JP3219886B2 - Powder cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powder cosmetic, and more particularly, to a component which is unstable in the presence of water or a component which, when dissolved in water, adversely affects the physical properties of a product (hereinafter referred to as "the component"). "Instable active ingredient") can be kept stable, and when it is rubbed at the time of use, it liquefies to produce a lotion-like property from the lotion. The present invention relates to a powder cosmetic capable of sufficiently exerting the function of a component.

[0002]

2. Description of the Related Art Cosmetics contain various active ingredients, which are easily decomposed in the presence of water.
In the case of an unstable active ingredient that is unstable such as being deteriorated or adversely affecting the physical properties of the product, its formulation is not only restricted in terms of the cosmetic formulation, but also in the form of containers and storage conditions. And various restrictions in handling and the like.

[0003]

Regarding such unstable active ingredients, irrespective of the invention of cosmetic containers and storage methods,
If it can be stabilized by the composition itself, its use range will expand,
Development of such a technique has been demanded since a more excellent cosmetic can be obtained.

[0004]

Means for Solving the Problems The present inventors have previously made the oily component and the aqueous component into powder by using a specific hydrophobized silicic acid anhydride and a fluorine compound-coated cosmetic powder, and then used as a powder. While using cosmetics, the refreshing feeling during use,
They have found that a cosmetic that gives a moist feeling and can impart affinity to the skin, emolliency, moisture and the like can be obtained, and has previously filed patent applications (Japanese Patent Application Nos. 4-46752 and 4-321).
946).

[0005] Then, when various investigations were made on the components that can be contained in this cosmetic, the unstable active ingredient, which was unexpectedly considered to be incapable of being incorporated into conventional cosmetics, was found in the cosmetic of this embodiment. Found that it can be stably blended.

The present invention has been completed based on this finding and comprises the following components (a) to (e): (a) 0.1 to 7% by weight of a hydrophobized silicic anhydride having a surface area of 80 m ² / g or more. (B) Fluorine compound-coated cosmetic powder 1 to 50% by weight (c) Oily component 0.5 to 40% by weight (d) Aqueous component 30 to 90% by weight (e) Contact with water, light and heat Disclosed is a powder cosmetic which contains 0.001 to 10% by weight of an unstable active ingredient which causes decomposition, deactivation, crystal precipitation, discoloration and discoloration due to an influence, and is liquefied by rubbing. .

The hydrophobized silicic anhydride of the component (a) used in the present invention is prepared by covering the surface of fine silicic acid anhydride with an organosilane compound, a silicone compound, a fluorine compound or the like. , Trimethylsiloxylated silicic anhydride, dimethylsiloxylated silicic anhydride, octylsiloxylated silicic anhydride, silicic anhydride treated with silicone oil, and a fluorine compound (I) or (I)
Silicic anhydride treated in I).

Among the above-mentioned hydrophobized silicic anhydrides, trimethylsiloxylated silicic acid is Cabosil TS-5.
30 (manufactured by Cabot Corp .; surface area: 325 m ² / g) is Esilyl R as dimethylsiloxylated silicic anhydride.
-972 (manufactured by Degussa; surface area 110 ± 20 m ² /
g) are listed as examples of commercially available products, and octylsiloxylated silicic anhydride is Esilyl R-
805 (manufactured by Degussa; surface area: 150 ± 25 m ² / g)
However, as silicic acid treated with silicone oil, Esilyl R-202 (manufactured by Degussa; surface area 100 ± 20 m)
² / g) are examples of commercially available products.

These hydrophobic silicic anhydrides have a surface area of 80 m.
² / g or more, and if the surface area is smaller than this, the particle size of the hydrophobized silicic acid anhydride becomes large, so that it is not possible to orient a large amount on the surface of the aqueous component, and the aqueous component is stably formed. There is a possibility that powdering cannot be performed.

