxotitanic acid obtained by reacting titanium alkoxide with hydrogen peroxide is used, titanium oxide-based particles in which the titanium oxide coating layer is rutile titanium oxide tend to be obtained.

The concentration of the peroxotitanic acid aqueous solution is preferably in the range of 1 to 30% by weight, preferably 2 to 20% by weight in terms of titanium oxide.
The amount of the titanium compound added is such that the titanium oxide coating layer is in the range of 1/20 to 1/4, preferably 1/10 to 1/6, of the average particle diameter of the resulting titanium oxide particles. The If it exists in this range, the above-mentioned titanium oxide type particle | grains which have a titanium oxide coating layer will be obtained.

The solid content concentration of the silica-based hollow fine particle dispersion is the same as in the first method.
The concentration after mixing the aqueous peroxotitanic acid solution with the silica-based hollow fine particle dispersion is preferably in the range of 0.1 to 30% by weight, more preferably 1 to 20% by weight as the solid content.

When the solid content concentration is low, productivity and production efficiency are lowered, and when the solid content concentration is too high, crystallinity of the obtained titanium oxide-based particles may be insufficient.
The step (c) of the second method is the same as the first method.
In the present invention, the following step (d) may be performed after step (c).

Step (d)
After the hydrothermal treatment in step (c), the dispersion is adjusted to pH 7.5 to 13.5, preferably 8 to 13.5.
Adjust to.

  For adjusting the pH of the dispersion, alkali metal hydroxides such as NaOH and KOH, ammonia, organic bases and the like can be used. Examples of the organic base include quaternary ammonium salts such as tetramethylammonium salt or amines such as hydroxide, monoethanolamine and diethanolamine.

  When the pH of the dispersion is neutral or acidic, the titanium oxide layer is amorphous. When the pH is in the above range, titanium oxide particles having a crystalline titanium oxide layer can be obtained. The type of crystal form varies depending on the type and amount of pH, alkali, organic base and the like. For example, if there are few organic bases, it will become an anatase type, and if there are many organic bases, it will become a brookite type.

The pH adjusted dispersion is hydrothermally treated at 80 to 350 ° C, preferably 80 to 200 ° C.
If the hydrothermal treatment temperature is low, crystallization may be insufficient or a long time may be required. Even if the hydrothermal treatment temperature is too high, aggregated titanium oxide-based particles may be obtained without further shortening the crystallization time or improving the crystallinity.

By this treatment, titanium oxide particles having a high spherical coefficient, a dense titanium oxide coating layer, and excellent crystallinity depending on production conditions can be obtained.
The hydrothermal treatment time varies depending on the temperature, but is usually 0.1 to 48 hours.

The dispersion after hydrothermal treatment may be washed or concentrated by an ultrafiltration membrane method or an ion exchange resin.
The titanium oxide-based particles thus obtained have an average particle diameter of 5 to 100 nm, more preferably 10 to 80 nm, depending on the average particle diameter of the silica-based hollow fine particles and the thickness of the titanium oxide coating layer. It is preferable. Moreover, it is preferable that the refractive index of the titanium oxide type particle | grains obtained exists in the range of 1.30-2.00, Furthermore, 1.30-1.80.

[Usage]
Such titanium oxide-based particles according to the present invention can be used for applications such as a photoelectric cell and a photocatalyst.
The photoelectric cell includes an electrode layer (1) on the surface and a substrate on which a metal oxide semiconductor film (2) having a photosensitizer adsorbed on the surface of the electrode layer (1) is formed; A substrate having an electrode layer (3) is disposed so that the electrode layer (1) and the electrode layer (3) face each other, and the metal oxide semiconductor film (2) and the electrode layer (3) In a photoelectric cell in which an electrolyte layer is provided therebetween, at least one of the substrate and the electrode has transparency, and the metal oxide semiconductor film (2) contains the titanium oxide-based particles of the present invention.

