JP5818680B2 - Water-in-oil emulsified cosmetic - Google Patents

Description

  The present invention relates to a water-in-oil emulsified cosmetic.

  The water-in-oil type emulsified cosmetic is an agent whose outer phase is an oil agent, and is thus easily imparted with water resistance, and is a dosage form that is often used in recent years for emulsified type foundations and sunscreens. Further, since it is relatively easy to impart a moisturizing feeling, it is a dosage form useful for skin care. On the other hand, water-in-oil type emulsified cosmetics have drawbacks in the oily feel and the weight when applied. In order to eliminate the drawbacks, volatile oils such as cyclic silicones and ethanol are used as oils, and silicone surfactants modified with polyethers and polyglycerins and organically modified clay minerals are used. (See Patent Document 1).

Japanese Patent No. 3023250

However, water-in-oil emulsified cosmetics using such a technique are likely to cause phenomena such as oil bleeding and separation, and it is very difficult to ensure storage stability. Further, if the viscosity is increased with wax or the like in order to ensure storage stability, the feeling becomes worse. As described above, it has been very difficult to make water-in-oil emulsified cosmetics compatible with both good storage stability and good touch.
In addition, in a water-in-oil emulsified cosmetic containing powder, when trying to give elasticity like a gel as a new feel, the dispersibility of the powder becomes worse and the feel when applied becomes worse. There was a problem.
Accordingly, an object of the present invention is to provide a powder-containing water-in-oil emulsified cosmetic that has excellent feel when applied, good storage stability, and has a unique elasticity in touch.

  Therefore, as a result of various studies to solve the above-mentioned problems in water-in-oil emulsified cosmetics containing powder, the present inventor adopted a liquid sorbitan fatty acid ester and / or diglycerin fatty acid ester at 25 ° C. If a certain amount of a polymer having a modified silicone such as polyether-modified silicone and an organopolysiloxane segment having a specific hydrophilic segment is within a certain range, the feel during application is smooth and good elasticity. It was found that a water-in-oil emulsified cosmetic having a good storage stability from low to high temperatures was obtained, and the present invention was completed.

  That is, the present invention provides (A) a sorbitan fatty acid ester and / or diglycerin fatty acid ester that is liquid at 25 ° C., (B) one kind selected from polyether-modified silicone, polyglycerin-modified silicone, and fluoropolyether co-modified silicone, or Two or more types, (C) 1.5 to 8% by mass of a polymer comprising a hydrophilic segment having a repeating unit of N-acylalkyleneimine and an organopolysiloxane segment as a constituent unit, based on the total amount of the cosmetic, and (D) A water-in-oil emulsified cosmetic comprising a powder is provided.

  The water-in-oil emulsified cosmetic of the present invention is excellent in touch at the time of application, has good storage stability, and has elasticity.

  As (A) sorbitan fatty acid ester and diglycerin fatty acid ester which are liquid at 25 ° C. used in the present invention, those having an HLB value of 6 or less are preferable. As the fatty acid part of such sorbitan fatty acid ester and diglycerin fatty acid ester, isostearic acid and oleic acid are preferable. Specific examples of component (A) include sorbitan monoisostearate, sorbitan monooleate, sorbitan sesquiisostearate, sorbitan sesquioleate, diglyceryl monoisostearate, diglyceryl monooleate, and the like at the time of coating. From the viewpoint of excellent touch, sorbitan monoisostearate is preferred.

  The content of the component (A) used in the present invention is preferably 0.3 to 5% by mass, more preferably 0.5 to 4% by mass, and further preferably 1 to 3% by mass based on the total amount of the cosmetic. %. Within this range, the dispersibility of the powder is good, and the feel during application is good without feeling the stickiness of the component (A) itself.

