JP6669556B2 - Water-in-oil emulsion composition - Google Patents

Description

  The present invention relates to a water-in-oil emulsion composition containing a sparingly soluble ultraviolet absorber, and more specifically, the generation of a precipitate in the composition is suppressed, the stability is excellent, and the feeling of use is good, and the finish of makeup is excellent. The present invention relates to a composition having excellent quality.

  Conventionally, a water-in-oil emulsion composition can efficiently spread an oil-soluble active ingredient, for example, an emollient oil, an oil-soluble drug, an ultraviolet absorber, etc., on the skin due to the adhesion of an oily component as an external phase. Therefore, it is a dosage form that has been used for external preparations for skin, and is widely used in the field of cosmetics for skin care cosmetics, hair cosmetics, makeup cosmetics, and the like. However, there is a difficulty in the feeling of stickiness on the skin due to the oily component, and a technique of blending silicone oil has been frequently used to improve this (for example, see Patent Documents 1 to 3).

  On the other hand, sunscreen cosmetics are intended to block ultraviolet rays in the sun's rays and protect the skin from the adverse effects of ultraviolet rays. However, many organic UV absorbers that have a high UV protection effect are poorly soluble (slightly soluble in water and non-polar oils), causing problems such as crystal precipitation. There were many. In addition, since the hardly soluble ultraviolet absorber has a strong tackiness, the finish quality of the makeup cosmetic may be adversely affected. Therefore, a technique of blending a highly polar ester oil (for example, see Patent Literatures 4 and 5) has been studied. However, in the presence of silicone oil, the solubility of the hardly soluble ultraviolet absorber in the ester oil is reduced. It is necessary to mix a large amount of ester oil, and in a water-in-oil emulsion composition, if a large amount of ester oil is mixed, it becomes difficult to obtain a viscosity, and a problem may occur in terms of stability of the emulsion itself. .

JP 2001-294753 A JP 2007-153751 A JP 2004-026833 A JP 2010-100553 A JP 2014-111583 A

  Therefore, even in the coexistence of a hardly soluble UV absorber and silicone oil, it is stable without crystal precipitation, has no stickiness, has a good feeling in use, and does not impair the finish quality of makeup cosmetics. The task was to provide a composition.

  In view of such circumstances, the present inventors have conducted intensive studies and have found that a water-in-oil emulsion composition containing a sparingly soluble ultraviolet absorber and containing a volatile silicone and a silicone-based surfactant contains a water-soluble emulsion. The present inventors have found that by combining and compounding the compound tripropylene glycol, it is possible to realize a stable and excellent feeling in use without crystal precipitation, and have completed the present invention.

That is, the present invention provides the following components (a) to (d):
An object of the present invention is to provide a water-in-oil emulsion composition containing (a) a volatile silicone, (b) a polyether-modified silicone, (c) tripropylene glycol, and (d) a sparingly soluble ultraviolet absorber.

  The water-in-oil emulsion composition of the present invention can contain a hardly soluble ultraviolet absorber stably, and has a non-sticky and smooth feeling of use, so that it can be applied to a makeup cosmetic. , Resulting in excellent finish quality.

Hereinafter, the present invention will be described in detail.
The component (a) volatile silicone used in the present invention is one kind or two or more kinds selected from the group consisting of silicone oils having a boiling point of 100 to 260 ° C. or less at 1 atm. Specifically, chain polysiloxanes such as methyltrimethicone, tetrakistrimethylsiloxysilane, dimethylpolysiloxane (kinematic viscosity 1-21.5 cs), methylphenylpolysiloxane, methylhydrogenpolysiloxane, and octamethylcyclotetrasiloxane And cyclic polysiloxanes such as decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and tetramethyltetrahydrogencyclotetrasiloxane; and caprylyl methicone. Of these, preferred are methyltrimethicone, tetrakistrimethylsiloxysilane, decamethylcyclopentasiloxane, and dimethylpolysiloxane (kinematic viscosity 1-21.5 cs), and more preferred are methyltrimethicone, tetrakistrimethylsiloxysilane, and decamethyl Cyclopentasiloxane.

