JP5201856B2 - Oily cosmetics - Google Patents

Description

  The present invention relates to an oily cosmetic having a skin unevenness covering force and good elongation and sticking on the skin.

  Conventionally, attempts have been made to use the optical properties of extender pigments as cosmetics that make it difficult to see the unevenness of the skin due to wrinkles, fine lines, pores, and the like. For example, Patent Document 1 proposes a cosmetic in which a powder obtained by coating the surface of a pigment with an inorganic silicon compound is used as a diffuse reflection type powder. In Patent Document 2, an attempt is made to make the unevenness of the skin such as wrinkles and pores difficult to see by combining spherical powders having different particle diameters.

  However, none of the cosmetics was effective in making the unevenness of the skin inconspicuous. When powder is blended at a high concentration in order to improve the unevenness covering power of the skin, there is a problem that the feeling of use is heavy, the powder does not adhere evenly on the skin and the result is a thick and powdery finish, and the natural finish cannot be obtained There was, and was not satisfactory.

JP 60-228406 A JP 10-338616 A

  SUMMARY OF THE INVENTION An object of the present invention is to provide an oily cosmetic material that has an uneven skin covering power, has good elongation and stickiness on the skin, and realizes a uniform and natural finish.

  The present inventors use a specific composite powder, a dialkyl phosphate polyvalent metal salt and a hydrocarbon oil in combination, so that the elongation and sticking on the skin is good, the unevenness covering power of the skin is high and uniform. It was found that an oily cosmetic material that achieves a natural finish can be obtained.

That is, the present invention includes the following components (A), (B) and (C);
(A) A composite powder having an average primary particle diameter of 10 to 100 nm and dispersed in aluminum hydroxide and / or aluminum oxide and having an average particle diameter of 0.5 to 10 μm, and the mass of the composite powder Provided is an oily cosmetic containing composite powder (B) dialkyl phosphate polyvalent metal salt (C) hydrocarbon oil in which the ratio of the mass of fine particle titanium oxide to 30% is 40%.

  The oily cosmetic of the present invention has a high unevenness covering power on the skin, has a good elongation and stickiness on the skin, and realizes a uniform and natural finish.

  The composite powder of component (A) used in the present invention has an average particle size of 0.5 to 10 μm in which fine titanium oxide having an average primary particle size of 10 to 100 nm is dispersed in aluminum hydroxide and / or aluminum oxide. It is.

The fine particle titanium oxide used in the composite powder may be in any form of anatase type, rutile type, and amorphous, and particularly a rutile type having a high refractive index. The shape can be any of spherical, spindle-shaped, rod-shaped, starfish-shaped, plate-shaped, and indefinite shape, but spherical, spindle-shaped, and rod-shaped are preferable from the viewpoint of excellent light scattering effect. As the fine particle titanium oxide, one whose surface is coated with a metal oxide such as alumina, silica or zirconia, or one obtained by doping a titanium oxide skeleton with a metal such as iron, manganese or cobalt can be used.
Furthermore, although the average primary particle diameter of the fine particle titanium oxide is 10 to 100 nm, it is particularly preferably 30 to 50 nm because both transparency and light scattering effect can be achieved. In addition, the particle diameter of fine particle titanium oxide is measured with an electron microscope.

  The composite powder is in a form in which the fine particle titanium oxide as described above is dispersed in aluminum hydroxide and / or aluminum oxide. Generally, a sol-gel method is used as a method for obtaining such a form. be able to. For example, when finely divided titanium oxide is dispersed in an aqueous aluminum sulfate solution, and a sodium carbonate aqueous solution is dropped while stirring, a composite in which finely divided titanium oxide is dispersed in an aluminum hydroxide gel is obtained. By washing, dehydrating and drying, an aluminum oxide / fine particle titanium oxide composite can be obtained. It is desirable to stop neutralization in a weakly acidic region to a neutral region. Moreover, the concentration of the aluminum salt in the metal salt solution in which fine particle titanium oxide such as an aluminum sulfate aqueous solution is dispersed is preferably 1 to 30% by mass, and particularly preferably 5 to 25% by mass. If the concentration is too high, a strong gel is formed, and desalting cannot be sufficiently performed. If the concentration is low, productivity is lowered, or the proportion of fine particle titanium oxide not taken into the gel increases. In addition, it can confirm with an electron microscope that fine particle titanium oxide is disperse | distributing in aluminum hydroxide and / or aluminum oxide.

