JP2016153437A - Water-in-oil type emulsion cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-in-oil type emulsion cosmetic that is excellent in temporal stability, has no stickiness, and has excellent spreading.SOLUTION: A water-in-oil type emulsion cosmetic comprises the following components (A)-(E): (A) 3-60 mass% of microparticulate metal oxide whose surface is treated with tri-alkoxyalkylsilane; (B) polyhydroxy stearic acid (but the formulation mass ratio of a component (A) and a component (B), (B)/(A), is 0.01-0.5); (C) 5-90 mass% of one or more kinds of non-silicone-based oil solutions selected from propylene glycol dicaprate, neopentylglycol dicaprate, isononyl isononanoic acid, isotridecyl isononanoic acid, 2-ethyl hexanoic acid cetyl, isododecane, isotetradecane, is hexadecane, and a liquid paraffin with a viscosity at 40°C of 11 mm2/s or less; (D) 0.1-10 mass% of polyoxyalkylene-alkyl covariant silicone with an HLB of 2-7 and/or polyglycerol alkyl covariant silicone with an HLB of 2-7; and (E) 10-70 mass% of an aqueous component.SELECTED DRAWING: None

Description

  The present invention relates to a water-in-oil emulsified cosmetic in which a particulate metal oxide surface-treated with a trialkoxyalkylsilane is dispersed in an oil layer with polyhydroxystearic acid. More specifically, the present invention relates to water-in-oil emulsified cosmetics. The present invention relates to a water-in-oil emulsified cosmetic material that spreads well.

  While fine metal oxides blended in cosmetics exhibit various functions, since they have high cohesiveness, it is very difficult to uniformly disperse in cosmetics and maintain stability over time. Consideration has been made. For example, cosmetics having an ultraviolet protection effect are blended with organic ultraviolet absorbers, inorganic ultraviolet scattering agents, and the like, and metal oxides such as titanium oxide and zinc oxide are used as inorganic ultraviolet scattering agents. However, since the refractive index is high, the skin becomes white after application, which is not preferable as a cosmetic. In order to improve the whiteness after coating, a technique for improving the visible light transmittance by making metal oxide fine particles has been reported (for example, see Patent Document 1). In addition, in order to improve the dispersibility of the finely divided metal oxide and improve the whiteness after coating, studies using dialkyl sodium sulfosuccinate as a dispersant (Patent Document 2), ester bond of polyhydroxystearic acid There is examination using a thing (patent document 3).

  Furthermore, in order to improve the dispersibility of the fine particle metal oxide, a dispersion composition in which the fine particle metal oxide is preliminarily dispersed is prepared and blended in cosmetics. Examples of the dispersion composition include a dispersion composition using trimethylsiloxysilicic acid or a dimethylpolysiloxane / methyl (polyoxyalkylene) siloxane copolymer as a dispersant (see, for example, Patent Document 4), and an acrylic-silicone graft as a dispersant. A dispersion composition using a polymer (see, for example, Patent Document 5), a dispersion composition using both ends siliconeized polyglycerin as a dispersing agent (see, for example, Patent Document 6), and a specific organopolysiloxane copolymer as a dispersing agent There is a technique for obtaining a dispersion composition using a coalescence (for example, see Patent Document 7) and a dispersion composition using polyglycerin-modified silicone as a dispersing agent (for example, see Patent Document 8), for improving dispersibility and usability. In addition, volatile silicone oil such as decamethylcyclopentasiloxane is used as a dispersion medium. To have. Studies using oils other than volatile silicone oils such as decamethylcyclopentasiloxane as dispersion media include ricinoleic acid and hydroxystearic acid as dispersants, and paraffin oil and triglyceride esters as dispersion media (for example, patents) There is a study using polyhydroxystearic acid as a dispersant and ester oil or triglyceride ester as a dispersion medium (see, for example, Patent Document 10).

  As a water-in-oil emulsified cosmetic compounded with a metal oxide, there is a technique using a specific dimethylpolysiloxane polyoxyalkylene copolymer (see, for example, Patent Document 11). In addition, as a water-in-oil emulsified cosmetic containing a fine particle metal oxide, a technique using a polyglycerin-modified silicone (see, for example, Patent Document 12), a long-chain alkyl / polyoxyalkylene / organopolysiloxane co-modified siloxane compound There is a technique using (for example, see Patent Document 13).

JP-A-9-175721 JP 2003-226615 A JP 2003-335649 A JP-A-9-208438 JP 2006-131547 A JP 2007-161648 A JP-A-11-263708 JP 2004-169015 A JP-A-6-39272 Special table 2009-508920 JP-A-63-250311 JP 2008-179628 A JP 2007-269690 A

  However, as disclosed in Patent Document 1, if the metal oxide is made into fine particles in order to improve the transparency, the surface area of the powder increases, the cohesive force becomes strong, and it becomes difficult to disperse. The dispersants used in Patent Documents 2 and 3 are semi-solid and sticky, and when used in cosmetics, there are problems in usability such as stickiness and poor spread. The silicone-based dispersant used in Patent Documents 4 to 8 is a low HLB surfactant in which a hydrophilic portion is introduced into a silicone chain, and is an oil-in-water emulsified cosmetic or water-in-oil emulsified blended with water. In cosmetics, the silicone dispersant may be oriented at the interface between oil and water, and the dispersibility of the particulate metal oxide may be reduced. Further, the silicone-based dispersants used in Patent Documents 4 to 8 are designed to have a large molecular weight for stabilizing the dispersion, and have problems in usability such as stickiness and poor spread. In particular, trimethylsiloxysilicic acid disclosed in Patent Document 4 is an adhesive resin and has a significant stickiness and a problem in usability. Furthermore, when a non-silicone oil is used as a dispersion medium, Patent Document 9 using non-silicone-based ricinoleic acid or hydroxystearic acid as a dispersant, and Patent Document 10 using polyhydroxystearic acid as a dispersant are: It was necessary to add a large amount of a dispersant, resulting in sticky usability, poor spread and poor temporal stability. In addition, as in Patent Documents 11 to 13, when a silicone surfactant and a silicone oil are combined, the usability and stability are improved, but when an oil agent other than silicone oil is used, the compatibility and stability are poor. In some cases, it was difficult to obtain good usability. As described above, water-in-oil emulsified cosmetics that are excellent in dispersibility and temporal stability of the particulate metal oxide, have no stickiness, and have good usability of spreading are not sufficient.

  Under such circumstances, the present inventor has conducted extensive research to solve the above problems, and as a result, when the fine metal oxide is dispersed in the oil layer containing the non-silicone oil agent, the surface treatment is performed with trialkoxyalkylsilane. In addition, the dispersibility of the fine metal oxide in the oil layer is improved by using polyhydroxy stearic acid as a dispersant, and the aqueous component is emulsified with a specific silicone surfactant. Thus, it was found that a water-in-oil emulsified cosmetic having excellent dispersibility and temporal stability of the particulate metal oxide, having no stickiness and good usability of spreading, and completing the present invention It came.

  Furthermore, by preparing a fine particle metal oxide dispersion composition in which a fine particle metal oxide surface-treated with trialkoxyalkylsilane is previously dispersed in a non-silicone oil with polyhydroxystearic acid, the fine particle metal oxide can be efficiently oxidized. The water-in-oil emulsified cosmetic can be dispersed, and the dispersibility and stability over time are further improved.

