JP2013028563A - Titanium dioxide pigment for cosmetic and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a spherical anatase-type titanium dioxide pigment, which has mild concealment and a satisfactory feeling derived from shapes and surface conditions, moderately absorbs sebum secreted from skin, and maintains adhesion to skin when it is used by being blended into a cosmetic, and to provide a method for producing the spherical anatase-type titanium dioxide pigment.SOLUTION: Titanyl sulfate is hydrolyzed under the temperature of ≥170°C and also under the pressure of the saturated vapor pressure or more at the temperature to obtain spherical water-containing titanium dioxide. Next, the spherical water-containing titanium dioxide is fired at the temperature of 600 to 800°C to obtain spherical anatase-type titanium dioxide. In the obtained spherical anatase-type titanium dioxide, the average particle diameter is 0.1 to 5 μm, the peak of the diameter of fine pores in a pore distribution measured by a nitrogen adsorption method is 5 to 50 nm, and further, pore volume lies in the range of 0.05 to 0.3 cm/g.

Description

  The present invention relates to a titanium dioxide white pigment. More specifically, the present invention relates to a titanium dioxide white pigment that gives a mild and natural hiding property, elongation at the time of application, touch feeling, and durability of a cosmetic effect after application to a blended cosmetic.

  In recent years, makeup cosmetics such as foundation, concealer, white powder, blusher, eye shadow, eyebrow, lipstick, etc. have excellent extensibility on the skin when applied, good touch, and good adhesion to the skin. There is a demand for it to be good and have a natural finish after application, and that it will last and have little makeup collapse. However, conventional titanium dioxide white pigments are irregular particles of 0.2 to 0.3 μm and exhibit high hiding properties in paints and plastics. However, they have strong cohesive strength in cosmetics and have excellent extensibility when applied. There was a tendency to hinder, whitening and unnatural finish.

  Therefore, for such a problem, for example, as a titanium oxide white pigment having an effect of excellent extensibility on the skin at the time of application, Patent Document 1 has a primary particle size of 0.5 to 2.0 μm. Particulate titanium dioxide is disclosed. Further, for example, as titanium dioxide having excellent sliding properties when blended in cosmetics, Patent Document 2 is formed from small spherical particles of titanium dioxide having an average primary particle diameter of 0.01 to 0.07 μm. A spherical titanium dioxide aggregate of 0.1 to 3 μm is disclosed.

WO2004 / 052786 JP 2000-191325 A

  The titanium dioxide described in Patent Document 1 has a large primary particle size of 0.5 to 2.0 μm and thus has a low cohesive force and improves the extensibility and finish during coating, but the particle surface is smooth. For this reason, problems such as stickiness due to oily components in cosmetics and sebum secreted from the skin, detachment from the skin, so-called makeup collapse cannot be solved. In addition, the spherical titanium dioxide aggregate described in Patent Document 2 can be expected to improve the stickiness due to the penetration of oily components into the gaps between the small spherical particles in addition to the improvement of the extensibility on the skin due to the large particle size. The size of the gap is not controlled and the effect is insufficient, the oil is absorbed so as to impair the function of the cosmetic, and the aggregate breaks into single small spherical particles that extend There is a risk of hindering the effects of sex and concealment.

  In other words, the titanium dioxide white pigments that have been improved so far have excellent elongation and feel when applied, but they are not always satisfactory for the needs for higher functionality and diversification of cosmetics. There has been a demand for improvement in adhesion during coating, finishing after coating, and sustainability of these effects.

Therefore, in order to solve such problems, the present inventors have intensively studied, and as a result, the peak of the pore distribution measured by the nitrogen adsorption method is 5 to 50 nm, and the pore volume is 0.05 to 0.00. When a spherical anatase-type titanium dioxide having a mean particle size of 0.1 to 5 μm in a range of ³ cm ³ / g is blended in cosmetics, the extensibility at the time of application, touch, adhesion, and natural after application The inventors have found that the finish and sustainability of the effect are greatly improved, and have completed the present invention.

  The spherical anatase-type titanium dioxide is obtained by a conventionally known hydrolysis method, ie, a method of hydrolyzing titanyl sulfate at a temperature of 170 ° C. or higher and a pressure equal to or higher than the saturated vapor pressure of the temperature. It is found that titanium dioxide can be obtained and then calcined at a temperature of 600 to 800 ° C. or can be produced by immersing the spherical hydrous titanium dioxide in hydrochloric acid and then calcining at a temperature of 400 to 600 ° C. Completed the invention.