  The content of the component (a) in the water-in-oil emulsion composition of the present invention is not particularly limited, but is preferably 5 to 50% by mass (hereinafter, simply abbreviated as%), more preferably 10 to 40%, and more preferably 15 to 40%. -30% is more preferable. Within this range, a more excellent feeling in use can be obtained.

  The component (b) polyether-modified silicone used in the present invention is a copolymer having at least an organopolysiloxane group and a hydrophilic group having a plurality of ether structures, and having the organopolysiloxane group as a main chain. The graft copolymer having the hydrophilic group in the chain may be a linear block copolymer in which the organopolysiloxane group and the hydrophilic group are alternately bonded. (B) does not include a crosslinked polymer. The organopolysiloxane group may be linear or have a branched structure. The hydrophilic group is not particularly limited, but a polyoxyalkylene group or a polyglyceryl group can be used. The component (b) may be one obtained by co-modifying an organic group such as an alkyl group or a fluorine-substituted alkyl group.

Although the component (b) is not particularly limited, specific examples of the above graft copolymer type having a main chain of an organopolysiloxane group having a linear structure and a polyoxyalkylene group in a side chain include: Polyoxyalkylene-modified organopolysiloxane (commercially available, for example, "KF-6017" manufactured by Shin-Etsu Chemical Co., Ltd.), and polyoxyalkylene-alkyl co-modified organopolysiloxane (commercially available as "5200 Formulation Aid" Dow Corning Toray) And the like). Further, as a product obtained by grafting a polyoxyalkylene group with an organopolysiloxane group having a branched structure as a main chain (silicone branched polyether-modified silicone), specifically, PEG-9 polydimethylsiloxyethyl dimethicone (commercially available) For example, "KF-6028" manufactured by Shin-Etsu Chemical Co., Ltd.), lauryl PEG-9 polydimethylsiloxyethyl dimethicone (commercially available products such as "KF-6038" manufactured by Shin-Etsu Chemical Co., Ltd.), cetyl PEG-9 polydimethylsiloxy Ethyl dimethicone and the like.
Specific examples of the block copolymer type include polyoxyethylene / butylene / dimethylpolysiloxane copolymer (commercially available, for example, “FZ-2250” manufactured by Dow Corning Toray), polyoxyethylene / polyethylene Oxypropylene / butylene / dimethylpolysiloxane copolymer (commercially available products “FZ-2233” manufactured by Dow Corning Toray, “SILWET 236-L” manufactured by Nippon Unicar) and the like.

  As the component (b), one or two or more of these examples can be used. Among them, the hydrophilic group is preferably a polyoxyalkylene chain, particularly a polyoxyethylene chain, and further the polymerization degree thereof. Is particularly preferably a polyether-modified silicone having 7 to 11. Further, from the viewpoint of the stability of the composition, a silicone-branched polyether-modified silicone is more preferable. The HLB of the component (b) is preferably from 1 to 7, more preferably from 2.5 to 5. The weight average molecular weight of the component (b) is not particularly limited, but is preferably from 500 to 200,000, and more preferably from 1,000 to 10,000.

  The content of the component (b) in the water-in-oil emulsion composition of the present invention is not particularly limited, but is preferably 0.5 to 10%, more preferably 1 to 7.5%, and further preferably 2 to 5%. preferable. Within this range, a more excellent feeling in use can be obtained.

