JP2017031080A - Water-in-oil type skin external preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-in-oil type skin external preparation which is excellent in ultraviolet shielding ability, viscosity stability and feeling of use.SOLUTION: There is provided a water-in-oil type skin external preparation which comprises a surface-treated powder (A) which contains at least one selected from titanium oxide and zinc oxide and has 4-tert-butyl-4'-methoxydibenzoylmethane on the surface, a polyglycerol fatty acid ester (B) and an unmodified or polyether-modified or polyglycerin-modified crosslinked organopolysiloxane polymer (C) in an oil phase.SELECTED DRAWING: None

Description

  The present invention relates to a water-in-oil external preparation for skin.

  Conventionally, various organic ultraviolet absorbers have been used to impart an ultraviolet shielding ability to external preparations for skin such as cosmetics. Among them, 4-tert-butyl-4′-methoxydibenzoylmethane is widely known as an ultraviolet absorber that can absorb ultraviolet rays in the UV-A region (wavelength 320 nm to 400 nm).

  Since organic ultraviolet absorbers such as 4-tert-butyl-4′-methoxydibenzoylmethane have low solubility in oils such as silicone oil, they may cause a problem of precipitation in a skin external preparation. Moreover, when the blending ratio of the oil agent is increased in order to avoid the problem of precipitation, stickiness may occur after application of the external preparation for skin, and the feeling of use may be impaired.

  From such a background, Patent Documents 1 and 2 disclose surface-treated powders obtained by coating an organic ultraviolet absorbent on an inorganic powder serving as a base material. This surface-treated powder is said to have high ultraviolet shielding ability and excellent dispersibility.

  Although the surface-treated powders disclosed in Patent Documents 1 and 2 are excellent in dispersibility, it is known that the viscosity of the emulsion-type composition changes with time when blended with the emulsion-type composition. . Thus, Patent Document 3 discloses a water-in-oil cosmetic containing surface-treated powder and a specific sorbitan fatty acid ester.

International Publication No. 2010/098249 JP 2012-121810 A JP2013-095699A

  Although the water-in-oil cosmetic disclosed in Patent Document 3 contains a specific sorbitan fatty acid ester, viscosity stability has been improved to some extent, but there is still room for improvement. In addition, the water-in-oil cosmetic disclosed in Patent Document 3 may feel sticky after application, and there is room for improvement in terms of usability.

  This invention is made | formed in view of the above situations, and makes it a subject to provide the water-in-oil type skin external preparation excellent in ultraviolet-ray shielding ability, viscosity stability, and a usability | use_condition.

Specific means for solving the above problems include the following embodiments.
<1> Surface-treated powder (A) containing at least one selected from titanium oxide and zinc oxide and having 4-tert-butyl-4′-methoxydibenzoylmethane on the surface, and polyglycerin fatty acid ester ( A water-in-oil external preparation containing B) and an unmodified, polyether-modified or polyglycerin-modified crosslinked organopolysiloxane polymer (C) in an oil phase.
<2> The surface-treated powder (A) has a surface-treated layer containing 4-tert-butyl-4′-methoxydibenzoylmethane on at least one surface selected from titanium oxide and zinc oxide <1> Water-in-oil type skin external preparation as described in 2.
<3> The water-in-oil skin external preparation according to <2>, wherein the surface treatment layer contains at least one selected from the group consisting of fatty acids and aluminum hydroxide.
<4> The oil according to any one of <1> to <3>, wherein the polyglycerol fatty acid ester (B) is an ester of a fatty acid having 8 to 22 carbon atoms and a polyglycerol having an average polymerization degree of 2 to 10. Medium water type skin external preparation.

<5> An organohydrogenpolysiloxane in which the crosslinked organopolysiloxane polymer (C) is represented by the following (a) and contains an average of 1.5 or more hydrogen atoms bonded to silicon atoms in the molecule; The compound according to any one of <1> to <4> obtained by addition polymerization of a compound having an average of 1.5 or more vinylic reaction sites in the molecule shown in (b) below: Water-in-oil type skin external preparation.
(A) at least selected from the group consisting of SiO ₂ units, HSiO _1.5 units, RSiO _1.5 units, RHSiO units, R ₂ SiO units, R ₃ SiO _0.5 units, and R ₂ HSiO _0.5 units. Organohydrogenpolysiloxane formed by one type of structural unit. R represents a monovalent organic group having 1 to 30 carbon atoms excluding an aliphatic unsaturated group.
(B) At least one compound selected from the group consisting of the following (b-1) to (b-3).
(B-1) SiO ₂ unit, (CH ₂ ═CH) SiO _1.5 unit, RSiO _1.5 unit, R (CH ₂ ═CH) SiO unit, R ₂ SiO unit, R ₃ SiO _0.5 unit, And R ₂ (CH ₂ ═CH) SiO An organopolysiloxane formed by at least one structural unit selected from the group consisting of _0.5 units. R represents a monovalent organic group having 1 to 30 carbon atoms excluding an aliphatic unsaturated group.
(B-2) Polyoxyalkylene represented by the following general formula (I).
_{C m H 2m-1 O (} C 2 H 4 O) h (C 3 H 6 O) i C m H 2m-1 ··· (I)
In the formula, h represents an integer of 2 to 200, i represents an integer of 0 to 200, and h + i is 3 to 200. m represents an integer of 2 to 6.
(B-3) A compound represented by the following general formula (II).
_{C p H 2p-1 O (} CH 2 CH (OH) CH 2 O) j C p H 2p-1 ··· (II)
In the formula, p represents an integer of 2 to 20, and j represents an integer of 1 to 20.

<6> The water-in-oil type external preparation for skin according to any one of <1> to <5>, further containing a clay mineral.
<7> The water-in-oil type external preparation for skin according to <6>, wherein the clay mineral is smectite.
<8> The content of the polyglycerin fatty acid ester (B) is 0.3% by mass to 10% by mass with respect to the total mass of the water-in-oil skin external preparation, and the crosslinked organopolysiloxane polymer (C ) Is 0.15% by mass to 5% by mass with respect to the total mass of the water-in-oil skin external preparation, and polyglycerin with respect to the content of the crosslinked organopolysiloxane polymer (C) The water-in-oil type external preparation for skin according to any one of <1> to <7>, wherein the content ratio of the fatty acid ester (B) is 0.06 to 67 on a mass basis.
<9> Water-in-oil type skin external preparation as described in any one of <1>-<8> whose viscosity in 25 degreeC is 8000mPa * s-18000mPa * s.

  ADVANTAGE OF THE INVENTION According to this invention, the water-in-oil type skin external preparation excellent in ultraviolet-ray shielding ability, viscosity stability, and a usability | use_condition can be provided.

  Hereinafter, an example of an embodiment of a water-in-oil skin external preparation to which the present invention is applied will be described. However, the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention.