[0010] The component (b) of the present invention is a cosmetic powder coated with a fluorine compound. This cosmetic powder is generally used in cosmetics. If it is not particularly limited, for example, talc, mica, kaolin, magnesium carbonate, calcium carbonate, aluminum silicate, magnesium silicate, calcium silicate, titanium oxide, zinc oxide, silicic anhydride, red iron oxide, yellow iron oxide,
Examples include black iron oxide, gunjou, konjo, tar dye, natural dye, titanium mica, titanium mica titanium oxide, bismuth oxychloride, nylon powder, silk powder, polyethylene powder, silicone powder and the like.

On the other hand, as a fluorine compound for coating these powders for cosmetics, a fluorine compound used for the purpose of imparting water repellency and oil repellency can be used. Examples include perfluoroalkylphosphate diethanolamine salts represented by the formula (I) and perfluoroalkylsilane represented by the general formula (II).

[0012]

Embedded image (In the formula, n represents an integer of 6 to 18, and m represents 1 or 2.)

Embedded image (In the formula, a represents an integer of 1 to 12, b represents an integer of 1 to 5, X represents the same or different and represents an alkoxy group, a halogen atom or an alkyl group. However, all Xs represent an alkyl group. Except in the case of

Preferred examples of these fluorine compounds include Asahigard AG530 (manufactured by Asahi Glass Co., Ltd.) and LS
-160, LS-360, LS-912, LS-108
0, LS-1090, LS-1465 (all manufactured by Shin-Etsu Chemical Co., Ltd.), XC95-418, XC95-46
6, XC95-467, XC95-468, XC95-
469, XC95-470, XC95-471, XC9
Commercially available products such as 5-472 (all manufactured by Toshiba Silicone Co., Ltd.) can be mentioned.

In the present invention, it is necessary that the powder of the component (b) is not only water-repellent but also coated with these fluorine compounds. In other words, in the field of powder cosmetics, in order to impart water repellency to powder, various surface treatments such as oil treatment such as silicone treatment and high melting point wax treatment, and metal soap treatment other than fluorine compound treated powder are used. Although those treated are known, these treated powders do not impart oil repellency, show wetness when mixed with oily components, and further wet hydrophobicized silicic anhydride, The function of pulverizing the aqueous component is also lost. If the water-repellent powder is used to forcibly powder the aqueous component, a large amount of hydrophobized silicic acid is required, and the aqueous component can be powdered, but liquefaction during use occurs smoothly. Is not preferred in terms of functionality.

In the present invention, a powder treated with a compound other than a fluorine compound or an untreated powder is used by mixing with a powder for cosmetics treated with a fluorine compound within a range not to impair the effects of the present invention. Of course you can.

In order to treat the cosmetic powder with the perfluoroalkyl phosphate ester / diethanolamine salt (I) to obtain the component (b), for example, water is added to the cosmetic powder. A slurry was formed, water was added thereto, and the mixture was stirred, and 0.1 to 5% by weight of an emulsion-form perfluoroalkyl phosphate ester / diethanolamine salt (I) was gradually added thereto and mixed. Alternatively, the emulsion may be broken by standing at a high temperature or the like, and the emulsion may be washed, filtered, and dried.

When a perfluoroalkylsilane represented by the general formula (II) is used, the method can be carried out in the same manner as the method for treating a hydrophobized powder treated with silicone or metal soap.
For example, perfluoroalkylsilane (II) may be added to a powder for cosmetics by spraying or dripping perfluoroalkylsilane (II) as it is or diluted with a solvent (eg, methanol, ethanol, chloroform, dichloromethane, volatile silicone, water, etc.). Then, after uniformly dispersing, drying at room temperature or under heating may be performed.

Further, as the oily component which is the component (c) of the present invention, various solid, semi-solid and liquid vegetable oils, animal oils, mineral oils and synthetic oils which are usually used in cosmetics can be used. .

Specifically, for example, fats and oils such as olive oil, jojoba oil, mink oil, and mokurou; waxes such as beeswax and candelilla wax; hydrocarbons such as liquid paraffin, microcrystalline wax and petrolatum; stearic acid; Fatty acids such as oleic acid; higher alcohols such as cetanol; esters such as isopropyl myristate;
Lanolin derivatives such as isopropyl lanolin fatty acid and lanolin alcohol; silicone compounds such as methylpolysiloxane and methylphenylpolysiloxane;

These components (c) can be used alone or in combination of two or more. In addition, organically modified clay minerals, starch fatty acid esters, dimethylpolysiloxane polymers having a three-dimensional cross-linked structure, etc. A so-called oily gelling agent can be used in combination.