  The content of fine particle titanium oxide in the composite powder is 30 to 40% by mass with respect to the total mass of the composite powder. Within this range, a good optical effect can be realized.

  Moreover, the average particle diameter of composite powder is 0.5-10 micrometers. Within this range, good coating feel, optical effect, adhesion and the like can be realized. The particle size of the composite powder is measured by electron microscope observation and particle size distribution measurement by a laser diffraction / scattering method. In the particle size distribution measurement, 10 parts by mass of the composite powder is dispersed with respect to 100 parts by mass of ethanol, and the obtained dispersion is measured with a particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.).

The composite powder is a porous body, and the specific surface area is preferably in the range of ²⁰ to 40 m ² / g by BET specific surface area measurement using nitrogen gas. Is possible.

  It is also possible to incorporate other additives such as inorganic and organic into the composite powder at the same time that the fine titanium oxide is fixed. Examples thereof include pearl pigments such as mica titanium, colored pigments such as iron oxide, plant extract, and organic ultraviolet absorbers.

  The composite powder of component (A) can be used after being subjected to various known hydrophobization treatments. Examples of a method for hydrophobizing powder include, for example, adsorbing fats and oils on the powder surface, or using ester or etherification using a functional group such as a hydroxyl group to make the pigment lipophilic. Oil treatment method; Metal soap treatment method using zinc salt or magnesium salt of fatty acid; Silicone treatment method using dimethylpolysiloxane or methylhydrogen polysiloxane; Method of treating with fluorine compound having perfluoroalkyl group .

  As the composite powder of component (A), one or more kinds can be used, and 0.05 to 30% by mass, particularly 0.1 to 25% by mass is contained in the total composition of the oily cosmetic of the present invention. It is preferable in terms of natural finish without being thick.

  Examples of the dialkyl phosphate polyvalent metal salt of component (B) include those represented by the following general formulas (1) to (3).

(Wherein R ¹ and R ² each independently represents a saturated or unsaturated linear or branched hydrocarbon group having 8 to 36 carbon atoms, m represents an integer of 1 to 3, and n represents An integer of 0 to 2, k represents 1 or 2, l represents 0 or 1, m + n = 3, and k + 1 = 2.

In general formulas (1) to (3), R ¹ and R ² preferably have 12 to 22 carbon atoms. R ¹ and R ² preferably represent a saturated linear hydrocarbon group having 12 to 20 carbon atoms.

  Examples of the hydrocarbon group having 8 to 36 carbon atoms include octyl, nonyl, decyl, dodecyl, undecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, Hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, hentriacontyl, dotriacontyl, octenyl, nonenyl, decenyl, dodecenyl, undecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonacenyl, triicosenyl Pentacocenyl, octacocenyl, nonacosenyl, triaco Tenenyl, Hentriacontenyl, Dotriacontenyl, Octadienyl, Undecadienyl, Tridecadienyl, Tetradedecadienyl, Pentadecadienyl, Hexadecadienyl, Heptadecadienyl, Octadecadienyl, Nonadecadienyl, Eicosadienyl, Henicosadi Enyl, docosadienyl, tricosadienyl, tetracosadienyl, pentacosadienyl, hexacosadienyl, heptacosadienyl, octacosadienyl, nonacosadienyl, triacontadienyl, entriacontadienyl, dotriacontadienyl, Examples include 2-hexyldecyl, 2-octylundecyl, 2-decyltetradecyl group and the like.

  Component (B) is a known compound and can be produced, for example, by the method described in JP-A No. 62-53913. Examples of the aluminum dialkyl phosphate represented by the general formula (1) include aluminum salts such as aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum phosphate, and aluminum carbonate, sodium dialkyl phosphate, potassium dialkyl phosphate, and dialkyl. Dialkyl phosphates such as triethanolamine phosphate and arginine dialkyl phosphate and an alkali hydroxide can be heated and reacted in an aqueous solution as necessary to cause salt exchange.

  The dialkyl phosphate iron salt represented by the general formula (2) includes, for example, iron salts such as ferric chloride, ferric sulfate, ferric nitrate, ferric phosphate, ferric carbonate, and dialkyl. Manufactured by a method in which dialkyl phosphates such as sodium phosphate, potassium dialkyl phosphate, triethanolamine dialkyl phosphate, arginine dialkyl phosphate and the like are reacted with alkali hydroxide in an aqueous solution by heating and reacting as necessary. can do.