In the present specification, a numerical range indicated using “to” means a range including the numerical values described before and after “to” as a minimum value and a maximum value, respectively.
In this specification, the amount of each component in the water-in-oil skin external preparation refers to the amount of each component in the oil unless there is a specific indication when there are a plurality of substances corresponding to each component in the water-in-oil skin external preparation. It means the total amount of a plurality of types of substances present in a water-type skin external preparation.
In the present specification, the “oil phase” means a continuous phase of a water-in-oil skin external preparation, and includes a liquid medium in a continuous phase and components dispersed or dissolved in the liquid medium.
In the present specification, the “aqueous phase” means a dispersed phase of the water-in-oil type skin external preparation, and includes a liquid medium in the dispersed phase and components dispersed or dissolved in the liquid medium.

<Water-in-oil type skin external preparation>
The water-in-oil type external preparation for skin of this embodiment contains at least one selected from titanium oxide and zinc oxide, and has a surface-treated powder having 4-tert-butyl-4′-methoxydibenzoylmethane on the surface (A), polyglycerol fatty acid ester (B), unmodified, polyether-modified or polyglycerol-modified crosslinked organopolysiloxane polymer (C) (hereinafter simply referred to as “crosslinked organopolysiloxane polymerization”) In the oil phase. The water-in-oil external preparation of this embodiment is excellent in ultraviolet shielding ability, viscosity stability, and usability by adopting the above configuration.

The reason why the water-in-oil external preparation of this embodiment is excellent in ultraviolet shielding ability, viscosity stability, and feeling of use is assumed as follows, for example.
That is, since the water-in-oil external preparation of this embodiment contains the surface-treated powder, it can shield ultraviolet rays harmful to the skin. Moreover, since the water-in-oil external preparation of this embodiment contains a polyglycerin fatty acid ester and a crosslinked organopolysiloxane polymer in addition to the surface-treated powder, the viscosity stability of the water-in-oil external preparation is as follows. Improves. Further, since the water-in-oil external preparation of this embodiment uses a polyglycerin fatty acid ester and a crosslinked organopolysiloxane polymer in combination, the stickiness and oiliness (feeling of oil film) after application are suppressed. , The feeling of use improves. Furthermore, since the water-in-oil type external preparation for skin of this embodiment contains the surface-treated powder in the oil phase, creaking at the time of application is suppressed, and the feeling of use is improved.

  In addition, when the skin external preparation is an oil-in-water type, blending the surface-treated powder with the oil phase that is the dispersed phase can suppress creaking at the time of application, but can increase the blending ratio of the surface-treated powder. It is difficult and the UV shielding ability tends to be insufficient. On the other hand, if the surface-treated powder is blended with an aqueous phase that is a continuous phase in order to increase the blending ratio of the surface-treated powder, creaking is likely to occur during coating.

  Hereinafter, components that can be contained in the water-in-oil external preparation of the present embodiment will be described in detail.

[Surface treatment powder (A)]
The water-in-oil type external preparation for skin of this embodiment contains at least one selected from titanium oxide and zinc oxide, and has a surface-treated powder having 4-tert-butyl-4′-methoxydibenzoylmethane on the surface In the oil phase. The water-in-oil type external preparation for skin may contain one kind of surface-treated powder, or two or more kinds.

  The surface-treated powder contains at least one selected from titanium oxide and zinc oxide. The surface-treated powder preferably contains titanium oxide from the viewpoint that the ultraviolet shielding wavelength region is different from that of 4-tert-butyl-4'-methoxydibenzoylmethane and the wavelength region exhibiting the ultraviolet shielding effect is expanded. In the present specification, at least one selected from titanium oxide and zinc oxide may be collectively referred to as “inorganic powder”.

The titanium oxide constituting the surface-treated powder is not particularly limited, and may be any crystal type titanium oxide such as anatase type, rutile type, brookite type, and the like. The crystal type of titanium oxide is preferably a rutile type from the viewpoint of improving the ultraviolet shielding ability.
As the zinc oxide constituting the surface-treated powder, those having a wurtzite crystal structure are preferable.

  The inorganic powder may be surface-treated with an inorganic substance such as aluminum hydroxide, silicon oxide or zirconium oxide, or may be surface-treated with a fatty acid such as stearic acid, isostearic acid or lauric acid. The surface treatment may be performed with both inorganic substances and fatty acids. By subjecting the inorganic powder to surface treatment with an inorganic substance such as aluminum hydroxide, the inorganic powder can be inactivated. Moreover, the surface of inorganic powder can be hydrophobized by surface-treating inorganic powder with fatty acids, such as stearic acid.

  The average primary particle diameter of the inorganic powder is, for example, preferably from 1 nm to 90 nm, and more preferably from 5 nm to 50 nm, from the viewpoints of ultraviolet shielding ability and transparency of the water-in-oil external preparation. The average primary particle diameter of the inorganic powder is a value obtained by photographing 1000 or more images with a transmission electron microscope, performing image processing on each photographed particle with an image analysis type particle size distribution measuring device, and measuring the equivalent circle diameter. . When using a commercial item, the average primary particle diameter described in the catalog etc. can be applied as it is.

  The surface-treated powder has 4-tert-butyl-4'-methoxydibenzoylmethane on the surface. Here, “having on the surface” means that 4-tert-butyl-4′-methoxydibenzoylmethane is present on at least a part of the outermost surface of the surface-treated powder. The surface-treated powder preferably has 4-tert-butyl-4′-methoxydibenzoylmethane on the entire outermost surface, but 4-tert-butyl-within a range not impairing the effects of the present invention. There may be a portion not having 4′-methoxydibenzoylmethane. Surface of the inorganic powder (inorganic powder or fatty acid disposed on the surface when the inorganic powder is treated with at least one of an inorganic substance and a fatty acid) and 4-tert-butyl-4′-methoxydibenzoylmethane The bonding mode is not particularly limited as long as the inorganic powder and 4-tert-butyl-4′-methoxydibenzoylmethane behave integrally, and may be a chemical bond such as a covalent bond. Or non-chemical bonds such as adsorption.

  The presence of 4-tert-butyl-4′-methoxydibenzoylmethane on the surface of the surface-treated powder is obtained by adding ethanol to the surface-treated powder and stirring, and measuring the absorbance of the supernatant liquid at a wavelength of 355 nm. This can be confirmed.

  As the surface treatment powder, for example, a powder having a surface treatment layer containing 4-tert-butyl-4′-methoxydibenzoylmethane on the surface of an inorganic powder can be used. As long as 4-tert-butyl-4′-methoxydibenzoylmethane is present on at least a part of the outermost surface of the surface-treated powder, the surface-treated layer may be a single layer or a multilayer, There may be a layer not containing 4-tert-butyl-4′-methoxydibenzoylmethane. The surface treatment layer is preferably present on the entire surface of the inorganic powder, but there may be a portion where the surface treatment layer does not exist as long as the effects of the present invention are not impaired.

  Moreover, it is preferable that a surface treatment layer contains at least 1 sort (s) chosen from the group which consists of a fatty acid and aluminum hydroxide. For example, as the surface treatment powder, an inorganic powder surface-treated with at least one selected from the group consisting of fatty acids and aluminum hydroxide is further surface-treated with 4-tert-butyl-4′-methoxydibenzoylmethane. Can be used.