That is, the present invention
(1) Spherical anatase-type titanium dioxide having an average particle size of 0.1 to 5 μm, having a pore diameter peak in the pore distribution measured by the nitrogen adsorption method at 5 to 50 nm, and having a pore volume of A titanium dioxide pigment for cosmetics in the range of 0.05 to 0.3 cm ³ / g,
(2) Titanyl sulfate is hydrolyzed at a temperature of 170 ° C. or higher and a pressure equal to or higher than the saturated vapor pressure of the temperature to obtain spherical hydrous titanium dioxide, and then the spherical hydrous titanium dioxide is heated to 600 to 800 ° C. The method for producing a titanium dioxide pigment for cosmetics according to (1), which is fired at a temperature;
(3) Titanyl sulfate was hydrolyzed at a temperature of 170 ° C. or higher and a pressure equal to or higher than the saturated vapor pressure of the temperature to obtain spherical hydrous titanium dioxide, and then the spherical hydrous titanium dioxide was immersed in hydrochloric acid. (1) The method for producing a titanium dioxide pigment for cosmetics according to (1), which is later fired at a temperature of 400 to 600 ° C.

  The present invention relates to a spherical anatase-type titanium dioxide pigment having a pore diameter peak and pore volume in a pore distribution measured by a nitrogen adsorption method in a specific range, and having a specific average particle size, When used in a blend, it has a mild hiding property and a good feel derived from its shape and surface condition, and absorbs sebum secreted from the skin to maintain its close contact with the skin. Can be used as a pigment in cosmetics.

  The titanium dioxide pigment of the present invention is used in cosmetics and has anatase type crystals. Moreover, it has a spherical particle shape, and the average particle diameter is 0.1 to 5 μm, preferably 0.1 to 1 μm, and more preferably 0.3 to 0.5 μm. If the average particle size is larger than 5 μm, the particle size distribution width of the particles is widened and the shape factor is small, which is not desirable. If the average particle size is smaller than 0.1 μm, the particles tend to aggregate and become irregular, and the shape factor is small. Therefore, it is not desirable. The spherical shape may be roughly spherical when observed with an electron micrograph, but the shape factor is preferably 0.7 to 1.0, more preferably a true sphere of 0.9 to 1.0. . If the shape factor is smaller than the above range, the particle shape is not necessarily desirable although it is a true spherical shape.

  In the present invention, the crystal form of the titanium dioxide pigment is confirmed by X-ray diffraction, and the particle shape is confirmed by an electron micrograph. In the present invention, the average particle size and shape factor are specifically determined as follows. First, a transmission electron micrograph (magnification 20000 times) of the obtained titanium dioxide pigment is subjected to image analysis using an image analysis apparatus manufactured by Nireco, and the area and maximum particle diameter (L) of each of about 100 particles are measured. . Next, based on the value of the area of the obtained particle, the diameter (D) when the particle is assumed to be a perfect circle is obtained. The number average value of the diameters (D) is defined as the average particle diameter (MD) of the particles. Moreover, let the average value of ratio (D / L) of the said diameter (D) and the largest particle diameter (L) be a shape factor of particle | grains.

The titanium dioxide pigment of the present invention has a porous shape and has mesopores in a diameter range of 5 to 50 nm, specifically, pores in a pore distribution measured by a nitrogen adsorption method in a range of 5 to 50 nm. Has a peak in diameter. Moreover, the pore volume is in the range of 0.05 to 0.3 cm ³ / g. By having such a porous state, when blended in cosmetics and used, the particles adhere to the skin with an appropriate strength, resulting in a uniform and smooth finish, and absorbing an appropriate oil content. It has excellent effects such as improved stickiness and makeup collapse.

The peak of the pore diameter is preferably in the range of 10 to 30 nm, and the pore volume is more preferably in the range of 0.05 to 0.15 cm ³ / g. If the pore diameter or pore volume is too small, that is, the particle surface will be smooth, the adhesion to the skin will be weak, whitening will occur due to uneven makeup, etc., oil absorption will be lost, The sticky and make-up breakage improvement effect is not exhibited. On the other hand, if the pore diameter or pore volume is too large, it will absorb a large amount of oil necessary for the cosmetic function, impairing the cosmetic function and causing thickening, and the particle surface is coated coarsely. The feeling of time gets worse.