As the photocatalyst, any titanium oxide-based particles may be used. As the photocatalyst, the above-described titanium oxide-based particles can be used as they are, or other active components are supported or doped on the titanium oxide-based particles. Or these tubular titanium oxide particles can be mixed and used. Furthermore, a binder component precursor may be included as necessary. There is no particular limitation on the use form of such a photocatalyst. For example, the tubular titanium oxide particles can be used as they are dispersed in a solvent such as water, or mixed with a binder component precursor and applied for forming a photocatalyst layer. It can also be used by forming a catalyst layer having a desired film thickness by coating and drying on a substrate such as glass, PET, metal, or ceramics. Furthermore, it can be formed into a spherical shape, a pellet shape, a honeycomb shape, or the like. Other active components include metal components used for antibacterial and antifungal purposes such as Ag, Cu, and Zn, as well as redox performance such as Pt, Pd, Rh, Ru, Os, Ir, Au, and Fe. A metal component is mentioned. Conventionally known methods can be used for loading and doping these metal components. For example, an aqueous solution of a soluble salt of a metal component is added to a dispersion of tubular titanium oxide particles, or hydrolyzed as necessary to precipitate. Can be prepared.

Moreover, it is useful as a negative electrode material of a battery in addition to a photoelectric cell and a photocatalyst, and a sensing part of a photosensor.
In addition, the titanium oxide-based particles of the present invention can be suitably used for visible light and ultraviolet light shielding film-forming paints, cosmetic compositions, transparent film-forming paints, and the like. For example, in the case of a coating material for forming an ultraviolet shielding film, it may be mixed with coloring pigment particles in a coating resin as required.

  What is necessary is just to mix | blend a titanium oxide type particle | grain with a raw material of about 1 to 80 weight% with respect to the composition whole quantity, when using for a cosmetic composition. Cosmetic compositions are usually various ingredients blended in cosmetics, for example, higher fatty alcohols, higher fatty acids, ester oils, paraffin oils, waxes and other oils, ethyl alcohol, propylene glycol, sorbitol and other alcohols, Moisturizers such as mucopolysaccharides, collagens, PCA salts, lactates, nonionic, cationic, anionic or amphoteric surfactants, gum arabic, xanthan gum, polyvinylpyrrolidone, ethylcellulose, carboxymethylcellulose, carboxyvinyl polymer, Thickeners such as modified or unmodified clay minerals, solvents such as ethyl acetate, acetone and toluene, inorganic and organic facial dyes, antioxidants such as BHT and tocophenol, water, chemicals, UV absorbers, organic PH consisting of acid or inorganic acid salts It may contain one or more of impactants, chelating agents, preservatives, fragrances, etc. If necessary, inorganic pigments such as silica, talc, kaolin, mica, sericite and synthetic inorganic compounds, various organic resins 1 type (s) or 2 or more types may be included.

  Moreover, when using for a transparent film, it should just contain the matrix components, such as a silica (polysiloxane) and transparent resin, and the titanium oxide type particle | grains of this invention.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to these Examples.

[Example 1]
Preparation of titanium oxide-based particles (1) Silica-based hollow fine particle dispersion (manufactured by Catalyst Kasei Kogyo Co., Ltd .: Thruria P1420, average particle size 50 nm, refractive index 1.30, solid content concentration 20% by weight, diluted 100 g) A silica-based hollow fine particle dispersion having a solid concentration of 5% by weight was added with 100 g of a titanium tetrachloride aqueous solution having a concentration of 2% by weight as TiO ₂ and ammonia water having a concentration of 4% by weight was added in 0.5 hour. Thus, a hydrated titanium oxide / silica hollow particle mixed slurry having a pH of 8.5 was obtained.

  Next, after standing at 40 ° C. for 2 hours for aging, this slurry was washed by filtration to obtain a mixed dispersion of hydrated titanium oxide / silica hollow particles having a solid content concentration of 4% by weight. The pH of the dispersion was 8.5.

After adding 13 g of 35% by weight hydrogen peroxide water to 500 g of the mixed dispersion, hydrothermal treatment was performed at 165 ° C. for 3 hours to prepare a titanium oxide-based particle (1) dispersion, which was applied to the ultrafiltration membrane method. Washed and concentrated to prepare a dispersion of titanium oxide particles (1) having a solid content of 20% by weight.

About the obtained titanium oxide-based particles (1), the average particle diameter, spherical coefficient, refractive index, thickness of the titanium oxide coating layer, crystal shape, characteristics (1) (glossiness (glare)) and characteristics (2) (Ultraviolet shielding performance: absorbance and transmittance) were measured, and the results are shown in the table.
The thickness of the titanium oxide coating layer was measured as the average particle size of the titanium oxide-based particles (1) and the average particle size of the silica-based hollow fine particles, and was shown as ½ of the difference in particle size.