  The ratio of the inorganic powder and 4-tert-butyl-4'-methoxydibenzoylmethane in the surface-treated powder is not particularly limited. From the viewpoint of the ultraviolet shielding ability as the surface-treated powder, for example, 0.03 parts by mass to 1 part by mass of 4-tert-butyl-4′-methoxydibenzoylmethane with respect to 1 part by mass of the inorganic powder. Can do.

The average particle size of the surface-treated powder is preferably less than 1 μm. If the average particle diameter of the surface-treated powder is less than 1 μm, coloring of the water-in-oil external preparation by the surface-treated powder itself is suppressed, and so-called whitening is difficult to occur. The average particle size of the surface-treated powder is more preferably 1 nm to 500 nm, and still more preferably 3 nm to 100 nm, from the viewpoints of ultraviolet shielding ability and usability.
The average particle diameter of the surface-treated powder can be measured by the same method as the average primary particle diameter of the inorganic powder.

  As the surface-treated powder, for example, the surface-treated powder disclosed in International Publication No. 2010/098249 can be used. The surface-treated powder is also available as a commercial product. Examples of commercially available surface-treated powders include HXMT-100ZA manufactured by Teika Co., Ltd. HXMT-100ZA is a titanium oxide surface-treated with aluminum hydroxide and stearic acid and further surface-treated with 4-tert-butyl-4′-methoxydibenzoylmethane.

  The content of the surface-treated powder in the water-in-oil external preparation is preferably, for example, 0.1% by mass to 50% by mass with respect to the total mass of the water-in-oil external preparation. More preferably, it is 5 mass%-25 mass%, and it is still more preferable that it is 1 mass%-15 mass%. If the content of the surface-treated powder is 0.1% by mass or more, the ultraviolet shielding ability tends to be improved. If the content of the surface-treated powder is 50% by mass or less, the water-in-oil type external skin The stability in the agent tends to be improved.

  The surface-treated powder is contained in the oil phase of the water-in-oil skin external preparation. When the surface-treated powder is contained in the oil phase, creaking at the time of application of the water-in-oil external preparation is suppressed, and the feeling of use tends to be improved.

When blending the surface-treated powder into the oil phase of the water-in-oil skin external preparation, a slurry may be prepared using silicone oil or the like and blended with other components in the form of a slurry.
The content of the surface-treated powder in the slurry is not particularly limited. In general, the content of the surface-treated powder in the slurry is preferably 10% by mass to 80% by mass, and more preferably 20% by mass to 60% by mass with respect to the total mass of the slurry. When the content of the surface-treated powder in the slurry is within the above range, the surface-treated powder tends to be stably blended with the water-in-oil external skin preparation.

[Polyglycerin fatty acid ester (B)]
The water-in-oil skin external preparation of this embodiment contains polyglycerin fatty acid ester in the oil phase. The water-in-oil type skin external preparation may contain one or more polyglycerol fatty acid esters, or may contain two or more.

  The polyglycerol fatty acid ester is not particularly limited. Examples of the polyglycerol fatty acid ester include esters of a fatty acid having 6 to 30 carbon atoms and a polyglycerol having an average polymerization degree of 2 to 10.

The fatty acid having 6 to 30 carbon atoms constituting the polyglycerin fatty acid ester may be linear or branched. Further, the fatty acid having 6 to 30 carbon atoms may be a saturated fatty acid or an unsaturated fatty acid. When the fatty acid has 6 or more carbon atoms, skin irritation and the like tend to be reduced. Moreover, it exists in the tendency for stability to improve because carbon number of a fatty acid is 30 or less.
Specific examples of fatty acids having 6 to 30 carbon atoms include hexanoic acid, octanoic acid (caprylic acid), nonanoic acid, decanoic acid (capric acid), dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), pentadecanoic acid, Linear saturated fatty acids such as hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), icosanoic acid, docosanoic acid (behenic acid); 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid, isotridecanoic acid Branched-chain saturated fatty acids such as 2-hexyldecanoic acid, 2-hexyldecanoic acid, 2-octyldecanoic acid, isostearic acid and 2-octyldodecanoic acid; 10-undecenoic acid (undecylenic acid), 9-tetradecenoic acid (myristolein) Acid), 2-hexadecenoic acid, 9-hexadecenoic acid, 9-octadecenoic acid (oleic acid), 1 -Unsaturated fatty acids such as docosenoic acid, 9,12-octadecandienoic acid (linoleic acid), 6,9,12-octadecanetrienoic acid (linolenic acid), toluic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA) Etc. As a C6-C30 fatty acid, a C8-C22 fatty acid is preferable from a reactive viewpoint, and a C12-C18 fatty acid is more preferable.

  The polyglycerin constituting the polyglycerin fatty acid ester may be linear, branched, or cyclic. The average degree of polymerization of polyglycerin is preferably 2 to 10, and more preferably 2 to 8.

  A polyglycerol fatty acid ester is obtained by esterifying a fatty acid having 6 to 30 carbon atoms and a polyglycerol having an average polymerization degree of 2 to 10, for example. The polyglycerol fatty acid ester may be obtained from any synthesis method. Examples of the method for producing polyglycerol fatty acid ester include esterification reaction between polyglycerol and fatty acid, ester exchange reaction between polyglycerol and fatty acid esters, ester exchange reaction between polyglycerol and fats and oils, and the like. The polyglycerin fatty acid ester may be an ester bond of one type of fatty acid to one molecule of polyglycerin, or may be one of two or more types of fatty acid ester linked to one molecule of polyglycerin.

Among the polyglycerol fatty acid esters, esters of fatty acids having 8 to 22 carbon atoms and polyglycerols having an average polymerization degree of 2 to 10 are preferable, and esters of fatty acids having 12 to 18 carbon atoms and polyglycerols having an average polymerization degree of 2 to 10 are preferred. Is more preferable.
Specifically, the polyglyceryl fatty acid ester is polyglyceryl myristate having an average degree of polymerization of 2-10, polyglyceryl oleate having an average degree of polymerization of 2-10, and an average degree of polymerization of polyglycerol of 2-10. Polyglyceryl caprylate, polyglyceryl laurate having an average degree of polymerization of polyglycerol of 2 to 10, polyglyceryl stearate having an average degree of polymerization of polyglycerol of 2 to 10, polyglyceryl diisostearate having an average degree of polymerization of polyglycerol of 2 to 10, And at least one selected from the group consisting of polyglyceryl pentastearate having an average degree of polymerization of polyglycerol of 2 to 10.

  The content of the polyglycerol fatty acid ester in the water-in-oil skin external preparation is preferably, for example, 0.1% by mass to 15% by mass with respect to the total mass of the water-in-oil skin external preparation, 0 More preferably, the content is 3% by mass to 10% by mass, and further preferably 0.5% by mass to 10% by mass. If the content of the polyglycerin fatty acid ester is 0.1% by mass or more, the dispersion stability of the surface-treated powder in the oil phase is improved. As a result, the viscosity stability of the water-in-oil external preparation tends to be improved. If the content of the polyglycerin fatty acid ester is 15% by mass or less, the stickiness after the application of the water-in-oil skin external preparation is suppressed, and the feeling of use tends to be improved.