The component (c) tripropylene glycol used in the present invention is a polyhydric alcohol composed of a propylene glycol trimer and represented by the following general formula (1):
H (OCH ₂ CH (CH ₃ )) _n OH (1)
(Where n is an average of 3)
The INCI name (International Nomenclature Cosmetic Ingredient labeling names) is represented by tripropylene glycol or PPG-3. The component (c) has a surface tension of 34 mN / m and a very small molecular weight of 192, and therefore has a property of being compatible with oil even though it is water-soluble. Although it is amphiphilic, it is a polyhydric alcohol which has no stickiness peculiar to a surfactant, has a smooth feeling of use, and also has a property of retaining moisture. In the present invention, the solubility of the hardly-soluble ultraviolet absorber contained in the water-in-oil type emulsified cosmetic can be enhanced, the generation of precipitates can be suppressed, and excellent use feeling without stickiness and excellent makeup can be achieved. Up finish can be given. Further, the component (c) is not particularly limited, but those used in ordinary cosmetics can be arbitrarily used, and commercially available products include Newpol PP-200 (manufactured by Sanyo Chemical Industries, Ltd.). .

  The content of the component (c) in the water-in-oil emulsion composition of the present invention is not particularly limited, but is preferably 1 to 30% from the viewpoint of the effect of suppressing precipitates, the feeling of use without stickiness, and the good finish of makeup. It is more preferably set to 3 to 25%.

  The component (d) hardly soluble ultraviolet absorber used in the present invention is an organic ultraviolet absorber which is hardly soluble in water and non-polar oil (silicone oil) and is solid at 25 ° C., for example, decamethyl It refers to those whose solubility at 0 ° C. in cyclopentasiloxane is 0.1 g / g or less. Specifically, 2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid hexyl ester, 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4 -Methoxyphenyl) -1,3,5-triazine), 4-tert-butyl-4'-methoxy-dibenzoylmethane, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1 , 3,5-triazine and the like, and these can be used commercially available products.

  The content of the component (d) in the water-in-oil emulsion composition of the present invention is not particularly limited. However, from the viewpoint of securing an excellent ultraviolet ray protection function, an effect of suppressing crystal precipitation, and a feeling of use of the composition, the content of the component (d) is preferably 0. It is preferably from 1 to 5%, more preferably from 0.3 to 3%.

  Furthermore, in the present invention, from the viewpoint of more effectively suppressing the generation of precipitates and further improving the stability and feeling of use of the composition, the content mass ratio of the component (d) to the component (c) (d). / (C) is preferably 0.01 to 0.15. Within this range, precipitates in the composition can be effectively suppressed, and an excellent feeling in use and an excellent finish at the time of makeup can be realized more effectively.

  In the water-in-oil emulsion composition of the present invention, it is preferable that a partially crosslinked organopolysiloxane polymer is further contained as the component (e) in terms of stability of the composition and excellent feeling of use without stickiness. The component (d) used in the present invention is a polymer partially having a three-dimensional crosslinked structure, obtained by crosslinking an organopolysiloxane.

  Specific examples of the component (e) include a partially cross-linked methylpolysiloxane such as (dimethicone / vinyl dimethicone) crosspolymer and a partially cross-linked methylphenylpolysiloxane such as (dimethicone / phenyldimethicone) crosspolymer, as represented by INCI names. Is mentioned. Examples of the polymer containing a polyoxyalkylene group in the molecule include a partially crosslinked polyether-modified silicone such as a (dimethicone / (PEG-10 / 15)) crosspolymer. Examples of the polymer containing a polyglycerin group in the molecule include a partially crosslinked polyglycerin-modified silicone such as a (dimethicone / polyglycerin-3) crosspolymer. Examples of the polymer containing a long-chain alkyl group in the molecule include a partially cross-linked alkyl-modified silicone such as a (vinyl dimethicone / lauryl dimethicone) crosspolymer. Examples of the polymer containing a polyoxyalkylene group and a long-chain alkyl group in the molecule include a partially cross-linked alkyl / polyether co-modified silicone such as PEG-15 lauryl dimethicone crosspolymer. Examples of the polymer containing a halogenated hydrocarbon group in the molecule include a partially cross-linked fluorine-modified silicone such as a (trifluoropropyl dimethicone / trifluoropropyl divinyl dimethicone) crosspolymer. One or two or more of these can be appropriately selected and used.