Characteristics (1)
Titanium oxide particles (1) with a solid content of 20% by weight Dispersion is diluted to a solid content of 10% by weight.
It was.

A coating solution for forming a glossy film was prepared by mixing 90 parts by weight of a dispersion of titanium oxide particles (1) having a solid concentration of 10% by weight and 10 parts by weight of an aqueous polyvinyl alcohol solution. This coating solution was applied onto a PET film using a bar coater, dried at 90 ° C. for 2 hours, and then heat-treated at 140 ° C. for 2 hours to form a glossy film.

  About the obtained glossy film, the glossiness was measured under the conditions of an incident angle of 60 ° and a light receiving angle of 60 ° with a gloss meter (manufactured by Suga Test Instruments Co., Ltd .: Digital variable angle gloss meter UGV-5D). Is shown in the table.

Characteristics (2)
Titanium oxide particles (1) with a solid content of 20% by weight are diluted to a solid content of 0.005
% By weight. With respect to this dispersion, the absorbance at a wavelength of 300 nm and the transmittance at a wavelength of 400 nm were measured with a spectrophotometer (manufactured by Hitachi, Ltd .: Model 330), and the results are shown in Table 1.
In addition, the refractive index of particle | grains was evaluated with the following method.

Standard refractive index liquid method
(1) Take the particle dispersion in an evaporator and evaporate the dispersion medium.
(2) This is dried at 120 ° C. to obtain a powder.
(3) A standard refracting liquid having a known refractive index is dropped on a glass plate in a few drops, and the above powder is mixed therewith.
(4) The above operation (3) is performed with various standard refractive liquids, and the refractive index of the standard refractive liquid when the mixed liquid becomes transparent is used as the refractive index of the fine particles.

[Example 2]
Preparation of titanium oxide-based particles (2) A dispersion of titanium oxide-based particles (2) was prepared in the same manner as in Example 1 except that 6.5 g of 35% by weight hydrogen peroxide water was added. With respect to the obtained titanium oxide-based particles (2), the average particle diameter, spherical coefficient, refractive index, thickness of the titanium oxide coating layer, crystal shape, characteristics (1) and characteristics (2) were measured, and the results are shown in the table. .

[Example 3]
Preparation of titanium oxide-based particles (3) A titanium oxide-based particle (3) dispersion was prepared in the same manner as in Example 1, except that 52 g of hydrogen peroxide solution having a concentration of 35% by weight was added.
The obtained titanium oxide-based particles (3) were measured for average particle diameter, spherical coefficient, refractive index, titanium oxide coating layer thickness, crystal shape, characteristic (1) and characteristic (2), and the results are shown in Table 1. Show.

[Example 4]
Preparation of titanium oxide-based particles (4) Silica-based hollow fine particle dispersion (manufactured by Catalyst Kasei Kogyo Co., Ltd .: Thruria P1420, average particle size 50 nm, refractive index 1.30, solid content concentration 20% by weight) was diluted 100 g. A silica-based hollow fine particle dispersion having a solid content concentration of 5% by weight was obtained. To this was added 50 g of a titanium tetrachloride aqueous solution having a concentration of 2% by weight as TiO ₂ , and then ammonia water having a concentration of 4% by weight was added in 0.5 hour, and the hydrated titanium oxide-silica system having a pH of 8.5. A hollow fine particle mixed slurry was obtained. Next, after standing at 40 ° C. for 2 hours for aging, this slurry was washed by filtration to obtain a mixed dispersion of hydrated titanium oxide / silica hollow particles having a solid content concentration of 4% by weight. The pH of the dispersion was 8.5.

To 500 g of this mixed dispersion, 3.2 g of 35% by weight hydrogen peroxide water was added and then hydrothermally treated at 165 ° C. for 3 hours to prepare a titanium oxide-based particle (4) dispersion. Subsequently, it was washed by an ultrafiltration membrane method and concentrated to prepare a dispersion of titanium oxide particles (4) having a solid content concentration of 20% by weight.
The obtained titanium oxide-based particles (4) were measured for average particle diameter, spherical coefficient, refractive index, titanium oxide coating layer thickness, crystal shape, characteristic (1) and characteristic (2), and the results are shown in Table 1. Indicated.