[Crosslinked organopolysiloxane polymer (C)]
The water-in-oil external preparation of this embodiment contains a crosslinked organopolysiloxane polymer that is unmodified, polyether-modified or polyglycerin-modified in the oil phase. The water-in-oil external preparation for skin may contain one type of crosslinked organopolysiloxane polymer, or two or more types.

  The cross-linked organopolysiloxane polymer is a polymer having a three-dimensional cross-linked structure in a part of the molecule, obtained by cross-linking organopolysiloxane. Examples of the crosslinked organopolysiloxane polymer include JP-B-8-6035, JP-A-4-272932, JP-A-5-140320, JP-A-2001-342255, and WO2003 / 024413. No., Japanese Patent Application Laid-Open No. 2010-202518, and the like.

As the crosslinked organopolysiloxane polymer, for example, an organohydrogenpolysiloxane containing 1.5 or more hydrogen atoms bonded to silicon atoms in the molecule as shown in (a) below, and the following ( A compound obtained by addition polymerization of a compound having an average of 1.5 or more vinylic reaction sites in the molecule shown in b) is preferred.
(A) at least selected from the group consisting of SiO ₂ units, HSiO _1.5 units, RSiO _1.5 units, RHSiO units, R ₂ SiO units, R ₃ SiO _0.5 units, and R ₂ HSiO _0.5 units. Organohydrogenpolysiloxane formed by one type of structural unit. R represents a monovalent organic group having 1 to 30 carbon atoms excluding an aliphatic unsaturated group.
(B) At least one compound selected from the group consisting of the following (b-1) to (b-3).
(B-1) SiO ₂ unit, (CH ₂ ═CH) SiO _1.5 unit, RSiO _1.5 unit, R (CH ₂ ═CH) SiO unit, R ₂ SiO unit, R ₃ SiO _0.5 unit, And R ₂ (CH ₂ ═CH) SiO An organopolysiloxane formed by at least one structural unit selected from the group consisting of _0.5 units. R represents a monovalent organic group having 1 to 30 carbon atoms excluding an aliphatic unsaturated group.
(B-2) Polyoxyalkylene represented by the following general formula (I).
_{C m H 2m-1 O (} C 2 H 4 O) h (C 3 H 6 O) i C m H 2m-1 ··· (I)
In the formula, h represents an integer of 2 to 200, i represents an integer of 0 to 200, and h + i is 3 to 200. m represents an integer of 2 to 6.
(B-3) A compound represented by the following general formula (II).
_{C p H 2p-1 O (} CH 2 CH (OH) CH 2 O) j C p H 2p-1 ··· (II)
In the formula, p represents an integer of 2 to 20, and j represents an integer of 1 to 20.

  R in the formulas in the above (a) and (b-1) each independently represents a monovalent organic group having 1 to 30 carbon atoms excluding an aliphatic unsaturated group. The monovalent organic group includes an alkyl group such as a methyl group, an ethyl group, and a propyl group; an aryl group such as a phenyl group and a tolyl group; an aralkyl in which a hydrogen atom of the alkyl group is substituted with an aryl group such as a phenyl group and a tolyl group A cycloalkyl group such as a cyclohexyl group; a halogenated hydrocarbon group having a halogen atom; a hydrocarbon group having an ethylene oxide group.

When at least one compound selected from the above (b-2) and (b-3) is used as the compound shown in the above (b), the crosslinked organopolysiloxane polymer has the following (b- A compound obtained by addition polymerization of the compound shown in 4) may be used.
(B-4) An unsaturated hydrocarbon represented by the following general formula (III).
_{C q H 2q-1 (CH} 2) k C q H 2q-1 ··· (III)
In the formula, q represents an integer of 2 to 6, and k represents an integer of 1 or more.

Specific examples of the crosslinked organopolysiloxane polymer include the following compounds. The compound name is expressed by INCI name (International Nomenclature Cosmetic Ingredient labeling names).
Non-modified cross-linked organopolysiloxane polymers include cross-linked methylphenyl polysiloxanes such as (dimethicone / vinyl dimethicone) cross polymer, (dimethicone / phenyl dimethicone) cross polymer, and (dimethicone / phenyl vinyl dimethicone) cross polymer. Can be mentioned.
Polyether-modified cross-linked organopolysiloxane polymers include (dimethicone / (PEG (polyethylene glycol) -10/15)) crosspolymer, (PEG-15 / lauryl dimethicone) crosspolymer, and (PEG-10 / lauryl). Dimethicone) cross polymer, (PEG-15 / lauryl polydimethylsiloxyethyl dimethicone) cross polymer, and the like.
Polyglycerin-modified cross-linked organopolysiloxane polymers include (dimethicone / polyglycerin-3) crosspolymer, (lauryl dimethicone / polyglycerin-3) crosspolymer, (polyglyceryl-3 / laurylpolydimethylsiloxyethyl dimethicone) Cross polymer etc. are mentioned.

  The crosslinked organopolysiloxane polymer is also available as a commercial product. As a commercial item, for example, KSG-15, KSG-16, KSG-1610, KSG-18A, KSP-100, KSP-101, KSP-102, KSP-105, KSP-300, KSG-210, KSG-240 , KSG-310, KSG-320, KSG-330, KSG-340, KSG-710, KSG-810, KSG-820, KSG-830, KSG-840, KSG-320Z, KSG-350Z, KSG-360Z, KSG -380Z, KSG-820Z, KSG-850Z (Shin-Etsu Chemical Co., Ltd.) and the like.

  The content of the crosslinked organopolysiloxane polymer in the water-in-oil skin external preparation is, for example, 0.1% by mass to 10% by mass with respect to the total mass of the water-in-oil skin external preparation. Preferably, it is 0.15 mass%-5 mass%, More preferably, it is 0.3 mass%-5 mass%. If the content of the cross-linked organopolysiloxane polymer is 0.1% by mass or more, viscosity is imparted to the oil phase and aggregation of the surface-treated powder is suppressed. As a result, the viscosity of the water-in-oil skin external preparation is increased. If the content of the cross-linked organopolysiloxane polymer is less than 10% by mass, the oiliness (feeling of oil film) after application of the water-in-oil external preparation is suppressed. , The feeling of use tends to improve.

  From the viewpoint of further improving the viscosity stability and usability of the water-in-oil external preparation, the content of the polyglycerin fatty acid ester is 0.3% by mass to the total mass of the water-in-oil external preparation. 10 mass%, and the content of the crosslinked organopolysiloxane polymer is 0.15 mass% to 5 mass% with respect to the total mass of the water-in-oil skin external preparation, and the crosslinked organopolysiloxane The ratio of the content of the polyglycerol fatty acid ester to the content of the siloxane polymer is preferably 0.06 to 67 on a mass basis. From the same viewpoint, the content of the polyglycerin fatty acid ester is 0.5% by mass to 10% by mass with respect to the total mass of the water-in-oil skin external preparation, and the content of the crosslinked organopolysiloxane polymer Is 0.3% by mass to 5% by mass with respect to the total mass of the water-in-oil external preparation, and the ratio of the content of the polyglycerin fatty acid ester to the content of the crosslinked organopolysiloxane polymer Is more preferably 0.1 to 33 on a mass basis.

