JP4160477B2 - Hydrophobic composite powder and cosmetics containing the same - Google Patents

Description

  The present invention relates to a hydrophobic composite powder and cosmetics containing the same, and particularly to improvement of dispersibility and stability in an oil.

In outdoor leisure and sports, sunscreen cream and the like have been used for a long time to prevent the skin from being exposed to excessive ultraviolet rays and causing inflammation.
In recent years, even in the unconsciously exposed ultraviolet rays in daily life, it has become known that it causes spots, buckwheat, wrinkles due to photoaging, skin cancer due to genetic damage of skin cells, etc. Experts such as dermatologists and dermatologists routinely recommend protecting the skin from ultraviolet radiation.

In response to this, at present, most of cosmetics such as lotion, milky lotion, cream, foundation and the like are provided with an ultraviolet protection function. Among substances having an ultraviolet protection function, there are organic substances as ultraviolet absorbers and inorganic substances as ultraviolet scattering agents, but inorganic substances that are considered to be highly safe are relatively preferred.
Titanium dioxide is most frequently used as an inorganic substance as an ultraviolet scattering agent. Titanium dioxide has the highest refractive index of 2.3 to 2.6 and the highest hiding power of white pigments. However, as an actual cosmetic, it is desirable that the white finish does not appear when applied and the finish is natural.

Therefore, recently, techniques for improving the transparency of powder by incorporating titanium dioxide into a silica support have been proposed (Japanese Patent Laid-Open Nos. 2000-344509, 2002-154915, and 2003-171575). Publication).
However, since the titanium-silica composite has a hydrophilic surface, it has poor dispersibility and stability in the oil, particularly in the emulsified oil, and is separated in the base with time. There were also problems such as causing breakage of the emulsion.
In addition, the cosmetics using this composite have problems such as insufficient UV protection and transparency, and poor elongation, which makes it impossible to apply uniformly.

On the other hand, in order to improve dispersibility in cosmetics, a technique of coating metal soap on the surface of fine particle titanium dioxide (for example, Japanese Patent Publication No. 1-57084, Japanese Patent Application Laid-Open No. 59-172415), and fine particle metal A technique for coating the surface of an oxide with a silane compound (for example, JP 2000-264824 A) is known.
JP 2000-344509 A JP 2002-154915 A JP 2003-171575 A Japanese Patent Publication No. 1-57084 JP 59-172415 A JP 2000-264824 A

However, even when the titanium-silica composite was coated by the above technique, desired stability and usability were not obtained.
The present invention has been made in view of the above-described conventional problems, and an object thereof is to provide a hydrophobic composite powder excellent in dispersibility and stability in an oil agent, and a cosmetic containing the same.

  In view of the above problems, as a result of intensive research by the present inventors, the surface of the titanium-silica composite is coated with one or more hydrophobicity-imparting compounds selected from two specific groups in the oil agent. It was found that the dispersibility and stability of the product improved.

The first subject of the present invention is that on the surface of a titanium-silica composite comprising silica and titanium oxide,
One or more selected from the group A of hydrophobicity comprising an organosilicon compound and a hydrocarbon lubricant;
One or more selected from the hydrophobicity-imparting compound B group consisting of higher fatty acids or metal salts thereof, organotitanium compounds, organoaluminum compounds, and fluorosurfactants;
It is a hydrophobic composite powder characterized by coating.

The surface of the titanium-silica composite containing silica and titanium oxide is coated with one or more selected from the group consisting of an inorganic aluminum compound, an inorganic silicon compound, and an inorganic zirconium compound, and further an organosilicon compound And one or more selected from the hydrophobicity-imparting compound A group consisting of a hydrocarbon-based lubricant,
One or more selected from the hydrophobicity-imparting compound B group consisting of higher fatty acids or metal salts thereof, organotitanium compounds, organoaluminum compounds, and fluorosurfactants;
It is a hydrophobic composite powder characterized by coating.

In the composite powder, the titanium-silica composite is preferably in a form in which a plurality of fine particle titanium oxide particles are scattered in a silica carrier with a substantially uniform density.
The second subject of the present invention is a cosmetic comprising the composite powder.

  According to the present invention, the surface of the titanium-silica composite is excellent in dispersibility and stability in an oil agent by coating each one or more hydrophobicity-imparting compounds selected from two specific groups. A hydrophobic composite powder can be provided. Moreover, the cosmetics of this invention can obtain the outstanding ultraviolet-ray protective ability, transparency, and a usability | use_condition by including this composite powder.

Hereinafter, preferred embodiments of the present invention will be described.
<Titanium silica composite>
In the present invention, the titanium-silica composite used as the substrate is described in, for example, Japanese Patent Application Laid-Open No. 2000-344509. This is because a plurality of fine particles of titanium oxide particles have a substantially uniform density in a silica carrier. It is scattered. These composites have better dispersibility of each particle and better ultraviolet shielding effect than those obtained by simply mixing silica and titanium.
In the present invention, titanium oxide includes low-order titanium oxide in addition to titanium dioxide.

  The silica carrier is not limited to these, but is a fine particle mesoporous powder, a rod-shaped mesoporous powder having an outer diameter of 20 to 200 nm and elongated mesopores in the longitudinal direction, or a rod-shaped macroporous powder having few mesopores. It is especially preferable that it is the form of these. In these forms, because the titanium oxide is retained in the silica support while being finely dispersed in a form close to primary particles, even if the composite is somewhat secondary aggregated, Since each particle is sufficiently dispersed, the ultraviolet shielding effect is not impaired.