That is, the present invention
[1] The following components (A) to (E);
(A) Fine particle metal oxide surface-treated with trialkoxyalkylsilane (B) Polyhydroxystearic acid (C) Non-silicone oil agent (D) Polyoxyalkylene / alkyl co-modified silicone of HLB2-7 and / or HLB2 The present invention provides a water-in-oil emulsified cosmetic comprising 7 polyglycerin / alkyl co-modified silicone (E) aqueous component.

  [2] In the above [1], the amount of the surface treatment with the trialkoxyalkylsilane of the component (A) is surface treatment agent / particulate metal oxide = 0.02 to 0.25 in mass ratio. The water-in-oil emulsified cosmetic described is provided.

  [3] The water-in-oil emulsified cosmetic according to [1] or [2], wherein the fine particle metal oxide of the component (A) is further surface-treated with a (dimethicone / methicone) copolymer. It is to provide.

  [4] The water-in-oil emulsion cosmetic according to any one of [1] to [3], wherein the non-silicone oil of component (C) is a hydrocarbon oil or an ester oil. To do.

[5] The above-mentioned [1] to [1], wherein the non-silicone oil agent of component (C) is a hydrocarbon oil having a viscosity at 40 ° C. of 16 mm ² / s or less or an ester oil having 27 or less carbon atoms. 4]. The water-in-oil emulsified cosmetic according to any one of 4) is provided.

[6] The non-silicone oil of component (C) is isododecane, isotetradecane, isohexadecane, liquid paraffin having a viscosity at 40 ° C. of 11 mm ² / s or less, propylene glycol dicaprate, neopentyl glycol dicaprate, isononyl isononanoate The water-in-oil emulsified cosmetic according to any one of the above [1] to [5], wherein the emulsion is one or more selected from isotridecyl isononanoate and cetyl 2-ethylhexanoate. To do.

[7] The polyoxyalkylene / alkyl co-modified silicone of component (D) is represented by the following general formula (1):
R ¹ _a R ² _b R ³ _c SiO _{(4-abc) / 2} (1)
(In the formula, R ¹ represents an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, a fluorine-substituted alkyl group, or the following general formula (2):
_{-C m H 2m -O- (C 2} H 4 O) d (C 3 H 6 O) e -R 4 ... (2)
R ² is the same or different organic group selected from the organic groups represented by the following general formula (3):
_{-C m H 2m -O- (C 2} H 4 O) f (C 3 H 6 O) g -R 5 ... (3)
R ³ is a polyoxyalkylene group represented by the following general formula (4)
_{^{-C n H 2n - (SiR 1}} R 1 O) h -SiR 1 3 ... (4)
R ⁴ is a hydrocarbon group having 4 to 30 carbon atoms or an organic group represented by R ^6- (CO)-, R ⁵ is a hydrogen atom or a hydrocarbon having 1 to 30 carbon atoms A group or an organic group represented by R ⁶ — (CO) —, R ⁶ is a hydrocarbon group having 1 to 30 carbon atoms. a, b and c are 1.0 ≦ a ≦ 2.5, 0.001 ≦ b ≦ 1.5 and 0.001 ≦ c ≦ 1.5, respectively, d and e are 0 ≦ d ≦ 50, 0 ≦ e ≦ 50, f and g are 2 ≦ f ≦ 200, 0 ≦ g ≦ 198, and f + g is an integer of 3 to 200, respectively. M is an integer of 0 ≦ m ≦ 15, h is an integer of 0 ≦ h ≦ 500, and n is a positive number of 1 ≦ n ≦ 5. The water-in-oil emulsified cosmetic according to any one of the above [1] to [6], which is a polyoxyalkylene / alkyl co-modified silicone represented by

[8] The polyglycerin / alkyl co-modified silicone of component (D) is represented by the following general formula (5):
_{^{R 7 p R 8 q R 9}} r SiO (4-p-q-r) / 2 ··· (5)
[In the formula (5), R ⁷ represents an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, a fluorine-substituted alkyl group, an amino-substituted alkyl group, a carboxyl-substituted alkyl group, or an organic group represented by the following general formula (6). Are the same or different organic groups selected from
_{-C U H 2U -O- (C 2} H 4 O) V (C 3 H 6 O) W R 10 ··· (6)
R ⁸ is a polyglycerin derivative represented by the following general formula (7) and / or (8),
(Wherein ^{R 10} is a hydrogen group or an alkyl group having 1 to 30 carbon atoms, or ^R 11 - (CO) - organic ^{group, R 11} represented by is a hydrocarbon group having 1 to 30 carbon atoms .Q ether A C3-20 divalent hydrocarbon group which may contain a bond or an ester bond is shown, s is an integer of 2-20, and t is an integer of 1-20.)
R ⁹ is a silicon-containing group represented by the following general formula (9).
(Wherein p, q and r are 1.0 ≦ p ≦ 2.5, 0.001 ≦ q ≦ 1.5 and 0 ≦ r ≦ 1.5, respectively, U, V and W are 0 ≦ U respectively. ≦ 15, 0 ≦ V ≦ 50, 0 ≦ W ≦ 50, j is an integer of 1 ≦ j ≦ 5, and k is an integer of 0 ≦ k ≦ 500.
The water-in-oil emulsified cosmetic according to any one of the above [1] to [7], which is a polyglycerin / alkyl co-modified silicone represented by

[9] A fine particle metal oxide dispersion composition is prepared by previously dispersing the component (A) into the component (B) and the component (C), and then the fine particle metal oxide dispersion composition, the component (D), and the component (E) is mix | blended, The water-in-oil type emulsified cosmetics in any one of said [1]-[8] characterized by the above-mentioned are provided.

  [10] The water-in-oil emulsified cosmetic according to [9], wherein the amount of the component (A) in the fine particle metal oxide dispersion composition is 30 to 70% by mass. It is.

  [11] The above-mentioned [9], wherein the blending mass ratio (B) / (A) of the component (A) and the component (B) in the fine particle metal oxide dispersion composition is 0.01 to 0.5. Or a water-in-oil emulsified cosmetic according to [10].

  [12] The water-in-oil emulsified cosmetic according to any one of [1] to [11] above, wherein the blending amount of the silicone-based oil in all the oils is 20% by mass or less. It is.

  Hereinafter, the present invention will be described in detail.

  The component (A) used in the present invention is a particulate metal oxide surface-treated with trialkoxyalkylsilane, and the particulate metal oxide constituting the component (A) is zinc oxide, titanium oxide, cerium oxide, oxidized Zirconium, iron oxide, etc. are mentioned, and these can be used alone or in combination of two or more. The shape and the like of these fine particle metal oxides are not particularly limited, but the average particle diameter is preferably 1 to 100 nm. Here, the average particle diameter is a value measured by an image analyzer (Luzex IIIU, manufactured by Nicoles).