[Polyether-modified silicone]
The water-in-oil type external preparation for skin of this embodiment may contain polyether-modified silicone. When the water-in-oil external preparation contains the polyether-modified silicone, the emulsion stability of the water-in-oil external preparation tends to be improved. The water-in-oil type external preparation for skin may contain polyether-modified silicone alone or in combination of two or more. The polyether-modified silicone does not include those corresponding to the crosslinked organopolysiloxane polymer.

  The polyether-modified silicone is a polymer having a silicone chain as a main chain and a polyether chain introduced by modification. The silicone chain may be a linear silicone chain or a branched silicone chain. Examples of the polyether chain include a polyethylene glycol (PEG) chain and a polypropylene glycol (PPG) chain. The polyether-modified silicone may further have an alkyl chain having 8 to 22 carbon atoms introduced by modification.

  The HLB (Hydrophile-Lipophile Balance) value of the polyether-modified silicone is preferably 1 to 10 and more preferably 2 to 8 from the viewpoint of the emulsion stability of the water-in-oil external preparation. In the present specification, the HLB value of the polyether-modified silicone is a value obtained from the molecular weight and the number of ethylene oxide groups. When using a commercial item, the HLB value described in the catalog etc. can be applied as it is.

Examples of the polyether-modified silicone include PEG-11 methyl ether dimethicone, PEG / PPG-20 / 22 butyl ether dimethicone, PEG / PPG-19 / 19 dimethicone, PEG-9 dimethicone, PEG-9 methyl ether dimethicone, PEG-10 dimethicone, PEG-21 methyl ether dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, and the like.
The polyether-modified silicone is also available as a commercial product. Examples of commercially available products include KF-6011, KF-6011P, KF-6012, KF-6013, KF-6015, KF-6016, KF-6017, KF-6017P, KF-6043, KF-6028, KF-6028P. KF-6038 (Shin-Etsu Chemical Co., Ltd.) and the like.

  The polyether-modified silicone is preferably a polyether-modified silicone having a branched silicone chain from the viewpoint of emulsion stability of the water-in-oil external preparation. Among these, the polyether-modified silicone is more preferably at least one selected from PEG-9 polydimethylsiloxyethyl dimethicone and lauryl PEG-9 polydimethylsiloxyethyl dimethicone.

  When the water-in-oil skin external preparation contains a polyether-modified silicone, the content of the polyether-modified silicone is, for example, 0.01% by mass to 10% by mass with respect to the total mass of the water-in-oil skin external preparation. %, More preferably 0.1% by mass to 8% by mass, and still more preferably 0.5% by mass to 6% by mass. If the content of the polyether-modified silicone is 0.01% by mass or more, the emulsification stability of the water-in-oil external preparation tends to be improved, and the content of the polyether-modified silicone is 10% by mass or less. For example, the stickiness after application of the water-in-oil external preparation tends to decrease.

[Clay minerals]
The water-in-oil type skin external preparation of this embodiment may contain a clay mineral. When the water-in-oil external preparation contains a clay mineral, the aggregation of the surface-treated powder is suppressed, and as a result, the viscosity stability of the water-in-oil external preparation tends to be improved. The water-in-oil type external preparation for skin may contain one kind of clay mineral alone or two or more kinds.

  The clay mineral is not particularly limited, and examples thereof include kaolinite, talc, smectite, vermiculite, and mica. Among these clay minerals, smectite having a trioctahedral three-layer structure is preferable from the viewpoint of improving the viscosity stability of the water-in-oil type skin external preparation. Examples of the smectite include fluorine hectorite, hectorite, saponite, and stevensite.

  The clay mineral may be surface-treated. Examples of the surface-treated clay mineral include a cation-modified clay mineral surface-treated with a quaternary ammonium salt type cationic surfactant, from the viewpoint of improving the viscosity stability of the water-in-oil type skin external preparation. Cationic modified smectite is preferred. Examples of the cation-modified smectite include dimethyl distearyl ammonium hectorite and benzyl dimethyl stearyl ammonium hectorite.

The clay mineral is also available as a commercial product. Examples of commercially available products of fluorine hectorite include Laponite B (Laporte), Lucentite (registered trademark) SWF (Coop Chemical Co., Ltd.), and the like.
Commercial products of hectorite include Laponite XLG (Laporte), Ionite (registered trademark) -H (Mizusawa Chemical Industry Co., Ltd.), Thixopy (registered trademark) W, Thixopy (registered trademark) R (Kyowa Chemical Industry) Co., Ltd.), Lucentite (registered trademark) SWN, Lucentite (registered trademark) SAN (above, Coop Chemical Co., Ltd.) and the like.
Examples of commercial products of saponite include Smecton SAI (Kunimine Industry Co., Ltd.).
Examples of commercially available products of stevensite include Ionite (registered trademark) -K, Ionite (registered trademark) -T (hereinafter referred to as Mizusawa Chemical Co., Ltd.), and the like.
Commercially available products of cation-modified smectite include NIKKOL (registered trademark) Nikomulus WO (Nikko Chemicals Co., Ltd.), BENTONE (registered trademark) 27V, BENTONE (registered trademark) 27VCG, BENTONE (registered trademark) 38V, and BENTONE (registered trademark). 38VCG (above, Elementis).

  When the water-in-oil external preparation contains clay mineral, the content of the clay mineral is, for example, 0.05% by mass to 10% by mass with respect to the total mass of the water-in-oil external preparation. Is preferable, 0.1 mass% to 5 mass% is more preferable, and 0.1 mass% to 2 mass% is still more preferable. If the clay mineral content is 0.05% by mass or more, the viscosity stability of the water-in-oil skin external preparation tends to be improved, and if the clay mineral content is 10% by mass or less, the elongation is increased. There is a tendency to obtain a good feeling of use.

[Surfactant]
The water-in-oil external preparation of this embodiment may contain a surfactant other than polyglycerin fatty acid ester. When the water-in-oil external preparation contains a surfactant, the viscosity stability of the water-in-oil external preparation tends to be improved. The water-in-oil type skin external preparation may contain one kind of surfactant alone or two or more kinds.

  As the surfactant, either a nonionic surfactant or an ionic surfactant may be used. Examples of the ionic surfactant include alkyl sulfonate, alkyl sulfate, monoalkyl phosphate, and lecithin. Nonionic surfactants include sorbitan fatty acid ester, glycerin fatty acid ester, organic acid monoglyceride, propylene glycol fatty acid ester, polyglycerin condensed ricinoleic acid ester, sucrose fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, poly Oxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene Castor oil, polyoxyethylene hydrogenated castor oil, and the like.

  When the water-in-oil skin external preparation contains a surfactant, the content of the surfactant is, for example, 0.01% by mass to 30% by mass with respect to the total mass of the water-in-oil skin external preparation. It is preferable that it is 0.05 mass%-20 mass%, and it is still more preferable that it is 0.1 mass%-10 mass%. If the surfactant content is 0.01% by mass or more, the viscosity stability of the water-in-oil external preparation tends to be improved. If the surfactant content is 30% by mass or less, The feeling of use tends to improve.

