JPH02247109A - Cosmetic - Google Patents

Abstract

PURPOSE:To obtain a cosmetic, containing powder prepared by subjecting titanium oxide of a generally spherical or irregular shape having a specific average particle diameter to coating treatment with a hydrated mixture consisting of hydrated silicic acid and hydrated alumina and further coating the surface thereof with a silicone oil and capable of preventing deterioration. CONSTITUTION:A cosmetic, obtained by sufficiently dispersing titanium oxide having 30-70nm average particle diameter in water so as to provide 5-40wt.% content thereof, adding an aqueous solution of a water-soluble alkali silicate, such as sodium silicate, therein so as to afford 1-4wt.% content thereof based on the titanium oxide expressed in terms of SiO2, sufficiently stirring the mixture, then adding an aqueous solution of a water-soluble Al compound, such as alumina sulfate, thereto so as to provide 6-12wt.% content thereof based on the titanium oxide expressed in terms of Al2O3, neutralizing the resultant mixture, coating the titanium oxide with the hydrated mixture, adding a silicone oil thereto while sufficiently stirring the obtained mixture, heating and calcining the mixture and providing treated powder and containing 1-25wt.% resultant powder. The above-mentioned cosmetic has stable hydrophobicity with time and is excellent in dispersibility and fluidity with high ultraviolet ray protecting effects.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a cosmetic product that has stable hydrophobicity over time, does not cause deterioration of the cosmetic oil, etc. it contains, and has excellent dispersibility and fluidity. Concerning cosmetics with high UV protection effect.

[Conventional technology and its problems]

Fine particle titanium oxide having an average particle size of 0.1 μm or less has a UV protection effect and has been widely used in the past to impart UV protection to cosmetics.

This fine-particle titanium oxide is often used after being hydrophobically treated with silicone to prevent makeup from fading due to sweat or water and to have compatibility with cosmetic oils. However,
If fine-particle titanium oxide is treated with silicon as it is, there are problems such as when exposed to sunlight, the silicon coating changes in quality due to the activity of titanium oxide, resulting in a decrease in hydrophobicity and the production of a strange odor.

Furthermore, such silicone-coated microparticle titanium oxide may cause deterioration of cosmetic oils, and because it is a microparticle, it has a strong cohesive force and is difficult to disperse, so it may not be able to fully exert its UV protection effect. I have a problem.

[Means to solve the problem]

Under these circumstances, the present inventors conducted intensive studies to solve the above-mentioned problems of the conventional silicon-coated fine particle titanium oxide, and as a result, the surface of the fine particle titanium oxide was
The present invention was completed based on the discovery that the above-mentioned problems could be solved by coating with silicic acid hydrate and alumina hydrate before silicon treatment.

That is, the present invention provides approximately spherical or amorphous titanium oxide with an average particle size of 30 to 70 nm, with a 5I
1 to 4% by weight of sodium silicate and A120G in terms of 02
Contains a powder coated with a mixed hydrate consisting of 6 to 12% by weight of aluminum hydrate and further coated with silicone oil (hereinafter referred to as treated powder). The present invention provides cosmetics characterized by:

In this specification, the average particle diameter was measured as a mesopore specific surface area equivalent diameter (particle diameter calculated excluding the specific surface area of pores of 20 Å or less) determined by the t-plot method. That is,
Assuming that the mesopore specific surface area of the particle is S (m'/g>, the density of the particle is ρ (g/cn!), and the shape of the particle is spherical, the average particle diameter D (μ) is calculated by the following formula: It is indicated by.

The treated powder used in the present invention is produced, for example, as follows.

First, 1 to 50% of titanium oxide with an average particle size of 30 to 70 nm is
It is well dispersed in water to a concentration of 5% to 40% by weight. At this time, a dispersant can be added if necessary. To this, an aqueous solution of a water-soluble alkali metal silicate such as sodium silicate is added in an amount of 1 to 4% by weight based on titanium oxide in terms of 5102, and stirred well. Next, an aqueous solution of water-soluble aluminum compounds such as aluminum sulfate, aluminum chloride, aluminum nitrate, and alum is added to the titanium oxide in an amount of 6 to 12% by weight based on A1゜03 to neutralize the titanium oxide particles. A coating material formed from an acid hydrate and an alumina hydrate or a composite thereof is deposited.