  The partially crosslinked organopolysiloxane polymer of the component (e) is considered to have an excellent effect even if it is not swelled in advance with an oil such as silicone oil. When the siloxane polymer is non-uniformly dispersed in a solid state, a cosmetic having a good feeling without stickiness and an excellent finish at the time of makeup cannot be obtained. For this reason, in the present invention, it is preferable that the cosmetic is present in a state of being swollen with an oil such as silicone oil. In addition, the partially crosslinked organopolysiloxane polymer of the component (e) is often commercially available as a mixture in a gelled state with an oil agent such as a hydrocarbon oil, a silicone oil, and an ester oil. This commercially available product can also be used. Component (e) is commercially available in the form of a mixture, and comprises KSG-15 (5% solids) as a mixture of partially crosslinked methylpolysiloxane and cyclic silicone, and a mixture of partially crosslinked methylpolysiloxane and dimethylpolysiloxane. KSG-16 (solid content 20 to 30%) as a mixture, KSG-18 (solid content 10 to 20%) as a mixture of partially cross-linked methylphenylpolysiloxane and phenyltrimethicone, partially cross-linked polyether-modified silicone and dimethyl KSG-210 (solid content 20 to 30%) as a mixture with polysiloxane, KSG-710 (solid content 20 to 30%) as a mixture of partially crosslinked polyglycerin-modified silicone and dimethylpolysiloxane, partially crosslinked alkyl modified KSG-41 (solids 25-35) as a mixture of silicone and oil ), KSG-42 (solids 20-30%), KSG-43 (solids 25-35%) and KSG-44 (solids 25-35%), partially crosslinked alkyl / polyether co-modified silicone and oil KSG-310 (solid content 25 to 35%), KSG-320 (solid content 20 to 30%), KSG-330 (solid content 15 to 25%), and KSG-340 (solid content 25 to 35%) ) And KSG-340 (25-35% solids). Further, the partially crosslinked fluorine-modified silicone is used as a mixture with a cyclic fluorine-containing silicone such as a fluoroalkyl group-containing cyclic organopolysiloxane, and is, for example, KSG-51 (solid content: 15 to 25%) (Shin-Etsu Chemical Co., Ltd.) Made). Among them, KSG-15, KSG-16, KSG-18, KSG-710, and KSG-51 are particularly preferable from the viewpoint of the stability of the composition and the excellent feeling of use without stickiness.

  The content of the component (e) in the water-in-oil emulsion composition of the present invention is preferably from 0.5 to 10%, and more preferably from 1 to 5%. When the compounding amount of the component (e) is in this range, the generation of precipitates can be suppressed, and an excellent feeling of use without stickiness and an excellent finish during makeup can be imparted. preferable.

  The water-in-oil emulsion composition of the present invention preferably further contains a powder as the component (f) from the viewpoint of imparting an excellent feeling of use without stickiness and an excellent finish during makeup.

  The powder is not particularly limited as long as it is used for ordinary cosmetics, and may be in the form of plate, spindle, needle, etc., fume, fine particle, pigment grade, etc., porous, non-porous, etc. There is no particular limitation on the particle structure of the porous material and the like, and examples thereof include inorganic powders, glitter powders, organic powders, dye powders, and composite powders. Specifically, konjo, ultramarine, red iron oxide, yellow iron oxide, black iron oxide, titanium oxide, zinc oxide, silicic anhydride, aluminum oxide, cerium oxide, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, chromium oxide, Inorganic powders such as chromium hydroxide, carbon black, aluminum silicate, magnesium silicate, aluminum magnesium silicate, mica, synthetic mica, synthetic sericite, sericite, talc, kaolin, silicon carbide, barium sulfate, boron nitride, etc. , Bismuth oxychloride, titanium mica, iron oxide treated mica, iron oxide treated mica titanium, organic pigment treated mica titanium, silicon dioxide / titanium oxide coated mica, titanium oxide treated glass powder, iron oxide titanium oxide treated glass powder, aluminum powder, etc. Glittering powders, magnesium stearate, Organic powders such as zinc thearate, N-acyl lysine, nylon, etc., pigment powders such as organic tar pigments, lake pigments of organic pigments, fine titanium oxide-coated mica titanium, fine zinc oxide-coated mica titanium, barium sulfate coated Composite powders such as mica titanium, titanium oxide-containing silicon dioxide, zinc oxide-containing silicon dioxide, and the like, silicic anhydride, and the like, and one or more of these can be used. A composite powder obtained by compounding two or more of these powders may be used. These powders may be those whose surfaces have been subjected to a modification treatment with a surface treatment agent. For example, as a treating agent used when hydrophobizing powder, a fluorine compound, a silicone compound, N-lauroyl-L-lysine, metal soap, hydrocarbon, higher fatty acid, higher alcohol, ester, wax, wax, Surfactants and the like can be mentioned, and a composite treatment combining these may be performed. The surface treatment can be performed by a conventional method such as mixing, heating, baking, or gas phase polymerization.