[Example 5]
Preparation of titanium oxide-based particles (5) Silica-based hollow fine particle dispersion (manufactured by Catalyst Kasei Kogyo Co., Ltd .: Thruria P1420, average particle size 50 nm, refractive index 1.30, solid content concentration 20% by weight) was diluted 100 g. A silica-based hollow fine particle dispersion having a solid content concentration of 5% by weight was obtained. To this was added 300 g of a titanium tetrachloride aqueous solution having a concentration of 2% by weight as TiO ₂ , and ammonia water having a concentration of 4% by weight was further added in 0.5 hour, and the hydrated titanium oxide / silica hollow with pH = 8.5 was added. A fine particle mixed slurry was obtained. Next, after standing at 40 ° C. for 2 hours for aging, this slurry was washed by filtration to obtain a mixed dispersion of hydrated titanium oxide / silica hollow particles having a solid content concentration of 3.5% by weight. The pH of the dispersion was 8.5.

After adding 84 g of hydrogen peroxide water having a concentration of 35% by weight to 700 g of this mixed dispersion, hydrothermal treatment was performed at 165 ° C. for 3 hours to prepare a titanium oxide particle (5) dispersion. Subsequently, it was washed by an ultrafiltration membrane method and concentrated to prepare a dispersion of titanium oxide particles (5) having a solid content concentration of 20% by weight.
With respect to the obtained titanium oxide-based particles (5), the average particle diameter, spherical coefficient, refractive index, thickness of the titanium oxide coating layer, crystal shape, characteristics (1) and characteristics (2) were measured, and the results are shown in Table 1. Indicated.

[Example 6]
Preparation of Titanium Oxide-Based Particles (6) To the titanium oxide-based particle (1) dispersion prepared in the same manner as in Example 1, 15% by weight ammonia water was added to adjust the pH of the dispersion to 9.0. Subsequently, a hydrothermal treatment was performed at 165 ° C. for 3 hours to prepare a titanium oxide particle (6) dispersion. Subsequently, it was washed by an ultrafiltration membrane method and concentrated to prepare a titanium oxide-based particle (6) dispersion having a solid content of 20% by weight.
With respect to the obtained titanium oxide-based particles (6), the average particle diameter, spherical coefficient, refractive index, thickness of the titanium oxide coating layer, crystal shape, characteristics (1) and characteristics (2) were measured, and the results are shown in Table 1. Indicated.

[Example 7]
Preparation of Titanium Oxide-Based Particles (7) To a dispersion of titanium oxide-based particles (1) prepared in the same manner as in Example 1, tetramethylammonium hydroxide (TMAH) with a concentration of 25% by weight was added to adjust the pH of the dispersion. Was then 12.0, followed by hydrothermal treatment at 165 ° C. for 3 hours to prepare a dispersion of titanium oxide particles (7).
Subsequently, it was washed by an ultrafiltration membrane method and concentrated to prepare a titanium oxide-based particle (7) dispersion having a solid concentration of 20% by weight.
With respect to the obtained titanium oxide-based particles (7), the average particle diameter, spherical coefficient, refractive index, thickness of the titanium oxide coating layer, crystal form, characteristics (1) and characteristics (2) were measured, and the results are shown in Table 1. Indicated.

[Example 8]
In Preparation Example 1 of the titanium oxide-based particles (8), an alcohol solution of a concentration of 1% by weight of tetraisopropyl titanate as TiO ₂ in place of the concentration of 2% by weight of the aqueous titanium tetrachloride solution 100g as TiO ₂ 20
A hydrated titanium oxide / silica hollow particle mixed slurry was prepared in the same manner except that 0 g was used. After aging and washing, hydrogen peroxide was added and hydrothermal treatment was performed to prepare a titanium oxide particle dispersion. Subsequently, aqueous ammonia having a concentration of 15% by weight was added to adjust the pH of the dispersion to 8.5, and then hydrothermally treated at 165 ° C. for 3 hours to prepare a dispersion of titanium oxide particles (8). The dispersion was washed by an ultrafiltration membrane method and concentrated to prepare a dispersion of titanium oxide particles (8) having a solid concentration of 20% by weight.