Further, as the component (c), an oily component is carried on a fine powder of a high melting point wax such as a microcrystalline wax, a porous powder such as magnesium carbonate, or a highly cohesive polymer such as an acrylate copolymer. Absorbed and powdered products, and those obtained by encapsulating an oily component with polymethyl methacrylate or the like can also be used.

Further, the aqueous component which is the component (d) of the present invention can be used without any particular limitation as long as it is an aqueous component used in ordinary cosmetics. For example, purified water, glycol, glycerin and the like can be used. Examples thereof include polyhydric alcohols and water-soluble polymers.

Lastly, the unstable active ingredient blended as the ingredient (e) of the present invention is a water-soluble ingredient which requires the intervention of water in order to exhibit its function. Instability in the presence of water, such as decomposition, deactivation, crystal precipitation, discoloration, and odor due to the influence of light, heat, etc. Or a component that, when dissolved in water, affects the physical properties of the preparation, and when mixed as it is, is a cosmetic component that causes separation, aggregation, thickening, etc., for example, enzymes such as lipase, protease, dialkyl ascorbyl, Examples include water-soluble ascorbic acid derivatives such as magnesium L-ascorbyl phosphate, pyridoxine hydrochloride, resorcinol, and sulfur.

Ingredients (a) to in the cosmetic of the present invention
The mixing ratio of (e) with respect to the total composition is as follows.

That is, the amount of component (a) is 0.1 to 0.1.
7% by weight (hereinafter simply indicated as%), preferably 2 to 4%
It is. If the amount of component (a) is less than 0.1%, the aqueous component may not be sufficiently pulverized, and the intended powder form may not be obtained. Also, 7
%, A large amount of the aqueous component can be powdered, but it may not liquefy even when rubbed at the time of use and may not have a liquid-like feel.

The amount of component (b) is 1 to 50%. If the blending amount of the component (b) is less than 1%, the blending of the component (c) may not be possible, and if it exceeds 50%, a liquid-like feel may not be obtained during use. Further, the amount of component (c) is 0.5 to 40%. If it is less than 0.5%, the hydrophobized silicic acid absorbs sweat and sebum when it is applied to the skin, causing skin roughness, powderiness, and a feeling of tightness. Silicic acid may be wet , and the hydrophobized silicic anhydride and the oil component may become a continuum, and may not have a powdering function or may not be able to liquefy smoothly.

Further, the amount of component (d) varies depending on the composition ratio and amount of component (a) and component (b), but is generally 30 to 90%. If it is less than 30%, liquefaction becomes difficult when rubbed, and if it exceeds 90%, it may not be possible to powder it, which is not preferred in terms of functionality. The amount of component (e), which is an unstable active ingredient, is
It is 0.001 to 10%, preferably 0.01 to 5%.

In the above composition, a surface area of 80
When silicic anhydride coated with a fluorine compound is selected as the hydrophobized silicic anhydride of m ² / g or more, component (a) and component (b) are the same. In this case, since the silicic anhydride has both the action as the component (a) and the action as the component (b), it is blended in the cosmetic as the total of the component (a) and the component (b). It should be understood that there is.

In the powder cosmetic of the present invention, in addition to the above essential components, various optional components used in ordinary cosmetics, such as fragrances, preservatives, ultraviolet absorbers, etc., do not impair the effects of the present invention. Can also be blended.

The powder cosmetic of the present invention is produced, for example, as follows in consideration of the composition and the amount of each component, the type of the active ingredient, and the like. A mixture of the component (a), the component (d) and the component (e) and powdered, and the component (b) and the component (c)
Are mixed and powdered. The component (a) is mixed with the powder obtained by mixing the component (b) and the component (c), and then the component (d) is added thereto.
And component (e) are mixed and powdered. A powder obtained by mixing the component (a) and the component (d) with the component (b), the component (c) and the component (e).
Are mixed and powdered. The component (b), the component (c) and the component (e) are mixed and powdered, and then the component (a) is mixed. Then, the component (d) is mixed with the powder and powdered.