  As the (B) polyether-modified silicone, polyglycerin-modified silicone, and fluoropolyether co-modified silicone used in the present invention, those having an HLB value of 6 or less are preferable. Examples of the polyether-modified silicone include silicone having a polyoxyethylene and / or polyoxypropylene group having an HLB value of 6 or less, and examples of the polyglycerin-modified silicone include silicone having a polyglycerin group having an HLB value of 6 or less. Examples of the fluorine polyether-modified silicone include silicones having a fluorine-substituted alkyl group having an HLB value of 6 or less and a polyoxyethylene and / or polyoxypropylene group. Preferable examples include those represented by the following formulas (1) and (2).

(Wherein, m is 50 to 1000, n is 1 to 40, and a and b are each an integer of 5 to 50)

(Wherein l, m and n are integers, l = 0 to 500, m = 1 to 500, n = ^{1 to} 500, and R ¹ is the same or different alkyl group having 1 to 20 carbon atoms. Or an aryl group having 6 to 14 carbon atoms, R ² is a fluorine-substituted alkyl group having 1 to 10 carbon atoms, and R ³ is —C _p H _2p O (C ₂ H ₄ O) _a (C ₃ H ₆ O) is a polyoxyalkylene group represented by _b R ^5, R ⁴ is any of R ^1, R ² or R ^3, R ⁵ is a hydrogen atom, an alkyl group or an acetyl group having 1 to 5 carbon atoms A, b, p are integers, a = 0 to 100, b = 0 to 100, a + b is 1 or more, and p = 2 to 6.

  Commercially available products such as BY22-008M (PEG / PPG-19 / 19 dimethicone, manufactured by Toray Dow Corning), BY11-030 (PEG / PPG-19 / 19 dimethicone, manufactured by Toray Dow Corning), etc. Silicone, polyglycerin-modified silicones such as KF-6104 (polyglyceryl-3 polydimethylsiloxyethyl dimethicone, manufactured by Shin-Etsu Chemical Co., Ltd.), KF-6105 (lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone, manufactured by Shin-Etsu Chemical Co., Ltd.), Fluorine polyether co-modified silicones such as FPD-6131 (PEG-8 trifluoropropyl dimethicone copolymer, manufactured by Shin-Etsu Chemical Co., Ltd.) can be mentioned.

  The content of the component (B) used in the present invention is preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass based on the total amount of the cosmetic. When the content falls within the above range, the storage stability is good, and the feel at the time of application is good without feeling the stickiness of the component (B) itself. The content ratio of component (A) to component (B) is preferably 3: 1 to 1: 5, more preferably 1: 1 to 1: 3. Within this range, the storage stability and the feel during application are good.

In the present invention, the HLB value means a value calculated by the following Kawakami equation (I).
HLB = 7 + 11.7 log (Mw / Mo) (I)
Here, in the formula (I), Mw represents the molecular weight of the hydrophilic base and Mo represents the molecular weight of the lipophilic base.

  Examples of the polymer having (C) N-acylalkylenimine as a repeating unit and an organopolysiloxane segment as structural units used in the present invention include those represented by the following formula (3).

(In the formula, n represents a number of 1 to 5, R ⁹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, m represents a degree of polymerization of the monomer, and represents a number of 1 to 1000; Represents an average of 10 to 2000, p represents an average of 0 to 20, q represents an average of 1 to 20, X ⁻ represents a counter ion of a quaternary ammonium ion, ethyl sulfate ion, methyl sulfate ion, chloride ion , Iodine ion, sulfate ion, p-toluenesulfonate ion or perchlorate ion, where a polymerization initiator residue is bonded to the N-terminal of the repeating unit of N-acylalkylenimine)
As the polymerization initiator, diethyl sulfate, dimethyl sulfate, hydrochloric acid, hydrogen iodide, sulfuric acid, p-toluenesulfonic acid, perchloric acid and the like are used, and these residues are bonded to the N-terminal after polymerization.
In particular, N-propionyl polyethyleneimine / methyl polysiloxane copolymer (POLYSILICON-9) is preferable.