  In addition, in this invention, it is suitable that the ratio of a titanium oxide is 0.5-90 mass% with respect to the whole titanium silica composite body, More preferably, it is 1-85 mass%. If the amount is less than 0.5% by mass, the UV protection effect is low, so that the practicality is poor. If the amount exceeds 90% by mass, further improvement in the UV protection effect is not recognized, and the transparency is deteriorated.

<Hydrophobicity imparting compound>
In the present invention, as a hydrophobicity imparting compound,
One or more selected from the group A of hydrophobicity comprising an organosilicon compound and a hydrocarbon lubricant;
One or more selected from the hydrophobicity-imparting compound B group consisting of higher fatty acids or metal salts thereof, organotitanium compounds, organoaluminum compounds, and fluorosurfactants;
Are used alone, as a mixture, or as a composite such as a pendant.

Hydrophobicity imparting compounds group A <organosilicon compounds>
Examples of the organosilicon compounds that can be used in the present invention include polyorganosiloxanes (silicone oil), silanes, and hydrolysis products thereof.
Polyorganosiloxanes whose side chains and terminals are modified with non-reactive hydrophobic functional groups such as alkyl groups, fluoroalkyl groups, higher fatty acids and phenyl groups, or hydrogen groups, epoxy groups, methacrylic groups. It is modified with a reactive hydrophobic functional group such as a group.

Silanes have non-reactive hydrophobic functional groups such as alkyl groups, fluoroalkyl groups, higher fatty acids, and phenyl groups, or reactive hydrophobic functional groups such as vinyl groups, epoxy groups, and methacryl groups. (Silane coupling agent).
Hydrolysis products of silanes are those in which hydrolyzable groups such as alkoxy groups, hydroxyl groups, and halogen groups of hydrolyzable silanes are hydrolyzed to form silanols, and silanols are polycondensed to have siloxane bonds. These are oligomers and monomers, and mixtures thereof.

  Among the polyorganosiloxanes, dimethylpolysiloxane, methylhydrogenpolysiloxane, and methylfluoropropyl polysiloxane are among the silanes, and n-butyltrimethoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxylane, n -Alkylsilanes such as octyltrimethoxysilane, and fluoroalkylsilanes such as fluoropropyltrimethoxysilane and tridecafluorooctyltrimethoxylane are particularly preferred because of their excellent affinity with other cosmetic ingredients.

<Hydrocarbon-based lubricant>
Examples of the hydrocarbon lubricant that can be used in the present invention include paraffin wax and polyethylene wax.

Hydrophobicity imparting compound group B <Organic titanium compound>
Examples of the organic titanium compound that can be used in the present invention include isopropylisostearoyl titanate (titanate coupling agent).
<Organic aluminum compound>
Examples of the organoaluminum compound that can be used in the present invention include acetoalkoxyaluminum diisopropylate (aluminum coupling agent).

<Fluorosurfactant>
Examples of the fluorosurfactant that can be used in the present invention include perfluoroalkyl phosphates and perfluoroalkyl carboxylates.
<Higher fatty acids and their metal salts>
Examples of higher fatty acids that can be used in the present invention include stearic acid, lauric acid, oleic acid, palmitic acid, linoleic acid, linolenic acid, and the like, and examples of metal salts of higher fatty acids include their aluminum salts, zinc salts, A magnesium salt, a calcium salt, a barium salt, etc. are mentioned. Of these, stearic acid, lauric acid, oleic acid and their aluminum salts and zinc salts are preferred because the desired effects are easily obtained.

In particular, it is preferable to use a combination of an organosilicon compound and a hydrophobizing compound selected from higher fatty acids or metal salts thereof because higher effects can be obtained.
The total coating amount of the hydrophobizing compound is preferably in the range of 1 to 70% by mass, particularly preferably in the range of 30 to 45% by mass with respect to the titanium silica composite. If it is less than 1% by mass, the dispersibility and stability in the oil agent tend to be inferior, and if it exceeds 70% by mass, the UV protection ability tends to be inferior, such being undesirable.

  Since the hydrophobic composite powder in the present invention is surface-coated with at least one hydrophobicity-providing compound selected from two specific groups, a plurality of oil agents such as an oil agent and a silicone-based dispersion medium are mixed. It has a high affinity with oily cosmetic ingredients and is excellent in stability when incorporated in cosmetics, particularly in emulsion systems such as water-in-oil emulsions and oil-in-water emulsions. Furthermore, this cosmetic is excellent in feeling of use such as elongation and uniformity.

<Inorganic compounds>
The hydrophobic composite powder of the present invention is such that the surface of the titanium-silica composite is coated with an inorganic compound and further coated with the hydrophobicity-imparting compound, so that productivity such as light resistance, filterability, and washability is achieved. Is preferable.
Examples of the inorganic compound include aluminum compounds such as aluminum nitride, sodium aluminate, aluminum sulfate, and aluminum nitrate, silicon compounds such as silicon nitride, silicon carbide, sodium silicate, and potassium silicate, zirconium nitride, zirconium silicide, and zirconium carbide. Zirconium compounds such as zirconium chloride can be used, and one of these can be coated, or two or more can be laminated, or two or more can be mixed and coated. In particular, these inorganic compounds are preferably at least one selected from aluminum nitride, silicon nitride, silicon carbide, zirconium nitride, zirconium silicide, and zirconium carbide.

The preferred coating amount of the inorganic compound depends on the type, but for example, if it is an oxide, hydroxide or hydrated oxide of aluminum, it is 1 to 50% by mass with respect to the titanium silica composite as A1 ₂ O ₃ . It is a range, More preferably, it is the range of 10-20 mass%. If it is less than 1% by mass, the effect of improving light resistance and productivity may not be sufficiently exhibited, and if it exceeds 50% by mass, the UV protection ability may be lowered.

