JP2544200B2 - Cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention has stable hydrophobicity over time, is free from alteration of cosmetic oils contained therein, and has excellent dispersibility and fluidity. The present invention relates to cosmetics having a high UV protection effect.

[Conventional technology and its problems]

Fine particle titanium oxide having an average particle diameter of 0.1 μm or less has a UV protection effect, and thus has been widely used in the past for imparting a UV protection effect to cosmetics. This fine particle titanium oxide is treated with silicone to make it hydrophobic, in order to prevent the makeup from being damaged by sweat and water, and the problem of compatibility with the oil agent for cosmetics.
Often used. However, when the fine particle titanium oxide is treated with silicon as it is, when exposed to sunlight, there is a problem that the activity of the titanium oxide causes the quality of the silicon film to deteriorate, resulting in a decrease in hydrophobicity and an offensive odor. Furthermore,
Such silicon-coated fine particles of titanium oxide modify the oil solution for cosmetics, and since they are fine particles, they have a strong cohesive force,
Since it is difficult to disperse them, there are problems that the ultraviolet protection effect cannot be fully exerted, and that the feeling of use such as elongation and squeaky feeling on the skin is not sufficient.

[Means for solving the problem]

Under such circumstances, the present inventors have conducted extensive studies to solve the above problems of the conventional silicon-coated fine particle titanium oxide, and as a result, the surface of the fine particle titanium oxide was treated with silicic acid before being treated with silicon. It was found that the above problems can be solved by using a composite powder in which a treated powder obtained by coating with a hydrate and a hydrate of alumina and a spherical powder are combined, and the present invention has been completed. did.

That is, according to the present invention, approximately spherical or amorphous titanium oxide having an average particle diameter of 30 to 70 nm is added to the titanium oxide in an amount of 1 to 4% by weight in terms of SiO ₂ and 6% in terms of Al ₂ O _3. Powder coated with mixed hydrate consisting of -12 wt% alumina hydrate and surface coated with silicon oil (hereinafter referred to as treated powder) and spherical with particle size of 0.5-100 μm The present invention provides a cosmetic characterized by containing a composite powder obtained by compounding with a powder.

In the present specification, the average particle size was measured as a mesopore specific surface area-converted size (particle size calculated by excluding the specific surface area of pores of 20 Å or less) determined by the t-plot method. That is,
The mesopore specific surface area of the particle is S (m ² / g), and the density of the particle is ρ
(G / cm ³ ), and assuming that the shape of the particles is spherical, the average particle diameter D (μ) is expressed by the following equation.

The treated powder used for compounding with the spherical powder in the present invention is manufactured, for example, as follows.

First, titanium oxide having an average particle size of 30 to 70 nm is well dispersed in water so as to be 1 to 50% by weight, preferably 5 to 40% by weight. At this time, a dispersant can be added if necessary. Thereto, with respect to titanium oxide aqueous solution of a water-soluble alkali metal silicate such as sodium silicate in terms of SiO ₂ 1-4
Add so that it becomes the weight% and stir well. Next, use an aqueous solution of a water-soluble aluminum compound such as aluminum sulfate, aluminum chloride, aluminum nitrate, and alum with Al.
A coating substance formed by adding 6 to 12% by weight of titanium oxide in terms of ₂ O ₃ and neutralizing it to form fine particle titanium oxide from a hydrate of silicic acid and a hydrate of alumina or a composite thereof. Deposit. Alternatively, an aqueous solution of a water-soluble aluminum compound may be added first, and then an aqueous solution of a water-soluble alkali metal silicate may be added for neutralization.

If the above operation does not provide sufficient neutralization, an alkali such as sodium hydroxide, potassium hydroxide or aqueous ammonia or an acid such as hydrochloric acid or sulfuric acid may be added for neutralization. Also, after finely particulate titanium oxide is well dispersed in water, an aqueous solution of a water-soluble alkali metal silicate such as sodium silicate as described above becomes 1 to 4% by weight based on titanium oxide in terms of SiO _2. In addition, after neutralizing with an acid as described above to deposit a coating material formed from a hydrate of silicic acid on particulate titanium oxide, an aqueous solution of a water-soluble aluminum compound such as aluminum sulfate as described above is added to Al. _It may be added in an amount of 6 to 12% by weight based on ₂ O ₃ with respect to titanium oxide, and may be neutralized with an alkali as described above to further deposit a coating material formed from a hydrate of alumina. Also in this case, the alumina hydrate may be coated first, and then the silicic acid hydrate may be coated in that order.