Alternatively, an aqueous solution of a water-soluble aluminum compound may be added first, and an aqueous solution of a water-soluble alkali metal silicate may be added thereto for neutralization.

If neutralization is insufficient in the above operations, neutralization may be carried out by adding an alkali such as sodium hydroxide, potassium hydroxide, or aqueous ammonia, or an acid such as hydrochloric acid or sulfuric acid. Further, after the fine particle titanium oxide is well dispersed in water, an aqueous solution of a water-soluble alkali metal silicate such as sodium silicate as described above is added to the titanium oxide in an amount of 1 to 4% by weight based on 5102. After neutralizing with the acid described above and depositing a film material formed from a hydrate of silicic acid on the fine titanium oxide particles, an aqueous solution of a water-soluble aluminum compound such as aluminum sulfate as described above was added to 1. It may be added in an amount of 6 to 12% by weight based on titanium oxide in terms of □03, neutralized with an alkali as described above, and further a coating material formed from alumina hydrate may be deposited. In this case as well, the alumina hydrate may be coated first and then the silicic acid hydrate may be coated in this order.

After the deposition of the coating substance described above is completed, it is filtered, washed, dried and, if necessary, pulverized using conventional methods.
A product obtained by treating fine particle titanium oxide with a coating material formed from a hydrate of silicic acid, a hydrate of alumina, or a composite thereof (hereinafter referred to as silica-alumina-treated titanium oxide) can be obtained.

The treated powder used in the present invention can be obtained by further coating the surface with silicon. The surface can be coated with silicon, for example, by the following method.

While sufficiently stirring the silica-alumina-treated titanium oxide, silicone oil is added as it is or dissolved in a solvent, and then stirred. A treated powder can be obtained by distilling off the solvent and baking the powder by heating, if necessary, and then pulverizing the powder if there are aggregates. In addition, silica-alumina-treated titanium oxide is dispersed in a volatile solvent, silicone oil is added to it as is or dissolved in a solvent, and then stirred, the solvent is removed, and if necessary, the aggregates are baked. In some cases, treated powder can also be obtained by pulverization.

At this time, silicone oils include methylhydrodienepolysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, polyether-modified silicone, olefin-modified silicone, fluorine-modified silicone, alcohol-modified silicone, higher fatty acid-modified silicone, amino-modified silicone, cyclic Silicon or the like can be used.

Further, it is desirable that the silicone oil be coated in an amount of 0.1 to 30% by weight, particularly 05 to 10% by weight, based on the silica-alumina treated titanium oxide.

By compounding the thus obtained treated powder with other spherical powder, it is possible to significantly improve the feeling of use, such as good spreadability and no squeaky feeling when reading.

As the spherical powder used for compounding, inorganic powder,
Any number of powders may be used, including spherical alumina,
Various ceramics such as spherical zirconia, various metal oxides such as spherical titanium oxide and spherical zinc oxide, spherical silica, polyester, polyethylene, polystyrene, methyl methacrylate resin, 12 nylon, 6 nylon, copolymers of styrene and acrylic acid, polypropylene, vinyl chloride, f
Preferred are various plastics such as 7D, acrylic beads, polyolefin, silicone resin, aluminum cellulose silicate, and the like. The particle size of spherical powder is 0.5-100
μm1 is particularly preferably 5 to 20 μm.

The processed powder and the spherical powder can be combined by, for example, roughly mixing them together and processing them using an impact crusher such as a ball mill or hammer mill, or a high-speed airflow impact machine such as a hybridizer manufactured by Nara Kikai Seisakusho. It is done. The weight ratio of the treated powder and the spherical powder used is 1 for the latter and 0.0 for the former.
A range of 0.01 to 100, particularly 0.1 to 1, is preferred. Through such treatment, the treated powder is attached, fixed, or formed into a film on the surface of the spherical powder, and a composite powder is obtained.

Cosmetics of the present invention include, for example, powder foundation, cream foundation, 0/W or W1.
Foundations such as 0 type emulsion foundation, 0/W or W10 type oil cake foundation; 0/W or W10 type cream, W/○ or O/W
In addition to cream emulsions such as mold emulsions, lip balms, sun care oils, and the like can be mentioned.