  The content of the component (f) in the water-in-oil emulsion composition of the present invention is preferably 0.5% to 15%, and more preferably 1% to 10%, from the viewpoint of imparting a non-sticky feeling of use and an excellent makeup finish. Is more preferable, and 2 to 7.5% by mass is further preferable.

  The present invention is a water-in-oil emulsion composition, and as a component constituting an aqueous phase, in addition to component (c), in addition to water, 1,3-butylene glycol, dipropylene glycol, glycerin, propylene glycol, and polyethylene Polyhydric alcohols such as glycols or polymers thereof, sorbitol, maltitol, sugar alcohols such as glucose, and aqueous components such as lower alcohols can be used. The water is not particularly limited, and includes plant-derived steam-distilled water such as ordinary water, purified water, hot spring water, deep water, lavender water, rose water, orange flower water, and the like, and one or more types are used. be able to. The amount of the aqueous component is preferably 5 to 60% of the total amount of the composition from the viewpoint of imparting emulsion viscosity and improving the stability of the composition.

In addition, the oil agent constituting the oil phase may be a solid, semi-solid, or liquid oil generally used in cosmetics in addition to the component (a), and may be a hydrocarbon oil regardless of animal oil, vegetable oil, mineral oil, or synthetic oil. , Oils and fats, waxes, esters, fatty acids, higher alcohols, silicone oils, fluorine-based oils, and the like, which can be used.
Examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalane, squalene, pristane, paraffin, isoparaffin, ceresin, petrolatum, microcrystalline wax, and the like, and one or more kinds can be used.
As liquid oils, linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, ginger oil, cinnamon oil, jojoba oil, grape oil, sunflower oil, Almond oil, rapeseed oil, sesame oil, wheat germ oil, rice germ oil, rice bran oil, cottonseed oil, soybean oil, peanut oil, teaseed oil, evening primrose oil, egg yolk oil, beef tallow, liver oil, triglycerin, glyceryl trioctanoate And glycerin triisopalmitate, and the like, and one or more kinds can be used. Examples of solid fats and oils include cocoa butter, coconut oil, palm oil, palm kernel oil, beef tallow, sheep tallow, lard, horse fat, hardened oil, hardened castor oil, mokurou, shea butter and the like.
Examples of waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibotaro wax, whale wax, montan wax, nuka wax, lanolin, reduced lanolin, hard lanolin, kapok wax, sugar cane wax, jojoba wax, shellac wax and the like.
Examples of ester oils include octanoic acid esters such as cetyl octanoate, lauric acid esters such as hexyl laurate, isopropyl myristate, myristic acid esters such as octyldodecyl myristate, palmitic acid esters such as octyl palmitate, and isocetyl stearate. Isostearate esters such as stearic acid ester, isopropyl isostearate, etc .; isopalmitic acid esters such as octyl isopalmitate; oleic acid esters such as isodecyl oleate; adipic acid diesters such as diisopropyl adipate; and sebacic acids such as diethyl sebacate. Diester, diisostearyl malate and the like can be mentioned, and one kind or two or more kinds can be used.
Examples of the silicone oil include dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and the like, and one or more kinds can be used. The compounding amount of the oil component is preferably 3 to 30%, more preferably 5 to 20% of the total amount of the composition.