<Manufacturing method>
Next, a general method for producing the hydrophobic composite powder of the present invention will be described.
[1] Production of Titanium Silica Composite First, a titanium silica composite to be a base is produced.
As a first method, for example, a titanium oxide fine particle dispersion is added to a silicon oxide fine particle dispersion, and when silicon oxide is precipitated, titanium oxide is included and combined; When titanium oxide fine particles are dispersed and silicon oxide is precipitated, titanium oxide is included and compounded; when titanium oxide fine particles are dispersed in a titanium oxide fine particle dispersion and silicon oxide is precipitated, titanium oxide is included. And a method of combining them.
Examples of the dispersion of silicon oxide fine particles include silica sol, and examples of the dispersion of titanium oxide fine particles include titania sol, but are not limited thereto.

The second production method is a method in which titanium oxide precursors of various forms are added to the silicon oxide fine particle dispersion, and titanium oxide is included and combined when silicon oxide is precipitated.
The titanium oxide precursor needs to be dissolved in a liquid, and examples thereof include, but are not limited to, titanium tetrachloride, titanium sulfate, titanyl sulfate, and titanium tetra-i-propoxide (TTIP).

As a third production method, various silicon-containing materials for precipitating silicates and various forms of titanium oxide are mixed, and when precipitating the silicates, titanium oxide is included and combined.
Examples of the silicon-containing substance include silicate, silicon alkoxide, water glass and the like. Examples of the silicate include Na ₂ SiO ₃ and Na ₄ SiO ₄ . Examples of the silicon alkoxide include tetramethylorthosilicate and tetraethylorthosilicate. Moreover, as water glass, JIS1, JIS2, JIS3 etc. are mentioned, for example. The silicon-containing material is not limited to those exemplified here.

  As a fourth production method, when various silicon-containing materials for precipitating silicates are deposited, precursors of various forms of titanium oxide are included and combined.

  In the first to fourth methods, in order to precipitate silicon oxide or silicates and include titanium oxide or a precursor thereof, a method of adding an acid or a base can be used, but the method is not limited thereto. Further, in the third and fourth methods, when silicon oxide is deposited under specific conditions according to the method for producing mesoporous powder described in WO 98/14399, the fine particle mesoporous powder, rod-shaped mesoporous powder, rod-shaped macro A titanium silica composite in the form of a porous powder can be produced. In the form of fine-particle mesoporous powder, rod-shaped mesoporous powder, and rod-shaped macroporous powder, titanium oxide is finely dispersed in a form close to primary particles and retained on silica. Even in the next agglomerated state, silica and titanium oxide are sufficiently dispersed in the composite powder, which is preferable because transparency becomes high.

Here, a method for producing the fine particle mesoporous powder, rod-like mesoporous powder, and rod-like macroporous powder will be described.
The method for producing fine particle mesoporous powder includes a dissolution step for dissolving silicate, a condensation step for precipitating silicic acid on the micelle, and a removal step for removing the surfactant. Fine particulate mesoporous powder dissolves 0 <SiO ₂ <Y ₂ O <2 silicate (Y: alkali metal atom) at a concentration of 0.1 to 5.0 M in the presence of a cationic surfactant at pH 11 or higher. The pH is 10.5 or less to form rod-like micelles with the cationic surfactant, and silicic acid is precipitated on the rod-like micelles to remove the cationic surfactant.

The rod-shaped mesoporous powder is obtained by dissolving the silicate at a concentration of 0.3 to 1.3 M in the dissolving step in the method for producing the fine particle mesoporous powder described above, and adjusting the pH to 10.5 or less within 30 minutes in the condensation step. Is obtained.
The rod-like macroporous powder is obtained by dissolving the silicate at a concentration of 1.3 to 2.0 M in the dissolution step and the pH within 30 minutes in the condensation step in the method for producing the fine particle mesoporous powder. It is obtained by setting it to 5 or less.

  In the production method, each porous form of the titanium-silica composite can be obtained by adding an aqueous solution of titanium oxide or a precursor thereof in any step. Even if it adds in any process, the property of the obtained titanium silica composite does not change.

[2] Inorganic compound coating When the composite is coated with an inorganic compound, a salt solution of the target inorganic compound is added to the slurry in which the composite is dispersed in a medium such as water, and then the acidic compound or group The inorganic compound is deposited on the surface of the composite by neutralizing by adding an organic compound or adding a salt of an inorganic compound and an acidic compound or a basic compound simultaneously. Examples of the acidic compound include inorganic acids such as sulfuric acid and hydrochloric acid, and organic acids such as acetic acid, and basic compounds include hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, and sodium carbonate. Products, carbonates, ammonium compounds such as ammonia, amines, and the like can be used.

[3] Coating with hydrophobicity-imparting compound Next, the hydrophobicity-imparting compound is coated on the titanium silica composite. As the method, for example, using a high-speed stirrer such as a Henschel mixer or a super mixer, the hydrophobicity-imparting compound and the composite are mixed and coated, or an airflow crusher such as a jet mill or an impact crusher such as a hammer mill. It is possible to use a dry process such as adding a hydrophobicity-imparting compound and a composite in a dry pulverizer such as coating and coating the composite while pulverizing it.
Alternatively, in the case where the hydrophobicity-imparting compound is a substance having reactivity with the complex and binding strongly, such as hydrolyzable silanes and hydrolysis products thereof, the hydrophobicity-imparting compound is added to the slurry of the complex. It is also possible to apply a wet process of adding, stirring and mixing to coat.