Ammonia water having a concentration of 15% by weight was added to the obtained dispersion to adjust the pH of the dispersion to 9.0, and again hydrothermally treated at 165 ° C. for 3 hours to prepare a titanium oxide particle (8) dispersion. did. Subsequently, it was washed by an ultrafiltration membrane method and concentrated to prepare a dispersion of titanium oxide particles (8) having a solid content concentration of 20% by weight.
With respect to the obtained titanium oxide-based particles (8), the average particle diameter, spherical coefficient, refractive index, thickness of the titanium oxide coating layer, crystal shape, characteristics (1) and characteristics (2) were measured, and the results are shown in Table 1. Indicated.

[Example 9]
Preparation of titanium oxide-based particles (9) Silica-based hollow fine particle dispersion (manufactured by Catalyst Kasei Kogyo Co., Ltd .: Thruria P1420, average particle size 50 nm, refractive index 1.30, solid content concentration 20% by weight) was diluted 100 g. A silica-based hollow fine particle dispersion having a solid content concentration of 5% by weight was obtained.

Separately, 4 wt% ammonia water was added to 100 g of 2 wt% titanium tetrachloride aqueous solution as TiO ₂ to hydrolyze titanium tetrachloride to obtain a hydrated titanium oxide gel slurry. After the gel slurry was washed, 14 g of hydrogen peroxide solution having a concentration of 35% by weight was added and dissolved for 1 hour at 30 ° C. to prepare a peroxotitanic acid aqueous solution having a concentration of 1.7% by weight as TiO ₂ .

  Next, a peroxotitanic acid aqueous solution was added to the silica-based hollow fine particle dispersion and hydrothermally treated at 165 ° C. for 3 hours to prepare a titanium oxide-based particle dispersion. Next, tetramethylammonium hydroxide (TMAH) with a concentration of 25% by weight was added to adjust the pH of the dispersion to 12, and then hydrothermally treated at 165 ° C. for 3 hours to prepare a dispersion of titanium oxide particles (9). .

Subsequently, it was washed by an ultrafiltration membrane method and concentrated to prepare a dispersion of titanium oxide-based particles (9) having a solid content concentration of 20% by weight.
A dispersion of 15% by weight of ammonia water was added to adjust the pH of the dispersion to 9.0, and the mixture was again hydrothermally treated at 165 ° C. for 3 hours to prepare a titanium oxide-based particle (9) dispersion. Subsequently, it was washed by an ultrafiltration membrane method and concentrated to prepare a dispersion of titanium oxide-based particles (9) having a solid content concentration of 20% by weight.

Surface-treated titanium oxide particles (9) After 100 g of the dispersion was solvent-substituted with ethanol, 3 g of methacrylsilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503) was added and heat-treated at 50 ° C. Then, using an ultrafiltration membrane, the solvent was replaced with ethanol to prepare an alcohol dispersion of titanium oxide particles (9) having a solid content concentration of 20% by weight.
The obtained titanium oxide particles (9) were measured for average particle diameter, spherical coefficient, refractive index, titanium oxide coating layer thickness, crystal shape, characteristic (1) and characteristic (2), and the results are shown in the table. It was.

[Example 10]
Preparation of titanium oxide particles (10)
(i) Preparation of silica-based hollow fine particles Silica / alumina sol (manufactured by Catalytic Chemical Industry Co., Ltd .: USBB-120, average particle size 25 nm, SiO ₂ · Al ₂ O ₃ concentration 20% by weight, containing Al ₂ O _{3 in} solid content the amount 27 wt%) 100 g of a mixture of pure water 3900g was warmed to 98 ° C., while maintaining this temperature, concentration 1 as SiO _2.
2090 g of 5 wt% sodium silicate aqueous solution and 700 g of 0.5 wt% sodium aluminate aqueous solution as Al ₂ O ₃ were added to obtain a SiO ₂ .Al ₂ O ₃ particle dispersion. The pH of the reaction solution at this time was 12.0.

Next, 1,125 g of pure water was added to 500 g of the dispersion of the composite oxide fine particles (1) having a solid concentration of 13 wt% by washing with an ultrafiltration membrane, and concentrated hydrochloric acid (concentration 35.5 wt%). Was dropped to pH 1.0, and dealumination was performed. Next, while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, the aluminum salt dissolved in the ultrafiltration membrane is separated and washed to obtain a silica-based hollow fine particle precursor having a solid content concentration of 20% by weight (P-1-2). An aqueous dispersion was obtained.