The cosmetic of the present invention produced as described above is a powdery cosmetic, but liquefies by rubbing and can stably hold an unstable active ingredient.

[0032]

The powder cosmetic of the present invention comprises component (c), component (d) and component (e) by component (a) and component (b).
When the force is applied by rubbing, this adsorption state is destroyed, and the powdered components (c) and (d) ooze out and liquefy, and the effectiveness of the component (e) Is exhibited.

The reason why the unstable active ingredient is stably retained in the cosmetic of the present invention is not yet clear,
It is presumed that suppression of decomposition and the like by suppressing the unstable active ingredient from coming into direct contact with water, blocking of light and heat by the powder, a buffering action, and the like are performed.

[0034]

Next, the present invention will be further described with reference to examples and test examples, but the present invention is not limited to these examples.

Example 1 Powder Cosmetic: A powder cosmetic was prepared according to the following composition and manufacturing method, in which resorcinol, a component which easily discolors by light in an aqueous cosmetic, was blended.

(Composition) (% by weight) (1) Trimethylsiloxylated silicic anhydride ^* 5.0 (2) Resorcin 0.5 (3) 1,3-butylene glycol 5.0 (4) Glycerin 5. 0 (5) Lactic acid 0.1 (6) Sodium lactate 0.1 (7) Preservatives 0.2 (8) Refined water residue (9) Asahigard AG530 5% treated talc ^** 5.0 ( 10) Asahigard AG530 5% treated nylon powder ^** 10.0 (11) Starch fatty acid ester 2.3 (12) Squalane 0.2

* Cabosil TS-530 (manufactured by Cabot) ** Manufactured as above using Asahigard AG530.

(Production method) A. Mix and crush (9) and (10). B. After heating and dissolving (11) and (12), mix with A and stir. C. Mix and stir (1) to (8). D. Mix B and C and fill into container.

Example 2 Powder Cosmetic: A powder cosmetic containing L-ascorbyl magnesium phosphate which is a component which easily causes crystal precipitation and precipitation in an aqueous cosmetic was prepared by the following composition and production method. .

(Composition) (% by weight) (1) Trimethylsiloxylated silicic anhydride ^* 5.0 (2) Magnesium L-ascorbyl phosphate 1.0 (3) Sodium citrate 1.0 (4) 1 , 3-butylene glycol 5.0 (5) Glycerin 5.0 (6) Preservatives 0.2 (7) Purified water residue (8) Asahigard AG530 5% treated mica ^** 5.0 (9) Asahigard AG530 5% treated polyethylene powder ^** 10.0 (10) Partially crosslinked organopolysiloxane polymer 1.0 (11) Dimethylpolysiloxane (100cs) 2.0

* Cabosil TS-530 (manufactured by Cabot) ** Manufactured as described above using Asahigard AG530.

(Production method) A. (8) and (9) are mixed and pulverized. B. Add (10) and (11) to A and mix with (1). C. Mix (2) to (7) and stir. D. Mix B and C and fill into container.

Test Example 1 The cosmetic of the present invention prepared in Examples 1 and 2
The residual amount of the unstable active ingredient when stored at 0 ° C was determined by HPL
C, and the residual ratio was determined from this. Table 1 shows the results.

[0044] As is clear from the results shown in Table 1, in the powder cosmetics of Examples 1 and 2, almost no unstable active ingredient remained even after 6 months at 40 ° C, and there was no problem in stability over time. Was.

Test Example 2 The stability of resorcinol in the cosmetic prepared in Example 1 was compared with the stability of a cosmetic prepared by a conventional method using Comparative Composition 1. Table 2 shows the results.

(Comparative composition 1) (% by weight) Lactic acid 0.1 Sodium lactate 0.1 Refined water Resorcinol 0.5 Ethanol 15.0 Preservative 0.1

(Stability test method) The cosmetic obtained in Example 1 and the cosmetic obtained in Comparative composition 1 were stored for 6 months under the conditions of room temperature, exposure room temperature and 40 ° C, and the presence or absence of yellowing was checked. Examined.