The coating with various hydrophobicity-imparting compounds may be performed simultaneously with two or more compounds or may be performed step by step. Moreover, when coat | covering in steps, when the order is performed in order of the following (1)-(5), since a hydrophobization rate becomes higher, it is preferable, but it is not limited to this.
(1) Silanes (organosilicon compounds)
(2) Organo-titanium compounds, organoaluminum compounds (3) Fluorosurfactants, higher fatty acids or their metal salts (4) Polyorganosilanes (organosilicon compounds)
(5) Hydrocarbon lubricant For example, isopropyl isostearoyl titanate (hydrophobicity imparting compound B group) and (4) methyl hydrogen polysiloxane (hydrophobicity imparting compound A group) are coated with isopropyl. It is preferable to coat with methylhydrogenpolysiloxane after coating with isostearoyl titanate.

Hydrolyzable silanes and hydrolysis products thereof are preferred when the pH of the slurry is made strongly acidic, since the bond with the complex or the complex coated with the inorganic compound is promoted. Further, when an alkali metal salt such as a sodium salt of higher fatty acid is used and neutralized in the slurry, the higher fatty acid is deposited on the surface of the composite or the composite covered with the inorganic compound, so the wet method is applied. You can also
In either method, the hydrophobicity-imparting compound may be added as a solution dissolved in an organic solvent such as alcohol or as a dispersion dispersed in water using a surfactant. The hydrolysis product may be prepared in advance by hydrolyzing silanes and water.

  The cosmetic of the present invention is a blend of the hydrophobic composite powder of the present invention for the purpose of ultraviolet protection and the like. In addition, the amount of the hydrophobic composite powder blended into the cosmetic can not be generally defined by the combination of the cosmetic dosage form and other blended components in view of a more specific purpose, 0.1-60.0 mass% of the whole cosmetics is preferable, and it is especially preferable that it is 1.0-40.0 mass%. If it is less than 0.1% by mass, a sufficient UV protection effect may not be obtained, and if it exceeds 60.0% by mass, the usability may be deteriorated.

  In addition to the above hydrophobic composite powder, the cosmetic of the present invention includes other components usually used in cosmetics and pharmaceuticals, for example, other powder components, liquid fats and oils, as long as the effects of the present invention are not impaired. , Solid fats, waxes, hydrocarbons, higher alcohols, esters, silicones, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, humectants, water-soluble polymers, thickeners, films Agent, ultraviolet absorber, sequestering agent, lower alcohol, polyhydric alcohol, sugar, amino acid, organic amine, polymer emulsion, pH adjuster, skin nutrient, vitamin, antioxidant, antioxidant aid, fragrance, Water or the like can be appropriately blended as necessary, and can be produced by a conventional method according to the intended dosage form.

  The cosmetic of the present invention can be widely applied to cosmetics, pharmaceuticals, and quasi-drugs 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. Further, the product form of the cosmetic of the present invention is optional, and facial cosmetics such as lotion, milky lotion, cream, and pack; makeups such as foundation, funny, blusher, lipstick, eye shadow, eyeliner, mascara and sunscreen Cosmetics; Body cosmetics; Fragrance cosmetics; Skin cleansers such as makeup removers, facial cleansers, body shampoos, etc .; 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. The blending amount (%) is mass%.
(Production Example 1)
1. Titanium tetrachloride was neutralized by adding 20% aqueous ammonia over 100 minutes to 100 L of titanium tetrachloride aqueous solution having a concentration of 50 g / L. The hydrous titanium oxide slurry obtained by neutralization was immediately filtered and dehydrated, and then repulped to obtain hydrous titanium oxide slurry, and 8 kg of concentrated sulfuric acid was added to the slurry, followed by heat treatment at 95 to 100 ° C. for 3 hours. Thereafter, a 5% strength aqueous sodium hydroxide solution was added over 10 hours to neutralize, filter and wash. Concentrated sulfuric acid and water were added to the resulting dehydrated cake and peptized, and the pH was adjusted to 1.6, followed by stirring for 7 hours to obtain a titania sol having a titanium oxide concentration of 15% by mass in terms of TiO ₂ . After mixing 10 L of this titania sol and 2.5 L of a commercially available 20% by mass silica sol (manufactured by Catalytic Chemical Industry), adjusting the pH to about 8 with sodium hydroxide, filtering, washing and drying, firing at 700 ° C. Then, it was pulverized with a hammer mill to obtain a particulate titanium silica composite.
2. While stirring 2 kg of the titanium-silica composite with a Henschel mixer, 200 g of dimethylpolysiloxane dissolved in 300 mL of ethanol and 200 g of perfluoroalkyl phosphate ester were added.

(Production Example 2)
1. 12.5 L of 10% silica sol and 0.75 kg of titanium tetrachloride aqueous solution in terms of titanium oxide were added, mixed and stirred, this aqueous solution was vacuum dried, and then fired at 700 ° C. to form a fine particle titanium silica composite. Obtained.
2. 2 kg of the titanium-silica composite was again made into an aqueous slurry and wet-ground using a sand mill. This slurry was heated to 80 ° C., and 1 L of 150 g / L zirconium sulfate aqueous solution in terms of ZrO ₂ and 100 g / L sodium hydroxide aqueous solution were simultaneously mixed for 20 minutes while maintaining the pH of the slurry at 8-9. Next, 0.5 g of a 300 g / L sodium aluminate aqueous solution in terms of Al ₂ O ₃ and 20% sulfuric acid were added simultaneously for 20 minutes while maintaining the pH of the slurry at 8-9. After stirring for 30 minutes, the mixture was neutralized with 20% sulfuric acid to a pH of 5.5 over 30 minutes, and the surface of the composite was coated with a mixture of zirconium oxide and aluminum oxide.
3. The slurry was adjusted to pH 3 with sulfuric acid, 100 g of n-hexyltrimethoxysilane was added, and the mixture was aged for 1 hour, neutralized, filtered, washed, dried, and pulverized using a hammer mill. While stirring this powder with a Henschel mixer, 300 g of isopropylisostearoyl titanate was added and stirred for 10 minutes after the addition was completed.