  The dialkyl phosphate calcium salt represented by the general formula (3) includes, for example, calcium salts such as calcium chloride, calcium sulfate, calcium nitrate, calcium phosphate, calcium carbonate, sodium dialkyl phosphate, potassium dialkyl phosphate, and triethanol dialkyl phosphate. It can be produced by a method in which a dialkyl phosphate such as an amine or arginine dialkyl phosphate and an alkali hydroxide are heated and reacted in an aqueous solution as necessary to cause salt exchange.

  Two or more dialkyl phosphoric acid polyvalent metal salts of component (B) may be used in combination, and the content thereof is 0. 0 in the oily cosmetic composition of the present invention from the viewpoint of gelation of component (C). 1-15 mass% is preferable, Furthermore, 0.5-10 mass% is preferable.

  The hydrocarbon oil as component (C) is preferably a liquid oil having fluidity at 25 ° C. Examples of the hydrocarbon oil include liquid paraffin, light isoparaffin, liquid isoparaffin, and linear or branched hydrocarbon such as squalane and squalene.

  The hydrocarbon oil of component (C) may be used in combination of two or more, and the content thereof is 5 to 80% by mass in the oily cosmetic of the present invention from the viewpoint of gelation by component (B). More preferably, it is 10 to 60% by mass.

  The preferred content ratio of the component (B) to the component (C) in the oily cosmetic composition of the present invention is 1: 5 to 1:30, more preferably 1: 6 to 1:25, particularly 1: 7 to 1:20.

  The oily cosmetic of the present invention can further contain a spherical powder having an average particle diameter of 2 to 20 μm as the component (D), which is more excellent in pore concealing effect and better in elongation.

The average particle diameter of the component (D) is measured by the same method as the average particle diameter of the composite powder of the component (A).
Further, the spherical shape of the spherical powder of the component (D) means from a spherical shape to an elliptical shape. Specifically, {(area of a circle corresponding to the maximum particle diameter in a particle projection image) / (particle projection area) } A sphericity given by x100 is 100 to 120.

  The spherical powder of component (D) is preferably water-insoluble and oil-insoluble. The spherical powder of component (D) may be a composite powder composed of a plurality of powders. For example, the component (D) may be coated and encapsulated with a color pigment, dye, dye, metal ion or the like by a usual method and colored. Component (D) may be either inorganic spherical powder or organic spherical powder. The component (D) preferably has a refractive index of 2.0 or less, particularly 1.3 to 2.0, and more preferably 1.4 to 1.8. Component (D) can also be used after subjecting it to a hydrophobic treatment similar to that described for component (A).

  Examples of the spherical powder include spherical silica, spherical cellulose powder, spherical polymethyl methacrylate, spherical nylon powder, spherical polyethylene powder, spherical polystyrene powder, spherical silicone powder, and spherical methylsiloxane network polymer.

  Two or more spherical powders of component (D) may be used in combination, and the content thereof is preferably 1 to 40% by mass in the oily cosmetic composition of the present invention from the viewpoint of uneven covering power and usability. Further, 2 to 30% by mass, particularly 3 to 30% by mass is preferable.

  A preferable content ratio by mass of the component (A) and the component (D) in the oily cosmetic composition of the present invention is preferably 1: 1 to 1:50 in terms of the uneven covering power and the feeling of use.

  In addition to these, the oily cosmetics of the present invention include oily components other than component (C), powders other than components (A) and (D), surfactants, wetting agents, preservatives, antioxidants, Components such as a fragrance, an intercellular lipid (ceramide, etc.), an ultraviolet absorber, and a medicinal component can be appropriately blended.

  Oil components other than component (C) include oils such as olive oil, castor oil, jojoba oil, mink oil, macadamian nut oil; waxes such as beeswax, carnauba wax, candelilla wax, gay wax; cetyl isoocta Nate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, glyceryl trioctanoate, polyglyceryl diisostearate, diglyceryl triisostearate, glyceryl tribehenate, rosin acid pentaerythritol ester, neopentyl glycol dioctanoate, cholesterol fatty acid ester, Ester oils such as N-lauroyl-L-glutamate di (cholesteryl, behenyl, octyldodecyl); stearic acid, lauric acid, myristic acid, behenic acid, isostearic acid Fatty acids such as acid, oleic acid, 12-hydroxystearic acid; higher alcohols such as stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, behenyl alcohol, octyldodecanol; low polymerization dimethylpolysiloxane, high Degree of polymerization dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, polyether-modified polysiloxane, polyoxyalkylene / alkylmethylpolysiloxane / methylpolysiloxane copolymer, alkoxy-modified polysiloxane, Silicone oils such as cross-linked organopolysiloxane and fluorine-modified polysiloxane; perfluorodecane, perfluorooctane, perfluoropoly Fluorine-based oils such as ether; lanolin, lanolin acetate, lanolin fatty acid isopropyl, and the like lanolin derivatives such as lanolin alcohols.