The pore diameter peak and pore volume are determined by measuring the specific surface area by the nitrogen adsorption method (BET method) and the mesopore distribution, diameter peak, volume, etc. by BJH analysis from the measured adsorption isotherm. calculate. Nitrogen adsorption method specific surface area measured by (BET method) is preferably about 10 to 100 m ² / g, about 10 to 70 m ² / g is more preferable.

  The anatase-type titanium dioxide pigment of the present invention has a whiteness comparable to that of conventional titanium dioxide pigments, but is made of a metal such as iron, copper, cerium, vanadium, antimony, chromium, tungsten, manganese, and cobalt. It may contain compounds and in this case has various hues. In particular, when an iron compound such as iron oxide is contained, it becomes a preferred beige color for cosmetics. Further, a metal compound such as aluminum, zinc, phosphorus or iron may be contained inside the titanium dioxide pigment particles. In this case, the oxidation activity and photoactivity peculiar to titanium dioxide are suppressed, which is preferable.

  The particle surface of the titanium dioxide pigment of the present invention is preferably coated with silicon oxide and / or aluminum oxide. Examples of the silicon oxide and aluminum oxide include at least one compound selected from silicon, an anhydrous oxide of aluminum, a hydrated oxide, and a hydrated oxide. The coating state is porous. Or may be dense and can be selected as appropriate. Each of them can be coated alone, or can be used in combination by laminating or mixing them. In particular, it is more preferable to coat the surface of titanium dioxide particles with silicon oxide and then coat the surface with aluminum oxide.

These preferable coating amounts are in the range of 0 to 10% by weight of silicon oxide in terms of SiO ₂ and 1 to 1 in terms of Al ₂ O _{3 with} respect to the weight basis of titanium dioxide particles in terms of TiO ₂ . It is in the range of 10% by weight. More preferably, each coating amount is in the range of 2 to 5% by weight and 1 to 6% by weight with respect to the weight basis of the titanium dioxide particles in terms of TiO ₂ .

  In the present invention, in addition to silicon oxide and aluminum oxide, inorganic compounds other than these may be coated. Examples of inorganic compounds include oxides such as zirconium, tin, titanium, and antimony, hydroxides, and phosphates.

Moreover, it is preferable that the particle surface of the titanium dioxide pigment of the present invention is coated with a silicone compound and / or a fluorine surfactant. Examples of the silicone compound include methyl hydrogen polysiloxane, trimethylsiloxysilicic acid, fluoroalkyl / polyoxyalkylene co-modified silicone, and the like. Examples of the fluorine surfactant include perfluoroalkyl phosphate esters and perfluoroalkyl carboxylates. The coating amount of the silicone compound and the fluorosurfactant is preferably in the range of 0.1 to 5% by weight and more preferably in the range of 0.1 to 2% by weight with respect to the weight basis of the titanium dioxide particles in terms of TiO ₂ .

  In the present invention, an organic compound other than these may be coated in addition to the silicone compound and the fluorine surfactant. Examples of organic compounds include polyol compounds (trimethylolpropane, trimethylolethane, ditrimethylolpropane, trimethylolpropane ethoxylate, pentaerythritol, etc.), alkanolamine compounds (monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine). , Triethanolamine, tripropanolamine, etc.) and derivatives thereof (acetate, oxalate, tartrate, formate, benzoate, etc.). Among these, a polyol compound is preferable because it has a high effect of improving dispersibility, and trimethylolpropane and trimethylolethane are more preferable. More preferably, the silicone compound, the fluorine surfactant and other organic compounds are coated on a coating of an inorganic compound such as silicon oxide or aluminum oxide.

  The titanium dioxide pigment of the present invention is obtained by hydrolyzing titanyl sulfate at a temperature of 170 ° C. or higher and a pressure equal to or higher than the saturated vapor pressure of the temperature to obtain spherical hydrous titanium dioxide. It can be manufactured by firing at a temperature of 600 to 800 ° C. As another method, the spherical hydrous titanium dioxide obtained by hydrolyzing under pressure by the above method can be produced by immersing it in hydrochloric acid and then baking it at a temperature of 400 to 600 ° C. Details of each step will be described below.

  First, spherical water-containing titanium dioxide is produced by hydrolyzing titanyl sulfate at a temperature of 170 ° C. or higher and a pressure equal to or higher than the saturated vapor pressure of the temperature.