  Content of the component (C) used for this invention is 1.5-8 mass% on the basis of cosmetics total amount, Preferably it is 1.5-7.5 mass%, More preferably, it is 2-4 % By mass. If the content is less than 1.5% by mass, an elastic gel cannot be obtained, and satisfactory results are not obtained in terms of storage stability. On the other hand, if it exceeds 8% by mass, an elastic gel can be formed, but the feel at the time of application becomes very heavy, and the storage stability is deteriorated.

  As the powder (D) used in the present invention, if it is a powder generally used in cosmetics, it has a spherical shape, a plate shape, a needle shape, a mist shape, fine particles, a particle size such as a pigment grade, a porous shape, It can be used without being particularly limited by the particle structure such as non-porous. Specifically, titanium oxide, black titanium oxide, conger, ultramarine, bengara, yellow iron oxide, black iron oxide, zinc oxide, aluminum oxide, silicon dioxide, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, chromium oxide, Chromium hydroxide, carbon black, aluminum silicate, magnesium silicate, magnesium aluminum silicate, mica, synthetic mica, synthetic sericite, sericite, talc, kaolin, silicon carbide, barium sulfate, bentonite, smectite, boron nitride, etc. Inorganic powders: bismuth oxychloride, titanium mica, iron oxide-coated mica, iron oxide mica titanium, organic pigment-treated mica titanium, aluminum powder and other glittering powders; amino acid powders such as lauroyl lysine; wool powder, Silk powder, crystal cell Organic powders such as silica; nylon, powder, polymethyl methacrylate, acrylonitrile-methacrylic acid copolymer powder, polyethylene powder, organopolysiloxane elastomer powder, polymethylsilsesquioxane powder, etc .; organic Dye powders such as tar pigments, organic pigment lake pigments; composites of fine particle titanium oxide coated mica titanium, fine particle zinc oxide coated mica titanium, barium sulfate coated mica titanium, titanium oxide containing silicon dioxide, zinc oxide containing silicon dioxide, etc. A powder etc. are mentioned, These can be used 1 type or 2 or more types.

  The content of the component (D) used in the present invention is preferably 0.5 to 20% by mass, more preferably 3 to 15% by mass based on the total amount of the cosmetic. Within this range, the concealing effect is high, the purpose as makeup cosmetics and sunscreen cosmetics can be achieved, and even when skin care cosmetics are used, the touch is good.

  In the water-in-oil emulsified cosmetic of the present invention, in addition to the above essential components, an oily component, water, a moisturizer, an emulsifier other than the above, a fragrance, an ultraviolet absorber, a preservative, a plant extract, etc. Can be blended. In addition, the content of water used in the water-in-oil emulsified cosmetic of the present invention is preferably 20 to 70% by mass, more preferably 30 to 70% by mass, from the viewpoint of storage stability.

  The water-in-oil emulsified cosmetic of the present invention can be produced by a conventional method, for example, by dispersing a powder component in an oil phase component, then adding the water phase component and stirring.

  Examples of the water-in-oil type emulsified cosmetics of the present invention include makeup bases, emulsified foundations, makeup cosmetics such as eye shadows, sunscreen cosmetics such as sunscreens, and skin care cosmetics such as creams and cosmetic liquids. .

This invention discloses the following cosmetics further regarding embodiment mentioned above.
The present invention is the following cosmetic <1>.
<1> (A) One or more selected from sorbitan fatty acid ester and / or diglycerin fatty acid ester which are liquid at 25 ° C., (B) polyether-modified silicone, polyglycerin-modified silicone and fluoropolyether co-modified silicone (C) 1.5 to 8% by mass of a polymer having a hydrophilic segment having N-acylalkyleneimine as a repeating unit and an organopolysiloxane segment as constituent units based on the total amount of the cosmetic, and (D) A water-in-oil emulsified cosmetic comprising a powder.