The cosmetic of the present invention can be obtained by mixing the above-mentioned treated powder or spherical powder with a general cosmetic base by a conventional method. The amount of processed powder or spherical powder w, blended in the chemical varies depending on the type of cosmetic, but as a processed powder it is 0.1
-50% by weight, especially 1-25% by weight is preferred.

Among the bases that can be used, powders include mica, talc,
Extending pigments such as sericite, kaolin, nylon powder, titanium oxide (excluding those with an average particle size of 30 to 70 nm)
, zinc white, iron oxide, inorganic pigments such as pearl, red 202,
Organic pigments such as Red 226, Yellow 4, and Aluminum Lake are used. Also, silicon treatment, metal soap treatment, N
- Powders subjected to known surface hydrophobization treatments such as acyl glutamic acid treatment may also be used. In addition, oil agents include silicone oils such as dimethylpolysiloxane, methylpolysiloxane, dimethylcyclopolysiloxane, and methylhydrodienepolysiloxane; hydrocarbons such as solid or liquid paraffin 1, crystal oil, jaresin, osikerite, and montan wax. ; Vegetable oils or animal fats and waxes such as olive, earth wax, carnauba wax, lanolin, spermaceti; and stearic acid, palmitic acid, oleic acid, chrycerin chinostearate, glyceryl distearate, and glycerin monooleate. , isopropyl myristate, isopropyl stearate, butyl stearate, and other fatty acids and their esters; alcohols such as ethyl alcohol, isopropyl alcohol, cetyl alcohol, stearyl alcohol, palmityl alcohol, hexyldodecyl alcohol, etc. . Further, polyhydric alcohols having a moisturizing effect such as glycol, glycerin, and sorbitol can also be used.

Furthermore, water, surfactants, thickening agents, preservatives, antioxidants, known ultraviolet absorbers, etc. commonly used in cosmetics can also be blended.

〔Example〕

The present invention will be explained in more detail with reference to specific synthesis examples and examples below, but the present invention is not limited to these examples.

Synthesis Example 1 10% by weight of fine particle titanium oxide with an average particle size of 0.05 μm
Disperse the solution well in water so that the solution becomes 10% by weight based on titanium oxide (calculated per S day), add a 10-sodium silicate solution (SiO2/NaJ molar ratio -0.5), and stir thoroughly. A 10% aluminum sulfate solution corresponding to 5% by weight of milk based on titanium oxide in terms of 1□03 was gradually added to deposit silicic acid hydrates and alumina hydrates on the surface of titanium oxide. After the reaction was completed, the mixture was filtered, washed, dried, and then ground in a jet mill. This was transferred to a Henschel mixer, 2% by weight of methylhydrodiene polysiloxane was added with sufficient stirring, and after mixing and stirring, a baking treatment was performed at 120°C to obtain treated powders. Synthesis Examples 2 to 7 Synthesis Example I The treated powders shown in Table 1 were obtained in the same manner as in Table 1 except that the amounts of silicic acid hydrate and alumina hydrate were changed.

1 g of the treated powder obtained in Synthesis Examples 1 to 7 was floated on 30 d of purified water in a 50-volume sample bottle.
Table 1 also shows the results of a one-month sunlight exposure test.

As is clear from Table 1, the treated powders used in the present invention (Synthesis Examples 1 and 2) were manufactured by the O/W type method of having the following composition by exposure to sunlight.

Composition> ■Beeswax ■Setanol ■Hydrogenated lanolin ■Squalane ■Fatty acid glycerin 5.5% by weight as shown below 4.5 3.5 ■Lipophilic glycerin monostearate 2% by weight ■Polyoxyethylene ( [020) Sorbitan monolaurate 2 o Treated powder of Synthesis Example 1 8 ■ Aroma
(Scattered amount ■ Preservatives: 0 Antioxidants: appropriate amount ■ Propylene glycol 4.5 weight 0 Purified ice
Appropriate amounts (Production method) Ingredients (1), (2), and (0) were stirred and mixed and kept at 80°C to obtain an aqueous phase. Mix other ingredients, heat and melt at 80°C,
An oil phase was obtained. The above-mentioned aqueous phase was added to this oil phase to pre-emulsify it, uniformly emulsified using a homomixer, and then cooled to 30°C to obtain a product.