  In the present invention, in addition to the above essential components, as long as the effects of the present invention are not impaired, the components usually contained in cosmetics include surfactants, water-soluble polymers, moisturizing components, and components other than component (d). An ultraviolet absorber, an antioxidant, a metal chelating agent, a preservative, a powder, a dye, a fragrance, various chemicals, and the like can be arbitrarily contained as long as the effects of the present invention are not impaired.

  The method for producing the water-in-oil emulsion composition of the present invention is not particularly limited, and is prepared by a conventional method. For example, it can be prepared by dissolving the components (a) to (d) in an oil agent by heating, if necessary, and then adding and mixing an aqueous component.

  The water-in-oil emulsion composition of the present invention is applicable to foundations, foundations, serums, sunscreen cosmetics, and the like, and is preferably a makeup cosmetic for foundations, foundations, and the like, which is expected to exhibit the effects of the present invention. Material, more preferably a substrate. Examples of the method of use include a method of using a hand or a finger, a method of impregnating a puff or a sponge, and the like. In addition, the properties can be implemented as cosmetics of various properties such as gel and liquid.

  Next, the present invention will be further described with reference to examples. These do not limit the present invention at all.

Examples 1 to 10 and Comparative Examples 1 to 6: Base Cosmetic A base cosmetic was prepared by the composition shown in Table 1 and the following production method, and by the method shown below, <1> stability (no crystal precipitation), <2> Evaluation of usability / finish (no unevenness), <3> Usability / finish (no thick coating), <4> Evaluation of usability / finish (no stickiness at initial application) Was. The results are also shown in Table 1.

(Evaluation method)
<1> Stability (no crystal precipitation)
Each sample was placed in a glass bottle and stored in a thermostat at 5 ° C. for one month. Thereafter, the state of precipitate generation of the sample taken out of the thermostat was visually observed, and judged based on the following criteria.
[Evaluation criteria]
◎: No precipitate was observed at all. ○: Slight precipitate was observed, but it was soft and crushed with a hand of 1 mm or less. Δ: Precipitate was observed and some of the hand hit 1 mm or more. ×: 3 mm The above precipitates are observed

<2-4> Usability / Finish (Less unevenness / Lack of thick coating / Lack of snagging)
After applying each sample to the face, the application condition and the finish condition of the decorative film when the following powder foundation was repeatedly applied were visually judged. The evaluation was performed by five professional panels according to the following evaluation criteria, and the average value was determined by applying the following criteria.
[Evaluation criteria]
<2> Evaluation criteria for non-uniformity 5 points: No non-uniformity 4 points: No non-uniformity 3 points: Neither of them 2 points: Some non-uniformity 1 point: Non-uniformity <3> Evaluation criteria for lack of thick coating 5 points: No thickening 4 points: No thickening 3 points: Neither 2 points: Somewhat thickening 1 point: Thickening <4> Evaluation criteria for the absence of snagging 5 points: No feeling of snagging 4 points: No feeling of snagging 3 points: Neither can be said 2 points: There is a feeling of snagging 1 point: There is a feeling of snagging [Criteria]
◎: 4.3 or more ：: 3.5 or more to less than 4.3 Δ: 2.0 or more to less than 3.5 ×: 1.0 or more to less than 2.0

[Prescription and manufacturing method of powder foundation used for evaluation]
(Ingredient) (%)
1. Titanium oxide coated mica 10
2. Plate-shaped barium sulfate 20
3. Titanium oxide 10
4. Talc 15
5. Nylon powder (spherical) 2
6. Iron oxide 0.5
7. Yellow iron oxide 1
8. Black iron oxide 0.1
9. Serisite remaining 10. Liquid paraffin 4
11. Cetyl isooctanoate 4
12. Octyl methoxycinnamate 3
(Production method)
A: Components 1 to 9 are mixed.
B: Components 10 to 12 are added to A and uniformly dispersed.
C: Purified water was added to B to form a slurry, poured into a metal dish, and dried and solidified at 30 ° C. for 48 hours to obtain a powdered solid foundation.