  The titanyl sulfate solution is a purified titanyl sulfate solution, a solution containing impurities such as iron sulfate obtained by leaching titanium ore with sulfuric acid, metatitanic acid or hydrous titanium dioxide obtained by neutralizing titanyl sulfate with an alkali, etc. A solution in which

The titanyl sulfate solution is put in a pressure vessel, and the vessel is sealed, and then heated to a predetermined temperature for hydrolysis. The concentration of titanyl sulfate is about 0.05 to 5 mol / l, preferably 0.5 to 3 mol / l in terms of TiO ₂ standard. If necessary, when adjusting the concentration of titanyl sulfate, the concentration of free sulfuric acid may be adjusted to about 50 to 800 g / l, preferably 150 to 400 g / l.

  The temperature at the time of hydrolysis is 170 ° C. or higher, desirably 180 ° C. to 300 ° C. When the temperature is lower than 170 ° C., it becomes difficult to obtain spherical hydrous titanium dioxide having a desired size and shape.

The pressure during hydrolysis is about the saturated vapor pressure at the temperature or higher than the saturated vapor pressure, preferably about 0 to 10 kg / cm ² higher than the saturated vapor pressure at the temperature. When the temperature at the time of hydrolysis is higher than 300 ° C. or when the pressure at the time of hydrolysis is significantly higher than the saturated vapor pressure, it is not preferable because usable devices are limited.

  The reaction time for hydrolysis is suitably 0.5 to 10 hours. After being hydrolyzed in this manner, it is cooled to an appropriate temperature, separated, washed as necessary, and dried to obtain spherical hydrous titanium dioxide.

Subsequently, the spherical hydrous titanium dioxide thus obtained is fired at a temperature of 600 to 800 ° C., and is a spherical anatase type titanium dioxide having an average particle diameter of 0.1 to 5 μm, which is measured by a nitrogen adsorption method. A titanium dioxide pigment for cosmetics having a pore diameter peak in the pore distribution of 5 to 50 nm and a pore volume in the range of 0.05 to 0.3 cm ³ / g. it can.

  When the firing temperature is higher than 800 ° C., the pore diameter becomes too large, the shape factor becomes small due to inter-particle sintering, etc., or the rutile type titanium dioxide partially generates and changes its shape. Not desirable. On the other hand, when the temperature is lower than 600 ° C., the pore diameter becomes too small or the pore volume becomes too large.

  In addition, the titanium dioxide pigment of the present invention can be produced by immersing the spherical hydrous titanium dioxide obtained by hydrolyzing titanyl sulfate under pressure, followed by firing at a temperature of 400 to 600 ° C. . Spherical hydrous titanium dioxide contains a large amount of sulfate radicals, but when immersed in hydrochloric acid, the residual amount of sulfate radicals can be reduced by a substitution reaction. For this reason, it can be fired at a lower temperature than when not immersed in hydrochloric acid.

Specifically, spherical water-containing titanium dioxide obtained by immersing in hydrochloric acid and then washing and drying, if necessary, is fired at a temperature of 400 to 600 ° C., and the average particle size is 0.1 to 0.1. 5 μm spherical anatase-type titanium dioxide having a pore diameter peak in a pore distribution measured by a nitrogen adsorption method of 5 to 50 nm and a pore volume of 0.05 to 0.3 cm ³ / g The titanium dioxide pigment used by blending with cosmetics in the range can be produced.

  When the firing temperature is higher than 600 ° C., the pore diameter becomes too large, the shape factor becomes small due to inter-particle sintering, etc., or the rutile type titanium dioxide partially generates and changes its shape. Not desirable. On the other hand, when the temperature is lower than 400 ° C., the pore diameter becomes too small or the pore volume becomes too large.

  The firing time is suitably about 0.5 to 10 hours. As a device used for firing, a general firing furnace such as a rotary furnace can be used. The spherical anatase-type titanium dioxide pigment of the present invention obtained by firing hardly retains the interparticle sintering during firing, and maintains the shape of spherical hydrous titanium dioxide. The anatase-type titanium dioxide pigment of the present invention can be crushed or pulverized with a crusher or the like depending on the application.

  If necessary, the particle surface of the spherical anatase-type titanium dioxide pigment is coated with silicon oxide or aluminum oxide. For this purpose, a spherical anatase-type titanium dioxide pigment is first dispersed in water, and wet pulverization is preferably performed using a vertical sand mill, horizontal sand mill, or the like to prepare an aqueous slurry. At this time, it is preferable to adjust the pH of the aqueous slurry to 9 or more because the spherical anatase-type titanium dioxide pigment is stably dispersed in water. Moreover, you may use dispersing agents, such as silicic acid compounds, such as phosphoric acid compounds, such as sodium hexametaphosphate and sodium pyrophosphate, sodium silicate, and potassium silicate, as needed. The solid content concentration of the spherical anatase-type titanium dioxide pigment in the aqueous slurry is in the range of 50 to 800 g / l, preferably in the range of 100 to 500 g / l.