Next, a mixed liquid of 150 g of an aqueous dispersion of silica-based hollow fine particle precursor (P-1-2), 500 g of pure water, 1,750 g of ethanol, and 626 g of ammonia water having a concentration of 28% by weight was heated to 35 ° C. Thereafter, 51 g of ethyl silicate (SiO ₂ concentration 28 wt%) was added to form a silica coating layer, and washed with an ultrafiltration membrane while adding 5 L of pure water to form a silica coating layer with a solid content concentration of 20 wt%. An aqueous dispersion of silica-based hollow fine particles (P-1-2) was obtained.

Next, aqueous ammonia was added to the silica-based hollow fine particle (P-1-2) dispersion having a silica coating layer to adjust the pH of the dispersion to 10.5, and then aged at 200 ° C. for 11 hours. Then, it is cooled to room temperature, ion-exchanged for 3 hours using 400 g of a cation exchange resin (Mitsubishi Chemical Corporation: Diaion SK1B), and further anion exchange resin (Mitsubishi Chemical Corporation: Diaion SA20A). Using 200 g for ion exchange for 3 hours, and using 200 g of cation exchange resin (Mitsubishi Chemical Co., Ltd .: Diaion SK1B) for ion exchange at 80 ° C. for 3 hours for washing, solid content concentration 20 weight An aqueous dispersion of silica-based fine particles (P-1-3) having a% solid content concentration of 20% by weight was obtained.

Next, again, the silica-based hollow fine particle (P-1-3) dispersion was hydrothermally treated at 150 ° C. for 11 hours, then cooled to room temperature, and a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: Diaion SK1B). Ion exchange was performed for 3 hours using 400 g, and further ion exchange was performed for 3 hours using 200 g of an anion exchange resin (Mitsubishi Chemical Corporation: Diaion SA20A). An aqueous dispersion of P-1-4) was obtained.
The refractive index and average particle diameter of the obtained silica-based hollow fine particles (P-1-4) were measured, and the results are shown in Table 1.

(ii) Formation of titanium oxide coating layer A silica-based hollow fine particle dispersion having a solid content concentration of 5% by weight was prepared by diluting 100 g of an aqueous dispersion of silica-based hollow fine particles (P-1-4) having a solid content concentration of 20% by weight. did. To this, 100 g of a titanium tetrachloride aqueous solution having a concentration of 2% by weight as TiO ₂ was added, and ammonia water having a concentration of 4% by weight was added in 0.5 hour, and the hydrated titanium oxide / silica hollow particles having a pH of 8.5. A mixed slurry was obtained. The slurry was allowed to stand at 40 ° C. for 2 hours for aging, followed by filtration and washing to obtain a mixed dispersion of hydrated titanium oxide / silica hollow particles having a solid concentration of 4% by weight. The pH of the dispersion was 8.5.

  To 500 g of this mixed dispersion, 13 g of hydrogen peroxide having a concentration of 35% by weight was added, followed by hydrothermal treatment at 165 ° C. for 3 hours to prepare a titanium oxide particle (10-1) dispersion. Subsequently, it was washed by an ultrafiltration membrane method and concentrated to prepare a dispersion of titanium oxide particles (10-2) having a solid content concentration of 20% by weight. Further, aqueous ammonia having a concentration of 15% by weight was added to adjust the pH of the dispersion to 9.0, and hydrothermal treatment was again performed at 165 ° C. for 3 hours to prepare a dispersion of titanium oxide particles (10). Subsequently, it was washed by an ultrafiltration membrane method and concentrated to prepare a dispersion of titanium oxide particles (10) having a solid content concentration of 20% by weight.

After the surface-treated titanium oxide-based particle (10) dispersion 100 g was solvent-substituted with ethanol, 3 g of methacrylsilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503) was added, and heat treatment was performed at 50 ° C. Then, the solvent was replaced with ethanol again using an ultrafiltration membrane to prepare an alcohol dispersion of titanium oxide-based particles (10) having a solid content concentration of 20% by weight.
With respect to the obtained titanium oxide-based particles (10), the average particle diameter, spherical coefficient, refractive index, thickness of the titanium oxide coating layer, crystal shape, characteristics (1) and characteristics (2) were measured, and the results are shown in Table 1. Indicated.