Comparative Example 1 In Example 1, the silicon-treated titanium oxide of Synthesis Example 6 was used instead of the treated powder of Synthesis Example 1, and an 0/W type cream was produced in the same manner as in Example 1.

Table 2 shows the results of a one-month sun exposure test for these creams.

Table 2 The cosmetic composition of the present invention was stable against sunlight exposure.

Example 2 (Powder Foundation) A powder foundation having the following composition was manufactured by the method shown below.

Composition> ■Remaining amount of mica ■Synthesis example 1
Processed powder 1o wt% ■ Talc
2゜■ Red Garra
0.8■ Yellow iron oxide 2.5■
Black iron oxide 0.1% by weight ■Liquid paraffin 8 ■Beeswax 2■Preservative
Appropriate amount of fragrance
Micro-manufacturing method: Mix and grind ingredients ■～■. This was transferred to a high-speed blender, and a mixture of components (1) to (4) mixed and dissolved at 80°C was added thereto and mixed uniformly. Component O was added to this mixture, mixed, and then ground again and passed through a sieve. This was compression molded into whole blood.

Example 3 (Cream foundation) A cream foundation having the following composition was manufactured by the method shown below.

Composition> ■ Stearic acid 5% by weight ■ Lipophilic glycerin monostearate 2.5 ■ Cetostearyl alcohol 1 ■ Propylene glycerol monolaurate ■ Squalane ■ Olive oil ■ Purified water ■ Preservative ■ Trietano ■ Sorbitol ■ Titanium oxide ■ Talc ■Colored pigment ■Synthesis example 1 ■Perfume production method> Components 0 to 0 were mixed and pulverized. Separately, a solution was prepared by mixing aqueous phase components 1 to 0, and after adding and dispersing the pulverized pigment, it was heated to 75°C. Oil phase components (1) to (2) were heated and dissolved at 80° C. and added to the previously prepared aqueous phase with stirring to emulsify. This was cooled with stirring, and the component [phase] was added at 50° C., and the treated powder of kohl-ruamine was cooled with stirring.

Example 4 (Oil-based foundation) An oil-based foundation having the following composition was manufactured by the method shown below.

Composition> ■ Treated powder of Synthesis Example 1 10% by weight ■ Talc remaining amount ■ Kaolin 12% by weight ■ Titanium oxide 5 ■ Red iron oxide 1.5 ■ Yellow iron oxide 2.0 ■ Black iron oxide
0.5 ■Liquid paraffin 15 ■Isopropyl pamyrutate 10 0 Lanolin alcohol 3 Weight%0 Microcrystalline wax 7 ■ Osikelite 80 Preservative
Appropriate amount 0 fragrance
Manufacturing method: Ingredients ■～■ were mixed and ground. Add this to 80% of the ingredients
It was gradually added to the oil phase which had been heated to 0.degree. C. and thoroughly dispersed. Ingredient (1) was added to this mixture and mixed, then filled into whole blood and cooled.

Example 5 (W10 type sun care cream) W10 type sun care cream having the following composition was manufactured by the method shown below.

Composition> ■α-Mono (methyl branched stearyl) Glyceryl ether ■Aluminum monostearate ■Liquid paraffin ■Octyldodecyl myrstate ■Dimethylpolysiloxane (5C3) ■Octyl methoxycinnamate ■B, H, T ■Synthesis example Processed powder of 1 ■ Potassium sulfate [phase] Sodium benzoate ■ Glycerin 2% by weight 0.1 0.02 0.5 0.3 ■ Flavor
0.1 ■ Appropriate amount of purified water
Method> Components (1), [phase], (2) and 0 were stirred and mixed and kept at 70°C to obtain an aqueous phase. Mix ingredients ■～■ and heat and dissolve for 70 minutes.
℃ to obtain an oil phase. Ingredient (1) was added to this oily part and dispersed uniformly, the above-mentioned aqueous phase was added and emulsified using an emulsifying machine, the mixture was cooled to 25°C, and component 0 was added to obtain a product.

Example 6 (W/○ type emulsion) A W10 type emulsion having the following composition was produced by the method shown below.