[Oil agent]
The water-in-oil type skin external preparation of this embodiment contains an oil agent. An oil agent is a component which becomes a solvent or a dispersion medium in a composition that forms an oil phase of a water-in-oil external skin preparation. The oil agent is not particularly limited as long as it is liquid at room temperature (25 ° C.). Examples of the oil agent include silicone oil, ester oil, hydrocarbon oil and the like, and can be selected according to the purpose. The water-in-oil external preparation for skin may contain one kind of oil or may contain two or more kinds.

Silicone oils include linear polysiloxanes such as dimethylpolysiloxane (dimethicone), methylphenylpolysiloxane, methylhydrogenpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethyltetra Examples thereof include cyclic polysiloxanes such as hydrogencyclotetrasiloxane, caprylyl methicone and the like.
Commercially available silicone oils include KF-96L-0.65cs, KF-96L-1cs, KF-96L-1.5cs, KF-96L-2cs, KF-96L-5cs, KF-96A-6cs, KF- 96-10cs, KF-96-20cs, KF-995 (Shin-Etsu Chemical Co., Ltd.), SH200 C Fluid 1CS, SH200 Fluid 1.5CS, SH200 C 2CS, SH200 C Fluid 5CS, SH200 C Fluid 6CS, SH200 C Fluid 10CS, SH200 C Fluid 20CS, 2-1184 Fluid, SH245 Fluid, DC246 Fluid, DC345 Fluid, SS-3408 (above, Toray Dow Corning Co., Ltd.), TSF404, TSF405, TSF4045 ( On, it includes the Momentive Performance Materials, Inc.), and the like.

  Ester oils include pentaerythrityl tetraethylhexanoate, cetyl ethylhexanoate, jojoba oil, dilauroyl glutamate (phytosteryl / octyldodecyl), triisostearin, glyceryl diisostearate, triethylhexanoin, dimerlinoleic acid (phytosteryl / behenyl). , Dimer linoleic acid (phytosteryl / isostearyl / cetyl / stearyl / behenyl), isopropyl palmitate, macadamia nut fatty acid phytosteryl, tetra (behenic acid / benzoic acid / ethylhexanoic acid) pentaerythrityl, ethylhexyl palmitate, myristyl myristate, Examples include tripropylene glycol dipivalate and isotridecyl isononanoate.

  The hydrocarbon oil may be either linear or branched. Examples of the hydrocarbon oil include isoalkanes (isoparaffins) having 8 to 16 carbon atoms such as isodecane, isododecane, and isohexadecane.

  The content of the oil agent in the water-in-oil skin external preparation is preferably, for example, 5% by mass to 80% by mass with respect to the total mass of the water-in-oil skin external preparation, and 10% by mass to 75% by mass. %, More preferably 15% by mass to 65% by mass.

[water]
The water-in-oil type skin external preparation of this embodiment contains water. Water is a component serving as a solvent or a dispersion medium in the composition forming the aqueous phase of the water-in-oil type skin external preparation. The water is not particularly limited as long as it can be applied to a skin external preparation.

[Polyhydric alcohol]
The water-in-oil type skin external preparation of this embodiment may contain a polyhydric alcohol. When the water-in-oil external preparation contains a polyhydric alcohol, the usability (moisturizing property) of the water-in-oil external preparation tends to be improved. The water-in-oil type external preparation for skin may contain one kind of polyhydric alcohol or two or more kinds.

  Examples of the polyhydric alcohol include glycerin, polyglycerin, ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,2-pentanediol, 1,2-hexanediol, polyethylene glycol, glucose, galactose, and sucrose. Sorbitol, maltitol, erythritol, xylitol, trehalose and the like.

[Other ingredients]
The water-in-oil external preparation of this embodiment may contain other components as long as the effects of the present invention are not impaired.
Other components include UV absorbers other than 4-tert-butyl-4′-methoxydibenzoylmethane, water-soluble organic solvents (such as ethanol), preservatives (such as phenoxyethanol and methylparaben), pH adjusters, emollients, Examples include humectants, antioxidants, whitening agents, colorants, and fragrances.

<Viscosity of water-in-oil type skin external preparation>
The viscosity of the water-in-oil external preparation at 25 ° C. is preferably 8000 mPa · s to 18000 mPa · s, and more preferably 8000 mPa · s to 16000 mPa · s. If the viscosity at 25 ° C. of the water-in-oil external preparation is 8000 mPa · s or more, the stability tends to be improved, and if the viscosity at 25 ° C. of the water-in-oil external preparation is 18000 mPa · s or less. The elongation when applying the water-in-oil type skin external preparation is good, and the feeling of use tends to be improved.
In the present specification, the viscosity of the water-in-oil external preparation at 25 ° C. is not limited as long as it is a known viscosity measuring method. For example, the viscosity can be measured by using a BL type viscometer (M3 rotor) and a value measured by stirring for 60 seconds at a rotor rotational speed of 6 revolutions / minute. As the BL type viscometer, for example, VISCOMETER TVB-10 manufactured by Toki Sangyo Co., Ltd. can be suitably used. However, the BL type viscometer is not limited to this.

<Use of water-in-oil type skin external preparation>
The water-in-oil external preparation of this embodiment can be applied to uses such as cosmetics and transdermal pharmaceutical products. Examples of cosmetics include skin care cosmetics, sunscreen cosmetics, makeup cosmetics such as makeup bases, but are not limited thereto.

<Method for producing water-in-oil type skin external preparation>
The manufacturing method of the water-in-oil type skin external preparation of this embodiment is not specifically limited, It can manufacture according to the manufacturing method of a well-known water-in-oil type skin external preparation.
For example, an oil phase composition containing the surface-treated powder and other oil phase components is prepared, and the obtained oil phase composition and the aqueous phase composition are mixed to prepare a water-in-oil skin external preparation. Can be manufactured.

  An emulsification method for obtaining a water-in-oil external skin preparation as a water-in-oil emulsion by mixing the oil phase composition and the water phase composition is not particularly limited, and can be performed according to a conventional method. .

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof.

[Examples 1 to 10, Comparative Examples 1 to 3, Comparative Examples 5 to 9]
Cyclopentasiloxane, surface-treated powder, and dimethicone 10CS were thoroughly mixed with a disper at room temperature. Thereafter, the remaining components contained in the oil phase composition were further added, mixed by stirring and homogenized to obtain an oil phase composition.
Next, the components contained in the aqueous phase composition were stirred and mixed at room temperature to obtain a uniform aqueous phase composition.
Next, the oil phase composition and the aqueous phase composition were mixed according to a conventional method, and using a homogenizer (HM-310, ASONE Co., Ltd.), 1000 rotations / minute (other than Example 6) or 4000 rotations / minute (implementation) By stirring for 10 minutes under the conditions of Example 6), water-in-oil type skin external preparations of Examples 1 to 10, Comparative Examples 1 to 3, and Comparative Examples 5 to 9 were obtained.