[Example 11]
Preparation of titanium oxide particles (11)
Surface treatment 100 parts of the titanium oxide particles (1) prepared in the same manner as in Example 1 were substituted with ethanol, and then 3 g of a methacrylsilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503) Was added, and heat treatment was performed at 50 ° C., and the solvent was replaced with ethanol again using an ultrafiltration membrane to prepare an alcohol dispersion of titanium oxide-based particles (11) having a solid content concentration of 20% by weight.
With respect to the obtained titanium oxide-based particles (11), the average particle diameter, spherical coefficient, refractive index, thickness of the titanium oxide coating layer, crystal shape, characteristics (1) and (2) were measured, and the results are shown in Table 1. It was.

[Comparative Example 1]
Preparation of Titanium Oxide Particles (R1) While stirring an aqueous solution of titanium sulfate having a concentration of 0.4% by weight as TiO ₂ , ammonia water having a concentration of 15% by weight was gradually added to obtain a white slurry having a pH of 8.5. The slurry was then filtered and washed to obtain a titania gel slurry having a solid content of 9% by weight. This cake 5.55 kg was mixed with 6.06 kg of hydrogen peroxide solution having a concentration of 33 wt% and 13.4 kg of water, heated at 80 ° C. for 5 hours, and an aqueous peroxotitanic acid solution having a concentration of 2.0 wt% as TiO _2. Got. At this time, the aqueous solution was brown and the pH was 8.1.

10 g of the obtained aqueous solution of peroxotitanic acid and 2000 g of water were mixed and heated at 95 ° C. for 2 hours to obtain a titania sol having a concentration of 0.01% by weight as TiO ₂ .
9 Kg of the previously prepared peroxotitanic acid aqueous solution (TiO ₂ concentration 2.0 wt%), 191 Kg of water and 130 g of titania sol (TiO ₂ concentration 0.01 wt%) were mixed and heated at 95 ° C. for 60 hours to oxidize. A dispersion of titanium particles (R1) was prepared.

The obtained titanium oxide particles (R1) were rod-shaped particles having a minor axis diameter of 11 nm, a major axis diameter of 57 nm, and an aspect ratio of 5.2. The crystal form was anatase and the refractive index was 2.1.
For the obtained titanium oxide-based particles (R1), the average particle diameter, spherical coefficient, refractive index, thickness of the titanium oxide coating layer, crystal form, characteristics (1) and characteristics (2) were measured, and the results are shown in Table 1. It was shown to.

[Comparative Example 2]
Preparation of titanium oxide particles (R2) Silica sol (manufactured by Catalyst Chemical Industry Co., Ltd .: SI-30, average particle size 12 nm, refractive index 1.4
4 and a solid content concentration of 40% by weight) was diluted to obtain a silica fine particle dispersion having a solid content concentration of 5% by weight. To this was added 100 g of a titanium tetrachloride aqueous solution with a concentration of 2% by weight as TiO ₂ , and then ammonia water with a concentration of 4% by weight was added in 0.5 hour, and the hydrated titanium oxide / silica fine particles having a pH of 8.5. A mixed slurry was obtained.

  Thereafter, the slurry was allowed to stand at 40 ° C. for 2 hours for aging, followed by filtration and washing to obtain a hydrated titanium oxide / silica fine particle mixed dispersion having a solid content concentration of 20% by weight. The pH of the dispersion was 8.5.

The obtained mixed dispersion was hydrothermally treated at 165 ° C. for 3 hours to prepare a titanium oxide particle (R2) dispersion. Subsequently, it was washed by an ultrafiltration membrane method and concentrated to prepare a titanium oxide particle (R2) dispersion having a solid concentration of 20% by weight. The titanium oxide particles (R2) were in an aggregated state. The crystal form was amorphous.
The obtained titanium oxide particles (R2) were measured for average particle diameter, spherical coefficient, refractive index, titanium oxide coating layer thickness, crystal shape, characteristic (1) and characteristic (2), and the results are shown in Table 1. It was shown to.