(Production Example 3)
1. In 25 L of 0.5 M sodium metasilicate aqueous solution, 2.5 mol of behenyltrimethylammonium chloride (BTC) was dissolved, and 10 L of 15 mass% titania sol of Production Example 1 was added to this aqueous solution. The temperature at this time was 70 ° C. After adjusting the pH to about 8 using hydrochloric acid, the dispersion was filtered, the residue was washed with water, dried, and then fired at 700 ° C. to obtain a fine particle mesoporous titanium silica composite. .
2. 2 kg of the titanium-silica composite was again made into an aqueous slurry and wet-ground using a sand mill. The slurry was heated to 80 ° C., and 1 g of 300 g / L sodium aluminate aqueous solution and 20% sulfuric acid in terms of Al ₂ O ₃ were added simultaneously for 20 minutes while maintaining the pH of the slurry at 8-9. After stirring for 10 minutes, the mixture was neutralized with 20% sulfuric acid to a pH of 5.5 over 30 minutes, and the surface of the composite was coated with aluminum oxide.
3. The slurry was adjusted to pH 3 with sulfuric acid, 200 g of n-octyltrimethoxysilane was added, and the mixture was aged for 60 minutes and neutralized. Next, 200 g of sodium stearate was added to the slurry, stirred for 30 minutes, and then neutralized with 20% sulfuric acid so that the pH was 6 over 40 minutes. This was filtered, washed, dried, and pulverized using a hammer mill.

(Production Example 4)
1. Dissolve 5 mol of behenyltrimethylammonium chloride (BTC) in 50 L of 0.5 M sodium metasilicate aqueous solution and add hydrochloric acid and 1.5 kg of titanium tetrachloride equivalent to titanium oxide to this aqueous solution to adjust the pH to around 8. did. The temperature at this time was 70 ° C. Thereafter, the dispersion was filtered, and the residue was washed with water and dried, followed by firing at 700 ° C. to obtain a fine particle mesoporous titanium silica composite.
2. 2 kg of the titanium-silica composite was again made into an aqueous slurry and wet-ground using a sand mill. This slurry was heated to 60 ° C., and ₃ g of a 100 g / L aqueous sodium silicate solution as SiO ₃ was added over 1 hour, then heated to 90 ° C. and aged for 1 hour. Next, the mixture was neutralized with 20% sulfuric acid so that the pH became 5.5, and the surface of the composite was coated with silica.
3. Next, the pH was adjusted to 3 with 20% sulfuric acid and 200 g of isobutyltrimethoxysilane was added and stirred for 30 minutes. Then, the pH was adjusted to 10 with sodium hydroxide and 300 g of aluminum laurate was added, followed by aging for 1 hour. This was neutralized, filtered, washed, dried, and pulverized using a jet mill.

(Production Example 5)
1. 5 mol of stearyltrimethylammonium chloride (STC) is dissolved in 50 L of 0.5 M sodium metasilicate aqueous solution, and an aqueous solution in which hydrochloric acid and 1.5 kg of titanyl sulfate in terms of titanium oxide are mixed is added to this aqueous solution to adjust the pH to 8 Adjusted back and forth. The temperature at this time was 70 ° C. Thereafter, this dispersion was filtered, and the residue was washed with water and dried, followed by firing at 700 ° C. to obtain a fine particle mesoporous titanium silica composite.
2. 2 kg of the titanium-silica composite was again made into an aqueous slurry and wet-ground using a sand mill. This slurry was heated to 60 ° C., and 1 L of 100 g / L sodium silicate aqueous solution as SiO ₃ and 0.5 L of 300 g / L sodium aluminate aqueous solution in terms of Al ₂ O ₃ were previously mixed. The product was added over 1 hour, then heated to 90 ° C. and aged for 1 hour. Next, the mixture was neutralized with 20% sulfuric acid to a pH of 5.5 over 30 minutes, filtered, washed and dried, and the surface of the composite was coated with a mixture of silica and aluminum oxide.
3. While stirring the powder with a Henschel mixer, 200 g of acetoalkoxyaluminum diisopropylate dissolved in 300 ml of ethanol and 100 g of paraffin wax dissolved in 200 ml of ethanol were sequentially added, and further pulverized using a jet mill.

(Production Example 6)
1. Titanium tetra-i-propoxide (TTIP) (1.5 kg) was dissolved in isopropyl alcohol (4.5 kg), and 1.25 kg of water was added to the aqueous solution to obtain titanium hydroxide. Thereafter, 0.01 mol of behenyltrimethylammonium chloride (BTC) was dissolved in 50 L of 0.5 M sodium metasilicate aqueous solution, and the titanium hydroxide aqueous solution obtained in the above process was added to this aqueous solution. The temperature at this time was 70 ° C. After adjusting the pH to about 8 using hydrochloric acid, the dispersion was filtered, and the residue was washed with water, dried and then fired at 700 ° C. to obtain a fine particle mesoporous titanium silica composite. .
2. 2 kg of the titanium-silica composite was again made into an aqueous slurry and wet-ground using a sand mill. This slurry was heated to 80 ° C. and previously mixed with 1 L of a zirconium sulfate aqueous solution of 100 g / L in terms of ZrO ₃ and 0.5 L of an aluminum sulfate aqueous solution of 300 g / L in terms of Al ₂ O ₃ Is slowly added over 1 hour, then neutralized with 20% sulfuric acid to a pH of 5.5 over 30 minutes, filtered, washed and dried, and the surface of the composite is mixed with a mixture of zirconium oxide and aluminum oxide. Covered.
3. While stirring the powder with a Henschel mixer, 100 g of zinc stearate dissolved in 300 mL of ethanol and 200 g of methylfluoropropylpolysiloxane dissolved in 200 mL of ethanol were sequentially added, and further pulverized using a jet mill.