  Two or more oily components other than the component (C) may be used in combination, and the content thereof is preferably 0.01 to 50% by mass in the oily cosmetic of the present invention from the viewpoint of feeling of use. Is preferably 0.1 to 40% by mass, particularly preferably 0.5 to 30% by mass.

  Examples of powders other than component (A) and component (D) include metal oxides such as iron oxide, titanium oxide, zinc oxide, fine particle titanium oxide, fine particle zinc oxide, flaky zinc oxide, zirconium oxide, and alumina; talc, Clay mineral powders such as mica, sericite, kaolin, bentonite, muscovite, synthetic mica, red mica, biotite, montmorillonite; inorganic pigments such as pearl pigments such as barium sulfate and titanium oxide-coated mica; Red No. 226 Organic coloring pigments such as yellow No. 401; organic dyes such as red No. 3, red No. 4, red No. 203 etc. raked, natural dyes raked; composite of inorganic powder and organic powder Examples thereof include organic powders such as composite powders.

  These powders may be fine particles, or two or more of these powders may be combined using mechanochemical means. Further, as these powders, the surface of the powder can be used after being subjected to the same hydrophobizing treatment as described for the component (A).

  The content of these powders in the cosmetic is preferably 0.01% by mass to 50% by mass, and more preferably 0.1% by mass to 40% by mass.

  The oily cosmetic composition of the present invention may further contain an oily gelling agent. Examples of the oily gelling agent include dextrin fatty acid ester, sucrose fatty acid ester, starch fatty acid ester, aluminum 12-hydroxystearate, calcium stearate and the like. Two or more kinds of these oily gelling agents may be used in combination, and the content thereof is preferably 0.1 to 10% by mass in the oily cosmetic of the present invention from the point of use feeling.

  The cosmetic of the present invention is an oily cosmetic, and preferably has a water content of 0.5% by mass even when water is not actively added and water is mixed in other ingredients. It is as follows. The oily cosmetic of the present invention can be in the form of, for example, a foundation or a base cosmetic.

  The oily cosmetic of the present invention is prepared, for example, by mixing the component (B), the component (C) and other oily components (if other oily components are included), and dissolving them by heating at 70 to 100 ° C. It can be obtained by adding the component (A) and other powders mixed in step 1, sufficiently mixing and stirring until it is uniform at 70 to 100 ° C., and cooling the resulting mixture.

Synthesis Example 1 (Production of composite powder)
As fine particle titanium oxide, rutile type titanium oxide having an average primary particle diameter of 35 nm was used. After dispersing 5.4 parts by mass of the fine particle titanium oxide in 100 parts by mass of purified water using a disper, 100 parts by mass of a 10% by mass aqueous solution of aluminum sulfate was mixed with the fine particle titanium oxide dispersion while stirring. Next, a 5% by mass aqueous solution of sodium carbonate was mixed with the fine particle titanium oxide dispersion while stirring, and about 100 parts by mass was added to neutralize the solution to pH 6.5. In addition, since it foamed vigorously at the time of injection | throwing and a gel was formed, it injected | threw in slowly. Next, the gel was transferred into 1000 parts by mass of purified water, stirred, filtered, and washed with purified water. Next, the obtained cake was blown and dried at 90 ° C., and then pulverized with a pulverizer and sieved to obtain a composite powder (average particle size 2.4 μm, specific surface area 32 m ² / g).
When this composite powder was observed with a transmission electron microscope, as shown in FIG. 1, fine particle titanium oxide was dispersed in aluminum oxide, and the content of fine particle titanium oxide was 33% by mass.

Synthesis Example 2 (Production of tri (dicetyl phosphate) aluminum)
Dicetyl phosphate (acid value: 103.0, molecular weight: 546) 15 g (0.027 mol) and aluminum isopropoxide 1.87 g (0.009 mol) are added to 70 mL of completely dehydrated benzene, and Widmer distillation is performed. When the apparatus is attached and heated and dissolved at 110 ° C. on an oil bath, isopropanol distills at 72 ° C. and benzene distills at 80 ° C. The remaining benzene was distilled off under reduced pressure to obtain 15 g of tri (dicetyl phosphate) aluminum as a white powder.
Actual value:
Phosphorus content 5.6%, aluminum content 1.6%
Theoretical value:
Phosphorus content 5.6%, aluminum content 1.6%

Examples 1-2, Comparative Examples 1-2 (oil-based foundation)
An oily foundation having the composition shown in Table 1 was produced by the following method. About the obtained oil-based foundation, the usability (goodness of elongation and goodness) and the finish (unevenness covering power) were evaluated. The results are also shown in Table 1.