  The trialkoxyalkylsilane constituting the component (A) is a compound in which three alkoxy groups and one alkyl group are bonded to a silicon atom, and the alkoxy group reacts with a hydroxyl group on the powder surface, It is a compound that coats the powder surface. Such trialkoxyalkylsilane can be represented by the following general formula (10). In the trialkoxyalkylsilane, the alkoxy group is preferably methoxy, ethoxy, propoxy or the like, which is an alkoxy group having 1 to 3 carbon atoms. In the trialkoxyalkylsilane, the alkyl group is preferably a hexyl group, octyl group, decyl group, octadecyl group or the like, which is an alkyl group having 6 to 18 carbon atoms. Such trialkoxyalkylsilanes include, for example, trimethoxyhexylsilane, trimethoxyoctylsilane, trimethoxydecylsilane, trimethoxyoctadecylsilane, triethoxyhexylsilane, triethoxyoctylsilane, triethoxydecylsilane, triethoxyoctadecylsilane These can be used, and one or more of these can be used.

(M and N are each a positive integer, M = 6 to 20, N = 1 to 3)

  Among these trialkoxyalkylsilanes, it is preferable that the alkyl group has 8 or more carbon atoms because the dispersion stability of the component (A) in the oil layer becomes good. In the general formula (10), M = 7, N It is preferable to use triethoxyoctylsilane in which = 2 because the dispersion stability of the component (A) in the oil layer is very excellent.

  In the present invention, the method of coating the surface treatment agent of trialkoxyalkylsilane on the surface of the particulate metal oxide is not particularly limited, and generally known treatment methods are used. Specifically, a method of directly mixing an alkyl titanate and a particulate metal oxide, a dry coating method of directly mixing with a particulate metal oxide and heating to coat, ethanol, isopropyl alcohol, n-hexane, methylene chloride, benzene, Dissolve or disperse trialkoxyalkylsilane in a solvent such as toluene, add a particulate metal oxide to this solution or dispersion, and after mixing, remove the solvent by drying, etc. Examples thereof include a vapor phase coating method and a mechanochemical method in which a trialkoxyalkylsilane dissolved or dispersed is spray-coated on a powder in a fluidized bed. Among these, the wet coating method is preferable.

  The amount of the surface treatment of the component (A) fine particle metal oxide by trialkoxyalkylsilane is preferably a mass ratio of surface treatment agent / fine particle metal oxide = 0.02 to 0.25, more preferably 0.03. ~ 0.18. Within this range, better usability can be provided, and dispersibility and stability over time are also improved. The surface treatment of the fine particle metal oxide may be a trialkoxyalkylsilane alone, and a (dimethicone / methicone) copolymer or other surface treatment agent may be combined.

  When the component (A) used in the present invention is further surface-treated with a (dimethicone / methicone) copolymer, the oil absorption of the component (A) decreases, and more of the component (A) is blended in the water-in-oil emulsified cosmetic. Can be preferable. The (dimethicone / methicone) copolymer is a compound listed as DIMETHICONE / METHICONE COPOLYMER in INTERNATIONAL NOMENCLATURE of COSMETIC INGREDIENTS, and is a copolymer composed of dimethylsiloxane and methylhydrogensiloxane. Usually, it is used as a surface treatment agent for powders, and is widely used as a surface treatment agent that imparts water repellency to powders and hardly generates hydrogen over time. Specifically, a compound represented by the following general formula (11) can be exemplified as a preferred compound.

(V and w are respectively positive integers, v + w = 7 to 50, v: w = 1: 0.2 to 1: 4)

  The amount of surface treatment with the component (A) (dimethicone / methicone) copolymer is (surface treatment agent) / (particulate metal oxide surface-treated with trialkoxyalkylsilane) = 0.01 to 0.15 in mass ratio. More preferably, it is 0.03-0.08. Within this range, better usability can be provided, and dispersibility and stability over time are also improved.

  The amount of component (A) in the present invention is preferably 3 to 60% by mass (hereinafter abbreviated as%), more preferably 5 to 30%. If it is this range, further favorable usability can be given.

  The component (B) polyhydroxystearic acid used in the present invention is used to disperse the component (A) in the oil layer. The hydroxyl group of hydroxystearic acid is preferably at position 12, and the degree of polymerization of hydroxystearic acid is 3 ~ 12 are preferred, and more preferably the degree of polymerization is 4-8. As a commercially available product, ALARACEL P-100 (manufactured by Unikema) can be mentioned.

  In the present invention, the blending mass ratio (B) / (A) of the component (A) and the component (B) is preferably 0.01 to 0.5, and more preferably 0.02 to 0.3. Within this range, better usability can be provided, and dispersibility and stability over time are also improved.

The non-silicone oil agent of component (C) used in the present invention is a medium in which component (A) is dispersed and is not particularly limited as long as it is an oil agent having no polysiloxane skeleton, such as animal oil, vegetable oil, and synthetic oil. The origin and the properties of solid oil, semi-solid oil, liquid oil, volatile oil and the like are not limited, but liquid oil that is liquid at normal temperature (25 ° C.) is preferable from the viewpoint of dispersibility of component (A). For example, hydrocarbons, fats and oils, hydrogenated oils, ester oils, fluorine-based oils, lanolin derivatives, etc. can be used, more specifically liquid paraffin, light liquid isoparaffin, dodecane, isododecane, tetradecane, Hydrocarbons such as isotetradecane, hexadecane, isohexadecane, squalane, vegetable squalane, petrolatum, polyisobutylene, polybutene, molasses, olive oil, castor oil, mink oil, macadamian nut oil, camelia oil, rose pip oil, avocado oil Oils, jojoba oil, cetyl 2-ethylhexanoate, isononyl isononanoate, isotridecyl isononanoate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, isotridecyl isononanoate, tri-2-ethylhexa Glyceryl acid, propylene glycol dicaprate, neopentyl glycol dicaprate, polyglyceryl diisostearate, diglyceryl triisostearate, glyceryl tribehenate, hexa (hydroxystearic acid / stearic acid / rosinic acid) dipentaerythrityl, diisostearyl malate, dioctanoic acid Neopentyl glycol, cholesteryl isostearate, cholesteryl hydroxystearate, cholesteryl stearate, lanolin fatty acid cholesteryl, oleic fatty acid phytosteryl, N-lauroyl-L-glutamate di (cholesteryl behenyl octyldodecyl), N-lauroyl-L-glutamate di Ester oils such as (phytosteryl, 2-octyldodecyl), ethyl p-aminobenzoate Oil-soluble UV absorbers such as sildimethyl, ethylhexyl salicylate, ethylhexyl methoxycinnamate, octocrylene, dineopentyl-4′-methoxybenzalmalonate, and fluorine-based oils such as perfluorodecane, perfluorooctane, and perfluoropolyether Lanolin derivatives such as lanolin, lanolin acetate, lanolin fatty acid isopropyl, and lanolin alcohol can be exemplified, and one or more of these can be used. Of these, hydrocarbon oils and ester oils are preferred. Among them, hydrocarbon oils having a viscosity at 40 ° C. of 16 mm ² / s or less or ester oils having 27 or less carbon atoms are preferred, and isododecane, isotetradecane, Isohexadecane, liquid paraffin having a viscosity at 40 ° C. of 11 mm ² / s or less, propylene glycol dicaprate, neopentyl glycol dicaprate, isononyl isononanoate, isotridecyl isononanoate, and cetyl 2-ethylhexanoate are preferable. When these oil agents are used, it is possible to obtain a water-in-oil emulsified cosmetic having no stickiness and good spreading. In addition, the viscosity here is measured based on the crude oil and petroleum product-kinematic viscosity test method and viscosity index calculation method described in JIS-K-2283.