(Production method)
A. Components (1) to (4) are uniformly dispersed.
B. Components (5) to (16) are heated and uniformly dissolved, and added to A with stirring.
C. After the components (17) to (23) were uniformly dissolved in B, they were added and uniformly stirred to obtain a base cosmetic.

  As is clear from the results in Table 1, the base cosmetics of Examples 1 to 10 were excellent in the effect of suppressing the generation of precipitates, and also had good feeling in use and finish of makeup. On the other hand, in Comparative Examples 1 to 4 in which a polyhydric alcohol other than the component (c) was blended, precipitates were liable to be formed, and stickiness was generated in use feeling and finished quality, and good results could not be obtained. In Comparative Example 5 in which an oil agent having a high solubility of the component (d) was blended, and in Comparative Example 6 in which a surfactant different from the component (b) was blended, although no crystal precipitation was observed, stickiness occurred in use feeling and finished quality. No good results were obtained.

Examples 11 to 20 and Comparative Examples 7 to 12: Water-in-oil emulsified foundation A composition shown in Table 2 and a water-in-oil emulsified foundation were prepared by the following production method, and the <1> stability ( No crystal precipitation), <2> feeling of use / finish (no unevenness), <3> feeling of use / finish (moisture), <4> feeling of use / finish (smooth elongation). . The results are also shown in Table 2.

(Evaluation method)
<1> Stability (no crystal precipitation)
Each sample was placed in a glass bottle and stored in a thermostat at 5 ° C. for one month. Thereafter, the state of precipitate generation of the sample taken out of the thermostat was visually observed, and judged based on the following criteria.
[Evaluation criteria]
：: No precipitate was observed at all. ：: Slight precipitate was observed, but there was only softness of 1 mm or less that could be crushed by hand. Δ: Precipitate was observed and some hit the hand of 1 mm or more. : Precipitation of 3 mm or more is observed

<2-4> Usability / Finish (No unevenness / Moisture / Smooth expansion)
When each sample was applied to the face, the applied condition and the finished condition of the decorative film were visually determined. The evaluation was performed by five professional panels according to the following evaluation criteria, and the average value was determined by applying the following criteria.
[Evaluation criteria]
<2> Evaluation criteria for non-uniformity 5 points: No non-uniformity 4 points: No non-uniformity 3 points: Neither can be said 2 points: Some non-uniformity 1 point: Some non-uniformity <3> Moisture feeling evaluation criteria 5 points: I feel quite moist 4 points: I feel moist 3 points: I can't say neither 2 points: I don't feel much moist 1 point: I don't feel moist <4> Smooth elongation Evaluation criteria for spread 5 points: Spread quite smoothly 4 points: Smoothly spread 3 points: Neither can be said 2 points: Feel slightly resistance to spread 1 Point: Feel resistance to spread [Judgment criteria]
◎: 4.3 or more ：: 3.5 or more to less than 4.3 Δ: 2.0 or more to less than 3.5 ×: 1.0 or more to less than 2.0

(Production method)
A. Components (1) to (6) are uniformly dispersed.
B. Components (7) to (19) are heated and uniformly dissolved, and added to A with stirring.
C. After the components (20) to (26) were uniformly dissolved in B, they were added and stirred uniformly to obtain a water-in-oil emulsion foundation.

  As is evident from the results in Table 2, the water-in-oil emulsified foundations of Examples 11 to 20 were excellent in the effect of suppressing the generation of precipitates, and also had good feeling in use and finish of makeup. On the other hand, in Comparative Examples 7 to 10 in which a polyhydric alcohol other than the component (c) was blended, precipitates were liable to be formed, and in the feeling of use and finished quality, unevenness due to stickiness and poor elongation occurred, resulting in good results. No results were obtained. In Comparative Example 11 in which an oil agent having high solubility of the component (d) was blended, and in Comparative Example 12 in which a surfactant different from the component (b) was blended, there was no crystal precipitation, but the use feeling and the finished quality were sticky. The feeling deteriorated, and good results could not be obtained.