After the deposition operation of the above-mentioned coating substance is completed, filtration, washing, and drying are carried out by a conventional method, and pulverization is carried out as necessary to obtain fine particle titanium oxide, hydrate of silicic acid and hydrate of alumina or a composite thereof. It is possible to obtain a product (hereinafter referred to as silica-alumina-treated titanium oxide) treated with a coating material formed from the product.

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

While thoroughly stirring the silica-alumina-treated titanium oxide,
After adding silicon oil as it is or by dissolving it in a solvent,
Stir further. If necessary, the solvent is distilled off, the mixture is heated and baked, and then, if aggregates are present, the powder is pulverized to obtain a treated powder. Also, disperse silica-alumina-treated titanium oxide in a volatile solvent,
It is also possible to obtain a treated powder by adding silicon oil as it is or by dissolving it in a solvent and adding it, stirring the mixture, removing the solvent, heating and baking if necessary, and then crushing when aggregates are present.

At this time, as the silicone oil, methyl hydrogen polysiloxane, dimethyl polysiloxane, methyl phenyl polysiloxane, polyether modified silicone, olefin modified silicone, fluorine modified silicone, alcohol modified silicone, higher fatty acid modified silicone, amino modified silicone, cyclic silicone Etc. can be used.

The coating of silicon oil is preferably performed in an amount of 0.1 to 30% by weight, particularly 0.5 to 10% by weight, based on the silica-alumina-treated titanium oxide.

When the treated powder thus obtained is combined with another spherical powder, it is possible to remarkably improve the feeling of use such as good elongation on the skin and lack of squeaky feeling.

The spherical powder used for compounding may be either an inorganic powder or an organic powder, among which, for example, 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, copolymer of styrene and acrylic acid, Polypropylene, vinyl chloride, Teflon, acrylic beads, various plastics such as polyolefin, silicone resin, aluminum silicate cellulose and the like are preferable. The particle size of the spherical powder is preferably 0.5 to 100 μm, particularly preferably 5 to 20 μm.

The composite of the treated powder and the spherical powder can be obtained by, for example, roughly mixing the two, and then using an impact type crusher such as a ball mill or a hammer mill.
It is carried out by treating with a high-speed airflow impactor such as a hybridizer manufactured by Nara Machinery Co., Ltd. The weight ratio of the treated powder to the spherical powder used is preferably 0.01 to 100 of the former, and more preferably 0.1 to 1 with respect to the latter 1. By such a treatment, the treated powder is adhered to, immobilized on, or formed into a film on the surface of the spherical powder to obtain a composite powder.

As the cosmetics of the present invention, for example, powder foundations, cream foundations, O / W or W / O type milky liquid foundations, foundations such as O / W or W / O type oil cake type foundations; O / W or
Cream emulsions such as W / O creams, W / O or O / W emulsions; suspension cosmetics in which powder is dispersed in a liquid such as water, aqueous alcohol, oil, lip cream, sun care oil , Cheek red, eye shadow, mascara and the like.

The cosmetic of the present invention can be obtained by mixing the above-mentioned composite powder with a general cosmetic base in a conventional manner. The blending amount of the composite powder in the cosmetic varies depending on the type of the cosmetic, but is 0.1 to 50% by weight, particularly 1 to 25% by weight as the composite powder.
Is preferred.