  The blending amount of component (C) in the present invention is preferably 5 to 90%, more preferably 10 to 60%. Within this range, a water-in-oil emulsified cosmetic with excellent spread can be obtained.

  Further, a fine particle metal oxide (component (A)) surface-treated with trialkoxyalkylsilane in advance is dispersed in a non-silicone oil agent (component (C)) as a dispersion medium, and polyhydroxystearic acid (component (component ( It is more preferable to prepare a fine particle metal oxide dispersion composition by performing a dispersion treatment using B)), and then blend the fine particle metal oxide dispersion composition into a water-in-oil emulsion cosmetic. By performing such a method, it becomes a water-in-oil emulsified cosmetic with further excellent dispersibility and temporal stability of the component (A).

  It is preferable that the compounding quantity of the component (A) in said fine particle metal oxide dispersion composition is 30 to 70%, More preferably, it is 40 to 60%. If it is this range, it will become the water-in-oil type emulsified cosmetics which were further excellent in stability with time.

  Further, the blending amounts of the component (B) and the component (C) in the fine particle metal oxide dispersion composition are preferably in the following ranges, respectively. The blending amount of the component (B) is preferably 0.3 to 15%, more preferably 0.5 to 10%, and the blending amount of the component (C) is preferably 30 to 70%, more preferably 40 to 60%. preferable. Within this range, the characteristics of various fine-particle metal oxides can be sufficiently exhibited, and a water-in-oil emulsified cosmetic having further excellent temporal stability can be obtained.

  Although the manufacturing method of said fine particle metal oxide dispersion composition is not specifically limited, For example, a component (B) and a component (C) are mixed, a component (A) is added to this, and it is uniform. It can be obtained by distributed processing. In this case, examples of the equipment for the dispersion treatment include a disper mixer, a homomixer, a ball mill, a bead mill, and the like, and a wet grinding equipment such as a ball mill and a bead mill using a medium is more preferable.

  In addition to the above components (A) to (C), the fine particle metal oxide dispersion composition includes oil agents and powders other than the above components in a quantitative and qualitative range depending on the purpose. Body, surfactant, gelling agent, antioxidant, preservative, coloring agent, fragrance, cosmetic ingredient and the like can be blended.

  1-80% is preferable and, as for the compounding quantity of said fine metal oxide dispersion composition in this invention, 5-60% is more preferable. Within this range, a water-in-oil emulsified cosmetic with no stickiness and excellent spread can be obtained. Moreover, 1 type, or 2 or more types can be used for a particulate metal oxide dispersion composition.

  Component (D) used in the present invention is HLB 2-7 polyoxyalkylene / alkyl co-modified silicone and / or HLB 2-7 polyglycerin / alkyl co-modified silicone, and is used as an emulsifier for water-in-oil emulsified cosmetics. It is done.

The component (D) HLB 2-7 polyoxyalkylene / alkyl co-modified silicone may be any HLB of 2 to 7 and linear or branched silicone modified with polyoxyalkylene and alkyl. Specifically, a compound represented by the following general formula (1) can be exemplified as a preferred compound.
R ¹ _a R ² _b R ³ _c SiO _{(4-abc) / 2} (1)
(In the formula, R ¹ represents an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, a fluorine-substituted alkyl group, or the following general formula (2):
_{-C m H 2m -O- (C 2} H 4 O) d (C 3 H 6 O) e -R 4 ... (2)
R ² is the same or different organic group selected from the organic groups represented by the following general formula (3):
_{-C m H 2m -O- (C 2} H 4 O) f (C 3 H 6 O) g -R 5 ... (3)
R ³ is a polyoxyalkylene group represented by the following general formula (4)
_{^{-C n H 2n - (SiR 1}} R 1 O) h -SiR 1 3 ... (4)
R ⁴ is a hydrocarbon group having 4 to 30 carbon atoms or an organic group represented by R ^6- (CO)-, R ⁵ is a hydrogen atom or a hydrocarbon having 1 to 30 carbon atoms A group or an organic group represented by R ⁶ — (CO) —, R ⁶ is a hydrocarbon group having 1 to 30 carbon atoms. a, b and c are 1.0 ≦ a ≦ 2.5, 0.001 ≦ b ≦ 1.5 and 0.001 ≦ c ≦ 1.5, respectively, d and e are 0 ≦ d ≦ 50, 0 ≦ e ≦ 50, f and g are 2 ≦ f ≦ 200, 0 ≦ g ≦ 198, and f + g is an integer of 3 to 200, respectively. M is an integer of 0 ≦ m ≦ 15, h is an integer of 0 ≦ h ≦ 500, and n is a positive number of 1 ≦ n ≦ 5.

Further preferred compounds include compounds represented by the following general formula (12).
(Wherein x is an integer of 10-100, y is an integer of 3-25, z is an integer of 8-25, D is an integer of 0-2, A is an integer of 5-7, B is an integer of 5-10 , I is an integer from 8 to 16)

In addition, the HLB 2-7 polyglycerin / alkyl co-modified silicone of component (D) may be any HLB that is 2 to 7 and is linear or branched silicone modified with polyglycerin and alkyl. Specifically, a compound represented by the following general formula (5) can be exemplified as a preferred compound.
_{^{R 7 p R 8 q R 9}} r SiO (4-p-q-r) / 2 (5)
[In the formula (5), R ⁷ represents an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, a fluorine-substituted alkyl group, an amino-substituted alkyl group, a carboxyl-substituted alkyl group, or an organic group represented by the following general formula (6). Are the same or different organic groups selected from
_{-C U H 2U -O- (C 2} H 4 O) V (C 3 H 6 O) W R 10 (6)
R ⁸ is a polyglycerin derivative represented by the following general formula (7) and / or (8),
(Wherein ^{R 10} is a hydrogen group or an alkyl group having 1 to 30 carbon atoms, or ^R 11 - (CO) - organic ^{group, R 11} represented by is a hydrocarbon group having 1 to 30 carbon atoms .Q ether A C3-20 divalent hydrocarbon group which may contain a bond or an ester bond is shown, s is an integer of 2-20, and t is an integer of 1-20.)
R ⁹ is a silicon-containing group represented by the following general formula (9).
(Wherein p, q and r are 1.0 ≦ p ≦ 2.5, 0.001 ≦ q ≦ 1.5 and 0 ≦ r ≦ 1.5, respectively, U, V and W are 0 ≦ U respectively. ≦ 15, 0 ≦ V ≦ 50, 0 ≦ W ≦ 50, j is an integer of 1 ≦ j ≦ 5, and k is an integer of 0 ≦ k ≦ 500.

  Commercially available products of the component (D) polyoxyalkylene / alkyl co-modified silicone include cetyl PEG / PPG-10 / 1 dimethicone (ABIL EM90 (manufactured by EVONIC GOLDSCHMIDT)), lauryl PEG-9 polydimethylsiloxyethyl dimethicone (KF- 6038 (manufactured by Shin-Etsu Chemical Co., Ltd.)) and the like, and examples of commercially available polyglycerin / alkyl co-modified silicone include lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone (KF-6105 (manufactured by Shin-Etsu Chemical Co., Ltd.)) Can be mentioned.