[Comparative Example 3]
Preparation of titanium oxide particles (R3) Silica sol (manufactured by Catalyst Chemical Industry Co., Ltd .: SI-30, average particle size 12 nm, refractive index 1.4
4 and a solid content concentration of 40% by weight) was diluted to obtain a silica fine particle dispersion having a solid content concentration of 5% by weight. To this, 100 g of a titanium tetrachloride aqueous solution having a concentration of 2% by weight as TiO ₂ , and a concentration of 4
Weight% aqueous ammonia was simultaneously added in 2 hours to obtain a mixed slurry of hydrated titanium oxide gel having pH = 8.5 and silica fine particles.

  The slurry was allowed to stand at 40 ° C. for 2 hours for aging, followed by filtration and washing to obtain a hydrated titanium oxide / silica fine particle mixed dispersion having a solid concentration of 20% by weight. The pH of the dispersion was 8.5.

  The obtained mixed dispersion was hydrothermally treated at 165 ° C. for 3 hours to prepare a titanium oxide particle (R3) dispersion, then washed by an ultrafiltration membrane method and concentrated to a solid concentration of 20% by weight. A dispersion of titanium oxide particles (R3) was prepared. The titanium oxide particles (R3) were in an aggregated state. The crystal form was amorphous.

  The resulting titanium oxide particles (R3) were measured for average particle diameter, spherical coefficient, refractive index, titanium oxide coating layer thickness, crystal shape, characteristic (1) and characteristic (2), and the results are shown in Table 1. It was shown to.

Claims (10)

It consists of silica-based hollow fine particles and a titanium oxide coating layer on the surface of the hollow fine particles,
The average particle size is in the range of 5 to 100 nm,
A titanium oxide-based particle having a refractive index in the range of 1.30 to 2.00.   2. The titanium oxide-based particles according to claim 1, wherein the silica-based hollow fine particles have an average particle diameter in the range of 3 to 100 nm and a refractive index in the range of 1.15 to 1.40. The average thickness of the titanium oxide coating layer is in the range of 0.1 to 20 nm (however, the thickness of the coating layer does not exceed 1/2 of the average particle diameter). The titanium oxide-based particles described. The titanium oxide particles according to any one of claims 1 to 3, wherein the titanium oxide particles have a spherical coefficient represented by the following formula (1) in a range of 0.5 to 1.
Spherical coefficient = (D _S ) / (D _L ) (1)
(However, (D _L ) is the longest average particle diameter, (D _S ) is the midpoint of the longest diameter and the average short diameter perpendicular to the longest diameter)   The titanium oxide particles according to any one of claims 1 to 4, wherein the titanium oxide coating layer is one or more types of titanium oxide selected from anatase type, rutile type, and brookite type. The titanium oxide-based particles according to any one of claims 1 to 5, wherein the titanium oxide-based particles are surface-treated with an organosilicon compound represented by the following formula (1) or a hydrolyzate thereof.
_{R n -SiX 4-n (1} )
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms or a silanol group) , Halogen, hydrogen, n: an integer of 0 to 3) The manufacturing method of the titanium oxide type particle | grains characterized by consisting of the following process (a)-(c).
(A) A step of hydrolyzing a silica-based hollow fine particle dispersion while adding a titanium compound aqueous solution or a titanium compound aqueous solution and an acid or alkali to precipitate a titanium compound hydrolyzate on the surface of the silica-based hollow fine particles.
(B) In a silica-based hollow fine particle dispersion having a titanium compound hydrolyzate deposited on the surface, the number of moles of hydrogen peroxide as H ₂ O ₂ (M _HP ) and the mole of titanium compound hydrolyzate as TiO ₂ the number (M _Ti) molar ratio of _{(M HP) / (M Ti} ) is the step of adding a hydrogen peroxide solution to be in the range of 2 to 50.
(C) A step of hydrothermally treating the dispersion at 80 to 350 ° C. The manufacturing method of the titanium oxide type particle | grains characterized by including the following process (ab)-(c).
(Ab) A step of adding a peroxotitanic acid aqueous solution to the silica-based hollow fine particle dispersion.
(C) A step of hydrothermally treating the dispersion at 80 to 350 ° C. The method for producing titanium oxide-based particles according to claim 6 or 7, wherein the following step (d) is performed after the step (c).
(D) A step of hydrothermally treating the dispersion adjusted to pH 7.5 to 13.5 at 80 to 350 ° C.   The method for producing titanium oxide-based particles according to any one of claims 6 to 8, wherein the average particle diameter is in the range of 5 to 500 nm and the refractive index is in the range of 1.3 to 2.0.