  Then, after adding a silicon compound and an aluminum compound to an aqueous slurry, a neutralizing agent is added, or if a silicon compound, an aluminum compound and a neutralizing agent are added simultaneously, the silicon oxide and the aluminum compound are added. Covered. Examples of the salt of the silicon compound include sodium silicate and potassium silicate. Examples of the aluminum compound salt include sodium aluminate, aluminum sulfate, and aluminum nitrate. Further, as the neutralizing agent, if it is a basic compound, hydroxides or carbonates such as alkali metals and alkaline earth metals, ammonium compounds such as ammonia, amines, etc., if acidic compounds, sulfuric acid And inorganic acids such as hydrochloric acid, and organic acids such as acetic acid and formic acid.

  As for the silicon oxide coated on the particle surface of the spherical anatase-type titanium dioxide pigment, porous treatment and dense treatment are known, and the porous silicon oxide coating can be obtained by the above-described method. If the dense silicon oxide is coated, a known method described in JP-A-53-33228 can be applied. If the method described in JP-A-53-33228 is used, the slurry preferably has a pH of 9-10. While maintaining the spherical anatase-type titanium dioxide pigment slurry at a temperature in the range of 80-100 ° C. While maintaining in the range of 5, sodium silicate is added rapidly and then neutralized at a pH of 9-10.5, after which a temperature in the range of 80-100 ° C. is held for 50-60 minutes. Or the method of neutralizing a silicic acid compound over 30 minutes can also be used. In this method, the neutralization is more preferably performed over 1 hour. If the neutralization pH is in the range of 4 to 7.5 and the temperature of the aqueous slurry at the time of neutralization is 80 ° C. or higher, it is preferable because a denser coating is easily formed. The range of more preferable neutralization pH is 4.5-7, and the neutralization temperature is 90 degreeC or more.

  Moreover, the particle | grain surface of a spherical anatase type titanium dioxide pigment is coat | covered with a silicone compound and / or a fluorosurfactant as needed. For example, a spherical anatase-type titanium dioxide pigment and a silicone compound and / or a fluorine surfactant can be coated by using a dry pulverizer or a high-speed stirrer and stirring and mixing them. In particular, a method using a dry pulverizer is preferable because the pulverization of the spherical anatase-type titanium dioxide pigment and the coating with the organic compound can be performed simultaneously. As the dry pulverizer, an airflow pulverizer such as a jet mill having good pulverization efficiency and excellent mixing properties is preferably used. Moreover, it can also coat | cover by adding a silicone compound and / or a fluorosurfactant to the aqueous | water-based slurry of a spherical anatase type titanium dioxide pigment.

  In the present invention, when an inorganic compound other than silicon oxide and aluminum oxide is coated on the particle surface of the spherical anatase-type titanium dioxide pigment, the same method as the coating of silicon oxide and aluminum oxide can be used. . Also, when the particle surface of the spherical anatase-type titanium dioxide pigment is coated with an organic compound other than the silicone compound and the fluorine surfactant, the same method as that for coating the silicone compound and the fluorine surfactant can be used. If the surface of spherical anatase-type titanium dioxide pigment particles is coated with an organic compound, use a spherical anatase-type titanium dioxide pigment coated with silicon oxide or aluminum oxide, a dry grinder or a high-speed stirrer. It is preferable to stir and mix. Spherical anatase-type titanium dioxide pigment coated with inorganic compounds such as silicon oxide and aluminum oxide, organic compounds such as silicone compounds and fluorine surfactants, dehydrated and solid-liquid separated from the slurry and dried, if necessary Can be dry pulverized. For dehydration, for example, a filter press, a roll press, or the like can be used. For example, a band heater, a batch heater, or the like can be used for drying. For the dry pulverization, for example, an impact pulverizer such as a hammer mill or a pin mill, a pulverizer or the like, a grinding pulverizer, an airflow pulverizer such as a jet mill, or a spray dryer such as a spray dryer can be used.

  The spherical anatase-type titanium dioxide pigment of the present invention is used by blending with cosmetics. The amount blended into the cosmetic can not be defined unconditionally depending on the dosage form of the cosmetic and other blending components in view of a more specific purpose, but is generally 0.1 to 0.1% of the entire cosmetic. 60.0% by weight is preferable, and 1.0 to 40.0% by weight is particularly preferable. If it is less than 0.1% by weight, a sufficient effect may not be obtained, and if it exceeds 60.0% by weight, the usability may be deteriorated.