  0.1 to 10% is preferable and, as for the compounding quantity of the component (D) in this invention, 1 to 5% is more preferable. Within this range, a water-in-oil emulsified cosmetic with no stickiness and excellent spread can be obtained. Moreover, 1 type, or 2 or more types can be used for a component (D).

  The aqueous component of the component (E) used in the present invention is a component constituting the inner water phase of the water-in-oil emulsified cosmetic, and in addition to purified water generally used in cosmetics, such as ethyl alcohol Alcohols, glycols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol, polyethylene glycol, glycerols such as glycerin, diglycerin, polyglycerin, aloe vera, witch hazel, hamamelis, cucumber, lemon, lavender, rose And plant extracts such as Although the compounding quantity of the component (E) in this invention is not specifically limited, 10 to 70% is preferable.

  The water-in-oil emulsified cosmetic of the present invention may further contain a silicone-based oil for adjusting the feel. Silicone oils are oils with a polysiloxane skeleton, such as low polymerization dimethylpolysiloxane, high polymerization dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, amino-modified organo Examples thereof include polysiloxane and fluorine-modified organopolysiloxane.

  In the water-in-oil emulsified cosmetic of the present invention, the amount of the silicone oil is preferably as small as possible. The blending amount of the silicone oil in all the oils in the water-in-oil emulsified cosmetic of the present invention is preferably 20% or less, more preferably 10% or less, and most preferably no silicone oil is blended. That is. Similarly, in the fine particle metal oxide dispersion composition, the amount of the silicone oil is preferably as small as possible. When the blending amount of the silicone-based oil agent in all the oil agents is increased, the viscosity of the fine particle metal oxide dispersion composition is increased, and the dispersibility of the component (A) is lowered.

  In the water-in-oil emulsified cosmetic of the present invention, as long as the effects of the present invention are not impaired, if necessary, oils other than the essential components, powders such as inorganic pigments, organic pigments and extender pigments, surface activity Ingredients usually used in cosmetics such as water, water-soluble polymers, aqueous components such as humectants, sugars, UV absorbers, antioxidants, anti-fading agents, preservatives, medicinal ingredients, stabilizers, pigments, and fragrances Ingredients can be appropriately blended for imparting various effects.

  As the powder component, in addition to the fine particle metal oxide of the component (A), a spherical shape, a plate shape, a needle shape, a fume shape, a fine particle, a particle size such as a pigment class, a porous material, a nonporous material, etc. It is not particularly limited by the particle structure and the like, and examples thereof include inorganic powders, glitter powders, organic powders, pigment powders, metal powders, composite powders and the like. Specific examples include white inorganic pigments such as barium sulfate, carbon black, titanium / titanium oxide sintered products, colored inorganic pigments such as chromium hydroxide, bitumen, ultramarine blue, talc, muscovite, phlogopite, red mica, Biotite, synthetic mica, sericite (sericite), synthetic sericite, silicon carbide, silicon dioxide, diatomaceous earth, aluminum silicate, magnesium aluminum silicate, calcium silicate, barium silicate, magnesium silicate, calcium carbonate , White body powders such as magnesium carbonate, hydroxyapatite, boron nitride, clay minerals such as kaolin, bentonite, smectite, hectorite, montmorillonite, and their organic modifications, titanium oxide-coated mica, titanium oxide-coated bismuth oxychloride, Iron oxide mica titanium, bitumen treated mica titanium, carmine treated mica Tan, bismuth oxychloride, fish scale foil, polyethylene terephthalate / aluminum / epoxy laminated powder, polyethylene terephthalate / polyolefin laminated film powder, polyethylene terephthalate / polymethylmethacrylate laminated film powder, titanium oxide coated glass flakes Organic resins such as resins, polyethylene resins, polyacrylic resins, polyester resins, fluorine resins, cellulose resins, polystyrene resins, copolymer resins such as styrene-acrylic copolymer resins, polypropylene resins, silicone resins, and urethane resins Polymer resin powder, organic low molecular weight powder such as zinc stearate, N-acyl lysine, natural organic powder such as silk powder, cellulose powder, red 201, red 202, red 205, red 22 No., Red No. 228, Orange No. 203, Orange No. 204, Blue No. 404, Yellow No. 401 and other organic pigment powders, Red No. 3, Red No. 104, Red No. 106, Orange No. 205, Yellow No. 4, Yellow No. 5 No. 3, Green No. 3, Blue No. 1 organic pigment powder such as zirconium, barium or aluminum lake or further metal powder such as aluminum powder, gold powder, silver powder, fine particle titanium oxide coated mica titanium, fine particle zinc oxide coated mica titanium And composite powders of barium sulfate-coated mica titanium, titanium oxide-containing silicon dioxide, zinc oxide-containing silicon dioxide, and the like. These powders may be used singly or in combination of two or more, and may be used in combination. These powders are one or two of fluorine compounds, silicone compounds, metal soaps, lecithins, hydrogenated lecithins, collagens, hydrocarbons, higher fatty acids, higher alcohols, esters, waxes, waxes, surfactants, etc. Surface treatment may be performed using the above.

  Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant in addition to the component (D). For example, nonionic surfactants include reoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil, hydrogenated castor oil, polyoxyethylene sorbitol tetra fatty acid ester, glycerin fatty acid ester, sorbitan fatty acid ester. , Polyglycerin fatty acid ester, sucrose fatty acid ester, alkyl polyglucoside, N-alkyldimethylamine oxide polyoxyethylene glyceryl fatty acid ester, polyoxyethylene cholesteryl ether, polyoxyethylene phytosteryl ether, polyoxyethylene alkyl ether, polyoxyethylene Polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyether-modified silicone, polyester Ether Shirokishiechiru co-modified silicone, polyglycerin modified silicone, and the like polyglycerol-Shirokishiechiru co-modified silicone. For example, anionic surfactants include sodium or triethanolamine salts of fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, sodium cocoyl methyl taurate, sodium lauroylmethyl taurate, sodium myristoyl methyl taurate, N-acylmethyl taurine salts such as sodium palmitoylmethyl taurate and sodium stearoylmethyl taurine, polyoxyethylene lauryl ether phosphate, polyoxyethylene cetyl ether phosphate, polyoxyethylene oleyl ether phosphate, polyoxyethylene nonylphenyl ether phosphate, etc. And polyoxyethylene alkyl ether phosphate esters. Examples of cationic surfactants include stearyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, behenyl trimethyl ammonium chloride, behenyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, distearyl dimethyl ammonium chloride, odor Distearyldimethylammonium chloride, dibehenyldimethylammonium chloride, dibehenyldimethylammonium bromide, dicetyldimethylammonium chloride, dicetyldimethylammonium bromide, stearyldimethylbenzylammonium chloride, dilauryldimethylammonium chloride, dipolyoxyethylene chloride ( 15E.O.) Coconut oil alkylmethylammonium chloride, dipolyoxyethylene chloride (4E.O.) lauryl ester -Tetradimethylammonium chloride, amidopropyltrimethylammonium chloride, dicocoylethylhydroxyethylmethylammonium methylsulfate and the like. For example, amphoteric surfactants include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, phosphatidylinositol, sphingophospholipid, soy lecithin, egg yolk lecithin, or hydrogenated products such as phospholipids and phospholipid / cholesterol composites. Body, and phospholipid complexes such as phospholipid / phytosterol complex.