(Production method)
Components (1) to (5) were mixed and dissolved by heating at 90 ° C. Furthermore, the components (6) to (15) mixed by the pulverizer were added, and the mixture was sufficiently mixed and stirred until it became uniform while maintaining at 90 ° C. An oily foundation was obtained by filling the mixture in a metal pan and cooling.

(Evaluation method)
(1) Feeling of use (good elongation, good feeling)
Ten professional panelists used each foundation, sensory-evaluated “goodness of growth” and “goodness of attachment”, and judged by the number of respondents who answered “good”.
(2) Finish (unevenness covering power)
Ten professional panelists used each foundation, sensory-evaluated the unevenness covering power such as pores, and judged by the number of people who answered that it was good.

  As shown in Table 1, the oil-based foundations of Examples 1 and 2 were good in both the feeling of use and the finish. Further, by using the oily foundations of Examples 1 and 2, a uniform and natural finish could be achieved.

Example 3 (oil-based foundation cosmetic)
Oily base cosmetics having the compositions shown in Table 2 were produced by the following method. The obtained base cosmetic was good in every sense of usability (good elongation, good adhesion, and finished (unevenness covering power)), and could have a uniform and natural finish.

(Production method)
Components (1) to (5) were mixed and dissolved by heating at 90 ° C. Furthermore, components (6) to (8) were added, and the mixture was sufficiently mixed and stirred until it became uniform while maintaining at 90 ° C. The mixture was cooled to obtain an oily base cosmetic.

Example 4 (oil-based foundation)
An oily foundation having the composition shown in Table 3 was produced by the following method. The obtained oil-based foundation was good both in terms of usability (good elongation and good adhesion) and finished (irregularity covering power), and could have a uniform and natural finish.

(Production method)
Components (1) to (6) were mixed and dissolved by heating at 90 ° C. Furthermore, the components (7) to (14) mixed by a pulverizer were added, and the mixture was sufficiently mixed and stirred until it became uniform while maintaining at 90 ° C. By cooling this mixture, an oily foundation was obtained.

Example 5 (oil-based foundation cosmetic)
Oily base cosmetics having the compositions shown in Table 4 were produced by the following method. The obtained base cosmetic was good both in terms of feeling of use (good elongation and good adhesion) and finished (unevenness covering power), and could have a uniform and natural finish.

(Production method)
Components (1) to (6) were mixed and dissolved by heating at 90 ° C. Furthermore, components (7) to (13) mixed by a pulverizer were added, and the mixture was sufficiently mixed and stirred until it became uniform while maintaining at 90 ° C. The mixture was cooled to obtain an oily base cosmetic.

4 is a diagram showing an example of a transmission electron micrograph of the composite powder produced in Synthesis Example 1. FIG.

Claims (6)

The following components (A), (B) and (C);
(A) A composite powder having an average primary particle diameter of 10 to 100 nm and dispersed in aluminum hydroxide and / or aluminum oxide and having an average particle diameter of 0.5 to 10 μm, and the mass of the composite powder containing fine particle fraction of the mass of titanium oxide Ri 30-40% der, a specific surface area of 20 to 40 m ² / g der Ru composite powder (B) a dialkyl phosphate polyvalent metal salt (C) a hydrocarbon oil for Oily cosmetics. Component (A), an oily cosmetic of claim 1, wherein were subjected to hydrophobic treatment. The oily cosmetic according to claim 1 or 2, comprising 0.05 to 30% by mass of component (A), 0.1 to 15% by mass of component (B), and 5 to 80% by mass of component (C). The oily cosmetic according to any one of claims 1 to 3 , wherein the content ratio (B) :( C) of the component (B) and the component (C) is 1: 5 to 1:30. Furthermore, the oil-based cosmetics of any one of Claims 1-4 containing spherical powder with a component (D) average particle diameter of 2-20 micrometers. The oily cosmetic according to claim 5, wherein the mass ratio (A) :( D) of the component (A) and the component (D) is from 1: 1 to 1:50.