(Result)

Evaluation: Symbol Evaluation contents ◎ The cosmetic did not yellow. ○ The cosmetic slightly yellowed. × Cosmetics clearly yellowed.

As is clear from the results in Table 2, the cosmetic of Comparative Composition 1 showed a clear yellowing under any conditions, whereas the cosmetic of Example 1 showed almost yellowing in appearance. This was not the case, and it was the same when liquefied by rubbing and observed.

Test Example 3 The stability of magnesium L-ascorbyl phosphate in the cosmetic prepared in Example 2 was compared with the stability of a cosmetic prepared in a conventional manner using Comparative Composition 2.

(Comparative composition 2) (% by weight) 1,3-butylene glycol 15.0 glycerin 2.0 L-ascorbyl magnesium phosphate 1.0 Preservative 0.1 alcohol 5.0 Refined water

(Stability Test Method) The cosmetic obtained in Example 2 and the cosmetic obtained in Comparative Composition 2 were stored at room temperature, exposure room temperature and 40 ° C. for 6 months to determine whether crystals were precipitated. Was examined. As a result, precipitation and precipitation of crystals were observed in the cosmetic of Comparative Composition 2 under any conditions, whereas the cosmetic of Example 1 had no change in appearance, was stable as a product, and had no problems. It was shown that.

Examples 3 and 4 Powder cosmetics containing an enzyme whose activity was known to be reduced by contact with water were produced by the following composition and production method.

(Composition) Example 3 Example 4 (1) Trimethylsiloxylated silicic anhydride ^* 5.0 5.0 (2) Asahigard AG530 5% -treated talc ^** 5.0 5.0 (3 Asahi Guard AG530 5% treated Niro 7.0 7.0 powder ^** (4) Lipase 0.5- (5) Protease-0.5 (6) 1,3-butylene glycol 5.0 5.0 ( 7) Glycerin 5.0 5.0 (8) Preservatives 0.2 0.2 (9) Residual purified water Residual residual (10) Partially crosslinked organopolysiloxane polymer 1.0 1.0 (11) ) Dimethyl polysiloxane (100 cs) 0.5 0.5

* Cabosil TS-530 (manufactured by Cabot Corporation) ** Manufactured as above using Asahigard AG530.

(Production method) A. (1) is mixed with (6) to (9). B. Mix (2) to (5), (10) and (11). C. Mix A and B.

Test Example 4 The cosmetics prepared in Examples 3 and 4 were stored at 40 ° C., and the enzymatic activity was measured by the method described below.
The remaining activity after 5 days was 83% and 54% , respectively. The aqueous solution of lipase and the aqueous protease solution diluted so as to show the same value as the initial activities of Examples 3 and 4 show no activity after 2 days. It was confirmed that it was extremely effective in improving the quality.

(Enzyme activity measurement) Lipase activity measurement: 2.0 ml of olive oil emulsion (substrate, manufactured by Sigma Chemical Co., Ltd.) was placed in a test tube, and pH was added thereto.
7.0 of 0.1 M phosphate buffer (0.1 M Na ₂ HPO)
₄ · 12H ₂ O and 0.1M-KH ₂ PO ₄ The combined pH7.
0.8 ml) and incubated at 37 ° C. for about 5 minutes. 0.4 ml of the sample solution is added to this,
Incubated at 37 ° C. for exactly 15 minutes. Thereafter, 5 ml of an acetone-ethanol mixed solution (1: 1) was added to stop the reaction, 3 drops of 0.9% thymolphthalein ethanol solution were added, and the mixture was titrated with a 0.05N aqueous solution of sodium hydroxide.

The enzyme activity is determined by the following formula,
1 lipase unit (Li)
pase Unit; LU).