  Examples of water-soluble polymers include guar gum, sodium chondroitin sulfate, sodium hyaluronate, gum arabic, sodium alginate, carrageenan and other semi-synthetic compounds such as methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyvinyl polymer, Synthetic compounds such as alkyl-added carboxyvinyl polymer, polyvinyl alcohol, polyvinyl pyrrolidone, and sodium polyacrylate, as well as proteins, mucopolysaccharides, collagen, elastin, keratin and the like.

  Although the manufacturing method of the water-in-oil emulsified cosmetic of the present invention is not particularly limited, for example, the component (E) is mixed with the component (A) to the component (D) and any oil component uniformly mixed. ) And any aqueous component uniformly mixed and emulsified, and then filled into a container or mold. Moreover, it is preferable to mix | blend, after mixing and dispersing component (A)-(C) previously as mentioned above.

  The water-in-oil emulsified cosmetic of the present invention is not particularly limited, and examples of the shape include liquid, semi-solid, and solid. The product forms include facial cleansing foams, creams, cleansings, massage creams, packs, lotions, emulsions, creams, cosmetics, makeup bases, sunscreens and other cosmetics for skin, foundations, white powder, eye shadows, eye Finishing cosmetics such as liner, mascara, eyebrow, concealer, lipstick, lip balm, hair mist, shampoo, rinse, treatment, hair tonic, hair cream, pomade, tic, liquid hair conditioner, set lotion, hair spray, hair dye, etc. For example, a cosmetic for hair. Among these, sunscreens, foundations, makeup bases and the like are water-in-oil emulsified cosmetics in which the effects of the present invention are easily exhibited.

  Next, the present invention will be described in more detail with reference to production examples and examples. The present invention is not limited at all by these.

Production Examples 1 to 7: Surface-treated fine particle metal oxide Surface-treated fine particle metal oxides having the compositions shown in Table 1 were prepared by the following production method.

(Note 1) MT-100SA (manufactured by Teica)
(Note 2) MZ-500 (manufactured by Teika)
(Note 3) KF-9901 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 4) KF-96A-100cs (Shin-Etsu Chemical Co., Ltd.)

(Production method)
100 parts of isopropyl alcohol and components 3 to 5 are mixed and mixed with components 1 and 2 in a Henschel mixer (Mitsui Mining Co., Ltd.). Thereafter, isopropyl alcohol was recovered at 60 ° C. under reduced pressure, and pulverized to obtain a surface-treated fine particle metal oxide.

Production Examples 8 to 15: Fine-particle metal oxide dispersion composition Fine-particle metal oxide dispersion compositions having the compositions shown in Table 2 were prepared by the following production method.

(Note 5) ARLACEL P-100 (manufactured by Unikema)
(Note 6) KLEAROL (manufactured by SONNEBORN)
(Note 7) KF-96A-6cs (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Production method)
Ingredients (1) to (9) were mixed uniformly, and the bead mill (LMZ-0.6) manufactured by Ashizawa Co., Ltd. was used with 3 mm of zirconia beads, a bead filling rate of 60%, and agitator rotation speed of 2000 rpm for 5 hours. Dispersion was performed to obtain a fine particle metal oxide dispersion composition.

Examples 1 to 11, Reference Examples, Examples 13 to 17 and Comparative Examples 1 to 7; Water-in-oil emulsified cosmetics Water-in-oil emulsified cosmetics having the compositions shown in Tables 3 to 5 were prepared by the following production method. Each sample was evaluated for “stability over time” and “goodness of spread”, and the results are also shown in Tables 3 to 5.

(Note 8) KP-540 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 9) KF-6038 (Shin-Etsu Chemical Co., Ltd.)
(Note 10) KF-6105 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 11) KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 12) KF-6014 (Shin-Etsu Chemical Co., Ltd.)

(Production method)
What uniformly mixed component (25)-(30) was added to what mixed component (1)-(24) uniformly, and it emulsified, defoamed, and obtained the water-in-oil emulsion cosmetic.

(Evaluation method) Stability over time The stability over time was evaluated by the following accelerated test. The accelerated test here is to store in a constant temperature bath at 50 ° C. for 4 weeks. If the water-in-oil emulsified cosmetics have good stability over time, the aggregation of the particulate metal oxide can be suppressed, and the viscosity change of the cosmetics before and after the acceleration test is small. On the other hand, when the stability over time is poor, the fine particle metal oxide aggregates, thereby generating a volume effect and causing the fine particle metal oxide to settle, resulting in a large change in viscosity before and after the acceleration test. As a specific method of the acceleration test, after each sample was manufactured, stored in a 30 ° C. constant temperature bath for one day, and then stored in a 50 ° C. constant temperature bath for 4 weeks using the viscosity value measured with a B-type viscometer as a reference value The viscosity value was measured after being stored in a constant temperature bath at 30 ° C. for one day, the viscosity value was compared with the reference value, and the change from the reference value was judged according to the following criteria.
(Evaluation): (Judgment)
Viscosity change is 0 mPa · s or more and less than ± 10000 mPa · s;
Viscosity change is ± 10000 mPa · s or more and less than ± 20000 mPa · s;
Viscosity change is ± 20000 mPa · s or more and less than ± 40000 mPa · s;
Viscosity change is ± 40000 mPa · s or more; ×

(Evaluation method) Good spread Each sample is used by 20 panelists specializing in cosmetics evaluation, rated according to the following absolute evaluation criteria, graded, and the average value from the total score of all panel members of each sample Was calculated and determined according to the following four-step criteria.

Absolute Evaluation Criteria (Score): (Evaluation)
6 points: Very good 5 points: Good 4 points: Slightly good 3 points: Normal 2 points: Slightly bad 1 point: Bad 4 grade criteria (judgment): (Average score)
◎: Over 5 points ○: Over 5 points and under 5 points △: Over 2 points over 3.5 points ×: Up to 2 points

  As shown in Tables 3 to 5, Examples 1 to 11, Reference Examples, and Examples 13 to 17 were excellent in both items of “stability with time” and “goodness of spread”. Of these, Examples 13 to 17 in which the fine particle metal oxide dispersion composition was previously prepared and blended with the components (A) to (C) were further excellent in stability over time. On the other hand, Comparative Example 1 in which no polyhydroxystearic acid was blended was in a non-uniform emulsified state, and was inferior in both items of “stability with time” and “goodness of spread”. In Comparative Example 2 in which an (acrylates / dimethicone) copolymer was blended instead of polyhydroxystearic acid, the stability over time was good, but the spread was poor. The comparative example 3 which mix | blended the particulate metal oxide surface-treated with dimethylposilyloxane instead of triethoxycaprylylsilane, and the comparative example 4 which mix | blended dimethylposilyloxane (6cs) instead of the liquid paraffin There was no fluidity, and it was inferior in both items of “stability with time” and “goodness of spread”. Comparative Example 5 in which polyoxyalkylene-modified silicone is blended in place of polyoxyalkylene / alkyl co-modified silicone, Comparative Example 6 in which polyglycerin-modified silicone is blended in place of polyglycerin / alkyl co-modified silicone, Polyoxyalkylene / alkyl co-polymer Comparative Example 7 in which sorbitan sesquiisostearate was blended in place of the modified silicone was not in a uniform emulsified state, and was inferior in both “stability with time” and “goodness of spread”.