Example 21 Foundation A foundation was prepared by the following composition and manufacturing method.
(Composition) (%)
(1) Dimethyl polysiloxane 3% treated titanium oxide 9.0
(2) Dimethylpolysiloxane 2% treated black iron oxide 0.3
(3) Dimethyl polysiloxane 2% treated yellow iron oxide 1.8
(4) Dimethylpolysiloxane 2% treated bengara 0.6
(5) Sericite treated with 3% dimethylpolysiloxane 1.0
(6) Mica titanium 2% treated with dimethylpolysiloxane 2% 2.0
(7) PEG-9 polydimethylsiloxyethyl dimethicone 3.0
(8) Decamethylcyclopentasiloxane 15.0
(9) Glyceryl tri-2-ethylhexanoate 3.0
(10) Dextrin palmitate (* 6) 0.5
(11) 2-Ethylhexyl paramethoxycinnamate 5.0
(12) 2- (4-diethylamino-2-hydroxybenzoyl)
Hexyl benzoate 0.7
(13) 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine 0.5
(14) Preservative appropriate amount (15) Purified water balance (16) Tripropylene glycol 5.0
(17) Ethyl alcohol 5.0
* 6 Leo Pearl KL2 (Chiba Flour Milling Co., Ltd.)

(Production method)
A. Components (1) to (7) are uniformly dispersed.
B. The components (8) to (13) are optionally heated to dissolve uniformly, and A is added with stirring.
C. While stirring B, components (14) to (17) were added and uniformly mixed to obtain a foundation.

  The foundation of Example 21 obtained as described above had extremely good stability, feeling of use, and finish.

Example 22 Sunscreen A sunscreen was prepared by the following composition and production method.
(Composition) (%)
(1) Decamethylcyclopentasiloxane 25.0
(2) Neopentyl glycol diethylhexanoate 1.0
(3) Lauryl PEG-9 polydimethylsiloxyethyl dimethicone 1.0
(4) Isotridecyl isononanoate 1.0
(5) Cetyl 2-ethylhexanoate 3.0
(6) 2-ethylhexyl paramethoxycinnamate 3.0
(7) 4-tert-butyl-4'-methoxy-dibenzoylmethane 1.0
(8) Dimethyl polysiloxane 1.0
(9) Methyl methacrylate crosspolymer (15 μm) 0.5
(10) Appropriate amount of fragrance (11) Purified water balance (12) Tripropylene glycol 15.0
(13) Sodium chloride 0.2
(14) 1,3-butylene glycol 1.0
(15) Ethanol 2.0
(16) Preservative appropriate amount

(Production method)
A. Components (1) to (10) are heated and uniformly dissolved.
B. After the components (11) to (16) are uniformly dissolved, they are added to A with stirring.
C. B was cooled and mixed with stirring to obtain a sunscreen.

  The sunscreen additive of Example 22 obtained as described above had extremely good composition stability, use feeling, and finish.

Claims (4)

A water-in-oil emulsion composition containing the following components (a) to (d).
(A) 5 to 50% by mass of volatile silicone
(B) Polyether-modified silicone (excluding a crosslinked polymer) 0.5 to 10% by mass
(C) 1 to 30% by mass of tripropylene glycol
(D) Hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate, 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxy Phenyl) -1,3,5-triazine), 4-tert-butyl-4'-methoxy-dibenzoylmethane, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3 One or two or more hardly soluble ultraviolet absorbers selected from 2,5-triazines in an amount of 0.1 to 5% by mass   The water-in-oil emulsion composition according to claim 1, wherein the content ratio (d) / (c) of the component (c) to the component (d) is in the range of 0.01 to 0.15.   3. The water-in-oil emulsion composition according to claim 1, further comprising a component (e) a partially crosslinked organopolysiloxane polymer.   The water-in-oil emulsion composition according to any one of claims 1 to 3, further comprising a component (f) powder.