(Comparative Production Example 1)
The production was performed in the same manner as in Production Example 3, except that the amount of sodium stearate added in Production Example 3 was 400 g and the addition of n-octyltrimethoxysilane was omitted.

(Comparative Production Example 2)
The production was performed in the same manner as in Production Example 3 except that the amount of n-octyltrimethoxysilane added in Production Example 3 was 400 g and the addition of sodium stearate was omitted.
(Comparative Production Example 3)
It was produced in the same manner as in Production Example 2 except that the amount of isopropylisostearoyl titanate in Production Example 2 was 600 g and the addition of n-hexyltrimethoxysilane was omitted.

(Comparative Production Example 4)
The production was performed in the same manner as in Production Example 4 except that the amount of aluminum laurate added in Production Example 4 was 600 g and the addition of isobutyltrimethoxysilane was omitted.
(Comparative Production Example 5)
The perfluoroalkyl phosphate ester of Production Example 1 was added in an amount of 400 g, and the production was performed in the same manner as in Production Example 1 except that the addition of dimethylpolysiloxane was omitted.

(Comparative Production Example 6)
It was produced in the same manner as in Production Example 5 except that the amount of paraffin wax added in Production Example 5 was 200 g, and the addition of acetoalkoxyaluminum diisopropylate was omitted.
(Comparative Production Example 7)
A titanium silica composite was produced in the same manner as in Production Example 1.

<I> Hydrophobization test 10 mL of a water / methanol mixed solution was placed in a 30 mL sample bottle, and about one cup of earpick was dropped on the liquid level. This was fixed to a shaker (TAITEC DOUBLE SHAKER NR-30: manufactured by TAITEC) and rotated at 180 rpm for 5 minutes. The same operation was repeated by changing the ratio of methanol in the mixed solution, and the methanol content (% by mass) of the mixed solution in which the sample was not suspended by visual judgment was defined as the degree of hydrophobicity. The results are shown in Table 1.

(Table 1)
  Production example 1 2 3 4 5 6
Hydrophobicity (%) 45 45 55 55 45 50
  Comparative production example 1 2 3 4 5 6 7
Hydrophobicity (%) 35 10 30 35 15 20 0

  In Comparative Production Examples 1 to 6 using one kind of hydrophobicity-imparting compound, the degree of hydrophobicity was 10 to 35%, and the hydrophobicity was not sufficient. In contrast, in Production Examples 1 to 6 using two types of hydrophobicity-imparting compounds from Group A and Group B, the degree of hydrophobicity dramatically increased. From the above, it was confirmed that the composite powder of the present invention is suitably hydrophobized on the surface by using two or more hydrophobicity-imparting compounds each selected from one or more from Group A and Group B. .

Formulation Example 1-1 W / O type protector Stearic acid-treated fine particle zinc oxide 2.0
2. Hydrophobic composite powder of Production Example 1 8.0
3. Octyl paraoxycinnamate 5.0
4.4-tertbutyl-4′-methoxybenzoylmethane 1.0
5. Oxybenzone 3.0
6). Decamethylcyclopentasiloxane 23.0
7). Dimethylpolysiloxane 2.0
8). Squalane 20.0
9. Glycerin diisostearate2.0
10. Organically modified montmorillonite 0.5
11. Preservative appropriate amount 12. Perfume proper amount13. Ion exchange water 28.5
14.1.3-Butylene glycol 5.0
(Manufacturing method)
3 to 12 were heated to 70 ° C. and dissolved. 1 and 2 were added thereto and dispersed with a homomixer. While continuing to disperse, 13 and 14 heated at 70 ° C. were added thereto and stirred until a uniform emulsion was obtained. The obtained emulsion was cooled with a heat exchanger and filled into a container.

  Instead of Production Example 1, those using Production Examples 2 to 6 were referred to as Formulation Examples 1-2 to 1-6, respectively, and those using Comparative Production Examples 1 to 7 were respectively Comparative Formulation Examples 1-1 to 1- It was set to 7.

<II> Hydrophobization degree stability test The hydrophobization degree stability of the W / O type protectors obtained in Formulation Examples 1-1 to 1-6 and Comparative Formulation Examples 1-1 to 1-7 is as follows. Examined. Each sample and glass beads having a diameter of 1 mm were placed in a container at a ratio of 1: 1 by volume, and shaken for 30 minutes using a PAINT SHAKER manufactured by ASADA. The sample before and after shaking was applied to the upper arm, dried for 5 minutes, then watered, and the turbidity of water when rubbed strongly with a finger was visually evaluated. The criteria for evaluation are as follows.
A: Water is transparent (no transfer of powder to water)
B: Water is slightly turbid C: Water is cloudy (a large amount of powder is transferred to water)
Table 2 shows the evaluation results.

(Table 2)
Formulation example 1-1 1-2 1-3 1-4 1-5 1-6
Before shaking A A A A A A
After shaking A A A A A A
Comparative formulation example 1-1 1-2 1-3 1-4 1-5 1-6 1-7
Before shaking A A A A A A C
After shaking BBBBBBBC

  In Comparative Formulation Example 1-7, the powder was transferred to water before shaking. In Comparative Formulation Examples 1-1 to 1-6, there was no migration of powder to water before shaking, but migration was observed after shaking. On the other hand, in the formulation examples 1-1 to 1-6, the powder was not transferred to water even after shaking. From this, it was confirmed that the hydrophobic composite powders obtained in Production Examples 1 to 6 have improved hydrophobization degree stability in the product system as compared with Comparative Formulation Examples 1-1 to 1-6. It was. Therefore, the hydrophobic composite powder of the present invention is excellent in dispersibility and stability in an oil agent by hydrophobizing at least two selected from Group A and Group B, respectively.