Example 18: Water-in-oil type emulsion sunscreen (component) (%)
1.2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine 1
2. Octyl methoxycinnamate 7
3. Isononyl isononanoate 5
4). Inulin stearate 1
5. Fine particle metal oxide dispersion composition of Production Example 11 20
6). Fine particle metal oxide dispersion composition of Production Example 13 15
7). Light liquid isoparaffin 15
8). Polyoxyethylene, polyoxypropylene, cetyl co-modified silicone (Note 13) 3
9. Purified water remaining amount 10. Methylenebisbenzotriazolyltetramethylbutylphenol aqueous dispersion (Note 14) 5
11 Sodium chloride 1
12 Methylparaben 0.2
13. Fragrance 0.1
(Note 13) ABIL EM90 (Evonic Goldschmidt GMBH)
(Note 14) TINOSORB M (BASF)

(Production method)
A: Components 1 to 4 are heated to 90 ° C. and dissolved and mixed.
B: Components 5 to 8 and 13 are added to A and mixed.
C: Components 9 to 12 are mixed.
D: C is added to B and emulsified.
E: D was defoamed to obtain a water-in-oil type emulsion sunscreen.

  Example 18 was a water-in-oil emulsified sunscreen with excellent temporal stability, good spread and no stickiness.

Example 19: Water-in-oil emulsion foundation (component) (%)
1. Dextrin palmitate 2
2. Titanium oxide 3
3. Iron oxide 2
4). Talc 5
5. Lecithin 0.5
6). Glyceryl trioctanoate 8
7). Dimethyl distearyl ammonium hectorite 1
8). Decamethylcyclopentasiloxane 5
9. Polyoxyalkylene / alkyl co-modified silicone (Note 9) 3
10. Fine particle metal oxide dispersion composition of Production Example 14 15
11 Decamethylcyclopentasiloxane 3
12 Octocrylene 10
13. Diethylaminohydroxybenzoylhexyl benzoate 2
14 Purified water remaining amount 15. Ethanol 5
16. 1,2-Pentanediol 1

(Production method)
A: Components 1 to 6 are heated to 90 ° C. and dispersed with a three-roller.
B: Components 7 to 13 are added to A, and the mixture is heated to 90 ° C. and dispersed.
C: Cool B to 45 ° C.
D: D is added to E: C which mixes components 14-16, and it emulsifies.
F: E was defoamed to obtain a water-in-oil emulsified foundation.

  Example 19 was a water-in-oil emulsified foundation having excellent stability over time, good spread and no stickiness.

Example 20: Water-in-oil emulsified serum (component) (%)
1. Propylene glycol dicaprate 20
2. Dimethylpolysiloxane (2cs) 5
3. Fine particle metal oxide dispersion composition of Production Example 15 3
4). Methyl trimethicone 5
5. Polyglycerin / alkyl co-modified silicone (Note 10) 3
6). (Lauryl dimethicone / polyglycerin-3) crosspolymer (Note 15) 2
7). (PEG15 / Lauryl Dimethicone) Crosspolymer (Note 16) 3
8.1,3-Butylene glycol 10
9. Xanthan gum 0.2
10. 1,2-pentanediol 0.5
11 Purified water remaining amount (Note 15) KSG-820 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 16) KSG-310 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Production method)
A: Components 1 to 7 are mixed.
B: Components 8 to 11 are heated to 75 ° C. and mixed.
C: A is added to B and emulsified.
D: C is cooled to 30 ° C.
E: D was defoamed to obtain a water-in-oil emulsified cosmetic liquid.

  Example 20 was a water-in-oil emulsified cosmetic liquid with excellent temporal stability, good spread and no stickiness.

Example 21: Water-in-oil type emulsion sunscreen (component) (%)
1.2,4,6-tris [4- (2-ethylhexyloxycarbonyl)
Anilino] -1,3,5-triazine 1
2. Octyl methoxycinnamate 5
3. Diethylaminohydroxybenzoylhexyl benzoate 2
4). Polysilicone-15 (Note 17) 1
5. Octocrylene 10
6). Butyl-methoxydibenzoylmethane (Note 18) 1
7). Fine particle metal oxide dispersion composition of Production Example 11 10
8). Fine particle metal oxide dispersion composition of Production Example 13 10
9. Light liquid isoparaffin 20
10. Polyoxyethylene, polyoxypropylene, cetyl co-modified silicone (Note 13) 3
11 Polyhydroxystearic acid (Note 5) 0.512. Purified water remaining amount 13. Methylenebisbenzotriazolyltetramethylbutylphenol aqueous dispersion (Note 14) 5
14 Phenylbenzimidazolesulfonic acid 2
15. Triethanolamine 1
16. Methylparaben 0.2
17. Fragrance 1
(Note 17) PARSOL SLX (made by DSM NUTRITIONAL PRODUCTS)
(Note 18) PARSOL 1789 (DSM NUTRITIONALPRODUCTS)

(Production method)
A: Components 1 to 6 are heated to 90 ° C. and dissolved and mixed.
B: Components 7 to 11 and 17 are added to A and mixed.
C: Components 12 to 16 are mixed.
D: C is added to B and emulsified.
E: D was defoamed to obtain a water-in-oil type emulsion sunscreen.

  Example 21 was a water-in-oil emulsified sunscreen with excellent stability over time, good spread and no stickiness.

Example 22: Water-in-oil type emulsion sunscreen (component) (%)
1.2,4,6-tris [4- (2-ethylhexyloxycarbonyl)
Anilino] -1,3,5-triazine 1
2. Octyl methoxycinnamate 5
3. Diethylaminohydroxybenzoylhexyl benzoate 2
4). Oxybenzone-3 (Note 19) 1
5. Octocrylene 5
6). Butyl-methoxydibenzoylmethane (Note 18) 1
7). Surface-treated fine particle metal oxide 10 of Production Example 10
8). Surface treated fine particle metal oxide 10 of Production Example 10
9. Light liquid isoparaffin 30
10. Polyoxyethylene / polyoxypropylene Cetyl co-modified silicone (Note 13) 3
11 Polyhydroxystearic acid (Note 5) 5
12 Purified water remaining amount 13. Methylenebisbenzotriazolyltetramethylbutylphenol aqueous dispersion (Note 14) 5
14 Phenylbenzimidazolesulfonic acid 2
15. Triethanolamine 1
16. Methylparaben 0.2
17. Fragrance 1
(Note 19) Biosoap 110 (manufactured by Kyodo Pharmaceutical)

(Production method)
A: Components 1 to 6 are heated to 90 ° C. and dissolved and mixed.
B: Components 7 to 11 and 17 are added to A and mixed.
C: Components 12 to 16 are mixed.
D: C is added to B and emulsified.
E: D was defoamed to obtain a water-in-oil type emulsion sunscreen.