Among the bases that can be used, powders include extenders such as mica, talc, sericite, kaolin, nylon powder, titanium oxide (excluding those having an average particle size of 30 to 70 nm),
Inorganic pigments such as zinc white, iron oxide, pearl, red 202, red 2
Organic pigments such as 26, yellow 4, and aluminum lake are used. Further, a powder subjected to a known surface-hydrophobicizing treatment such as silicon treatment, metal soap treatment, N-acylglutamic acid treatment may also be used. As the oil agent, silicone oil such as dimethylpolysiloxane, methylpolysiloxane, dimethylcyclopolysiloxane, and methylhydrogenpolysiloxane; hydrocarbons such as solid or liquid paraffin, crystal oil, ceresin, ozokerite, montan wax, and the like; Vegetable or animal oils and fats such as olive, ground wax, carnauba wax, lanolin and whale wax; and stearic acid, palmitic acid, oleic acid, glycerin monostearate ester, glycerin distearate ester, glycerin monooleate ester, isopropyl Fatty acids and their esters such as myristic acid ester, isopropyl stearic acid ester, butyl stearic acid ester; ethyl alcohol,
Examples thereof include alcohols such as isopropyl alcohol, cetyl alcohol, stearyl alcohol, palmityl alcohol, and hexyldecyl alcohol. Further, polyhydric alcohols having a moisturizing action such as glycol, glycerin and sorbitol can also be used.

Further, water, a surfactant, a thickener, an antiseptic, an antioxidant, a known ultraviolet absorber and the like, which are usually used in cosmetics, can be added.

〔Example〕

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

Synthesis Example 1 The average particle diameter 0.05μm fine titanium oxide is well dispersed in water to a 10 wt%, 10% sodium silicate solution corresponding to 2% by weight with respect to titanium oxide in terms of SiO ₂ (SiO ₂ / N
a ₂ O molar ratio = 0.5) and thoroughly stirred, and then 10% aluminum sulfate solution equivalent to 7.5% by weight of titanium oxide in terms of Al ₂ O ₃ was gradually added to the surface of titanium oxide. Acid hydrate and alumina hydrate were deposited. After completion of the reaction, the mixture was filtered, washed, dried, and then pulverized with a jet mill. This was transferred to a Henschel mixer, 2% by weight of methylhydrogenpolysiloxane was added with sufficient stirring, and after mixing and stirring, firing treatment was carried out at 120 ° C. to obtain a treated powder.

Synthetic Examples 2 to 7 Treated powders shown in Table 1 were obtained in the same manner as in Synthetic Example 1, except that the amounts of silicic acid hydrate and alumina hydrate were changed.

Table 1 also shows the results of a 1-month sun exposure test of 1 g of the treated powder obtained in Synthesis Examples 1 to 7 floated in 30 ml of purified water in a 50 ml sample bottle.

As is clear from Table 1, the treated powders used in the present invention (Synthesis Examples 1 and 2) did not lose their hydrophobicity even when exposed to sunlight.

Synthetic Example 8 40 g of the treated powder obtained in Synthetic Example 1 and 60 g of spherical polymethylmethacrylate powder (average particle size 8 μ) were placed in a ball mill, mixed and pulverized for 1 hour, and the treated powder and polymethylmethacrylate powder were combined. 90 g of powder was obtained.

Synthesis Example 9 50 g of the treated powder obtained in Synthesis Example 1 and 50 g of spherical nylon powder (average particle size 6 μ) were treated with a hybridizer to obtain 95 g of composite powder of the treated powder and nylon powder.

Synthesis Example 10 50 g of the silicon-treated titanium oxide obtained in Synthesis Example 6 and 50 g of spherical nylon powder (average particle size 6 μ) were treated with a hybridizer to obtain 95 g of a composite powder of silicon-treated titanium oxide and nylon powder. .

Test Example 1 With respect to the composite powders prepared in Synthesis Examples 8, 9 and 10, the feel on the skin was evaluated and the relative friction coefficient was measured.

Evaluation of the feel on the skin was performed by 10 expert panelists.
The following evaluation criteria were used.

○: 8 to 10 people judged that it felt good on the skin △: 5 to 7 people 〃 ×: 0 to 4 people 〃 Relative coefficient of friction was measured by Shinto Kagaku Co., Ltd. The friction coefficient of freeze-dried pig skin coated with a certain amount of the composite powder was measured, and the ratio to the friction coefficient of the freeze-dried pig skin itself was taken as the relative friction coefficient.

 The results are shown in Table 3.

Example 1 (Powder foundation) A powder foundation having the following composition was produced by the method shown below.