  In cosmetics, in addition to the spherical anatase-type titanium dioxide pigment of the present invention, other components usually used in cosmetics and pharmaceuticals, for example, other powder components, liquid fats and oils, solid fats and oils, as long as the effect is not impaired Wax, hydrocarbon, higher alcohol, ester, silicone, anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant, moisturizer, water-soluble polymer, thickener, film agent, UV absorption Agent, sequestering agent, lower alcohol, polyhydric alcohol, sugar, amino acid, organic amine, polymer emulsion, pH adjuster, skin nutrient, vitamin, antioxidant, antioxidant aid, fragrance, water, etc. are required Depending on the dosage form, it can be prepared by a conventional method according to the intended dosage form.

  Cosmetics can be widely applied to cosmetics, pharmaceuticals, and quasi drugs that are applied to the outer skin. The dosage form is arbitrary, such as solution system, solubilization system, emulsification system, powder dispersion system, water-oil two-layer system, water-oil-powder three-layer system, gel, aerosol, mist, capsule, etc. It can be provided in the form. In addition, the product form of the cosmetic is also arbitrary, facial cosmetics such as lotion, milky lotion, cream and pack; makeup cosmetics such as foundation, funny, blusher, lipstick, eye shadow, eyeliner, mascara and sunscreen; Body cosmetics; Aromatic cosmetics; Makeup removers, facial cleansers, skin cleansers such as body shampoos; hair cosmetics such as hair rinses and shampoos; ointments; bath preparations; It can be applied in any form.

  Hereinafter, preferred embodiments of the present invention will be described in more detail. In addition, this invention is not limited by this.

Example 1
An aqueous solution of titanyl sulfate having a concentration of 150 g / dm ^{3 in} terms of TiO ₂ was charged into an autoclave, a nucleating agent for hydrolysis was added, and the pressure was higher than the saturated vapor pressure of 100 kg / cm ² at a temperature of 250 ° C. for 4 hours. Then, it was hydrolyzed, filtered, washed and dried to obtain a spherical hydrous titanium dioxide dry powder. The dried powder was calcined at 700 ° C., the average particle diameter was 380 nm, the pore diameter peak in the pore distribution measured by the nitrogen adsorption method was 12 nm, and the pore volume was 0.19 cm ³ / g. Porous spherical anatase-type titanium dioxide particles (a) were obtained. The specific surface area of the particles was 27 m ² / g, and the shape factor was 0.95.
The particle shape of the sample was confirmed by observing a transmission electron micrograph (magnification 20000 times). Further, the average particle diameter and shape factor were calculated by analyzing a transmission electron micrograph (magnification 20000 times) of about 100 particles with an image analysis apparatus manufactured by Nireco.
The crystal form was confirmed by X-ray diffraction. BELSOPR-miniII manufactured by Nippon Bell Co., Ltd. was used for measurement of specific surface area, peak of pore diameter, and pore volume.

Example 2
In Example 1, except that the firing temperature was 620 ° C., the average particle diameter was 400 nm, and the peak of the pore diameter in the pore distribution measured by the nitrogen adsorption method was 5.2 nm. Moreover, porous spherical anatase-type titanium dioxide particles (b) having a pore volume of 0.12 cm ³ / g were obtained. The specific surface area of these particles was 47 m ² / g, and the shape factor was 0.96.

Example 3
In Example 1, except that the calcination temperature is 780 ° C., the average particle size is 350 nm, the peak of the pore diameter in the pore distribution measured by the nitrogen adsorption method is 40 nm, and Then, porous spherical anatase-type titanium dioxide particles (c) having a pore volume of 0.13 cm ³ / g were obtained. The specific surface area of these particles was 16 m ² / g, and the shape factor was 0.93.

Example 4
An aqueous solution of titanyl sulfate having a concentration of 150 g / dm ^{3 in} terms of TiO ₂ was charged into an autoclave, a nucleating agent for hydrolysis was added, and the pressure was higher than the saturated vapor pressure of 100 kg / cm ² at a temperature of 250 ° C. for 4 hours. Then, it was hydrolyzed, filtered, washed and dried to obtain a spherical hydrous titanium dioxide dry powder. 150 g of this dry powder was suspended in 500 cm ³ of 7% hydrochloric acid, heated to 60 ° C. and stirred for 1 hour, then neutralized with 20% aqueous sodium hydroxide solution, filtered and washed. The obtained washed cake was baked at 500 ° C., the average particle size was 400 nm, the peak of the pore diameter in the pore distribution measured by the nitrogen adsorption method was 12 nm, and the pore volume was 0.14 cm ³ / g of porous spherical anatase-type titanium dioxide particles (d) were obtained. The specific surface area of the particles was 28 m ² / g, and the shape factor was 0.97.