Composition> ■Squalane 5% by weight■Methylpolycyclosiloxane 20■Methylphenylpolysiloxane (KP-56) 10■Methylpolysiloxane (5C3) 5■Dimethylpolysiloxane polyoxyalkylene copolymer 0.4■Silicon Treated talc 100 Treated powder of Synthesis Example 1
3 ■Small amount of fragrance■
Ethyl alcohol 10% by weight Glycerin 10 ■Purified water
Appropriate amounts (Production method) Ingredients (1) to (2) were stirred and mixed to obtain an oil phase. Ingredients (1) to (0) were stirred and mixed to obtain an aqueous phase. After adding other ingredients to the above-mentioned oil phase and uniformly dispersing the powder using a homomixer, the aqueous phase was added to perform emulsification, and component (2) was added to obtain a product.

Comparative Example 2 In Example 2, a powder foundation was produced by the same method as in Example 2, using the silicon-treated titanium oxide of Synthesis Example 6 instead of the treated titanium oxide of Synthesis Example 1.

This foundation and the foundation of Example 2 were dispersed in an oil, and the visible-ultraviolet transmission spectra were measured. The results are shown in Figure 1.

As is clear from Figure 1, the treated powder used in the present invention has good dispersibility, so the powder foundation of the present invention has higher transparency in the visible region and lower absorption in the ultraviolet region than the comparative product. It's big.

Synthesis Example 8 40g of the treated powder obtained in Synthesis Example 1 and 60g of polymethyl methacrylate powder were placed in a ball mill and mixed for 1 hour.
The powder was pulverized to obtain 90 g of a composite powder of the treated powder and the polymethyl methacrylate powder.

Synthesis Example 9 50 g of the treated powder obtained in Synthesis Example 1 and 50 g of nylon powder were treated with a hybridizer to obtain 95 g of a composite powder of the treated powder and nylon powder.

Synthesis Example 10 50 g of silicon-treated titanium oxide obtained in Synthesis Example 6 and 50 g of nylon powder were treated with a hybridizer,
95 g of composite powder of silicon-treated titanium oxide and nylon powder was obtained.

Test Example 1 The composite powders prepared in Synthesis Examples 8, 9 and 10 were evaluated for feel when read and measured for relative coefficient of friction.

The feeling of reading was evaluated by 10 expert panelists.
The following evaluation criteria were used.

○: 8-10 people judged that the reading experience was good △: 5-7
People 〃 ×: 0 to 4 people 〃 Relative friction coefficient was determined by measuring the friction coefficient of freeze-dried pork skin coated with a certain amount of composite powder using a surface measuring device Heidon 14 manufactured by Shinto Kagakusha Co., Ltd. The ratio to the friction coefficient of freeze-dried pork skin itself was defined as the relative friction coefficient.

These results are shown in Table 3.

Table 3 A powder foundation having the following composition was manufactured by the method shown below.

<Composition> ■ Mica remaining amount ■ Composite powder of Synthesis Example 9 10% by weight ■ Talc
Remaining amount ■ Red Garla
0.8% by weight■Yellow iron oxide
2.5■Black iron oxide 0.1■Liquid paraffin 8■Beeswax 2■Preservative
Appropriate amount ■Fragrance
Small amount (Production method) Ingredients ■ to ■ were mixed and ground. This was transferred to a high-speed blender, and a mixture of components (1) to (4) mixed and dissolved at 80°C was added thereto and mixed uniformly. Component O was added to this mixture, mixed, and then ground again and passed through a sieve. This was compression molded into whole blood.

Example 7 (Pressed Powder) A pressed powder having the following composition was manufactured by the method shown below.

Composition> ■Mica remaining amount■Composite powder of Synthesis Example 8 10% by weight■Talc remaining amount■Red iron 0.1% by weight■
Yellow iron oxide 0.1■Black iron oxide
0.01■Liquid paraffin
8 ■Beeswax 2■Preservative
Appropriate amount ■Fragrance
Manufacturing method: Ingredients ■～■ were mixed and ground. This was transferred to a high-speed blender, and a mixture of components (1) to (4) mixed and dissolved at 80°C was added thereto and mixed uniformly. Ingredient (1) was added to this mixture, mixed, and then ground again and passed through a sieve. This was compression molded into whole blood.

Example 8 (O/W type cream) An O/W type mulberry cream having the following composition was manufactured by the method shown below.