<Composition> Mica Residual amount Composite powder of Synthesis Example 9 10% by weight Talc Residual amount of red iron oxide 0.8% by weight Iron oxide yellow 2.5 Iron oxide black black 0.1 Liquid paraffin 8 Beeswax 2 Preservative A suitable amount Perfume Fine amount <Production method> Ingredients ~ Were mixed and ground. This was transferred to a high-speed blender, and components (1) to (3) were mixed and dissolved at 80 ° C, and the components were mixed uniformly. The ingredients were added to this mixture, mixed, and then ground again and passed through a sieve. This was compression molded on a gold plate.

Example 2 (Pressed powder) A pressed powder having the following composition was produced by the method shown below.

<Composition> Mica Residual amount Composite powder of Synthesis Example 8 10% by weight Talc Residual amount Bengal 0.1% by weight Yellow iron oxide 0.1 Black iron oxide 0.01 Liquid paraffin 8 Beeswax 2 Preservative Suitable amount Perfume Fine amount <Production method> Ingredients ~ Were mixed and ground. This was transferred to a high-speed blender, and components (1) to (3) were mixed and dissolved at 80 ° C, and the components were mixed uniformly. The ingredients were added to this mixture, mixed, and then ground again and passed through a sieve. This was compression molded on a gold plate.

Example 3 (O / W type cream) An O / W type cream having the following composition was produced by the method shown below.

<Composition> Beeswax 5.5 wt% cetanol 4.5 Hydrogenated lanolin 7 Squalane 33 Fatty acid glycerin 3.5 Lipophilic glyceryl monostearate 2 Polyoxyethylene (E020) sorbitan monolaurate 2 Synthetic powder of Synthesis Example 8 8 Fragrance minute amount Preservative Appropriate amount Antioxidant Appropriate amount Propylene glycol 4.5 wt% Purified water Appropriate amount <Production Method> The components and were mixed with stirring, and the mixture was kept at 80 ° C to obtain an aqueous phase part. The other components were mixed and dissolved by heating to 80 ° C to obtain an oil phase part. The above-mentioned water phase part was added to this oil phase part to carry out preliminary emulsification, and after homogenizing with a homomixer, the product was obtained by cooling to 30 ° C.

Example 4 (Cream foundation) <Composition> Stearic acid 5% by weight Lipophilic monoglyceryl monostearate 2.5 Cetostearyl alcohol 1 Propylene glycol monolaurate 3 Squalane 7 Olive oil 8 Purified water Residual amount Preservative Appropriate amount Triethanolamine 1.2 % By weight Solbit 3 Composite powder of Synthesis Example 9 10 Talc 5 Coloring pigment Appropriate amount Fragrance Fine amount <Production method> Ingredients were mixed and pulverized. Separately water phase component ~
A solution was prepared by mixing, and a crushed pigment was added to disperse the solution and then heated to 75 ° C. The ingredients were dispersed in a solution obtained by heating and dissolving the oil phase ingredients to 80 ° C., and the ingredients were added to the previously prepared aqueous phase while stirring and emulsified. This was cooled with stirring, the components were added at 50 ° C., and cooled with stirring.

[Effects of the Invention] As described above, according to the present invention, a silicon-treated titanium oxide and spherical particles in which a coating layer composed of silicic acid hydrate and alumina hydrate is interposed between the silicon coating layer and titanium oxide. By using the composite powder in which the powder and the powder are composited, it is possible to provide a cosmetic that prevents the silicone film and the oil agent for cosmetics from deteriorating and further improves the dispersibility to have an excellent ultraviolet protection effect.

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Claims (1)

(57) [Claims] 1. A substantially spherical or amorphous titanium oxide having an average particle size of 30 to 70 nm is contained in an amount of 1 to 4% by weight of silicic acid hydrate in terms of SiO ₂ and 6 in terms of Al ₂ O ₃ with respect to the titanium oxide. ~ 12% by weight mixed hydrate consisting of hydrated alumina and coated with silicon oil on the surface and powder 0.5 ~ 100
A cosmetic comprising a composite powder obtained by combining a spherical powder having a diameter of μm.