Example 5
In Example 4, the average particle diameter is 400 nm and the peak of the pore diameter in the pore distribution measured by the nitrogen adsorption method is 6.1 nm, except that the firing temperature is 420 ° C. Moreover, porous spherical anatase-type titanium dioxide particles (e) having a pore volume of 0.07 cm ³ / g were obtained. The specific surface area of these particles was 51 m ² / g, and the shape factor was 0.94.

Example 6
In Example 4, the average particle diameter was 390 nm, and the peak of the pore diameter in the pore distribution measured by the nitrogen adsorption method was 38 nm, except that the firing temperature was 580 ° C., and Then, porous spherical anatase type titanium dioxide particles (f) having a pore volume of 0.10 cm ³ / g were obtained. The specific surface area of the particles was 14 m ² / g and the shape factor was 0.95.

Example 7
The titanium dioxide particles (d) obtained in Example 4 were adjusted to an aqueous slurry having a TiO ₂ concentration of 200 g / dm ³ , and 0.4% by weight of sodium hexametaphosphate as P ₂ O ₅ was added to the titanium dioxide weight. The mixture was wet pulverized with a bead mill and coarsely separated with 200 mesh to obtain a titanium dioxide slurry. The slurry after coarse grain separation was adjusted to 200 g / dm ³ , heated to 70 ° C., and 3 wt% sodium silicate aqueous solution in terms of SiO _{2 was} added over 30 minutes to TiO ₂ minutes, and 85 ° C. The temperature was raised to. After stirring for 30 minutes, dilute sulfuric acid was slowly added dropwise over 40 minutes to neutralize to pH 7.0.
Subsequently, the titanium dioxide slurry was cooled to 70 ° C., adjusted to pH 5.5 with dilute sulfuric acid, and 1 wt% sodium aluminate aqueous solution in terms of Al ₂ O ₃ was added to TiO ₂ minutes over 30 minutes. Added. After stirring for 30 minutes, the pH was adjusted again to 5.5 with dilute sulfuric acid, washed by filtration, dried at 120 ° C., and air-flow pulverized to obtain porous spherical anatase-type titanium dioxide particles (g). These particles had an average particle diameter of 400 nm, a peak of pore diameter in the pore distribution measured by the nitrogen adsorption method was 8.0 nm, and a pore volume of 0.09 cm ³ / g. Moreover, the specific surface area of this particle | grain was 25 m < ² > / g, and the shape factor was 0.96.

Comparative Example 1
In Example 1, except that the calcination temperature is 400 ° C., the average particle diameter is 400 nm, and the peak of the pore diameter in the pore distribution measured by the nitrogen adsorption method is 2.4 nm, as in Example 1. Moreover, porous spherical anatase-type titanium dioxide particles (h) having a pore volume of 0.08 cm ³ / g were obtained. The specific surface area of these particles was 105 m ² / g, and the shape factor was 0.96.

Comparative Example 2
In Example 1, except that the firing temperature is 900 ° C., the average particle size is 200 nm, the peak of the pore diameter in the pore distribution measured by the nitrogen adsorption method is 72 nm, and Thus, porous spherical anatase-type titanium dioxide particles (i) having a pore volume of 0.07 cm ³ / g were obtained. The specific surface area of these particles was 5 m ² / g, and the shape factor was 0.77.

Comparative Example 3
A nucleating agent for hydrolysis was added to an aqueous solution of titanyl sulfate having a concentration of 200 g / dm ^{3 in} terms of TiO ₂ , and thermal hydrolysis was performed at 105 ° C. under atmospheric pressure. The cake obtained by filtering and washing the precipitate was added to a 0.2 wt% aluminum sulfate solution in terms of Al ₂ O ₃ , a 0.4 wt% potassium hydroxide solution in terms of K ₂ CO ₃ , and ZnO to TiO ₂ minutes. Zinc white was added and mixed so as to be 0.4% by weight in terms of conversion, and evaporated to dryness. The dried product was pulverized with a sample mill and fired at 980 ° C. to obtain rutile amorphous titanium dioxide particles (j) having a particle size of 1 μm. With respect to the titanium dioxide particles, data indicating the presence of pores could not be obtained even when the pore distribution was measured by the nitrogen adsorption method. The specific surface area of the particles was 2 m ² / g, and the shape factor was 0.52.