Example 22 was a water-in-oil emulsified sunscreen with excellent stability over time, good spread and no stickiness.

Claims (11)

The following components (A) to (E);
(A) 3-60 mass% of fine particle metal oxide surface-treated with trialkoxyalkylsilane
(B) Polyhydroxystearic acid (however, the blending mass ratio of component (A) to component (B) (B) / (A) is 0.01 to 0.5)
(C) propylene glycol dicaprate, neopentyl glycol dicaprate, isononyl isononanoate, isotridecyl isononanoate, cetyl 2-ethylhexanoate, isododecane, isotetradecane, isohexadecane and liquid paraffin having a viscosity at 40 ° C. of 11 mm ² / s or less 1 to 2 or more non-silicone oils selected from 5 to 90% by mass
(D) HLB 2-7 polyoxyalkylene / alkyl co-modified silicone and / or HLB 2-7 polyglycerin / alkyl co-modified silicone 0.1-10% by mass
(E) 10-70 mass% of aqueous components
A water-in-oil emulsified cosmetic characterized by comprising   2. The water-in-oil type according to claim 1, wherein the surface treatment amount of the component (A) by trialkoxyalkylsilane is, by mass ratio, surface treatment agent / particulate metal oxide = 0.02 to 0.25. Emulsified cosmetic.   The water-in-oil emulsified cosmetic according to claim 1 or 2, wherein the trialkoxyalkylsilane is triethoxyoctylsilane.   The water-in-oil emulsified cosmetic according to any one of claims 1 to 3, wherein the particulate metal oxide of component (A) is further surface-treated with a (dimethicone / methicone) copolymer.   The surface treatment amount of the component (A) by the (dimethicone / methicone) copolymer is ((dimethicone / methicone) copolymer) / (particulate metal oxide surface-treated with trialkoxyalkylsilane) = 0.01 to 0 in mass ratio. The water-in-oil emulsified cosmetic according to claim 4, which is .15.   The hydroxystearic acid of component (B) is a polyhydroxystearic acid having a hydroxyl group at the 12-position and a polymerization degree of 4 to 8, according to any one of claims 1 to 5. Water-in-oil emulsified cosmetic. The polyoxyalkylene / alkyl co-modified silicone of component (D) is represented by the following general formula (1)
R ¹ _a R ² _b R ³ _c SiO _{(4-abc) / 2} (1)
(In the formula, R ¹ represents an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, a fluorine-substituted alkyl group, or the following general formula (2):
_{-C m H 2m -O- (C 2} H 4 O) d (C 3 H 6 O) e -R 4 ... (2)
R ² is the same or different organic group selected from the organic groups represented by the following general formula (3):
_{-C m H 2m -O- (C 2} H 4 O) f (C 3 H 6 O) g -R 5 ... (3)
R ³ is a polyoxyalkylene group represented by the following general formula (4)
_{^{-C n H 2n - (SiR 1}} R 1 O) h -SiR 1 3 ... (4)
R ⁴ is a hydrocarbon group having 4 to 30 carbon atoms or an organic group represented by R ^6- (CO)-, R ⁵ is a hydrogen atom or a hydrocarbon having 1 to 30 carbon atoms A group or an organic group represented by R ⁶ — (CO) —, R ⁶ is a hydrocarbon group having 1 to 30 carbon atoms. a, b and c are 1.0 ≦ a ≦ 2.5, 0.001 ≦ b ≦ 1.5 and 0.001 ≦ c ≦ 1.5, respectively, d and e are 0 ≦ d ≦ 50, 0 ≦ e ≦ 50, f and g are 2 ≦ f ≦ 200, 0 ≦ g ≦ 198, and f + g is an integer of 3 to 200, respectively. M is an integer of 0 ≦ m ≦ 15, h is an integer of 0 ≦ h ≦ 500, and n is a positive number of 1 ≦ n ≦ 5. The water-in-oil emulsified cosmetic according to any one of claims 1 to 6, which is a polyoxyalkylene / alkyl co-modified silicone represented by formula (1). The polyglycerin / alkyl co-modified silicone of component (D) is represented by the following general formula (5)
_{^{R 7 p R 8 q R 9}} r SiO (4-p-q-r) / 2 ··· (5)
[In the formula (5), R ⁷ represents an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, a fluorine-substituted alkyl group, an amino-substituted alkyl group, a carboxyl-substituted alkyl group, or an organic group represented by the following general formula (6). Are the same or different organic groups selected from
_{-C U H 2U -O- (C 2} H 4 O) V (C 3 H 6 O) W R 10 ··· (6)
R ⁸ is a polyglycerin derivative represented by the following general formula (7) and / or (8),
(Wherein ^{R 10} is a hydrogen group or an alkyl group having 1 to 30 carbon atoms, or ^R 11 - (CO) - organic ^{group, R 11} represented by is a hydrocarbon group having 1 to 30 carbon atoms .Q ether A C3-20 divalent hydrocarbon group which may contain a bond or an ester bond is shown, s is an integer of 2-20, and t is an integer of 1-20.)
R ⁹ is a silicon-containing group represented by the following general formula (9).
(Wherein p, q and r are 1.0 ≦ p ≦ 2.5, 0.001 ≦ q ≦ 1.5 and 0 ≦ r ≦ 1.5, respectively, U, V and W are 0 ≦ U respectively. ≦ 15, 0 ≦ V ≦ 50, 0 ≦ W ≦ 50, j is an integer of 1 ≦ j ≦ 5, and k is an integer of 0 ≦ k ≦ 500.
The water-in-oil emulsified cosmetic according to any one of claims 1 to 7, which is a polyglycerin / alkyl co-modified silicone represented by:   The water-in-oil emulsified cosmetic according to any one of claims 1 to 8, wherein the amount of the silicone-based oil in all the oils is 20% by mass or less. Component (A) 3 to 60% by mass of fine particle metal oxide surface-treated with trialkoxyalkylsilane,
Component (B) Polyhydroxystearic acid (provided that the blending mass ratio of component (A) to component (B) (B) / (A) is 0.01 to 0.5), and component (C) propylene glycol dicaprate 1 or 2 selected from the group consisting of neopentyl glycol dicaprate, isononyl isononanoate, isotridecyl isononanoate, cetyl 2-ethylhexanoate, isododecane, isotetradecane, isohexadecane, and liquid paraffin having a viscosity at 40 ° C. of 11 mm ² / s or less 5 to 90 mass% of non-silicone based oil agent
To prepare a fine particle metal oxide dispersion composition by dispersion treatment,
Then the particulate metal oxide dispersion composition;
Component (D) HLB 2-7 polyoxyalkylene-alkyl co-modified silicone and / or HLB 2-7 polyglycerin-alkyl co-modified silicone 0.1-10 mass%,
The manufacturing method of the water-in-oil type emulsion cosmetic characterized by mix | blending component (E) 10-70 mass% of aqueous components. The method for producing a water-in-oil emulsified cosmetic according to claim 10, wherein the compounding amount of the component (A) in the fine particle metal oxide dispersion composition is 30 to 70% by mass.