[Comparative Example 4]
Cyclopentasiloxane and dimethicone 10CS were thoroughly mixed with a disper at room temperature. Thereafter, the remaining components contained in the oil phase composition were further added, mixed by stirring and homogenized to obtain an oil phase composition.
Next, the components contained in the aqueous phase composition were stirred and mixed at room temperature to obtain a uniform aqueous phase composition.
Subsequently, the oil phase composition and the aqueous phase composition were mixed according to a conventional method, and stirred for 10 minutes under the condition of 1000 revolutions / minute using a homogenizer (HM-310, AS ONE Co., Ltd.), so that Comparative Example 4 The oil-in-water type external preparation for skin was obtained.

Tables 1 to 6 show the content of each component in the skin external preparations of Examples 1 to 10 and Comparative Examples 1 to 9. In Tables 1 to 6, “%” indicates “% by mass”, and “−” indicates that the component is not contained. “B / C ratio” in Table 6 means the ratio (mass basis) of the content of the polyglycerin fatty acid ester (B) to the content of the crosslinked organopolysiloxane polymer (C).
In addition, Example 1 described in Table 1 and Table 5 is redundantly described for convenience of comparison, and both are the same. In addition, Example 3 described in Tables 3 and 6 is redundantly described for convenience of comparison, and both are the same.
The details of each component described in Tables 1 to 6 are as follows.

-Surface treatment powder: HXMT-100ZA (Taika Co., Ltd.)
PEG-9 polydimethylsiloxyethyl dimethicone: KF-6028 (Shin-Etsu Chemical Co., Ltd.)
-Polyglyceryl-2 diisostearate: EMALEX DISG-2 (Japan Emulsion Co., Ltd.)
-(Dimethicone / vinyl dimethicone) crosspolymer: KSG-16 (volume average particle diameter 5 μm, Shin-Etsu Chemical Co., Ltd.)
・ (Dimethicone / (PEG-10 / 15) crosspolymer: KSG-210 (Shin-Etsu Chemical Co., Ltd.)
Polyglyceryl stearate-2: NIKKOL (registered trademark) DGMS (Nikko Chemicals Co., Ltd.)
-Sorbitan stearate: NIKKOL (registered trademark) SS-10V (Nikko Chemicals Corporation)
・ Glyceryl stearate: NIKKOL (registered trademark) MGS-AV (Nikko Chemicals Co., Ltd.)
・ Methylphenyl silicone oil: KF-53 (Shin-Etsu Chemical Co., Ltd.)
Dextrin palmitate: Leopard (registered trademark) TL2 (Chiba Flour Milling Co., Ltd.)
• Disteardimonium hectorite: NIKKOL (registered trademark) Nikomulus WO (Nikko Chemicals Corporation)

[Evaluation]
About each skin external preparation of Examples 1-10 and Comparative Examples 1-9, each following evaluation was performed. The results are shown in Tables 1-6. Note that the external preparation for skin of Comparative Example 1 had a very low viscosity, and could not be evaluated for viscosity stability, stickiness, oiliness (oil film feeling), and creaking. Further, in the external preparation for skin of Comparative Example 2, the oil phase and the aqueous phase were separated over time, and the viscosity stability could not be evaluated.

(Evaluation of viscosity stability)
Using a BL-type viscometer (VISCOMETER TVB-10, Toki Sangyo Co., Ltd., M3 rotor), the skin external preparations of Examples 1 to 10 and Comparative Examples 3 to 9 were rotated at a rotor rotation speed of 6 rotations / minute for 60 seconds. The mixture was stirred and the viscosity (initial viscosity) at 25 ° C. was measured. Subsequently, the skin external preparations of Examples 1 to 10 and Comparative Examples 3 to 9 were placed in a thermostatic bath at 60 ° C., and the viscosity at 25 ° C. (viscosity with time) was measured using a BL type viscometer after 14 days. Then, as an index for evaluating the viscosity stability, the relative value of the time-dependent viscosity when the initial viscosity was 100% was defined by the following formula as an indication of how much the increase or decrease of the viscosity was suppressed from the initial viscosity. The results are shown in Tables 1-6. If the relative value of the viscosity with time is 60% or more, it is considered acceptable in practice.
Relative viscosity value (%) = (viscosity / initial viscosity) × 100

(Evaluation of stickiness)
Ten specialist panelists applied the skin external preparations of Examples 1 to 10 and Comparative Examples 2 to 9 to their faces with their fingers, and the stickiness after application was evaluated according to the following five evaluation criteria. . Then, the evaluation values obtained by the 10 expert panelists were averaged, and the value obtained by rounding off the first decimal place was taken as the evaluation result of the stickiness. The results are shown in Tables 1-6. If the evaluation result is 3 or more, it is considered acceptable in practice.
The “stickiness” refers to a feeling after the skin external preparation is applied to the skin, and refers to a touch with sticking or adhesion between a finger or the like and the skin to which the skin external preparation is applied.
-Evaluation criteria-
5: I do not feel stickiness 4: I feel almost no stickiness 3: I feel a little stickiness 2: I feel stickiness 1: I feel stickiness strongly

(Evaluation of oiliness (feeling of oil film))
Ten professional panelists applied the skin external preparations of Examples 1 to 10 and Comparative Examples 2 to 9 to their faces with their fingers, and the oiliness (oil film feeling) after application was evaluated in the following five levels. We had you evaluate by standard. And the evaluation value by 10 professional panelists was averaged, and the value rounded off to the first decimal place was taken as the evaluation result of oiliness (oil film feeling). The results are shown in Tables 1-6. If the evaluation result is 3 or more, it is considered acceptable in practice.
The “oiliness (feeling of oil film)” refers to the feeling after the external preparation for skin is applied to the skin, and between the fingers and the skin to which the external preparation for skin is applied. It refers to a touch that is smooth and slimy.
-Evaluation criteria-
5: Does not feel oily (feeling oil film) 4: Feels almost oily (feeling oil film) 3: Feels a little oily (feeling oil film) 2: Feels oily (feeling oil film) I feel oily (feeling oil film) strongly

(Evaluation of Kisimi)
Ten specialist panelists applied the skin external preparations of Example 1 and Comparative Examples 2 to 4 to their faces with their fingers, and evaluated the creaking at the time of application according to the following five evaluation criteria. Then, the evaluation values by 10 expert panelists were averaged, and the value rounded to the first decimal place was taken as the evaluation result of Kisimi. The results are shown in Table 1. If the evaluation result is 3 or more, it is considered acceptable in practice.
“Kishimi” refers to a feeling when the skin preparation is applied to the skin, and refers to a feeling lacking in smoothness caused by friction when the powder components are in direct contact with each other.
-Evaluation criteria-
5: I don't feel Kisimi 4: I almost don't feel Kisimi 3: I feel a little Kisimi 2: I feel Kisimi 1: I feel Kisimi strongly

(Evaluation of elongation)
Ten professional panelists applied the external preparations of Example 1 and Example 6 to their faces with their fingers, and the elongation at the time of application was evaluated according to the following five evaluation criteria. And the evaluation value by 10 expert panelists was averaged, and the value rounded to the first decimal place was taken as the evaluation result of growth. The results are shown in Table 5. If the evaluation result is 3 or more, it is considered acceptable in practice.
The term “elongation” refers to a feeling when the external preparation for skin is applied to the skin, and a feeling that spreads on the skin.
-Evaluation criteria-
5: Elongation is very excellent 4: Elongation is excellent 3: Elongation is felt 2: Elongation is inferior 1: Elongation is very inferior

(Evaluation of UV shielding ability)
Based on the in vitro measurement method of ISO 24443: 2012, 32.5 mg of the topical skin preparations of Examples 1 to 10 and Comparative Examples 1 to 9 were uniformly applied to a polymethyl methacrylate (PMMA) plate (HELIOPLATE HD6, HelioScreen). It applied and the measurement sample was produced. Two measurement samples were prepared for each sample.
About this measurement sample, the transmittance | permeability was measured using SPF (Sun Protection Factor) analyzer (UV-2000S, Labsphere), and SPF value was calculated | required. The SPF value was measured as 5 samples (n = 5) for each of the two samples, and the average value was obtained.
When the SPF value is 30 or more, it is “G1”, and when it is less than 30, it is “NG”. The results are shown in Tables 1-6.