Enzyme activity (LU / ml = μmole / min / ml) =
N × f × (V _T −V _B ) / 1000 × 10 ⁶ × 1 / V _S × 1
/ T

N: NaOH normality (= 0.05) f:
NaOH normality coefficient V _T : titration (ml) V _B : blank titration (ml) V _S : sample volume (= 0.4 ml) T: incubation time (= 15 minutes)

Measurement of protease activity: 3.0 ml of casein solution (* 1) was placed in a test tube, and kept at 37 ° C. in advance, and 0.6 ml of enzyme sample solution (* 2) was added to 37 ° C.
After warming for 20 minutes, 3.0m of protein precipitation reagent (Note 3)
The enzyme reaction was stopped by adding 1 and filtered. Filtrate 0.8
Transfer to a test tube, add 2.0 ml of 0.55 M sodium carbonate aqueous solution and 0.4 ml of Folin reagent (Note 4), and heat at 37 ° C. for 30 minutes to develop a color.
Was measured. Enzyme activity was indicated amount of enzyme to 1 increase the absorbance at 660nm in the above measurement conditions in one minute as 1U _660.

(Note 1) Casein solution Casein (manufactured by Hammarsten) 50 g per 1.2 g
160 ml of an aqueous solution of mM disodium hydrogen phosphate
Heat to completely dissolve, adjust the pH to 7.5 with dilute hydrochloric acid, and add purified water to make 200 ml.

[0065] (2) so that the enzyme sample solution tested proteases _0.2~1.0U 660 / ml, which was diluted in diluent. The diluent was prepared by dissolving 0.57 g of sodium dihydrogen phosphate in 80 ml of purified water, adjusting the pH to 7.5 with diluted hydrochloric acid, and adding purified water to make 100 ml.

(Note 3) Protein precipitation reagent Trichloroacetic acid 18.0 g Sodium acetate 18.0 g Acetic acid 19.0 ml The above compound was dissolved in purified water to make 1 liter.

(Note 4) Folin reagent A commercially available folin reagent (manufactured by Merck) diluted three times with purified water.

[0068]

The powder cosmetic of the present invention, while being a powder, is liquefied by rubbing at the time of use, gives a refreshing feeling and moist feeling during use, and is excellent in affinity for skin, emollient, moisture, etc. And can provide a good feeling of use and finish, and can stably maintain an unstable active ingredient in the composition, which was conventionally considered difficult to be incorporated into cosmetics. It can be widely used as a new type of cosmetic. that's all

──────────────────────────────────────────────────の Continued on the front page (72) Inventor Kimie Hayashi 48-18 Sakaemachi, Kita-ku, Tokyo Inside Kose Research Institute Co., Ltd. (72) Inventor Kenshi Takada 48-18 Sakaemachi, Kita-ku, Tokyo Kose Research, Inc. (56) References JP-A-5-65212 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61K ^7/ 00-7/50

Claims (3)

(57) [Claims] 1. The following components (a) to (e): (a) 0.1 to 7% by weight of hydrophobized silicic anhydride having a surface area of 80 m ² / g or more (b) Fluorine compound-coated cosmetic powder 1 (C) oily component 0.5 to 40% by weight (d) aqueous component 30 to 90% by weight (e) Decomposition, deactivation, crystal precipitation, discoloration due to contact with water, light and heat A powder cosmetic, which contains 0.001 to 10% by weight of an unstable active ingredient that produces an unpleasant odor, and is liquefied by rubbing. 2. The method according to claim 2, wherein the unstable active ingredient of the component (e) is an enzyme,
Water-soluble ascorbic acid derivatives, pyridoxine hydrochloride, powder cosmetic as in claim 1 wherein a compound selected from resorcinol and sulfur. 3. The fluorine compound used for coating the component (b) with a fluorine compound is represented by the following general formula (I): (Wherein n represents an integer of 6 to 18 and m represents 1 or 2) and a perfluoroalkyl phosphate diethanolamine salt represented by the following general formula (II): (In the formula, a represents an integer of 1 to 12, b represents an integer of 1 to 5, X represents the same or different and represents an alkoxy group, a halogen atom or an alkyl group. However, all X represents an alkyl group. one or two or more at which claim powder cosmetic of claim 1 wherein the compound selected from perfluoroalkyl silanes represented by unless).