The present invention preferably further comprises the following cosmetics.
<2> Component (A) has an HLB value of 6 or less, preferably selected from sorbitan monoisostearate, sorbitan monooleate, sorbitan sesquiisostearate, diglyceryl monoisostearate, diglyceryl monooleate The water-in-oil emulsified cosmetic according to <1>, which is one type or two or more types, more preferably sorbitan monoisostearate.
<3> The content of the component (A) is 0.3 to 5% by mass, preferably 0.5 to 4% by mass, more preferably 1 to 3% by mass based on the total amount of the cosmetic. <1> or <2> The water-in-oil emulsified cosmetic according to <2>.
<4> Component (B) has an HLB value of 6 or less, PEG / PPG-19 / 19 dimethicone, PEG / PPG-19 / 19 dimethicone, polyglyceryl-3 polydimethylsiloxyethyl dimethicone, lauryl polyglyceryl-3 The water-in-oil emulsified cosmetic according to any one of <1> to <3>, which is one or more selected from polydimethylsiloxyethyl dimethicone and PEG-8 trifluoropropyl dimethicone copolymer.
<5> The content of the component (B) is 0.5 to 5% by mass, preferably 1 to 3% by mass, based on the total amount of the cosmetic, and is any one of <1> to <4>. Water-in-oil emulsified cosmetic.
<6> The water-in-oil emulsion cosmetic according to any one of <1> to <5>, wherein the component (C) is an N-propionylpolyethyleneimine / methylpolysiloxane copolymer.
<7> The water-in-oil according to any one of <1> to <6>, wherein the content of the component (C) is 1.5 to 7.5% by mass, more preferably 2 to 4% by mass. Type emulsified cosmetic.
<8> The content of the component (D) is 0.5 to 20% by mass, more preferably 3 to 15% by mass, based on the total amount of the cosmetic, and any one of <1> to <7> Water-in-oil emulsified cosmetic.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is further explained in full detail, this invention is not limited by this.

(Evaluation method)
(1) Use characteristic test Each sample of Examples and Comparative Examples was applied to the faces of 20 female panelists, and the use characteristics were evaluated according to the number of respondents who answered "feel is smooth". The evaluation criteria are as follows.

18 people or more; ◎
15-17 people; ○
7-14 people; △
Number of people is 6 or less; ×

(2) Storage stability test A sample prepared by a predetermined method was left in a thermostatic bath at 0 ° C, 25 ° C and 45 ° C, and the storage stability after 3 weeks was evaluated according to the following criteria.

No oil blinding; ○
Slightly oily △△
There is oil smearing; ×

(3) Elasticity test elasticity; ○
Somewhat elastic △
There is no elasticity; ×

<Method for preparing water-in-oil emulsified cosmetic>
For Examples 1 to 5 and Comparative Examples 1 to 5, an aqueous phase component was added to the oil phase component, and after dispersion, an N-propionyl polyethyleneimine / methyl polysiloxane copolymer ethanol dispersion was added and dispersed. The desired water-in-oil emulsified cosmetic is obtained.
For Example 6 and Comparative Example 6, the oil phase component was heated to 80 ° C., and the water phase component and N-propionylpolyethyleneimine / methylpolysiloxane copolymer aqueous dispersion heated in advance at 80 ° C. were added. After the dispersion, the mixture is stirred and cooled to room temperature to obtain the desired water-in-oil emulsified cosmetic.

<Examples 1-6, Comparative Examples 1-6 Water-in-oil emulsion foundation>
An emulsion foundation having the composition described in Table 1 was produced by the above preparation method, and the above tests were performed. The results are also shown in Table 1.

  As shown in Table 1, the emulsified foundations of Examples 1 to 6 are clearly superior to the emulsified foundations of Comparative Examples 1 to 6 in all the points of smoothness of touch, storage stability, and elasticity.