Formulation Example 2 Cream Type W / O Type Sunscreen Hydrophobic composite powder of Production Example 10.0
2. Hydrophobized sericite 10.0
3. Squalane 20.0
4). Decamethylcyclopentasiloxane 12.0
5. Glycerin diisostearate3.0
6). Organically modified montmorillonite 1.5
7). Preservative appropriate amount 8. Perfume appropriate amount 9. Ion exchange water 38.5
10.1, 3-butylene glycol 5.0
(Manufacturing method)
3 to 7 were heated to 70 ° C. and dissolved. 1 and 2 were added in this, and it disperse | distributed with the homomixer. 9 and 10 were mixed and heated to 70 ° C, and the mixture was emulsified with a homomixer. Further, 8 was mixed and filled into a container.

Comparative formulation example 2
A cream type W / O sunscreen was obtained in the same manner as in Formulation Example 2 except that Comparative Production Example 1 was used instead of Production Example 1.

Formulation Example 3 Two-layer type W / O sunscreen Talc 1.0
2. Hydrophobic composite powder of Production Example 10.0
3. Stearic acid-treated fine particle zinc oxide 15.0
4). Liquid paraffin 1.0
5. Decamethylcyclopentasiloxane 26.8
6). Dimethylpolysiloxane 21.0
7). POE-modified dimethylpolysiloxane 2.0
8). Ion exchange water 15.0
9.1.3-Butylene glycol 8.0
10. Preservative 0.1
11. Fragrance 0.1
(Manufacturing method)
4 to 7 were heated and mixed at 70 ° C. (oil phase). Separately, 9 and 10 were dissolved in 8 and heated to 70 ° C. (aqueous phase). 1-3 powders were added to the oil phase and dispersed with a homomixer. The previous aqueous phase was added to this and emulsified with a homomixer. Further, 11 was mixed and filled into a container.

(Comparative Formulation Example 3)
A two-layer type W / O sunscreen was obtained in the same manner as in Formulation Example 3 except that Comparative Production Example 1 was used instead of Production Example 1.

<III> Transparency and UV Protection Test The transparency and UV protection of Formulation Examples 2 and 3 and Comparative Formulation Examples 2 and 3 were examined by the following method.
Two adhesive sheets of 3M Transpore ^TM surgical tape manufactured by Sumitomo 3M Co., Ltd. were bonded together to create two 50 mm × 50 mm measurement sheets. 50 mg of each sample was placed on each sheet and spread evenly with fingers. After drying for 15 minutes, a transmittance of 700 to 280 nm was measured using a self-recording spectrophotometer U-3410 manufactured by Hitachi, Ltd.
The wavelength range is 400 to 800 nm for visible light, 320 to 400 nm for ultraviolet light (UVA), and 280 to 320 nm for ultraviolet light (UVB). Therefore, the higher the transmittance of 700 to 400 nm, the higher the transparency, and 400 to 280 nm. The lower the transmittance, the higher the UV protection ability.

  FIG. 1 shows the results of Formulation Example 2 and Comparative Formulation Example 2. From the results of FIG. 1, it can be seen that Formulation Example 2 has a higher transmittance than Comparative Formulation Example 2 in the wavelength region of 400 nm or more, and a transmittance lower than that of Comparative Formulation Example 2 in the ultraviolet region of 280 nm to 400 nm. Thereby, the hydrophobic composite powder obtained in Formulation Example 2 is hydrophobized with two or more selected from Group A and Group B, respectively, thereby improving the transparency and UV protection ability of the formulation. It was confirmed.

  FIG. 2 shows the results of Formulation Example 3 and Comparative Formulation Example 3. From the results shown in FIG. 2, the prescription example 3 has a higher transmittance than the comparative prescription example 3 in the wavelength region of 400 nm or more, and has a lower transmittance than the comparative prescription example 3 in the ultraviolet region of 280 nm to 400 nm, particularly in the UVB region. Recognize. As a result, even in the hydrophobic composite powder obtained in Formulation Example 3, the transparency of the preparation and the UV protection ability are improved by hydrophobizing at least one selected from Group A and Group B. Confirmed to do.

Formulation Example 4-1 W / O-type Foundation Sericite 5.0
2. Bengala 0.36
3. Yellow iron oxide 0.8
4). Black iron oxide 0.16
5. Hydrophobic composite powder of Production Example 1 14.0
6). Liquid paraffin 5.0
7). Decamethylcyclopentasiloxane 29.0
8). POE-modified dimethylpolysiloxane 4.5
9. Ion exchange water 36.0
10.1.3-Butylene glycol 5.0
11. Preservative 0.1
12 Perfume 0.08
(Manufacturing method)
6 to 8 were dissolved by heating at 70 to 80 degrees (oil phase). Further, 10 and 11 were dissolved in 9 (aqueous phase). 1-5 were mixed, the previous oil phase was added to this, and it mixed with the homomixer. After adding 12 and mixing, the aqueous phase was added and emulsified and filled into a container.

  Instead of Production Example 1, those using Production Examples 2 to 6 were designated as Prescription Examples 4-2 to 4-6, respectively, and those using Comparative Production Examples 1 to 7 were respectively Comparative Prescription Examples 4-1 to 4- It was set to 7.