<Composition> ■Beeswax 5.5% by weight■Cetanol 4.5■Hydrogenated lanolin 7■Squalane
33 ■ Fatty acid glycerin 3.5 ■ Lipophilic glycerin monostearate 2 ■ Polyoxyethylene (8020) sorbitan monolaurate 2 ■ Composite powder of Synthesis Example 8 8 ■ Fragrance Slight
Amount ■ Preservative appropriate amount ■ Antioxidant appropriate amount ■ Propylene glycol
4.5 wt%0 purified ice
Appropriate amounts (Production method) Ingredients (1), (2), and (0) were stirred and mixed and kept at 80°C to obtain an aqueous phase. Mix other ingredients, heat and melt at 80°C,
An oil phase was obtained. The above-mentioned aqueous phase was added to this oil phase to pre-emulsify it, uniformly emulsified using a homomixer, and then cooled to 30°C to obtain a product.

Example 9 (Cream foundation) Composition ■ Stearic acid 5% by weight ■ Lipophilic glycerin monostearate 2.5 ■ Cetostearyl alcohol l ■ Propylene glycol monolaurate 3 ■ Squalane 7 ■ Olive oil 8 ■ Purified water
Remaining amount■Preservative
Appropriate amount ■ Triethanolamine 12% by weight
0 Sorbit 3 ■ Composite powder of Synthesis Example 9 10 Production method [Effects of the invention] As described above, according to the present invention, in silicon-treated titanium oxide, which is a cosmetic ingredient, the silicon coating layer and the titanium oxide By interposing a coating layer consisting of hydrated silicic acid and hydrated alumina, the silicone film and cosmetic oils are prevented from deteriorating, and the dispersion ability is improved, making this a cosmetic with excellent UV protection. is provided.

[Brief explanation of drawings]

Figure 1 shows a cosmetic using microparticle titanium oxide that was coated with silicic acid hydrate and alumina hydrate before the silicon treatment of the present invention, and a cosmetic that uses microparticle titanium oxide that was only subjected to conventional silicon treatment. It is a figure showing the difference in the absorption effect in the visible to ultraviolet region with the cosmetics used. Above Figure-1 Wavelength (nm) Procedural amendment written spontaneously) April 25, 1989 ■, Indication of the case 1999 Patent Application No. 68697 2, Name of the invention Cosmetics 3, Person making the amendment Related Applicant name (091) Kao Corporation 4, agent address 1-3-6, Nihonbashi Ningyocho, Chuo-ku, Tokyo (〒
103) Column 7 of “Detailed Description of the Invention” of the specification to be amended, contents of the amendment (1) In the specification, page 6, line 5, “Additionally stirred” was replaced with “Additionally stirred.” ”, he corrected. (2) On page 8, line 15, after "Ream emulsions," insert "suspension type cosmetics in which powder is dispersed in a liquid such as water, aqueous alcohol, or oil." (3) On page 8, line 16, after the word ``il'', insert [, habo-ko, eye shadow, mascara''. (4) On page 16, line 15, "components ■ to ■" should be corrected to "components 0 to 0." (5) In the 3rd line from the bottom of page 16, the phrase "by heating and melting," is corrected to "by dispersing the ingredient (■) into the heat and melting," 6°. The bottom line of page 26, ``<Manufacturing method>'' should be corrected as follows. ``Talc 50 Coloring pigment Appropriate amount ■Fragrance
Small amount <Manufacturing method> Component (■) and [phase] were mixed and ground. Separately, aqueous phase component
A solution of the [phases] was prepared, and after adding and dispersing the crushed pigment, it was heated to 75°C. Oil phase components ■～■8
Component 0 was dispersed in the solution heated to 0° C., and added to the previously prepared aqueous phase with stirring to emulsify. This was cooled with stirring, and component (2) was added at 50°C, followed by cooling with stirring. ”

Claims (1)

[Claims] 1 Approximately spherical or amorphous titanium oxide with an average particle size of 30 to 70 nm is added to the titanium oxide in an amount of 1 in terms of SiO_2.
~4% by weight of silicic acid hydrate and 6 in terms of Al_2O_3
A cosmetic comprising a powder coated with a mixed hydrate comprising ~12% by weight of alumina hydrate and further coated on the surface with silicone oil.