  As shown in Tables 1 to 6, the water-in-oil skin of Examples 1 to 10 containing the surface-treated powder, polyglycerin fatty acid ester, and crosslinked organopolysiloxane polymer in the oil phase. All of the external preparations were excellent in ultraviolet shielding ability and viscosity stability, and were less sticky and oily (feeling of oil film) after coating, and were excellent in use feeling.

On the other hand, the skin external preparation of Comparative Example 1 obtained by removing the surface-treated powder from the skin external preparation of Example 1 was very low in viscosity and did not have an ultraviolet shielding ability and was not practically acceptable. .
In addition, the skin external preparation of Comparative Example 2 obtained by removing the polyglycerin fatty acid ester from the skin external preparation of Example 1 has an oil phase and an aqueous phase that are separated with time, and the viscosity stability is extremely inferior. Oily feeling (oil film feeling) was felt and the feeling of use was also inferior.
Moreover, the skin external preparation of Comparative Example 3 obtained by removing the cross-linked organopolysiloxane polymer from the skin external preparation of Example 1 was inferior in viscosity stability, felt sticky after application, and inferior in use.
Moreover, although the external preparation for skin of Comparative Example 4 contains the same components as the external preparation for skin of Example 1, due to the fact that the surface-treated powder is contained in the aqueous phase, creaking is strongly felt at the time of application. The feeling of use was inferior.

  Further, the skin external preparations of Comparative Examples 5 to 7 in which the polyglycerin fatty acid ester in the external preparation for Example 2 was changed to other components, and the cross-linked organopolysiloxane polymer in the external preparation for skin of Example 2 were changed to other components. The skin external preparations of Comparative Example 8 and Comparative Example 9 that were changed to the components were inferior in viscosity stability and usability.

In addition, when Example 4 and Example 5 are contrasted, it turns out that viscosity stability improves, when a skin external preparation contains a clay mineral (Table 4).
Moreover, when Example 1 and Example 6 are compared, it turns out that elongation becomes favorable and a usability improves by setting the viscosity of a skin external preparation appropriately (Table 5).
Moreover, when Example 3, Example 9, and Example 10, and Example 7 and Example 8 are contrasted, content and content of polyglyceryl fatty acid ester and cross-linked organopolysiloxane polymer in the external preparation for skin It can be seen that the usability is further improved by appropriately setting the ratio (Table 6).

Claims (9)

A surface-treated powder (A) containing at least one selected from titanium oxide and zinc oxide and having 4-tert-butyl-4′-methoxydibenzoylmethane on the surface;
Polyglycerol fatty acid ester (B),
Unmodified or polyether-modified or polyglycerol-modified crosslinked organopolysiloxane polymer (C);
A water-in-oil type external preparation for skin containing an oil phase.   The surface-treated powder (A) has a surface-treated layer containing 4-tert-butyl-4'-methoxydibenzoylmethane on at least one surface selected from titanium oxide and zinc oxide. Water-in-oil type skin external preparation.   The water-in-oil skin external preparation according to claim 2, wherein the surface treatment layer contains at least one selected from the group consisting of fatty acids and aluminum hydroxide.   The water-in-oil type according to any one of claims 1 to 3, wherein the polyglycerol fatty acid ester (B) is an ester of a fatty acid having 8 to 22 carbon atoms and a polyglycerol having an average degree of polymerization of 2 to 10. Skin external preparation. The crosslinked organopolysiloxane polymer (C) is an organohydrogenpolysiloxane having an average of 1.5 or more hydrogen atoms bonded to silicon atoms in the molecule shown in (a) below, and the following ( The water-in-oil according to any one of claims 1 to 4, which is obtained by addition polymerization with a compound having an average of 1.5 or more vinylic reaction sites in the molecule shown in b). Type skin external preparation.
(A) at least selected from the group consisting of SiO ₂ units, HSiO _1.5 units, RSiO _1.5 units, RHSiO units, R ₂ SiO units, R ₃ SiO _0.5 units, and R ₂ HSiO _0.5 units. Organohydrogenpolysiloxane formed by one type of structural unit. R represents a monovalent organic group having 1 to 30 carbon atoms excluding an aliphatic unsaturated group.
(B) At least one compound selected from the group consisting of the following (b-1) to (b-3).
(B-1) SiO ₂ unit, (CH ₂ ═CH) SiO _1.5 unit, RSiO _1.5 unit, R (CH ₂ ═CH) SiO unit, R ₂ SiO unit, R ₃ SiO _0.5 unit, And R ₂ (CH ₂ ═CH) SiO An organopolysiloxane formed by at least one structural unit selected from the group consisting of _0.5 units. R represents a monovalent organic group having 1 to 30 carbon atoms excluding an aliphatic unsaturated group.
(B-2) Polyoxyalkylene represented by the following general formula (I).
_{C m H 2m-1 O (} C 2 H 4 O) h (C 3 H 6 O) i C m H 2m-1 ··· (I)
In the formula, h represents an integer of 2 to 200, i represents an integer of 0 to 200, and h + i is 3 to 200. m represents an integer of 2 to 6.
(B-3) A compound represented by the following general formula (II).
_{C p H 2p-1 O (} CH 2 CH (OH) CH 2 O) j C p H 2p-1 ··· (II)
In the formula, p represents an integer of 2 to 20, and j represents an integer of 1 to 20.   The water-in-oil type external preparation for skin according to any one of claims 1 to 5, further comprising a clay mineral.   The water-in-oil type external preparation for skin according to claim 6, wherein the clay mineral is smectite.   The content of the polyglycerin fatty acid ester (B) is 0.3% by mass to 10% by mass with respect to the total mass of the water-in-oil skin external preparation, and the content of the crosslinked organopolysiloxane polymer (C) The amount is 0.15% by mass to 5% by mass with respect to the total mass of the water-in-oil skin external preparation, and the polyglycerin fatty acid ester relative to the content of the crosslinked organopolysiloxane polymer (C) ( The ratio of the content of B) is 0.06 to 67 on a mass basis, The water-in-oil type external preparation for skin according to any one of claims 1 to 7.   The water-in-oil type skin external preparation of any one of Claims 1-8 whose viscosity in 25 degreeC is 8000 mPa * s-18000 mPa * s.