<IV> Sensory evaluation In order to perform sensory evaluation of the W / O type foundations obtained in Formulation Examples 4-1 to 4-6 and Comparative Formulation Examples 4-1 to 4-7, preference was given using a panel of 20 people. Sexuality was evaluated. Each person applied each W / O type foundation to the face and asked to evaluate the good elongation at the time of application.
The evaluation criteria were as follows.
A: 16 or more people out of 20 feel good and can be applied uniformly B: 10 to 15 people out of 20 feel good and can apply uniformly C: Less than 10 out of 20 people , Feels stretchable and can be applied evenly

Table 3 shows the evaluation results.
(Table 3)
Formulation example
4-1 4-2 4-3 4-4 4-5 4-6
Sensory evaluation A A A A A A
Comparative formulation example
4-1 4-2 4-3 4-4 4-5 4-6 4-7
Sensory evaluation C C C C C C C

  Comparative formulation example 4-7 including comparative production example 7 not coated with a hydrophobicity-imparting compound, and comparative formulation examples 4-1 to 4-6 including comparative production examples 1 to 6 using only one hydrophobicity-imparting compound , Which both squeaked and tended to lose its smoothness, but included formulations 1 to 6 using two types of hydrophobicity-imparting compounds selected from group A and group B, respectively. Examples 4-1 to 4-6 were excellent in elongation, could be applied uniformly, and had a smooth and excellent feeling of use. Therefore, it is confirmed that the cosmetic of the present invention improves the usability by including a composite powder coated with two or more hydrophobicity-imparting compounds each selected from one or more from Group A and Group B. It was.

The cosmetics of the following formulation examples had good dispersibility of the composite powder, and had excellent UV protection, transparency, and feeling of use.
Formulation Example 5 Oily Stick Foundation Hydrophobic composite powder of the present invention 8.0
2. Talc 2.8
3. Kaolin 16
4). Mica 3.0
5. Titanium dioxide 16.0
6). Bengala 1.0
7). Yellow iron oxide 3.0
8). Black iron oxide 0.2
9. Solid paraffin 3.0
10. Microcrystalline wax 7.0
11. Vaseline 15.0
12 Dimethylpolysiloxane 3.0
13. Squalane 5.0
14 Isopropyl palmitate 17.0
15. Antioxidant appropriate amount16. Perfume appropriate amount (Manufacturing method)
9-15 was melt | dissolved at 85 degreeC, and 1-8 fully mixed with this was added with stirring, and it grind | pulverized and dispersed with the colloid mill. 16 was added, and after deaeration, the mixture was poured into a container at 70 ° C. and cooled to obtain Formulation Example 5.

Formulation Example 6 Solid Powder Foundation Silicone-treated talc 11.4
2. Silicone-treated mica 41.0
3. Silicone-treated titanium dioxide 10.0
4). Hydrophobic composite powder of the present invention 10.0
5. Silicone-treated zinc oxide 8.0
6). Silicone-treated Bengala 1.0
7). Silicone-treated yellow iron oxide 3.0
8). Silicone-treated black iron oxide 0.2
9. Nylon powder 2.0
10. Dimethylpolysiloxane 8.5
11. Octyl methoxycinnamate 1.0
12 POE-modified dimethylpolysiloxane 0.6
13. Monooleic acid POE sorbitan 1.0
14 Isocetyl octoate 2.0
15. Ethylparaben 0.2
16. Fragrance 0.1
(Manufacturing method)
10 to 15 were dissolved by heating (oil phase). Separately, 1 to 9 were mixed with a blender and mixed with the previous oil phase. Further, 16 was sprayed and mixed uniformly. This was pulverized by a pulverizer and compression-molded into an inner dish.

Formulation Example 7 Lipstick Hydrophobic composite powder of the present invention 10.0
2. Red No. 201 0.6
3. Red No. 202 1.0
4). Red 223 0.2
5. Candelilla Row 9.0
6). Solid paraffin 8.0
7). Beeswax 5.0
8). Carnavalou 5.0
9. Lanolin 11.0
10. Castor oil 23.2
11.2-Cetyl ethylhexanoate 17.0
12 Isopropyl myristic acid ester 10.0
13. Antioxidant appropriate amount14. Perfume appropriate amount (Manufacturing method)
1-3 were mixed with a part of 10 and subjected to roller treatment (pigment part). 4 was dissolved in a part of 10 (dye part). 5 to 13 were mixed and dissolved by heating, and then the pigment part and the dye part were added and dispersed uniformly with a homomixer. After 14 was added and mixed, it was poured into a mold and rapidly cooled to form a stick.

It is a figure which shows the light transmittance of the prescription example 2 and the comparative prescription example 2. FIG. It is a figure which shows the light transmittance of the prescription example 3 and the comparative prescription example 3. FIG.

Claims (4)

On the surface of the titanium-silica composite containing silica and titanium oxide,
One or more selected from the group A of hydrophobicity comprising an organosilicon compound and a hydrocarbon lubricant;
One or more selected from the hydrophobicity-imparting compound B group consisting of higher fatty acids or metal salts thereof, organotitanium compounds, organoaluminum compounds, and fluorosurfactants;
Hydrophobic composite powder characterized in that it is coated. The surface of a titanium-silica composite containing silica and titanium oxide is coated with one or more selected from the group consisting of an inorganic aluminum compound, an inorganic silicon compound, and an inorganic zirconium compound, and further an organosilicon compound, and 1 type or 2 types or more selected from the hydrophobicity-imparting compound A group consisting of a hydrocarbon-based lubricant,
One or more selected from the hydrophobicity-imparting compound B group consisting of higher fatty acids or metal salts thereof, organotitanium compounds, organoaluminum compounds, and fluorosurfactants;
Hydrophobic composite powder characterized in that it is coated. 3. The composite powder according to claim 1, wherein the titanium-silica composite is in a form in which a plurality of fine particles of titanium oxide are scattered at a substantially uniform density in a silica carrier. Composite powder. A cosmetic comprising the composite powder according to any one of claims 1 to 3.

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