Comparative Example 4
Aqueous hydrogen peroxide in an aqueous titanyl sulfate solution of concentration of 200 g / dm ³ in terms of TiO ₂ was added 5% by weight relative to TiO ₂ minutes _H 2 _{O 2} converted, under a pressure of 20 kg / cm ^2, the 220 ° C. The hydrolysis was carried out at temperature for 4 hours. After the resulting reaction solution was allowed to cool to 40 ° C., the precipitate was filtered from the reaction solution, washed, and dried, so that the average particle size was 500 nm, and the pores in the pore distribution measured by the nitrogen adsorption method A spherical titanium dioxide aggregate (k) having a diameter peak of 3.2 nm and a pore volume of 0.35 cm ³ / g was obtained. The specific surface area of the particles was 370 m ² / g, and the shape factor was 0.92.

Evaluation Example A cream foundation was prepared using the titanium dioxide obtained in Examples 1 to 7 and Comparative Examples 1 to 4. The following oil phase component and aqueous phase component were heated and mixed at 70 ° C., respectively, and then the oil phase was slowly poured into the aqueous phase maintained at 70 ° C. and then emulsified with a homomixer. Subsequently, it cooled to room temperature, stirring, and obtained cosmetics.
<Oil phase>
NIKKOL Decaglyn 5-HS 2.0 wt%
NIKKOL Hexaglyn PR-15 0.6% by weight
NIKKOL Squalane 2.0% by weight
NIKKOL CIO 8.0 wt%
NIKKOL IPM-EX 4.0 wt%
Decamethylcyclopentasiloxane 19.0% by weight
Iron oxide 1.0% by weight
Titanium dioxide 10.0% by weight
<Water phase>
Glycerin 5.0% by weight
Magnesium sulfate heptahydrate 0.5% by weight as MgSO ₄
Purified water balance

Five panelists evaluated the feel of the cream foundation (no creaking, good extensibility), natural finish, mild hiding power that is not too strong but not too weak, and makeup retention. The number of panelists judged to be excellent was evaluated according to the following classification. The evaluation results are shown in Table 1.
◎: 4 or more people, ○: 2-3 people, △: 1 people, X: 0 people

  The titanium dioxide pigment of the present invention is a porous spherical anatase-type titanium dioxide, and when used in cosmetics, it has a mild hiding property and a good feel derived from the shape and surface state and is secreted from the skin. Since sebum is absorbed moderately and the adhesion to the skin is maintained, it is useful as a pigment for various cosmetics.

Claims (7)

Spherical anatase-type titanium dioxide having an average particle diameter of 0.1 to 5 μm, the peak of the pore diameter in the pore distribution measured by the nitrogen adsorption method is 5 to 50 nm, and the pore volume is 0.05 A titanium dioxide pigment for cosmetics in the range of ~ 0.3 cm ³ / g. There peak pore diameter in the 10 to 30 nm, moreover, cosmetic titanium dioxide pigment according to claim 1 pore volume is 0.05~0.15cm ³ / g.   The titanium dioxide pigment for cosmetics according to claim 1 or 2, wherein the shape factor is 0.9 to 1.0.   The titanium dioxide pigment for cosmetics according to any one of claims 1 to 3, wherein the particle surface is coated with silicon oxide and / or aluminum oxide.   The titanium dioxide pigment for cosmetics according to any one of claims 1 to 4, wherein the particle surface is coated with a silicone compound and / or a fluorine surfactant.   Titanyl sulfate is hydrolyzed at a temperature of 170 ° C. or higher and a pressure equal to or higher than the saturated vapor pressure of the temperature to obtain spherical hydrous titanium dioxide, and then the spherical hydrous titanium dioxide is calcined at a temperature of 600 to 800 ° C. The manufacturing method of the titanium dioxide pigment for cosmetics as described in any one of Claims 1-3.   Titanyl sulfate was hydrolyzed at a temperature of 170 ° C. or higher and at a pressure equal to or higher than the saturated vapor pressure of the temperature to obtain spherical hydrous titanium dioxide, and then the spherical hydrous titanium dioxide was immersed in hydrochloric acid after 400 to 400 The manufacturing method of the titanium dioxide pigment for cosmetics as described in any one of Claims 1-3 baked at the temperature of 600 degreeC.