The following water-in-oil emulsified cosmetics are also excellent in terms of smoothness of touch, storage stability, and elasticity.
Example 7 Gel-like foundation (oil phase) (mass%)
Sorbitan monoisostearate 1.0
Fluoropolyether co-modified silicone * 1 2.0
Decamethylcyclopentasiloxane 25.0
Methyl trimethicone * 7 4.0
Cross-linked methylpolysiloxane dispersion * 4 2.0
2-Ethylhexyl paramethoxycinnamate 4.0
Polyalkylsilsesquioxane dispersion * 8 7.0
Isononyl isononanoate 3.0
Soybean-derived lecithin 0.2
(Water phase)
Dipropylene glycol 3.0
Sodium chloride 1.0
Purified water to 100.0
Sage extract 0.1
Hydrolyzed silk 0.1
(Alcohol phase)
N-propionyl polyethyleneimine methylpolysiloxane copolymer * 5
Ethanol dispersion (pure content: 30% by mass) 8.0
Ethanol 4.4
Purified water 3.52
(Powder)
ASI-treated titanium oxide * 9 8.0
ASI-treated iron oxide * 9 1.0
ASI processing talc * 9 3.0
Plate-like barium sulfate 1.0
Polyalkyl acrylate 1.0
* 7: TMF-1.5 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 8: 670 FLUID (Toray Dow Corning)
* 9: Surface treatment with sodium lauroyl aspartate, isopropyl titanium triisostearate, zinc chloride (manufactured by Daito Kasei Kogyo Co., Ltd.)

Production Method Disperse the powder in the oil phase component, add the aqueous phase component, and after dispersion, add and disperse the alcohol phase component to obtain the desired gel-like foundation.

Example 8 Moisturizing gel cream (oil phase) (mass%)
Sorbitan monoisostearate 1.0
Fluoropolyether co-modified silicone * 1 2.0
Decamethylcyclopentasiloxane 25.0
Methyl trimethicone * 7 3.0
Pentaerythrityl tripolyhydroxystearate * 10 5.0
Cross-linked methylpolysiloxane dispersion * 11 3.0
Isononyl isononanoate 3.0
Soybean-derived lecithin 0.2
(Water phase)
Purified water to 100.0
Dipropylene glycol 3.0
Sodium chloride 0.5
Phenoxyethanol 0.4
Hydrolyzed conchiolin 0.1
Royal Jelly Extract 0.1
N-propionyl polyethyleneimine methylpolysiloxane copolymer * 5
Water dispersion (pure content: 12% by mass) 20.0
(Powder)
Nε-lauroyl-L-lysine 5.0
* 10: Saracos WO-6 (Nisshin Oillio Group)
* 11: KSG-16 (manufactured by Shin-Etsu Chemical Co., Ltd.)

Manufacturing method Disperse powder in oil phase component, heat to 80 ° C., add water phase component and N-propionyl polyethyleneimine / methyl polysiloxane copolymer aqueous dispersion heated to 80 ° C. in advance, Disperse while maintaining at 0 ° C. and stir and cool to room temperature to obtain the desired moisturizing gel cream.

Claims (4)

(A) 1 type chosen from sorbitan fatty acid ester and / or diglycerin fatty acid ester 0.3-5 mass% which are liquid at 25 ° C., (B) polyether-modified silicone, polyglycerin-modified silicone and fluoropolyether co-modified silicone Or 2 to 0.5% by mass , and (C) a polymer having a hydrophilic segment having N-acylalkyleneimine as a repeating unit and an organopolysiloxane segment as structural units, based on the total amount of the cosmetic. A water-in-oil type emulsified cosmetic comprising 0.5 to 4.5 % by mass and (D) 0.5 to 20% by mass of powder. The water-in-oil emulsified cosmetic according to claim 1, wherein the component (B) has an HLB value of 6 or less. The water-in-oil emulsified cosmetic according to claim 1 or 2, wherein the content ratio of the component (A) to the component (B) is 3: 1 to 1: 5. Water content in water is 20-70 mass%, The water-in-oil type emulsified cosmetics of any one of Claims 1-3.